JP2022116052A - Polyimide precursor, polyimide, polyimide film and substrate, and tetracarboxylic acid dianhydride used in production of polyimide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polyimide that has excellent properties such as transparency, bending resistance, high heat resistance, and low coefficient of linear thermal expansion, and to provide a precursor thereof.

SOLUTION: Provided are a polyimide precursor in which the structure derived from the tetracarboxylic acid component contains at least one repeating unit having a structure represented by either the following chemical formula (A-1) or (A-3), and a polyimide. (In the formula, R₁, R₂, R₃, R₅, and R₆ are each independently -CH₂-, -CH₂CH₂-, or -CH=CH-.).

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

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

In recent years, with the advent of an advanced information society, the development of optical materials such as optical fibers and optical waveguides in the field of optical communication, and liquid crystal alignment films and protective films for color filters in the field of display devices has progressed. In the field of display devices in particular, studies on plastic substrates that are lightweight and excellent in flexibility as an alternative to glass substrates and development of displays that can be bent or rolled are being actively pursued. Therefore, there is a demand for higher performance optical materials that can be used for such applications.

Aromatic polyimides are inherently colored yellowish brown due to intramolecular conjugation and formation of charge-transfer complexes. For this reason, as a means of suppressing coloration, intramolecular conjugation and formation of charge-transfer complexes are inhibited by, for example, introducing fluorine atoms into the molecule, imparting flexibility to the main chain, and introducing bulky groups as side chains. Then, a method of developing transparency has been proposed.

Also proposed is a method of developing transparency by using a semi-alicyclic or fully alicyclic polyimide that does not, in principle, form a charge-transfer complex. In particular, a highly transparent semi-alicyclic polyimide using an aromatic tetracarboxylic dianhydride as the tetracarboxylic acid component and an alicyclic diamine as the diamine component, and an alicyclic tetracarboxylic acid diamine as the tetracarboxylic acid component. Many highly transparent semi-alicyclic polyimides using aromatic diamines as anhydride and diamine components have been proposed.

For example, Patent Document 1 discloses 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 aromatic Semialicyclic polyimide precursors and polyimides derived from an aromatic diamine component having a tricyclic ring are disclosed. Specifically, in the examples of Patent Document 1, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, decahydro-1 ,4:5,8-dimethanonaphthalene-2,3,6,7-tetracarboxylic dianhydride and the like are used, and as an aromatic diamine component having an amide bond and an aromatic ring, 4,4 '-Diaminobenzanilide and the like are used. Further, in Examples of Patent Document 1, p-phenylenediamine, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-oxydianiline and the like are used as other diamine components.

Further, Patent Document 2 discloses a method for producing a polyamic acid, characterized by reacting a specific alicyclic tetracarboxylic dianhydride and a diamine in the presence of an inorganic salt as a catalyst. there is In Example 8 of Patent Document 2, in the presence of calcium chloride as a catalyst, hexacyclo[6.6.1.1 ^3,6 . 1 ^{10, 13} . 0 ^{2, 7} . 0 ^9,14 ]heptadeca-4,5,11,13-tetracarboxylic dianhydride and 4,4′-diaminodiphenyl ether are reacted to synthesize polyamic acid, which is then imidized 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 ]heptadeca-4,5,11,13-tetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether are reacted to synthesize polyamic acid, and the resulting polyimide is imidized. It shows that η _inh was low and could not be made into a film.

Regarding semi-alicyclic polyimides, Non-Patent Document 1 further describes relaxation in soluble alicyclic polyimides obtained from tricyclodecenetetracarboxylic dianhydride (an addition product of benzene and maleic anhydride) and diaminodiphenyl ether. Interrelationships between displacement and strength properties are disclosed.

WO2012/124664 JP-A-5-271409

Izvestiya Akademii Nauk Kazakhskoi SSR, Seriya Khimicheskaya, 1987, No.5, p.40

An object of the present invention is to provide a novel polyimide having excellent properties such as transparency, bending resistance, high heat resistance and a low coefficient of linear thermal expansion, and a precursor thereof. Another object of the present invention is to provide a novel tetracarboxylic dianhydride used in the production of polyimide and a method for producing the same.

The present invention relates to each of the following items.
1. containing at least one repeating unit represented by the following chemical formula (1-1),
A polyimide precursor characterized in that the total content of repeating units represented by the chemical formula (1-1) is 50 mol % or more with respect to all repeating units.

（式中、Ａ_１１は、下記化学式（Ａ－１）で表される４価の基、または下記化学式（Ａ－２）で表される４価の基であり、Ｂ_１１は、下記化学式（Ｂ－１）で表される２価の基、または下記化学式（Ｂ－２）で表される２価の基であり、Ｘ_１、Ｘ_２は、それぞれ独立に、水素、炭素数１～６のアルキル基、または炭素数３～９のアルキルシリル基である。）

(In the formula, A ₁₁ is a tetravalent group represented by the following chemical formula (A-1) or a tetravalent group represented by the following chemical formula (A-2), and B ₁₁ is the following chemical formula ( B-1) or a divalent group represented by the following chemical formula (B-2), wherein X ₁ and X ₂ are each independently hydrogen and have 1 to 6 carbon atoms. or an alkylsilyl group having 3 to 9 carbon atoms.)

（式中、Ｒ_１、Ｒ_２、Ｒ_３は、それぞれ独立に、－ＣＨ_２－、－ＣＨ_２ＣＨ_２－、または－ＣＨ＝ＣＨ－である。）

(Wherein, R ₁ , R ₂ and R ₃ are each independently -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-.)

（式中、Ｒ_４は、－ＣＨ_２－、－ＣＨ_２ＣＨ_２－、または－ＣＨ＝ＣＨ－である。）

(wherein R ₄ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-).

（式中、ｎ_１は０～３の整数を示し、ｎ_２は０～３の整数を示す。Ｙ_１、Ｙ_２、Ｙ_３は、それぞれ独立に、水素原子、メチル基、トリフルオロメチル基よりなる群から選択される１種を示し、Ｑ_１、Ｑ_２は、それぞれ独立に、直接結合、または 式：－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－、－ＯＣＯ－で表される基よりなる群から選択される１種を示す。）

(In the formula, n ₁ represents an integer of 0 to 3, and n ₂ represents an integer of 0 to 3. Y ₁ , Y ₂ , and Y ₃ each independently represent a hydrogen atom, a methyl group, or a trifluoromethyl group. wherein Q ₁ and Q ₂ are each independently a direct bond or a group represented by the formula: -NHCO-, -CONH-, -COO-, -OCO- It shows one selected from the group consisting of.)

（式中、Ｙ_４は、水素原子、または炭素数１～４のアルキル基を示す。）

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

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

（式中、Ａ_１２は、下記化学式（Ａ－３）で表される４価の基、または下記化学式（Ａ－４）で表される４価の基であり、Ｂ_１２は、芳香族環または脂環構造を有する２価の基であり、Ｘ_３、Ｘ_４は、それぞれ独立に、水素、炭素数１～６のアルキル基、または炭素数３～９のアルキルシリル基である。）

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

（式中、Ｒ_５、Ｒ_６は、それぞれ独立に、－ＣＨ_２－、－ＣＨ_２ＣＨ_２－、または－ＣＨ＝ＣＨ－である。）

(Wherein, R ₅ and R ₆ are each independently -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-.)

（式中、Ｒ_７は、－ＣＨ_２ＣＨ_２－、または－ＣＨ＝ＣＨ－である。）
３． 前記化学式（１－２）で表される繰り返し単位の合計含有量が、全繰り返し単位に対して、５０モル％以上であることを特徴とする前記項２に記載のポリイミド前駆体。

(Wherein, R ₇ is —CH ₂ CH ₂ — or —CH═CH—.)
3. 3. The polyimide precursor according to item 2, wherein the total content of repeating units represented by the chemical formula (1-2) is 50 mol % or more based on all repeating units.

4. containing at least one type of repeating unit represented by the following chemical formula (2-1),
A polyimide having a total content of repeating units represented by the chemical formula (2-1) of 50 mol % or more based on all repeating units.

（式中、Ａ_２１は、下記化学式（Ａ－１）で表される４価の基、または下記化学式（Ａ－２）で表される４価の基であり、Ｂ_２１は、下記化学式（Ｂ－１）で表される２価の基、または下記化学式（Ｂ－２）で表される２価の基である。）

(wherein A ₂₁ is a tetravalent group represented by the following chemical formula (A-1) or a tetravalent group represented by the following chemical formula (A-2), and B ₂₁ is represented by the following chemical formula ( B-1) or a divalent group represented by the following chemical formula (B-2).)

（式中、Ｒ_１、Ｒ_２、Ｒ_３は、それぞれ独立に、－ＣＨ_２－、－ＣＨ_２ＣＨ_２－、または－ＣＨ＝ＣＨ－である。）

(Wherein, R ₁ , R ₂ and R ₃ are each independently -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-.)

（式中、Ｒ_４は、－ＣＨ_２－、－ＣＨ_２ＣＨ_２－、または－ＣＨ＝ＣＨ－である。）

(wherein R ₄ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-).

（式中、ｎ_１は０～３の整数を示し、ｎ_２は０～３の整数を示す。Ｙ_１、Ｙ_２、Ｙ_３は、それぞれ独立に、水素原子、メチル基、トリフルオロメチル基よりなる群から選択される１種を示し、Ｑ_１、Ｑ_２は、それぞれ独立に、直接結合、または 式：－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－、－ＯＣＯ－で表される基よりなる群から選択される１種を示す。）

(In the formula, n ₁ represents an integer of 0 to 3, and n ₂ represents an integer of 0 to 3. Y ₁ , Y ₂ , and Y ₃ each independently represent a hydrogen atom, a methyl group, or a trifluoromethyl group. wherein Q ₁ and Q ₂ are each independently a direct bond or a group represented by the formula: -NHCO-, -CONH-, -COO-, -OCO- It shows one selected from the group consisting of.)

（式中、Ｙ_４は、水素原子、または炭素数１～４のアルキル基を示す。）

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

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

（式中、Ａ_２２は、下記化学式（Ａ－３）で表される４価の基、または下記化学式（Ａ－４）で表される４価の基であり、Ｂ_２２は、芳香族環または脂環構造を有する２価の基である。）

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

（式中、Ｒ_５、Ｒ_６は、それぞれ独立に、－ＣＨ_２－、－ＣＨ_２ＣＨ_２－、または－ＣＨ＝ＣＨ－である。）

(Wherein, R ₅ and R ₆ are each independently -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-.)

（式中、Ｒ_７は、－ＣＨ_２ＣＨ_２－、または－ＣＨ＝ＣＨ－である。）
６． 前記化学式（２－２）で表される繰り返し単位の合計含有量が、全繰り返し単位に対して、５０モル％以上であることを特徴とする前記項５に記載のポリイミド。

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

7. A polyimide obtained from the polyimide precursor according to any one of items 1 to 3.
8. A polyimide obtained from the polyimide precursor according to any one of items 1 to 3, or a film mainly composed of the polyimide according to any one of items 4 to 6.
9. A varnish containing the polyimide precursor according to any one of items 1 to 3, or the polyimide according to any one of items 4 to 6.
10. A polyimide film obtained by using the polyimide precursor according to any one of Items 1 to 3 or the varnish containing the polyimide according to any one of Items 4 to 6.
11. A polyimide obtained from the polyimide precursor according to any one of the above items 1 to 3, or a display, for a touch panel, or for a solar cell, comprising the polyimide according to any one of the above items 4 to 6. substrate.

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

（式中、Ｒ_５’、Ｒ_６’は、それぞれ独立に、－ＣＨ_２－、または－ＣＨ_２ＣＨ_２－である。）
１３． 下記化学式（Ｍ－２）で表されるテトラエステル化合物。

(Wherein, 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、Ｒ_５’、Ｒ_６’は、それぞれ独立に、－ＣＨ_２－、または－ＣＨ_２ＣＨ_２－であり、Ｒ_１１、Ｒ_１２、Ｒ_１３、Ｒ_１４は、それぞれ独立に、炭素数１～１０のアルキル基である。）
１４． 下記化学式（Ｍ－３）で表されるテトラエステル化合物。

(wherein 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 carbon It is an alkyl group of numbers 1 to 10.)
14. A tetraester compound represented by the following chemical formula (M-3).

（式中、Ｒ_５’、Ｒ_６’は、それぞれ独立に、－ＣＨ_２－、または－ＣＨ_２ＣＨ_２－であり、Ｒ_１１、Ｒ_１２、Ｒ_１３、Ｒ_１４は、それぞれ独立に、炭素数１～１０のアルキル基である。）

(wherein 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 carbon It is an alkyl group of numbers 1 to 10.)

15. (A) in the presence of a base, an olefin compound represented by the following chemical formula (MA-1)

（式中、Ｒ_５’、Ｒ_６’は、それぞれ独立に、－ＣＨ_２－、または－ＣＨ_２ＣＨ_２－である。）
と脂肪族スルホン酸クロリドまたは芳香族スルホン酸クロリドとを反応させて、下記化学式（Ｍ－Ａ－２）で表されるオレフィン化合物

(Wherein, R ₅ ' and R ₆ ' are each independently -CH ₂ - or -CH ₂ CH ₂ -.)
and an aliphatic sulfonyl chloride or an aromatic sulfonyl chloride to obtain an olefin compound represented by the following chemical formula (MA-2)

（式中、Ｒ_５’、Ｒ_６’は、前記と同義であり、Ｒは、置換基を有していてもよいアルキル基またはアリール基である。）
を得る工程、
（Ｂ）前記化学式（Ｍ－Ａ－２）で表されるオレフィン化合物を、パラジウム触媒と銅化合物存在下、アルコール化合物と一酸化炭素と反応させて、下記化学式（Ｍ－Ａ－３）で表されるテトラエステル化合物

(Wherein, R ₅ ' and R ₆ ' are as defined above, and R is an optionally substituted alkyl group or aryl group.)
a step of obtaining
(B) The olefin compound represented by the chemical formula (MA-2) is reacted with an alcohol compound and carbon monoxide in the presence of a palladium catalyst and a copper compound to obtain the chemical represented by the following chemical formula (MA-3). tetraester compound to be

（式中、Ｒ_５’、Ｒ_６’、Ｒは、前記と同義であり、Ｒ_１１、Ｒ_１２、Ｒ_１３、Ｒ_１４は、それぞれ独立に、炭素数１～１０のアルキル基である。）
を得る工程、
（Ｃ）前記化学式（Ｍ－Ａ－３）で表されるテトラエステル化合物より、下記化学式（Ｍ－３）で表されるテトラエステル化合物

(In the formula, R ₅ ', R ₆ ' and R are as defined above, and R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently an alkyl group having 1 to 10 carbon atoms.)
a step of obtaining
(C) a tetraester compound represented by the following chemical formula (M-3) from the tetraester compound represented by the chemical formula (MA-3)

（式中、Ｒ_５’、Ｒ_６’、Ｒ_１１、Ｒ_１２、Ｒ_１３、Ｒ_１４は、前記と同義である。）
を得る工程、
（Ｄ）前記化学式（Ｍ－３）で表されるテトラエステル化合物の酸化反応により、下記化学式（Ｍ－２）で表されるテトラエステル化合物

(Wherein, R ₅ ', R ₆ ', R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are as defined above.)
a step of obtaining
(D) a tetraester compound represented by the following chemical formula (M-2) by oxidation reaction of the tetraester compound represented by the chemical formula (M-3)

（式中、Ｒ_５’、Ｒ_６’、Ｒ_１１、Ｒ_１２、Ｒ_１３、Ｒ_１４は、前記と同義である。）
を得る工程、
（Ｅ）前記化学式（Ｍ－２）で表されるテトラエステル化合物を酸触媒の存在下、有機溶媒中で反応させて、下記化学式（Ｍ－１）で表されるテトラカルボン酸二無水物

(Wherein, R ₅ ', R ₆ ', R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are as defined above.)
a step of obtaining
(E) reacting the tetraester compound represented by the chemical formula (M-2) in the presence of an acid catalyst in an organic solvent to obtain a tetracarboxylic dianhydride represented by the following chemical formula (M-1);

（式中、Ｒ_５’、Ｒ_６’は、前記と同義である。）
を得る工程、
を含むことを特徴とするテトラカルボン酸二無水物の製造方法。

(In the formula, R ₅ ' and R ₆ ' have the same definitions as above.)
a step of obtaining
A method for producing a tetracarboxylic dianhydride, comprising:

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

（式中、Ｒ_７は、－ＣＨ_２ＣＨ_２－、または－ＣＨ＝ＣＨ－である。）
１７． 下記化学式（Ｍ－５）で表されるテトラエステル化合物。

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

（式中、Ｒ_７は、－ＣＨ_２ＣＨ_２－、または－ＣＨ＝ＣＨ－であり、Ｒ_２１、Ｒ_２２、Ｒ_２３、Ｒ_２４は、それぞれ独立に、炭素数１～１０のアルキル基である。）
１８． 下記化学式（Ｍ－６）で表されるジハロゲノジカルボン酸無水物。

(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 carbon atoms. be.)
18. A dihalogenodicarboxylic anhydride represented by the following chemical formula (M-6).

