TWI791277B - Polyimide precursor, polyimide, polyimide film and substrate, and tetracarboxylic dianhydride used in manufacture of polyimide - Google Patents

Abstract

The present invention relates to a polyimide precursor and a polyimide containing at least one type of repeating unit in which the structure derived from the tetracarboxylic acid component is a structure represented by any one of formulas (A-1) to (A-4) shown below.

(In the formula, each of R₁ , R₂ and R₃ independently represents -CH₂ -, -CH₂ CH₂ -, or -CH=CH-.)

(In the formula, R₄ represents -CH₂ -, -CH₂ CH₂ -, or -CH=CH-.)

(In the formula, each of R₅ and R₆ independently represents -CH₂ -, -CH₂ CH₂ -, or -CH=CH-.)

(In the formula, R₇ represents -CH₂ CH₂ - or -CH=CH-.)

Description

Polyimide precursor, polyimide, polyimide film and substrate, and tetracarboxylic dianhydride used in the manufacture of polyimide

The present invention relates to polyimides having excellent properties such as transparency, bending resistance, high heat resistance, and low linear thermal expansion coefficient, their precursors, and tetracarboxylic dianhydrides used in their production.

In recent years, with the advent of a highly informationized society, the development of optical materials such as optical fibers in the field of optical communications, optical waveguides, and other display devices, such as liquid crystal alignment films and protective films for color filters, is in progress. Especially in the field of display devices, research on lightweight and highly flexible plastic substrates to replace glass substrates, and the development of bendable or roundable displays are actively underway. Therefore, there is a need for higher performance optical materials that can be used in such applications.

Aromatic polyimides, which are inherently yellow-brown in color due to the formation of intramolecular conjugation or charge-transfer complexes. In order to suppress coloring, it has been suggested that, for example, introducing fluorine atoms into the molecule, imparting flexibility to the main chain, introducing bulky groups as side chains, etc., to prevent the formation of intramolecular conjugation or charge transfer complexes and make them exhibit method of transparency.

Also, a method of using a semi-alicyclic or fully alicyclic polyimide that theoretically does not form a charge transfer complex to exhibit transparency has been proposed. In particular, aromatic tetracarboxylic dianhydrides are used as tetracarboxylic acid components, alicyclic diamines are used as highly transparent semi-alicyclic polyimides as diamine components, and alicyclic tetracarboxylic dianhydrides are used as tetracarboxylic acid dianhydrides. Carboxylic acid components and aromatic diamines have been proposed as highly transparent semi-alicyclic polyimides as diamine components.

For example: Patent Document 1 discloses the composition of an alicyclic tetracarboxylic acid component having at least one aliphatic 6-membered ring and no aromatic ring in its chemical structure and at least one amide bond and an aromatic ring in its chemical structure Semi-alicyclic polyimide precursor obtained from aromatic diamine components, and polyimide. Specifically, in the examples of Patent Document 1, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, decahydro- 1,4: 5,8-Naphthalene-2,3,6,7-tetracarboxylic dianhydride, etc. For aromatic diamine components having amide bonds and aromatic rings, use 4,4 '-Diaminobenzoyl for aniline and so on. In addition, in Examples of Patent Document 1, p-phenylenediamine, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-oxydiphenylamine, etc. were used as other diamine components.

Moreover, patent document 2 discloses the manufacturing method of the polyamic acid characterized by making specific alicyclic tetracarboxylic dianhydride and diamine react in the presence of the inorganic salts which are catalysts. Also, in Example 8 of Patent Document 2, the cycloaliphatic tetracarboxylic dianhydride hexacyclo[6.6.1.1 ^3,6 .1 ^10,13 .0 ^2,7 is made in the presence of calcium chloride as a catalyst. .0 ^9,14 ] Heptadecyl-4,5,11,13-tetracarboxylic dianhydride reacts with 4,4'-diaminodiphenyl ether to synthesize polyamic acid and imidize it to obtain Polyimide. However, in Comparative Example 5 of Patent Document 2, hexacyclo[6.6.1.1 ^3,6 .1 ^10,13 .0 ^2,7 .0 ^9,14 ] heptadecane was made without adding calcium chloride as a catalyst. 4,5,11,13-tetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether are reacted to synthesize polyamic acid, and the polyimide obtained by imidization is obtained. Polyimide has a low η _inh and cannot be formed into a film.

For semi-alicyclic polyimides, Non-Patent Document 1 discloses a soluble alicyclic polyimide obtained from tricyclodecene tetracarboxylic dianhydride (addition product of benzene and maleic anhydride) and diaminodiphenyl ether. Interaction of relaxation shift and strength properties in imides. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2012/124664 [Patent Document 2] Japanese Patent Application Laid-Open No. 5-271409 [Non-patent literature]

[Non-Patent Document 1] Izvestiya Akademii Nauk Kazakhskoi SSR, Seriya Khimicheskaya, 1987, No.5, p.40

[Problem to be solved by the invention] The object of the present invention is to provide novel polyimides and their precursors with excellent properties such as transparency, bending resistance, high heat resistance, and low linear thermal expansion coefficient. Moreover, the object of this invention is to provide the novel tetracarboxylic dianhydride used for manufacturing polyimide, and its manufacturing method. [How to solve the problem]

The present invention relates to the following items. 1. A polyimide precursor is characterized in that: comprise at least 1 in the repeating unit represented by following chemical formula (1-1), the total content of the repeating unit represented by chemical formula (1-1) is relative to all repeating units More than 50 mol%;

式中，A₁₁ 係下列化學式(A-1)表示之4價基、或下列化學式(A-2)表示之4價基，B₁₁ 係下列化學式(B-1)表示之2價基、或下列化學式(B-2)表示之2價基，X₁ 、X₂ 各自獨立地為氫、碳數1~6之烷基、或碳數3~9之烷基矽基；[chemical 1]

In the formula, A ₁₁ is a quaternary 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 divalent group represented by the following chemical formula (B-1), or In the divalent group represented by the following chemical formula (B-2), X ₁ and X ₂ are each independently hydrogen, an alkyl group with 1 to 6 carbons, or an alkylsilyl group with 3 to 9 carbons;

式中，R₁ 、R₂ 、R₃ 各自獨立地為-CH₂ -、-CH₂ CH₂ -、或-CH＝CH-；[Chem 2]

In the formula, R ₁ , R ₂ , and R ₃ are each independently -CH ₂ -, -CH ₂ CH ₂ -, or -CH═CH-;

式中，R₄ 為-CH₂ -、-CH₂ CH₂ -、或-CH＝CH-；[Chem 3]

In the formula, R ₄ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-;

式中，n₁ 表示0~3之整數、n₂ 表示0~3之整數；Y₁ 、Y₂ 、Y₃ 各自獨立地表示選自於由氫原子、甲基、三氟甲基構成之群組中之1種，Q₁ 、Q₂ 各自獨立地表示選自於由直接鍵結、或式：-NHCO-、-CONH-、-COO-、-OCO-表示之基構成之群組中之1種；[chemical 4]

In the formula, n ₁ represents an integer of 0 to 3, n ₂ represents an integer of 0 to 3; Y ₁ , Y ₂ , and Y ₃ each independently represent a group selected from a hydrogen atom, a methyl group, and a trifluoromethyl group. One of the group, Q ₁ and Q ₂ each independently represent one selected from the group consisting of direct bonds, or groups represented by the formula: -NHCO-, -CONH-, -COO-, -OCO- 1 type;

式中，Y₄ 表示氫原子、或碳數1~4之烷基。[chemical 5]

In the formula, Y ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

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

式中，A₁₂ 為下列化學式(A-3)表示之4價基、或下列化學式(A-4)表示之4價基，B₁₂ 為具有芳香族環或脂環結構之2價基，X₃ 、X₄ 各自獨立地為氫、碳數1~6之烷基、或碳數3~9之烷基矽基；[chemical 6]

In the formula, A ₁₂ is a quaternary 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 divalent group having an aromatic ring or alicyclic structure, X _{3. X4} are each independently hydrogen, an alkyl group with 1 to 6 carbons, or an alkylsilyl group with 3 to 9 carbons;

式中，R₅ 、R₆ 各自獨立地為-CH₂ -、-CH₂ CH₂ -、或-CH＝CH-；[chemical 7]

In the formula, R ₅ and R ₆ are each independently -CH ₂ -, -CH ₂ CH ₂ -, or -CH═CH-;

式中，R₇ 為-CH₂ CH₂ -、或-CH＝CH-。 3. 如2.之聚醯亞胺前驅體，其中，該化學式(1-2)表示之重複單元之合計含量相對於全部重複單元為50莫耳%以上。[chemical 8]

In the formula, R ₇ is -CH ₂ CH ₂ -, or -CH═CH-. 3. The polyimide precursor as in 2., wherein the total content of the repeating units represented by the chemical formula (1-2) is 50 mol% or more relative to all the repeating units.

4. A polyimide characterized in that at least one of the repeating units represented by the following chemical formula (2-1) is included, and the total content of the repeating units represented by the chemical formula (2-1) is 50 mole relative to all the repeating units More than ear%;

式中，A₂₁ 為下列化學式(A-1)表示之4價基、或下列化學式(A-2)表示之4價基，B₂₁ 為下列化學式(B-1)表示之2價基、或下列化學式(B-2)表示之2價基；[chemical 9]

In the formula, A ₂₁ is a quaternary 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 divalent group represented by the following chemical formula (B-1), or A divalent group represented by the following chemical formula (B-2);

式中，R₁ 、R₂ 、R₃ 各自獨立地為-CH₂ -、-CH₂ CH₂ -、或-CH＝CH-；[chemical 10]

In the formula, R ₁ , R ₂ , and R ₃ are each independently -CH ₂ -, -CH ₂ CH ₂ -, or -CH═CH-;

式中，R₄ 為-CH₂ -、-CH₂ CH₂ -、或-CH＝CH-；[chemical 11]

In the formula, R ₄ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-;

式中，n₁ 表示0~3之整數，n₂ 表示0~3之整數；Y₁ 、Y₂ 、Y₃ 各自獨立地表示選自於由氫原子、甲基、三氟甲基構成之群組中之1種，Q₁ 、Q₂ 各自獨立地表示選自於由直接鍵結、或式：-NHCO-、-CONH-、-COO-、-OCO-表示之基構成之群組中之1種；[chemical 12]

In the formula, n ₁ represents an integer of 0 to 3, n ₂ represents an integer of 0 to 3; Y ₁ , Y ₂ , and Y ₃ each independently represent a group selected from a hydrogen atom, a methyl group, and a trifluoromethyl group. One of the group, Q ₁ and Q ₂ each independently represent one selected from the group consisting of direct bonds, or groups represented by the formula: -NHCO-, -CONH-, -COO-, -OCO- 1 type;

式中，Y₄ 表示氫原子、或碳數1~4之烷基。[chemical 13]

In the formula, Y ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

5. A polyimide, characterized by: comprising at least one of the repeating units represented by the following chemical formula (2-2);

式中，A₂₂ 為下列化學式(A-3)表示之4價基、或下列化學式(A-4)表示之4價基，B₂₂ 為具有芳香族環或脂環結構之2價基；[chemical 14]

In the formula, A ₂₂ is a quaternary 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 divalent group having an aromatic ring or alicyclic structure;

式中，R₅ 、R₆ 各自獨立地為-CH₂ -、-CH₂ CH₂ -、或-CH＝CH-；[chemical 15]

In the formula, R ₅ and R ₆ are each independently -CH ₂ -, -CH ₂ CH ₂ -, or -CH═CH-;

式中，R₇ 為-CH₂ CH₂ -、或-CH＝CH-。 6. 如5.之聚醯亞胺，其中，該化學式(2-2)表示之重複單元之合計含量相對於全部重複單元為50莫耳%以上。[chemical 16]

In the formula, R ₇ is -CH ₂ CH ₂ -, or -CH═CH-. 6. The polyimide according to 5., wherein the total content of the repeating units represented by the chemical formula (2-2) is 50 mol% or more relative to all the repeating units.

7. A polyimide obtained by the polyimide precursor as in any one of 1. to 3. 8. A film made of polyimide obtained from a polyimide precursor as in any one of 1. to 3., or a polyimide as in any one of 4. to 6. become. 9. A varnish, comprising the polyimide precursor as in any one of 1. to 3., or the polyimide as in any one of 4. to 6. 10. A polyimide film obtained by using a varnish containing the polyimide precursor according to any one of 1. to 3. or the polyimide according to any one of 4. to 6. 11. A substrate for a display, a touch panel, or a solar cell, characterized by: containing polyimide obtained from a polyimide precursor as in any one of 1. to 3., or such as 4. The polyimide according to any one of 6.

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

式中，R₅ ’、R₆ ’各自獨立地為-CH₂ -、或-CH₂ CH₂ -。 13. 一種下列化學式(M-2)表示之四酯化合物；[chemical 17]

In the formula, R ₅ ′ and R ₆ ′ are each independently —CH ₂ — or —CH ₂ CH ₂ —. 13. A tetraester compound represented by the following chemical formula (M-2);

式中，R₅ ’、R₆ ’各自獨立地為-CH₂ -、或-CH₂ CH₂ -，R₁₁ 、R₁₂ 、R₁₃ 、R₁₄ 各自獨立地為碳數1~10之烷基。 14. 一種下列化學式(M-3)表示之四酯化合物；[chemical 18]

In the formula, R ₅ ' and R ₆ ' are each independently -CH ₂ - or -CH ₂ CH ₂ -, R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each independently an alkyl group with 1 to 10 carbons . 14. A tetraester compound represented by the following chemical formula (M-3);

式中，R₅ ’、R₆ ’各自獨立地為-CH₂ -、或-CH₂ CH₂ -，R₁₁ 、R₁₂ 、R₁₃ 、R₁₄ 各自獨立地為碳數1~10之烷基。[chemical 19]

In the formula, R ₅ ' and R ₆ ' are each independently -CH ₂ - or -CH ₂ CH ₂ -, R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each independently an alkyl group with 1 to 10 carbons .

15. A method for producing tetracarboxylic dianhydride, characterized by comprising the following steps: (A) In the presence of a base, the alkene compound represented by the following chemical formula (M-A-1) is reacted with aliphatic sulfonyl chloride or aromatic sulfonyl chloride to obtain an alkene compound represented by the following chemical formula (M-A-2);

式中，R₅ ’、R₆ ’各自獨立地為-CH₂ -、或-CH₂ CH₂ -；[chemical 20]

In the formula, R ₅ ' and R ₆ ' are each independently -CH ₂ -, or -CH ₂ CH ₂ -;

式中，R₅ ’、R₆ ’之含意同前述，R為也可以有取代基之烷基或芳基； (B)使該化學式(M-A-2)表示之烯烴化合物於鈀觸媒與銅化合物存在下和醇化合物與一氧化碳反應，而獲得下列化學式(M-A-3)表示之四酯化合物；[chem 21]

In the formula, the meanings of R ₅ ' and R ₆ ' are the same as those mentioned above, and R is an alkyl or aryl group that may also have a substituent; In the presence of the compound, react with the alcohol compound and carbon monoxide to obtain the tetraester compound represented by the following chemical formula (MA-3);

式中，R₅ ’、R₆ ’、R之含意同前述，R₁₁ 、R₁₂ 、R₁₃ 、R₁₄ 各自獨立地為碳數1~10之烷基； (C)從該化學式(M-A-3)表示之四酯化合物獲得下列化學式(M-3)表示之四酯化合物；[chem 22]

In the formula, R ₅ ′, R ₆ ′, and R have the same meanings as above, and R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each independently an alkyl group with 1 to 10 carbon atoms; (C) from the chemical formula (MA- 3) the tetraester compound represented obtains the tetraester compound represented by the following chemical formula (M-3);

式中，R₅ ’、R₆ ’、R₁₁ 、R₁₂ 、R₁₃ 、R₁₄ 之含意同前述； (D)由該化學式(M-3)表示之四酯化合物之氧化反應獲得下列化學式(M-2)表示之四酯化合物；[chem 23]

In the formula, R ₅ ', R ₆ ', R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ have the same meaning as above; (D) the oxidation reaction of the tetraester compound represented by the chemical formula (M-3) obtains the following chemical formula ( Tetraester compounds represented by M-2);

式中，R₅ ’、R₆ ’、R₁₁ 、R₁₂ 、R₁₃ 、R₁₄ 之含意同前述； (E)使該化學式(M-2)表示之四酯化合物於酸觸媒存在下於有機溶劑中反應，獲得下列化學式(M-1)表示之四羧酸二酐；[chem 24]

In the formula, R ₅ ', R ₆ ', R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ have the same meaning as above; (E) make the tetraester compound represented by the chemical formula (M-2) in the presence of an acid catalyst React in organic solvent, obtain the tetracarboxylic dianhydride represented by following chemical formula (M-1);

式中，R₅ ’、R₆ ’之含意同前述。[chem 25]

In the formula, the meanings of R ₅ ' and R ₆ ' are the same as above.

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

式中，R₇ 為-CH₂ CH₂ -、或-CH＝CH-。 17. 一種下列化學式(M-5)表示之四酯化合物；[chem 26]

In the formula, R ₇ is -CH ₂ CH ₂ -, or -CH═CH-. 17. A tetraester compound represented by the following chemical formula (M-5);

式中，R₇ 為-CH₂ CH₂ -、或-CH＝CH-，R₂₁ 、R₂₂ 、R₂₃ 、R₂₄ 各自獨立地為碳數1~10之烷基。 18. 一種下列化學式(M-6)表示之二鹵代二羧酸酐；[chem 27]

In the formula, R ₇ is -CH ₂ CH ₂ -, or -CH=CH-, and R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are each independently an alkyl group having 1 to 10 carbons. 18. A dihalogenated dicarboxylic anhydride represented by the following chemical formula (M-6);

式中，X₁₁ 、X₁₂ 各自獨立地表示-F、-Cl、-Br、或-I中之任一者。 19. 一種下列化學式(M-7)表示之二羧酸酐；[chem 28]

In the formula, X ₁₁ and X ₁₂ each independently represent any one of -F, -Cl, -Br, or -I. 19. A dicarboxylic anhydride represented by the following chemical formula (M-7);

[chem 29]

20. A method for producing tetracarboxylic dianhydride, characterized by comprising the following steps: (A) react the dicarboxylic acid anhydride represented by the following chemical formula (M-B) with 1,3-butadiene to obtain the dicarboxylic anhydride represented by the following chemical formula (M-7);

[chem 30]

(B)使該化學式(M-7)表示之二羧酸酐與二鹵化劑反應，而獲得下列化學式(M-6)表示之二鹵代二羧酸酐；[chem 31]

(B) react the dicarboxylic anhydride represented by the chemical formula (M-7) with a dihalogenating agent to obtain the dihalogenated dicarboxylic anhydride represented by the following chemical formula (M-6);

式中，X₁₁ 、X₁₂ 各自獨立地表示-F、-Cl、-Br、或-I中之任一者； (C)使該化學式(M-6)表示之二鹵代二羧酸酐與馬來酸酐反應，而獲得下列化學式(M-4-1)表示之四羧酸二酐；[chem 32]

In the formula, X ₁₁ and X ₁₂ each independently represent any one of -F, -Cl, -Br, or -I; (C) make the dihalogenated dicarboxylic anhydride represented by the chemical formula (M-6) and Maleic anhydride reaction, and obtain the tetracarboxylic dianhydride represented by following chemical formula (M-4-1);

(D)使該化學式(M-4-1)表示之四羧酸二酐於酸存在下與醇化合物反應而獲得下列化學式(M-5-1)表示之四酯化合物；[chem 33]

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

式中，R₂₁ 、R₂₂ 、R₂₃ 、R₂₄ 各自獨立地為碳數1~10之烷基； (E)使該化學式(M-5-1)表示之四酯化合物於金屬觸媒存在下與氫反應而獲得下列化學式(M-5-2)表示之四酯化合物；[chem 34]

In the formula, R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are each independently an alkyl group with 1 to 10 carbon atoms; (E) making the tetraester compound represented by the chemical formula (M-5-1) exist in a metal catalyst Reaction with hydrogen to obtain the tetraester compound represented by the following chemical formula (M-5-2);

式中，R₂₁ 、R₂₂ 、R₂₃ 、R₂₄ 之含意同前述； (F)使該化學式(M-5-2)表示之四酯化合物於酸觸媒存在下於有機溶劑中反應，獲得下列化學式(M-4-2)表示之四羧酸二酐；[chem 35]

In the formula, R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ have the same meanings as above; (F) react the tetraester compound represented by the chemical formula (M-5-2) in an organic solvent in the presence of an acid catalyst to obtain Tetracarboxylic dianhydride represented by the following chemical formula (M-4-2);

。[chem 36]

.