（式中、Ｘ_１１、Ｘ_１２は、それぞれ独立に、－Ｆ、－Ｃｌ、－Ｂｒ、または－Ｉのいずれかを示す。）
１９． 下記化学式（Ｍ－７）で表されるジカルボン酸無水物。

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

20. (A) a dicarboxylic anhydride represented by the following chemical formula (MB)

と１，３－ブタジエンとを反応させて、下記化学式（Ｍ－７）で表されるジカルボン酸無水物

and 1,3-butadiene to obtain a dicarboxylic anhydride represented by the following chemical formula (M-7)

を得る工程、
（Ｂ）前記化学式（Ｍ－７）で表されるジカルボン酸無水物とジハロゲン化剤とを反応させて、下記化学式（Ｍ－６）で表されるジハロゲノジカルボン酸無水物

a step of obtaining
(B) a dihalogenodicarboxylic anhydride represented by the following chemical formula (M-6) by reacting the dicarboxylic anhydride represented by the chemical formula (M-7) with a dihalogenating agent;

（式中、Ｘ_１１、Ｘ_１２は、それぞれ独立に、－Ｆ、－Ｃｌ、－Ｂｒ、または－Ｉのいずれかを示す。）
を得る工程、
（Ｃ）前記化学式（Ｍ－６）で表されるジハロゲノジカルボン酸無水物を無水マレイン酸と反応させて、下記化学式（Ｍ－４－１）で表されるテトラカルボン酸二無水物

(Wherein, X ₁₁ and X ₁₂ each independently represent -F, -Cl, -Br, or -I.)
a step of obtaining
(C) reacting the dihalogenodicarboxylic anhydride represented by the chemical formula (M-6) with maleic anhydride to obtain a tetracarboxylic dianhydride represented by the following chemical formula (M-4-1);

を得る工程、
（Ｄ）前記化学式（Ｍ－４－１）で表されるテトラカルボン酸二無水物を、酸の存在下、アルコール化合物と反応させて、下記化学式（Ｍ－５－１）で表されるテトラエステル化合物

a step of obtaining
(D) The tetracarboxylic dianhydride represented by the chemical formula (M-4-1) is reacted with an alcohol compound in the presence of an acid to form a tetracarboxylic acid represented by the following chemical formula (M-5-1). ester compound

（式中、Ｒ_２１、Ｒ_２２、Ｒ_２３、Ｒ_２４は、それぞれ独立に、炭素数１～１０のアルキル基である。）
を得る工程、
（Ｅ）前記化学式（Ｍ－５－１）で表されるテトラエステル化合物を金属触媒存在下、水素と反応させて、下記化学式（Ｍ－５－２）で表されるテトラエステル化合物

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

（式中、Ｒ_２１、Ｒ_２２、Ｒ_２３、Ｒ_２４は、前記と同義である。）
を得る工程、
（Ｆ）前記化学式（Ｍ－５－２）で表されるテトラエステル化合物を酸触媒の存在下、有機溶媒中で反応させて、下記化学式（Ｍ－４－２）で表されるテトラカルボン酸二無水物

(Wherein, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are as defined above.)
a step of obtaining
(F) reacting the tetraester compound represented by the chemical formula (M-5-2) in the presence of an acid catalyst in an organic solvent to obtain a tetracarboxylic acid represented by the following chemical formula (M-4-2); dianhydride

を得る工程、
を含むことを特徴とするテトラカルボン酸二無水物の製造方法。

a step of obtaining
A method for producing a tetracarboxylic dianhydride, comprising:

21. (A) a diene compound represented by the following chemical formula (MC-1)

（式中、Ｒ_４は、－ＣＨ_２－、－ＣＨ_２ＣＨ_２－、または－ＣＨ＝ＣＨ－である。）
と下記化学式（Ｍ－Ｃ－２）で表されるアセチレン化合物

(wherein R ₄ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-).
and an acetylene compound represented by the following chemical formula (MC-2)

（式中、Ｒ_３１、Ｒ_３２は、それぞれ独立に、炭素数１～１０のアルキル基、またはフェニル基である。）
とを反応させて、下記化学式（Ｍ－Ｃ－３）で表されるジエステル化合物

(In the formula, R ₃₁ and R ₃₂ are each independently an alkyl group having 1 to 10 carbon atoms or a phenyl group.)
By reacting with, a diester compound represented by the following chemical formula (MC-3)

（式中、Ｒ_４、Ｒ_３１、Ｒ_３２は、前記と同義である。）
を得る工程、
（Ｂ）前記化学式（Ｍ－Ｃ－３）で表されるジエステル化合物の酸化反応により、下記化学式（Ｍ－Ｃ－４）で表されるジエステル化合物

(Wherein, R ₄ , R ₃₁ and R ₃₂ are as defined above.)
a step of obtaining
(B) a diester compound represented by the following chemical formula (MC-4) by oxidation reaction of the diester compound represented by the chemical formula (MC-3)

（式中、Ｒ_４、Ｒ_３１、Ｒ_３２は、前記と同義である。）
を得る工程、
（Ｃ）前記化学式（Ｍ－Ｃ－４）で表されるジエステル化合物を、パラジウム触媒及び銅化合物存在下、アルコール化合物と一酸化炭素と反応させて、下記化学式（Ｍ－Ｃ－５）で表されるテトラエステル化合物

(Wherein, R ₄ , R ₃₁ and R ₃₂ are as defined above.)
a step of obtaining
(C) The diester compound represented by the above chemical formula (MC-4) is reacted with an alcohol compound and carbon monoxide in the presence of a palladium catalyst and a copper compound to obtain a compound represented by the following chemical formula (MC-5). tetraester compound to be

（式中、Ｒ_４、Ｒ_３１、Ｒ_３２は、前記と同義であり、Ｒ_３３、Ｒ_３４は、それぞれ独立に、炭素数１～１０のアルキル基である。）
を得る工程、
（Ｄ）前記化学式（Ｍ－Ｃ－５）で表されるテトラエステル化合物を酸触媒の存在下、有機溶媒中で反応させて、下記化学式（Ｍ－９）で表されるテトラカルボン酸二無水物

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

（式中、Ｒ_４は、前記と同義である。）
を得る工程、
を含むことを特徴とするテトラカルボン酸二無水物の製造方法。

(In the formula, R ₄ has the same definition as above.)
a step of obtaining
A method for producing a tetracarboxylic dianhydride, comprising:

According to the present invention, a novel polyimide having excellent properties such as transparency, bending resistance, high heat resistance, and a low coefficient of linear thermal expansion, a precursor thereof, and a novel tetracarboxylic acid dicarboxylic acid used for the production thereof. Anhydrides and methods for making the same can be provided.

The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention facilitate the formation of fine circuits, and can be suitably used to form substrates for display applications and the like. Moreover, the polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention can be suitably used for forming substrates for touch panels and solar cells.

The polyimide precursor of the first aspect of the present invention (hereinafter sometimes referred to as "polyimide precursor (1-1)") contains at least one repeating unit represented by the chemical formula (1-1) and the total content of repeating units represented by the chemical formula (1-1) is 50 mol % or more with respect to all repeating units. However, in the above chemical formula (1-1), one of the four bonds of A ₁₁ , which is a tetravalent group derived from a tetracarboxylic acid component, is bonded to -CONH-, and one is -CONH-B ₁₁ . -, one bound to -COOX ₁ and one bound to -COOX ₂ , and the above chemical formula (1-1) includes all structural isomers thereof.

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

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

In other words, the polyimide precursor (1-1) of the present invention is a tetracarboxylic acid component that provides the structure of the chemical formula (A-1) and/or a tetracarboxylic acid component that provides the structure of the chemical formula (A-2). A polyimide precursor obtained from a tetracarboxylic acid component containing .

The tetracarboxylic acid component that provides the repeating unit of the chemical formula (1-1) includes a tetracarboxylic acid component that provides the structure of the chemical formula (A-1) and a tetracarboxylic acid component that provides the structure of the chemical formula (A-2). is. Examples of the tetracarboxylic acid component giving the structure of the chemical formula (A-1) include tetradecahydro-1H,3H-4,12:5,11:6,10-trimethanoanthra[2,3-c: 6,7-c′]difuran-1,3,7,9-tetraone, tetradecahydro-1H,3H-4,12-ethano-5,11:6,10-dimethanoanthra[2,3-c:6 ,7-c′]difuran-1,3,7,9-tetraone, tetradecahydro-1H,3H-4,12:5,11-diethano-6,10-methanoanthra[2,3-c:6, 7-c′]difuran-1,3,7,9-tetraone, tetradecahydro-1H,3H-4,12:5,11:6,10-triethanoanthra[2,3-c:6,7 -c′] difuran-1,3,7,9-tetraone, tetradecahydro-1H,3H-5,11-ethano-4,12:6,10-dimethanoanthra[2,3-c:6,7- c'] difuran-1,3,7,9-tetraone, tetradecahydro-1H,3H-4,12-etheno-5,11:6,10-dimethanoanthra[2,3-c:6,7-c '] difuran-1,3,7,9-tetraone, tetradecahydro-1H,3H-4,12:5,11-dietheno-6,10-methanoanthra [2,3-c:6,7-c' ] difuran-1,3,7,9-tetraone, tetradecahydro-1H,3H-4,12:5,11:6,10-triethenoanthra[2,3-c:6,7-c′] difuran-1,3,7,9-tetraone, tetradecahydro-1H,3H-5,11-etheno-4,12:6,10-dimethanoanthra[2,3-c:6,7-c′]difuran -1,3,7,9-tetraone, and corresponding tetracarboxylic acids, tetracarboxylic acid derivatives other than tetracarboxylic acid dianhydrides, etc., and tetracarboxylic acids that give the structure of the chemical formula (A-2) Components include, 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-ethanonaphtho[2,3-c:6,7-c′]difuran-1,3,6,8-tetraone, 3a,4, 10,10a-tetrahydro-1H,3H-4,10-ethenonaphtho[2,3-c:6,7-c′]difuran-1,3,6,8-tetraone, and corresponding Examples include tetracarboxylic acids and tetracarboxylic acid derivatives other than tetracarboxylic dianhydrides. These tetracarboxylic acid components (tetracarboxylic acids, etc.) may be used singly or in combination. Here, tetracarboxylic acids and the like represent tetracarboxylic acids and tetracarboxylic acid derivatives such as tetracarboxylic acid dianhydrides, tetracarboxylic acid silyl esters, tetracarboxylic acid esters, and tetracarboxylic acid chlorides.

The diamine component that gives the repeating unit of the chemical formula (1-1) is a diamine component that gives the structure of the chemical formula (B-1) and a diamine component that gives the structure of the chemical formula (B-2).

The diamine component that gives the structure of the chemical formula (B-1) has an aromatic ring, and when it has a plurality of aromatic rings, the aromatic rings are each independently linked by a direct bond, an amide bond, or an ester bond. be. The linking position between the aromatic rings is not particularly limited, but it is preferable to bond at the 4-position with respect to the amino group or the linking group between the aromatic rings. That is, in the group represented by the chemical formula (B-1), the position at which the aromatic rings are linked is not particularly limited, but the amide group (—CONH—) attached to A ₁₁ or the linking group between the aromatic rings Binding at the 4-position is preferred. Such bonding may result in a linear structure and low linear thermal expansion of the resulting polyimide. When the diamine component giving the structure of the chemical formula (B-1) has one aromatic ring, it preferably has a p-phenylene structure. That is, when the group represented by the chemical formula (B-1) has one aromatic ring (when n ₁ and n ₂ are 0), the group represented by the chemical formula (B-1) is substituted It is preferably p-phenylene optionally having a group (Y ₁ ), preferably unsubstituted p-phenylene. Moreover, the aromatic ring may be substituted with a methyl group or a trifluoromethyl group. In addition, a substitution position is not specifically limited.

The diamine component that gives the structure of the chemical formula (B-2) has an aliphatic 6-membered ring, and the aliphatic 6-membered ring has a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , an isobutyl group, a sec-butyl group, a tert-butyl group, or the like, may be substituted with an alkyl group having 1 to 4 carbon atoms, but from the viewpoint of the heat resistance and linear thermal expansion coefficient of the resulting polyimide, unsubstituted is preferably an aliphatic 6-membered ring of That is, in the group represented by the chemical formula (B-2), Y ₄ is preferably a hydrogen atom. In addition, a substitution position is not specifically limited. Further, the diamine component giving the structure of the chemical formula (B-2) preferably has a 1,4-cyclohexane structure as an aliphatic 6-membered ring. That is, the group represented by the chemical formula (B-2) is 1,4-cyclohexylene optionally having a substituent (Y ₄ ), preferably unsubstituted 1,4-cyclohexylene. is preferred.

The diamine component that gives the structure of the chemical formula (B-1) is not particularly limited, but examples include p-phenylenediamine, m-phenylenediamine, benzidine, 3,3′-diamino-biphenyl, 2,2 '-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, m-tolidine, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, N,N'- Bis(4-aminophenyl)terephthalamide, N,N'-p-phenylenebis(p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis(4-aminophenyl)terephthalate, biphenyl-4,4 '-dicarboxylic acid bis(4-aminophenyl) ester, p-phenylene bis(p-aminobenzoate), bis(4-aminophenyl)-[1,1'-biphenyl]-4,4'-dicarboxylate, [1,1′-biphenyl]-4,4′-diylbis(4-aminobenzoate) and the like. Examples of diamine components that give the structure of the chemical formula (B-2) include 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4-diamino -2-n-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1,4-diamino-2 -sec-butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, 1,2-diaminocyclohexane and the like. As the diamine component that provides the structure of the chemical formula (B-2), 1,4-diaminocyclohexane is more preferable, since the resulting polyimide has a low linear thermal expansion coefficient. Moreover, although the steric structure of the 1,4-positions of the diamine having the above 1,4-cyclohexane structure is not particularly limited, it is preferably a trans structure. In the case of the trans structure, the coloring of the obtained polyimide may be more suppressed than in the case of the cis structure. These diamine components may be used singly or in combination.

B ₁₁ in the chemical formula (1-1), that is, the divalent group represented by the chemical formula (B-1) and the divalent group represented by the chemical formula (B-2) are represented by the following chemical formulas: A group represented by any one of (B-1-1) to (B-1-6) and (B-2-1) is preferred.

The diamine component that provides the repeating unit of the chemical formula (1-1) wherein B ₁₁ is represented by the chemical formula (B-1-1) or (B-1-2) is 4,4′-diamino The diamine component that provides the repeating unit of the chemical formula (1-1) which is a benzanilide and B ₁₁ is represented by the chemical formula (B-1-3) is bis(4-aminophenyl) terephthalate, B ₁₁ is represented by the chemical formula (B-1-4) The diamine component that gives the repeating unit of the chemical formula (1-1) is p-phenylenediamine, and B ₁₁ is represented by the chemical formula (B-1 -5) is 2,2′-bis(trifluoromethyl)benzidine, and B ₁₁ is represented by the chemical formula (B-1- 6) The diamine component that gives the repeating unit of the chemical formula (1-1) represented by the formula (1-1) is m-tolidine, and B ₁₁ is represented by the chemical formula (B-2-1). The diamine component that gives the repeating unit of formula (1-1) is 1,4-diaminocyclohexane.

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

The polyimide precursor (1-1) of the present invention can contain repeating units other than the repeating unit represented by the chemical formula (1-1). In one embodiment, a repeating unit other than the repeating unit represented by the chemical formula (1-1), such as a tetravalent group derived from a tetracarboxylic acid component, is represented by the chemical formula (A-1). or a tetravalent group represented by the chemical formula (A-2), wherein the divalent group derived from the diamine component has a plurality of aromatic rings, and the aromatic rings are ether bonds ( —O—) in all repeating units, preferably 30 mol% or less, 25 mol% or less, 20 mol% or less, or 10 mol% or less. Sometimes. In one embodiment, depending on the required properties and applications, the tetravalent group derived from the tetracarboxylic acid component is the tetravalent group represented by the chemical formula (A-1) or the chemical formula (A-2). A repeating unit in which the divalent group derived from the diamine component has a plurality of aromatic rings and the aromatic rings are connected to each other by an ether bond (-O-), In some cases, it may be preferable that the content be, for example, 40 mol % or less, preferably 35 mol % or less, in all repeating units.

Other aromatic or aliphatic tetracarboxylic acids can be used as the tetracarboxylic acid component that provides other repeating units. Examples include, but are not limited to, 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′-benzophenonetetracarboxylic acid, 3,3′,4,4′-biphenyltetracarboxylic acid, 2,3, 3′,4′-biphenyltetracarboxylic acid, 4,4′-oxydiphthalic acid, bis(3,4-dicarboxyphenyl)sulfone dianhydride, m-terphenyl-3,4,3′,4′-tetra carboxylic dianhydride, p-terphenyl-3,4,3′,4′-tetracarboxylic dianhydride, biscarboxyphenyldimethylsilane, bisdicarboxyphenoxydiphenyl sulfide, sulfonyldiphthalic acid, 1,2, 3,4-cyclobutanetetracarboxylic acid, isopropylidenediphenoxybisphthalic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, [1,1′-bi(cyclohexane)]-3,3′,4, 4'-tetracarboxylic acid, [1,1'-bi(cyclohexane)]-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′-sulfonylbis(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]octa- 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-dimethanonaphthalene-2,3,6,7-tetracarboxylic acid, norbornane-2-spiro-α-cyclopentanone-α' -spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic acid derivatives and their acid dianhydrides. These tetracarboxylic acid components (tetracarboxylic acids, etc.) may be used singly or in combination. Among these are 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-dimethanonaphthalene-2,3,6,7-tetracarboxylic acid, norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5, Derivatives such as 5″,6,6″-tetracarboxylic acid and acid dianhydrides thereof are preferred.

Further, when the diamine component to be combined is a diamine other than the diamine component giving the structure of the chemical formula (B-1) and the diamine component giving the structure of the chemical formula (B-2), other repeating units are provided. As the tetracarboxylic acid component, one or more of a tetracarboxylic acid component giving the structure of the chemical formula (A-1) and a tetracarboxylic acid component giving the structure of the chemical formula (A-2) can be used. .

Other aromatic or aliphatic diamines can be used as the diamine component providing other repeating units. Examples include, but are not limited to, 4,4'-oxydianiline, 3,4'-oxydianiline, 3,3'-oxydianiline, 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)sulfone, 3,3-bis((aminophenoxy)phenyl)propane , 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(4-(4-aminophenoxy)diphenyl)sulfone, bis(4-(3-aminophenoxy)diphenyl)sulfone, octafluoro benzidine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 9,9 -bis(4-aminophenyl)fluorene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, and derivatives thereof. These diamine components may be used singly or in combination.

Further, the tetracarboxylic acid component to be combined is other tetracarboxylic acids other than the tetracarboxylic acid component giving the structure of the chemical formula (A-1) and the tetracarboxylic acid component giving the structure of the chemical formula (A-2). In some cases, as the diamine component that provides other repeating units, one or more of a diamine component that provides the structure of the chemical formula (B-1) and a diamine component that provides the structure of the chemical formula (B-2) is used. can also

In one embodiment, for example, 4,4'-oxydianiline, 4,4'-bis(4-aminophenoxy)biphenyl, etc. have multiple aromatic rings, and the aromatic rings are ether bonded (-O- ) in 100 mol % of the diamine component, for example 30 mol % or less, alternatively 25 mol % or less, alternatively 20 mol % or less, alternatively 10 mol % or less. . In one embodiment, depending on the required properties and applications, a diamine component having a plurality of aromatic rings and the aromatic rings linked to each other by an ether bond (-O-) is added to 100 mol% of the diamine component, for example , 40 mol % or less, preferably 35 mol % or less.

The polyimide precursor of the second aspect of the present invention (hereinafter sometimes referred to as "polyimide precursor (1-2)") contains at least one repeating unit represented by the chemical formula (1-2) is a polyimide precursor containing However, in the above chemical formula (1-2), one of the four bonds of A ₁₂ , which is a tetravalent group derived from a tetracarboxylic acid component, is bonded to -CONH- and one is -CONH-B ₁₂ . -, one bound to -COOX ₃ , and one bound to -COOX ₄ , and the above chemical formula (1-2) includes all structural isomers thereof.

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

The polyimide precursor (1-2) of the present invention may contain two or more repeating units represented by the chemical formula (1-2) with different A ₁₂ and/or B ₁₂ . In the polyimide precursor (1-2) of the present invention, A ₁₂ is a tetravalent group represented by the chemical formula (A-3), one or two repeating units of the chemical formula (1-2). and a repeating unit of the chemical formula (1-2) wherein A ₁₂ is a tetravalent group represented by the chemical formula (A-4).

In other words, the polyimide precursor (1-2) of the present invention is a tetracarboxylic acid component that provides the structure of the chemical formula (A-3) and/or a tetracarboxylic acid component that provides the structure of the chemical formula (A-4). is a polyimide precursor obtained from a tetracarboxylic acid component containing and a diamine component containing 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 chemical formula (1-2) includes a tetracarboxylic acid component that gives the structure of the chemical formula (A-3) and a tetracarboxylic acid component that gives the structure of the chemical formula (A-4). is. Examples of the tetracarboxylic acid component that gives the structure of the chemical formula (A-3) include 3a,4,6,6a,9a,10,12,12a-octahydro-1H,3H-4,12:6,10- Dimethanoanthra[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-ethano-6,10-methanoanthra[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-diethanoanthra[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-etheno-6,10-methanoanthra[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-diethenoanthra[2,3-c:6,7-c′]difuran-1 , 3,7,9-tetraone, corresponding tetracarboxylic acids, tetracarboxylic acid derivatives other than tetracarboxylic dianhydrides, etc., and the tetracarboxylic acid component that gives the structure of the chemical formula (A-4) is, for example, decahydro-1H,3H-4,10-ethano-5,9-methanonaphtho[2,3-c:6,7-c′]difuran-1,3,6,8-tetraone, and the corresponding Examples include tetracarboxylic acids and tetracarboxylic acid derivatives other than tetracarboxylic dianhydrides. These tetracarboxylic acid components (tetracarboxylic acids, etc.) may be used singly or in combination. Here, tetracarboxylic acids and the like represent tetracarboxylic acids and tetracarboxylic acid derivatives such as tetracarboxylic acid dianhydrides, tetracarboxylic acid silyl esters, tetracarboxylic acid esters, and tetracarboxylic acid chlorides.

B ₁₂ in the chemical formula (1-2) is a divalent group having an aromatic ring or an alicyclic structure, and from the viewpoint of the heat resistance of the resulting polyimide, it is a divalent group having an aromatic ring. is preferred. B ₁₂ in the chemical formula (1-2), that is, the diamine component is not particularly limited, and can be appropriately selected according to desired properties and applications.

Examples of the diamine component that provides the repeating unit of the chemical formula (1-2) include, for example, the diamine component that provides the structure of the chemical formula (B-1) of the polyimide precursor (1-1) and the chemical formula (B-2). In addition, a diamine that provides other repeating units other than the diamine component that provides the structure of the chemical formula (B-1) and the diamine component that provides the structure of the chemical formula (B-2) The same ones as those mentioned as the component can be mentioned, and any of them can be suitably used. Also in the polyimide precursor (1-2), these diamine components may be used singly or in combination.

B ₁₂ in the chemical formula (1-2) is preferably a divalent group having an aromatic ring having 6 to 40 carbon atoms, and the polyimide precursor (1-1) exemplified in the chemical formula (B- A group represented by 1) is more preferable. Further, the group represented by the chemical formula (B-2) exemplified in the polyimide precursor (1-1) is also preferable. B ₁₂ in the chemical formula (1-2) is, among others, a group represented by any one of the chemical formulas (B-1-1) to (B-1-6) and (B-2-1). Especially preferred.

B ₁₂ in the chemical formula (1-2) is also preferably a divalent group having a plurality of aromatic rings, wherein some or all of the aromatic rings are linked by an ether bond (-O-), A group represented by any one of the following chemical formulas (B-3-1) to (B-3-4) is also particularly preferred.

The diamine component giving the repeating unit of the chemical formula ( _1-2 ) wherein B12 is represented by the chemical formula (B-3-1) is 4,4'-oxydianiline, and _B12 is The diamine component that gives the repeating unit of the chemical formula (1-2) represented by the chemical formula (B-3-2) is 1,4-bis(4-aminophenoxy)benzene, and B ₁₂ is the above The diamine component that gives the repeating unit of the chemical formula (1-2) represented by the chemical formula (B-3-3) is 1,3-bis(4-aminophenoxy)benzene, and B ₁₂ is the chemical formula The diamine component that gives the repeating unit of formula (1-2) represented by (B-3-4) is 4,4'-bis(4-aminophenoxy)biphenyl.

As described above, B ₁₂ in the chemical formula (1-2), that is, the diamine component can be appropriately selected depending on the required properties and applications. In one embodiment, in B ₁₂ in the chemical formula (1-2), the group represented by the chemical formula (B-1) and/or the group represented by the chemical formula (B-2), more preferably The total proportion of the groups represented by any of the chemical formulas (B-1-1) to (B-1-6) and (B-2-1) is, for example, 50 mol% or more, more preferably It is preferably 60 mol % or more, more preferably 65 mol % or more, more preferably 70 mol % or more, or 75 mol % or more. In one embodiment, B ₁₂ in the chemical formula (1-2) has a plurality of aromatic rings, and some or all of the aromatic rings are linked by ether bonds (—O—). group, more preferably the total proportion of the groups represented by any of the chemical formulas (B-3-1) to (B-3-4) is, for example, 30 mol% or more, more preferably 50 mol % or more. In one embodiment, the ratio of the group represented by the chemical formula (B-1) and/or the group represented by the chemical formula (B-2) in B ₁₂ in the chemical formula (1-2) is The total is 60 mol% or more, preferably 65 mol% or more, alternatively 70 mol% or more, alternatively 75 mol% or more, and any one of the chemical formulas (B-3-1) to (B-3-4) It is preferred that the proportion of the groups represented in total is 40 mol % or less, preferably 35 mol % or less, alternatively 30 mol % or less, alternatively 25 mol % or less.

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

As the tetracarboxylic acid component that provides other repeating units, other aromatic or aliphatic tetracarboxylic acids can be used. The same as those mentioned as the acid component can be mentioned. Further, a tetracarboxylic acid component giving the repeating unit of the chemical formula (1-1) (that is, a tetracarboxylic acid component giving the structure of the chemical formula (A-1) and a tetracarboxylic acid component giving the structure of the chemical formula (A-2) Carboxylic acid component) can also be used. Also in the polyimide precursor (1-2), the tetracarboxylic acid component that gives these other repeating units may be used singly or in combination.

Further, when the diamine component to be combined is a diamine having no aromatic ring or alicyclic structure, the tetracarboxylic acid component providing the structure of the chemical formula (A-3) is used as the tetracarboxylic acid component providing another repeating unit. and one or more tetracarboxylic acid components that give the structure of the chemical formula (A-4).

As the diamine component that provides other repeating units, other aromatic or aliphatic diamines can be used, for example, the diamine component that provides other repeating units in the polyimide precursor (1-1) The same thing is mentioned. In addition, the diamine component that gives the repeating unit of the chemical formula (1-1) (that is, the diamine component that gives the structure of the chemical formula (B-1) and the diamine component that gives the structure of the chemical formula (B-2)). can also be used. Also in the polyimide precursor (1-2), the diamine component that gives these other repeating units may be used singly or in combination of two or more.

In the polyimide precursor [polyimide precursor (1-1), polyimide precursor (1-2)] of the present invention, X ₁ and X _{2 in} the chemical formula (1-1) and the chemical formula (1-2) X ₃ and X ₄ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms. The types of functional groups of X ₁ , X ₂ , X ₃ and X ₄ and the introduction rate of the functional groups can be changed according to the manufacturing method described below.

When X ₁ and X ₂ , X ₃ and X ₄ are hydrogen, polyimides tend to be easier to make.

When X ₁ and X ₂ , X ₃ and X ₄ are alkyl groups having 1 to 6 carbon atoms, preferably 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 groups or ethyl groups.

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

_{The introduction rate} of the functional _group is not particularly limited. 75% or more can be alkyl groups or alkylsilyl groups.

The polyimide precursor of the present invention is composed of 1) polyamic acid (X ₁ and X ₂ , X ₃ and X ₄ are hydrogen), 2) polyamic acid ester, depending on the chemical structure of X ₁ and X ₂ , X ₃ and X ₄ . (at least a portion of X ₁ and X ₂ are alkyl groups, at least a portion of X ₃ and X ₄ are alkyl groups), 3) 4) polyamic acid silyl ester (at least a portion of X ₁ and X ₂ are alkylsilyl groups , X ₃ and at least part of X ₄ are alkylsilyl groups). The polyimide precursor of the present invention can be easily produced by the following production methods for each of these classifications. However, the method for producing the polyimide precursor of the present invention is not limited to the following production method.

1) Polyamic acid The polyimide precursor of the present invention contains a tetracarboxylic acid dianhydride as a tetracarboxylic acid component and a diamine component in a solvent in a substantially equimolar ratio, preferably the molar ratio of the diamine component to the tetracarboxylic acid component [diamine Mole number of component/mol number of tetracarboxylic acid component] is preferably 0.90 to 1.10, more preferably 0.95 to 1.05, for example, imidation at a relatively low temperature of 120 ° C. or less can be suitably obtained as a polyimide precursor solution composition by reacting while suppressing

The method for synthesizing the polyimide precursor of the present invention is not limited, but more specifically, diamine is dissolved in an organic solvent, and tetracarboxylic dianhydride is gradually added to this solution while stirring. , 0 to 120° C., preferably 5 to 80° C., for 1 to 72 hours to obtain a polyimide precursor. When the reaction is carried out at 80° C. or higher, the molecular weight fluctuates depending on the temperature history during polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be stably produced. The order of addition of the diamine and the tetracarboxylic dianhydride in the above production method is preferable because the molecular weight of the polyimide precursor tends to increase. In addition, it is possible to reverse the order of addition of the diamine and the tetracarboxylic dianhydride in the production method described above, which is preferable because the precipitates are reduced.

Further, when the molar ratio of the tetracarboxylic acid component and the diamine component is in excess of the diamine component, an amount of a carboxylic acid derivative approximately corresponding to the excess molar number of the diamine component is added as necessary, and the tetracarboxylic acid component and the diamine are The molar ratios of the components can be approximated to equivalence. As the carboxylic acid derivative here, tetracarboxylic acid that does not substantially increase the viscosity of the polyimide precursor solution, that is, does not substantially participate in molecular chain elongation, or tricarboxylic acid and its anhydride that function as a terminal terminator, Dicarboxylic acids and their anhydrides are preferred.

2) Polyamic Acid Ester A tetracarboxylic acid dianhydride is reacted with any alcohol to obtain a diester dicarboxylic acid, which is then reacted with a chlorinating reagent (thionyl chloride, oxalyl chloride, etc.) to obtain a diester dicarboxylic acid chloride. The diester dicarboxylic acid chloride and diamine are stirred at −20 to 120° C., preferably −5 to 80° C. for 1 to 72 hours to obtain a polyimide precursor. When the reaction is carried out at 80° C. or higher, the molecular weight fluctuates depending on the temperature history during polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be stably produced. A polyimide precursor can also be easily obtained by subjecting a diester dicarboxylic acid and a diamine to dehydration condensation using a phosphorus-based condensing agent, a carbodiimide condensing agent, or the like.

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

3) Polyamic acid silyl ester (indirect method)
A diamine and a silylating agent are reacted in advance to obtain a silylated diamine. If necessary, the silylated diamine is purified by distillation or the like. Then, the silylated diamine is dissolved in the dehydrated solvent, and tetracarboxylic dianhydride is gradually added while stirring, and the Stirring for ~72 hours gives the polyimide precursor. When the reaction is carried out at 80° C. or higher, the molecular weight fluctuates depending on the temperature history during polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be stably produced.

As the silylating agent used here, it is preferable to use a chlorine-free silylating agent because it is not necessary to purify the silylated diamine. The chlorine atom-free silylating agent includes N,O-bis(trimethylsilyl)trifluoroacetamide, N,O-bis(trimethylsilyl)acetamide and hexamethyldisilazane. N,O-bis(trimethylsilyl)acetamide and hexamethyldisilazane are particularly preferred because they do not contain fluorine atoms and are low in cost.

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

4) Polyamic acid silyl ester (direct method)
The polyamic acid solution obtained by the method of 1) and the silylating agent are mixed and stirred at 0 to 120° C., preferably 5 to 80° C. for 1 to 72 hours to obtain a polyimide precursor. When the reaction is carried out at 80° C. or higher, the molecular weight fluctuates depending on the temperature history during polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be stably produced.

It is preferable to use a chlorine-free silylating agent as the silylating agent used here, since it is not necessary to purify the silylated polyamic acid or the obtained polyimide. The chlorine atom-free silylating agent includes N,O-bis(trimethylsilyl)trifluoroacetamide, N,O-bis(trimethylsilyl)acetamide and hexamethyldisilazane. N,O-bis(trimethylsilyl)acetamide and hexamethyldisilazane are particularly preferred because they do not contain fluorine atoms and are low in cost.

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

Solvents used in preparing polyimide precursors include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide Aprotic solvents such as are preferred, and N,N-dimethylacetamide and N-methyl-2-pyrrolidone are particularly preferred. Since it can be used without problems, it is not particularly limited to its structure. Solvents include N,N-dimethylformamide, N,N-dimethylacetamide, amide solvents such as N-methylpyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α- Cyclic ester solvents such as methyl-γ-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, phenols such as m-cresol, p-cresol, 3-chlorophenol and 4-chlorophenol system solvent, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethylsulfoxide, etc. are preferably employed. In addition, other common organic solvents, namely phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran. , dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpene, mineral spirits, petroleum naphtha Solvents and the like can also be used. In addition, a solvent can also be used in combination of multiple types.

In the present invention, the logarithmic viscosity of the polyimide precursor is not particularly limited. 0.3 dL/g or more is preferred. When the logarithmic viscosity is 0.2 dL/g or more, the molecular weight of the polyimide precursor is high, and the obtained polyimide is excellent in mechanical strength and heat resistance.

In the present invention, the polyimide precursor varnish contains at least the polyimide precursor of the present invention [polyimide precursor (1-1) and/or polyimide precursor (1-2)] and a solvent. The total amount of 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, relative to the total amount of the solvent, the tetracarboxylic acid component, and the diamine component. is preferred. In general, the total amount of the tetracarboxylic acid component and the diamine component is preferably 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. is. This concentration is a concentration that is approximately close to the solid content concentration resulting from the polyimide precursor, but if this concentration is too low, for example, it becomes difficult to control the thickness of the polyimide film obtained when producing the polyimide film. Sometimes.

As for the solvent used for the varnish of the polyimide precursor of the present invention, there is no problem as long as the polyimide precursor is dissolved, and the structure is not particularly limited. Solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone , α-methyl-γ-butyrolactone and other cyclic ester solvents, ethylene carbonate, propylene carbonate and other carbonate solvents, triethylene glycol and other glycol solvents, m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol phenolic solvents such as acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethylsulfoxide and the like are preferably employed. In addition, other common organic solvents, namely phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran. , dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpene, mineral spirits, petroleum naphtha Solvents and the like can also be used. Moreover, these can also be used in combination of multiple types. As the solvent for the varnish of the polyimide precursor, the solvent used in preparing the polyimide precursor can be used as it is.

In the present invention, the viscosity (rotational viscosity) of the ^varnish of the polyimide precursor is not particularly limited. 1000 Pa·sec is preferable, and 0.1 to 100 Pa·sec is more preferable. In addition, thixotropy can be imparted as necessary. When the viscosity is within the above range, handling is easy during coating or film formation, repelling is suppressed, and leveling is excellent, so that a good film can be obtained.

The polyimide precursor varnish of the present invention may optionally contain chemical imidizing agents (acid anhydrides such as acetic anhydride, pyridine, amine compounds such as isoquinoline), antioxidants, fillers (inorganic particles such as silica, etc.). ), dyes, pigments, coupling agents such as silane coupling agents, primers, flame retardants, antifoaming agents, leveling agents, rheology control agents (fluidity aids), release agents, and the like can be added.