21. A method for producing tetracarboxylic dianhydride, characterized by comprising the following steps: (A) react 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);

式中，R₄ 為-CH₂ -、-CH₂ CH₂ -、或-CH＝CH-；[chem 37]

In the formula, R ₄ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-;

式中，R₃₁ 、R₃₂ 各自獨立地為碳數1~10之烷基、或苯基；[chem 38]

In the formula, R ₃₁ and R ₃₂ are each independently an alkyl group with 1 to 10 carbons, or a phenyl group;

式中，R₄ 、R₃₁ 、R₃₂ 之含意同前述； (B)利用該化學式(M-C-3)表示之二酯化合物之氧化反應，獲得下列化學式(M-C-4)表示之二酯化合物；[chem 39]

In the formula, the meanings of R ₄ , R ₃₁ , and R ₃₂ are the same as above; (B) use the oxidation reaction of the diester compound represented by the chemical formula (MC-3) to obtain the diester compound represented by the following chemical formula (MC-4);

式中，R₄ 、R₃₁ 、R₃₂ 之含意同前述； (C)使該化學式(M-C-4)表示之二酯化合物於鈀觸媒及銅化合物存在下和醇化合物與一氧化碳反應而獲得下列化學式(M-C-5)表示之四酯化合物；[chemical 40]

In the formula, R ₄ , R ₃₁ , R ₃₂ have the same meaning as above; (C) make the diester compound represented by the chemical formula (MC-4) react with alcohol compound and carbon monoxide in the presence of palladium catalyst and copper compound to obtain the following Tetraester compounds represented by chemical formula (MC-5);

式中，R₄ 、R₃₁ 、R₃₂ 之含意同前述，R₃₃ 、R₃₄ 各自獨立地為碳數1~10之烷基； (D)使該化學式(M-C-5)表示之四酯化合物於酸觸媒存在下於有機溶劑中反應，獲得下列化學式(M-9)表示之四羧酸二酐；[chem 41]

In the formula, the meanings of R ₄ , R ₃₁ , and R ₃₂ are the same as above, and R ₃₃ and R ₃₄ are each independently an alkyl group with 1 to 10 carbon atoms; (D) the tetraester compound represented by the chemical formula (MC-5) React in an organic solvent in the presence of an acid catalyst to obtain tetracarboxylic dianhydride represented by the following chemical formula (M-9);

式中，R₄ 之含意同前述。 [發明之效果][chem 42]

In the formula, R ₄ has the same meaning as above. [Effect of Invention]

According to the present invention, novel polyimides having excellent properties such as transparency, bending resistance, high heat resistance, and low linear thermal expansion coefficient, and their precursors, and novel tetracarboxylic dicarboxylic acids used in their manufacture can be provided. Anhydrides, and methods for their manufacture.

The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention are easy to form fine circuits, and are suitable for use in forming substrates for displays and the like. Also, the polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention are suitably used as substrates for touch panels and solar cells.

The polyimide precursor of the first aspect of the present invention (hereinafter also referred to as "polyimide precursor (1-1)") includes at least one of the repeating units represented by the aforementioned chemical formula (1-1) One type of polyimide precursor in which the total content of repeating units represented by the chemical formula (1-1) is 50 mol% or more relative to all repeating units. However, the aforementioned chemical formula (1-1) shows that among the 4 atoms bonded from the tetravalent group A ₁₁ of the tetracarboxylic acid component, 1 is bonded to -CONH-, and 1 is bonded to -CONH-B ₁₁ -, One is bonded to -COOX ₁ , and one is bonded to -COOX ₂ , and the aforementioned chemical formula (1-1) includes all structural isomers thereof.

The polyimide precursor (1-1) of the present invention is preferably one or more repeating units represented by the aforementioned chemical formula (1-1), accounting for more than 50 mol% of all repeating units, more preferably 60 mol% % or more, more preferably more than 70 mol%, and especially preferably more than 80 mol%.

Moreover, the polyimide precursor (1-1) of this invention may contain 2 or more types of repeating units of the said chemical formula (1-1) which differ in _A11 and/or _B11 . Also, the polyimide precursor ( _1-1 ) of the present invention may also contain one of the repeating units of the aforementioned chemical formula (1-1) in which A is a tetravalent group represented by the aforementioned chemical formula (A-1) Or two or more of the repeating units of the aforementioned chemical formula (1-1) in which A ₁₁ is a tetravalent group represented by the aforementioned chemical formula (A-2).

In other words, the polyimide precursor (1-1) of the present invention is composed of a tetracarboxylic acid component that gives the structure of the aforementioned chemical formula (A-1) and/or a tetracarboxylic acid component that gives the structure of the aforementioned chemical formula (A-2). Tetracarboxylic acid component of the carboxylic acid component, polyamide obtained from a diamine component including a diamine component giving the structure of the aforementioned chemical formula (B-1) and/or a diamine component giving the structure of the aforementioned chemical formula (B-2) Imine precursors.

The tetracarboxylic acid component that gives the repeating unit of the aforementioned chemical formula (1-1) is the tetracarboxylic acid component that gives the structure of the aforementioned chemical formula (A-1), and the tetracarboxylic acid component that gives the structure of the aforementioned chemical formula (A-2) . Give the tetracarboxylic acid component of the structure of the aforementioned chemical formula (A-1), for example: tetradetrahydro-1H, 3H-4, 12: 5, 11: 6, 10-trimethyl bridge anthracene [2,3-c: 6 ,7-c']difuran-1,3,7,9-tetraketone, Tetrahydro-1H,3H-4,12-Ethyro-5,11: 6,10-Dimethylbridged anthracene[2 ,3-c: 6,7-c']difuran-1,3,7,9-tetraketone, Tetrahydro-1H,3H-4,12: 5,11-diethyl bridge-6,10- A bridge anthracene[2,3-c:6,7-c']difuran-1,3,7,9-tetraketone, tetradetrahydro-1H,3H-4,12:5,11:6, 10-Trimethylpoanthracene[2,3-c:6,7-c']difuran-1,3,7,9-tetraketone, Tetradecylhydro-1H,3H-5,11-Ethyro-4 ,12: 6,10-dimethyl bridge anthracene[2,3-c:6,7-c']difuran-1,3,7,9-tetraketone, tetradetrahydro-1H,3H-4, 12-vinyl bridge-5,11: 6,10-dimethyl bridge anthracene [2,3-c: 6,7-c'] difuran-1,3,7,9-tetraketone, tetradetrahydro- 1H,3H-4,12: 5,11-divinyl bridge-6,10-methano-anthracene[2,3-c:6,7-c']difuran-1,3,7,9-tetra Ketone, tetradetrahydro-1H,3H-4,12:5,11:6,10-trivinyl bridge anthraceno[2,3-c:6,7-c']difuran-1,3,7, 9-tetraketone, tetradetrahydro-1H,3H-5,11-vinyl bridge-4,12:6,10-dimethylanthracene[2,3-c:6,7-c']difuran- 1,3,7,9-tetraketone, and the corresponding tetracarboxylic acid, tetracarboxylic acid derivatives other than tetracarboxylic dianhydride, etc., give the tetracarboxylic acid component of the structure of the aforementioned chemical formula (A-2), for example: 3a,4,10,10a-tetrahydro-1H,3H-4,10-methanonaphtho[2,3-c:6,7-c']difuran-1,3,6,8-tetraone , 3a,4,10,10a-tetrahydro-1H,3H-4,10-ethonaphtho[2,3-c:6,7-c']difuran-1,3,6,8-tetra Ketone, 3a,4,10,10a-tetrahydro-1H,3H-4,10-vinylapeno[2,3-c:6,7-c']difuran-1,3,6,8- Tetraketone, and the corresponding tetracarboxylic acid, tetracarboxylic acid derivatives other than tetracarboxylic dianhydride, etc. These tetracarboxylic acid components (tetracarboxylic acids etc.) may be used individually by 1 type and may use it in combination of several types. Here, tetracarboxylic acids and the like represent tetracarboxylic acid derivatives such as tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic silicon ester, tetracarboxylic acid ester, and tetracarboxylic acid chloride.

The diamine component imparting the repeating unit of the aforementioned chemical formula (1-1) is the diamine component imparting the structure of the aforementioned chemical formula (B-1) and the diamine component imparting the structure of the aforementioned chemical formula (B-2).

When the diamine component having the structure of the aforementioned chemical formula (B-1) has an aromatic ring and has a plurality of aromatic rings, the aromatic rings are each independently directly bonded, amide bonded, or ester bonded. The linking position of the aromatic rings is not particularly limited, and it is preferable to link at the 4-position with respect to the amine group or the linking group between the aromatic rings. That is to say, in the group represented by the aforementioned chemical formula (B-1), the linking position of the aromatic rings is not particularly limited, with respect to the amide group (-CONH-) to which _A11 is bonded or the linking group between the aromatic rings, 4-position bonding is preferred. By bonding in this way, the obtained polyimide becomes a linear structure, and the linear thermal expansion may become low. When the diamine component given the structure of the aforementioned chemical formula (B-1) has one aromatic ring, it preferably has a p-phenylene structure. That is, when the group represented by the aforementioned chemical formula (B-1) has one aromatic ring (n ₁ and n ₂ are 0), the group represented by the aforementioned chemical formula (B-1) may have a substituent (Y ₁ ) The para-phenylene group is preferably an unsubstituted para-phenylene group. In addition, the aromatic ring may be substituted with a methyl group or a trifluoromethyl group. Also, the substitution position is not particularly limited.

The diamine component given the structure of the aforementioned chemical formula (B-2) has an aliphatic 6-membered ring, and the aliphatic 6-membered ring can also be replaced by methyl, ethyl, n-propyl, isopropyl, n-butyl , isobutyl, second butyl, third butyl and other alkyl groups with 1 to 4 carbon atoms are substituted, but considering the heat resistance and linear thermal expansion coefficient of the obtained polyimide, the unsubstituted aliphatic 6-membered ring is relatively good. That is, among the groups represented by the aforementioned chemical formula (B-2), Y ₄ is preferably a hydrogen atom. Also, the substitution position is not particularly limited. In addition, the diamine component giving the structure of the aforementioned chemical formula (B-2) preferably has a 1,4-cyclohexane structure for the aliphatic 6-membered ring. That is, the group represented by the aforementioned chemical formula (B-2) is a 1,4-cyclohexylene group which may also have a substituent (Y ₄ ), preferably an unsubstituted 1,4-cyclohexylene group.

The diamine component given the structure of the aforementioned chemical formula (B-1) is not particularly limited, for example: p-phenylenediamine, m-phenylenediamine, benzidine, 3,3'-diamino-biphenyl, 2,2'- Bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, m-toluidine, 4,4'-diaminobenzoyl aniline, 3,4'-diamine N,N'-bis(4-aminophenyl)terephthalamide, N,N'-p-phenylenebis(p-aminobenzamide), 4-aminobenzamide phenylphenoxy-4-diaminobenzoate, bis(4-aminophenyl)terephthalate, biphenyl-4,4'-dicarboxylate bis(4-aminophenyl) ) ester, p-phenylene bis(p-aminobenzoate), bis(4-aminophenyl)-[1,1'-biphenyl]-4,4'-dicarboxylate, [1 ,1'-biphenyl]-4,4'-diyl bis(4-aminobenzoate) and so on. The diamine component giving the structure of the aforementioned chemical formula (B-2) includes 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diaminocyclohexane, -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-second butylcyclohexane, 1,4-di Amino-2-tert-butylcyclohexane, 1,2-diaminocyclohexane, etc. Given the diamine component of the structure of the aforementioned chemical formula (B-2), 1,4-diaminocyclohexane is more preferable in view of the low thermal expansion coefficient of the obtained polyimide. Also, the stereostructure of the 1,4-position of the above-mentioned diamine having a 1,4-cyclohexane structure is not particularly limited, and it is preferably a trans structure. In the case of the trans structure, compared with the case of the cis structure, coloring of the obtained polyimide may be suppressed more. These diamine components may be used individually by 1 type and may use it in combination of several types.

B ₁₁ in the aforementioned chemical formula (1-1), that is, the divalent group represented by the aforementioned chemical formula (B-1) and the divalent group represented by the aforementioned chemical formula (B-2), should be the following chemical formula (B-1- The group represented by any one of 1)~(B-1-6) and (B-2-1) is preferable.

[chem 43]

Also, giving _B11 to the diamine component of the repeating unit of the aforementioned chemical formula (1-1) represented by the aforementioned chemical formula (B-1-1) or (B-1-2) is 4,4'-diamine Phenylaniline, giving B ₁₁ the diamine component of the repeating unit of the aforementioned chemical formula (1-1) represented by the aforementioned chemical formula (B-1-3), is bis(4-aminophenyl)terephthalylene Ester, giving B ₁₁ is the diamine component of the repeating unit of the aforementioned chemical formula (1-1) represented by the aforementioned chemical formula (B-1-4), is p-phenylenediamine, giving B ₁₁ is the aforementioned chemical formula (B-1 -5) The diamine component of the repeating unit of the aforementioned chemical formula (1-1) represented by 2,2'-bis(trifluoromethyl)benzidine, given B ₁₁ is the aforementioned chemical formula (B-1-6) The diamine component of the repeating unit of the aforementioned chemical formula (1-1) represented by m-toluidine is given to the repeating unit of the aforementioned chemical formula ( _1-1 ) represented by the aforementioned chemical formula (B-2-1). The diamine component is 1,4-diaminocyclohexane.

In _B11 in the aforementioned chemical formula (1-1), the ratio of the bases represented by any one of the aforementioned chemical formulas (B-1-1) to (B-1-6), (B-2-1), the total ratio Preferably it is at least 30 mol%, more preferably at least 50 mol%, and most preferably at least 70 mol%.

The polyimide precursor (1-1) of the present invention may contain other repeating units other than the repeating unit represented by the aforementioned chemical formula (1-1). In a certain embodiment, the quaternary group of other repeating units other than the repeating unit represented by the aforementioned chemical formula (1-1), such as a tetracarboxylic acid component, is the quaternary group represented by the aforementioned chemical formula (A-1) or the aforementioned chemical formula The content of the repeating unit in which the tetravalent group represented by (A-2) and the divalent group derived from the diamine component has a plurality of aromatic rings and the aromatic rings are linked to each other by ether bonds (-O-), in all repeating units For example: less than 30 mol%, or less than 25 mol%, or less than 20 mol%, or less than 10 mol%. In a certain embodiment, depending on the required properties and uses, the quaternary group derived from the tetracarboxylic acid component is the quaternary group represented by the aforementioned chemical formula (A-1) or the quaternary group represented by the aforementioned chemical formula (A-2) and The divalent group derived from the diamine component is a repeating unit that has multiple aromatic rings and the aromatic rings are linked to each other by ether bonds (-O-). The content in all repeating units is, for example: 40 mole % or less, preferably It is better below 35 mol%.

As the tetracarboxylic acid component imparting other repeating units, aromatic or aliphatic tetracarboxylic acids can be used. Although not particularly limited, for example: 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3, 4-tetrahydronaphthalene-1,2-dicarboxylic acid, pyromellitic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 3,3',4,4'-biphenyl tetracarboxylic acid Acid, 2,3,3',4'-biphenyltetracarboxylic acid, 4,4'-oxydiphthalic acid, bis(3,4-dicarboxyphenyl)diphenyl anhydrate, intermediate three Benzene-3,4,3',4'-tetracarboxylic dianhydride, p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, biscarboxyphenyldimethylsilane, bisdicarboxy Phenoxydiphenyl sulfide, sulfonyl diphthalic acid, 1,2,3,4-cyclobutane tetracarboxylic acid, isopropylidene diphenoxy diphthalic acid, cyclohexane -1,2,4,5-tetracarboxylic acid, [1,1'-bi(cyclohexane)]-3,3',4,4'-tetracarboxylic acid, [1,1'-bi(cyclohexane) Hexane)]-2,3,3',4'-tetracarboxylic acid, [1,1'-bi(cyclohexane)]-2,2',3,3'-tetracarboxylic acid, 4,4 '-Methylenebis(cyclohexane-1,2-dicarboxylic acid), 4,4'-(propane-2,2-diyl)bis(cyclohexane-1,2-dicarboxylic acid), 4,4'-Oxybis(cyclohexane-1,2-dicarboxylic acid), 4,4'-thiobis(cyclohexane-1,2-dicarboxylic acid), 4,4'-sulfonyl Bis(cyclohexane-1,2-dicarboxylic acid), 4,4'-(dimethylsilanediyl)bis(cyclohexane-1,2-dicarboxylic acid), 4,4'-( Tetrafluoropropane-2,2-diyl)bis(cyclohexane-1,2-dicarboxylic acid), octahydropentalene-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, 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-dimethylonaphthalene-2,3,6,7-tetracarboxylic acid, norbornane-2-spiro -α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid and other derivatives, and their acid dianhydrides. These tetracarboxylic acid components (tetracarboxylic acids etc.) may be used individually by 1 type and may use it in combination of several types. Among them, 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-Norbornane-2,3,6,7-tetracarboxylic acid, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane Derivatives such as alkane-5,5'',6,6''-tetracarboxylic acid and their dianhydrides are preferred.

Also, when the combined diamine component is the diamine component giving the structure of the aforementioned chemical formula (B-1) and other diamines other than the diamine component giving the structure of the aforementioned chemical formula (B-2), other repeating units are given As the tetracarboxylic acid component, one or two or more of the tetracarboxylic acid component giving the structure of the aforementioned chemical formula (A-1) and the tetracarboxylic acid component giving the structure of the aforementioned chemical formula (A-2) can be used.

As the diamine component imparting other repeating units, other aromatic or aliphatic diamines can be used. Although not particularly limited, for example: 4,4'-oxydiphenylamine, 3,4'-oxydiphenylamine, 3,3'-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, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, Bis(4-aminophenyl)phenyl, 3,3-bis((aminophenoxy)phenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, Bis(4-(4-aminophenoxy)diphenyl)pyridine, bis(4-(3-aminophenoxy)diphenyl)pyridine, octafluorobenzidine, 3,3'-dimethyl Oxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl Benzene, 9,9-bis(4-aminophenyl) fluorine, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy) Biphenyl, etc., and their derivatives. These diamine components may be used individually by 1 type and may use it in combination of several types.

Also, when the combined tetracarboxylic acid component is a tetracarboxylic acid component giving the structure of the aforementioned chemical formula (A-1) and other tetracarboxylic acids other than the tetracarboxylic acid component giving the structure of the aforementioned chemical formula (A-2), the For the diamine component giving other repeating units, one or both of the diamine component giving the structure of the aforementioned chemical formula (B-1) and the diamine component giving the structure of the aforementioned chemical formula (B-2) can also be used above.

In a certain embodiment, for example: 4,4'-oxydiphenylamine, 4,4'-bis(4-aminophenoxy)biphenyl, etc. have multiple aromatic rings, and the aromatic rings are bonded to each other through ether bonds (- The content of the diamine component linked by O-) in 100 mol% of the diamine component is preferably, for example, 30 mol% or less, or 25 mol% or less, or 20 mol% or less, or 10 mol% or less better. Also, in a certain embodiment, depending on the required characteristics and applications, the usage amount of diamine components having multiple aromatic rings and the aromatic rings are linked by ether bonds (-O-) in 100 mol% of diamine components For example, it is preferably less than 40 mol%, preferably less than 35 mol%.

The polyimide precursor of the second aspect of the present invention (hereinafter also referred to as "polyimide precursor (1-2)") contains at least one of the repeating units represented by the aforementioned chemical formula (1-2) 1 kind of polyimide precursor. However, the aforementioned chemical formula (1-2) represents that among the 4 atoms bonded from the tetravalent group A ₁₂ of the tetracarboxylic acid component, one is bonded to -CONH-, and one is bonded to -CONH-B ₁₂ -, One is bonded to -COOX ₃ , and one is bonded to -COOX ₄ , and the aforementioned chemical 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 relative to all the repeating units. That is to say, in the polyimide precursor (1-2) of the present invention, the content of one or more repeating units represented by the aforementioned chemical formula (1-2) is preferably 50 mol% or more in total in all repeating units, More preferably, it is at least 60 mol%, more preferably at least 70 mol%, even more preferably at least 80 mol%, and most preferably at least 90 mol%.

Also, the polyimide precursor (1-2) of the present invention may contain two or more repeating units of the aforementioned chemical formula (1-2) having different _A12 and/or _B12 . Also, the polyimide precursor (1-2) of the present invention can also contain A ₁₂ is the repeating unit 1 or 2 of the aforementioned chemical formula (1-2) of the quaternary group represented by the aforementioned chemical formula (A-3). The above and A ₁₂ are repeating units of the aforementioned chemical formula (1-2) of the tetravalent group represented by the aforementioned chemical formula (A-4).

In other words, the polyimide precursor (1-2) of the present invention is composed of a tetracarboxylic acid component that gives the structure of the aforementioned chemical formula (A-3) and/or a tetracarboxylic acid component that gives the structure of the aforementioned chemical formula (A-4). Polyimide precursor obtained from a tetracarboxylic acid component of a carboxylic acid component, and a diamine component containing a diamine component having an aromatic ring or alicyclic structure (that is, an aromatic diamine or an alicyclic diamine) .