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

The chemical formula (2-1) corresponds to the chemical formula (1-1) of the polyimide precursor (1-1), and A ₂₁ and B ₂₁ in the chemical formula (2-1) are respectively the It corresponds to A ₁₁ and B ₁₁ in chemical formula (1-1).

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

The chemical formula (2-2) corresponds to the chemical formula (1-2) of the polyimide precursor (1-2), and A ₂₂ and B ₂₂ in the chemical formula (2-2) are respectively the It corresponds to A ₁₂ and B ₁₂ in chemical formula (1-2).

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

Forms of the obtained polyimide include films, laminates of polyimide films and other substrates, coating films, powders, beads, moldings, foams, varnishes, and the like.

In the present invention, the logarithmic viscosity of the polyimide is not particularly limited, but the logarithmic viscosity in an N,N-dimethylacetamide solution having a concentration of 0.5 g/dL at 30° C. is 0.2 dL/g or more, more preferably 0.4 dL. /g or more, particularly preferably 0.5 dL/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 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass, based on the total amount of the solvent and the polyimide. As mentioned above, it is particularly preferable that the ratio is 20% by mass or more. If this concentration is too low, it may become difficult to control the thickness of the polyimide film obtained, for example, when producing the polyimide film.

As for the solvent used for the polyimide varnish of the present invention, there is no problem as long as the polyimide is dissolved, and the structure is not particularly limited. As the solvent, the solvent used for the varnish of the polyimide precursor of the present invention can be used in the same manner.

In the present invention, the viscosity (rotational viscosity) of the polyimide ^varnish is not particularly limited. sec is preferred, and 0.1 to 100 Pa·sec is more preferred. In addition, thixotropy can be imparted as necessary. When the viscosity is within the above range, handling is easy during coating or film formation, repelling is suppressed, and leveling is excellent, so that a good film can be obtained.

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

The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention are not particularly limited, but the linear thermal expansion coefficient from 100 ° C. to 250 ° C. when made into a film is preferably 45 ppm / K or less, more preferably It can be 40 ppm/K or less. If the coefficient of linear thermal expansion is large, the difference in coefficient of linear thermal expansion from conductors such as metals is large, and problems such as increased warpage may occur 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, but the total light transmittance (average light transmittance at a wavelength of 380 nm to 780 nm) in a film having a thickness of 10 μm is preferably 70%. or more, more preferably 75% or more, and still more preferably 80% or more. When used for displays, etc., if the total light transmittance is low, the light source needs to be strong, which may cause problems such as energy consumption.

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, still more preferably 1 μm to 50 μm, and particularly preferably 1 μm to 30 μm, depending on the application. be. When the polyimide film is used for applications such as display applications through which light is transmitted, 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. can be. When forming a gas barrier film or the like on polyimide, such as by forming a transistor on polyimide, if the heat resistance is low, swelling may occur between the polyimide and the barrier film due to outgassing due to the decomposition of polyimide, etc. .

The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention can be suitably used, for example, in applications such as 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. However, it is not limited to the following methods.

For example, the varnish of the polyimide precursor of the present invention is cast on a base material such as ceramic (glass, silicon, alumina, etc.), metal (copper, aluminum, stainless steel, etc.), heat-resistant plastic film (polyimide film, etc.), and in a vacuum. , in an inert gas such as nitrogen, or in the air, using hot air or infrared rays, in a temperature range of 20 to 180°C, preferably 20 to 150°C. Next, the obtained polyimide precursor film is placed on the substrate, or the polyimide precursor film is peeled off from the substrate, and in a state where the edge of the film is fixed, in vacuum, in an inert gas such as nitrogen, Alternatively, a polyimide film/substrate laminate or a polyimide film can be produced by thermal imidization at a temperature of about 200 to 500° C., more preferably about 250 to 460° C., using hot air or infrared rays in the air. can. In order to prevent the obtained polyimide film from being oxidized and degraded, it is desirable to perform the imidization by heating in a vacuum or in an inert gas. As long as the heat imidization temperature is not too high, it may be carried out in air.

Further, in the imidization reaction of the polyimide precursor, instead of heat imidization by heat treatment as described above, the polyimide precursor contains a dehydration cyclization reagent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine. It is also possible to carry out by chemical treatment such as immersing in a solution that dissolves. Alternatively, a partially imidized polyimide precursor can be prepared by previously adding and stirring these dehydration cyclization reagents into the varnish of the polyimide precursor, and casting and drying it on the base material. Also, the resulting partially imidized polyimide precursor film is placed on the substrate, or the polyimide precursor film is peeled off from the substrate, and the edges of the film are fixed, and further as described above. A polyimide film/substrate laminate or a polyimide film can be obtained by heat treatment.

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

A flexible conductive substrate can be obtained, for example, by the following method. That is, as the first method, a conductive material (metal or metal oxide) is applied to the surface of the polyimide film by sputtering, vapor deposition, printing, etc., without peeling the polyimide film from the base material. conductive organic material, conductive carbon, etc.) to form a conductive layer/polyimide film/substrate conductive laminate. Thereafter, if necessary, the conductive layer/polyimide film laminate can be peeled off from the base material to obtain a transparent and flexible conductive substrate composed of the conductive layer/polyimide film laminate.

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

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

A circuit is preferably formed on the conductive layer by a method such as a photolithography method, various printing methods, an inkjet method, or the like.

The substrate of the present invention thus obtained has a conductive layer circuit on the surface of the polyimide film composed of the polyimide of the present invention, optionally via a gas barrier layer or an inorganic layer. This substrate is flexible and facilitates the formation of fine circuits. Therefore, this substrate can be suitably used as a substrate for displays, touch panels, or solar cells.

That is, on this substrate, a transistor (inorganic transistor, organic transistor) is further formed by vapor deposition, various printing methods, ink jet method, etc. to manufacture a flexible thin film transistor, and a liquid crystal element for a display device, an EL element, a photoelectric It is preferably used as an element.

The polyimide precursor (1-2) of the present invention and the tetracarboxylic acid dianhydride represented by the chemical formula (M-1), which is a tetracarboxylic acid dianhydride used for the production of the polyimide (2-2) of the present invention. The anhydride and the tetracarboxylic dianhydride represented by the chemical formula (M-4) are novel compounds.

A method for producing the tetracarboxylic dianhydride represented by the chemical formula (M-1) is described below.

The tetracarboxylic dianhydride represented by the chemical formula (M-1) is described in JP-A-2010-184898, J. Am. 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., and can be synthesized, for example, according to the reaction scheme shown below. Here, 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-dimethanoanthra[2,3-c:6,7-c']difuran-1,3,7,9-tetraone (DMADA) is described as an example. , and other tetracarboxylic dianhydrides can be produced in the same manner.

（式中、Ｒは、置換基を有していてもよいアルキル基またはアリール基であり、Ｒ_１１、Ｒ_１２、Ｒ_１３、Ｒ_１４は、それぞれ独立に、炭素数１～１０のアルキル基である。）

(In the formula, R is an optionally substituted alkyl group or aryl group, and R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently an alkyl group having 1 to 10 carbon atoms. be.)

(First step)
In the first 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) to synthesize 1,4,4a,5,8,8a,9a,10a-octahydro-1,4:5,8-dimethanoanthracene-9,10-dione (DNBQ). When synthesizing the tetracarboxylic dianhydride of the chemical formula (M-1) in which R ₅ ' and R ₆ ' are —CH ₂ CH ₂ —, 1,3- Cyclohexadiene may be reacted with BQ.

The amount of cyclopentadiene (or 1,3-cyclohexadiene, etc.) used is preferably 1.0 to 20 mol, more preferably 1.5 to 10.0 mol, per 1 mol of p-benzoquinone (BQ). is.

This reaction is usually performed in an organic solvent. The organic solvent to be used is not particularly limited as long as it does not inhibit the reaction. Examples include amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ureas such as lysinone; sulfoxides such as dimethylsulfoxide and sulfolane; nitriles such as acetonitrile and propionitrile; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and t-butyl alcohol Ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and cyclopropyl methyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Aliphatic hydrocarbons such as hexane, cyclohexane, heptane and octane; Methylene chloride and chloroform , 1,2-dichloroethane, chlorobenzene, and other halogenated hydrocarbons; ethyl acetate, butyl acetate, and other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., preferably alcohols and aromatic hydrocarbons. is used. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent to be used is appropriately adjusted depending on the homogeneity and stirrability of the reaction solution, and is preferably 1 to 50 g, more preferably 2 to 30 g, relative to 1 g of BQ.

This reaction is carried out, for example, by mixing BQ and CP in an organic solvent and stirring the mixture. The reaction temperature at that time is preferably 0 to 150° C., more preferably 15 to 60° C., and the reaction pressure is not particularly limited.

(Second step)
In the second step, the DNBQ obtained in the first step is reacted with sodium borohydride to give 1,4,4a,5,8,8a,9,9a,10,10a-decahydro-1,4: Synthesize 5,8-dimethanoanthracene-9,10-diol (DNHQ).

The amount of sodium borohydride used is preferably 0.5 to 10 mol, more preferably 1.5 to 5.0 mol, per 1 mol of DNBQ.

This reaction is usually performed in an organic solvent. The organic solvent to be used is not particularly limited as long as it does not inhibit the reaction. Examples include amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ureas such as lysinone; sulfoxides such as dimethylsulfoxide and sulfolane; nitriles such as acetonitrile and propionitrile; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and t-butyl alcohol Ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and cyclopropyl methyl ether; Aromatic hydrocarbons such as benzene, toluene, and xylene; Aliphatic hydrocarbons such as hexane, cyclohexane, heptane, and octane; Ethyl acetate, acetic acid Esters such as butyl; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., but preferably alcohols, ethers and aromatic hydrocarbons are used. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent to be used is appropriately adjusted depending on the homogeneity and stirrability of the reaction solution, and is preferably 1 to 100 g, more preferably 5 to 50 g, per 1 g of DNBQ.

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

(Third step)
In the third step, the DNHQ obtained in the second step is reacted with methanesulfonyl chloride in the presence of a base to give 1,4,4a,5,8,8a,9,9a,10,10a-decahydro -1,4:5,8-dimethanoanthracene-9,10-diyl dimethanesulfonate (DNCMS; where R is —CH ₃ [—SO ₂ R is a mesyl group (—SO ₂ CH ₃ )]) Synthesize. Other aliphatic sulfonyl chlorides or aromatic sulfonyl chlorides can be used instead of methanesulfonyl chloride.

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

The amount of the base to be used is preferably 0.01 to 200 mol, more preferably 0.1 to 100 mol, per 1 mol of DNHQ.

Sulfonic acid chloride is used in this reaction. Examples of the sulfonyl chloride used in this reaction include aliphatic sulfonyl chlorides such as methanesulfonyl chloride, ethanesulfonyl chloride, and trifluoromethanesulfonyl chloride; benzenesulfonyl chloride, toluenesulfonyl chloride, and nitrobenzenesulfonate; Aromatic sulfonyl chlorides such as chloride can be used, but aliphatic sulfonyl chlorides are preferably used. These sulfonyl chlorides may be used alone or in combination of two or more.

The amount of the sulfonyl chloride used is preferably 1.5 to 10 mol, more preferably 1.8 to 5 mol, per 1 mol of DNHQ.

This reaction is usually performed in an organic solvent. The organic solvent to be used is not particularly limited as long as it does not inhibit the reaction. Examples include amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ureas such as lysinone; pyridines such as pyridine, methylpyridine and dimethylaminopyridine; quinolines such as quinoline, isoquinoline and methylquinoline; sulfoxides such as dimethylsulfoxide and sulfolane; nitriles such as acetonitrile and propionitrile; Ethers such as diisopropyl ether, dioxane, tetrahydrofuran, cyclopropyl methyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene; Aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane; Ethyl acetate, butyl acetate, etc. esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., but preferably pyridines are used. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent to be used is appropriately adjusted depending on the homogeneity and stirrability of the reaction solution, and is preferably 1 to 200 g, more preferably 10 to 100 g, per 1 g of DNHQ.

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

(Fourth step)
In the fourth step, in the presence of a palladium catalyst and a copper compound, methanol and carbon monoxide are reacted with the DNCMS obtained in the third step to give tetramethyl-9,10-bis((methylsulfonyl)oxy) Tetradecahydro-1,4:5,8-dimethanoanthracene-2,3,6,7-tetracarboxylate (DNMTE; where R ₁₁ to R ₁₄ are methyl groups) is synthesized. Other alcohol compounds corresponding to the desired ester compounds can be used in place of methanol.

Examples of alcohol compounds used in this reaction include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, pentyl alcohol, methoxyethanol, ethoxyethanol, and ethylene glycol. , triethylene glycol, etc., preferably methanol, ethanol, n-propyl alcohol or isopropyl alcohol, more preferably methanol, ethanol or isopropyl alcohol. These alcohol compounds may be used singly or in combination of two or more.

The amount of the alcohol compound used is preferably 1-100 g, more preferably 5-50 g, per 1 g of DNCMS.

A palladium catalyst is used in this reaction. The palladium catalyst used in this reaction is not particularly limited as long as it contains palladium. Palladium inorganic acid salts such as palladium and palladium sulfate; palladium-on-carbon and palladium-alumina in which palladium is supported on a carrier such as carbon and alumina; and palladium chloride and palladium-on-carbon are preferably used.

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

A copper compound is used in this reaction. Examples of the copper compound used in this reaction include monovalent copper compounds such as copper (I) oxide, copper (I) chloride, copper (I) bromide, copper (II) oxide, copper (II) chloride, A divalent copper compound such as copper (II) bromide can be used, preferably a divalent copper compound, more preferably copper (II) chloride. In addition, you may use these copper compounds individually or in mixture of 2 or more types.

The amount of the copper compound used is preferably 1.0 to 50 mol, more preferably 4.0 to 20 mol, per 1 mol of DNCMS.

In this reaction, an organic solvent other than the alcohol compound may be used. The organic solvent to be used is not particularly limited as long as it does not inhibit the reaction. , trifluoromethanesulfonic acid, etc.), ketones (e.g., acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (e.g., n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas (N,N'-dimethylimidazolidinone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane , 1,2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (e.g., chlorobenzene, 1,2-dichlorobenzene, 1,3 -dichlorobenzene, 1,4-dichlorobenzene, etc.), nitrated aromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, etc.) ), carboxylic acid esters (e.g., ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (e.g., acetonitrile, propionitrile, benzonitrile, etc.), sulfoxides (e.g., dimethyl sulfoxide, etc.), sulfones (e.g., , sulfolane, etc.). Aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and halogenated aromatic hydrocarbons are preferably used. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent to be used is appropriately adjusted depending on the homogeneity and stirrability of the reaction solution, and is preferably 1 to 100 g, more preferably 5 to 50 g, per 1 g of DNCMS.

This reaction is carried out, for example, by mixing DNCMS and an alcohol compound, a palladium catalyst and a copper compound in an organic solvent and stirring the mixture in an atmosphere of carbon monoxide. The reaction temperature at that time is preferably −20 to 100° C., more preferably 0 to 50° C., and the reaction pressure is not particularly limited.

(Fifth step)
In the fifth step, the DNMTE obtained in the fourth step is demethanesulfonylated to give tetramethyl-1,2,3,4,4a,5,6,7,8,9a-decahydro-1,4: Synthesize 5,8-dimethanoanthracene-2,3,6,7-tetracarboxylate (DMHAE). The compound obtained in the fifth step is a tetraester compound represented by the chemical formula (M-3) and is a novel compound.

This reaction is carried out, for example, by stirring DNMTE in an organic solvent while heating if necessary. The reaction temperature at that time is preferably −20 to 200° C., more preferably 25 to 180° C., and the reaction pressure is not particularly limited.

This reaction proceeds by heating and stirring without adding a base to the reaction solution, but it is desirable to use a base in order to capture strongly acidic methanesulfonic acid produced as a by-product. The base to be used is not particularly limited as long as it does not inhibit the reaction. Examples include secondary amines such as dibutylamine, piperidine and 2-pipecoline; tertiary amines such as triethylamine and tributylamine; pyridine and methylpyridine. , pyridines such as dimethylaminopyridine; quinolines such as quinoline, isoquinoline and methylquinoline; alkali metal hydrides such as sodium hydride and potassium hydride; sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium t- Alkali metal alkoxides such as butoxide; Alkali metal carbonates such as sodium carbonate, potassium carbonate and lithium carbonate; Alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide tertiary amines, pyridines, quinolines, and alkali metal carbonates are preferably used. These bases may be used alone or in combination of two or more.

The amount of the base used is preferably 1.5 to 5 mol, more preferably 1.8 to 3 mol, per 1 mol of DNMTE.

This reaction is usually performed in an organic solvent. The organic solvent to be used is not particularly limited as long as it does not inhibit the reaction. Examples include amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and N,N-dimethylisobutyramide ureas such as N,N-dimethylimidazolidinone; sulfoxides such as dimethylsulfoxide and sulfolane; nitriles such as acetonitrile and propionitrile; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol , t-butyl alcohol and other alcohols; diisopropyl ether, dioxane, tetrahydrofuran, cyclopropyl methyl ether and other ethers; benzene, toluene, xylene and other aromatic hydrocarbons; hexane, cyclohexane, heptane, octane and other aliphatics hydrocarbons; halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene; esters such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone and the like, preferably Amides, ureas, nitriles are used. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent to be used is appropriately adjusted depending on the homogeneity and stirrability of the reaction solution, and is preferably 1 to 100 g, more preferably 2 to 50 g, per 1 g of DNMTE.

(6th step)
In the sixth step, DMHAE obtained in the fifth step is aromatized (oxidized) to give tetramethyl-1,2,3,4,5,6,7,8-octahydro-1,4:5. ,8-dimethanoanthracene-2,3,6,7-tetracarboxylate (DMAME). The compound obtained in the sixth step is a tetraester compound represented by the chemical formula (M-2) and is a novel compound.

This reaction is carried out, for example, by stirring DMHAE and an oxidizing agent for aromatization in a solvent with heating if necessary. The reaction temperature at that time is preferably 25 to 150° C., more preferably 40 to 120° C., and the reaction pressure is not particularly limited.

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

The amount of the oxidizing agent used is preferably 0.5 to 5 mol, more preferably 0.8 to 3 mol, per 1 mol of DMHAE.

This reaction is usually performed in a solvent. The solvent to be used is not particularly limited as long as it does not inhibit the reaction. Examples include water; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylisobutyramide, amides; ureas such as N,N-dimethylimidazolidinone; nitriles such as acetonitrile and propionitrile; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and t-butyl alcohol Ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and cyclopropyl methyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Aliphatic hydrocarbons such as hexane, cyclohexane, heptane and octane; Methylene chloride and chloroform , 1,2-dichloroethane, chlorobenzene, and other halogenated hydrocarbons; ethyl acetate, butyl acetate, and other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; Hydrocarbons, ethers, alcohols and water are used. These solvents may be used alone or in combination of two or more.

The amount of the solvent to be used is appropriately adjusted depending on the homogeneity and stirrability of the reaction solution, and is preferably 1 to 100 g, more preferably 2 to 50 g, per 1 g of DMHAE.

(Seventh step)
In the seventh step, the DMAME obtained in the sixth step is dehydrated to give 3a,4,6,6a,9a,10,12,12a-octahydro-1H,3H-4,12:6,10-dimethanoanthra. Synthesize [2,3-c:6,7-c′]difuran-1,3,7,9-tetraone (DMADA). The compound obtained in the seventh step is the tetracarboxylic dianhydride represented by the chemical formula (M-1).

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

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

The amount of the acid catalyst used is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.05 mol, per 1 mol of DMAME.

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

The amount of the solvent to be used is appropriately adjusted depending on the homogeneity and stirrability of the reaction solution, and is preferably 0.1 to 100 g, more preferably 1 to 10 g, relative to 1 g of DMAME.

The details of each reaction will be described in Examples, but those skilled in the art can change the solvent, amount charged, reaction conditions, etc., and after completion of each reaction, for example, filtration, extraction, distillation, The reaction product may be isolated and purified by general methods such as sublimation, recrystallization and column chromatography.

A method for producing the tetracarboxylic dianhydride represented by the chemical formula (M-4) is described below.

The tetracarboxylic dianhydride represented by the chemical formula (M-4) can be obtained from Helv. Chim. Acta. 1975, 58, 160, Macromolecules 1993, 26, 3490, etc., and can be synthesized, for example, according to the reaction scheme shown below.

（式中、Ｘ_１１、Ｘ_１２は、それぞれ独立に、－Ｆ、－Ｃｌ、－Ｂｒ、または－Ｉであり、Ｒ_２１、Ｒ_２２、Ｒ_２３、Ｒ_２４は、それぞれ独立に、炭素数１～１０のアルキル基である。）

(wherein X ₁₁ and X ₁₂ are each independently —F, —Cl, —Br, or —I; R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ each independently have 1 carbon atom; ~10 alkyl groups.)

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

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

The amount of 1,3-butadiene used is preferably 0.5 to 5 mol, more preferably 0.8 to 3 mol, per 1 mol of NA.

This reaction may or may not use an organic solvent. The solvent to be used is not particularly limited as long as it does not inhibit the reaction. Examples include ketones (eg, acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (eg, n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylisobutylamide, etc.), ureas (N,N'- dimethylimidazolidinone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogens aromatic hydrocarbons (e.g. chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene etc.), nitrated aromatic hydrocarbons (e.g. nitrobenzene etc.), halogenated Hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, etc.), carboxylic acid esters (e.g., ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (e.g., acetonitrile, propio nitrile, benzonitrile, etc.), sulfoxides (eg, dimethylsulfoxide, etc.), sulfones (eg, sulfolane, etc.), phenols (phenol, methylphenol, parachlorophenol, etc.), and the like. Aliphatic hydrocarbons and aromatic hydrocarbons are preferably used. These organic solvents may be used alone or in combination of two or more.

When an organic solvent is used, the amount of the organic solvent used is appropriately adjusted depending on the homogeneity and stirrability of the reaction solution, and is preferably 0.1 to 100 g, more preferably 1 to 50 g, per 1 g of NA. .

(Second step)
In the second step, the OMNA obtained in the first step is reacted with bromine as a dihalogenating agent to give 6,7-dibromodecahydro-4,9-methanonaphtho[2,3-c]furan-1. , 3-dione (DBDNA; in this case, X ₁₁ and X ₁₂ are -Br). In place of bromine, other dihalogenating agents, as described below, can also be used. The compound obtained in the second step is a dihalogenodicarboxylic anhydride represented by the chemical formula (M-6) and is a novel compound.

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

A dihalogenating agent such as bromine is used in this reaction. The dihalogenating agent used in this reaction is not particularly limited as long as it can dihalogenate an olefin. Tribromide salts such as trimethylammonium tribromide, halogen compounds such as chlorine fluoride, bromine chloride, iodine chloride, iodine bromide, and iodine tribromide, and pyridinium salts and ammonium salts thereof, preferably halogens, Bromine is particularly preferably used.

The amount of the dihalogenating agent to be used is preferably 0.5 to 5 mol, more preferably 0.8 to 2 mol, per 1 mol of OMNA.

This reaction is usually performed in an organic solvent. The solvent to be used is not particularly limited as long as it does not inhibit the reaction. Examples include ketones (eg, acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (eg, n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylisobutylamide, etc.), ureas (N,N'- dimethylimidazolidinone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogens aromatic hydrocarbons (e.g. chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene etc.), nitrated aromatic hydrocarbons (e.g. nitrobenzene etc.), halogenated Hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, etc.), carboxylic acid esters (e.g., ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (e.g., acetonitrile, propio nitrile, benzonitrile, etc.), sulfoxides (eg, dimethylsulfoxide, etc.), sulfones (eg, sulfolane, etc.), phenols (phenol, methylphenol, parachlorophenol), and the like. Aliphatic hydrocarbons and halogenated hydrocarbons are preferably used. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent to be used is appropriately adjusted depending on the homogeneity and stirrability of the reaction solution, and is preferably 0.1 to 100 g, more preferably 1 to 50 g, per 1 g of OMNA.

(Third step)
In the third step, the DBDNA obtained in the second step is reacted with maleic anhydride to give 3a,4,4a,5,5a,8a,9,9a,10,10a-decahydro-1H,3H-4. ,10-ethano-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 chemical formula (M-4) in which R ₇ is -CH=CH-, and is a novel compound.

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

The amount of maleic anhydride to be used is generally 1 mol or more, preferably 2 mol or more, more preferably 4 mol or more, per 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 mol, but if about 1 mol is used, the reactant after the reaction is solidified in the reaction vessel, making it difficult to take out. be. On the other hand, when maleic anhydride (melting point 52-56° C.) is used in an amount exceeding an equimolar amount, the excess maleic anhydride is liquid because the reaction temperature is higher than the melting point of maleic anhydride. It acts as a solvent and the reaction system becomes a suspension. After completion of the reaction, after cooling from the reaction temperature to a temperature suitable for work (for example, about 100° C.), an organic solvent is added to the system and filtered to obtain EEMDA of high purity.

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

The amount of the organic solvent to be used is appropriately adjusted depending on the homogeneity and stirability of the prepared solution, and is preferably 0.1 to 30 mL, more preferably 0.5 to 20 mL, relative to 1 g of DBDNA.

(Fourth step)
In the fourth step, the EEMDA obtained in the third step is reacted with methanol to obtain tetramethyl-1,4,4a,5,6,7,8,8a-octahydro-1,4-ethano-5. ,8-methanonaphthalene-6,7,10,11-tetracarboxylate (EEMDE; in this case, R ₂₁ to R ₂₄ are methyl groups). Other alcohol compounds corresponding to the desired ester compounds can be used in place of methanol. The compound obtained in the fourth step is a tetraester compound represented by the chemical formula (M-5) in which R ₇ is -CH=CH-, and is a novel compound.

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

An acid is used in this reaction. The acid used in this reaction is not particularly limited, but examples include mineral acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, chlorosulfuric acid, and nitric acid; methanesulfonic acid, benzenesulfonic acid, p-toluene. organic sulfonic acids such as sulfonic acid; halogenated carboxylic acids such as chloroacetic acid and trifluoroacetic acid; ion exchange resins; silica gel sulfate; zeolite; Mineral acids are used. These acids may be used alone or in combination of two or more.

The amount of the acid used is preferably 0.01 to 10 mol, more preferably 0.05 to 3 mol, per 1 mol of EEMDA.

An alcohol compound is used in this reaction. Examples of alcohol compounds used in this reaction include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, pentyl alcohol, methoxyethanol, ethoxyethanol, and ethylene glycol. , triethylene glycol and the like, preferably methanol, ethanol, n-propyl alcohol and isopropyl alcohol, more preferably methanol and ethanol. These alcohol compounds may be used singly or in combination of two or more.

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

In this reaction, an organic solvent other than the alcohols may be used. The organic solvent to be used is not particularly limited as long as it does not inhibit the reaction. , trifluoromethanesulfonic acid, etc.), ketones (e.g., acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (e.g., n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas (N,N'-dimethylimidazolidinone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane , 1,2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (e.g., chlorobenzene, 1,2-dichlorobenzene, 1,3 -dichlorobenzene, 1,4-dichlorobenzene, etc.), nitrated aromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, etc.) ), carboxylic acid esters (e.g., ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (e.g., acetonitrile, propionitrile, benzonitrile, etc.), sulfoxides (e.g., dimethyl sulfoxide, etc.), sulfones (e.g., , sulfolane, etc.). Aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and halogenated aromatic hydrocarbons are preferably used. These organic solvents may be used alone or in combination of two or more.

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

Orthoesters are used in this reaction. The orthoesters to be used include compounds represented by the following formulas, such as trimethyl orthoformate and triethyl orthoformate, preferably trimethyl orthoformate.

In the formula, R ^f represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. Also, R ^e represents 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 's may be the same or different, but are preferably the same.

The amount of the orthoester used is preferably 0.5 g or more, more preferably 1 to 5 g, per 1 g of EEMDA.

(Fifth step)
In the fifth step, the EEMDE obtained in the fourth step is reacted with hydrogen to give tetramethyl-decahydro-1,4-ethano-5,8-methanonaphthalene-2,3,6,7-tetracarboxylate ( EMDE). The compound obtained in the fifth step is a tetraester compound represented by the chemical formula (M-5) in which R ₇ is —CH ₂ CH ₂ —, and is a novel compound.

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

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

A metal catalyst is used in this reaction. The metal catalyst to be used is not particularly limited as long as it can hydrogenate the olefin portion in the structure of EEMDE. , palladium silica gel, etc.), platinum-based catalysts (platinum carbon, platinum alumina, etc.), nickel-based catalysts (Raney nickel catalyst, sponge nickel catalyst, etc.). Rhodium-based catalysts and palladium-based catalysts are preferred, and rhodium-based catalysts are more preferred.

The amount of the metal catalyst used is preferably 0.0001 to 1 mol, more preferably 0.001 to 0.8 mol, per 1 mol of EEMDE in terms of metal atoms.

It is preferable to use a solvent in this reaction. The solvent to be used is not particularly limited as long as it does not inhibit the reaction. Examples include water, alcohols (methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t- butyl alcohol, etc.), ketones (e.g., acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (e.g., n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (e.g., N, N -dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylisobutyramide, etc.), ureas (N,N'-dimethylimidazolidinone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (e.g., chlorobenzene, 1,2-dioxybenzene, etc.) chlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitrated aromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride, 1 , 2-dichloroethane, etc.), carboxylic acid esters (e.g., ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (e.g., acetonitrile, propionitrile, benzonitrile, etc.), sulfoxides (e.g., dimethyl sulfoxide, etc.) , sulfones (eg, sulfolane, etc.), phenols (phenol, methylphenol, parachlorophenol), and the like. Alcohols, amides, aliphatic hydrocarbons and aromatic hydrocarbons are preferably used. These solvents may be used alone or in combination of two or more.

The amount of the solvent used is appropriately adjusted depending on the homogeneity and stirrability of the reaction solution, and is preferably 0.1 to 100 g, more preferably 1 to 50 g, per 1 g of EEMDE.

(6th step)
In the sixth step, decahydro-1H,3H-4,10-ethano-5,9-methanonaphtho[2,3-c:6,7-c′] is obtained by dehydration reaction of EMDE obtained in the fifth step. Difuran-1,3,6,8-tetraone (EMDA) is synthesized. The compound obtained in the sixth step is the tetracarboxylic dianhydride represented by the above chemical formula (M-4) in which R ₇ is —CH ₂ CH ₂ —.

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

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

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

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

The amount of the solvent to be used is appropriately adjusted depending on the homogeneity and stirrability of the reaction solution, and is preferably 0.1 to 100 g, more preferably 1 to 10 g, per 1 g of EMDE.

The details of each reaction will be described in Examples, but those skilled in the art can change the solvent, amount charged, reaction conditions, etc., and after completion of each reaction, for example, filtration, extraction, distillation, The reaction product may be isolated and purified by general methods such as sublimation, recrystallization and column chromatography.

The present invention can also provide a novel method for producing the tetracarboxylic dianhydride represented by the chemical formula (M-9), which is the tetracarboxylic acid component giving the structure of the chemical formula (A-2). The manufacturing method thereof will be described below.

The tetracarboxylic dianhydride represented by the chemical formula (M-9) can be obtained from Can. J. Chem. 1975, 53, 256, Tetrahedron Lett. 2003, 44, 561, etc., for example, according to the reaction scheme shown below. Here, the 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-methanonaphtho [ 2,3-c:6,7-c′]difuran-1,3,6,8-tetraone (BNDA) will be described as an example, but other tetracarboxylic dianhydrides can be produced in the same manner. can.

（式中、Ｒ_３１、Ｒ_３２は、それぞれ独立に、炭素数１～１０のアルキル基、またはフェニル基であり、Ｒ_３３、Ｒ_３４は、それぞれ独立に、炭素数１～１０のアルキル基である。）

(In the formula, R ₃₁ and R ₃₂ are each independently an alkyl group having 1 to 10 carbon atoms or a phenyl group, and R ₃₃ and R ₃₄ are each independently an alkyl group having 1 to 10 carbon atoms. be.)

(First step)
In the first step, cis _- 1,4-dichloro- ₂ -butene (DCB) and It reacts with cyclopentadiene (CP) to synthesize 5,6-bis(chloromethyl)bicyclo[2.2.1]hept-2-ene (BCMN). When synthesizing the tetracarboxylic dianhydride of formula (M-9) where R ₄ is —CH ₂ CH ₂ —, 1,3-cyclohexadiene is used as DCB instead of cyclopentadiene (CP). It should be reacted.

This reaction is carried out, for example, by mixing DCB and CP and stirring the mixture. The reaction temperature at that time is preferably 50 to 250° C., more preferably 150 to 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 to 200°C. The CP used in this first step can also be used by being generated in the system by thermal decomposition of DCP. DCP is the compound shown in the scheme.

The amount of CP used is preferably 0.2 to 10 mol, more preferably 0.5 to 5 mol, per 1 mol of DCB.

This reaction may or may not use an organic solvent. The organic solvent to be used is not particularly limited as long as it does not inhibit the reaction. , trifluoromethanesulfonic acid, etc.), alcohols (e.g., methanol, ethanol, isopropyl alcohol, t-butyl alcohol, ethylene glycol, triethylene glycol, etc.), ketones (e.g., acetone, butanone, cyclohexanone, etc.), aliphatic carbonization Hydrogens (e.g., n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas ( N,N'-dimethylimidazolidinone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (eg, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitrated aromatic hydrocarbons (eg, nitrobenzene etc.), halogenated hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, etc.), carboxylic acid esters (e.g., ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (e.g., , acetonitrile, propionitrile, benzonitrile, etc.), sulfoxides (eg, dimethylsulfoxide, etc.), sulfones (eg, sulfolane, etc.), phenols (phenol, methylphenol, parachlorophenol, etc.), and the like. Aliphatic hydrocarbons and aromatic hydrocarbons are preferably used. These organic solvents may be used alone or in combination of two or more.

When an organic solvent is used, the amount of the organic solvent to be used is appropriately adjusted depending on the homogeneity and stirrability of the reaction solution. is.

(Second step)
In the second step, the BCMN obtained in the first step is dehydrochlorinated by reacting with a base to synthesize 5,6-dimethylenebicyclo[2.2.1]hept-2-ene (CYDE). do.

This reaction is carried out, for example, by mixing BCMN and a base in a solvent and stirring the mixture. The reaction temperature at that time is preferably 0 to 150° C., more preferably 20 to 120° C., and the reaction pressure is not particularly limited.

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

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

This reaction is usually desirably carried out in a solvent. The solvent to be used is not particularly limited as long as it does not inhibit the reaction. Hydrocarbons (e.g., n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas (N,N'-dimethylimidazolidinone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene) , xylene, etc.), sulfoxides (eg, dimethylsulfoxide, etc.), sulfones (eg, sulfolane, etc.), and the like. Water, alcohols and ethers are preferably used. These solvents may be used alone or in combination of two or more.

The amount of the solvent to be used is appropriately adjusted depending on the homogeneity and stirrability of the reaction solution, and is preferably 0.1 to 100 g, more preferably 0.2 to 50 g, per 1 g of BCMN.

(Third step)
In the third step, the CYDE obtained in the second step is reacted with dimethyl acetylenedicarboxylate (DMAD) to give dimethyl 1,4,5,8-tetrahydro-1,4-methanonaphthalene-6,7-di A carboxylate (CYME; in this case, R ₃₁ and R ₃₂ are methyl groups) is synthesized. In place of dimethyl acetylenedicarboxylate, other acetylenedicarboxylic acid diesters, which will be described later, can also be used.