The tetracarboxylic acid component that gives the repeating unit of the aforementioned chemical formula (1-2) is the tetracarboxylic acid component that gives the structure of the aforementioned chemical formula (A-3), and the tetracarboxylic acid component that gives the structure of the aforementioned chemical formula (A-4) . Give the tetracarboxylic acid component of the structure of the aforementioned chemical formula (A-3), for example: 3a, 4, 6, 6a, 9a, 10, 12, 12a-octahydro-1H, 3H-4, 12: 6, 10-di Apoanthrano[2,3-c:6,7-c']difuran-1,3,7,9-tetraone, 3a,4,6,6a,9a,10,12,12a-octahydro -1H,3H-4,12-Etho-6,10-methanoanthracene[2,3-c:6,7-c']difuran-1,3,7,9-tetraone, 3a, 4,6,6a,9a,10,12,12a-Octahydro-1H,3H-4,12:6,10-Diethyloanthracene[2,3-c:6,7-c']difuran -1,3,7,9-tetraketone, 3a,4,6,6a,9a,10,12,12a-octahydro-1H,3H-4,12-vinyl bridge-6,10-methyl bridge anthracene [2,3-c:6,7-c']difuran-1,3,7,9-tetraone, 3a,4,6,6a,9a,10,12,12a-octahydro-1H,3H -4,12: 6,10-divinyl bridge anthracene [2,3-c: 6,7-c'] difuran-1,3,7,9-tetraketone, and the corresponding tetracarboxylic acid, tetra Tetracarboxylic acid derivatives other than carboxylic acid dianhydride, etc., giving the tetracarboxylic acid component of the structure of the aforementioned chemical formula (A-4), for example: decahydro-1H,3H-4,10-ethano-5,9-methanol Naphtho[2,3-c:6,7-c']difuran-1,3,6,8-tetraketone, and the corresponding tetracarboxylic acid, derivatives of tetracarboxylic acid other than tetracarboxylic dianhydride things etc. These tetracarboxylic acid components (tetracarboxylic acids etc.) may be used individually by 1 type and may use it in combination of several types. Here, tetracarboxylic acids and the like refer to tetracarboxylic acid derivatives such as tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic silicon ester, tetracarboxylic acid ester, and tetracarboxylic acid chloride.

B ₁₂ in the aforementioned chemical formula (1-2) is a divalent group having an aromatic ring or an alicyclic structure. Considering the heat resistance of the obtained polyimide, it is preferable to use a divalent group having an aromatic ring rather than a divalent group having an aromatic ring. good. B ₁₂ in the chemical formula (1-2), that is, the diamine component is not particularly limited, and can be appropriately selected according to the required properties and uses.

Give the diamine component of the repeating unit of the aforementioned chemical formula (1-2), for example, give the diamine component of the structure of the aforementioned chemical formula (B-1) of the aforementioned polyimide precursor (1-1) and give the aforementioned chemical formula ( The diamine component of the structure of B-2) is listed, and furthermore, it can be listed in addition to the diamine component giving the structure of the aforementioned chemical formula (B-1) and the diamine component giving the structure of the aforementioned chemical formula (B-2) Those listed as diamine components of other repeating units can be ideally used. In the polyimide precursor (1-2), these diamine components may be used alone or in combination.

_B12 in the aforementioned chemical formula (1-2) is preferably a divalent group having an aromatic ring with carbon numbers of 6 to 40, and the aforementioned chemical formula (B-1) exemplified by the aforementioned polyimide precursor (1-1) ) represents a more ideal base. Moreover, the group represented by the said chemical formula (B-2) exemplified by the said polyimide precursor (1-1) is also preferable. B ₁₂ in the aforementioned chemical formula (1-2) is preferably a group represented by any one of the aforementioned chemical formulas (B-1-1) to (B-1-6) and (B-2-1).

_B12 in the aforementioned chemical formula (1-2) should be a divalent group with a plurality of aromatic rings and one or all of the aromatic rings linked with ether bonds (-O-), the following chemical formula (B-3-1)~( The group represented by any one of B-3-4) is particularly desirable.

[chem 44]

Also, giving B ₁₂ the diamine component of the repeating unit of the aforementioned chemical formula (1-2) represented by the aforementioned chemical formula (B-3-1) is 4,4'-oxydiphenylamine, and giving B ₁₂ the aforementioned chemical formula The diamine component of the repeating unit of the aforementioned chemical formula (1-2) represented by (B-3-2) is 1,4-bis(4-aminophenoxy)benzene, giving B ₁₂ is the aforementioned chemical formula (B -3-3) The diamine component of the repeating unit of the aforementioned chemical formula (1-2) represented by the person is 1,3-bis(4-aminophenoxy)benzene, and B ₁₂ is the aforementioned chemical formula (B-3) -4) The diamine component of the repeating unit represented by the aforementioned chemical formula (1-2) is 4,4'-bis(4-aminophenoxy)biphenyl.

As mentioned above, B ₁₂ in the chemical formula (1-2), that is, the diamine component, can be appropriately selected according to the required properties and uses. In a certain embodiment, in _B12 in the aforementioned chemical formula (1-2), the group represented by the aforementioned chemical formula (B-1) and/or the group represented by the aforementioned chemical formula (B-2) is more preferably the aforementioned chemical formula (B -1-1)~(B-1-6), (B-2-1), the proportion of the base represented by any one, the total should be, for example: more than 50 mole%, more preferably more than 60 mole% , more preferably at least 65 mol%, more preferably at least 70 mol%, or more preferably at least 75 mol%. In a certain embodiment, in _B12 in the aforementioned chemical formula (1-2), there are a plurality of aromatic rings and a divalent group in which some or all of the aromatic rings are linked by ether bonds (-O-), more preferably the aforementioned chemical formula The ratio of the bases represented by any one of (B-3-1) to (B-3-4) is, for example, 30 mole % or more, more preferably 50 mole % or more. In a certain embodiment, in _B12 in the aforementioned chemical formula (1-2), the ratio of the base represented by the aforementioned chemical formula (B-1) and/or the ratio of the base represented by the aforementioned chemical formula (B-2) is 60 moles in total % or more, preferably 65 mol% or more, or 70 mol% or more, or 75 mol% or more, the base represented by any one of the aforementioned chemical formulas (B-3-1)~(B-3-4) The ratio of the total is 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 other repeating units other than the repeating unit represented by the aforementioned chemical formula (1-2).

Other aromatic or aliphatic tetracarboxylic acids can be used for the tetracarboxylic acid component imparting other repeating units, for example, the tetracarboxylic acid component imparting other repeating units in the aforementioned polyimide precursor (1-1) can be listed for the same. Also, it is possible to use the tetracarboxylic acid component that gives the repeating unit of the aforementioned chemical formula (1-1) (that is, the tetracarboxylic acid component that gives the structure of the aforementioned chemical formula (A-1), and the tetracarboxylic acid component that gives the aforementioned chemical formula (A-2) The tetracarboxylic acid component of the structure) listed. In the polyimide precursor (1-2), the tetracarboxylic acid component imparting these other repeating units may be used alone or in combination.

Also, when the combined diamine component is a diamine that does not have an aromatic ring and an alicyclic structure, the tetracarboxylic acid that gives the structure of the aforementioned chemical formula (A-3) can be used for the tetracarboxylic acid component that gives other repeating units. One or more of the components and the tetracarboxylic acid component giving the structure of the aforementioned chemical formula (A-4).

As for the diamine component imparting other repeating units, other aromatic or aliphatic diamines can be used, for example and the diamine component imparting other repeating units in the aforementioned polyimide precursor (1-1) listed Those are the same. Also, the diamine component giving the repeating unit of the aforementioned chemical formula (1-1) (that is, the diamine component giving the structure of the aforementioned chemical formula (B-1) and the structure of the aforementioned chemical formula (B-2) can be used The diamine component) enumerates. In the polyimide precursor (1-2), the diamine component imparting these other repeating units may be used alone or in combination.

In the polyimide precursor [polyimide precursor (1-1), polyimide precursor (1-2)] of the present invention, X ₁ and X ₂ in the aforementioned chemical formula (1-1) _, and X ₃ and X ₄ in the aforementioned chemical formula (1-2) are each independently hydrogen, 1 to 6 carbons, preferably an alkyl group with 1 to 3 carbons, or an alkyl silicon group with 3 to 9 carbons any of the bases. For X ₁ , X ₂ , X ₃ , and X ₄ , the type of functional group and the introduction rate of the functional group can be changed according to the production method described later.

When X ₁ and X ₂ , X ₃ and X ₄ are hydrogen, the production of polyimide tends to be easy.

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

When X ₁ and X ₂ , X ₃ and X ₄ are alkylsilyl groups with 3 to 9 carbon atoms, the solubility of the imide precursor tends to be excellent. In this case. X ₁ and X ₂ , X ₃ and X ₄ are preferably trimethylsilyl or tertiary butyldimethylsilyl.

The introduction rate of functional groups is not particularly limited. When introducing an alkyl group or an alkylsilyl group, each of X ₁ and X ₂ , X ₃ and X ₄ can be 25% or more, preferably 50% or more, more preferably 75% or more For alkyl or alkyl silyl.

The polyimide precursor of _the present invention can be classified into _{: 1) polyimide (X 1 and} X ₂ , _{X 3 and X 4} is hydrogen), 2) polyamide ester (at least a part of _X1 and _X2 is an alkyl group, at least a part of _X3 and _X4 is an alkyl group), 3) 4) polyamide silicon ester ( _X1 and at least a part of _X2 is an alkylsilyl group, and at least a part of _X3 and _X4 is an alkylsilyl group). Furthermore, the polyimide precursor of the present invention can be easily produced by the following production methods in terms of its classification. However, the production method of the polyimide precursor of the present invention is not limited to the following production methods.

1) Polyamide The polyimide precursor of the present invention can be obtained by dissolving the tetracarboxylic dianhydride and the diamine component as the tetracarboxylic acid component in the solvent in an approximately equimolar ratio, preferably the ratio of the diamine component to the tetracarboxylic acid component. The molar ratio [the number of moles of the diamine component/the number of moles of the tetracarboxylic acid component] is preferably 0.90~1.10, more preferably a ratio of 0.95~1.05. The imidization side reaction is suitably obtained in the form of a polyimide precursor solution composition.

The synthesis method of the polyimide precursor of the present invention is not limited, but more specifically, diamine can be dissolved in an organic solvent, and tetracarboxylic dianhydride is slowly added to the solution while stirring, at 0~120 °C, preferably in the range of 5-80 °C, stirring for 1-72 hours to obtain a polyimide precursor. When reacting at 80°C or higher, the molecular weight will fluctuate depending on the temperature history during polymerization, and imidization will proceed due to heat, so it may not be possible to stably produce a polyimide precursor. In the above-mentioned production method, the order of adding diamine and tetracarboxylic dianhydride is preferable because it is easy to increase the molecular weight of the polyimide precursor. Moreover, the order of addition of diamine and tetracarboxylic dianhydride in the above-mentioned production method may be reversed, and it is preferable from the viewpoint of reducing precipitates.

Also, when the molar ratio of the tetracarboxylic acid component and the diamine component is excessive with the diamine component, a carboxylic acid derivative approximately equivalent to the excess molar number of the diamine component may be added as needed, so that the tetracarboxylic acid component and the diamine component The molar ratio of the amine components is approximately equivalent. Here, the carboxylic acid derivative is preferably a tetracarboxylic acid that does not substantially increase the viscosity of the polyimide precursor solution, that is, a tetracarboxylic acid that does not substantially extend the molecular chain, or a tricarboxylic acid that functions as a terminal stopper and Its anhydrides, dicarboxylic acids and their anhydrides, etc.

2) Polyamide ester Diester dicarboxylic acid is obtained by reacting tetracarboxylic dianhydride with any alcohol, and then reacted with chlorination reagents (thionyl chloride, oxalyl chloride, etc.) to obtain diester dicarboxylic acid chloride. A polyimide precursor can be obtained by stirring the diester dicarboxylate chloride and diamine at -20-120°C, preferably -5-80°C for 1-72 hours. When reacting at 80°C or higher, the molecular weight will fluctuate depending on the temperature history during polymerization, and imidization will proceed due to heat, so it may not be possible to stably produce a polyimide precursor. Moreover, the polyimide precursor can also be obtained simply by performing dehydration condensation of a diester dicarboxylic acid and a diamine using a phosphorus-type condensing agent, a carbodiimide condensing agent, etc.

Since the polyimide precursor obtained by this method is stable, it can be refined by adding solvents such as water and alcohol and performing reprecipitation.

3) Silicone polyamide (indirect method) The diamine is reacted with a silylating agent in advance to obtain a silylated diamine. Purification of the silylated diamine is carried out by distillation or the like, if necessary. And dissolve the siliconized diamine in the dehydrated solvent first, slowly add tetracarboxylic dianhydride while stirring, and stir for 1-72 hours at 0-120°C, preferably 5-80°C, to obtain polyimide precursors. When reacting above 80°C, the molecular weight will fluctuate depending on the temperature history during polymerization, and imidization will proceed due to heat, so it may not be possible to stably produce a polyimide precursor.

If the silylation agent used here is a chlorine-free silylation agent, it is not necessary to refine the silylated diamine, so it is ideal. Silylating agents that do not contain chlorine atoms include N,O-bis(trimethylsilyl)trifluoroacetamide, N,O-bis(trimethylsilyl)acetamide, hexamethyldisilazide Azane. N,O-bis(trimethylsilyl)acetamide and hexamethyldisilazane are particularly preferable from the viewpoint of not containing fluorine atoms and being low cost.

In addition, in the silylation reaction of diamine, in order to accelerate the reaction, an amine-based catalyst such as pyridine, piperidine, or triethylamine can be used. This catalyst can be directly used as a polymerization catalyst of polyimide precursor.

4) Silicone polyamide (direct method) Mix the polyamic acid solution obtained by the method 1) with the siliconizing agent, and stir at 0-120°C, preferably 5-80°C, for 1-72 hours to obtain a polyimide precursor. When reacting above 80°C, the molecular weight will vary depending on the temperature history during polymerization, and imidization will proceed due to heat, so it may not be possible to stably produce the polyimide precursor.

If the silylation agent used here is a chlorine-free silylation agent, it is not necessary to refine the silylated polyamic acid or the obtained polyimide, which is ideal. Silylating agents that do not contain chlorine atoms include N,O-bis(trimethylsilyl)trifluoroacetamide, N,O-bis(trimethylsilyl)acetamide, hexamethyldisilazide Azane. In consideration of fluorine-free and low-cost, N,O-bis(trimethylsilyl)acetamide and hexamethyldisilazane are particularly preferable.

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

Solvents used in the preparation of polyimide precursors, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl Aprotic solvents such as N, N-dimethylacetamide and N-methyl-2-pyrrolidone are ideal, but as long as the raw material monomers The components and the resulting polyimide precursor will dissolve, and any kind of solvent can be used without problems, so its structure is not particularly limited. The solvent should be amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, etc. Cyclic ester solvents such as lactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, etc., carbonate solvents such as ethylene carbonate and propylene carbonate, triethylene glycol, etc. Diol-based solvents, m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol and other phenol-based solvents, acetophenone, 1,3-dimethyl-2-imidazolidinone, cyclobutane, di Methyl sulfide, etc. are ideal. Furthermore, other common organic solvents can also be used, namely phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellolosu, butylcellosol Threon, 2-Methylcellothreoacetate, Ethylcellothreoacetate, Butylcellothreoacetate, 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 essence , Petroleum-based solvents, etc. In addition, a plurality of solvents may be used in combination.

In the present invention, the logarithmic viscosity of the polyimide precursor is not particularly limited, and the logarithmic viscosity in 0.5g/dL N,N-dimethylacetamide solution at 30°C is above 0.2dL/g, more preferably Preferably it is 0.3 dL/g or more. When the logarithmic viscosity is 0.2 dL/g or more, the molecular weight of the polyimide precursor is high, and the obtained polyimide has excellent mechanical strength and heat resistance.

In the present invention, the varnish of the polyimide precursor contains at least the polyimide precursor of the present invention [polyimide precursor (1-1) and/or polyimide precursor (1-2)] with solvents. The total amount of the tetracarboxylic acid component and the diamine component relative to the total amount of the solvent, the tetracarboxylic acid component, and the diamine component is 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more . Also, usually, the total amount of the tetracarboxylic acid component and the diamine component is 60% by mass or less, preferably 50% by mass or less, based on the total amount of the solvent, the tetracarboxylic acid component, and the diamine component. This concentration is roughly similar to the concentration of the solid content originating from the polyimide precursor. If the concentration is too low, it will be difficult to control the film thickness of the obtained polyimide film when producing a polyimide film, for example.

The solvent used in the polyimide precursor varnish of the present invention is not a problem as long as the polyimide precursor is dissolved, and its structure is not particularly limited. Examples of the solvent include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, Cyclic ester solvents such as δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, etc., carbonate solvents such as ethylene carbonate and propylene carbonate, triethyl Diol-based solvents such as diol, phenol-based solvents such as m-cresol, p-cresol, 3-chlorophenol, and 4-chlorophenol, acetophenone, 1,3-dimethyl-2-imidazolidinone, cyclobutanol Pine, dimethyl sulfide, etc. are ideal. Furthermore, other common organic solvents, namely phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosulo, butyl cellosulo, 2 -Methylcellosylacetate, ethylcellosylacetate, butylcellosylacetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethyl Diol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpene, mineral concentrate, naphtha Solvents and the like can also be used. Moreover, many types of these can be used in combination. In addition, as the solvent for the varnish of the polyimide precursor, the solvent used in the preparation of the polyimide precursor can be used as it is.

In the present invention, the viscosity (rotational viscosity) of the polyimide precursor varnish is not particularly limited, and the rotational viscosity measured by using an E-type rotational viscometer at a temperature of 25°C and a shear rate of 20sec ^-1 is 0.01~1000Pa·sec More ideal, 0.1~100Pa·sec is more ideal. Moreover, thixotropy can also be imparted as needed. When the viscosity is in the above-mentioned range, it is easy to handle and can suppress eye holes when coating and film-forming, and it has excellent leveling property and can obtain a good film.

The varnish of the polyimide precursor of the present invention can also add chemical imidization agents (acid anhydrides such as acetic anhydride, amine compounds such as pyridine and isoquinoline), antioxidants, fillers (inorganic particles such as silicon dioxide) etc.), dyes, pigments, silane coupling agents and other coupling agents, primers, flame retardants, defoamers, leveling agents, rheology control agents (flow aids), stripping agents, etc.

The polyimide (hereinafter also referred to as "polyimide (2-1)") of the first aspect of the present invention contains at least one of the repeating units represented by the aforementioned chemical formula (2-1), and A polyimide in which the total content of repeating units represented by the chemical formula (2-1) is 50 mol% or more relative to all repeating units. That is, the polyimide (2-1) of the present invention can be obtained by using the aforementioned tetracarboxylic acid component and diamine component used to obtain the polyimide precursor (1-1) of the present invention. The carboxylic acid component and the diamine component are also the same as the aforementioned polyimide precursor (1-1) of the present invention.

Also, the aforementioned chemical formula (2-1) corresponds to the aforementioned chemical formula (1-1) of the polyimide precursor (1-1), and each of A ₂₁ and B ₂₁ in the aforementioned chemical formula (2-1) corresponds to the aforementioned chemical formula A ₁₁ and B ₁₁ in (1-1).

The polyimide (hereinafter also referred to as "polyimide (2-2)") of the second aspect of the present invention is a polyamide containing at least one repeating unit represented by the aforementioned chemical formula (2-2). imide. The total content of the repeating units represented by the chemical formula (2-2) is not particularly limited, and is preferably 50 mol% or more relative to all the repeating units. That is, the polyimide (2-2) of the present invention can be obtained using the aforementioned tetracarboxylic acid component and diamine component used to obtain the polyimide precursor (1-2) of the present invention. The tetracarboxylic acid component and the diamine component are also the same as the aforementioned polyimide precursor (1-2) of the present invention.

Also, the aforementioned chemical formula (2-2) corresponds to the aforementioned chemical formula (1-2) of the polyimide precursor (1-2), and A ₂₂ and B ₂₂ in the aforementioned chemical formula (2-2) correspond to the aforementioned chemical formula A ₁₂ and B ₁₂ in (1-2).

The polyimide (2-1) of the present invention can be ideally produced by subjecting the polyimide precursor (1-1) of the present invention to a dehydration ring-closure reaction (imidization reaction). The polyimide (2-2) of the present invention can be ideally produced by subjecting the polyimide precursor (1-2) of the present invention 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 can be preferably used.

The form of the polyimide to be obtained is preferably a film, a laminate of a polyimide film and other substrates, a coating film, powder, beads, molded body, foam, and varnish.

In the present invention, the logarithmic viscosity of polyimide is not particularly limited, and the logarithmic viscosity in 0.5g/dL N,N-dimethylacetamide solution at 30°C is above 0.2dL/g, more preferably 0.4dL/g or more, especially preferably 0.5dL/g or more. When the logarithmic viscosity is 0.2 dL/g or more, the obtained polyimide has excellent mechanical strength and heat resistance.

In the present invention, the polyimide varnish contains at least the polyimide of the present invention and a solvent, and the polyimide is at least 5% by mass, preferably 10% by mass, relative to the total amount of the solvent and polyimide. More than above, more preferably at least 15% by mass, especially preferably at least 20% by mass. If the concentration is too low, for example, it will be difficult to control the film thickness of the obtained polyimide film when producing the polyimide film.

The solvent used for the polyimide varnish of the present invention has no problem if the polyimide is soluble, and its structure is not particularly limited. As the solvent, the same solvent used for the varnish of the polyimide precursor of the present invention can be used.