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

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

The amount of the acetylenedicarboxylic acid diester such as DMAD to be used is preferably 0.8 to 20 mol, more preferably 1 to 10 mol, per 1 mol of CYDE.

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

The amount of the solvent used is appropriately adjusted depending on the homogeneity and stirrability of the reaction solution, and is preferably 0.2 to 200 g, more preferably 0.3 to 100 g, per 1 g of CYME.

(Fourth step)
In the fourth step, dimethyl 1,4-dihydro-1,4-methanonaphthalene-6,7-dicarboxylate (CYPDM) is synthesized by the aromatization reaction (oxidation reaction) of CYME obtained in the third step. do.

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

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

The amount of the oxidizing agent used is preferably 0.5 to 10 mol, more preferably 0.8 to 5 mol, per 1 mol of CYME.

This reaction is usually carried out in a solvent. The solvent to be used is not particularly limited as long as it does not inhibit the reaction. Examples include water; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylisobutyramide, amides; ureas such as N,N-dimethylimidazolidinone; nitriles such as acetonitrile and propionitrile; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and t-butyl alcohol Ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and cyclopropyl methyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Aliphatic hydrocarbons such as hexane, cyclohexane, heptane and octane; Methylene chloride and chloroform , 1,2-dichloroethane, chlorobenzene, and other halogenated hydrocarbons; ethyl acetate, butyl acetate, and other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; Hydrocarbons, ethers, alcohols and water are used. These solvents may be used alone or in combination of two or more.

The amount of the solvent to be used is appropriately adjusted depending on the homogeneity and stirrability of the reaction solution, and is preferably 1 to 100 g, more preferably 2 to 50 g, per 1 g of CYME.

(Fifth step)
In the fifth step, the CYPDM obtained in the fourth step, methanol, and carbon monoxide are reacted in the presence of a palladium catalyst and a copper compound to give tetramethyl-1,2,3,4-tetrahydro-1,4. -methanonaphthalene-2,3,6,7-tetracarboxylate (BNME; in this case, R ₃₁ to R ₃₄ are methyl groups). Other alcohol compounds corresponding to the desired ester compounds can be used in place of methanol.

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

An alcohol compound is used in this reaction. Examples of alcohol compounds used in this reaction include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, pentyl alcohol, methoxyethanol, ethoxyethanol, and ethylene glycol. , triethylene glycol, etc., preferably methanol, ethanol, n-propyl alcohol or isopropyl alcohol, more preferably methanol, ethanol or isopropyl alcohol. These alcohol compounds may be used singly or in combination of two or more.

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

In this reaction, an organic solvent other than the alcohols may be used. The organic solvent to be used is not particularly limited as long as it does not inhibit the reaction. , trifluoromethanesulfonic acid, etc.), aliphatic hydrocarbons (e.g., n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, etc.), ureas (N,N'-dimethylimidazolidinone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-methylenedioxybenzene, etc.), aromatic family hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (e.g., chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), Nitrated aromatic hydrocarbons (e.g. nitrobenzene etc.), halogenated hydrocarbons (e.g. methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane etc.), carboxylic acid esters (e.g. ethyl acetate, acetic acid propyl, butyl acetate, etc.), nitriles (eg, acetonitrile, propionitrile, benzonitrile, etc.), sulfoxides (eg, dimethylsulfoxide, etc.), sulfones (eg, sulfolane, etc.), and the like. Aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and halogenated aromatic hydrocarbons are preferably used. These organic solvents may be used alone or in combination of two or more.

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

The palladium catalyst used in this reaction is not particularly limited as long as it contains palladium. palladium inorganic acid salts such as palladium and palladium sulfate; palladium complexes such as bis(acetylacetonato)palladium and bis(1,1,1-5,5,5-hexafluoroacetylacetonato)palladium; palladium-carbon and palladium-alumina supported on a carrier such as palladium chloride and alumina are preferred, but palladium chloride and palladium-carbon are preferably used.

The amount of the palladium catalyst used is preferably 0.0001 to 0.2 mol, more preferably 0.001 to 0.1 mol, per 1 mol of CYPDM.

The copper compound used in this reaction is particularly limited as long as it can oxidize Pd(0) to Pd(II) when Pd(II) in the palladium catalyst is reduced to Pd(0). Examples include copper compounds and iron compounds, preferably copper compounds. Specific examples of the copper compound used in this reaction include copper, copper acetate, copper propionate, copper normal butyrate, copper 2-methylpropionate, copper pivalate, copper lactate, copper butyrate, copper benzoate, tri Copper fluoroacetate, copper bis(acetylacetonato), copper bis(1,1,1-5,5,5-hexafluoroacetylacetonato), copper chloride, copper bromide, copper iodide, copper nitrate, nitrite Copper, copper sulfate, copper phosphate, copper oxide, copper hydroxide, copper trifluoromethanesulfonate, copper p-toluenesulfonate, and copper cyanide. Further, specific examples of iron compounds include ferric chloride, ferric nitrate, ferric sulfate, and ferric acetate. Preferably a divalent copper compound is used, more preferably copper(II) chloride. Here, the term "copper compound" is used in the sense of including so-called compounds as well as elemental copper. In addition, you may use these copper compounds individually or in mixture of 2 or more types.

The amount of the copper compound used is preferably 4 to 50 mol, more preferably 5 to 20 mol, per 1 mol of CYPDM.

(6th step)
In the sixth step, the BNME obtained in the fifth step is dehydrated to give 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 the tetracarboxylic dianhydride represented by the chemical formula (M-9).

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

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

The amount of the acid catalyst used is preferably 0.001 to 0.5 mol, more preferably 0.001 to 0.2 mol, per 1 mol of BNME.

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

The amount of the solvent to be used is appropriately adjusted depending on the homogeneity and stirrability of the reaction solution, and is preferably 0.1 to 100 g, more preferably 1 to 10 g, relative to 1 g of BNME.

The details of each reaction will be described in Examples, but those skilled in the art can change the solvent, amount charged, reaction conditions, etc., and after completion of each reaction, for example, filtration, extraction, distillation, The reaction product may be isolated and purified by general methods such as sublimation, recrystallization and column chromatography.

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

Evaluation was performed in each of the following examples by the following methods.

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

[Tensile modulus, breaking elongation, breaking strength]
A polyimide film was punched into a dumbbell shape of IEC-540 (S) standard to make a test piece (width: 4 mm), and using TENSILON manufactured by ORIENTEC, the chuck length was 30 mm, the tensile speed was 2 mm / min, and the initial tensile modulus was measured. , elongation at break, and breaking strength were measured.

[Coefficient of linear thermal expansion (CTE), Tg]
A polyimide film with a film thickness of 10 μm was cut into a strip shape with a width of 4 mm to make a test piece. was heated up to 500°C. A linear thermal expansion coefficient from 100° C. to 250° C. was obtained from the obtained TMA curve. Also, the inflection point of the TMA curve was defined as Tg (glass transition temperature).

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

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

[Diamine component]
DABAN: 4,4'-diaminobenzanilide PPD: p-phenylenediamine TFMB: 2,2'-bis(trifluoromethyl)benzidine 4,4'-ODA: 4,4'-oxydianiline TPE-R: 1 , 3-bis(4-aminophenoxy)benzene BAPB: 4,4′-bis(4-aminophenoxy)biphenyl tra-DACH: trans-1,4-diaminocyclohexane [tetracarboxylic acid component]
TNDA: tetradecahydro-1H,3H-4,12:5,11:6,10-trimethanoanthra[2,3-c:6,7-c′]difuran-1,3,7,9-tetraone BNDA: 3a,4,10,10a-tetrahydro-1H,3H-4,10-methanonaphtho[2,3-c:6,7-c′]difuran-1,3,6,8-tetraone DMADA: 3a, 4,6,6a,9a,10,12,12a-octahydro-1H,3H-4,12:6,10-dimethanoanthra[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-ethano-5, 9-methanonaphtho[2,3-c:6,7-c′]difuran-1,3,6,8-tetraone

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

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

[Example S-1 (Synthesis of DMADA)]

容量２Ｌの反応容器に、トルエン１５００ｍＬとｐ－ベンゾキノン（ＢＱ）１５３．３ｇ（１．３９ｍｏｌ）を入れた。そして、温度２５－３０℃を保ちながら、シクロペンタジエン１８３．５ｇ（２．７８ｍｍｏｌ）を２時間かけて滴下した後、２５℃で２０時間反応させた。反応液を濃縮乾固し、得られた濃縮物にエタノール１４９０ｇを加え、終夜撹拌を行った。その後、固体をろ過し、エタノールで洗浄後、６０℃で真空乾燥して、薄赤色固体２２７ｇを得た。得られた薄赤色固体２２７ｇにエタノール１３５０ｇを加え、８０℃で１時間撹拌し、固体をろ過した。ろ物をクロロホルム１０８０ｇで溶解させ、活性炭１０ｇを添加し、１時間撹拌した。その後、ろ過を行い、ろ液を濃縮乾固し、得られた固体を６０℃で真空乾燥して、白色固体として１，４，４ａ，５，８，８ａ，９ａ，１０ａ－オクタヒドロ－１，４：５，８－ジメタノアントラセン－９，１０－ジオン（ＤＮＢＱ）１８４ｇを得た（^１Ｈ－ＮＭＲ分析による純度１００％、収率５５．３％）。

1500 mL of toluene and 153.3 g (1.39 mol) of p-benzoquinone (BQ) were placed in a 2 L reactor. Then, 183.5 g (2.78 mmol) of cyclopentadiene was added dropwise over 2 hours while maintaining the temperature at 25 to 30°C, and the reaction was allowed to proceed at 25°C for 20 hours. The reaction solution was concentrated to dryness, 1490 g of ethanol was added to the resulting concentrate, and the mixture was stirred overnight. After that, the solid was filtered, washed with ethanol, and vacuum-dried at 60° C. to obtain 227 g of a pale 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 filter cake was dissolved in 1080 g of chloroform, 10 g of activated carbon was added, and the mixture was stirred for 1 hour. Thereafter, filtration is carried out, the filtrate is concentrated to dryness, and the obtained solid is vacuum-dried at 60° C. to obtain 1,4,4a,5,8,8a,9a,10a-octahydro-1, as a white solid. 184 g of 4:5,8-dimethanoanthracene-9,10-dione (DNBQ) were obtained (100% pure by ¹ H-NMR analysis, 55.3% yield).

The physical property values of DNBQ were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.29 (d, J = 8.5 Hz, 2H), 1.46 (d, J = 8.5 Hz, 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 5 L reaction vessel. Then, 30.0 g (60.3 mmol) of sodium borohydride was added at a temperature of 5° C. over 1 hour, and then reacted at a temperature of 5 to 10° C. for 7 hours. Then, 1 L of a saturated ammonium chloride aqueous solution was added dropwise at a temperature of 5°C, and then the temperature was raised to 25°C. A 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. Thereafter, the white solid was filtered, washed twice with 200 mL of ion-exchanged water, washed twice with 100 mL of ethyl acetate, and dried under vacuum to obtain white solids 1,4,4a,5,8,8a, 84.2 g of 9,9a,10,10a-decahydro-1,4:5,8-dimethanoanthracene-9,10-diol (DNHQ) were obtained (100% pure by ¹ H-NMR analysis, yield 82 %).

The physical property values of DNHQ were as follows.

¹ H-NMR (DMSO-d _6, σ (ppm)); 0.99 (d, J = 7.8 Hz, 1H), 1.16 (d, J = 7.8 Hz, 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 5 L reaction vessel and cooled to 5°C. After 87.0 g (760 mmol) of mesyl 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. Subsequently, 2500 g of ion-exchanged water was added dropwise, and the precipitated white solid was filtered. The resulting white solid was washed five times with 200 mL of 10% hydrochloric acid, 200 mL of 10% aqueous sodium hydrogencarbonate solution, and 200 mL of deionized water, and dried in vacuum. 128.9 g of the obtained white solid was dissolved in 2800 g of ethyl acetate and dried (dehydrated) with 35 g of anhydrous magnesium sulfate. Subsequently, this ethyl acetate solution is passed through a silica gel column, and the solvent is distilled off by an evaporator to obtain 1,4,4a,5,8,8a,9,9a,10,10a-decahydro-1, as a white solid. 4: 124.5 g of 5,8-dimethanoanthracene-9,10-diyl dimethanesulfonate (DNCMS) were obtained (99% pure by ¹ H-NMR analysis, 87.4% yield).

The physical property values of DNCMS were as follows.

¹ H-NMR (DMSO-d _6, σ (ppm)); 1.18 (d, J = 8.3 Hz, 1H), 1.32 (d, J = 8.2 Hz, 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 1 L reactor and stirred. After the atmosphere in the system was gas-substituted with carbon monoxide, a solution of 27 g (67.3 mmol) of DNCMS dissolved in 178 g of chloroform was added dropwise over 3 hours and reacted at 20-25° C. for 4 hours. Then, after replacing the atmosphere in the system from carbon monoxide with argon, the solvent was distilled off from the reaction mixture, and 621 g of chloroform was added. A similar operation was repeated two more times. Then, insoluble matter was removed by filtration from the resulting brown-green suspension. The resulting solution was washed three times with 324 g of a saturated aqueous sodium hydrogencarbonate solution and three 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, after filtering the solution, it was concentrated under reduced pressure to obtain 51 g of a white solid. Then, purification by silica gel chromatography (developing solvent; hexane:ethyl acetate=10:1 (volume ratio)) was performed, and 9,10-bis((methylsulfonyl)oxy)tetradecahydro-1,4: was obtained as a white solid. 27 g of 5,8-dimethanoanthracene-2,3,6,7-tetracarboxylate (DNMTE) were obtained (purity by HPLC analysis 97.1 pa %, yield 64.4%).

The physical property values of DNMTE were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.49 (d, J = 10 Hz, 2H), 2.31 (d, J = 10 Hz, 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 having a capacity of 500 mL, and the temperature was raised to 150°C. Subsequently, 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 reacted at the same temperature for 15 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure to obtain 22.4 g of a white solid. Then, purification by silica gel chromatography (developing solvent: hexane:ethyl acetate = 10:1 (volume ratio)), followed by purification by recrystallization (solvent ratio: toluene/heptane = 2:3), gave a tetra Methyl 1,2,3,4,4a,5,6,7,8,9a-decahydro-1,4:5,8-dimethanoanthracene-2,3,6,7-tetracarboxylate (DMHAE) 13 95.1 pa% pure by HPLC analysis, yield 72.2%).

The physical property values of DMHAE were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.36 (d, J = 10 Hz, 1 H), 1.56 (d, J = 10 Hz, 1 H), 2.05 (d, J = 10 Hz, 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)

A 300 mL reactor was charged with 68 mL of toluene and 7.3 g (31.9 mmol) of 2,3-dichloro-5,6-dicyano-p-benzoquinone, and the temperature was raised to 80°C. A solution of 13.5 g (30.4 mmol) of DMHAE dissolved in 200 mL of toluene was added dropwise and reacted for 8 hours. After completion of the reaction, the reaction solution was concentrated, and 130 mL of chloroform was added to the concentrate to obtain a reddish-brown suspension. Then, it was filtered to separate into a dark reddish-black filtrate and a filtrate. After the filtrate was washed with 100 mL of a saturated aqueous sodium hydrogencarbonate solution three times, 12 g of anhydrous magnesium sulfate was added to the obtained organic layer for dehydration. Then, filtration was performed, and the filtrate was concentrated to dryness to obtain 5.6 g of a reddish brown solid. Further, 100 mL of chloroform was added to the dark reddish black filter cake, and the same operation was performed to obtain 4.0 g of a reddish brown solid. 9.6 g of the resulting reddish brown solid was purified by recrystallization (solvent ratio: toluene:heptane = 1:7) to obtain tetramethyl-1,2,3,4,5,6,7 as a milky white solid. 7.4 g of ,8-octahydro-1,4:5,8-dimethanoanthracene-2,3,6,7-tetracarboxylate (DMAME) were obtained (purity by HPLC analysis 99.9 pa%, yield 56 .6%).

The physical property values of DMAME were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.80 (d, J = 9.6 Hz, 2H), 2.43 (d, J = 9.6 Hz, 2H), 2.68 (d, J = 1.6 Hz, 4H), 3.53 (s, 4H), 3.67 (s, 12H), 7.06 (s, 2H)
CI-MS (m/z); 442 (M+1)

5.27 g (11.9 mmol) of DMAME, 26.3 g of formic acid, and 47 mg (0.24 mmol) of p-toluenesulfonic acid monohydrate were placed in a reaction vessel having a volume of 100 mL, and reacted at a temperature of 98° C. for 30 hours. After completion of 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 to distill off the formic acid almost completely. After filtering the obtained suspension and washing the obtained solid with 30 g of toluene, it was vacuum-dried at 80° C. to obtain 4.0 g of a milky white solid. Thereafter, recrystallization with acetic anhydride and further recrystallization with N,N'-dimethylacetamide were performed to obtain 3a,4,6,6a,9a,10,12,12a-octahydro-1H,3H-4,12 as a white solid. :6,10-dimethanoanthra[2,3-c:6,7-c′]difuran-1,3,7,9-tetraone (DMADA) 3.28 g were obtained (purity 98.0 according to ¹ H-NMR analysis). 3%, 77.3% yield).

The physical property values of DMADA were as follows.