In the present invention, the viscosity (rotational viscosity) of the polyimide varnish is not particularly limited, and the rotational viscosity measured by using an E-type rotational viscometer at a temperature of 25°C and a shear rate of 20sec ^-1 is ideally 0.01~1000Pa·sec , 0.1~100Pa·sec is more ideal. Moreover, thixotropy can also be imparted as needed. The viscosity in the above range is easy to handle during coating and film formation, and eye holes are suppressed, excellent leveling property, and good film can be obtained.

In the polyimide varnish of the present invention, antioxidants, fillers (inorganic particles such as silicon dioxide, etc.), dyes, pigments, coupling agents such as silane coupling agents, primers, and flame-retardant materials can also be added as needed. , defoaming agent, leveling agent, rheological empty preparation (flow aid), stripping agent, etc.

The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention are not particularly limited, and the coefficient of linear thermal expansion at 100°C to 250°C when formed into a film is preferably below 45ppm/K, more preferably 40ppm/K or less. If the coefficient of linear thermal expansion is large, the difference between the coefficient of linear thermal expansion and that of conductors such as metals is large, and there may be disadvantages such as increased warping when 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 of wavelength 380nm ~ 780nm) of a film with a thickness of 10 μm is preferably More than 70%, more preferably more than 75%, and more preferably more than 80%. When used in display applications, etc., if the total light transmittance is low, the light source needs to be strengthened, and problems such as energy consumption will occur.

Also, depending on the application, the film made of the polyimide of the present invention has a thickness of preferably 1 μm to 250 μm, more preferably 1 μm to 150 μm, more preferably 1 μm to 50 μm, and especially preferably 1 μm to 30 μm. When the polyimide film is used for light-transmitting applications such as display applications, if the polyimide film is too thick, the light transmittance may decrease.

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 loss temperature, which is an indicator of the heat resistance of polyimide, is preferably 420° C. or higher. Preferably it is above 450°C. When forming transistors etc. on polyimide and forming a gas barrier film etc. on polyimide, if the heat resistance is low, there may be problems between the polyimide and the barrier film due to the decomposition of polyimide, etc. The accompanying outgassing causes uplift to occur.

The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention are applicable to, for example, transparent substrates for displays, transparent substrates for touch panels, or substrates for solar cells.

An example of a method for producing a polyimide film/substrate laminate or a polyimide film using the polyimide precursor of the present invention will be described below. But not limited to the following methods.

Cast the polyimide precursor varnish of the present invention on substrates such as ceramics (glass, silicon, alumina, etc.), metals (copper, aluminum, stainless steel, etc.), heat-resistant plastic films (polyimide films, etc.) Materials are dried in a vacuum in an inert gas such as nitrogen, or in air using hot air or infrared rays at a temperature range of 20~180°C, preferably 20~150°C. Secondly, the obtained polyimide precursor film can be placed on the substrate, or the polyimide precursor film can be peeled off from the substrate, and in the state where the end of the film is fixed, in a vacuum, nitrogen and other inert In inert gas or air, use hot air or infrared rays, for example, heat imidization at a temperature of 200~500°C, preferably at a temperature of about 250~460°C, to produce a polyimide film/substrate laminate , or polyimide film. In addition, in order to prevent the obtained polyimide film from being oxidized and degraded, the heating imidization is preferably carried out in a vacuum or in an inert gas. If the temperature of imidization by heating is not too high, it may be carried out in the air.

In addition, the imidization reaction of the polyimide precursor can also be replaced by the use of the polyimide precursor in the presence of tertiary amines such as pyridine and triethylamine. Chemical treatment such as immersion in a solution containing dehydration and cyclization reagents such as acetic anhydride. Also, by putting these dehydrating cyclization reagents into the varnish of the polyimide precursor in advance and stirring, casting it on the substrate and drying it, to obtain a partially imidized polyimide Amine precursor, the obtained partially imidized polyimide precursor film is placed on the substrate, or the polyimide precursor film is peeled off from the substrate and fixed at the end of the film , further performing heat treatment as described above, a polyimide film/substrate laminate or a polyimide film can be obtained.

A flexible conductive substrate can be obtained by forming a conductive layer on one or both sides of the polyimide film/substrate laminate or polyimide film obtained in this way.

A flexible conductive substrate can be obtained, for example, as follows. That is, with regard to the first method, the polyimide film/substrate laminate is not peeled off from the substrate, but the surface of the polyimide film is deposited by sputtering, vapor deposition, or printing. Form a conductive layer of conductive substances (metal or metal oxide, conductive organic matter, conductive carbon, etc.) to prepare a conductive laminate of conductive layer/polyimide film/substrate. Thereafter, if necessary, the conductive layer/polyimide film laminate is peeled off from the substrate, whereby a transparent and flexible conductive substrate composed of the conductive layer/polyimide film laminate is obtained .

In the second method, the polyimide film can be peeled off from the base material of the polyimide film/substrate laminate to obtain a polyimide film, and the surface of the polyimide film is in the same manner as the first method Form a conductive layer of a conductive substance (metal or metal oxide, conductive organic matter, conductive carbon, etc.), and obtain a laminated body of conductive layer/polyimide film, or conductive layer/polyimide film/ A transparent and flexible conductive substrate composed of conductive laminates.

Also, in the first and second methods, if necessary, before forming a conductive layer on the surface of the polyimide film, gas barrier layers such as water vapor and oxygen can be formed by sputtering, vapor deposition, gel-sol method, etc. , light adjustment layer and other inorganic layers.

In addition, the conductive layer can be suitably formed into a circuit by methods such as photolithography, various printing methods, and inkjet methods.

In the substrate of the present invention obtained in this way, a circuit with a conductive layer is formed on the surface of the polyimide film composed of the polyimide of the present invention, if necessary, via a gas barrier layer and an inorganic layer. This substrate is flexible, and it is easy to form fine circuits. Therefore, this substrate is suitable as a substrate for displays, touch panels, or solar cells.

That is, on this substrate, use evaporation, various printing methods, or inkjet methods to further form transistors (inorganic transistors, organic transistors) and manufacture flexible thin film transistors, which are suitable for liquid crystal elements for displays, EL Components, optoelectronic components.

The tetracarboxylic dianhydride used in the manufacture of the polyimide precursor (1-2) of the present invention and the polyimide (2-2) of the present invention is the tetracarboxylic dianhydride represented by the aforementioned chemical formula (M-1). Anhydrides and tetracarboxylic dianhydrides represented by the aforementioned chemical formula (M-4) are novel compounds.

Hereinafter, it describes about the manufacturing method of the tetracarboxylic dianhydride represented by said chemical formula (M-1).

For the tetracarboxylic dianhydride represented by the aforementioned chemical formula (M-1), please refer to JP-A-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, etc., synthesized according to the reaction scheme shown below, for example. Here, it is the tetracarboxylic dianhydride represented by the chemical formula (M-1) in which R ₅ ′ and R ₆ ′ are -CH ₂ -, that is, 3a, 4, 6, 6a, 9a, 10, 12, 12a- Octahydro-1H,3H-4,12:6,10-Dimethyloanthracene[2,3-c:6,7-c']difuran-1,3,7,9-tetraone (DMADA) Although it demonstrates as an example, other tetracarboxylic dianhydrides can also be manufactured similarly.

式中，R為也可以有取代基之烷基或芳基，R₁₁ 、R₁₂ 、R₁₃ 、R₁₄ 各自獨立地為碳數1~10之烷基。[chem 45]

In the formula, R is an alkyl or aryl group which may have a substituent, and R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each independently an alkyl group having 1 to 10 carbon atoms.

(1st step) In the 1st step, when synthesizing the tetracarboxylic dianhydride (DMADA) of the chemical formula (M-1) in which R ₅ ' and R ₆ ' are -CH ₂ -, p-benzoquinone (BQ) and Cyclopentadiene (CP) reaction, synthesis of 1,4,4a,5,8,8a,9a,10a-octahydro-1,4:5,8-dimethylpoanthrene-9,10-dione (DNBQ ). When synthesizing tetracarboxylic dianhydride of chemical formula (M-1) where R ₅ ' and R ₆ ' are -CH ₂ CH ₂ -, here, cyclopentadiene (CP) is replaced by 1,3-cyclohexanedi Alkenes can be reacted with BQ.

The usage amount of the aforementioned cyclopentadiene (or 1,3-cyclohexadiene, etc.) is preferably 1.0-20 moles, more preferably 1.5-10.0 moles relative to 1 mole of p-benzoquinone (BQ). .

This reaction is usually carried out in an organic solvent. The organic solvent used is not particularly limited as long as it does not hinder the reaction, for example: amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone; N,N -Ureas such as dimethyl imidazolidinone; methoxides such as dimethyl sulfide and cyclobutylene; nitriles such as acetonitrile and propionitrile; methanol, ethanol, n-propanol, isopropanol, n-butanol, Alcohols such as tributanol; Ethers such as diisopropyl ether, dioxane, tetrahydrofuran, cyclopropyl methyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene; Hexane, cyclohexane, heptane, octane Aliphatic hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene and other halogenated hydrocarbons; ethyl acetate, butyl acetate and other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., Alcohols and aromatic hydrocarbons are preferable. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The usage amount of the above-mentioned organic solvent can be properly adjusted by utilizing the uniformity and agitation of the reaction liquid, and it is preferably 1-50 g relative to 1 g of BQ, and more preferably 2-30 g.

This reaction can be implemented, for example, by a method of mixing and stirring BQ and CP in an organic solvent. The reaction temperature at this time is preferably 0-150°C, more preferably 15-60°C, and the reaction pressure is not particularly limited.

(step 2) The second step is to react the DNBQ obtained in the first step with sodium borohydride to synthesize 1,4,4a,5,8,8a, 9,9a,10,10a-decahydro-1,4:5,8- Dimethylanthracene-9,10-diol (DNHQ).

The amount of sodium borohydride used is preferably 0.5-10 moles, more preferably 1.5-5.0 moles relative to 1 mole of DNBQ.

This reaction is usually carried out in an organic solvent. The organic solvent used is not particularly limited as long as it does not hinder the reaction, for example: amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone; N,N -Ureas such as dimethyl imidazolidinone; methoxides such as dimethyl sulfide and cyclobutylene; nitriles such as acetonitrile and propionitrile; methanol, ethanol, n-propanol, isopropanol, n-butanol, Alcohols such as tributanol; Ethers such as diisopropyl ether, dioxane, tetrahydrofuran, cyclopropyl methyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene; Hexane, cyclohexane, heptane, octane Aliphatic hydrocarbons such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., preferably alcohols, ethers, and aromatic hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The usage amount of the aforementioned organic solvent can be properly adjusted according to the uniformity and agitation of the reaction liquid, but relative to 1 g of DNBQ, it is preferably 1-100 g, and more preferably 5-50 g.

This reaction can be carried out, for example, by mixing and stirring DNBQ and sodium borohydride in an organic solvent. The reaction temperature at this time is preferably -20~150°C, more preferably 0~50°C, and the reaction pressure is not particularly limited.

(The third step) The third step is to react the DNHQ obtained in the second step with methanesulfonyl chloride in the presence of a base to synthesize dimethanesulfonic acid 1,4,4a,5,8,8a,9,9a,10 ,10a-decahydro-1,4: 5,8-Dimethylanthracene-9,10-diester (DNCMS; in this case R is -CH ₃ [-SO ₂ R is methylsulfonyl (-SO ₂ CH ₃ )]). Methanesulfonyl chloride can also be replaced by other aliphatic sulfonyl chloride or aromatic sulfonyl chloride.

This reaction uses a base. In this reaction, the base used, for example: secondary amines such as dibutylamine, piperidine, and 2-methylpiperidine; tertiary amines such as triethylamine and tributylamine; pyridine, picoline, dimethylamine, etc. Pyridines such as basepyridine; quinolines such as quinoline, isoquinoline, and methylquinoline; alkali metal hydrides such as sodium hydride and potassium hydride; sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium tert-butoxide, etc. Alkali metal alkoxides; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, preferably tertiary amines Classes, pyridines, quinolines, alkali metal carbonates. Moreover, these bases can be used individually or in mixture of 2 or more types.

The usage amount of the aforementioned alkali is preferably 0.01-200 moles, more preferably 0.1-100 moles relative to 1 mole of DNHQ.

This reaction uses sulfonyl chloride. Sulfonyl chloride used in this reaction, for example: aliphatic sulfonyl chloride such as methanesulfonyl chloride, ethanesulfonyl chloride, trifluoromethanesulfonyl chloride; benzenesulfonyl chloride, toluenesulfonyl chloride, nitrobenzenesulfonyl chloride Aromatic sulfonyl chlorides such as chlorine, preferably aliphatic sulfonyl chlorides. In addition, these sulfonyl chlorides may be used alone or in combination of two or more.

The usage amount of the aforementioned sulfonyl chloride is preferably 1.5-10 moles, more preferably 1.8-5 moles relative to 1 mole of DNHQ.

This reaction is usually carried out in an organic solvent. The organic solvent used is not particularly limited as long as it does not hinder the reaction, for example: amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone; N,N -Ureas such as dimethylimidazolidinone; pyridines such as pyridine, picoline, and dimethylaminopyridine; quinolines such as quinoline, isoquinoline, and methylquinoline; Acetonitrile and other arginines; acetonitrile, propionitrile and other nitriles; diisopropyl ether, dioxane, tetrahydrofuran, cyclopropyl methyl ether and other ethers; benzene, toluene, xylene and other aromatic hydrocarbons; hexane, cyclohexane Aliphatic hydrocarbons such as alkanes, heptanes, and octanes; esters such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., preferably pyridines. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The usage amount of the above-mentioned organic solvent can be appropriately adjusted by utilizing the uniformity and agitation of the reaction liquid, and it is preferably 1-200 g relative to 1 g of DNHQ, and more preferably 10-100 g.

This reaction can be carried out by, for example, mixing and stirring DNHQ, a base, and sulfonyl chloride in an organic solvent. The reaction temperature at this time is preferably -20~150°C, more preferably 0~50°C, and the reaction pressure is not particularly limited.

(4th step) In the 4th step, react methanol with carbon monoxide and the DNCMS obtained in the 3rd step in the presence of a palladium catalyst and a copper compound to synthesize 9,10-bis((methylsulfonyl)oxy)tetradecine Hydrogen-1,4: tetramethyl 5,8-dimethylpyrthracene-2,3,6,7-tetracarboxylate (DNMTE; in this case R ₁₁ to R ₁₄ are methyl). It is also possible to replace methanol with other alcohol compounds corresponding to the desired ester compound.

Alcohol compounds used in this reaction, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, amyl alcohol, methoxyethanol, ethoxyethanol, ethylene glycol Alcohol, triethylene glycol, etc., preferably methanol, ethanol, n-propanol, isopropanol, more preferably methanol, ethanol, isopropanol. Moreover, these alcohol compounds can be used individually or in mixture of 2 or more types.

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

This reaction uses a palladium catalyst. The palladium catalyst used in this reaction is not particularly limited as long as it contains palladium, for example: 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 supported on carbon, alumina and other supports formed of palladium carbon, palladium alumina, etc., preferably palladium chloride, palladium carbon.

The usage amount of the aforementioned palladium catalyst is preferably 0.001-1 mole, more preferably 0.01-0.5 mole relative to 1 mole of DNCMS.

This reaction uses a copper compound. Copper compounds used in this reaction, for example: copper (I) oxide, copper (I) chloride, copper (I) bromide and other monovalent copper compounds, copper (II) oxide, copper (II) chloride, bromide Divalent copper compounds such as copper (II) are preferably divalent copper compounds, more preferably copper (II) chloride. Moreover, these copper compounds can be used individually or in mixture of 2 or more types.

The usage amount of the aforementioned copper compound is preferably 1.0-50 moles, more preferably 4.0-20 moles relative to 1 mole of DNCMS.

In this reaction, an organic solvent other than the aforementioned alcohol compound can also be used. The organic solvent used is not particularly limited as long as it does not hinder the reaction, for example: aliphatic carboxylic acids (such as: formic acid, acetic acid, propionic acid, trifluoroacetic acid, etc.), organic sulfonic acids (such as: methanesulfonic acid, trifluoromethanesulfonic acid, etc.) etc.), ketones (such as: acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (such as: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (such as: N , N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.), urea (N,N'-dimethylimidazolidinone, etc.), ethers (such as : diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-methylenedioxybenzene, etc.), aromatic hydrocarbons (such as benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (such as : chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitroated aromatic hydrocarbons (such as: nitrobenzene, etc.), halogenated hydrocarbons ( For example: dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, etc.), carboxylic acid esters (such as: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (such as: Acetonitrile, propionitrile, benzonitrile, etc.), pyrenes (eg, dimethylsulfene, etc.), pyrenes (eg, cyclobutene, etc.), and the like. Preferred are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and halogenated aromatic hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The usage amount of the above-mentioned organic solvent can be appropriately adjusted by utilizing the uniformity and agitation of the reaction liquid, and it is preferably 1-100 g, more preferably 5-50 g relative to 1 g of DNCMS.

This reaction can be carried out by mixing DNCMS, alcohol compound, palladium catalyst and copper compound in an organic solvent, and stirring in an atmosphere of carbon monoxide. The reaction temperature at this time is preferably -20~100°C, more preferably 0~50°C, and the reaction pressure is not particularly limited.

(step 5) In the fifth step, 1,2,3,4,4a,5,6,7,8,9a-decahydro-1,4 was synthesized by the demethanylsulfonylation reaction of DNMTE obtained in the fourth step: Tetramethyl 5,8-dimethylpyrthracene-2,3,6,7-tetracarboxylate (DMHAE). The compound obtained in the fifth step is a tetraester compound represented by the aforementioned chemical formula (M-3), which is a novel compound.

This reaction can be carried out, for example, by a method such as dissolving DNMTE in an organic solvent, stirring while heating if necessary. The reaction temperature at this time is preferably -20~200°C, more preferably 25~180°C, and the reaction pressure is not particularly limited.

This reaction can be carried out by heating and stirring even without adding a base to the reaction liquid, but in order to capture the by-product strongly acidic methanesulfonic acid, a base is preferably used. The base used is not particularly limited as long as it does not interfere with the reaction, for example: secondary amines such as dibutylamine, piperidine, and 2-methylpiperidine; tertiary amines such as triethylamine and tributylamine; pyridine and picoline , dimethylaminopyridine and other pyridines; quinoline, isoquinoline, methyl quinoline and other quinolines; alkali metal hydrides such as sodium hydride and potassium hydride; sodium methoxide, sodium ethoxide, sodium isopropoxide, third Alkali metal alkoxides such as potassium butoxide; Alkali metal carbonates such as sodium carbonate, potassium carbonate and lithium carbonate; Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide , preferably tertiary amines, pyridines, quinolines, and alkali metal carbonates. Moreover, these bases can be used individually or in mixture of 2 or more types.

The usage amount of the aforementioned alkali is preferably 1.5-5 moles, more preferably 1.8-3 moles relative to 1 mole of DNMTE.

This reaction is usually carried out in an organic solvent. The organic solvent used is not particularly limited as long as it does not interfere with the reaction, for example: N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethyl Amides such as isobutylamide; Ureas such as N,N-dimethylimidazolidinone; Dimethylidene, cyclobutylene and other ureas; Nitriles such as acetonitrile and propionitrile; Methanol, ethanol, Alcohols such as n-propanol, isopropanol, n-butanol and tertiary butanol; ethers such as diisopropyl ether, dioxane, tetrahydrofuran and cyclopropyl methyl ether; aromatic hydrocarbons such as benzene, toluene and xylene ; Hexane, cyclohexane, heptane, octane and other aliphatic hydrocarbons; dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene and other halogenated hydrocarbons; ethyl acetate, butyl acetate and other esters Class; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., preferably amides, urea, nitriles. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The usage amount of the above-mentioned organic solvent can be appropriately adjusted by utilizing the uniformity and agitation of the reaction liquid, and it is preferably 1-100 g relative to 1 g of DNMTE, and more preferably 2-50 g.

(step 6) In the sixth step, 1,2,3,4,5,6,7,8-octahydro-1,4:5,8- Dimethylpyronate-2,3,6,7-tetracarboxylic acid tetramethyl ester (DMAME). The compound obtained in the sixth step is a tetraester compound represented by the aforementioned chemical formula (M-2), which is a novel compound.

This reaction can be carried out, for example, by a method such as heating and stirring DMHAE and an oxidizing agent for aromatization in a solvent as necessary. The reaction temperature at this time is preferably 25-150°C, more preferably 40-120°C, and the reaction pressure is not particularly limited.

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

The amount of the aforementioned oxidizing agent is preferably 0.5-5 moles, more preferably 0.8-3 moles relative to 1 mole of DMHAE.

This reaction is usually carried out in a solvent. The solvent used is not particularly limited as long as it does not interfere with the reaction, for example: water; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylformamide Amides such as isobutylamide; N, N-dimethyl imidazolidinone and other urea; Acetonitrile, propionitrile and other nitriles; Methanol, ethanol, n-propanol, isopropanol, n-butanol, Alcohols such as tributanol; Ethers such as diisopropyl ether, dioxane, tetrahydrofuran, cyclopropyl methyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene; Hexane, cyclohexane, heptane, octane Aliphatic hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene and other halogenated hydrocarbons; ethyl acetate, butyl acetate and other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., Preferred are aromatic hydrocarbons, halogenated hydrocarbons, ethers, alcohols, and water. Moreover, these solvents can be used individually or in mixture of 2 or more types.