¹ H-NMR (DMSO-d _6, σ (ppm)); 1.61 (d, J = 10.8 Hz, 2H), 1.81 (d, J = 10.8 Hz, 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)]

容量３Ｌのオートクレーブに、シス－５－ノルボルネン－エンド－２，３－ジカルボン酸無水物（ｅｎｄｏ－ＮＡ）６００ｇ（３．６６ｍｏｌ）を入れ、次に、２，６－ジブチルヒドロキシトルエン１．２０ｇを入れた。系内を窒素置換した後、温度－２５℃で１，３－ブタジエン２２１ｇ（４．０９ｍｏｌ）を添加し、温度１５０－１６０℃で一晩反応させて、白色固体７６０ｇを得た。以上の操作をさらに２回繰り返し、白色固体２２５８ｇを得た（収率３６％）。そして、得られた白色固体２２５８ｇにトルエン９．７Ｌを加え、温度１０２℃で加熱撹拌し、固体を溶解させた。同温度で１０分間撹拌した後、ヘプタン２．６Ｌを加え、室温まで冷却して一晩撹拌し、析出した固体をろ過した。得られた固体をヘプタン２．６Ｌで洗浄した後、４０℃で５時間、真空乾燥して白色固体６９１ｇを得た。

600 g (3.66 mol) of cis-5-norbornene-endo-2,3-dicarboxylic anhydride (endo-NA) was placed in an autoclave with a capacity of 3 L, followed by 1.20 g of 2,6-dibutylhydroxytoluene. I put it in. After the inside of the system was replaced with nitrogen, 221 g (4.09 mol) of 1,3-butadiene was added at -25°C and reacted overnight at 150-160°C to obtain 760 g of a white solid. The above operation was repeated twice to obtain 2258 g of a white solid (36% yield). 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, the mixture was cooled to room temperature and stirred overnight, and the precipitated solid was filtered. After washing the obtained solid with 2.6 L of heptane, it was 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 5 L reactor. After heating and stirring at a temperature of 98° C., 1.1 L of heptane was added, cooled to room temperature, and further stirred overnight. The precipitated solid was filtered, washed with 1.1 L of heptane, and vacuum-dried at 40° C. for 3 hours to give (3aR,4S,9R,9aS)-3a,4,4a,5,8, as a white solid. 634 g of 8a,9,9a-octahydro-4,9-methanonaphtho[2,3-c]furan-1,3-dione (OMNAdx) were obtained (purity by ¹ H-NMR analysis 99.1%, yield 26 %).

The physical property values of OMNAdx were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.50 (d, J = 11 Hz, 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 having a capacity of 20 L. A solution of 496 g (3.1 mol) of bromine dissolved in 4.9 L of dichloromethane was added dropwise while cooling to a temperature of -55 to -43°C, and the mixture was reacted for 1 hour. After completion of the reaction, the solvent was removed by an evaporator, 600 mL of heptane was added to the obtained solid, and the mixture was stirred. Then, the white solid was filtered, washed with 4.5 L of heptane, and dried under reduced pressure at 40° C. to obtain (3aR,4S,9R,9aS)-6,7-dibromodecahydro-4,9- as a white solid. 805 g of methanonaphtho[2,3-c]furan-1,3-dione (DBDNAdx) were obtained (100% pure by ¹ H-NMR analysis, 78% yield).

The physical property values of DBDNAdx were 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 = 3.3 Hz, J = 3.5 Hz, 1H)
CI-MS (m/z); 379 (M+1)

130 g (1.33 mol) of maleic anhydride and 100 g (264.5 mmol) of DBDNAdx were added to a reaction vessel having a capacity of 2 L, and reacted at a temperature of 187° C. for 2 hours. After completion of the reaction, the temperature was cooled to 100° C., and 400 mL of toluene was added. After cooling to around room temperature, the precipitated solid was filtered, washed with toluene, and vacuum-dried at 60° C. to obtain (3aR, 4R, 5S, 5aR, 8aS, 9R, 10S, 10aS)-3a, as a gray solid. 4,4a,5,5a,8a,9,9a,10,10a-decahydro-1H,3H-4,10-ethano-5,9-methanonaphtho[2,3-c:6,7-c′]difuran 75 g of -1,3,6,8-tetraone (EEMDAdx) were obtained (98.4% pure by ¹ H-NMR analysis, 89% yield).

The physical property values of EEMDAdx were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.04 (d, J = 10.8 Hz, 1 H), 1.82 (s, 2 H), 2.30 (d, J = 10.8 Hz, 1H), 2.62 (s, 2H), 3.20 (s, 2H), 3.39 (m, 2H), 3.42 (d, J = 2.1 Hz, J = 3.4 Hz, 2H) , 6.20 (dd, J=3.2 Hz, J=4.5 Hz, 2H)
CI-MS (m/z); 314 (M+1)

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

The physical property values of EEMDEdx were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 0.81 (d, J = 11 Hz, 1H), 2.29 (s, 2H), 2.43 (s, 2H), 2.58 (d , J = 11 Hz, 1 H), 2.86 (t, J = 2.0 Hz, 2 H), 3.00 (brs, 2 H), 3.05 (s, 2 H), 3.57 (s, 6 H), 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 NE Chemcat, containing 50 wt % water) were added to a reaction vessel having a capacity of 200 mL. After the inside of the system was replaced with hydrogen, hydrogen was pressurized to 0.9 MPa, and the reaction was carried out at an internal temperature of 80° C. for 4 hours. After completion of the reaction, the reactant was washed with 100 mL of N,N'-dimethylformamide and taken out. After the obtained reaction suspension was filtered through celite, it was concentrated under reduced pressure to obtain a white solid. This operation was repeated 7 times to obtain 41.2 g of a white solid (purity by GC analysis: 99.9%, yield: 97%). Then, purification was performed with a silica gel column (developing solvent: hexane/ethyl acetate = 3/1 (v/v)), and tetramethyl (1R, 2R, 3S, 4S, 5R, 6S, 7R, 8S)- was obtained as a white solid. 35 g of decahydro-1,4-ethano-5,8-methanonaphthalene-2,3,6,7-tetracarboxylate (EMDEdx) were obtained (100% pure by GC analysis, 83% yield).

The physical property values of EMDEdx were as follows.
¹ H-NMR (CDCl _3, σ (ppm)); 1.25 (d, J = 11 Hz, 1 H), 1.49 (d, J = 9.0 Hz, 2 H), 1.79 (d, J = 9.0 Hz, 2H), 2.00 (s, 2H), 2.14 (s, 2H), 2.24 (d, J = 11 Hz, 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)

30 g (73.4 mmol) of EMDEdx, 150 g of formic acid, and 280 mg (1.47 mmol) of p-toluenesulfonic acid monohydrate were added to a reaction vessel having a volume of 300 mL, and reacted at a temperature of 95° C. to 99° C. for 16 hours. After completion of 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 to distill off the formic acid almost completely. After filtering the obtained suspension and washing the obtained solid with 35 mL of toluene, it was vacuum-dried at 80° C. to obtain 23.4 g of a gray solid. Thereafter, recrystallization with acetic anhydride and N,N'-dimethylacetamide was repeated to give (3aR,4R,5S,5aR,8aS,9R,10S,10aS)-decahydro-1H,3H-4,10-ethano as a white solid. 18.9 g of 5,9-methanonaphtho[2,3-c:6,7-c′]difuran-1,3,6,8-tetraone (EMDAdx) were obtained (purity 98.0 by ¹ H-NMR analysis). 5%, 80% yield).

The physical property values of EMDAdx were as follows.

¹ H-NMR (DMSO-d _6, σ (ppm)); 1.17 (d, J = 9.9 Hz, 2H), 1.48 (d, J = 12 Hz, 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)]

３Ｌのオートクレーブに、シス－５－ノルボルネン－エキソ－２，３－ジカルボン酸無水物（ｅｘｏ－ＮＡ）６００ｇ（３．６６ｍｏｌ）、２，６－ジブチルヒドロキシトルエン３００ｍｇを入れた。系内を窒素置換した後、内温－２５℃で１，３－ブタジエン３１９ｇ（５．９１ｍｏｌ）を添加し、反応温度１４０～１６６℃で３５時間撹拌して、白色固体８６６．２ｇを得た（収率５８％）。そして、得られた白色固体８６６．２ｇをトルエンで再結晶して、白色結晶として（３ａＲ，４Ｒ，９Ｓ，９ａＳ）－３ａ，４，４ａ，５，８，８ａ，９，９ａ－オクタヒドロ－４，９－メタノナフト［２，３－ｃ］フラン－１，３－ジオン（ＯＭＮＡｘｘ）３５９ｇを得た（^１Ｈ－ＮＭＲ分析による純度１００％、収率４５％）。

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

The physical property values of OMNAxx were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.19 (d, J = 12 Hz, 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 added to a 3 L reaction vessel. A solution of 105.4 g (660 mmol) of bromine dissolved in 200 mL of dichloromethane was added dropwise over 2 hours while cooling to a temperature of -65 to -60°C, and the reaction was allowed to proceed for 1 hour. This operation was performed twice. Then, the two reaction liquids were collected and concentrated by an evaporator to obtain a pale brown solid. 1.5 L of heptane was added to the obtained light brown solid, and the mixture was filtered. The filtered solid was washed with 500 mL of heptane, dried in vacuo, and (3aR,4R,9S,9aS)-6,7-dibromodecahydro-4,9-methanonaphtho[2,3- 313 g of c]furan-1,3-dione (DBDNAxx) were obtained (100% pure by ¹ H-NMR analysis, 75% yield). Further, the filtrate was concentrated under reduced pressure, washed with 500 mL of heptane, and then vacuum-dried to obtain 78.1 g of DBDNAxx as a white solid (100% pure by ¹ H-NMR analysis, 19% yield).

The physical property values of DBDNAxx were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.28 (d, J = 12 Hz, 1 H), 1.62 (q, J = 12 Hz, 1 H), 1.84-2.24 (m, 5H), 2.59 (s, 2H), 3.03 (dd, J = 7.3 Hz, J = 23 Hz, 2H), 4.32 (ddd, J = 3.3 Hz, J = 5.5 Hz, 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 having a capacity of 2 L and reacted at a reaction temperature of 190° C. for 2 hours. After completion of the reaction, the temperature was cooled to 100° C., and 900 mL of toluene was added. After cooling to around room temperature, the precipitated solid was separated by filtration. After washing the obtained solid with 900 mL of toluene, it was dried under reduced pressure at 60° C. for 3 hours to obtain (3aR, 4R, 5S, 5aS, 8aR, 9R, 10S, 10aS)-3a, 4 as a pale brown solid. ,4a,5,5a,8a,9,9a,10,10a-decahydro-1H,3H-4,10-ethano-5,9-methanonaphtho[2,3-c:6,7-c′]difuran- 140.2 g of 1,3,6,8-tetraone (EEMDAxx) were obtained (97.2% purity by ¹ H-NMR analysis, 82% yield).

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

The physical property values of EEMDAxx were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 0.59 (d, J = 12 Hz, 1 H), 2.01 (s, 2 H), 2.12 (d, J = 12 Hz, 1 H), 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 added to a 20 L reaction vessel and stirred at a temperature of 61 to 67° C. for 79 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure to obtain 513 g of a gray solid. The resulting solid was dissolved in 3256 g of chloroform and added dropwise to 1700 g of a 7 wt % sodium hydrogen carbonate aqueous solution. 31.6 g of anhydrous magnesium sulfate and 26.8 g of activated carbon were added to the separated organic layer, and the mixture was stirred at room temperature for 1 hour and then filtered. .3 g was obtained. The obtained gray solid was recrystallized with methanol to give tetramethyl(1R,4S,5R,6R,7S,8S,10S,11R)-1,4,4a,5,6,7, as a white solid. 294.9 g of 8,8a-octahydro-1,4-ethano-5,8-methanonaphthalene-6,7,10,11-tetracarboxylate (EEMDExx) were obtained (100% purity by GC analysis, yield 91%). %).

The physical property values of EEMDExx were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.55 (d, J = 11 Hz, 1 H), 1.61 (s, 2 H), 2.29 (d, J = 11 Hz, 1 H), 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 charged into an autoclave having a capacity of 3 L, and 49.1 g of 10% rhodium-carbon catalyst (manufactured by NE Chemcat, 50% water content) was added. After the inside of the system was replaced with hydrogen, hydrogen was pressurized to 0.9 MPa, and the reaction was carried out at an internal temperature of 80° C. for 4 hours. After completion of the reaction, the precipitated solid was dissolved in 3235 g of N,N'-dimethylformamide, and the reactant was taken out and filtered through celite to remove the catalyst. This operation was performed twice more on 97.3 g (239 mmol) of EEMDExx. All filtrates were then combined and concentrated under reduced pressure to obtain 289.1 g of a gray solid. The resulting gray solid was recrystallized from 700 g of chloroform and 4373 g of heptane to give tetramethyl(1R,2R,3S,4S,5R,6R,7S,8S)-decahydro-1,4-ethano-5 as a slightly gray solid. 283.0 g of ,8-methanonaphthalene-2,3,6,7-tetracarboxylate (EMDExx) were obtained (purity by GC analysis 99.9 pa %, yield 96%).

The physical property values of EMDExx were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.52 (d, J = 9.0 Hz, 2H), 1.58 (s, 2H), 1.76 (d, J = 9.0 Hz, 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)

282.0 g (689.7 mmol) of EMDExx, 1410 g of formic acid, and 3.28 g (17 mmol) of p-toluenesulfonic acid monohydrate were added to a reaction vessel having a capacity of 3 L, and reacted at a temperature of 95° C. to 97° C. for 19 hours. After completion of 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 to distill off the formic acid almost completely. After filtering the obtained suspension and washing the obtained solid with 490 mL of toluene, it was vacuum-dried at 80° C. to obtain 219.6 g of a gray solid. Thereafter, recrystallization with acetic anhydride and further recrystallization with N,N'-dimethylformamide were performed to give (3aR,4R,5S,5aS,8aR,9R,10S,10aS)-decahydro-1H,3H-4 as a white solid. ,10-ethano-5,9-methanonaphtho[2,3-c:6,7-c′]difuran-1,3,6,8-tetraone (EMDAxx) 175.9 g were obtained ( ¹ H-NMR analysis Purity 99.4%, yield 96%).

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

The physical property values of EMDAxx were as follows.

¹ H-NMR (DMSO-d _6, σ (ppm)); 0.98 (d, J = 13 Hz, 1H), 1.15 (d, J = 9.4 Hz, 2H), 1.57 (d, J = 9.4 Hz, 2H), 1.81 (s, 2H), 1.91 (d, J = 13 Hz, 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)]

容量１Ｌのオートクレーブに、シス－１，４－ジクロロ－２－ブテン２３３ｇ（１．７６ｍｏｌ）、ジシクロペンタジエン２４５ｇ（１．９６ｍｏｌ）、トルエン１７６ｍＬを入れた。系内を窒素置換した後、温度１８０℃で５時間反応させた。オートクレーブを開けて、反応物を取り出し、濃縮した。

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 a 1-liter autoclave. After the inside of the system was replaced with nitrogen, the reaction was carried out at a temperature of 180° C. for 5 hours. The autoclave was opened and the reaction was removed and concentrated.

Subsequently, 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 a 1-liter autoclave. After the inside of the system was replaced with nitrogen, the reaction was carried out at a temperature of 180° C. for 5 hours. The autoclave was opened and the reaction was removed and concentrated.

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

The physical property values of BCMN were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.37 (d, J=8.4 Hz, 1 H), 1.56 (d, J=8.4 Hz, 1 H), 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)

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

The physical property values of CYDE were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.57 (d, J = 8.2 Hz, 1H), 1.77 (d, J = 8.2 Hz, 1H), 3.30 (d, J = 1.8 Hz, 2H), 4.95 (s, 2H), 5.16 (s, 2H), 6.19 (s, 2H)
CI-MS (m/z); 119 (M+1)

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

The physical property values of CYME were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.98 (d, J = 0.8 Hz, 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)

126 g of fraction (1) containing CYME (purity 85.6 pa%; 414.4 mmol), 1.3 L of methylene chloride, 2,3-dichloro-5,6-dicyano- 138 g (607.9 mmol) of p-benzoquinone was added and reacted at 20° C. for 7 hours.

In addition, 177 g of fraction (2) containing CYME (purity 50.9 pa%; 346.1 mmol), 890 mL of methylene chloride, 2,3-dichloro-5,6-dicyano- 97.7 g (430.4 mmol) of p-benzoquinone was added and 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. Subsequently, purification was performed by silica gel chromatography (developing solvent: hexane:ethyl acetate=15:1 (volume ratio)) to obtain 248.9 g of a red oily substance. This oily substance was dissolved in 2 L of ethyl acetate, washed three times with 500 mL of saturated aqueous sodium hydrogencarbonate solution, further washed with 500 mL of saturated brine, dehydrated and dried over sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. 146 g of dimethyl 1,4-dihydro-1,4-methanonaphthalene-6,7-dicarboxylate (CYPDM) was obtained as a red oily substance (99.1 pa% purity by GC analysis, yield 74%).

The physical property values of CYPDM were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 2.26 (d, J = 7.6 Hz, 1 H), 2.36 (d, J = 7.6 Hz, 1 H), 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 having a capacity of 500 mL. After the atmosphere in the system was gas-substituted with carbon monoxide, a solution of 20 g (76.7 mmol) of CYPDM dissolved in 66 g of chloroform was added dropwise over 6 hours and reacted at room temperature for 3 hours. Then, after replacing the atmosphere in the system from carbon monoxide with argon, the solvent was distilled off from the reaction mixture, and 300 g of chloroform was added. Further, the residue was concentrated under reduced pressure to distill off the solvent, and 300 g of chloroform was added. Then, insoluble matter was removed by filtration from the resulting brown-green suspension. The resulting solution was washed three times with 240 g of saturated aqueous sodium hydrogencarbonate solution and three 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. After the solution was filtered, it was concentrated under reduced pressure to obtain 26.7 g of a light brown solid. Then, purification by silica gel chromatography (developing solvent: hexane:ethyl acetate = 15:1 (volume ratio)) followed by recrystallization (solvent ratio: toluene/heptane = 2.5:1 (volume ratio)). to give 22.4 g of tetramethyl-1,2,3,4-tetrahydro-1,4-methanonaphthalene-2,3,6,7-tetracarboxylate (BNME) as a white solid (purity by HPLC analysis 94.8 pa%, yield 67.5%).