The usage amount of the aforementioned solvent can be properly adjusted by utilizing the uniformity and agitation of the reaction liquid, but it is preferably 1-100 g relative to 1 g of DMHAE, and more preferably 2-50 g.

(step 7) In the seventh step, 3a, 4, 6, 6a, 9a, 10, 12, 12a-octahydro-1H, 3H-4, 12: 6, 10-di Meclidanthrano[2,3-c:6,7-c']difuran-1,3,7,9-tetraone (DMADA). The compound obtained in the seventh step is tetracarboxylic dianhydride represented by the aforementioned chemical formula (M-1).

This reaction can be carried out by, for example, heating and stirring DMAME in an organic solvent in the presence of an acid catalyst. The reaction temperature at this time is preferably 50-130°C, more preferably 80-120°C, and the reaction pressure is not particularly limited.

This reaction uses an acid catalyst. The acid catalyst used in this reaction is not particularly limited as long as it is an acid, for example: hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, chlorosulfuric acid, nitric acid and other inorganic acids; methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc. Organic sulfonic acids; halogenated carboxylic acids such as chloroacetic acid and trifluoroacetic acid, ion exchange resins, silica gel sulfate, zeolite, acidic alumina, etc., preferably inorganic acids and organic sulfonic acids, and more preferably organic sulfonic acids. Moreover, these acids can be used individually or in mixture of 2 or more types.

The usage amount of the aforementioned acid catalyst is preferably 0.0001-0.1 mole, more preferably 0.001-0.05 mole relative to 1 mole of DMAME.

This reaction is preferably carried out in a solvent. The solvent used should be an organic acid solvent such as formic acid, acetic acid, propionic acid, etc. Moreover, these solvents can be used individually or in mixture of 2 or more types.

The usage amount of the above-mentioned solvent can be appropriately adjusted by utilizing the uniformity and agitation of the reaction solution, and it is preferably 0.1-100 g, and more preferably 1-10 g, relative to 1 g of DMAME.

The details of each reaction are described in accordance with the examples, but those with ordinary knowledge in this technical field can change the solvent, feed amount, reaction conditions, etc., and after each reaction is completed, for example, filtration, extraction, distillation, sublimation, General methods such as recrystallization and column chromatography are used to isolate and purify the reaction product.

The manufacturing method of the tetracarboxylic dianhydride represented by said chemical formula (M-4) is demonstrated below.

The tetracarboxylic dianhydride represented by the aforementioned chemical formula (M-4) can be synthesized according to the following reaction scheme with reference to Helv. Chim. Acta. 1975, 58, 160, Macromolecules 1993, 26, 3490, etc.

式中，X₁₁ 、X₁₂ 各自獨立地為-F、-Cl、-Br、或-I，R₂₁ 、R₂₂ 、R₂₃ 、R₂₄ 各自獨立地為碳數1~10之烷基。[chem 46]

In the formula, X ₁₁ and X ₁₂ are each independently -F, -Cl, -Br, or -I, and R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are each independently an alkyl group with 1 to 10 carbons.

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

This reaction can be carried out, for example, by charging NA in a pressure vessel such as an autoclave, introducing 1,3-butadiene, and heating and stirring. The reaction temperature at this time is preferably 80-220°C, more preferably 100-180°C, and the reaction pressure is not particularly limited.

The usage-amount of the aforementioned 1,3-butadiene is preferably 0.5-5 moles, more preferably 0.8-3 moles relative to 1 moles of NA.

This reaction may or may not use an organic solvent. The solvent used is not particularly limited as long as it does not hinder the reaction, for example: ketones (such as: acetone, methyl ethyl ketone, cyclohexanone, etc.), aliphatic hydrocarbons (such as: n-pentane, n-hexane, n-heptane, cyclohexane alkanes, etc.), amides (for example: N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylisobutylamide etc.), urea (N,N'-dimethyl imidazolidinone, etc.), ethers (such as: diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-methylenedioxybenzene, etc. ), aromatic hydrocarbons (such as benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (such as: chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene chlorobenzene, etc.), nitroated aromatic hydrocarbons (such as: nitrobenzene, etc.), halogenated hydrocarbons (such as: methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, etc.), carboxyl Esters (such as: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (such as: acetonitrile, propionitrile, benzonitrile, etc.), sulfides (such as: dimethylsulfoxide, etc.), Phenols (such as cyclobutane, etc.), phenols (phenol, methylphenol, p-chlorophenol, etc.), etc. Preferably, aliphatic hydrocarbons and aromatic hydrocarbons are used. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

When an organic solvent is used, the usage amount of the aforementioned organic solvent can be appropriately adjusted by utilizing the uniformity and agitation of the reaction solution. Relative to 1 g of NA, it is preferably 0.1-100 g, and more preferably 1-50 g.

(2nd step) In the 2nd step, the OMNA obtained in the 1st step is reacted with bromine as a dihalogenating agent to synthesize 6,7-dibromodecahydro-4,9-methonaphtho[2,3-c ]furan-1,3-dione (DBDNA; in this case X ₁₁ , X ₁₂ are —Br). Instead of bromine, other dihalogenating agents described later may be used. The compound obtained in the second step is the dihalogenated dicarboxylic anhydride represented by the aforementioned chemical formula (M-6), which is a novel compound.

This reaction can be carried out by, for example, mixing and stirring OMNA and a dihalogenating agent in an organic solvent. The reaction temperature at this time is preferably -100~50°C, more preferably -80~30°C, and the reaction pressure is not particularly limited.

In this reaction, a dihalogenating agent such as bromine is used. The dihalogenating agent used in this reaction is not particularly limited as long as it can dihalogenate the olefin, and examples include halogens such as fluorine, chlorine, bromine, and iodine, and pyridinium salts, ammonium salts, tribromopyridine, and tribromobenzyltrimethyl Tribromide salts such as ammonium tribromide, chlorine fluoride, bromine chloride, iodine chloride, iodine bromide, iodine tribromide and other halogen compounds, and pyridinium salts, ammonium salts, etc., preferably halogens, especially bromine.

The usage amount of the aforementioned dihalogenating agent is preferably 0.5-5 moles, more preferably 0.8-2 moles relative to 1 mole of OMNA.

This reaction is usually carried out in an organic solvent. The solvent used is not particularly limited as long as it does not hinder the reaction, for example: ketones (such as: acetone, methyl ethyl ketone, cyclohexanone, etc.), aliphatic hydrocarbons (such as: n-pentane, n-hexane, n-heptane, cyclohexane alkanes, etc.), amides (for example: N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylisobutylamide etc.), urea (N,N'-dimethyl imidazolidinone, etc.), ethers (such as: diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-methylene dioxide, etc.) , aromatic hydrocarbons (such as: benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (such as: chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene Benzene, etc.), nitroated aromatic hydrocarbons (such as nitrobenzene, etc.), halogenated hydrocarbons (such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, etc.), carboxylic acids Esters (e.g. ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (e.g. acetonitrile, propionitrile, benzonitrile, etc.), sulfides (e.g. dimethyl sulfide, etc.), sulfides Classes (such as cyclobutylene, etc.), phenols (phenol, methylphenol, p-chlorophenol), etc. Preferable are aliphatic hydrocarbons and halogenated hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The usage amount of the above-mentioned organic solvent can be properly adjusted by utilizing the uniformity and agitation of the reaction solution. Relative to 1 g of OMNA, it is preferably 0.1-100 g, and more preferably 1-50 g.

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

This reaction can be carried out by, for example, mixing DBDNA and maleic anhydride, heating and stirring. The reaction temperature at this time is preferably 100-250°C, more preferably 120-230°C, and the reaction pressure is not particularly limited.

The amount of maleic anhydride used is usually 1 mol or more, preferably 2 mol or more, and more preferably 4 mol or more, relative to 1 mol of DBDNA.

In this reaction, solid DBDNA and maleic anhydride are mixed and reacted. The theoretically necessary amount of maleic anhydride relative to DBDNA is 1 mole, but when using about 1 mole, the reactant after the reaction may solidify in the reaction container and be difficult to take out. On the other hand, when maleic anhydride (melting point 52-56°C) is used in an amount of more than equimolar, because the reaction temperature is higher than the melting point of maleic anhydride, the excess maleic anhydride is liquid, and acts as a solvent to react system becomes a suspension. After the reaction is completed, after cooling from the reaction temperature to a temperature suitable for operation (for example: about 100°C), adding an organic solvent into the system and filtering, high-purity EEMDA can be obtained.

Organic solvents added after the reaction, such as: ketones (such as: acetone, methyl ethyl ketone, cyclohexanone, etc.), aliphatic hydrocarbons (such as: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), acyl Amines (such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylisobutylamide, etc.), urea (N,N'-dimethyl imidazolidinone, etc.), ethers (such as: diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-methylene dioxide, etc.), aromatic hydrocarbons (for example: benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (for example: chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitric acid Hydrogenated aromatic hydrocarbons (such as nitrobenzene, etc.), halogenated hydrocarbons (such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, etc.), carboxylic acid esters (such as: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (such as: acetonitrile, propionitrile, benzonitrile, etc.), sulfides (such as: dimethylsulfoxide, etc.), sulfides (such as: cyclic Ding Ting, etc.) and so on. Preferable are aliphatic hydrocarbons and aromatic hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The usage amount of the aforementioned organic solvent can be appropriately adjusted by utilizing the homogeneity and agitation of the prepared solution, and it is preferably 0.1-30 mL, and more preferably 0.5-20 mL relative to 1 g of DBDNA.

(4th step) In the 4th step, the EEMDA obtained in the 3rd step is reacted with methanol to synthesize 1,4,4a,5,6,7,8,8a-octahydro-1,4-ethano-5 , Tetramethyl 8-methyronaphthyl-6,7,10,11-tetracarboxylate (EEMDE; in this case, R ₂₁ ~R ₂₄ are methyl). It is also possible to replace methanol with other alcohol compounds corresponding to the desired ester compound. The compound obtained in the fourth step is a tetraester compound represented by the aforementioned chemical formula (M-5) in which R ₇ is -CH=CH-, and is a novel compound.

This reaction can be carried out by, for example, mixing and stirring EEMDA, orthoesters, and alcohols in the presence of an acid. The reaction temperature at this time is preferably 20-150°C, more preferably 50-100°C, and the reaction pressure is not particularly limited.

This reaction uses an acid. The acid used in this reaction is not particularly limited, for example: inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, chlorosulfuric acid, nitric acid; organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid; chloroacetic acid , trifluoroacetic acid and other halogenated carboxylic acids, ion exchange resins, silica gel sulfate, zeolite, acidic alumina, etc., preferably inorganic acids and organic sulfonic acids, and more preferably inorganic acids. Moreover, these acids can be used individually or in mixture of 2 or more types.

The usage-amount of the aforementioned acid is preferably 0.01-10 moles, more preferably 0.05-3 moles relative to 1 mole of EEMDA.

This reaction uses an alcohol compound. Alcohol compounds used in this reaction, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, amyl alcohol, methoxyethanol, ethoxyethanol, ethylene glycol Alcohol, triethylene glycol, etc., preferably methanol, ethanol, n-propanol, isopropanol, more preferably methanol, ethanol. Moreover, these alcohol compounds can be used individually or in mixture of 2 or more types.

The usage-amount of the said alcohol compound is preferably 0.1-200 g with respect to EEMDA1g, More preferably, it is 1-100g.

In this reaction, organic solvents other than the aforementioned alcohols can also be used. The organic solvent used is not particularly limited as long as it does not hinder the reaction, for example: aliphatic carboxylic acids (for example: formic acid, acetic acid, propionic acid, trifluoroacetic acid, etc.), organic sulfonic acids (for example: methanesulfonic acid, trifluoromethanesulfonic acid, etc.) etc.), ketones (such as: acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (such as: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (such as: N , N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.), urea (N,N'-dimethylimidazolidinone, etc.), ethers (such as : diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-methylene dioxide, etc.), aromatic hydrocarbons (such as benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (such as : chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitroated aromatic hydrocarbons (such as: nitrobenzene, etc.), halogenated hydrocarbons ( For example: dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, etc.), carboxylic acid esters (such as: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (such as: Acetonitrile, propionitrile, benzonitrile, etc.), pyrenes (eg, dimethylsulfene, etc.), pyrenes (eg, cyclobutene, etc.), and the like. Preferred are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and halogenated aromatic hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

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

Orthoesters can be used in this reaction. The orthoesters used may include compounds represented by the following formulas, for example: trimethyl orthoformate, triethyl orthoformate, preferably trimethyl orthoformate.

[chem 47]

In the formula, R ^f is 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. Also, R ^e is an alkyl group having 1 to 5 carbon atoms, preferably a methyl group or an ethyl group, more preferably a methyl group. The three R ^e may be the same or different, preferably the same.

The usage-amount of the aforementioned raw esters is preferably 0.5 g or more, more preferably 1 to 5 g, relative to 1 g of EEMDA.

(5th step) In the 5th step, the EEMDE obtained in the 4th step is reacted with hydrogen to synthesize decahydro-1,4-ethano-5,8-methyronaphthyl-2,3,6,7-tetracarboxylic Tetramethyl Ester (EMDE). The compound obtained in the fifth step is a tetraester compound represented by the aforementioned chemical formula (M-5) in which R ₇ is -CH ₂ CH ₂ -, and is a novel compound.

This reaction can be carried out by, for example, mixing EEMDE and a metal catalyst in a solvent, heating and stirring as necessary under a hydrogen atmosphere, and the like. The reaction temperature at this time is preferably from 0 to 150°C, more preferably from 10 to 120°C. The reaction pressure is preferably 0.1-20 MPa, more preferably 0.1-5 MPa.

This reaction uses hydrogen. The amount of hydrogen used is preferably 0.8-100 moles, more preferably 1-50 moles relative to 1 mole of EEMDE.

This reaction uses a metal catalyst. The metal catalyst used is not particularly limited as long as it can hydrogenate the olefin part in the structure of EEMDE, for example: rhodium-based catalyst (rhodium carbon, Wilkinson complex, etc.) palladium-based catalyst (palladium carbon, palladium alumina, palladium silica gel, etc.), platinum catalysts (platinum carbon, platinum alumina, etc.), nickel catalysts (Lenny nickel catalyst, sponge nickel catalyst, etc.). Preferred are rhodium-based catalysts and palladium-based catalysts, and more preferably rhodium-based catalysts.

The usage amount of the aforementioned metal catalyst is preferably 0.0001-1 mole, more preferably 0.001-0.8 mole, relative to 1 mole of EEMDE in terms of metal atoms.

This reaction preferably uses a solvent. The solvent used is not particularly limited as long as it does not hinder the reaction, for example: water, alcohols (methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, etc.), ketones ( For example: acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (for example: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (for example: N,N-dimethyl Formamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylisobutylamide, etc.), urea (N,N'-dimethylimidazolidinone etc.), ethers (such as: diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-methylene dioxide, etc.), aromatic hydrocarbons (such as: benzene, toluene, xylene, etc.), Halogenated aromatic hydrocarbons (such as: chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitroated aromatic hydrocarbons (such as: nitrobenzene etc.), halogenated hydrocarbons (such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, etc.), carboxylic acid esters (such as: ethyl acetate, propyl acetate, butyl acetate, etc. ), nitriles (such as: acetonitrile, propionitrile, benzonitrile, etc.), sulfides (such as: dimethylsulfoxide, etc.), nitriles (such as: cyclobutylene, etc.), phenols (phenol, methyl phenol, p-chlorophenol), etc. Preferred are alcohols, amides, aliphatic hydrocarbons, and aromatic hydrocarbons. Moreover, these solvents can be used individually or in mixture of 2 or more types.

The usage amount of the above-mentioned solvent can be appropriately adjusted by taking advantage of the uniformity and agitation of the reaction liquid, and it is preferably 0.1-100 g, more preferably 1-50 g relative to 1 g of EEMDE.

(Step 6) In step 6, decahydro-1H,3H-4,10-ethano-5,9-methonaphtho[2,3 -c: 6,7-c']difuran-1,3,6,8-tetraone (EMDA). The compound obtained in the sixth step is a tetracarboxylic dianhydride represented by the aforementioned chemical formula (M-4) in which R ₇ is -CH ₂ CH _{2 -} .

This reaction can be carried out by, for example, heating EMDE in an organic solvent in the presence of an acid catalyst while stirring. The reaction temperature at this time is preferably 50-130°C, more preferably 80-120°C, and the reaction pressure is not particularly limited.

This reaction uses an acid catalyst. The acid catalyst used in this reaction is not particularly limited as long as it is an acid, for example: hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, chlorosulfuric acid, nitric acid and other inorganic acids; methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc. Organic sulfonic acids; halogenated carboxylic acids such as chloroacetic acid and trifluoroacetic acid, ion exchange resins, silica gel sulfate, zeolite, acidic alumina, etc., preferably inorganic acids and organic sulfonic acids, and more preferably organic sulfonic acids. Moreover, these acids can be used individually or in mixture of 2 or more types.

The usage amount of the aforementioned acid catalyst is preferably 0.001-0.5 mole, more preferably 0.001-0.2 mole relative to 1 mole of EMDE.

This reaction is preferably carried out in a solvent. The solvent used should be organic acid solvents such as formic acid, acetic acid, and propionic acid. Moreover, these solvents can be used individually or in mixture of 2 or more types.

The usage amount of the above-mentioned solvent can be appropriately adjusted by utilizing the uniformity and agitation of the reaction solution, and it is preferably 0.1-100 g, more preferably 1-10 g relative to 1 g of EMDE.

The details of each reaction are explained in accordance with the examples. Those with ordinary knowledge in this technical field can change the solvent, feed amount, reaction conditions, etc., and after each reaction is completed, for example: filtration, extraction, distillation, sublimation, resublimation, etc. can be used. General methods such as crystallization and column chromatography are used to isolate and purify the reaction product.

According to this invention, the novel manufacturing method of the tetracarboxylic dianhydride represented by the said chemical formula (M-9) which is the tetracarboxylic acid component which gives the structure of the said chemical formula (A-2) can be provided. The production method thereof will be described below.

The tetracarboxylic dianhydride represented by the aforementioned chemical formula (M-9) can be synthesized according to the following reaction scheme with reference to Can. J. Chem. 1975, 53, 256, Tetrahedron Lett. 2003, 44, 561, etc. Here, it is a tetracarboxylic dianhydride represented by the chemical formula (M-9) in which R ₄ is -CH ₂ -, that is, 3a, 4, 10, 10a-tetrahydro-1H, 3H-4, 10-methyl bridge Naphtho[2,3-c:6,7-c′]difuran-1,3,6,8-tetraketone (BNDA) is used as an example, but other tetracarboxylic dianhydrides can be similarly produced.

式中，R₃₁ 、R₃₂ 各自獨立地為碳數1~10之烷基、或苯基，R₃₃ 、R₃₄ 各自獨立地為碳數1~10之烷基。[chem 48]

In the formula, R ₃₁ and R ₃₂ are each independently an alkyl group with 1 to 10 carbons, or a phenyl group, and R ₃₃ and R ₃₄ are each independently an alkyl group with 1 to 10 carbons.

(1st step) In the 1st step, when synthesizing the tetracarboxylic dianhydride (BNDA) of chemical formula (M-9) in which R ₄ is -CH ₂ -, cis-1,4-dichloro-2- Butene (DCB) reacts with cyclopentadiene (CP) to synthesize 5,6-bis(chloromethyl)bicyclo[2.2.1]hept-2-ene (BCMN). When synthesizing the tetracarboxylic dianhydride of the chemical formula (M-9) whose R ₄ is -CH ₂ CH ₂ -, here, just replace cyclopentadiene (CP) with 1,3-cyclohexadiene, and DCB Just react.

This reaction can be performed, for example, by mixing and stirring DCB and CP. The reaction temperature at this time is preferably 50-250°C, more preferably 150-220°C, and the reaction pressure is not particularly limited.

CP is a monomer of dicyclopentadiene (DCP), and CP can be obtained quantitatively by heating DCP at 160~200°C. The CP used in the first step can also be used after it is generated in the system by thermal decomposition of DCP. DCP is the compound shown in the scheme.

The usage amount of the aforementioned CP is preferably 0.2-10 moles, more preferably 0.5-5 moles relative to 1 mole of DCB.

This reaction may or may not use an organic solvent. The organic solvent used is not particularly limited as long as it does not hinder the reaction, for example: aliphatic carboxylic acids (for example: formic acid, acetic acid, propionic acid, trifluoroacetic acid, etc.), organic sulfonic acids (for example: methanesulfonic acid, trifluoromethanesulfonic acid, etc.) etc.), alcohols (e.g. methanol, ethanol, isopropanol, tertiary butanol, ethylene glycol, triethylene glycol, etc.), ketones (e.g. acetone, methyl ethyl ketone, cyclohexanone, etc.), aliphatic Hydrocarbons (for example: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (for example: N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.), urea (N,N'-dimethylimidazolidinone, etc.), ethers (such as: diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-methylene Benzene dioxide, etc.), aromatic hydrocarbons (such as benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (such as: chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1 , 4-dichlorobenzene, etc.), nitroated aromatic hydrocarbons (such as: nitrobenzene, etc.), halogenated hydrocarbons (such as: dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane etc.), carboxylic acid esters (such as: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (such as: acetonitrile, propionitrile, benzonitrile, etc.), sulfides (such as: dimethyl sulfide Phenol, etc.), Pyrene (such as cyclobutane, etc.), phenols (phenol, methylphenol, p-chlorophenol, etc.), etc. Preferable are aliphatic hydrocarbons and aromatic hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

When an organic solvent is used, the usage amount of the aforementioned organic solvent can be properly adjusted by utilizing the uniformity and agitation of the reaction liquid, and it is preferably 0.2-10 g, more preferably 0.3-5 g relative to 1 g of DCB.

(step 2) In the second step, the reaction of BCMN obtained in the first step with a base is used for dehydrochlorination to synthesize 5,6-dimethylenebicyclo[2.2.1]hept-2-ene (CYDE).

This reaction can be performed, for example, by mixing and stirring BCMN and a base in a solvent. The reaction temperature at this time is preferably 0-150°C, more preferably 20-120°C, and the reaction pressure is not particularly limited.

This reaction uses a base. The base used in this reaction, such as: secondary amines such as dibutylamine, piperidine, and 2-methylpiperidine; tertiary amines such as triethylamine and tributylamine; pyridine, picoline, and dimethylaminopyridine Pyridines such as quinoline, isoquinoline, methyl quinoline and other quinolines; alkali metal hydrides such as sodium hydride and potassium hydride; alkali metals such as sodium methoxide, sodium ethoxide, sodium isopropoxide and potassium tert-butoxide Alkoxides; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, preferably tertiary amines, Alkali metal alkoxides, alkali metal carbonates, alkali metal hydroxides. Moreover, these bases can be used individually or in mixture of 2 or more types.

The usage amount of the aforementioned alkali is preferably 1-20 moles, more preferably 1.5-10 moles relative to 1 mole of BCMN.

This reaction is usually preferably carried out in a solvent. The solvent used is not particularly limited as long as it does not hinder the reaction, for example: water, alcohols (such as: methanol, ethanol, isopropanol, tertiary butanol, ethylene glycol, triethylene glycol, etc.), aliphatic hydrocarbons ( For example: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (for example: N,N-dimethylformamide, N,N-dimethylacetamide, N-formamide pyrrolidone, etc.), urea (N,N'-dimethyl imidazolidinone, etc.), ethers (such as: diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-methylene dioxide benzene etc.), aromatic hydrocarbons (such as benzene, toluene, xylene, etc.), pyrenes (such as dimethylsulfoxide, etc.), pyrenes (such as cyclobutylene, etc.), etc. Water, alcohols and ethers are preferred. Moreover, these solvents can be used individually or in mixture of 2 or more types.

The usage amount of the above-mentioned solvent can be properly adjusted by utilizing the uniformity and agitation of the reaction solution, and it is preferably 0.1-100 g, and more preferably 0.2-50 g, relative to 1 g of BCMN.

(Third step) In the third step, the CYDE obtained in the second step is reacted with dimethyl acetylene dicarboxylate (DMAD) to synthesize 1,4,5,8-tetrahydro-1,4-methynaphthalene -Dimethyl 6,7-dicarboxylate (CYME; in this case R ₃₁ , R ₃₂ are methyl). Dimethyl acetylene dicarboxylate may be replaced with another diester of acetylene dicarboxylate described later.

This reaction can be carried out, for example, by mixing and stirring CYDE and DMAD in a solvent. The reaction temperature at this time is preferably 0-150°C, more preferably 20-120°C, and the reaction pressure is not particularly limited.

This reaction uses an acetylenedicarboxylic acid diester such as DMAD. The diester of acetylene dicarboxylate used is selected to correspond to the desired ester compound. The acetylene dicarboxylate diester used in this reaction can include dimethyl acetylene dicarboxylate, diethyl acetylene dicarboxylate, dipropyl acetylene dicarboxylate, etc., preferably dimethyl acetylene dicarboxylate, acetylene dicarboxylate, etc. Diethyl carboxylate. In addition, diphenyl acetylene dicarboxylate can also be used. The two substituents bonded to acetylene may be the same or different.

The amount of acetylene dicarboxylic acid diesters such as DMAD used is preferably 0.8-20 moles, more preferably 1-10 moles relative to 1 mole of CYDE.

This reaction is usually preferably carried out in a solvent. The solvent used is not particularly limited as long as it does not hinder the reaction, for example: water, alcohols (for example: methanol, ethanol, isopropanol, tertiary butanol, ethylene glycol, triethylene glycol, etc.), ketones (for example: acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (such as: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (such as: N,N-dimethylformamide Amines, N,N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas (N,N'-dimethylimidazolidinone, etc.), ethers (such as: diethyl ether, diisopropyl ether , tetrahydrofuran, dioxane, 1,2-methylene dioxide, etc.), aromatic hydrocarbons (such as: benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (such as: chlorobenzene, 1,2- Dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitroated aromatic hydrocarbons (such as: nitrobenzene, etc.), halogenated hydrocarbons (such as: dichloromethane, chloroform, Carbon tetrachloride, 1,2-dichloroethane, etc.), carboxylic acid esters (such as: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (such as: acetonitrile, propionitrile, benzonitrile etc.), sulfones (eg, dimethylsulfoxide, etc.), sulfides (eg, cyclobutylene, etc.), phenols (phenol, methylphenol, p-chlorophenol, etc.), etc. Water, alcohols, ethers, aliphatic hydrocarbons, and aromatic hydrocarbons are preferred. Moreover, these solvents can be used individually or in mixture of 2 or more types.

The usage amount of the above-mentioned solvent can be properly adjusted by taking advantage of the homogeneity and agitation of the reaction liquid, and it is preferably 0.2~200g, more preferably 0.3~100g relative to 1g of CYME.

(step 4) In the 4th step, use the aromatization reaction (oxidation reaction) of CYME obtained in the 3rd step to synthesize 1,4-dihydro-1,4-methycin-6,7-dicarboxylic acid dimethyl ester (CYPDM ).

This reaction can be carried out by, for example, stirring CYME and an oxidizing agent for aromatization in a solvent. The reaction temperature at this time is preferably -20~150°C, more preferably 0~120°C, and the reaction pressure is not particularly limited.

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

The usage amount of the aforementioned oxidizing agent is preferably 0.5-10 moles, more preferably 0.8-5 moles relative to 1 mole of CYME.

This reaction is usually carried out in a solvent. The solvent used is not particularly limited as long as it does not interfere with the reaction, for example: water; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylformamide Amides such as isobutylamide; N, N-dimethyl imidazolidinone and other urea; Acetonitrile, propionitrile and other nitriles; Methanol, ethanol, n-propanol, isopropanol, n-butanol, Alcohols such as tributanol; Ethers such as diisopropyl ether, dioxane, tetrahydrofuran, cyclopropyl methyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene; Hexane, cyclohexane, heptane, octane Aliphatic hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene and other halogenated hydrocarbons; ethyl acetate, butyl acetate and other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., Preferred are aromatic hydrocarbons, halogenated hydrocarbons, ethers, alcohols, and water. Moreover, these solvents can be used individually or in mixture of 2 or more types.

The usage amount of the above-mentioned solvent can be properly adjusted by utilizing the uniformity and agitation of the reaction solution. Compared with 1 g of CYME, it is preferably 1-100 g, and more preferably 2-50 g.

(5th step) In the 5th step, the CYPDM obtained in the 4th step is reacted with methanol in the presence of a palladium catalyst and a copper compound in the presence of carbon monoxide to synthesize 1,2,3,4-tetrahydro-1,4- Tetramethyl-2,3,6,7-tetracarboxylate (BNME; in this case R ₃₁ -R ₃₄ are methyl). It is also possible to replace methanol with other alcohol compounds corresponding to the desired ester compound.

This reaction can be carried out by, for example, mixing CYPDM, the alcohol corresponding to the desired ester compound, a palladium catalyst, and a copper compound in an organic solvent, and stirring in an atmosphere of carbon monoxide. The reaction temperature at this time is preferably -10~100°C, more preferably -10~70°C, and the reaction pressure is not particularly limited.

This reaction uses an alcohol compound. Alcohol compounds used in this reaction, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, amyl alcohol, methoxyethanol, ethoxyethanol, ethylene glycol Alcohol, triethylene glycol, etc., preferably methanol, ethanol, n-propanol, isopropanol, more preferably methanol, ethanol, isopropanol. Moreover, these alcohol compounds can be used individually or in mixture of 2 or more types.

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

In this reaction, organic solvents other than the aforementioned alcohols can also be used. The organic solvent used is not particularly limited as long as it does not interfere with the reaction, for example: formic acid, aliphatic carboxylic acids (such as: acetic acid, propionic acid, trifluoroacetic acid, etc.), organic sulfonic acids (such as: methanesulfonic acid, trifluoromethanesulfonic acid, etc.) etc.), aliphatic hydrocarbons (for example: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (for example: N,N-dimethylformamide, N,N-dimethylformamide Acetamide, N-methylpyrrolidone, etc.), urea (N,N'-dimethylimidazolidinone, etc.), ethers (such as: diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1, 2-methylene dioxide, benzene, etc.), aromatic hydrocarbons (such as benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (such as: chlorobenzene, 1,2-dichlorobenzene, 1,3- Dichlorobenzene, 1,4-dichlorobenzene, etc.), nitroated aromatic hydrocarbons (such as: nitrobenzene, etc.), halogenated hydrocarbons (such as: dichloromethane, chloroform, carbon tetrachloride, 1,2 -dichloroethane, etc.), carboxylic acid esters (such as: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (such as: acetonitrile, propionitrile, benzonitrile, etc.), sulfides (such as : dimethylsulfene, etc.), pyrenes (for example: cyclobutane, etc.) and the like. Preferred are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and halogenated aromatic hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

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

The palladium catalyst used in this reaction is not particularly limited as long as it contains palladium, for example: 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(1,1,1-5,5,5-hexafluoroacetylacetonate) palladium, etc.; palladium supported on carbon, oxide Palladium carbon, palladium alumina, etc. obtained from a support such as aluminum, preferably palladium chloride, palladium carbon.

The usage amount of the aforementioned palladium catalyst is preferably 0.0001-0.2 mole, more preferably 0.001-0.1 mole relative to 1 mole of CYPDM.

The copper compound used in this reaction is not particularly limited as long as the Pd(II) in the aforementioned palladium catalyst is reduced to Pd(0), as long as it can oxidize Pd(0) to Pd(II), for example: copper compound , iron compounds, etc., preferably copper compounds. Copper compounds used in this reaction, specifically copper, copper acetate, copper propionate, copper n-butyrate, copper 2-methylpropionate, trimethyl copper acetate, copper lactate, copper butyrate, benzoic acid Copper, copper trifluoroacetate, copper bis(acetylacetonate), copper bis(1,1,1-5,5,5-hexafluoroacetylacetonate), copper chloride, copper bromide, iodine Copper oxide, copper nitrate, copper nitrite, copper sulfate, copper phosphate, copper oxide, copper hydroxide, copper trifluoromethanesulfonate, copper p-toluenesulfonate, and copper cyanide, etc. Moreover, specific examples of the iron compound include iron (III) chloride, iron (III) nitrate, iron (III) sulfate, and iron (III) acetate. It is preferable to use a divalent copper compound, and it is more preferable to use copper(II) chloride. Here, the "copper compound" is used in the meaning including copper alone in addition to various compounds. Moreover, these copper compounds can be used individually or in mixture of 2 or more types.

The usage amount of the aforementioned copper compound is preferably 4-50 moles, more preferably 5-20 moles relative to 1 moles of CYPDM.

(step 6) In the sixth step, 3a,4,10,10a-tetrahydro-1H,3H-4,10-methanonaphtho[2,3-c:6, 7-c']difuran-1,3,6,8-tetraone (BNDA). The compound obtained in the sixth step is tetracarboxylic dianhydride represented by the aforementioned chemical formula (M-9).

This reaction can be carried out, for example, by heating and stirring BNME in an organic solvent in the presence of an acid catalyst. The reaction temperature at this time is preferably 50-130°C, more preferably 80-120°C, and the reaction pressure is not particularly limited.

This reaction uses an acid catalyst. The acid catalyst used in this reaction is not particularly limited as long as it is an acid, for example: hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, chlorosulfuric acid, nitric acid and other inorganic acids; methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc. Organic sulfonic acids; halogenated carboxylic acids such as chloroacetic acid and trifluoroacetic acid, ion exchange resins, silica gel sulfate, zeolite, acidic alumina, etc., preferably inorganic acids, organic sulfonic acids, and more preferably organic sulfonic acids. Moreover, these acids can be used individually or in mixture of 2 or more types.

The usage amount of the aforementioned acid catalyst is preferably 0.001-0.5 mole, more preferably 0.001-0.2 mole relative to 1 mole of BNME.

This reaction is preferably carried out in a solvent. The solvent used should be organic acid solvents such as formic acid, acetic acid, and propionic acid. Moreover, these solvents can be used individually or in mixture of 2 or more types.

The usage amount of the aforementioned solvent can be appropriately adjusted by utilizing the uniformity and agitation of the reaction liquid, and it is preferably 0.1-100 g relative to 1 g of BNME, and more preferably 1-10 g.

The details of each reaction are illustrated by examples, but those skilled in the art can change the solvent, feed amount, reaction conditions, etc., and after the completion of each reaction, for example: filtration, extraction, distillation, sublimation, General methods such as recrystallization and column chromatography are used to isolate and purify the reaction product. [Example]

The present invention will be further described according to the examples and comparative examples below. In addition, the present invention is not limited to the following examples.

The evaluation of each of the following examples was carried out by the following method.

＜Evaluation of Polyimide Film＞ [Total light transmittance] Using a UV-visible spectrophotometer/V-650DS (manufactured by JASCO), the total light transmittance (average transmittance of 380 nm to 780 nm) of a polyimide film with a film thickness of 10 μm was measured.

[tensile elastic modulus, breaking elongation, breaking strength] Punch the polyimide film into the shape of a dumbbell according to the IEC-540 (S) standard, as a test piece (width: 4mm), use TENSILON manufactured by ORIENTEC, and measure the initial The tensile elastic modulus, elongation at break point, and break strength.

[Linear coefficient of thermal expansion (CTE), Tg] Cut a polyimide film with a film thickness of 10 μm into strips with a width of 4 mm, and use TMA/SS6100 (manufactured by SII Technology Co., Ltd.) as a test piece with a length between chucks of 15 mm, a load of 2 g, and a heating rate of 20°C /min to 500°C. The coefficient of linear thermal expansion from 100°C to 250°C was found from the obtained TMA curve. Also, the inflection point of the TMA curve is defined as Tg (glass transition temperature).

[5% weight loss temperature] A polyimide film with a film thickness of 10 μm was used as a test piece, and the temperature was raised from 25°C to 600°C at a heating rate of 10°C/min in a nitrogen flow using a thermogravimetric measuring device (Q5000IR) manufactured by TA Instruments. The 5% weight loss temperature was determined from the obtained weight curve.

The abbreviations of the raw materials used in the following examples are as follows.

[Diamine component] DABAN: 4,4'-Diaminobenzoylaniline PPD: p-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 ingredient] TNDA: Tetrahydro-1H, 3H-4, 12: 5, 11: 6, 10-Trimethylpyroanthracene[2,3-c: 6,7-c']difuran-1,3,7,9 -tetraketone BNDA: 3a,4,10,10a-tetrahydro-1H,3H-4,10-methanonaphtho[2,3-c:6,7-c']difuran-1,3,6,8- Tetraketone DMADA: 3a,4,6,6a,9a,10,12,12a-Octahydro-1H,3H-4,12:6,10-Dimethyloanthracene[2,3-c:6,7-c ']difuran-1,3,7,9-tetraone EMDAdx: (3aR,4R,5S,5aR,8aS,9R,10S,10aS)-decahydro-1H,3H-4,10-ethano-5,9-methanonaphtho[2,3-c:6 ,7-c']difuran-1,3,6,8-tetraone EMDAxx: (3aR,4R,5S,5aS,8aR,9R,10S,10aS)-Decahydro-1H,3H-4,10-Etho-5,9-Methonaphtho[2,3-c:6 ,7-c']difuran-1,3,6,8-tetraone

[solvent] NMP: N-methyl-2-pyrrolidone DMAc: N,N-Dimethylacetamide

Table 1 describes the structural formulas of tetracarboxylic acid components and diamine components used in Examples and Comparative Examples.

【Table 1】

[Example S-1 (Synthesis of DMADA)]

於容量2L之反應容器裝入甲苯1500mL與對苯醌(BQ)153.3g(1.39mol)。然後保持溫度25-30℃，費時2小時滴加環戊二烯183.5g(2.78mmol)後，於25℃反應20小時。將反應液濃縮乾固，並於獲得之濃縮物中添加乙醇1490g，終夜攪拌。之後將固體過濾，以乙醇洗淨後，於60℃進行真空乾燥，獲得淡紅色固體227g。於獲得之淡紅色固體227g添加乙醇1350g，於80℃攪拌1小時，並將固體過濾。將過濾物以氯仿1080g溶解，添加活性碳10g並攪拌1小時。之後進行過濾，將濾液濃縮乾固，並將獲得之固體於60℃真空乾燥，獲得1,4,4a,5,8,8a,9a,10a-八氫-1,4：5,8-二甲橋蒽-9,10-二酮(DNBQ)之白色固體184g (¹ H-NMR分析測得純度100%、產率55.3%)。[chem 49]

1500 mL of toluene and 153.3 g (1.39 mol) of p-benzoquinone (BQ) were placed in a reaction vessel with a capacity of 2 L. Then, keeping the temperature at 25-30°C, 183.5 g (2.78 mmol) of cyclopentadiene was added dropwise over 2 hours, and then reacted at 25°C for 20 hours. The reaction solution was concentrated to dryness, and 1490 g of ethanol was added to the obtained concentrate, followed by stirring overnight. Thereafter, the solid was filtered, washed with ethanol, and vacuum-dried at 60° C. to obtain 227 g of a light red solid. 1350 g of ethanol was added to 227 g of the obtained pale red solid, and the mixture was stirred at 80° C. for 1 hour, and the solid was filtered. The filtrate was dissolved in 1080 g of chloroform, 10 g of activated carbon was added, and the mixture was stirred for 1 hour. After filtering, the filtrate was concentrated to dryness, and the obtained solid was vacuum-dried at 60°C to obtain 1,4,4a,5,8,8a,9a,10a-octahydro-1,4:5,8-di 184 g of a white solid of methanthracene-9,10-dione (DNBQ) (purity 100% by ¹ H-NMR analysis, yield 55.3%).

The physical properties of DNBQ are as follows.

¹ H-NMR (CDCl _3, 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) CI-MS(m/z); 241(M+1)

100.5 g (31.7 mmol) of DNBQ, 1.5 L of methanol, and 1.5 L of tetrahydrofuran were added to a reaction vessel with a capacity of 5 L. Then, after adding 30.0 g (60.3 mmol) of sodium borohydride at a temperature of 5° C. over a period of 1 hour, the reaction was carried out at a temperature of 5 to 10° C. for 7 hours. Next, 1 L of saturated ammonium chloride aqueous solution was added dropwise at a temperature of 5°C, and then the temperature was raised to 25°C. 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, 1.5 L of ion-exchanged water was added to the obtained white solid, and the mixture was stirred at 40° C. for 1 hour. After that, the white solid was filtered, washed twice with 200 mL of ion-exchanged water, washed twice with 100 mL of ethyl acetate, and dried in vacuum to obtain 1, 4, 4a, 5, 8, 8a, 9, 9a, 10, 10a - Decahydro-1,4: 84.2 g of white solid of 5,8-dimethylpyrroanthracene-9,10-diol (DNHQ) (purity 100%, yield 82% as determined by ¹ H-NMR analysis).

The physical properties of DNHQ are as follows.

¹ H-NMR (DMSO-d _6, 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) CI-MS(m/z); 245(M+1)

87.0 g (356 mmol) of DNHQ, 4.3 g (35.2 mmol) of N,N-dimethylaminopyridine, and 1740 g of pyridine were added to a reaction vessel with a capacity of 5 L, and cooled to a temperature of 5°C. Then, after 87.0 g (760 mmol) of methanesulfonyl chloride was added dropwise over 20 minutes, the temperature was raised to 25° C., and the reaction was carried out at the same temperature for 9 hours. Then, 2500 g of ion-exchanged water was added dropwise, and the precipitated white solid was filtered. The obtained white solid was washed 5 times with 200 mL of 10% hydrochloric acid, 200 mL of 10% aqueous sodium bicarbonate solution, and 200 mL of ion-exchanged water, and dried in vacuo. 128.9 g of the obtained white solid was dissolved in 2800 g of ethyl acetate, and dried (dehydrated) over 35 g of anhydrous magnesium sulfate. Then, this ethyl acetate solution was passed into a silica gel column, and the solvent was distilled off with an evaporator to obtain dimethanesulfonic acid 1,4,4a,5,8,8a,9,9a,10,10a-decahydro -1,4: 124.5 g of white solid of 5,8-dimethylpyrroanthracene-9,10-diester (DNCMS) (purity 99%, yield 87.4% as determined by ¹ H-NMR analysis).

The physical property values of DNCMS are as follows.

¹ H-NMR (DMSO-d _6, 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) CI-MS(m/z); 401(M+1)

364 g of methanol, 62 g of chloroform, 136 g (1011 mmol) of copper (II) chloride, and 6 g (33.7 mmol) of palladium chloride were placed in a reaction vessel with a capacity of 1 L and stirred. After replacing the gas environment in the system with carbon monoxide, a solution obtained by dissolving 27g (67.3mmol) of DNCMS in 178g of chloroform was added dropwise over 3 hours, and reacted at 20-25°C for 4 hours. Next, after replacing the gas atmosphere in the system from carbon monoxide to argon, the solvent was distilled off from the reaction mixture, and 621 g of chloroform was added. Repeat the same operation 2 more times. And, the insoluble matter was removed by filtration from the obtained tea-green suspension. The obtained solution was washed 3 times with 324 g of saturated aqueous sodium bicarbonate solution and 3 times with 324 g of purified water, and then 2.7 g of anhydrous magnesium sulfate and 2.7 g of activated carbon were added to the organic layer and stirred. Then, the solution was filtered and concentrated under reduced pressure to obtain 51 g of a white solid. Next, purification by silica gel chromatography (developing solvent; hexane:ethyl acetate=10:1 (volume ratio)) was carried out to obtain 9,10-bis((methylsulfonyl)oxy)tetrahydro- 1,4: 27 g of white solid of 5,8-dimethylpyrroanthracene-2,3,6,7-tetracarboxylate (DNMTE), the purity was 97.1pa% and the yield was 64.4% by HPLC analysis).

The physical properties of DNMTE are as follows.

¹ H-NMR (CDCl _3, 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) CI-MS (m/z); 637 (M+1)

6.4 g (86.8 mmol) of lithium carbonate and 130 g of N,N'-dimethylformamide were placed in a reaction vessel with a capacity of 500 mL, and the temperature was raised to 150°C. Then, a mixture of 27.6 g (42.1 mol) of DNMTE and 130 g of N,N'-dimethylformamide was added dropwise over 1 hour, and the mixture was reacted at the same temperature for 15 hours. After the reaction, the reaction solution was concentrated under reduced pressure to obtain 22.4 g of a white solid. Next, perform purification by silica gel chromatography (developing solvent; hexane: ethyl acetate = 10:1 (volume ratio)), and then perform recrystallization (solvent ratio; toluene/heptane = 2:3) Refined to obtain 1,2,3,4,4a,5,6,7,8,9a-decahydro-1,4:5,8-dimethylpyrroanthracene-2,3,6,7-tetracarboxylic acid Tetramethyl ester (DMHAE) white solid 13.9g (purity 95.1pa% by HPLC analysis, yield 72.2%).

The physical properties of DMHAE are as follows.

¹ H-NMR (CDCl _3, 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) CI-MS(m/z); 445(M+1)

68 mL of toluene and 7.3 g (31.9 mmol) of 2,3-dichloro-5,6-dicyano-p-benzoquinone were placed in a 300 mL reaction vessel, and the temperature was raised to 80°C. A solution obtained by dissolving 13.5 g of DMHAE (30.4 mmol) in 200 mL of toluene was added dropwise, and reacted for 8 hours. After the reaction was completed, the reaction solution was concentrated, and 130 mL of chloroform was added to the concentrate to obtain a black-brown suspension. Next, filter and separate into dark red and black filtrate and filtrate. After the filtrate was washed three times with 100 mL of a saturated aqueous sodium bicarbonate solution, 12 g of anhydrous magnesium sulfate was added to the obtained organic layer and dehydrated. Next, it was filtered, and the filtrate was concentrated to dryness to obtain 5.6 g of a reddish-brown solid. Moreover, 100 mL of chloroform was added to the filtrate of deep red-black, and the same operation was performed to obtain 4.0 g of a reddish-brown solid. 9.6 g of the obtained reddish-brown solid was purified by recrystallization (solvent ratio; toluene:heptane=1:7) to obtain 1,2,3,4,5,6,7,8-octahydro-1 ,4: 7.4 g of milky white solid of tetramethyl 5,8-dimethylpyrthracene-2,3,6,7-tetracarboxylate (DMAME) (purity 99.9 pa%, yield 56.6% by HPLC analysis).

The physical properties of DMAME are as follows.

¹ H-NMR (CDCl _3, 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) CI-MS(m/z); 442(M+1)

5.27g (11.9mmol) of DMAME, 26.3g of formic acid, and 47mg (0.24mmol) of p-toluenesulfonic acid monohydrate were placed in a 100mL reaction vessel, and reacted at 98°C for 30 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and 30 g of toluene was added to the concentrate. This operation was repeated 6 times, and the formic acid was almost completely distilled off. The obtained suspension was filtered, the obtained solid was washed with 30 g of toluene, and vacuum-dried at 80° C. to obtain 4.0 g of a milky white solid. Then recrystallize with acetic anhydride and then recrystallize with N,N'-dimethylacetamide to obtain 3a,4,6,6a,9a,10,12,12a-octahydro-1H,3H-4 ,12: 3.28g of white solid of 6,10-dimethyloanthracene[2,3-c:6,7-c']difuran-1,3,7,9-tetraketone (DMADA) ( ¹ H -NMR analysis shows a purity of 98.3%, a yield of 77.3%).

The physical properties of DMADA are as follows.

¹ H-NMR (DMSO-d _6, 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) CI-MS(m/z); 351(M+1)

[Example S-2-1 (synthesis of EMDAdx)]

於容量3L之高壓釜中裝入順式-5-降莰烯-內向-2,3-二羧酸酐(endo -NA) 600g(3.66mol)，然後裝入2,6-二丁基羥基甲苯1.20g。將系內進行氮氣取代後，於溫度-25℃添加1,3-丁二烯221g(4.09mol)，於溫度150-160℃反應一晩，獲得白色固體760g。將以上之操作再重複2次，獲得白色固體2258g(產率36%)。然後，於獲得之白色固體2258g添加甲苯9.7L，於溫度102℃加熱攪拌，使固體溶解。於同溫度攪拌10分鐘後，添加庚烷2.6L，冷卻到室溫並攪拌一晩，將析出之固體過濾。將獲得之固體以庚烷2.6L洗淨後，於40℃進行5小時真空乾燥，獲得白色固體691g。[chemical 50]

Put 600g (3.66mol) of cis-5-norbornene-endo-2,3-dicarboxylic acid anhydride ( endo -NA) into an autoclave with a capacity of 3L, and then add 2,6-dibutylhydroxytoluene 1.20g. After replacing the system with nitrogen, 221 g (4.09 mol) of 1,3-butadiene was added at a temperature of -25°C, and reacted overnight at a temperature of 150-160°C to obtain 760 g of a white solid. The above operation was repeated twice to obtain 2258 g of white solid (yield 36%). Then, 9.7 L of toluene was added to 2258 g of the obtained white solid, and the mixture was heated and stirred at a temperature of 102° C. to dissolve the solid. After stirring at the same temperature for 10 minutes, 2.6 L of heptane was added, cooled to room temperature and stirred overnight, and the precipitated solid was filtered. The obtained solid was washed with 2.6 L of heptane, and vacuum-dried at 40° C. for 5 hours to obtain 691 g of a white solid.

691 g of the obtained white solid and 2.1 L of toluene were placed in a reaction vessel with a capacity of 5 L. After heating and stirring at a temperature of 98°C, 1.1 L of heptane was added, cooled to room temperature, and stirred overnight. The precipitated solid was filtered, washed with 1.1 L of heptane, and vacuum-dried at 40°C for 3 hours to obtain (3aR,4S,9R,9aS)-3a,4,4a,5,8,8a,9,9a - 634 g of white solid of octahydro-4,9-methyl-naphtho[2,3-c]furan-1,3-dione (OMNAdx) (purity 99.1%, yield 26% as determined by ¹ H-NMR analysis ).

The physical properties of OMNAdx are as follows.

¹ H-NMR (CDCl _3, 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) CI-MS (m/z); 219(M+1)

560 g (2.54 mol) of OMNAdx and 9.5 L of dichloromethane were added to a reaction vessel with a capacity of 20 L. While cooling to a temperature of -55~-43°C, a solution obtained by dissolving 496g (3.1mol) of bromine in 4.9L of dichloromethane was added dropwise, and reacted for 1 hour. After the reaction, the solvent was removed by an evaporator, and 600 mL of heptane was added to the obtained solid, followed by stirring. And filter the white solid, wash it with 4.5 L of heptane, and dry it under reduced pressure at 40°C to obtain (3aR,4S,9R,9aS)-6,7-dibromodecahydro-4,9-methonaphthonaphtho 805 g of white solid of [2,3-c]furan-1,3-dione (DBDNAdx) (purity 100%, yield 78% as determined by ¹ H-NMR analysis).

The physical properties of DBDNAdx are as follows.

¹ H-NMR (CDCl _3, 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) CI- MS(m/z); 379(M+1)

Add 130 g (1.33 mol) of maleic anhydride and 100 g (264.5 mmol) of DBDNAdx into a reaction vessel with a capacity of 2 L, and react at a temperature of 187° C. for 2 hours. After the reaction was completed, it was cooled to a temperature of 100° C., and 400 mL of toluene was added. After cooling to room temperature, the precipitated solid was filtered, washed with toluene, and then vacuum-dried at 60°C to obtain (3aR, 4R, 5S, 5aR, 8aS, 9R, 10S, 10aS)-3a, 4, 4a, 5,5a,8a, 9,9a,10,10a-Decahydro-1H,3H-4,10-Etho-5,9-Methonaphtho[2,3-c:6,7-c'] Difuran-1,3,6,8-tetraketone (EEMDAdx) gray solid 75g (purity 98.4%, yield 89% as determined by ¹ H-NMR analysis).

The physical property values of EEMDAdx are as follows.

¹ H-NMR (CDCl _3, 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) CI -MS(m/z); 314(M+1)

75g (239mmol) of EEMDAdx, 152g of trimethyl orthoformate, 1500g of methanol, and 22.5g of concentrated sulfuric acid were added to a reaction vessel with a capacity of 2L, and the reaction was carried out at 63°C for 23 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and 600 g of saturated aqueous sodium bicarbonate solution was added to the concentrated residue, followed by extraction with 500 g of chloroform. The organic layer was washed twice with 200 g of water, dried (dehydrated) over anhydrous magnesium sulfate (MgSO ₄ ) and filtered, and the filtrate was concentrated under reduced pressure to obtain 80.7 g of a solid. Then implement crystallization using 150 g of toluene and 450 g of heptane to obtain (1R, 4S, 5R, 6S, 7R, 8S, 10S, 11R)-1,4,4a,5,6,7,8,8a-eight Hydrogen-1,4-ethano-5,8-methynaphthalene-6,7,10,11-tetracarboxylic acid tetramethyl ester (EEMDEdx) white solid 75g (purity 100% as determined by ¹ H-NMR analysis, Yield 77%).

The physical property values of EEMDEdx are as follows.

¹ H-NMR (CDCl _3, 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) CI-MS(m/z); 407(M+1)

6 g (14.8 mmol) of EEMDEdx, 120 g of methanol, and 3 g of a 10% rhodium-carbon catalyst (manufactured by N.E. Chemcat, containing 50 wt % of water) were added to a reaction vessel with a capacity of 200 mL. After replacing the system with hydrogen, pressurize the hydrogen to 0.9MPa, and react at an internal temperature of 80°C for 4 hours. After the reaction, the reactant was washed with 100 mL of N,N'-dimethylformamide and taken out. The obtained reaction suspension was filtered through celite and then concentrated under reduced pressure to obtain a white solid. This operation was repeated 7 times to obtain 41.2 g of white solid (99.9% purity and 97% yield as measured by GC analysis). Next, refine with a silica gel column (developing solvent; hexane/ethyl acetate = 3/1 (v/v)) to obtain (1R, 2R, 3S, 4S, 5R, 6S, 7R, 8S)-decahydro 35g of white solid (purity 100% and yield 83% by GC analysis) ).

The property values of EMDEdx are as follows. ¹ H-NMR (CDCl _3, σ(ppm)); 1.25 (d, J=11Hz, 1H), 1.49 (d, J=9.0Hz, 2H), 1.79 (d, J=9.0Hz, 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) CI-MS(m/z); 409(M+1)

Add 30 g (73.4 mmol) of EMDEdx, 150 g formic acid, and 280 mg (1.47 mmol) of p-toluenesulfonic acid monohydrate to a reaction vessel with a capacity of 300 mL, and react at a temperature of 95°C to 99°C for 16 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and 72 mL of toluene was added to the concentrate. This operation was repeated 6 times, and the formic acid was almost completely distilled off. The obtained suspension was filtered, the obtained solid was washed with 35 mL of toluene, and vacuum-dried at 80°C to obtain 23.4 g of a gray solid. Afterwards, the recrystallization by acetic anhydride and N,N'-dimethylacetamide was repeated to obtain (3aR, 4R, 5S, 5aR, 8aS, 9R, 10S, 10aS)-decahydro-1H, 3H-4, 18.9g white solid of 10-ethano-5,9-methanonaphtho[2,3-c:6,7-c']difuran-1,3,6,8-tetraketone (EMDAdx) ( ¹ H-NMR analysis records a purity of 98.5%, a yield of 80%).

The physical property values of EMDAdx are as follows.

¹ H-NMR (DMSO-d _6, 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) CI-MS(m/z); 317(M+1)

[Example S-2-2 (synthesis of EMDAxx)]

於3L之高壓釜內裝入順式-5-降莰烯-外向-2,3-二羧酸酐(exo -NA)600g(3.66mol)、2,6-二丁基羥基甲苯300mg。將系內進行氮氣取代後，於內溫-25℃添加1,3-丁二烯319g(5.91mol)，於反應溫度140~166℃進行35小時攪拌，獲得白色固體866.2g(產率58%)。然後將獲得之白色固體866.2g以甲苯再結晶，獲得(3aR,4R,9S,9aS)-3a,4,4a,5,8,8a,9,9a-八氫-4,9-甲橋萘并[2,3-c]呋喃-1,3-二酮(OMNAxx)之白色結晶359g(¹ H-NMR分析測得純度100%、產率45%)。[Chemical 51]

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

The physical properties of OMNAxx are as follows.

¹ H-NMR (CDCl _3, 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) CI-MS(m /z); 219(M+1)

120 g (550 mmol) of OMNAxx and 2.2 L of dichloromethane were placed in a reaction vessel with a capacity of 3 L. While cooling to a temperature of -65~-60°C, a solution obtained by dissolving 105.4 g (660 mmol) of bromine in 200 mL of dichloromethane was added dropwise over 2 hours, and reacted for 1 hour. This operation is performed 2 times. And the reaction liquid of 2 times was collected and concentrated by an evaporator to obtain a light brown solid. Add 1.5 L of heptane to the obtained pale brown solid and filter. And the filtered solid was washed with 500 mL of heptane, and dried in vacuo to obtain (3aR,4R,9S,9aS)-6,7-dibromodecahydro-4,9-methanonaphtho[2,3- c] 313 g of white solid of furan-1,3-dione (DBDNAxx) (purity 100%, yield 75% as determined by ¹ H-NMR analysis). Also, the filtrate was concentrated under reduced pressure, washed with 500 mL of heptane, and dried in vacuo to obtain 78.1 g of a white solid of DBDNAxx (purity 100%, yield 19% as determined by ¹ H-NMR analysis).

The physical properties of DBDNAxx are as follows.

¹ H-NMR (CDCl _3, 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) CI-MS(m/z); 379(M+1)

259 g (2.64 mol) of maleic anhydride and 200 g (529 mmol) of DBDNAxx were added to a reaction vessel with a capacity of 2 L, and the reaction was carried out at a reaction temperature of 190° C. for 2 hours. After the reaction was completed, it was cooled to a temperature of 100° C., and 900 mL of toluene was added. Cool to around room temperature and filter the precipitated solid. The obtained solid was washed with 900 mL of toluene, and then dried under reduced pressure at 60°C for 3 hours to obtain (3aR, 4R, 5S, 5aS, 8aR, 9R, 10S, 10aS)-3a, 4, 4a, 5 ,5a,8a,9,9a,10,10a-decahydro-1H,3H-4,10-Ethyro-5,9-methanonaphtho[2,3-c:6,7-c']di 140.2 g of light brown solid of furan-1,3,6,8-tetraketone (EEMDAxx) (purity 97.2%, yield 82% as determined by ¹ H-NMR analysis).

Also, the same operation was performed on 180 g (476 mmol) of DBDNAxx to obtain 139.2 g of a pale brown solid of EEMDAxx ( 98.9% purity by ¹ H-NMR, 92% yield).

The physical properties of EEMDAxx are as follows.

¹ H-NMR (CDCl _3, 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) CI-MS(m/z); 314(M+1)

254.9 g (794.8 mmol) of EEMDAxx, 10 L of methanol, 533 g of trimethyl orthoformate, and 63 g of concentrated sulfuric acid were placed in a reaction vessel with a capacity of 20 L, and stirred at a temperature of 61-67° C. for 79 hours. After the reaction, the reaction solution was concentrated under reduced pressure to obtain 513 g of a gray solid. The obtained solid was dissolved in 3256 g of chloroform, and was added dropwise to 1700 g of a 7% by weight aqueous sodium bicarbonate solution. 31.6 g of anhydrous magnesium sulfate and 26.8 g of activated carbon were added to the separated organic layer, stirred at room temperature for 1 hour, and then filtered. The filtrate was washed with 322 g of chloroform and concentrated under reduced pressure to obtain 325.3 g of a gray solid. The obtained gray solid was then recrystallized from methanol to obtain (1R,4S,5R,6R,7S,8S,10S,11R)-1,4,4a,6,7,8,8a-octahydro-1, 294.9 g of white solid (purity 100% and yield 91% by GC analysis) of tetramethyl 4-ethano-5,8-methaphthalene-6,7,10,11-tetracarboxylate (EEMDExx).

The physical properties of EEMDExx are as follows.

¹ H-NMR (CDCl _3, 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) CI-MS(m/z); 407(M+1)

98.2 g (242 mmol) of EEMDExx and 1720 g of methanol were added to an autoclave with a capacity of 3 L, and 49.1 g of a 10% rhodium-carbon catalyst (manufactured by N.E. Chemcat, containing 50% water) was added. After replacing the system with hydrogen, pressurize the hydrogen to 0.9MPa, and react at an internal temperature of 80°C for 4 hours. After the reaction was completed, the precipitated solid was dissolved in 3235 g of N,N'-dimethylformamide, and the reactant was taken out, filtered through diatomaceous earth, and the catalyst was removed. This operation was performed twice more for EEMDExx97.3g (239mmol). Then all the filtrates were combined and concentrated under reduced pressure to obtain 289.1 g of a gray solid. The obtained gray solid was recrystallized with 700 g of chloroform and 4373 g of heptane to obtain (1R, 2R, 3S, 4S, 5R, 6R, 7S, 8S)-decahydro-1,4-ethano-5,8-methano Naphthalene-2,3,6,7-tetramethyl-2,3,6,7-tetracarboxylate (EMDExx) was 283.0 g of grayish solid (purity 99.9 pa%, yield 96% by GC analysis).

The physical properties of EMDExx are as follows.

¹ H-NMR (CDCl _3, 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) CI-MS(m/z );409(M+1)

Add 282.0g (689.7mmol) of EMDExx, 1410g of formic acid, and 3.28g (17mmol) of p-toluenesulfonic acid monohydrate into a reaction vessel with a capacity of 3L, and react at a temperature of 95°C to 97°C for 19 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and 700 mL of toluene was added to the concentrate. This operation was repeated 6 times, and the formic acid was almost completely distilled off. The obtained suspension was filtered, the obtained solid was washed with 490 mL of toluene, and vacuum-dried at 80° C. to obtain 219.6 g of a gray solid. Recrystallization by acetic anhydride followed by recrystallization by N,N'-dimethylformamide gave (3aR, 4R, 5S, 5aS, 8aR, 9R, 10S, 10aS)-decahydro -1H,3H-4,10-Etho-5,9-methanonaphtho[2,3-c:6,7-c']difuran-1,3,6,8-tetraone (EMDAxx) The resulting white solid was 175.9 g (purity 99.4%, yield 96% as determined by ¹ H-NMR analysis).

Furthermore, 150 g of the obtained EMDAxx was purified under sublimation conditions of 250-290° C./5 Pa to obtain 146 g of EMDAxx as a white solid (purity 100% by ¹ H-NMR analysis, recovery 97.6%).

The physical properties of EMDAxx are as follows.

¹ H-NMR (DMSO-d _6, 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) CI-MS( m/z); 317(M+1)

[Example S-3 (synthesis of BNDA)]

於容量1L之高壓釜中裝入順式-1,4-二氯-2-丁烯233g(1.76mol)、二環戊二烯245g(1.96mol)、甲苯176mL。將系內進行氮氣取代後，於溫度180℃反應5小時。打開高壓釜，取出反應物並濃縮。[Chemical 52]

233 g (1.76 mol) of cis-1,4-dichloro-2-butene, 245 g (1.96 mol) of dicyclopentadiene, and 176 mL of toluene were placed in an autoclave with a capacity of 1 L. After replacing the system with nitrogen, it was reacted at a temperature of 180° C. for 5 hours. The autoclave was opened, the reaction was removed and concentrated.

Then, 149 g (1.13 mol) of cis-1,4-dichloro-2-butene, 156 g (1.25 mol) of dicyclopentadiene, and 112 mL of toluene were placed in an autoclave with a capacity of 1 L. After replacing the system with nitrogen, react at a temperature of 180° C. for 5 hours. The autoclave was opened, the reaction was removed and concentrated.

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

The physical properties of BCMN are as follows.

¹ H-NMR (CDCl _3, 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) CI-MS(m/z); 191(M+1)

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

The physical properties of CYDE are as follows.

¹ H-NMR (CDCl _3, 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) CI-MS(m/z); 119(M+1)

Add 2424 g of the ethanol solution of CYDE obtained and 264.3 g (1.86 mol) of dimethyl acetylene dicarboxylate to a reaction vessel with a capacity of 10 L, and react for 17 hours at a reaction temperature of 70-78°C. After completion of the reaction, ethanol was distilled off under reduced pressure to obtain 369.3 g of a brown liquid. Secondly, it was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 15:1 (volume ratio)) to obtain a brown liquid containing 1,4,5,8-tetrahydro-1,4 -Fraction (1) 126g (purity 85.6pa% by GC analysis) and fraction (2) 177g (purity 50.9pa% by GC analysis) of dimethyl naphthalene-6,7-dicarboxylate (CYME) 2 kinds of fractions [total yield (yield of BCMN benchmark) 49%].

The physical properties of CYME are as follows.

¹ H-NMR (CDCl _3, 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) CI-MS(m/z); 261(M+1)

In a reaction vessel with a capacity of 3L, 126g of fraction (1) containing CYME (purity 85.6pa%; 414.4mmol), 1.3L of dichloromethane, 2,3-dichloro-5,6-bis 138g (607.9mmol) of cyano-p-benzoquinone was reacted at 20°C for 7 hours.

Also, in a reaction vessel with a capacity of 3L, 177g of fraction (2) containing CYME (purity 50.9pa%; 346.1mmol), 890mL of dichloromethane, 2,3-dichloro-5,6- 97.7 g (430.4 mmol) of dicyano-p-benzoquinone was reacted at 20° C. for 7 hours.

The reactants obtained from the two reactions were combined and concentrated under reduced pressure to obtain 457.4 g of a brown liquid. Thereafter, it was purified by silica gel chromatography (developing solvent; hexane:ethyl acetate=15:1 (volume ratio)) to obtain 248.9 g of a red oily substance. The oily substance was dissolved in 2 L of ethyl acetate, washed three times with 500 mL of saturated aqueous sodium bicarbonate solution, and then washed with 500 mL of saturated brine, dried with sodium sulfate and filtered, and the filtrate was concentrated under reduced pressure to obtain 146 g of red oily substance of 1,4-dihydro-1,4-methydronaphthalene-6,7-dicarboxylate dimethyl ester (CYPDM) (purity 99.1pa% by GC analysis, yield 74%).

The physical properties of CYPDM are as follows.

¹ H-NMR (CDCl _3, 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) CI-MS(m/z); 259(M+1)

135 g of methanol, 41 g of chloroform, 52 g (387 mmol) of copper(II) chloride, and 14 mg (0.08 mmol) of palladium chloride were placed in a reaction vessel with a capacity of 500 mL. After replacing the gas environment in the system with carbon monoxide, a solution obtained by dissolving 20 g (76.7 mmol) of CYPDM in 66 g of chloroform was added dropwise over 6 hours, and reacted at room temperature for 3 hours. Next, after replacing the gas atmosphere in the system from carbon monoxide to argon, the solvent was distilled off from the reaction mixture, and 300 g of chloroform was added. After concentration under reduced pressure, the solvent was distilled off, and 300 g of chloroform was added. And the insoluble matter was removed by filtration from the obtained tea-green suspension. The obtained solution was washed 3 times with 240 g of saturated aqueous sodium bicarbonate solution and 3 times with 240 g of purified water, and then 4 g of anhydrous magnesium sulfate and 2 g of activated carbon were added to the organic layer and stirred. Then, the solution was filtered and then concentrated under reduced pressure to obtain 26.7 g of a light brown solid. Next, refine by silica gel chromatography (developing solvent; hexane:ethyl acetate=15:1 (volume ratio)), and then implement recrystallization (solvent ratio; toluene/heptane=2.5:1 (volume ratio) )) to obtain 1,2,3,4-tetrahydro-1,4-methyronaphthyl-2,3,6,7-tetracarboxylic acid tetramethyl ester (BNME) white solid 22.4g (HPLC The analysis determined the purity to be 94.8pa%, and the yield to be 67.5%).

The physical properties of BNME are as follows.

¹ H-NMR (CDCl _3, 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) CI-MS(m/z); 377(M+1)

Add 20g (50.4mmol) of BNME, 60g of formic acid, and 194.2mg (1.02mmol) of p-toluenesulfonic acid monohydrate into a 200mL reaction vessel, and react at an internal temperature of 95°C to 99°C for 57 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and 42 g of toluene was added to the concentrate. This operation was repeated 7 times, and the formic acid was almost completely distilled off. The obtained suspension was filtered, and the obtained solid was washed with 21 g of toluene, and vacuum-dried at 80° C. to obtain 16.1 g of a milky white solid. Recrystallization by acetic anhydride followed by recrystallization by N,N'-dimethylacetamide gave 3a,4,10,10a-tetrahydro-1H,3H-4,10-methanol 8.39 g of white solid of Naphtho[2,3-c:6,7-c']difuran-1,3,6,8-tetraketone (BNDA) (purity 98.8% as determined by ¹ H-NMR analysis, Yield 57.9%).

Furthermore, 15 g of the obtained BNDA was purified under sublimation conditions of 220-230° C./5 Pa to obtain 11.6 g of a white solid of BNDA (purity 100% by ¹ H-NMR analysis, recovery 76.4%).

The physical properties of BNDA are as follows.

¹ H-NMR (DMSO-d _6, 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) CI-MS(m/z); 285(M+1)

[Example 1] 0.60 g (2.6 millimoles) of DABAN was charged into a reaction vessel substituted with nitrogen, and 6.29 g of NMP was added in such an amount that the total mass of the feed monomer (the sum of the diamine component and the carboxylic acid component) became 20% by mass amount, and stirred at room temperature for 1 hour. 1.12 g (2.6 mmoles) of TNDA was slowly added to this solution. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

Apply the polyimide precursor solution filtered through a PTFE filter membrane on a glass substrate, and heat imide directly on the glass substrate from room temperature to 440°C in a nitrogen atmosphere (oxygen concentration below 200ppm) Chemically, a colorless and transparent polyimide film/glass laminate was obtained. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film with a film thickness of 10 μm.

Table 2 shows the results of measuring the properties of this polyimide film.

[Example 2] DABAN1.00g (4.4mmol), PPD0.07g (0.6mmol), and BAPB0.46g (1.3mmol) were charged into a reaction vessel replaced by nitrogen, and NMP11.54g was added. The total mass of the feed monomers (sum of the diamine component and the carboxylic acid component) was 25% by mass, and stirred at room temperature for 1 hour. 2.32 g (6.3 millimoles) of TNDA was slowly added to this solution. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

Apply the polyimide precursor solution filtered through a PTFE filter membrane on a glass substrate, and heat it directly on the glass substrate from room temperature to 460°C in a nitrogen atmosphere (oxygen concentration below 200ppm) to perform thermal imide Chemically, a colorless and transparent polyimide film/glass laminate was obtained. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film with a film thickness of 10 μm.

Table 2 shows the results of measuring the properties of this polyimide film.

[Comparative example 1] 1.00 g (2.7 millimoles) of BAPB was charged into a reaction vessel replaced by nitrogen, and 6.00 g of NMP was added so that the total mass of the feed monomer (the sum of the diamine component and the carboxylic acid component) became 25% by mass amount, and stirred at room temperature for 1 hour. 1.00 g (2.7 mmol) of TNDA was slowly added to this solution. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

Apply the polyimide precursor solution filtered through a PTFE filter membrane on a glass substrate, and heat it directly on the glass substrate from room temperature to 430°C in a nitrogen atmosphere (oxygen concentration below 200ppm) for thermal imidization , to obtain a colorless and transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film with a film thickness of 10 μm.

Table 2 shows the results of measuring the properties of this polyimide film.

[Comparative example 2] Charge 4,4'-ODA 0.70g (3.5mmol) in a reaction vessel replaced by nitrogen, add DMAc 7.95g, this amount is the total mass of feed monomer (sum of diamine component and carboxylic acid component ) in an amount of 20% by mass, and stirred at room temperature for 1 hour. 1.29 g (3.5 mmol) of TNDA was slowly added to this solution. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

Apply the polyimide precursor solution filtered through a PTFE filter membrane on a glass substrate, and heat it directly on the glass substrate from room temperature to 430°C in a nitrogen atmosphere (oxygen concentration below 200ppm) for thermal imidization , to obtain a colorless and transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film with a film thickness of 10 μm.

Table 2 shows the results of measuring the properties of this polyimide film.

[Example 3] 0.23 g (1.0 millimole) of DABAN was charged into a reaction vessel replaced by nitrogen, and 2.70 g of NMP was added so that the total mass of the monomers fed (the sum of the diamine component and the carboxylic acid component) became 16% by mass amount, and stirred at room temperature for 1 hour. To this solution, 0.29 g (1.0 mmol) of BNDA obtained in Example S-3 was slowly added. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

Apply the polyimide precursor solution filtered through a PTFE filter membrane on a glass substrate, and heat it directly on the glass substrate from room temperature to 320°C in a nitrogen atmosphere (oxygen concentration below 200ppm) for thermal imidization , to obtain a colorless and transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film with a film thickness of 10 μm.

Table 2 shows the results of measuring the properties of this polyimide film.

[Example 4] PPD0.40g (3.7 millimoles) was charged into a nitrogen-substituted reaction vessel, and NMP5.81g was added so that the total mass of the monomers fed (the sum of the diamine component and the carboxylic acid component) became 20% by mass amount, and stirred at room temperature for 1 hour. 1.05 g (3.7 millimoles) of BNDA obtained in Example S-3 was slowly added to this solution. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

Apply the polyimide precursor solution filtered through a PTFE filter membrane on a glass substrate, and heat it directly on the glass substrate from room temperature to 350°C in a nitrogen atmosphere (oxygen concentration below 200ppm) for thermal imidization , to obtain a colorless and transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film with a film thickness of 10 μm.

Table 2 shows the results of measuring the properties of this polyimide film.

[Example 5] Put 1.52g (4.7mmol) of TFMB into a reaction vessel replaced by nitrogen, and add 11.41g of NMP so that the total mass of the feed monomer (the sum of the diamine component and the carboxylic acid component) becomes 20% by mass amount, and stirred at room temperature for 1 hour. 1.35 g (4.7 millimoles) of BNDA obtained in Example S-3 was slowly added to this solution. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

Apply the polyimide precursor solution filtered through a PTFE filter membrane on a glass substrate, and heat it directly on the glass substrate from room temperature to 320°C in a nitrogen atmosphere (oxygen concentration below 200ppm) for thermal imidization , to obtain a colorless and transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film with a film thickness of 10 μm.

Table 2 shows the results of measuring the properties of this polyimide film.

[Example 6] DABAN0.40g (1.8mmol), TFMB0.70g (2.2mmol), and BAPB0.16g (0.4mmol) were charged into a reaction vessel replaced by nitrogen, and NMP10.00g was added. The total mass of the feed monomers (sum of the diamine component and the carboxylic acid component) was 20% by mass, and stirred at room temperature for 1 hour. 1.24 g (4.4 millimoles) of BNDA obtained in Example S-3 was slowly added to this solution. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

Apply the polyimide precursor solution filtered through a PTFE filter membrane on a glass substrate, and heat it directly on the glass substrate from room temperature to 350°C in a nitrogen atmosphere (oxygen concentration below 200ppm) for thermal imidization , to obtain a colorless and transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film with a film thickness of 10 μm.

Table 2 shows the results of measuring the properties of this polyimide film.

[Example 7] Put 0.39g (3.5mmol) of tra-DACH into a reaction vessel replaced by nitrogen, and add 11.14g of NMP. The amount of mass % was stirred at room temperature for 1 hour. To this solution, 0.98 g (3.5 millimoles) of BNDA obtained in Example S-3 was slowly added. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

Apply the polyimide precursor solution filtered through a PTFE filter membrane on a glass substrate, and heat it directly on the glass substrate from room temperature to 320°C in a nitrogen atmosphere (oxygen concentration below 200ppm) for thermal imidization , to obtain a colorless and transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film with a film thickness of 10 μm.

Table 2 shows the results of measuring the properties of this polyimide film.

[Comparative example 3] Charge 4,4'-ODA0.60g (3.0mmol) into a reaction vessel replaced by nitrogen, add NMP13.06g, this amount is the total mass of feed monomer (sum of diamine component and carboxylic acid component ) in an amount of 10% by mass, and stirred at room temperature for 1 hour. Here, 0.85 g (3.0 millimoles) of BNDA obtained in Example S-3 was slowly added. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

Apply the polyimide precursor solution filtered through a PTFE filter membrane on a glass substrate, and heat it directly on the glass substrate from room temperature to 320°C in a nitrogen atmosphere (oxygen concentration below 200ppm) for thermal imidization , to obtain a colorless and transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film with a film thickness of 10 μm.

Table 2 shows the results of measuring the properties of this polyimide film.

[Example 8] 4,4'-ODA 0.70g (3.5mmol) was charged into a reaction vessel replaced by nitrogen, and NMP 25.57g was added. ) into an amount of 7% by mass, and stirred at room temperature for 1 hour. 1.22 g (3.5 millimoles) of DMADA obtained in Example S-1 was slowly added to this solution. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

Apply the polyimide precursor solution filtered through a PTFE filter membrane on a glass substrate, and heat it directly on the glass substrate from room temperature to 350°C in a nitrogen atmosphere (oxygen concentration below 200ppm) for thermal imidization , to obtain a colorless and transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film with a film thickness of 10 μm.

Table 2 shows the results of measuring the properties of this polyimide film.

[Example 9] Put 1.20g (4.1mmol) of TPE-R into the reaction vessel replaced by nitrogen, and add 11.39g of NMP. The amount of mass % was stirred at room temperature for 1 hour. 1.32 g (4.1 millimoles) of EMDAxx obtained in Example S-2-2 was slowly added to this solution. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

Apply the polyimide precursor solution filtered through a PTFE filter membrane on a glass substrate, and heat imidization directly on the glass substrate from room temperature to 450°C in a nitrogen atmosphere (oxygen concentration below 200ppm) , to obtain a colorless and transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film with a film thickness of 10 μm.

Table 2 shows the results of measuring the properties of this polyimide film.

【Table 2】

From the results shown in Table 2-1, it can be seen that using TNDA as the tetracarboxylic acid component, compared with only using diamines (4,4'-ODA, BAPB) with ether linkages (-O-) as the diamine component When using diamines (DABAN, PPD) of the aforementioned chemical formula (B-1) that do not have an ether bond (-O-), sufficient transparency and mechanical properties can be maintained, and the polyimide obtained has High heat resistance and low coefficient of linear thermal expansion (Examples 1, 2 and Comparative Examples 1, 2). In the case of using BNDA as the tetracarboxylic acid component, compared to using only diamine (4,4'-ODA) with ether bond (-O-) as the diamine component, the When using the diamine (DABAN, PPD, TFMB) of the structure of the aforementioned chemical formula (B-1) and the diamine (tra-DACH) given the structure of the aforementioned chemical formula (B-2), sufficient transparency and mechanical properties, and the obtained polyimide has an extremely low coefficient of linear thermal expansion, and its heat resistance is equal or above (Examples 3-7 and Comparative Example 3).

Also, it can be seen that when the diamine components in combination are the same, when DMADA is used as the tetracarboxylic acid component, the linear thermal expansion coefficient of the polyimide obtained is lower than when BNDA is used (Example 8 and Comparative Example 3).

Also, when EMDA was used as the tetracarboxylic acid component, a polyimide having a low coefficient of linear thermal expansion, high heat resistance, and sufficient properties was obtained (Example 9). [Industrial Utilization]

According to the present invention, it is possible to provide polyimides having excellent properties such as transparency, bending resistance, high heat resistance, and low linear thermal expansion coefficient, and their precursors, as well as novel tetracarboxylic acid dicarboxylic acids used in their production. anhydride. 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 fine circuits, and have solvent resistance, and are especially suitable for forming Substrates for display applications, etc.

Claims (8)

A polyimide precursor, characterized in that it includes at least one of the repeating units represented by the following chemical formula (1-1), and the total content of the repeating units represented by the chemical formula (1-1) is 50% relative to all repeating units More than mole%;

In the formula, A ₁₁ is a quaternary 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 divalent group represented by the following chemical formula (B-1), or In the divalent group represented by the following chemical formula (B-2), X ₁ and X ₂ are each independently hydrogen, an alkyl group with 1 to 6 carbons, or an alkylsilyl group with 3 to 9 carbons, and when A ₁₁ is selected During chemical formula (A-1), B ₁₁ selects chemical formula (B-1); [Chemical 2]

In the formula, R ₁ , R ₂ , and R ₃ are each independently -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-;

In the formula, R ₄ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-; [Chem. 4]

In the formula, n ₁ represents an integer of 0 to 3, n ₂ represents an integer of 0 to 3; Y ₁ , Y ₂ , and Y ₃ each independently represent a group selected from a hydrogen atom, a methyl group, and a trifluoromethyl group. One of the group, Q ₁ and Q ₂ each independently represent one selected from the group consisting of direct bonds, or groups represented by the formula: -NHCO-, -CONH-, -COO-, -OCO- 1 type;

In the formula, Y ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A polyimide characterized by comprising at least one of the repeating units represented by the following chemical formula (2-1), and the total content of the repeating units represented by the chemical formula (2-1) is 50 mol% relative to all repeating units above;

In the formula, A ₂₁ is a quaternary 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 divalent group represented by the following chemical formula (B-1), or A divalent group represented by the following chemical formula (B-2), and when A ₂₁ selects chemical formula (A-1), B ₂₁ selects chemical formula (B-1);

In the formula, R ₁ , R ₂ , and R ₃ are each independently -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-;

In the formula, R ₄ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-;

In the formula, n ₁ represents an integer of 0 to 3, n ₂ represents an integer of 0 to 3; Y ₁ , Y ₂ , and Y ₃ each independently represent a group selected from a hydrogen atom, a methyl group, and a trifluoromethyl group. One of the group, Q ₁ and Q ₂ each independently represent one selected from the group consisting of direct bonds, or groups represented by the formula: -NHCO-, -CONH-, -COO-, -OCO- 1 type;

In the formula, Y ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A polyimide is obtained from the polyimide precursor as described in item 1 of the scope of the patent application. A film is mainly made of polyimide obtained from the polyimide precursor of the first item of the patent application, or the polyimide of the second item of the patent application. A varnish, including the polyimide precursor as in item 1 of the scope of application, or the polyimide as in item 2 of the scope of application. A polyimide film is obtained by using a varnish containing the polyimide precursor as in item 1 of the patent application, or the polyimide as in item 2 of the patent application. A substrate for displays, touch panels, or solar cells, characterized by: containing polyimide obtained from the polyimide precursor as in item 1 of the patent application, or as in the second item of the patent application item of polyimide. A method for producing tetracarboxylic dianhydride, characterized by comprising the following steps: (A) reacting a diene compound represented by the following chemical formula (MC-1) with an acetylene compound represented by the following chemical formula (MC-2) to obtain the following chemical formula Diester compounds represented by (MC-3);

In the formula, R ₄ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-; [Chemical 38]

In the formula, R ₃₁ and R ₃₂ are each independently an alkyl group with 1 to 10 carbons, or a phenyl group;

In the formula, the meanings of R ₄ , R ₃₁ , and R ₃₂ are the same as above; (B) utilize the oxidation reaction of the diester compound represented by the chemical formula (MC-3) to obtain the diester compound represented by the following chemical formula (MC-4);

In the formula, R ₄ , R ₃₁ , R ₃₂ have the same meaning as above; (C) make the diester compound represented by the chemical formula (MC-4) react with alcohol compound and carbon monoxide in the presence of palladium catalyst and copper compound to obtain the following Tetraester compounds represented by chemical formula (MC-5);

In the formula, R ₄ , R ₃₁ , and R ₃₂ have the same meanings as above, and R ₃₃ and R ₃₄ are each independently an alkyl group with 1 to 10 carbons; (D) the tetraester compound represented by the chemical formula (MC-5) In the presence of an acid catalyst, react in an organic solvent to obtain tetracarboxylic dianhydride represented by the following chemical formula (M-9); [Chemical 42]

In the formula, R ₄ has the same meaning as above.