The physical property values of BNME were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.89 (d, J=10 Hz, 1 H), 2.54 (d, J=10 Hz, 1 H), 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)

20 g (50.4 mmol) of BNME, 60 g of formic acid, and 194.2 mg (1.02 mmol) of p-toluenesulfonic acid monohydrate were added to a reaction vessel having a volume of 200 mL, and reacted 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 to distill off the formic acid almost completely. After filtering the obtained suspension and washing the obtained solid with 21 g of toluene, it was vacuum-dried at 80° C. to obtain 16.1 g of a milky white solid. Thereafter, recrystallization with acetic anhydride and further recrystallization with N,N'-dimethylacetamide were performed to obtain 3a,4,10,10a-tetrahydro-1H,3H-4,10-methanonaphtho[2,3-c as a white solid. : 6,7-c′]difuran-1,3,6,8-tetraone (BNDA) 8.39 g were obtained (98.8% pure by ¹ H-NMR analysis, 57.9% yield).

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

The physical property values of BNDA were as follows.

¹ H-NMR (DMSO-d _6, σ (ppm)); 1.79 (d, J = 15 Hz, 1 H), 1.93 (d, J = 15 Hz, 1 H), 3.21 (s, 2 H) , 4.05(s, 2H), 8.07(s, 2H)
CI-MS (m/z); 285 (M+1)

[Example 1]
0.60 g (2.6 mmol) of DABAN was placed in a reaction vessel purged with nitrogen gas, and 6.29 g of NMP was added so that the total mass of charged monomers (sum of diamine component and carboxylic acid component) was 20% by mass. was added and stirred at room temperature for 1 hour. 1.12 g (2.6 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.

A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate and heated from room temperature to 440° C. on the glass substrate as it is under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) to thermally imidize and colorless. A transparent polyimide film/glass laminate was obtained. Then, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a thickness of 10 μm.

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

[Example 2]
1.00 g (4.4 mmol) of DABAN, 0.07 g (0.6 mmol) of PPD, and 0.46 g (1.3 mmol) of BAPB were placed in a reaction vessel purged with nitrogen gas, and NMP was added to the total amount of charged monomers. 11.54 g was added so that the mass (sum of the diamine component and the carboxylic acid component) was 25% by mass, and the mixture was stirred at room temperature for 1 hour. 2.32 g (6.3 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.

A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate and heated from room temperature to 460 ° C. on the glass substrate as it is under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) to thermally imidize and colorless. A transparent polyimide film/glass laminate was obtained. Then, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a 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 placed in a reaction vessel purged with nitrogen gas, and 6.00 g of NMP was added so that the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) was 25% by mass. was added 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.

A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate and heated from room temperature to 430 ° C. on the glass substrate as it is under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) to thermally imidize and colorless. A transparent polyimide film/glass laminate was obtained. Then, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a thickness of 10 μm.

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

[Comparative Example 2]
0.70 g (3.5 mmol) of 4,4'-ODA was placed in a reaction vessel purged with nitrogen gas, and DMAc was added so that the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) was 20% by mass. An amount of 7.95 g was added 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.

A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate and heated from room temperature to 430 ° C. on the glass substrate as it is under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) to thermally imidize and colorless. A transparent polyimide film/glass laminate was obtained. Then, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a thickness of 10 μm.

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

[Example 3]
0.23 g (1.0 mmol) of DABAN was placed in a reaction vessel purged with nitrogen gas, and 2.70 g of NMP was added in such an amount that the total mass of charged monomers (sum of diamine component and carboxylic acid component) was 16% by mass. was added and stirred at room temperature for 1 hour. 0.29 g (1.0 mmol) of BNDA obtained in Example S-3 was gradually added to this solution. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), it is thermally imidized by heating from room temperature to 320 ° C. on the glass substrate as it is, and is colorless. A transparent polyimide film/glass laminate was obtained. Then, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a thickness of 10 μm.

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

[Example 4]
0.40 g (3.7 millimoles) of PPD was placed in a reaction vessel purged with nitrogen gas, and 5.81 g of NMP was added so that the total mass of charged monomers (sum of diamine component and carboxylic acid component) was 20% by mass. was added and stirred at room temperature for 1 hour. 1.05 g (3.7 mmol) of BNDA obtained in Example S-3 was gradually added to this solution. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), it is thermally imidized by heating from room temperature to 350 ° C. on the glass substrate as it is, and is colorless. A transparent polyimide film/glass laminate was obtained. Then, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a thickness of 10 μm.

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

[Example 5]
1.52 g (4.7 millimoles) of TFMB was placed in a reaction vessel purged with nitrogen gas, and 11.41 g of NMP was added in such an amount that the total mass of charged monomers (sum of diamine component and carboxylic acid component) was 20% by mass. was added and stirred at room temperature for 1 hour. 1.35 g (4.7 mmol) of BNDA obtained in Example S-3 was gradually added to this solution. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), it is thermally imidized by heating from room temperature to 320 ° C. on the glass substrate as it is, and is colorless. A transparent polyimide film/glass laminate was obtained. Then, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a thickness of 10 μm.

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

[Example 6]
0.40 g (1.8 mmol) of DABAN, 0.70 g (2.2 mmol) of TFMB, and 0.16 g (0.4 mmol) of BAPB were placed in a reaction vessel purged with nitrogen gas, and NMP was added to the total amount of charged monomers. 10.00 g was added so that the mass (sum of the diamine component and the carboxylic acid component) was 20% by mass, and the mixture was stirred at room temperature for 1 hour. 1.24 g (4.4 mmol) of BNDA obtained in Example S-3 was gradually added to this solution. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), it is thermally imidized by heating from room temperature to 350 ° C. on the glass substrate as it is, and is colorless. A transparent polyimide film/glass laminate was obtained. Then, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a thickness of 10 μm.

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

[Example 7]
0.39 g (3.5 mmol) of tra-DACH was placed in a reaction vessel purged with nitrogen gas, and NMP was added to the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) was 11% by mass. .14 g was added and stirred at room temperature for 1 hour. 0.98 g (3.5 mmol) of BNDA obtained in Example S-3 was gradually added to this solution. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), it is thermally imidized by heating from room temperature to 320 ° C. on the glass substrate as it is, and is colorless. A transparent polyimide film/glass laminate was obtained. Then, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a thickness of 10 μm.

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

[Comparative Example 3]
0.60 g (3.0 mmol) of 4,4′-ODA is placed in a reaction vessel purged with nitrogen gas, and NMP is added so that the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) becomes 10% by mass. of 13.06 g was added and stirred at room temperature for 1 hour. 0.85 g (3.0 mmol) of BNDA obtained in Example S-3 was gradually added to this solution. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), it is thermally imidized by heating from room temperature to 320 ° C. on the glass substrate as it is, and is colorless. A transparent polyimide film/glass laminate was obtained. Then, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a thickness of 10 μm.

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

[Example 8]
0.70 g (3.5 mmol) of 4,4'-ODA was placed in a reaction vessel purged with nitrogen gas, and NMP was added so that the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) was 7% by mass. 25.57 g was added and stirred at room temperature for 1 hour. 1.22 g (3.5 mmol) 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.

A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), it is thermally imidized by heating from room temperature to 350 ° C. on the glass substrate as it is, and is colorless. A transparent polyimide film/glass laminate was obtained. Then, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a thickness of 10 μm.

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

[Example 9]
1.20 g (4.1 mmol) of TPE-R was placed in a reaction vessel purged with nitrogen gas, and NMP was added to 11 in an amount such that the total mass of charged monomers (sum of diamine component and carboxylic acid component) was 25% by mass. .39 g was added and stirred at room temperature for 1 hour. 1.32 g (4.1 mmol) of EMDAxx obtained in Example S-2-2 was gradually added to this solution. After stirring at room temperature for 48 hours, a uniform and viscous polyimide precursor solution was obtained.

A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate and heated from room temperature to 450 ° C. on the glass substrate as it is under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) to thermally imidize and colorless. A transparent polyimide film/glass laminate was obtained. Then, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a thickness of 10 μm.

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

From the results shown in Table 2-1, when TNDA is used as the tetracarboxylic acid component, as the diamine component, only diamines (4,4'-ODA, BAPB) having an ether bond (-O-) are used. In comparison, when using a diamine (DABAN, PPD) that does not have an ether bond (-O-) and gives the structure of the chemical formula (B-1), sufficient transparency and mechanical properties can be maintained. It can be seen that the polyimide obtained has high heat resistance and a low coefficient of linear thermal expansion (Examples 1 and 2 and Comparative Examples 1 and 2). When using BNDA as a tetracarboxylic acid component, as a diamine component, compared with the case of using only a diamine (4,4'-ODA) having an ether bond (-O-), the ether bond (-O-) When using a diamine (DABAN, PPD, TFMB) that gives the structure of the chemical formula (B-1) that does not have a diamine (tra-DACH) that gives the structure of the chemical formula (B-2), sufficient transparency, It can be seen that the coefficient of linear thermal expansion of the obtained polyimide is extremely low while maintaining the mechanical properties, and the heat resistance is equivalent or higher (Examples 3 to 7 and Comparative Example 3).

In addition, when the diamine components to be combined 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 is used as the tetracarboxylic acid component, a polyimide having a low coefficient of linear thermal expansion, high heat resistance, and sufficient properties can be obtained (Example 9).

According to the present invention, a polyimide having excellent properties such as transparency, bending resistance, high heat resistance, and a low coefficient of linear thermal expansion, a precursor thereof, and a novel tetracarboxylic dianhydride used for the production thereof can be provided. The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention are highly transparent, have a low linear thermal expansion coefficient, facilitate formation of fine circuits, and also have solvent resistance. , particularly for forming substrates for display applications.

Claims (21)

containing at least one repeating unit represented by the following chemical formula (1-1),
A polyimide precursor characterized in that the total content of repeating units represented by the chemical formula (1-1) is 50 mol % or more with respect to all repeating units.

(In the formula, A ₁₁ is a tetravalent group represented by the following chemical formula (A-1) or a tetravalent group represented by the following chemical formula (A-2), and B ₁₁ is the following chemical formula ( B-1) or a divalent group represented by the following chemical formula (B-2), wherein X ₁ and X ₂ are each independently hydrogen and have 1 to 6 carbon atoms. or an alkylsilyl group having 3 to 9 carbon atoms.)

(Wherein, R ₁ , R ₂ and R ₃ are each independently -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-.)

(wherein R ₄ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-).

(In the formula, n ₁ represents an integer of 0 to 3, and n ₂ represents an integer of 0 to 3. Y ₁ , Y ₂ , and Y ₃ each independently represent a hydrogen atom, a methyl group, or a trifluoromethyl group. wherein Q ₁ and Q ₂ are each independently a direct bond or a group represented by the formula: -NHCO-, -CONH-, -COO-, -OCO- It shows one selected from the group consisting of.)

(In the formula, Y ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) A polyimide precursor comprising at least one repeating unit represented by the following chemical formula (1-2).

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

(Wherein, R ₅ and R ₆ are each independently -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-.)

(Wherein, R ₇ is —CH ₂ CH ₂ — or —CH═CH—.) 3. The polyimide precursor according to claim 2, wherein the total content of repeating units represented by the chemical formula (1-2) is 50 mol % or more based on all repeating units. containing at least one type of repeating unit represented by the following chemical formula (2-1),
A polyimide having a total content of repeating units represented by the chemical formula (2-1) of 50 mol % or more based on all repeating units.

(wherein A ₂₁ is a tetravalent group represented by the following chemical formula (A-1) or a tetravalent group represented by the following chemical formula (A-2), and B ₂₁ is represented by the following chemical formula ( B-1) or a divalent group represented by the following chemical formula (B-2).)

(Wherein, R ₁ , R ₂ and R ₃ are each independently -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-.)

(wherein R ₄ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-).

(In the formula, n ₁ represents an integer of 0 to 3, and n ₂ represents an integer of 0 to 3. Y ₁ , Y ₂ , and Y ₃ each independently represent a hydrogen atom, a methyl group, or a trifluoromethyl group. wherein Q ₁ and Q ₂ are each independently a direct bond or a group represented by the formula: -NHCO-, -CONH-, -COO-, -OCO- It shows one selected from the group consisting of.)

(In the formula, Y ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) A polyimide comprising at least one repeating unit represented by the following chemical formula (2-2).

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

(Wherein, R ₅ and R ₆ are each independently -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-.)

(Wherein, R ₇ is —CH ₂ CH ₂ — or —CH═CH—.) 6. The polyimide according to claim 5, wherein the total content of repeating units represented by the chemical formula (2-2) is 50 mol % or more with respect to all repeating units. A polyimide obtained from the polyimide precursor according to any one of claims 1 to 3. A polyimide obtained from the polyimide precursor according to any one of claims 1 to 3, or a film mainly composed of the polyimide according to any one of claims 4 to 6. A varnish comprising the polyimide precursor according to any one of claims 1 to 3 or the polyimide according to any one of claims 4 to 6. A polyimide film obtained using the polyimide precursor according to any one of claims 1 to 3 or the varnish containing the polyimide according to any one of claims 4 to 6. Polyimide obtained from the polyimide precursor according to any one of claims 1 to 3, or for a display comprising the polyimide according to any one of claims 4 to 6, for a touch panel, or for a solar cell substrate. A tetracarboxylic dianhydride represented by the following chemical formula (M-1).

(Wherein, R ₅ ' and R ₆ ' are each independently -CH ₂ - or -CH ₂ CH ₂ -.) A tetraester compound represented by the following chemical formula (M-2).

(wherein 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 carbon It is an alkyl group of numbers 1 to 10.) A tetraester compound represented by the following chemical formula (M-3).

(wherein 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 carbon It is an alkyl group of numbers 1 to 10.) (A) in the presence of a base, an olefin compound represented by the following chemical formula (MA-1)

(Wherein, R ₅ ' and R ₆ ' are each independently -CH ₂ - or -CH ₂ CH ₂ -.)
and an aliphatic sulfonyl chloride or an aromatic sulfonyl chloride to obtain an olefin compound represented by the following chemical formula (MA-2)

(Wherein, R ₅ ' and R ₆ ' are as defined above, and R is an optionally substituted alkyl group or aryl group.)
a step of obtaining
(B) The olefin compound represented by the chemical formula (MA-2) is reacted with an alcohol compound and carbon monoxide in the presence of a palladium catalyst and a copper compound to obtain the chemical represented by the following chemical formula (MA-3). tetraester compound to be

(In the formula, R ₅ ', R ₆ ' and R are as defined above, and R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently an alkyl group having 1 to 10 carbon atoms.)
a step of obtaining
(C) a tetraester compound represented by the following chemical formula (M-3) from the tetraester compound represented by the chemical formula (MA-3)

(Wherein, R ₅ ', R ₆ ', R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are as defined above.)
a step of obtaining
(D) a tetraester compound represented by the following chemical formula (M-2) by oxidation reaction of the tetraester compound represented by the chemical formula (M-3)

(Wherein, R ₅ ', R ₆ ', R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are as defined above.)
a step of obtaining
(E) reacting the tetraester compound represented by the chemical formula (M-2) in the presence of an acid catalyst in an organic solvent to obtain a tetracarboxylic dianhydride represented by the following chemical formula (M-1);

(In the formula, R ₅ ' and R ₆ ' have the same definitions as above.)
a step of obtaining
A method for producing a tetracarboxylic dianhydride, comprising: A tetracarboxylic dianhydride represented by the following chemical formula (M-4).

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

(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 carbon atoms. be.) A dihalogenodicarboxylic anhydride represented by the following chemical formula (M-6).

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

(A) a dicarboxylic anhydride represented by the following chemical formula (MB)

and 1,3-butadiene to obtain a dicarboxylic anhydride represented by the following chemical formula (M-7)

a step of obtaining
(B) a dihalogenodicarboxylic anhydride represented by the following chemical formula (M-6) by reacting the dicarboxylic anhydride represented by the chemical formula (M-7) with a dihalogenating agent;

(Wherein, X ₁₁ and X ₁₂ each independently represent -F, -Cl, -Br, or -I.)
a step of obtaining
(C) reacting the dihalogenodicarboxylic anhydride represented by the chemical formula (M-6) with maleic anhydride to obtain a tetracarboxylic dianhydride represented by the following chemical formula (M-4-1);

a step of obtaining
(D) The tetracarboxylic dianhydride represented by the chemical formula (M-4-1) is reacted with an alcohol compound in the presence of an acid to form a tetracarboxylic acid represented by the following chemical formula (M-5-1). ester compound

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

(Wherein, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are as defined above.)
a step of obtaining
(F) reacting the tetraester compound represented by the chemical formula (M-5-2) in the presence of an acid catalyst in an organic solvent to obtain a tetracarboxylic acid represented by the following chemical formula (M-4-2); dianhydride

a step of obtaining
A method for producing a tetracarboxylic dianhydride, comprising: (A) a diene compound represented by the following chemical formula (MC-1)

(wherein R ₄ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH=CH-).
and an acetylene compound represented by the following chemical formula (MC-2)

(In the formula, R ₃₁ and R ₃₂ are each independently an alkyl group having 1 to 10 carbon atoms or a phenyl group.)
By reacting with, a diester compound represented by the following chemical formula (MC-3)

(Wherein, R ₄ , R ₃₁ and R ₃₂ are as defined above.)
a step of obtaining
(B) a diester compound represented by the following chemical formula (MC-4) by oxidation reaction of the diester compound represented by the chemical formula (MC-3)

(Wherein, R ₄ , R ₃₁ and R ₃₂ are as defined above.)
a step of obtaining
(C) The diester compound represented by the above chemical formula (MC-4) is reacted with an alcohol compound and carbon monoxide in the presence of a palladium catalyst and a copper compound to obtain a compound represented by the following chemical formula (MC-5). tetraester compound to be

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

(In the formula, R ₄ has the same definition as above.)
a step of obtaining
A method for producing a tetracarboxylic dianhydride, comprising: