TW201041848A - Tetracarboxylic acid derivatives, processes for producing same, and liquid-crystal alignment material - Google Patents

Abstract

A novel tetracarboxylic acid dialkyl ester including a cyclobutane ring having an alkyl group thereon; a novel bis(chlorocarbonyl) compound obtained by chlorinating the ester; and processes for producing the compounds. Furthermore provided is a process for producing specific isomers of these. The tetracarboxylic acid dialkyl ester is represented by formula [1] or [2]. (In the formulae, R1 is a C 1-5 aLkyl, R2 is a C 1-5 alkyl, and n is 1-4.)

Description

201041848 VI. Description of the Invention: [Technical Field] The present invention relates to a novel bis(chlorocarbonyl) compound obtained by chlorinating a novel dialkyl tetracarboxylate, and the like The compound is a raw material of a polyphthalic acid and/or a liquid crystal alignment agent of polyimine. [Prior Art] 四 A tetracarboxylic acid dialkyl ester, and a tetracarboxylic acid derivative such as a bis(chlorocarbonyl) compound obtained by chlorination, are used as a raw material of polyamine, polyester or polyimine. Important substance. For example, a synthesis example of a polyimine having a cyclobutane skeleton in the main chain is reported to have 'transacted dimethyl bis(chlorocarbonyl)cyclobutanedicarboxylate with a diamine to obtain a polymethyl phthalate. This is heated to obtain a polyimine sample (refer to Non-Patent Document 1). However, in the case of the cyclobutane tetracarboxylic acid having a substituent on the cyclobutane ring, and the absence of the synthetic dicarboxylic acid tetraalkyl ester and the bis(chlorocarbonyl) compound obtained by chlorinating the compound. Further, resins such as polyimine are characterized by high mechanical strength, heat resistance, insulation, and solvent resistance. Therefore, they are widely used as protective materials for liquid crystal display elements and semiconductors, insulating materials, and color filters. In the case of other electronic materials, it has recently been expected to be used for optical communication materials such as optical waveguide materials. Therefore, in recent years, resins used in such fields have been required to have higher characteristics and qualities, and therefore, it is required to have a higher level of emphasis on the structure and quality of the raw materials for these resins. -5- 201041848 In addition, liquid crystal display elements used for liquid crystal televisions, liquid crystal displays, etc. generally have a liquid crystal alignment film for controlling the arrangement state of liquid crystals in the element, and the liquid crystal alignment film is used when the most popular method in the industry is used. The polyimine film formed on the electrode can be wiped in one direction by a cloth such as cotton, nylon or polyester, that is, by rubbing treatment. The method of rubbing the polyimide film is simple and excellent in productivity, and is suitable for industrial methods. However, as the requirements for high performance, high definition, and large size of liquid crystal display elements increase, the occurrence of damage to the surface of the alignment film, the influence of dust, mechanical strength, and static electricity during the rubbing treatment, alignment treatment Various problems such as uniformity in the plane. A method of replacing the rubbing treatment is known, for example, by irradiating a polarized radiation to impart a light alignment method to the liquid crystal alignment energy. In the liquid crystal alignment mechanism using the photo-alignment method, a mechanism using a photo-sensitization change reaction, a photo-crosslinking reaction, and a photo-decomposition reaction has been proposed (see Non-Patent Document 2). Patent Document 1 proposes that a photo-alignment method uses a polyimine having a condensed ring structure such as a cyclobutane ring in its main chain. When the alignment film is a photo-alignment method using polyimine, it is expected to have usefulness because of its high heat resistance. The above-mentioned photo-alignment method is a method that does not require a rubbing alignment treatment, and industrially has the advantage of being able to be produced in a simple manufacturing process, and has become a new type of liquid crystal alignment processing method which is attracting attention, but it is used in liquid crystal televisions and liquid crystal displays. There are problems such as alignment regulation of liquid crystals, electrical characteristics for liquid crystal display elements, and stability of these characteristics, and therefore, they are generally not practical. That is, the liquid crystal alignment film which is subjected to the alignment treatment by the rubbing method has a high anisotropy with respect to the rubbing direction by extending the polymer chain by the physical strength of -6 to 201041848. When the anisotropy is high, a high liquid crystal alignment regulating force can be found. On the other hand, the liquid crystal alignment film obtained by the photo-alignment method has a problem that the anisotropy with respect to the alignment direction of the polymer film is small when the object obtained by the friction is compared. [Prior Art Document] [Patent Document] Patent Document 1: JP-A-9-2973 No. 3, Non-Patent Document Non-Patent Document 1: High Performance Polymers, (1 998), 10(1) , pi 1-2 1 Non-Patent Document 2: Miki Tosuke Jun, Shimura Kokuhiro, Liquid Crystal Light Alignment Film, Monthly Journal Functional Materials 1 November 997, CMC Corporation Publishing, Vol. 17, No. 11, pl3 -22 Ο [Summary of the Invention] [Problems to be Solved by the Invention] [Problems to be Solved by the Invention] An object of the present invention is to provide a novel dialkyl tetracarboxylate having an alkyl group on a cyclobutane ring, and chlorine thereof Novel bis(chlorocarbonyl) compounds, methods for producing the same, and methods for producing the specific isomers thereof, and the object of the present invention is to provide a compound containing the above bis(chlorocarbonyl) compound. A liquid crystal alignment agent of a polyamic acid and/or a polyimine of a raw material. 201041848 [Means for Solving the Problems] The present invention has been made to solve the above problems, and has the following gist. A dicarboxylic acid tetraalkyl ester which is represented by the following formula [1] or formula [2], [Chemical Formula 1]

(wherein R1 is an alkyl group having 1 to 5 carbon atoms, R2 is a group having 1 to 5 carbon atoms, and η is 1 to 4). 2. The dialkyl tetracarboxylate as described in the above 1, which is represented by the following formula Π-a], the formula [2-a] or the formula [2-b], [Chemical 2]

(wherein 'R1 is an alkyl group having 1 to 5 carbon atoms, and R2 is a burning group having 1 to s carbon atoms). a bis(chlorocarbonyl) compound which is represented by the following formula [3] or formula -8 - 201041848 [4], [Chemical 3]

[4-b]

(wherein R1 is an alkyl group having 1 to 5 carbon atoms, R2 is a carbon number group, and η is 1 to 4). 4. The bis(chlorocarbonyl) compound described in the above 3. The formula [3-a], the formula [4-a] or the formula [4-b], [Chemical 4]

(wherein R1 is a group having a carbon number of 1 to 5, and R2 is a carbon number group). 5. A method for producing a tetracarboxylic acid represented by the above formula [1] or formula [2], which is a reaction of an alcohol having two to five tetracarboxylic acids represented by the following formula [5] to an alkane of 5; It is as follows -C! -OR1 to 5 alkane ^ hospital based vinegar sweat and carbon number 1 201041848 [Chemical 5]

Ί5 (wherein R2 is a fluorenyl group having 1 to 5 carbon atoms, η is 1 to 4 6·-the above-described formula Π-a] or a method for producing tetralithium represented by the formula [2-a], The alcohol reaction of the four-figure number 1 to 5 represented by the following formula [5-a], ?? acid dialkyl ester|acid dianhydride and carbon [chemical 6]

[5-a] (wherein R2 is an alkyl group having 1 to 5 carbon atoms). 7. The tetracarboxylic acid two-cylinder method represented by the above formula [2-b], which is an alcohol reacted with a tetracarboxylic dianhydride represented by the following formula [5-b], and the carbon number of the ester is produced. 1 to 5 [7]

-10" 201041848 (wherein R2 is an alkyl group having 1 to 5 carbon atoms). The production method according to any one of the above items 5 to 7, wherein the tetracarboxylic acid is reacted with an alcohol having 1 to 5 carbon atoms in the presence of an acidic compound or a basic compound. 9. The production method according to any one of the above items 5 to 7, wherein the tetradecanoic dianhydride is reacted with a carbon number of 1 to 5 in the presence of a basic compound. Ο10. A method for producing a bis(chlorocarbonyl) compound represented by the above formula [3] or formula [4], which is a dialkyl tetracarboxylate represented by the above formula [1] or formula [2] Reacts with chlorinating agents. 1 1. A method for producing a bis(chlorocarbonyl) compound represented by the above formula [3-a], which comprises reacting a dialkyl tetracarboxylate represented by the above formula [1-a] with a chlorinating agent. I2. A method for producing a bis(chlorocarbonyl) compound represented by the above formula [4-a], which is a reaction of a dialkyl tetracarboxylate represented by the above formula [2-a] with a hydrazine chlorinating agent . A method for producing a bis(chlorocarbonyl) compound represented by the above formula [4-b], which comprises reacting a dialkyl tetracarboxylate represented by the above formula [2-b] with a chlorinating agent. The production method as described in any one of the above items 10 to 13. wherein the dialkyl tetracarboxylic acid is reacted with a chlorinating agent in the presence of a basic compound. The production method as described in any one of the above-mentioned items 1 to 3, wherein the dialkyl tetracarboxylic acid is reacted with a chlorinating agent in the presence of pyridine. -11 - 201041848 16. A liquid crystal alignment agent comprising a ruthenium ring containing 60 mol% or more of a cyclobutane ring, a chlorocarbonyl group bonded to the 3 position, and an alkyl ester group bonded at the 2,4 position. a polyglycolate obtained by reacting a bis(chlorocarbonyl) compound of an acid chloride represented by the following formula (101) with a diamine [Chemical Formula 8]

(101) wherein R1 is an alkyl group having 1 to 5 carbon atoms, and R2, R3, r4 and r5 are a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms may be the same or different. (1) The liquid crystal alignment agent according to the above, wherein the acid chloride has a structure represented by the following formula (102), [102] (102) Min 0"*/^rcl 0 0 (wherein And Ri is an alkyl group having 1 to 5 carbon atoms, and R6 is a hydrocarbon group having 1 to 30 carbon atoms). The liquid crystal alignment agent according to the above, wherein the acid chloride is a structure represented by the following formula (103), -12-(103) (103)201041848 [in the formula, R! is an alkyl group having 1 to 5 carbon atoms). 1 . A liquid crystal alignment film which is obtained by irradiating a polarized radiation to a film obtained by baking the liquid crystal alignment agent according to any one of the above-mentioned 16 to 19. In the method of producing a liquid crystal alignment film, the liquid crystal alignment agent described in any one of the above-mentioned 16 to 19. is sprayed on the film obtained by irradiating the radiation of the polarized light. [Effects of the Invention] The present invention can provide a novel dicarboxylic acid dialkyl ester having an alkyl group on a cyclobutane ring, and a novel bis(chlorocarbonyl) compound having an alkyl group on a cyclobutane ring. In addition, these specific isomers can be produced efficiently. When the liquid crystal alignment agent of the present invention is heated and the imidization is carried out, the polymer chain does not undergo a decomposition reaction, and a high-order polymer film can be obtained, so that the alignment direction can be obtained even by using the photo-alignment method. Anisotropic liquid crystal alignment film. Further, the liquid crystal alignment film of the present invention has stability to an external environment such as temperature and humidity. Therefore, when used as a liquid crystal display element, it can have a high voltage holding ratio and a low ion density at a high temperature of '-13-201041848'. The liquid crystal that is stable and has good characteristics is not obvious. [Form of the invention] [Dialkyl tetracarboxylate] The following general formula π] or formula [2] The dialkyl tetracarboxylate of the invention is a compound represented. [11]

[1]

(wherein R1 is an alkyl group having 1 to 5 carbon atoms; R2 is an alkyl group having 1 to 5 carbon atoms, and η is 1 to 4). R1 is an alkyl group having 1 to 5 carbon atoms, and specific examples of the alkyl group are, for example, 'methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl. Wait. Further, when the polyphthalide is synthesized from the dialkyl tetracarboxylate of the present invention, when ruthenium is used as the polyimine, R1 is preferably a substance having a small carbon number and is easily detached, more preferably a methyl group. . R2 is an alkyl group having 1 to 5 carbon atoms, and specific examples of the alkyl group are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl. Wait. η is from 1 to 4, preferably 2. Hereinafter, specific examples of the tetracarboxylic acid dialkyl-14-201041848 ester of the present invention when R2 is a methyl group and η is 2, but the tetracarboxylic acid dialkyl ester of the present invention is not limited thereto. Further, in the following tables, a to a4 and bl to b4 represent respective positions represented by the following formula [6], and the meanings of the symbols in the table are as follows.

Me : methyl, Et: ethyl, Pr-n : n-propyl ' Pr-iso : isopropyl, Bu-n: n-butyl, Bu-sec: sec-butyl, Bu-iso: isobutyl, Bu-t: tert-butyl, Pen-n: n-pentyl, OMe: methoxy, OEt: ethoxy, OPr-n: n-propyl ether, OPr-iso: isopropyl ether, OBu- 〇η : n-butoxy, OBu-sec: sec-butoxy, OBu-iso · • isobutoxy, OBu-t: tert-butoxy, OPen-n: n-pentyl ether [Chemical 12]

A1 a2 \b1 / b2 b3 \ [6] -15- 201041848 [Table η Compound (11) (1.2) (1-3) al a3 a4 bl b2 b3 b4 OH OMe OH OMe Me H Me H OH OMe OH OMe Me HH Me OH OMe OH OMe H Me H Me

\/ \—/ 4 5 6 111 /V /ι\ /V Η Η Ηο ο ο t Η ο ο t t t Ε Ε 0 0-0 ee 丨 Μ Μ Η Θ Η HMe

MeH Η lee Η Μ Μ \»/ \—/ \—/ 7 00 9 111 ί\ /\ /ι\ Η Η Ηο ο ο

Opr- n OH Opr- -n Me H Me H OPr — n OH Opi.- -n Me HH Me OPr —n OH Opr- -n H Me H Me (1-10) OH OPr —iso OH OPr— iso Me H Me H (1-11) OH OPr —iso OH OPr —iso Me HH Me (1-12) OH OPr— iso OH OPr — iso H Me H Me

\»/ \—/ \—/ 3 4 5 111· 1* Ίχ Ti is /V /V Η Η Ηο ο ο OBu — n OH OBu- -n Me H Me H OBu — n OH OBu- -n Me HH Me OBu — n OH OBu- -n H Me H Me

(116) OH OBu - -sec OH OBu - -sec Me H Me H (1-17) OH OBu - -sec OH OBu - -•sec Me HH Me (1-18) OH OBu ~ -sec OH OBu - - Sec H Me H Me \ϊ/ \t/ \ 9 0 1 2 2 IX Ίχ 1Χ /ι\ /ί\ /ι\

OHOHOH OBu - -iso OH OBu — iso Me H Me H OBu - -iso OH OBu — iso Me HH Me OBu - -iso OH OBu an iso H Me H Me (1-22) OH OB ii — t OH OB ii — t Me H Me H (1-23) OH OBvi — t OH OB u — t Me HH Me (1-24) OH OBu — t OH OB u — t H Me H Me (1-25) OH Open — n OH Open- n Me H Me H (1.26) OH Open- n OH Open- n Me HH Me (1-27) OH Open-n OH Open —n H Me H Me -16- 201041848 [Table 2] a:3 compound Al a2 a4 bl b2 b3 b4

(2-1) OH OMe OMe OH Me H Me H (2-2) OH OMe OMe OH Me H H Me (2-3) OH OMe OMe OH Me Me H

(2-4) OH OEt. OEt OH Me H Me H (2-5) OH OEt OEt OH Me H H Me (2.6) OH OEt OEt OH H Me Me H

ΟΡι,一iso OPi. — iso OPi· — iso O Pr — iso OPi· — iso OPr —iso (2-10) (2-11) (2*12) (2-13) OH OBu — sec OBu— sec OH Me H Me H (2-14) OH OBu —sec OBu — sec OH Me HH Me (2-15) OH OBu — sec OBu —sec OH H Me Me H (2-16) OH OBu — sec OBu — sec OH Me H Me H (2-17) OH OBu — sec OBu — sec OH Me HH Me (2-18) OH OBu — sec OBu — sec OH H Me Me H (2-19) OH OBu — iso OBu —iso OH Me H Me H (2-20) OH OBu — iso OBu — iso OH Me HH Me (2-21) OH OBu — iso OBu — iso OH H Me Me H (2-22) OH OB u — t OBu — t OH Me H Me H (2-23) OH OB u — t OBu — t· OH Me HH Me (2-24) OH OBu—t OBu —t OH H Me Me H (2-25) OH Open—n Open — n OH Me H Me H (2-26) OH Open— n Open — n OH Me HH Me (2-27) OH Open— n Open — n OH H Me Me H o 〇, n is 2, and The compound wherein R2 is ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or n-pentyl may be each of bl to b4 in the above table, each of which is Et, Pr- n, Pr-iso, Bu-n Bu-sec, Bu-iso, Bu-t or Pen-n-substituted compounds. The dialkyl tetracarboxylate of the present invention is easy to synthesize a compound and a yield. The particularly preferred compound is a compound represented by the following formula [1-a], [2-a] or [2-b]. VI/ V)/ 7 8 9 2·2·2· /V /V /(\ OH Opr— n Opr —n OH Opr— n Opr —n OH Opr— n 0 pr — n Η Η Ho o o

H Μ H e丨 e Μ Η M H HMe eel Μ Μ H

OHOHOH Η Η Ho o o

Hm€h e丨 e Μ Η M H HMe eel Μ Μ H -17- 201041848 [Chem. 13]

When a high-purity product of [1-a] is used, a polymer having a molecular weight higher than that of a high-purity product of [2_a] or a mixture of [1-a] and [2-a] can be obtained, Therefore, the viewpoint of producing a polymer having a high molecular weight and a low dispersion is preferably a dialkyl tetracarboxylate represented by Π-a]. The dialkyl tetracarboxylic acid ester of the present invention can be obtained by reacting a tetracarboxylic dianhydride [5] with an alcohol having 1 to 5 carbon atoms represented by RhH by the following reaction formula.

(wherein R1 is an alkyl group having 1 to 5 carbon atoms, R2 is an alkyl group having 1 to 5 carbon atoms, and η is 1 to 4). The above reaction can be carried out in the corresponding alcohol (R1 〇Η ). If necessary, a solvent can be used. The solvent may be inactive to the reaction, and is not particularly limited to, for example, hydrocarbons such as hexane, heptane or toluene, halogenated hydrocarbons such as chloroform, 1,2-dichloroethane or chlorobenzene, and diethyl ether. Ethers such as ether or I,4-dioxane-18-201041848, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, and mixtures thereof. It is preferably ethyl acetate or acetonitrile, more preferably acetonitrile. The alcohol (R 1 ◦ Η ) is usually used in an amount of 2 to 100 moles, preferably 2 to 40 moles, more preferably 2 to 20 moles per mole of the tetracarboxylic dianhydride [5]. The above reaction is carried out under neutral conditions, and a base or an acid may be added. The alkali hydrazine or acid is not particularly limited. Alkali such as 'sodium hydroxide' potassium hydroxide, potassium carbonate or sodium bicarbonate, inorganic bases, triethylamine, pyridine, quinoline, 8-quinolinol, 1,10-phenanthroline, phenanthroline , dimethyldiphenylphenanthroline (BCP), 2,2,-bipyridine, 2-phenylpyridine, 2,6-diphenylaminopyridine, 2-dimethylaminopyristyl, 4-dimethylaminopyridine, 2-(2-hydroxyethyl)pyridine, hydrazine, hydrazine-dimethylaniline, 1,8-diazabicyclo[5_4.0]-7-residue DBU) and other organic bases' and metal alkane oxides such as sodium methoxide, potassium methoxide or potassium t-butoxide. Preferred is sodium methoxide, potassium methoxide or pyridine, more preferably pyridine. Acids such as heteropolyacids such as phosphomolybdic acid and phosphotungstic acid, organic acids such as trimethylborate and triphenylphosphine, mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid, carbonization of formic acid, acetic acid or P-toluenesulfonic acid Hydrogen acid, and halogenated hydrocarbon acid such as trifluoroethylene. P-toluenesulfonic acid, phosphoric acid or acetic acid is preferred, and p-toluenesulfonic acid is more preferred. The base or acid is used in an amount of usually from 0 to 100 moles, preferably from 0.01 to 10 moles per mole of the tetracarboxylic dianhydride [5]. The reaction temperature is not particularly limited and may be, for example, from -9 to 200. (:, preferably -19- 201041848 is _ 3 0 to 1 0 Ot: The reaction time is generally Ο 〇 5 to 2 Ο 0 hours, preferably 〇 · 5 to 〇〇 。 hours. Efficiently, in the tetracarboxylic acid dialkyl ester of the present invention in which the n is 2 in the general formula [1] or [2], the above-mentioned formula Π-a], the formula [2-a] of the specific positional isomer or The method of the compound represented by the formula [2_b]. The compound represented by the formula [1-a] or the formula [2-a] can be obtained by using the following formula [tetracarboxylic dianhydride [5] of the above reaction formula [ 5_a] obtained by the tetracarboxylic dianhydride. [Chem. 15]

(wherein 'R2 is an alkyl group having 1 to 5 carbon atoms). When the reaction temperature at this time is low, the selectivity of the formula [H] can be increased. Therefore, when the reaction yield of the formula Π-a] is to be increased, the reaction temperature is more preferably 10 to 3 ° C. When the reaction yield of the formula [2-a] is further increased, the reaction temperature is more preferably from 50 to 100 °C. Further, when a reaction is carried out by adding a base or an acid, the selectivity of the formula [1-a] and the reaction rate are also improved, and it is more preferable to add an inspective compound. The test or acid used at this time is as described above, preferably the base or acid and preferably added in the same amount as described above. -20- 201041848 [Chem. 16]

The compound represented by the formula [2-b] can be obtained by reacting a tetracarboxylic dianhydride represented by the following formula [5-b] with an alcohol having 1 to 5 carbon atoms (the above-mentioned RhH). [Chem. 17]

[5-b] (wherein R2 is an alkyl group having 1 to 5 carbon atoms). At this time, the addition of a base or an acid to carry out the reaction enhances the selectivity of the formula [2-b] and the reaction rate, and more preferably adds a basic compound. The base or acid used at this time is preferably the same as the above-mentioned ones, preferably a base or an acid, and preferably added in the same amount as described above. [Chem. 18]

£5-b] 〇 〇2p2〇

R1〇H HoXllJ-QH κο1ιιΓ0β1 O 0 [2-b] -21 - 201041848 (wherein R1 is an alkyl group having 1 to 5 carbon atoms, and R2 is a hospital group having 1 to 5 carbon atoms). Further, the present invention is characterized in that it is easy to separate the object of reaction formation. For example, when the compound [5-a] is used as a raw material, the reaction is completed, and the alcohol used is distilled off, and the precipitated crystal is heated and refluxed in an organic solvent, and then cooled, filtered, and the precipitated crystal is washed and dried. A primary crystallization of a high purity product of the formula Π-a] is available. The organic solvent to be used may be toluene, acetonitrile, ethyl acetate, ethyl acetate, η-heptane mixture, ethyl acetate, various alcohol mixtures, acetonitrile, various alcohol mixtures, and the like. Preference is given to acetonitrile, ethyl acetate 'ethyl acetate · various alcohol mixtures, or acetonitrile and various alcohol mixtures. Various alcohols such as methanol, ethanol, propanol, butanol, isopropanol and the like. One crystallization can be upgraded by washing and recrystallization to improve purity. The recrystallization method is, for example, a method in which an organic solvent is added to a single crystal, and after heating, it is ice-cooled, filtered, and dried. The organic solvent to be used may be a mixture of toluene, acetonitrile, ethyl acetate, ethyl acetate, η-heptane, ethyl acetate, various alcohol mixtures, acetonitrile, various alcohol mixtures, and the like. Preferably, it is acetonitrile, ethyl acetate, ethyl acetate, a mixture of various alcohols, or a mixture of acetonitrile and various alcohols. Various alcohols such as methanol, ethanol, propanol, butanol, isopropanol and the like. The amount of the organic solvent used in the production of the primary crystallization is generally 2 to 20 times the amount based on the weight of the raw material for the purpose of producing the desired product in 100% yield. Further, in order to increase the yield, it is preferred to reduce the amount of the organic solvent used, and it is preferred to increase the amount of the organic solvent used in order to obtain a high-purity product. Therefore, it is considered that the yield and purity are preferably 2.5 times to 5 times. -22- 201041848 Further, by washing and recrystallizing to obtain a filtrate at the time of primary crystallization, a high-purity product of the formula [2-a] can be obtained. In other words, after the solvent is distilled off, the precipitated crystal is heated and refluxed in an organic solvent, and after cooling, the precipitated crystal is filtered, washed, and dried to obtain a high-purity product of the formula [2 - a]. Secondary crystallization. The organic solvent to be used may be a mixture of toluene, acetonitrile, ethyl acetate, ethyl acetate, η-heptane, ethyl acetate, various alcohol mixtures, acetonitrile, various alcohol mixtures, and the like. Preferably, it is acetonitrile, ethyl acetate, ethyl acetate, a mixture of various alcohols, or a mixture of acetonitrile and various alcohols. Various alcohols such as methanol, ethanol, propanol, butanol, isopropanol and the like. Secondary crystallization can be further enhanced by washing and recrystallization. The recrystallization method is, for example, a method in which an organic solvent is added to a secondary crystallization, and after heating, it is ice-cooled, filtered, and dried. The organic solvent to be used is, for example, toluene, acetonitrile, ethyl acetate, ethyl acetate, η-heptane, ethyl acetate, various alcohol mixtures, acetonitrile, various alcohol mixtures, and the like. It is preferably acetonitrile, ethyl acetate, ethyl acetate, various alcohol mixtures, or acetonitrile. Various © alcohols such as 'methanol, ethanol, propanol, butanol, isopropanol and the like. The amount of the organic solvent used in the production of the secondary crystallization is generally from 2 times to 20 times the weight of the primary crystallization obtained by subtracting the weight of the primary crystal taken out from the raw material for the purpose of producing the raw material in 100% yield. Times. Further, in order to increase the yield, it is preferred to reduce the amount of the organic solvent used, and it is preferred to increase the amount of the organic solvent used in order to obtain a high purity product. Therefore, it is considered that the yield and the purity are preferably 2.5 times to 5 times. When the compound [5-b] is used as a raw material, the reaction is completed, the alcohol to be used is distilled off, and the precipitated crystal is heated and refluxed in an organic solvent, and after cooling, the crystal precipitated by -23-201041848 is filtered and washed. Drying provides a primary crystallization of a high purity product of the formula [2-b]. The organic solvent to be used may be a mixture of toluene, acetonitrile, ethyl acetate, ethyl acetate, η-heptane, ethyl acetate, various alcohol mixtures, acetonitrile, various alcohol mixtures, and the like. Preferably, it is acetonitrile, ethyl acetate, ethyl acetate, a mixture of various alcohols, or a mixture of acetonitrile and various alcohols. The refining method for another crystallization can be further improved by the washing method and the recrystallization method. The washing method is, for example, a method in which an organic solvent is added to one crystal, and after heating, it is ice-cooled, filtered, and dried. The organic solvent to be used may be a mixture of toluene, acetonitrile, ethyl acetate, ethyl acetate, η-heptane, ethyl acetate, various alcohol mixtures, acetonitrile, various alcohol mixtures, and the like. Preferred are acetonitrile, ethyl acetate, ethyl acetate, various alcohol mixtures, or acetonitrile. Various alcohol mixtures. Various alcohols such as methanol, ethanol, propanol, butanol, isopropanol and the like. The amount of the organic solvent used in the production of such primary crystallization is generally from 2 times to 20 times the amount used in the case of producing the intended product from the raw material in 100% yield. Further, in order to improve the yield, it is preferred to reduce the amount of the organic solvent used, and it is preferred to increase the amount of the organic solvent used in order to obtain a high-purity product. Therefore, the yield and purity are preferably from 2.5 times to 5 times. [Bis(chlorocarbonyl) compound] The bis(chlorocarbonyl) compound of the present invention is a compound represented by the following general formula [3] or [4]. -24- 201041848 [Chem. 19]

(wherein R1 is an alkyl group having 1 to 5 carbon atoms, R2 is an alkyl group having 1 to 5 carbon atoms, and η is 1 to 4). 0 R1 is an alkyl group having 1 to 5 carbon atoms, and specific examples of the alkyl group are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl Base. When the poly(phthalic acid) compound is synthesized from the bis(chlorocarbonyl) compound of the present invention and the ruthenium is used as the polyimide, R2 is preferably a substance having a small carbon number and is easily detached, and more preferably a methyl group. R2 is an alkyl group having 1 to 5 carbon atoms, and specific examples of the alkyl group are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl. Wait. Q η is from 1 to 4, preferably 2. The following is a specific example of the bis(chlorocarbonyl) compound of the present invention when R2 is a methyl group and η is 2, but the bis(chlorocarbonyl) compound of the present invention is not limited thereto. Further, in the following tables, 'al to a4 and bl to b4 are the meanings of the respective positions shown in the following formula [6], and the meanings of the symbols are as follows.

Me : methyl group, Et: ethyl group, Pr-n: n-propyl group, Pr-iso: isopropyl group, Bu-n: n-butyl group, Bu-sec: sec-butyl group, Bu-iso: isobutyl group,

Bu-t: tert-butyl, Pen-n··n-pentyl, 〇Me.methyl, OEt·ethoxy, OPr-n: n-propyl ether, 0Pr-iso: isopropyl ether, 0Bu- n : n-butoxy group, OBu-sec: sec-butoxy group, 〇Bu-iso: isobutoxy group, -25- 201041848 OBu-t ··tert-butoxy group, OPen-n: n-pentyl ether 20]

[Table 3 Compound a a2 a 3 a4 bl b2 b3 b4 (3-1) Cl OMe Cl OMe Me H Me H (3-2) Cl OMe Cl OMe Me HH Me (3-3) Cl OMe Cl OMe H Me H Me \1/ \/ \t/ 4 5 6 CO 33 IX IX 11Jc ccttt EEE ooo

Lx lx 11 _1 —'-•'-' /L· iv /IN t t t E E Eo o o

e e [Μ Μ H

ΘΗ Η M

ΘMeH H

[e eΗ Μ M \—/ \f/ \)/ 7 00 9 °J3-C0 ΤΑ —1 lx ”-''-''.-' 'w /IV (

Opr- -n Cl Opr- -n Me H Me H Opr_ -n Cl Opr- -n Me HH Me Opr- -n Cl Opr- -n H Me H Me (3-10) Cl OPr —iso Cl OPr —iso Me H Me H (311) Cl OPr — iso Cl OPr —iso Me HH Me (3-12) Cl OPr —iso Cl OPr —iso H Me H Me (3-13) Cl OBu — n Cl OBu- -n Me H Me H (3-14) 01 OBu— li Cl OBu- _ n Me HH Me (3-15) Cl OBu— n Cl OBu- -n H Me H Me (3-16) Cl OBu ~ sec Cl OBu - ,sec Me H Me H (3 17) Cl OBu — sec Cl OBu 1-sec Me HH Me (3 18) Cl OBu — sec Cl OBu- -sec H Me H Me (3-19) Cl OBu - -iso Cl OBu — iso Me H Me H (3-20) Cl OBu - -iso Cl OBu — iso Me HH Me (3-21) Cl OBu - -iso Cl OBu — iso H Me H Me (3-22) Cl OBu— t Cl OB n — t Me H Me H (3-23) Cl OB u — t Cl OB u — t Me HH Me (3-24) Cl OBu— t Cl OB ii — t H Me H Me (3-25 Cl Open- n Cl Open — n Me H Me H (3-26) Cl Open — n Cl Open— n Me HH Me (3-27) Cl Open— n Cl Open — n H Me H Me -26- 201041848 [Table 4] Compound a a2 a 3 a4 ΓΤΐ b2 b3~ b4 \»/ N—/ \)/ 123 4·4·4· T1 11 11 -1Γ .-- f- '/ V / f \ (

OMe OMe Cl Me H Me H OMe OMe Cl Me H H Me OMe OMe Cl Me Me H

(4-4) Cl OEt OEt Cl Me H Me H (4-5) Cl OEt. OEt Cl Me H H Me (4-6) Cl OEt OEt Cl H Me Me H

(4-7) Cl OPr — n OPr—n Cl Me H Me H (4-8) Cl OPr —n OPr-n Cl Me H H Me (4-9) Cl OPr—n OPr-n Cl Me Me H

(4-10) Cl OPr-iso OPr-iso Cl Me H Me H (4-11) Cl OPr-iso OPr —iso Cl Me H H Me (4-12) Cl OPr — iso OPr —iso Cl H Me Me H

(4-22) Cl OBu— t OBu —t Cl Me H Me H (4-23) Cl OBu—t OBu — t Cl Me HH Me (4-24) Cl OBu— t. OBu —t G1 H Me Me H (4·2δ) (4-26) (4-27)

Further, a compound wherein η is 2 and R 2 is an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group or n-pentyl group, such as bl to b4 in the above table A compound in which each of Me is substituted with Et, Pr-n, Pr-iso, Bu-n, Bu-sec, Bu-iso, Bu-t or Pen-n. The bis(chlorocarbonyl) compound of the present invention is easy to obtain a dialkyl tetracarboxylate for use as a raw material and has a high yield, particularly preferably the following formula [3-a], [4-a] or Μ-ΐ? The compound represented. □

\—/ \—/ \—/ 3 4 5 111· 44-4 ./V /l\ /V IX 11 11 Γ-r .-'Γ-' ( /1.

OBu — n OBu- -n Cl Me H Me H OBu— n OBu- -n Cl Me H H Me OBu— n OBu- -n Cl H Me Me H 6 7 8 111 4 4 4 /IN /(, /1.

Cl OBu — sec OBu — sec Cl Me H Me H Cl OBu — sec OBu — sec Cl Me H H Me Cl OBu — sec OBu — sec Cl H Me Me H (4 19) (4-20) (4-21)

OBu-iso OBu-iso Cl Me H Me H OBu — iso OBu — iso Cl Me H H Me OBu — iso OBu- iso Cl H Me Me H ΊΛ lx r .-1-1-'r ^ i, rv c.

Open-n Open — n Cl Me H Me H Open—n Open —n Cl Me H H Me Open—n Open —n Cl H Me Me H -27- 201041848 [Chem. 21]

Rl〇Tl[rOR1 ο ο [4-b] (wherein R1 is an alkyl group having 1 to 5 carbon atoms, and R2 is a hospital group having 1 to 5 carbon atoms). Further, by using a polymer of a high purity product of the formula [3-a], a polymer having a molecular weight higher than that of a high purity product of the formula [4-a] or a mixture of the formula [3-a] and the formula [4-a] can be obtained. The polymer which is high and low-dispersed is therefore preferably a compound represented by the formula [3 a] in terms of producing a polymer having a high molecular weight and a low dispersion. The bis(chlorocarbonyl) compound [3] or the compound [4] of the present invention can be obtained by chlorinating a dialkyl tetracarboxylate represented by the formula [2] or the formula [2] as shown in the following reaction formula. [1k22]

[3]

(wherein R1 is an alkyl group having 1 to 5 carbon atoms, R2 is an alkyl group having 1 to 5-28 to 201041848, and η is 1 to 4). The substitution position of R2 in the above formula [3] and formula [4] is the same as the substitution position of the corresponding formula [1] and formula [2]. That is, the 'bis(chlorocarbonyl) compound [3-a] can be obtained by chlorinating the aforementioned tetracarboxylic acid dialkyl ester Π-a], and likewise the compound [4-a] can be obtained by the compound [2_a] ] Chlorination, the compound [4-b] can be obtained by chlorinating the compound [2-b]. The chlorinating agent used in the above reaction is, for example, thionyl chloride, chlorinated ruthenium chloride, phosgene, chlorine, phosphorus oxychloride, phosphorus pentachloride, ruthenium N-chlorosuccinate or the like. Preferred are sulfinium chloride, chlorpyrifos chloride, phosgene, chlorine, oxyphosphorus chloride or phosphorus pentachloride. More preferably, it is sulfite, chlorpyrifos chloride or phosgene. The chlorinating agent is usually used in an amount of from 2 to 1 mole per mole, preferably from 2 to 30 moles, more preferably from 2 to 3 moles per mole of the dialkyl tetracarboxylate. The above reaction can be carried out in a chlorinating agent such as sulfinium chloride, but a solvent can be used as necessary. The solvent may be one in which the reaction is inactive, and is not particularly limited.

D ' may be, for example, a hydrocarbon-based chloroform such as hexane, heptane or toluene, a halogenated hydrocarbon such as 1>2-dichloroethane or chlorobenzene, diethyl ether or hydrazine, 4-dioxane, or the like. An ester such as an ether or ethyl acetate; a ketone such as acetone or methyl ethyl ketone; a nitrile such as acetonitrile or propionitrile; and a mixture thereof. It is preferably hexane, heptane or toluene. More preferably, it is hexane or heptane. Further, the above reaction can be carried out without a catalyst, but the addition of a catalyst can reduce the amount of the chlorinating agent used and carry out the reaction rapidly. Specific examples of the catalyst include, for example, triethylamine, pyridine, quinoline, N,N-dimethylaniline, N,N-dimethylformamide, and the like, and sodium methoxide, potassium methoxide or potassium. T_butyl oxide, etc. • 29- 201041848 Metal alkoxides, but are not limited thereto. Preferred is triethylamine, pyridine or N,N-dimethylformamide, more preferably pyridine. These catalysts are generally used in an amount of from 100 to 100 moles, preferably from 0.01 to 10 moles per mole of the dialkyl tetracarboxylate. The reaction temperature is not particularly limited and is usually -90 to 200 ° C, preferably -30 to 100 ° C, more preferably 50 to 80 ° C. The reaction time is usually 〇 · 〇 5 to 200 hours, preferably 0.5 to 100 hours, more preferably 0.5 to 5 hours. Further, the bis(chlorocarbonyl) compound obtained above can be, for example, subjected to the following purification. After the completion of the reaction, the remaining chlorinating agent was distilled off, and a certain amount of a solvent was added thereto, followed by heating and stirring. Thereafter, the precipitated crystals were taken out after cooling, washed, and dried to obtain a primary crystal of the desired product. Further, in the case of the above heating and stirring, after insoluble crystallization, if necessary, the insoluble matter can be filtered by hot filtration, and thereafter, the same operation can be carried out to obtain a higher purity target. When the chlorinating agent is more easily distilled than the solvent to be used, a certain amount of residual chlorinating agent and solvent may be distilled off after the reaction is completed, and the residual liquid is heated to dissolve or stir the crystal, and then cooled and then filtered. The precipitated crystals are washed and dried to obtain a primary crystal of the object. The temperature at which the solvent is distilled off, and when heated and dissolved or heated and stirred is, for example, 30 to 1 ° C, preferably 30 to 50 ° C. The organic solvent to be used may be a mixture of toluene, acetonitrile, ethyl acetate, η-hexane, n-heptane or ethyl acetate·η-heptane, a mixture of ethyl acetate, η_house, and the like. Preferably, it is a mixture of η-hexan or η_Gengyuan, ethyl acetate·η-hexane, or a mixture of ethyl acetate·η-heptane. Further, the crystallization may be further purified by a washing method and a recrystallization method -30-201041848. For the recrystallization method, for example, a mixed liquid of toluene, acetonitrile, ethyl acetate, η-hexane, η-heptane or ethyl acetate·n-heptane, and a mixture of ethyl acetate and η-hexane are added to the primary crystal. After heating and dissolving the crystal, it is ice-cooled, filtered and dried to obtain a high-purity product. In still another treatment, after the reaction is completed, the remaining chlorinating agent is distilled off, and the residue is distilled to obtain the desired product. Further, a single stereoisomer of high purity ruthenium [1] obtained by purifying a dialkyl carboxylic acid for use as a raw material is subjected to a chlorination reaction, and after completion of the reaction, a higher purity compound can be obtained in a high yield [ 3]. Similarly, a high-purity single stereoisomer [2] can be used to obtain a high-purity compound in high yield [4]. The dicarboxylic acid dialkyl ester or bis(chlorocarbonyl) compound of the present invention obtained above can be used as a monomer raw material of polyamine, polyimine or polyester. For example, a polyfluorene can be synthesized by polycondensation of a dialkyl tetracarboxylate of the present invention and various diamine compounds in the presence of a condensing agent, or by reacting a bis(chlorocarbonyl) compound of the present invention with various diamine compounds. amine. If necessary, the catalyst is added to the polyamines. After heating, the polyimide can be synthesized. Further, the above diamine compound may be substituted with a variety of diol compounds to synthesize a polyester. As described above, the compounds of the present invention can provide a polyimine, a polyamine or a polyester having an alkyl group on a cyclobutane ring suitable for a material or the like. [Liquid Crystal Aligning Agent] A liquid crystal alignment film obtained by photo-alignment method of anisotropic photodecomposition reaction of polyimine which is generated by radiation of polarized light, and generally obtained by rubbing with a film of -31 - 201041848 It can reduce the alignment with respect to the polymer chain. It is inferred that the amount of aggregation can be reduced by the photodecomposition reaction, and the low molecular weight component is mostly present in the alignment direction. The polyimine precursor used in the alignment direction is imidized with the diamine and the acid. The dianhydride undergoes a reverse reaction. The molecular weight of the polyimine is lower than that of the original polyamine. To reduce the molecular weight and anisotropy. Further, the poly-proline of acid II can be randomly present in the following four types of structures in which the bonding sites of the guanamine bond are different in the following formulas (A), (B), and (wherein, the structure is randomly present. When the ring of proline is coated, polyimine can be formed, but the polyamines of the above four structures are present when the imidization is not completely ruthenium, so the order is lowered, and the order of the polymer chain is lowered. The interaction between the stereotypes and the celestial bodies is such that high order cannot be obtained. Therefore, it is concluded that the bonding position of the guanamine groups in the poly-proline is less relative to the orientation direction of the obtained polyimide film. -JLILB- I [(A) p-H〇s~VS~ _Sir〇_ direction other than the molecule of the isotropic imine. The calcination is carried out, and the resulting calcination is obtained as an anhydride and a diamine: (D) is made by (D), and the molecular chain film is dehydrated and closed, which will leave the rank rejection of the random polymer chain and reduce the poly-polyimine film when it is random, which will reduce the heterogeneity. (B) 32- 201041848 [Chem. 24]

-Η1ΤΗ- <c, H〇rrOH After intensive research by the present inventors, it was found that by using a polymer chain which is highly ordered and which does not lower the molecular weight of the polyimide precursor when calcined, even The above photo-alignment method can also obtain a polyimide film having high anisotropy with respect to the alignment direction. Specifically, a highly ordered polyglycolate obtained by controlling a highly symmetrical acid chloride and a diamine obtained by controlling a position of a chlorocarbonyl group and an ester group on a cyclobutane ring is used as a liquid crystal alignment. In the case of the above-mentioned photo-alignment method, a polyimide film having a high anisotropy with respect to the alignment treatment direction can be obtained, and the present invention has been completed based on this finding. [Acid Chloride] The acid chloride of the chlorocarbonyl group and the 2,4-bonded ester group at the 1,3 position of the cyclobutane ring used in the present invention is represented by the following formula (101). [Chem. 25]

(101)

Ri

(wherein R! is an alkyl group having 1 to 5 carbon atoms, and R2, R3, R4, R5-33-201041848 are a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, which may be the same or different) In the acid chloride represented by (101), I is an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl 'isobutyl group, a t-butyl group, a n-pentyl group and the like. Generally, the polyacids of the female acid 曰 曰 fei fei 商 于 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基Therefore, the viewpoint of imidization by heat is preferably a methyl group or an ethyl group, and particularly preferably a methyl group. In the acid chloride represented by the formula (1 01 ), R2, R3, r4 and R5 are a hydrogen atom and a monovalent hydrocarbon group having 1 to 30 carbon atoms, which may be the same or different. a monovalent hydrocarbon group such as an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group or a decyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; a bicyclic ring such as a dicyclohexyl group; Alkyl; vinyl, 1-propenyl, 2-propenyl, isopropenyl, fluorenyl-methyl-2-propenyl, 1 or 2 or 3-butenyl, hexenyl and the like; An aryl group such as a benzyl group, a xylyl group, a tolyl group, a biphenyl group or a naphthyl group; an aralkyl group such as a benzyl group or a phenylcyclohexyl group; and the like. Further, some or all of the hydrogen atoms of the monovalent hydrocarbon group may be a halogen atom, a diester group, an ester group, a thioester group, a decylamino group, a nitro group, an organic oxy group, an organic decyl group, an organic thio group, a fluorenyl group. Substituted by alkyl, cycloalkyl, bicycloalkyl, alkenyl, aryl, aralkyl, and the like. From the viewpoint of liquid crystal alignment, R2, R3, R4 and Rs are preferably a substituent having a small steric hindrance, and particularly preferably a hydrogen atom or a methyl group. Further, in order to obtain a liquid crystal alignment film having high anisotropy with respect to the alignment direction, R2, R3, and Rs are preferably all the same substituents, or R2, R4 and R3, and Rs are the same substituents of -34-201041848. . Specific examples of the three-dimensional arrangement of R2, R3, R4, R5, chlorocarbonyl and ester groups are as shown in the following formulas (106) to (121). [Chem. 26]

0 0

(108) [Chem. 27]

-35- 201041848 [化30]

In the above, the high degree of symmetry of the acid chloride is obtained, and the high-order polyphthalate is obtained, and the linearity of the polymer chain is high, and the high-order polymer film can be formed by lowering the imidization. The formulas (106), (i 〇7), (1 〇8), and (1 0 9 ) having a liquid crystal alignment film having a high anisotropy with respect to the alignment direction are particularly preferable. The specific structure of the acid chloride when one or more of R2, R3, R4 and r5 in the formula (101) is a hydrogen atom is as described in the following formulae (I22) to (129). [化31]

-36- (129) 201041848 [Chem. 33]

a-ORj

Preferably, the symmetry of the acid chloride is high to obtain a high-order polyphthalate, and the linearity of the polymer chain is high, which lowers the oxime imidization rate and forms a high order. The polymer film is obtained by the formula (I26) or (I27) having a liquid crystal alignment film having a high anisotropy. Further, it is particularly preferable that the chlorocarbonyl group and the R2 or R.4 ring are substituted for the same carbon of the cyclobutane ring, and the heterogeneity from heat can be suppressed, and the symmetry of the monomer or the polymer is not dispelled even at a high temperature. (126). Further, when R2, R3, R4 and Rs are the same substituent, the symmetry of the acid chloride can be improved, and the following formula (1 0 2 ) of the high-order polycarbamate is preferred. 〇 [Chem. 34] JL (102) 11,0 π β^Γα ο ο In the formula (102), Rl is the carbon number! To the alkyl group of 4, r6 is a hydrocarbon group of carbon number i to 30%. The indole hydrocarbon group is, for example, the same structure as that listed in ι and R5. -37- 201041848 The specific example of the acid chloride represented by the above formula (1 〇 1 ) is particularly preferably the formula (103) or (104). [化35]

J L ci—χ~~〇Κχ

Ri〇nifrcl ο ο

Cl-4sf|--0R1 (104) Ο Ο The acid chloride of the formula (ιοί) can be synthesized by a two-stage reaction of esterification of a tetracarboxylic dianhydride and chlorination of a carboxylic acid by the following.

The esterification reaction in the first stage can be carried out by reacting a tetracarboxylic dianhydride with an alcohol represented by R, ο 。 . The reaction temperature may be, for example, _ 9 Torr to 200 ° C, preferably -3 0 to 1 〇 〇 °C. The reaction time may be, for example, from 5 to 2,000 hours, preferably from 0.5 to 1,000 hours. The alcohol used in the reaction may be, for example, 2 to 100 moles, more preferably 2 to 4 moles, more preferably 2 to 20 moles, per mole of the tetracarboxylic acid -38 to 201041848 dianhydride. After the above esterification reaction, many of the isomers having a majority of ester groups other than the 2,4 position are contained. Therefore, in order to obtain the acid chloride used in the present invention, it is preferred to refine the ester of the ester group at the 2,4 position. Things. The purification method is, for example, various refining methods such as recrystallization and column chromatography, but it is preferably purified by a recrystallization method in terms of ease of handling. The recrystallization solvent may be a combination of various organic solvents. Ο The second stage chlorination reaction can be carried out by reacting the above-obtained ester with a chlorinating agent in the presence of an organic solvent. The reaction temperature may be, for example, -90 to 200 ° C, preferably -30 to 100 ° C, more preferably 50 to 80 ° C. The reaction time may be, for example, 0.5 to 200 hours, preferably 0.5 to 100 hours, more preferably 0.5 to 5 hours. The chlorinating agent used in the reaction may be, for example, 2 to 100 moles, preferably 2 to 30 moles, more preferably 2 to 3 moles, per mole of the ester. The chlorinating agent is, for example, thionyl chloride, chlorpyrifos chloride, phosgene, chlorine, oxonium W-based phosphorus chloride, phosphorus pentachloride, bismuth N-chlorosuccinate or the like. The reaction solvent may be any one which is inactive to the reaction, and examples thereof include hydrocarbons such as hexane, heptane or toluene, halogenated hydrocarbons such as chloroform, 1,2-dichloroethane or chlorobenzene, and diethyl ether. An ether such as an ether or 1,4-dioxane, an ester such as ethyl acetate, a ketone such as acetone or methyl ethyl group, a nitrile such as acetonitrile or propionitrile, or a mixture thereof. The above chlorination reaction can be carried out without a catalyst, but the addition of a catalyst can reduce the amount of the chlorinating agent used and accelerate the reaction. Catalysts such as triethylamine, pyridine, quinoline, hydrazine, hydrazine-dimethylaniline, N,N-dimethylformamide, etc. -39- 201041848 Organic bases, and sodium methoxide, potassium methoxide Or metal alkoxides such as potassium t-butoxide. These catalysts may be used in an amount of, for example, 0 to 100 moles, preferably 0.01 to 10 moles per mole of the ester. When the purity of the acid chloride is high, the molecular weight of the obtained polyphthalate is increased, so that the chlorination reaction is preferably followed by the purification reaction product. The refining method is, for example, recrystallization, and the recrystallization solvent may be an organic solvent which does not react with the acid chloride, and is not particularly limited. [Polyurethane] The polyphthalate used in the liquid crystal alignment agent of the present invention is a bis(chlorocarbonyl) compound having an acid chloride represented by the above formula (101) containing an essential component and reacting with a diamine. And what you get. The bis(chlorocarbonyl) compound used in the reaction may be mixed with an acid chloride other than the one represented by the formula (1 0 1 ), such as cyclobutane. The 1, 4-position bonded chlorocarbonyl group, the 2, 3-position bonded alkane The acid chloride of the ester group, but the acid chloride represented by the formula (1 0 1 ) is preferably 60 mol% or more. The acid chloride represented by the formula (1 〇 1 ) is preferably 8 〇 mol% or more in terms of making the obtained polyphthalate ester more highly ordered and further improving the anisotropy with respect to the alignment treatment direction. More preferably, it is 9 5 to 1 0 0% by mole. The diamine which is reacted with the bis(chlorocarbonyl) compound is a diamine represented by the following formula (130). [Chem. 3 7] H2N-X-NH2 (30) (X is a divalent organic group). -40 - 201041848 The following is a specific example of the configuration of X in the formula (130), but the present invention is not limited thereto. [化38]

〇 [Chem. 39] CH, CH,

:H3 (A-16) (A-17) (A-18)

(A-19) CH2

(A-20) 〇 (A-21) (A-22) (A-23) (A-24) 201041848 [Chem. 40] 8:

(A-26) (A-27)

(A-28) H (A-25) {A-29) (A-30) (A-31) (A-32) [Chem. 41] o o (A43) (A-34) (A-35)

(A-36) O H3CCH3 F3CCF3 F3CCF3H3〇x^CH39C6 (A-37) (A-38) (A-39) (a3〇) [Chem. 42]

-42- 201041848 - (CH2)2-C-(CH2)5- Η ch3 <jh3 ch3 I(CH2)2~C-(CH2)2—(CH2)4*<i_( CH2)3-CH3 CH3 (A-53) (A-54) (A-55) ?h3 ch3 ch3 ch3 -CH2-C-(CH2)2-C-(CH2)2- -CH2-C~(CH2 )2-C-(CH2)3-(A-56) (A-57) ch3 —(CH2)4-C-(CH2)5—(CH2)3-〇-(CH2)2—〇-( CH2) 3—

(A-58) (A-59) [Chem. 44]

[化45]

43- 201041848 -〇-(〇Η2)η-〇Η ^iloj^o"(CH2)"〇X^j0x n=3~5 n=2~5 n=2-5

n=2^5 (A-73) p-(CH2)nQ' n=2~5 (A-74) n=2~5 (A-75) V〇r In the method for producing a liquid crystal alignment film of the present invention When an aromatic ring is present in the diamine compound, the aromatic ring is a light absorbing site, which promotes a cracking reaction of the cyclobutane ring. Therefore, from the viewpoint of photoreaction efficiency, the diamine compound is preferably an aromatic diamine. Moreover, the linearity of the molecular chain of the polyimine formed by the ruthenium imidization can improve the liquid crystal alignment property. Therefore, it is particularly preferable to be 'A_7' A-ll, A-12 'A-13, A-14. , A-20, A-22, A-23, A-24, A-26, A-27 'A-28, A-30 'A-42, A-43, A-44, A-45 A- 46. A-48, A-63, A-69, A-71, A-72, A-73, A- 7 4 or A-75. [Synthetic Polyurethane] The polyglycolate can be used in the presence of a base and an organic solvent at from -20 ° C to 150 ° C, preferably hydrazine. <: to 50T: The diamine is reacted with a bis(chlorine) compound for 30 minutes to 24 hours', preferably 1 to 4 hours. As the base, pyridine, triethylamine, 4-dimethylaminopyridine or the like can be used, but in order to carry out the reaction stably, it is preferably a ratio of D to D. When the amount of addition is too large, -44 - 201041848 will be difficult to remove, and if it is too small, the molecular weight will be reduced, so it is preferably 2 to 4 times moles relative to the bis(chlorocarbonyl) compound. The solvent for the synthesis of the polyphthalate ester is preferably N-methyl-2-pyrrolidone or γ-butyrolactone, and may be used alone or in combination of two or more. When the concentration at the time of synthesis is too high, the polymer is easily precipitated, and when it is too low, the molecular weight cannot be increased, so it is preferably from 1 to 30% by weight, more preferably from 5 to 20% by weight. Further, in order to prevent the bis(chlorocarbonyl) compound from being hydrated, the solvent for synthesizing the polyphthalate can be dehydrated as much as possible, and the outside air can be prevented from being mixed in the nitrogen atmosphere. The polyaurethane solution obtained above is thoroughly stirred while being injected into a weak solvent to precipitate a polymer. After several precipitations, it is washed with a weak solvent and dried at room temperature or by heating to obtain a purified polyphthalate powder. The weak solvent is not particularly limited and may be water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene or the like. 〇 ^ [Molecular weight of polyglycolate] The ratio of the diamine component to the bis(chlorocarbonyl) compound for the polymerization reaction is preferably from a viewpoint of controlling the molecular weight, and the molar ratio is from 1.0/0.5 to 1.0. When the molar ratio is close to 1:1, the molecular weight of the obtained polymer can be increased. The molecular weight of the polymer affects the viscosity of the liquid crystal alignment agent and the physical strength of the liquid crystal alignment film. When the molecular weight of the polymer is too large, the coating workability and uniformity of the liquid crystal alignment agent are deteriorated, and when the molecular weight is too small, The strength of the coating film obtained by the liquid crystal alignment agent will be insufficient. Therefore, the polymer used in the liquid crystal alignment agent of the present invention preferably has a molecular weight of from 2,000 to 500,000, more preferably from 5,000 to 300,000, more preferably from 10,000 to 1,000,000. [Liquid crystal alignment agent] The liquid crystal alignment agent of the present invention is obtained by uniformly dissolving the polymer obtained above in an organic solvent to form a coating liquid for a liquid crystal alignment agent. The solvent used in the liquid crystal alignment agent of the present invention may be one which is capable of dissolving the polymer contained in the liquid crystal alignment agent, and is specifically, for example, ruthenium, osmium-dimethylformamide, ruthenium, osmium-diethyl Formamide, hydrazine, hydrazine-dimethylacetamide, hydrazine-methyl-2-pyrrolidone, hydrazine-methyl caprolactam, 2-pyrrolidone, hydrazine-ethylpyrrolidone, hydrazine-vinyl Pyrrolidone, dimethyl hydrazine, dimethyl mill, hexamethyl yam, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-indole, Ν-dimethyl Propane guanamine and the like. These may be used alone or in combination of two or more. In the range where the polymer is not precipitated, it is possible to mix a solvent which does not dissolve the polymer when used alone. Further, a solvent for improving the uniformity of the coating film when the liquid crystal alignment agent is applied to the substrate can be added. The solvent is, for example, ethyl cellosolve, butyl cellosolve, hexyl cellosolve, ethyl cellosolve acetate, butyl cellosolve acetate, ethyl carbitol, butyl carbitol, ethyl card Alcohol acetate, butyl carbitol acetate, ethylene glycol 'diethylene glycol diethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol -1-monoethyl ether-2-acetate, dipropylene glycol, dipropylene glycol monomethyl ether, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, lactic acid II-propyl ester, η-butyl lactate, isoamyl lactate-46-〇201041848 ester, and the like. These solvents may be used in combination of two or more kinds. The polymer concentration of the liquid crystal alignment agent of the present invention can be appropriately changed depending on the film thickness of the liquid crystal alignment film of the prior art, but it is preferably 1 to 1 Å]. When it is less than 1% by weight, it is difficult to form a uniform and defect-free coating film. When it is %, the preservation stability of the solution is deteriorated. The liquid crystal alignment agent of the present invention may be added with an additive such as a decane coupling agent in order to improve the compatibility with respect to the substrate. The above-mentioned decane coupling is known to be unknown, and the type thereof is not limited. When the coupling agent is added, it reacts with the polymer after heating, and the influence on the properties of the liquid crystal alignment agent can be suppressed. It can be reacted at 20 ° C to 80 ° C, preferably 40 ° C to 60 ° C. When the amount of the decane coupling agent added is too large, the unreacted material may exhibit an effect of adhesion when the orientation is too small. Therefore, the compound powder is preferably 〇1 to 5.0% by weight, more preferably 0.1. 5% by weight The liquid crystal alignment agent of the present invention may additionally use various additives such as a crosslinking agent and a hydrazine. Further, the liquid crystal alignment agent of the present invention contains two or more kinds, and at least one of them is a polyglycine of the present invention. The polymer type of the polymer is not limited. [Method for Producing Liquid Crystal Aligning Agent] The liquid crystal alignment agent of the present invention can be produced by the following method. The polyphthalate powder was dissolved in the above solvent to obtain a % by mass. The weight of the 10 weight film can be increased after the addition of [24 hours of liquid crystal for the poly 1.0 heavy chemical promoted, and its amine ester -47- 201041848 solution. The polymer concentration at this time is preferably from 1 〇 to 30%, particularly 15 %. It can be heated when the polyphthalate powder is dissolved. Heating from 20 ° C to 15 (TC, particularly preferably 2 (TC to 80 ° C. The concentration of the obtained polyamidomate solution is diluted with the solvent described above to obtain the liquid crystal alignment agent of the present invention. Adding a decane coupling agent In the case of the crosslinking agent, in order to prevent the addition of the imidization accelerator before the addition of the solvent having low solubility to the polymer, it is added after the ruthenium imidization step by heating. [Production of Liquid Crystal Alignment Film The liquid crystal alignment agent of the present invention is filtered, applied to a substrate, and fired to form a coating film, and then the coating film surface alignment film is treated by alignment treatment. The coating method of the liquid crystal alignment agent is, for example, a spin coating method. print

The drying and calcination steps of Avfr Temple 0 after coating the liquid crystal alignment agent and the time and time. For example, in order to sufficiently remove the liquid crystal alignment agent, it can be dried at 50 ° C to 120 ° C for 1 minute to 10 minutes, and its father 3 〇〇 t is baked for 5 minutes to 120 minutes. When the thickness of the coating film after baking is too thick, it will be disadvantageous for the power consuming surface of the liquid crystal. When it is too thin, the reliability of the liquid crystal display element is preferably 5 to 300 nm, more preferably 10 to 200 nm. For the treatment of the coating film, for example, the rubbing method and the photo-matching are preferably 10 to a temperature at which the polymer is preferably a certain amount of the polymer. Adding hydrazine is preferably diluted, and then drying, and the liquid crystal method and the inkjet method can be used with any warm organic solvent at 150 ° C to show the extinction of the component, so the comparative treatment method is -48-201041848, Further, the liquid crystal alignment agent of the present invention is particularly suitable for use in a photo-alignment treatment method, for example, a radiation having a biased direction is irradiated onto the surface of the coating film by a certain direction, and may be further 150 to 25 depending on the case. 0 °c A method of imparting heat treatment to a liquid crystal alignment energy. The radiation used may be ultraviolet light having a wavelength of from 100 nm to 800 nm and visible light. Among them, ultraviolet rays having a wavelength of from 10 nm to 4 Å Onm are preferable, and those having a wavelength of from 200 nm to 400 nm are particularly preferable. Further, in order to improve the liquid crystal alignment, the coated substrate can be heated at 50 to 250°, and the radiation can be irradiated. The irradiation amount of the above-mentioned radiation is preferably from 1 to 10 Torr, 〇〇〇mJ/cm2, particularly preferably from 1 Torr to 5,000 mJ/cm2. According to the liquid crystal alignment film produced as described above, the liquid crystal molecules can be stably aligned in a certain direction. [Embodiment] The present invention will now be described in more detail by way of examples, but the invention is not limited thereto. <Example 1 > Synthesis of dialkyl tetracarboxylate under neutral conditions at 65 ° C [Chem. 47]

(5-1) -49- 201041848 1,3 -Dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride (compound of formula (5-1), hereinafter referred to as i , 3-DM-CBDA) 220g (0-98 lmol), and 2200g of methanol (6.87mol, 10wt times relative to 1,3-DM-CBDA) were placed in a 3L four-necked flask and heated at 65 ° C for reflux After 30 minutes, a homogeneous solution was obtained. The reaction solution was directly heated to reflux for 4 hours and 30 minutes while stirring. The reaction liquid is measured by high-speed liquid chromatography (hereinafter abbreviated as HPLC), and the measurement results are as described later. After distilling off the solvent from the reaction mixture using an evaporator, ethyl acetate 1 3 0 1 g was added and heated to 80 ° C, and refluxed for 30 minutes. Next, the internal temperature was cooled to 25 ° C at a rate of 2 to 3 ° C in 10 minutes, and stirred at 25 ° C for 30 minutes. The white crystals which precipitated were taken out by filtration, and the crystals were washed twice with ethyl acetate (1, 4 g), and then dried under reduced pressure to give white crystals of 3.97 g. The crystal was analyzed by 1 H NMR analysis and X-ray crystal structure, and as a result, compound (1-1) (yield area: 97.5%) was obtained (yield 3 6.8%). 1 H NMR (DMSO-d6, 5 ppm): 1 2.8 2 (s, 2 Η), 3.6 0 (s, 6 Η), 3.39 (s, 2 Η), 1.40 (s, 6 Η). Hereinafter, the compound (1-1) of 2,4-bis(methoxycarbonyl)-1,3-dimethylcyclobutane-1,3-dicarboxylic acid is simply referred to as id-DM-CBDE. Further, the furnace liquid obtained by taking out the above white crystals from the evaporator was saturated with a solvent to obtain white crystals of 17.2 2.2 g. Acetonitrile 3 8 5.0 9 g was added to the white crystal 1 5 6.0 1 g, and heated to 6 5 to completely dissolve the crystal. Next, it was cooled to 30 ° C in 1 hour, and then cooled to 2 5 ° C in 2 hours. After stirring for 30 minutes at 25 ° C -50-201041848, the precipitated white crystals were taken out by filtration, and the crystals were washed with acetonitrile (3. 7 g). After drying under reduced pressure, 52.74 g of white crystals were obtained. The crystal was analyzed by 1 H NMR analysis and X-ray crystal structure, and the compound (2-1) (HPLC relative area: 99.2%) (yield 2 0.6%) was confirmed. 1 H NMR (DMS0-d6, 8 ppm): 1 2 · 8 2 (s, 2 Η), 3 · 6 Ο ( s, 6 Η), 3.48 (s, 1 Η), 3.30 (s, 1 Η), 1.45 ( s, 3Η), 1.38 (s, 3Η). 〇 The compound (1 -1 ), the compound (2-1), and the like obtained as described above are used as a standard, and the ratio of the result of the HPLC measurement data at the time of completion of the reaction to the compound (1-1) of the entire reaction product is 'The relative area of HPLC is 50%, and the compound (2 -1 ) is 47%. Further, in the filtrate obtained by crystallizing the compound (1 -1 ) from the reaction liquid, the ratio of the compound (1-1) was 21% in the HPLC relative area, and the compound (2-1) was 74%. [X-ray crystal structure analysis] 装置 Device: DIP2030 (manufactured by MacScience) X-ray: Moka (40kV, 200mA)

Measurement temperature: 298. OK The sample for measurement was a single crystal prepared by dissolving the obtained compound in & The analysis result of the single crystal X-ray measurement of the compound (1-1) is shown in Fig. 1. Crystallographic data formula c12h16o8 -51 - 201041848 Molecular weight 288.252 Hue, shape colorless, block Crystal Monoclinic space group P2!/c Lattice constant a=8.3460(10)A, b=8.256(2) person, c=10.630(2) A α = 90.00°, β = 1 09.73 8 ( 1 0)°, γ = 90.00° V = 68 9.4(3 ) A3 Z値=2 R(gt) = 0.1 1 1 wR(gt) = 0.548 Compound (2 - 1) The analysis result of the single crystal X-ray measurement is shown in Figure 2.

Crystallization data formula C, 2 Η 1 6 〇8 Molecular weight 2 8 8.252 Hue shape colorless, cube crystal system tri clinic space group P-1 lattice constant a = 7.422(2)A, b=8.0390(10)A, c= 12.232(2)A α=106·05 5 ( 1 0)°, β = 9 9 · 0 1 8 (1 0) °, γ = 1 0 3 · 5 3 7 ( 1 0 ) V = 662.4 ( 2 ) A3 Z値2 2 R(gt) = 0.06 wR(gt) = 0.07 -52- 201041848 <Example 2> Synthesis of dialkyl tetracarboxylate under neutral conditions at 20 ° C under nitrogen flow DM-CBDA 10 g (0.045 mol) 50 g (1 - 56 mol, 5 wt. 1,3-DM-CBDA) was added to a four-necked flask, and after stirring at 14 to 2 Torr for 69 hours, a solution was obtained. The reaction liquid was analyzed by HP LC, and as a result, the relative area of the compound (HPLC) was 56%, and the HPLC phase of the compound (2-1) was 44%. After the solvent was distilled off from the reaction liquid using an evaporator, 60 g of B was added and heated to 80. After refluxing for 30 minutes at ° C. Next, the internal temperature was cooled to 25 ° C at a rate of 10 minutes to 3 ° C, and stirred at 25 ° C for 30 minutes. The precipitated white crystals were removed by filtration, and then 6.43 g of ethyl acetate. The mixture was dried under reduced pressure to give white crystals (yield: 550 g). The crystals were subjected to 1H NMR analysis and X-ray crystal structure to confirm compound (1-1) (HPLC relative area: 99.0%) 4 5.7%). <Example 3> Synthesis of dialkyl tetracarboxylate under neutral conditions at 40 ° C under nitrogen conditions, 1,3-DM-CBDA 10 g (0.045 mol) 50 g (1 - 56 mol, for 1,3-DM-CBDA The mixture was placed in a four-necked flask at 5 wt., and stirred at 40 ° C for 7 hours and 30 minutes to obtain a reaction solution. The reaction liquid was analyzed by HPLC, and as a result, the relative area of the compound (] Η PLC was 48%, the compound (2 - 1 ) was 45% in the PLC phase, and the methanol 200 mL was evenly reversed -1) in the area of the acid ethyl ester. Take 2 minutes. Washing 2, the ratio of the yield (yield and methanol of 2000 m L -1) to the area -53-201041848 <Example 4> 2 5 ° C, the synthesis of dialkyl tetracarboxylate nitrogen in the presence of pyridine 1,3-DM-CBDA 240 g (1.07 mol) and 720 g of ethyl acetate were placed in a 3-L four-necked flask under reflux, and 8.47 g (0.107 mol) of pyridine was added, followed by stirring at 25 ° C using a magnetic stirrer. . The internal temperature was 25° (the methanol 60 (^(18.73111〇1, 1,3-〇1^-CBDA was 2·5 wt times) was dropped into the suspension in 1 hour, and the mixture was stirred and 20 was stirred. The reaction solution was homogeneously analyzed in a minute. The reaction mixture was analyzed by HP LC. The compound (1-1) had a HPLC relative area of 77%, and the compound (2-1) had an HPLC relative area of 22%. 4 ° ° C, 170 to 140 Torr, the solvent was distilled off from the reaction liquid to make the content of 56 1.65 g, and then added with ethyl acetate 丨 450 g and stirred, and then the solvent was distilled off using a water bath at 40 ° C, 170 to 140 Torr. After the content was 5 97.5 1 g, ethyl acetate MSOg was added again, and after stirring, the solvent was distilled off in a water bath at 40 ° C, 1 70 to 140 Torr to give a content of 1 8 5 2 g. The solvent distilled off at this time was analyzed by phase chromatography, and the area % of methanol was 0.3%. Thereafter, the remaining slurry solution was heated to 80 ° C. After reflux for 30 minutes, it was 2 to 3 in 1 minute. The internal temperature was cooled to 25 ° C at a rate of ° C. After stirring at 25 ° C for 30 minutes, the precipitated white crystals were removed by filtration and washed with ethyl acetate 1 92.8 8 g. The crystals were crystallized twice. After drying under reduced pressure, 223.77 g of white crystals were obtained. The crystals were subjected to 1H NMR analysis to confirm the compound (1-1) (HPLC relative area of 9,9 %) (yield 7 2 · 5) %) -54- 201041848 <Example 5> Synthesis of dialkyl tetracarboxylate in the presence of pyridine and pyridine 1,3-DM-CBDA 5 g (0.022 mol), methanol 25 g (0.78 mol, The 1,3-DM-CBDA was 5 wt times) and the pyridine 0.176 g (0.0022 mol) was placed in a 10 m round four-necked flask, and stirred at 〇 ° C for 8 hours using a magnetic stirrer to obtain a homogeneous reaction solution. The reaction liquid was analyzed by HPLC, and as a result, the HPLC relative area of the compound (1-1) was 79%, and the relative area of the compound (2 -1 ) was 20%. 〇 <Example 6> 40°c, pyridine In the presence of dialkyl tetracarboxylate, 1,3-DM-CBDA 5g (0.022mol), methanol 25g (0.78mol, 5wt times 1,3-DM-CBDA) and pyridine 0.176g ( 0.0022) Mol) was placed in a 100 mL four-necked flask, and stirred at 40 ° C for 20 minutes using a magnetic stirrer to obtain a homogeneous reaction solution. The reaction solution was analyzed by HPLC to give the compound (1-1). HPLC relative area of 74%, HPLC Compound (2-1) of the relative area of 25%. 〇 <Examples 7 to 14> A series of operations were carried out in the same manner as in Example 4, wherein the number of pyridine equivalents and the temperature to be added were each as shown in the following table. Further, the obtained reaction liquid was analyzed from HP LC, and the results of the reaction liquids obtained in Examples 1 to 6 are shown in the table. HPLC analysis conditions

Column: Atlantis cdl8 (Waters), 5um, 4.6x250mm Oven: 40 °C -55- 201041848 Dissolution: acetonitrile / hydrazine · 5% aqueous phosphoric acid = 22 / 78, inspection wavelength: 209 nm Flow rate: 1 · 0 m L /min, sample injection amount: 10 μl [Table 5] Pyridine addition amount Temperature reaction time isomer ratio (HPLC area - (equivalent) CC) (hour) (1-1) (2-1) Example 1 - 6 5 0. 5 5 0 4 7 'Example 2 - 2 0 6 9 5 6 4 4 ^ Example 3 - 4 0 7. 5 4 8 4 5 ' Example 4 0. 1 2 5 1 . 2 7 7 2 2 'Example 5 0. 1 0 13 7 9 2 0 Example 6 0. 1 4 0 1 7 4 2 5 Example 7 2 0 2 5 0 . 0 3 7 6 2 2 ' Example 8 2 2 5 0. 3 7 8 -—. 2 1 Example 9 1 2 5 0. 3 7 7 2 2 ^ Example 10 0. 14 4 2 5 0. 8 7 7 2 2^ Example 11 0. 0 7 9 2 5 1 . 4 7 6 ._ ---- 2 3 Example 12 0.0 5 2 5 1 7 4 2 5 Example 13 0. 0 2 6 2 5 2. 8 7 4 2^6~~~ Example 14 0.001 2 5 2 4 6 7 ----- 3 2 ----. <Examples 15 to 43> A series of operations were carried out in the same manner as in Example 4, in which the reaction was carried out with various additives, ear beta pyridine. The type of the additive at this time 'the equivalent weight g of the additive, the temperature, the reaction time, and the analysis result of the reaction liquid derived from Η P L C are shown in the following table. The additives described in the table are as follows. A dd -1 : potassium methoxide Add-2 : potassium carbonate Add-3 : triethylamine Add-4 : potassium t-butoxy-56- 201041848 A dd - 5 : quinoline Add-6 : 8- quin Porphyrin Add-7 : 1 , 1 0-phenanthroline Add-8 : phenanthroline Addine : dimethyldiphenylphenanthroline Add-ΙΟ : 2,2 '-bipyridine Add- 1 1 : 2 -Phenylpyridinium A dd -1 2 : 2,6-diphenylaminopyridine A dd - 1 3 : 2 -dimethylaminopyridine A dd -1 4 : 4 -dimethylamine Pyridine A dd -1 5 : 2 - (2-hydroxyethyl)pyridine Add-16 : 5-bromo-2-chloropyridine

Add-17: 1,8-diazabicyclo[5,4,0]-7-residue Addine: p-toluene acid addition Add-1 9 :phosphoric acid π M Add-20 :carboxylic acid

Add-21: Triphenylphosphine Add-22: Trimethyl borate

Add-23: phosphotungstic acid (H3[PW1204〇] · 30H2O) Add-24: phosphomolybdic acid (H3[PM〇i2O40 . 30H2O) Add-25 : water-57- 201041848 [Table 6] Addition amount of additives ( Equivalent) Temperature ro Reaction time (hours) Isomer ratio (Η [PLC area%) (1-1) (2-1) Example 15 Add-1 0. 1 2 5 0. 5 7 6 2 2 Example 16 Add-1 0. 0 1 2 5 2. 4 7 2 2 8 Example 17 Add-1 0. 0 0 1 2 5 7 5 6 4 3 Example 18 Add-2 0. 1 2 5 0. 5 7 7 2 2 Example 19 Add-2 0.0 1 2 5 1 7 2 2 8 Example 20 Add-2 0.001 2 5 15 6 7 3 2 Example 21 Add-3 0. 1 2 5 0. 2 7 0 2 9 Example 22 Add-4 0. 1 2 5 0. 2 7 0 2 4 Example 23 Add-5 0. 1 2 5 1. 5 7 4 2 5 Example 24 Add-6 1 2 3 0. 2 6 8 2 3 Example 25 Add-7 1 2 0 0. 5 7 3 2 6 Example 26 Add-8 1 2 0 17 6 2 3 7 Example 27 Add-9 1 2 0 17 6 8 3 0 Example 28 Add -10 1 2 0 0. 5 5 2 2 2 Example 29 Add-11 1 2 0 0. 3 6 6 3 0 Example 30 Add-12 0. 1 2 5 2 8 6 0 3 5 Example 31 Add- 13 0. 1 2 5 0. 3 7 0 2 9 Example 32 Add-14 0. 1 2 5 1 7 0 3 0 Example 33 Add-15 0. 1 2 5 0. 8 7 4 2 5 Example 3 4 Add-16 0. 1 2 5 7 2 5 5 4 3 Example 35 Add-17 0. 1 2 5 0. 3 6 5 2 7 Example 36 Add-18 0. 1 2 5 5 7 8 2 1 Implementation Example 37 Add-19 0.7 1 2 5 5 0 6 3 3 7 Example 38 Add-20 1 2 5 5 0 5 5 4 5 Example 39 Add-21 0. 1 2 5 7 0 6 5 3 3 Example 40 Add-22 0. 1 2 5 5 6 4 3 3 3 Example 41 Add-23 0. 1 2 3 3. 5 6 2 3 5 Example 42 Add-24 0. 1 2 3 3. 5 6 2 3 5 Example 43 Add-25 2. 7 2 5 3 5 6 4 4 <Example 4 4 > Synthesis of Compound (1 - 4 ) and (2 - 4 ) -58 - 201041848 [Chem. 48] 0 Me 〇 (5 -1)

1,3-DM-CBDA 10g (0.045mol) and tetrahydrofuran 50g were placed in a 200 mL four-necked flask under nitrogen flow, and then added to a shaku-sharp. 59 g (O 〇.〇〇4 mol) and magnetically stirred at 25 ° C. After stirring and stirring, 50 g of ethanol (1.561 mol, 5 wt. 1,3-DM-CBDA) was added dropwise over 1 hour. After the completion of the dropping, the mixture was stirred for 5 days to obtain a homogeneous reaction solution. After the solvent was distilled off from the reaction liquid using an evaporator, 70.5 g of ethyl acetate was added thereto, and the mixture was heated and stirred to 80 ° C. After refluxing for 30 minutes, the internal temperature was cooled to 25 at a rate of 2 to 3 ° C for 10 minutes. After stirring at 25 ° C for 30 minutes, the precipitated white crystals were taken out by filtration, and the crystals were washed twice with ethyl acetate 7. 5 g. After drying under reduced pressure, white crystals of 9 · 15 g were obtained. 1 The 1 H N M R analysis of the crystal was confirmed to be the compound (1 - 4 ) (the relative area of Η P L C 9 9 · 6 %) (yield 64.8 %). 1 NMR (DMSO-d6, δρρπι): 12.82 (s, 2H), 4.09-4.04 (q, 4H), 3.36 (s, 2H), 1.41 (s, 6H), 1.16-1.41 (t, 6H). Using the standard analysis of the reaction solution by the PLC, the data was determined by PLC. As a result, the HPLC relative areas of the compounds (1-4) and (2-4) were 83% and 17%, respectively. <Example 45> Synthesis of Compound (1-10) And (2-10) -59- 201041848 [化49]

(5·1) (1-10) (2-10) 1,3-DM-CBDA 10g (0.045mol) and acetonitrile 50g were placed in a 200 mL four-necked flask under nitrogen flow, and pyridine 0.3 5 3 g (0.0) was added. 0 4 5 m ο 1 ), stir at 25 ° C with a magnetic stirrer, and then add 2-propanol 50 g (0.416 mol, 1,3-DM-CBDA to 2 _ 5) over 1 hour. Wt times). After the completion of the dripping, the mixture was stirred for 12 days. After the solvent was distilled off from the reaction liquid using an evaporator (13.05 g), 52.20 g of acetonitrile and 6.53 g of 2-propanol were added, and the mixture was further heated to dissolve to 71 ° C. Then, it was allowed to cool to an internal temperature of 2 7 for 1 hour. After stirring for 1 hour under water cooling, the precipitated white crystals were removed by filtration, and the crystals were washed with acetonitrile 13.0 5 g. After decompression and drying, white crystals were obtained at 6·088 °. The crystallization was subjected to 1 Η N M R analysis. As a result, it was confirmed that S was for (1 -1 0 ) (the relative area of Η P L C was 88.8 %) (yield 4 6.6 %). 1 NMR (DMSO-d6, 5 ppm): I2.76 (s, 2H), 4.92 - 4.85 (m, 2H), 3.31 (s, 2H), 1.4l (s, 6H), 1.19-1.17 (q, 6H) H Using the standard to analyze the H p LC of the reaction solution, the results showed that the HPLC relative areas of the compounds (l-io) and (2-10) were 88% and 12%, respectively. -60-201041848 <Example 46> Synthesis of Compounds (1-10) and (2-10) 1,3-DM-CBDA 10 g (0.045 mol) 50 g (1.22 mol, for 1,3-DM) under a nitrogen stream -CBDA is 5wt times) into a four-necked flask, adding 0.3 53g (0.004 5mol) of pyridine, heating and stirring with a magnetic stirrer, and then dropping 2-propane (0.416 mol, 1,3-DM) in 1 hour. -CBDA is 2.5wt times). Stir for 7 days.反应 The reaction solution was analyzed by HPLC, and the HPLC relative area % of the compound (1-10) and ) was 83% and 17%, respectively. <Example 47> Synthesis of bis(chlorocarbonyl) compound (3-1) and acetonitrile 200 mL, 50 〇C alcohol 50 g after dripping (2-10 [50]

The compound (1 -1 ) 23 4.1 5 g (0.81 mol) of the compound 1170.778 (^.6811101, 5wt times) was placed in a 3 L of a gas stream under a nitrogen stream, and 0.64 g (0.01 mol) of pyridine was added thereto, followed by heating at 75 t using a magnetic stirrer. Next, 289.93 g (1: ) of thionyl chloride was added dropwise over 1 hour, and the dropping liquid was immediately foamed, and the reaction solution was uniformly stirred for 30 minutes after the dropping was completed, and foaming was stopped. Then, the mixture was directly stirred for 30 minutes, and then the solvent was distilled off at 40 ° C in a water bath to obtain 924.42 g of the solvent. The mixture is heated to 60 ° C to distill off the solvent in the -61 - and η-gum bottles, and stirred until 6 8 mo 1 to form a 1 hour capacity for the crystallization solution 201041848 solution, at 60 ° C The insoluble matter was removed by filtration under heat, and the filtrate was cooled to 25 ° C at a rate of 1 ° C in 10 minutes, and stirred at 25 ° C for 30 minutes, and the precipitated white crystals were removed by filtration, and then η- The crystals were washed with heptane 264.21 g. After drying under reduced pressure, white crystals 2 2 6.0 9 g. Then, 226.09 g of the white crystals obtained above and 452.1 g of n-heptane were placed in a three-liter four-necked flask under a nitrogen stream, and the crystals were dissolved by heating under stirring at TC (cooling at a rate of 1 ° C in 10 minutes). After stirring to 25 ° C, the crystals were precipitated. After stirring at 25 ° C for 1 hour, the precipitated white crystals were removed by filtration, and the crystals were washed with η-hexane 1 1 3.04 g, and dried under reduced pressure to give white crystals. 203.9 1 g. 1H NMR analysis of the crystal was confirmed to be the compound (3-1), that is, dimethyl-1,3-bis(chlorocarbonyl)-1,3-dimethylcyclobutane-2. 4-dicarboxylate (hereinafter referred to as 1,3-DM-CBDE-C1) (HPLC relative area: 99.5%) (yield 77.2%). 1H NMR (CDC13, 6 ppm): 3.78 (s, 6H) 3.72 (s, 2H), 1.69 (s, 6H). <Examples 48 to 53> A series of operations were carried out in the same manner as in Example 47, in which the catalyst type, the number of catalyst equivalents, and the temperature were as shown in the following table. The time for ending the reaction is the time when the reaction solution is a homogeneous solution and the gas is completely stopped. -62- 201041848

Solvent thionyl chloride catalyst temperature reaction time [equivalent] species [寞%%] re) (hours) Example 47 η-heptane 3 pyridine 1 7 0 2 Example 48 η-heptane 3 pyridine 1 8 0 1 Example 49 η-heptane 3 pyridine 2 8 0 0 . 5 Example 50 η-heptane 3 DMF 2 8 0 2 Example 51 η-heptane 3 DMF 5 8 0 1 Example 52 η-赖 3 - 8 0 12Φ when the above Example 53 chlorosulfinyl βϊί 12 — — 8 0 7 Ο <Example 54> Synthesis of bis(chlorocarbonyl) compound (4-1) [Chem. 51]

20.01 g (69.38 mmol) of compound (2-1) and η-heptane 1 g of the compound (2-1) were placed in a 200 mL four-necked flask under nitrogen flow, and then pyridine ruthenium (55 g (0.69 mm 〇l) was added thereto, and magnetic force was used. The stirrer was heated and stirred to 70 °C. Next, 24.75 g (208.1 5 mmol) of thionyl chloride was added dropwise at 72 ° C for 1 hour. The drip will start to foam immediately, and will stop sending 1 hour after the end of the drip.

bubble. Then, the mixture was stirred at 73 ° C for 1 hour and 30 minutes, and the solvent was distilled off at 40 ° C in a water bath to give a content of 53.9 g. Thereafter, the residue was heated to 60 ° C, heated and stirred for 3 minutes, and then cooled to MX: for 30 minutes. After stirring at 20 ° C for 30 minutes, the precipitated white crystals were taken out by filtration, and the crystals were washed with 22.5 g of η-heptane, and dried under reduced pressure to yield white crystals of 1-2 g. The crystal was subjected to 1H NMR analysis, and was confirmed to be compound - 63 - 201041848 (4-1) (HPLC relative area 98.5%) (yield 9 7.2 %). 1H NMR (CDC13, 5 ppm): 4.15 (s, 1H), 3.84 (s, 3H), 3.80 (s, 3H), 3.44 (s, 1H), 1.74 (s, 3H), 1.59 (s, 3H). <Example 55> Synthesis of Compound (2-2) [Chem. 52]

1,2-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride (compound of formula (5-2) 'hereinafter abbreviated as l,2-DM-CBDA) 19.9 g (under nitrogen gas flow) 0.089 mol) and 49.7 g of ethyl acetate were placed in a 3 L four-necked flask, and after adding 0.70 g ( 0.009 m〇l) of lysine, stirring was carried out under a magnetic stirrer at 25T: and then methanol was added dropwise for 1 hour. 4 9 · 7 5 g (1 · 5 5 m ο 1, 2.5Wt times for 1,2-DM-CBDA) The internal temperature is 30 ° C or less. After the completion of the dropwise addition for 20 minutes, it was completely dissolved in the reaction solution, and stirred at 2 Torr to 3 ° C for 40 minutes. An evaporator was used to bathe 40. (:, 170 to 140 Torr, the solvent was distilled off from the reaction liquid to make the content of 5 1.18 g, and then ethyl acetate 1 2 7 · 9 4 g was added to mix 'reuse the evaporator to a water bath of 40 ° C, The solvent was distilled off from 1 7 0 to 1 4 0 T 〇 rr to give a content of 51.18 g. Thereafter, 12,794 g of ethyl acetate was added again, and the mixture was stirred and then used in a water bath for 4 0. (:, 170 to 1400 The solvent was distilled off from T 〇 rr so that the content of -64-201041848 was 1 1 7 · 7 1 g. The solvent distilled at this time was also measured by gas chromatography, and the area of methanol was 0.3%. The remaining slurry was then deposited. The solution was heated to 80 ° C, refluxed for 30 minutes, and then cooled to 2 5 ° C at a rate of 2 to 3 ° C for 10 minutes. After stirring at 30 ° C for 30 minutes, the precipitate was removed by filtration. The crystals were white crystals, and the crystals were washed twice with ethyl acetate (1, 2.8 g), and dried under reduced pressure to give white crystals: 16.96 g. The crystals were subjected to 1H NMR analysis to confirm the compound (2-2) (HPLC relative area Ο 9 5 · 5 % ) (yield 6 6.7 %). 1 H NMR (DMSO-d6, 5 ppm) : 1 3 · 1 6 (s, 2 Η ), 3.5 6 (s, 6 Η ), 3.21 (s, 2Η), 1.30(s,6Η). The reaction solution was Analytical HPLC data of measurement, the results of the compound (2-2) HPLC relative area of 96%: Example Embodiment 56 > Synthesis of bis (chlorocarbonyl) Compound (4-2 square [of 53].

HO MeO Ττ' •OH SOCI2 -» -OMe ci- Πΐί-c.JJom (2-2) (4-2) Put the compound (2-2) 16_46g (0_06mol) and n-heptane 82.3g under a nitrogen stream. Into a 3 L four-necked flask, 0.045 g (0.6 tnmol) of pyridine was added, and the mixture was stirred and heated to 75 ° C using a magnetic stirrer. Next, 20.3 8 g (0.17 mol) of thionyl chloride was added dropwise over 1 hour, and the dropping solution was started. -65-201041848, the foaming was completed. After the dropping liquid was finished for 30 minutes, the reaction solution was homogenized and the foaming was stopped. Then, the mixture was stirred at 75 ° C for 1 hour and 30 minutes, and the solvent was distilled off in a water bath at 4 ° C to give a content of 64.98 g. When it is heated to 60 ° C, the crystals precipitated when the solvent is saturated are dissolved, and then 6 (rc is heated to remove insoluble matter, the filtrate is cooled to 25 ° C at a speed of 丨t in 1 minute. After stirring at 25 ° C for 30 minutes, the precipitated white crystals were taken out, and the crystals were washed with η-heptane 丨 8.5 7 g. After drying under reduced pressure, 16.42 g of white crystals were obtained. The result was confirmed to be Compound (4-2) (HPLC relative area 95.5%) (yield 88.5%) 〇1H NMR (CDC13, 5 ppm): 3.72 (s, 6H), 3.42 (s, 2H), 1.82 (s, 6H) <Reference Example 1> [Chem. 54]

CB-2.4-DME CB-23-DME

Under a nitrogen stream, cyclobutane-1,2,3,4-tetracarboxylic acid-1:2,3:4-dianhydride (hereinafter abbreviated as CBDA) 300g (1.53mol) and acetonitrile 900g were placed in 4 L of 3 L. In the flask, after adding pyridine 1 2 ·〗g ( 0 _ 1 5 3 m ο 1 ), the mixture was stirred at 2 5 ° C using a magnetic stirrer, and then dropped into methanol-66 - 201041848 7 50g over 1 hour ( 23.4 mol ' is 2.5 wt times for CBDA) so that the internal temperature is 30 ° C or less. After the completion of the dropping for 20 minutes, the reaction solution was completely dissolved, and then 2 〇 to 3 〇. (: stirring for 1 hour. The reaction liquid was analyzed by HPLC, and as a result, the relative areas of cB-2,4-DME and CB-2,3-DME were 49.2% and 49.8%, respectively, and therefore it was impossible to carry out the reaction even in the presence of pyridine. The selectivity of the positional isomer was obtained. The solvent was distilled off from the reaction liquid in an aqueous bath at 40 ° C to make the content 〇 796.08 g, then acetonitrile was added to 995.log, and then evaporated in a water bath at 40 ° C using an evaporator. The content of the solvent was 796.08 g. The acetonitrile 9 95. 1 Og was again added, and after stirring, the solvent was distilled off in a water bath at 40 ° C to obtain a content of 796.08 g. The gas fraction was used for the distillation. Solvent, the area of methanol was 0.3%. Then 398.04g of acetonitrile was added, heated to 80 t, refluxed for 30 minutes, and then cooled to 251 at a rate of 2 to 3 ° C in 10 minutes. Stirring at 25 ° C After 30 minutes, the precipitated white crystals were separated by filtration, and the crystals were washed twice with acetonitrile 1 99.02 g, and dried under reduced pressure to give white crystals (1, 7.54 g). CB-2,4-DME (HPLC relative area 96.4%) (yield 3 9.6%). 1 H NMR (DMSO-d6, 5 ppm) : 1 2 · 8 1 (s, 2Η), 3.6 1 (s, 6Η), 3.59-3.54 (m, 2H) ° <Application Example 1> Polymeric compound (3-1) and p-phenylenediamine Amine 0.6005g (5_5527mm〇l), N-methylpyrrolidone 10mL, γ-butyrolactone 10mL, pyridine 1.06mL were placed in a 2-neck flask of -67-201041848 5 OmL, and 25 was stirred under a magnetic stirrer. The phenylamine was completely dissolved. After the reaction solution was ice-cooled, the compound (3 _ 丨) was added using a funnel with stirring using a magnetic stirrer for 30 seconds, followed by washing with N _ methyl pradinone 3 m L. After the nitrogen substitution, the mixture was stirred for 20 minutes under 〇t. After 20 minutes, the temperature was raised to 20 ° C, and further stirred at 2 ° C for 3 hours. After 1 hour, 2 hours later, the polymerization solution was sampled to determine the viscosity. The result was 1 hour later (1 300 m P a · S ), 2 hours later (15 OO mP a · s). <Application Example 2 > Polymeric compound (4 丨 丨) and p-phenylenediamine nitrogen flow Put p-phenylenediamine 〇6005 g (5.5 527 mmol), N-methylpyrrolidone 10 mL, γ-butyrolactone 10 mL, and pyridine 1.06 mL into a 50 mL 2-neck flask, using magnetic under 251 Stirrer so that p-phenylenediamine was completely dissolved. Then the reaction solution was ice-cooling, while stirring using a magnetic stirrer to a funnel 30 sec. Addition of Compound (4-1). Then, the funnel for addition was washed with 3 m of N-methylpyrrolidone, and after nitrogen substitution, the mixture was further stirred for 20 minutes. After 20 minutes, the temperature was raised to 20 °C, 20. (: stirring for another 3 hours. After 1 hour, the polymerization solution was sampled after 2 hours to determine the viscosity. The result was 1 hour later (2 8 m P a · s ), 2 hours later (2 8 m P a • s ) ° <Synthesis Example 1 〇1 to 1 0 4, Comparative Synthesis Example 1 〇1 to 1 〇3, Example i ο i to 1 1 1 , Comparative Example 1 0 1 to 1 0 7 > Synthesis Examples, Comparative Synthesis Examples, Examples and Comparative Examples -68- 201041848 Compound code and structure used. 1,3-DM-CBDA : 1,3-monomethyl-1,2,3,4-ring Butyl phthalate anhydride l,3-DM-CBDE: 2,4-bis(methoxycarbonyl)-1,3-dimethylcyclobutane-1,3-dicarboxylic acid p-PDA : p Phenylene diamine

[化55]

1,3-DM-CBDA p-PDA [化56]

〇 (organic solvent) NMP : N-methyl-2-pyrrolidone γ-BL: γ-butyrolactone BCS : butyl cellosolve DMF : Ν, Ν-dimethylformamide DEF : Ν, Ν-diethyl The form of the methotrexate is measured by WNMR, FT_IR, X-ray crystal structure analysis, viscosity, molecular weight, anisotropy of the alignment film, voltage holding ratio, and ion density. -69- 201041848 ['HNMR] Apparatus: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (manufactured by Varian): 400 MHz Reference material: tetramethyl decane (TMS) [FT-IR] Device: NICOLET5 700 (manufactured by Thermo ELECTRON) Smart Orbit Detector measurement method: ATR method [X-ray crystal structure analysis] Device: DIP2030 (manufactured by MacScience) X-ray: Moka (40kV, 200mA)

Measuring temperature: 298.0K

[Viscosity] In the synthesis example, the viscosity of the polyphthalate and the polyaminic acid solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1. lmL and a cone gyrator TE-1 ( Γ34', R24), temperature 2 5 °C. [Molecular weight] Further, the molecular weights of polyglycolate and polylysine were measured by GPC (normal temperature gel permeation chromatography) apparatus, and the number of polyethylene glycol and polyepoxy-70 - 201041848 was calculated. Average molecular weight (Μη) and weight average molecular weight (Mw) ° GPC device: manufactured by Shodex Co., Ltd. (GPC-101) Pipe column: made by Shodex (inline KD803, KD805)

Column temperature: 50 ° C Dissolution: N,N-dimethylformamide (LiBr·H20 for additive is 30 mmol/L, and phosphoric acid anhydride crystals (〇_phosphate) 30 mm〇 l/L, tetrahydrofuran (THF) is 10 ml/L) Flow rate: 1.0 ml/min. Standard sample for making the calibration line: TSK standard poly epoxy plant made by Dongsuo Co., Ltd. (weight average molecular weight (Mw) is about 900,000, 150,000, 100,000, 30,000) and polyethylene glycol manufactured by Polymer La Pola (peak mass (Mp) of about 12,000, 4,000, 1, 〇〇〇). In order to avoid peak overlap, separate samples of 900, 0 0 〇, 1 〇〇, 〇〇〇, 1 2, 〇〇〇, 1,000 are mixed in the measurement' and mixed 150,000, 30,000, 4, 〇〇 〇 3 kinds of 〇 samples. [Anisotropy of Alignment Film] The anisotropy of the alignment film was measured by the following method. The measurement was carried out using a liquid crystal alignment film evaluation series manufactured by Moridia Co., Ltd. (LYS-LH3 0S-1A). After the ultraviolet ray was applied to the polyimine film having a film thickness of 1 〇 〇 n m by a polarizing plate, the anisotropy of the alignment direction with respect to the obtained alignment film was measured. -71 - 201041848 [Voltage holding ratio] The voltage holding ratio of the liquid crystal cell was measured by the following method. A voltage of 4 V was applied between 60 μs and the voltage after 1 6.6 7 m s was measured, and the change from the initial enthalpy was calculated as the voltage holding ratio. The measurement was carried out at a temperature of 23 ° C and 60 ° C of each liquid crystal cell. [Ion Density] The ion density of the liquid crystal cell was measured by the following method. The measurement was carried out using a 6254 liquid crystal property evaluation device manufactured by Dongyang Technology Co., Ltd. After applying a triangular wave of 10 V and 0.01 Hz, the area corresponding to the ion density in the obtained waveform was calculated by a triangle approximation as the ion density. The measurement was carried out at a temperature of 23 ° C and 60 ° C in the liquid crystal cell. (Synthesis Example 1 0 1 ) <Synthesis of dimethyl1,3-1,3-(chlorocarbonyl)·1,3-dimethylcyclobutane·2,4-dicarboxylate (1,3-DM-CBDE) -C1) > [化57] ° Me ° cl^rjL〇Me^ΧμΓΓ1

1,3-DM-CBDE-CI

U3-DM-CBDE 234.15g (0.81 mol) and η-heptane 1170_77g obtained in the same manner as in Example 1 were placed in a 3-liter 4-72-201041848 flask to add 'pyridine pyridine 0.64 g (O. After Olmol), the mixture was heated and stirred to 75 ° C using a magnetic stirrer. Next, 2 8 9.9 3 g (1 1.68 mol) of thionyl chloride was added dropwise over 1 hour, and the dropping liquid was immediately foamed. After the liquid was finished for 30 minutes, the reaction solution was homogenized and foaming was stopped. Then, the mixture was stirred at 75 ° C for 1 hour and 30 minutes, and the solvent was distilled off in a water bath at 40 ° C using an evaporator to give a content of 924.42 g. This was heated to 60 ° C to dissolve the crystals precipitated when the solvent was distilled off, and then filtered at a temperature of 60 ° C to remove insoluble matter. The filtrate was cooled to 25 ° C at a rate of 10 ° C in 10 minutes, and stirred at 25 ° C for 30 minutes. The precipitated white crystals were removed by filtration, and the crystals were washed with η-heptane 2 64.2 1 g. . After drying under reduced pressure, white crystals 2 2 6.0 9 g. Next, 226.09 g of the obtained white crystals and 452.1 g of η-heptane were placed in a 3-L four-necked flask under a nitrogen stream, and the mixture was heated and stirred at 60 ° C to dissolve the crystals. Then, the mixture was cooled and cooled to 25 ° C at a rate of 1 ° C in 1 minute, and crystals were precipitated. After stirring directly at 25 ° C for 1 hour, the precipitated white crystals were taken out by filtration, and the crystals were washed with η-hexane 1 1 3.04 g, and dried under reduced pressure to give white crystals 2 03.9 1 g ( HPLC The relative area is 99.5%). 1H NMR analysis of the crystal was carried out, and it was confirmed that the objective compound was 1,3-DM-CBDE-C1, that is, the 1, 3-position bonded chlorocarbonyl group and the 2, 4-bonded methyl ester group of the ring of the ring. Acid chloride. NMR (CDC13, δρριη): 3.78 (s, 6H), 3.72 (s, 2H), 1.69 (s, 6H). (Synthesis Example 102) Production of Polyurethane Resin (Al) 0.60 g (5.55 mmol) of P-PDA was placed in a 50 mL four-necked flask equipped with a stirring apparatus of -73-201041848 under nitrogen flow, and NMP 27.5 g and a base were added. 1.03 g (13.0 5 mmol) of pyridine was used and dissolved by stirring. Next, while stirring the diamine solution, 1.77 g (5.4 4 mm ο 1 ) of 1,3-DM-CBDE-C1 of Synthesis Example 101 was added, and after reacting for 2 hours under water cooling, the obtained solution of the poly-branched acid ester was put into The precipitated white precipitate was collected by filtration in 1 97 g of water, and then washed once with 197 g of water. Then, it was washed once with 197 g of methanol, and then washed three times with 49 g of methanol to obtain white after drying. The polyphthalate resin (A-1) powder was 1.72 g. The yield was 87.4%. Further, the molecular weight of the polyglycolate was Mn = 24,868' Mw = 51,727. (Synthesis Example 103) Production of Polyurethane Resin (A-2) 2.820 g (26.08 mmol) of p-PDA and 1.357 g (6.519 mmol) of 4,4'-diaminodiphenylacetylene were placed under nitrogen. To a 300 mL four-necked flask of a stirring apparatus, 226 g of NMP and 5.82 g (7 3.54 mmol) of pyridine for alkali were added, followed by stirring and dissolving. Next, the diamine solution was stirred while adding 1, 3-DM-CBDE-C 1 9.963 g (30.64 mtnol ) of Synthesis Example 1, and reacted under water cooling for 4 hours. The obtained polyphthalate solution was placed in a stirred water of 1 1 90 g, and the precipitated white precipitate was collected by filtration, washed once with water 1 190 g, and once with ethanol 1 190 g, and thereafter. The mixture was washed three times with 298 g of ethanol, and dried to obtain 10.64 g of a white polyphthalate resin (A-2) powder. The yield was 89.4%, and the molecular weight of the polyglycolate was 14,153, Mw = 3 5, 23 9 . (Synthesis Example 1〇4) Production of Polyurethane Resin Resin (A-3) -74- 201041848 4,4'-Extended Ethyldiphenylamine 0.998 g (4.70 mmol) was placed in a stirring apparatus at 50 m. In a L four-necked flask, 19.7 g of NMP and 783 g (9.89 mmol) of a pyridinium base were added, followed by stirring to dissolve. Next, the diamine solution was stirred while adding Synthesis Example 1 〇 1 , 3 - D Μ - C B D E - C 1 1 · 5 3 2 g (4.71 mmol), and reacted under water cooling for 2 hours. The obtained polyphthalate solution was put into a stirred water of 1,97 g, and the precipitated white precipitate was collected by filtration, washed once with 219 g of water, and then washed once with 219 g of methanol, followed by methanol. 55 g was washed three times, and after drying, 1.70 g of a white polyphthalate resin (A-3) powder was obtained. The yield was 77.7%, and the molecular weight of the polyphthalate was Mn = 19,210 and Mw = 35,076. (Comparative Synthesis Example 101) Preparation of a solution of poly-proline (B-1) 1,3-DM-CBDA 1 9 _ 0 5 g ( 8 5 · 9 8 m ο 1 ) was placed in a stirring device and nitrogen introduction In a 30 mL four-necked flask, 63 g of γ-BL was added, and nitrogen was added thereto while stirring and dissolved. After stirring the acid dianhydride solution, NMP Ο l〇〇g was added, p-PDA 8_87 (82.02 mmol) was added, and then NMP was added to make the solid concentration of the solid component 10% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a polyfluorene. Amino acid (B-1) solution. The polyglycine solution has a viscosity of 356 mPa·s at a temperature of 25 ° C, and the molecular weight of the poly-proline is Mn = 21,137, Mw = 43,1 45 〇 (Comparative Synthesis Example 102) The solution of acid (B-2) was charged with p-PDA 1.73g (16.Ommol) and 4,4'-diaminodiphenylacetylene.835g (4.01g) into a stirring device and nitrogen introduction. Tube-75-201041848 100 mL four-necked flask was charged with 21.23 g of γ-BL and 24.81 g of NMP, and then stirred and dissolved while feeding nitrogen. After stirring the diamine solution, 4.46 g (19.90 mol) of 1,3-DM-CBDA was added, and NMP was added to a solid concentration of 1 〇 mass%, and stirred at room temperature for 24 hours to obtain polyglycine (B). -2) Solution. The polyglycine solution had a viscosity of 158.8 mPa·s at a temperature of 25 ° C, and the molecular weight of the poly-proline was Mn = 15,213 and Mw = 31,700. (Comparative Synthesis Example 1 03) Preparation of Polylysine (B-3) Solution 4.14 g (20.3 2 mmol) of 4,4'-extended ethyldiphenylamine was placed in a stirring apparatus and a nitrogen introduction tube. In a four-necked flask, 26.90 g of γ-BL and 30.73 g of NMP were added, and then nitrogen was added thereto while stirring and dissolved. After stirring the diamine solution, 4.45 g (19.85 mol) of 1,3-DM-CBDA was added, NMP was added to make a solid concentration of 10% by mass, and the mixture was stirred at room temperature for 24 hours to obtain poly-proline (B-3). ) solution. The polyglycine solution had a viscosity at a temperature of 25 ° C of 168.7 mPa · s, and the molecular weight of the poly-proline was Mn = 1,9,322, Mw = 45,601 ° &lt;Example 101&gt; Modulation of liquid crystal alignment agent (AI) 1.28 g of the polyacetate resin (A-1) powder obtained in Synthesis Example 102 was placed in a 50 mL Erlenmeyer flask with a stirrer, and DEF 1 2.7 1 g was added thereto, and the mixture was stirred at room temperature for 24 hours, and dissolved. A polyamine resin solution was obtained. 4.36 g of γ-BL and 4.20 g of BCS were added to the solution, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (A-I) of the present invention. -76-201041848 &lt;Example 1 〇2 &gt; Modulation of liquid crystal alignment agent (A-11) 1.66 g of polyphthalate resin (Ad) obtained in Synthesis Example 1 放入3 was placed in a 50 mL conical flask with a stir bar After adding 1.96 g of 1,5, the mixture was stirred at room temperature for 24 hours, and dissolved to obtain a solution of polyglycolate (A-2). After another 6.61 g of a 50 mL Erlenmeyer flask with a stirrer, γ-BL 2.20 g and BCS 2.20 g were added for stirring for 30 minutes using a stirrer to obtain a liquid crystal alignment agent (A-II) of the present invention. Example 1〇3&gt; Modulation of Liquid Crystal Aligning Agent (A-III) 1.15 g of the polyphthalate resin (A-3) obtained in Synthesis Example 104 was placed in a 50 mL Erlenmeyer flask with a stirrer, 'after adding l.42 g After stirring at room temperature for 24 hours, it was dissolved to obtain a solution of polyamine (A-3). After 5.66 g of a 50 mL Erlenmeyer flask with a stirrer, γ-BL 1.90 g and BCS 1.92 g were added, and the mixture was stirred for 30 minutes using a stirrer to obtain a liquid crystal alignment agent (A-III) of the present invention. Example 1〇4&gt; Preparation of Liquid Crystal Aligning Agent (A-IV) 4.12 g of the polyphthalate resin (A-2) obtained in Example 1〇2 was placed in a 50 mL Erlenmeyer flask equipped with a stir bar, and 1.38 g and 1.-α ωΐ, Ν-ω2-tris-t-butoxycarbonyl-L-arginine (hereinafter abbreviated as Arg) 0.1 084g (relative to polyamine) for the addition of bismuth imidization promoter after BCS 1.40g The acid ester group 1 molar was 0.1 mol, and the Boc-Arg was completely dissolved by stirring at room temperature for 30 minutes to obtain a clear liquid crystal alignment agent (A-IV). Powder DEF resin takes the magnetic powder DEF resin to take the magnetic solution γ-BL, NB 〇c - ear as the hair -77-201041848 &lt;Example 1〇5&gt; Modulation of liquid crystal alignment agent (AV) Example 1 0 3 3.16 g of the obtained polyphthalate resin (A - 3 ) solution was placed in a 50 mL Erlenmeyer flask with a stir bar, and γ-BL 1.03 g and BCS l. 〇 3 g were added, followed by the addition of Boc imidization accelerator to Boc. - Arg 0.0650 g (0.1 molar equivalent to the polyamidolate group 1 molar), and the Boc-Arg was completely dissolved by stirring at room temperature for 30 minutes to obtain a liquid crystal alignment agent (AV) of the present invention. &lt;Comparative Example 1〇1&gt; Preparation of Liquid Crystal Aligning Agent (BI) 14.10 g of the polylysine (B -1 ) solution obtained in Comparative Synthesis Example 1 0 1 was placed in a 50 mL conical flask equipped with a stir bar, and NMP 13.57 was added. After g and BCS 6.93 g, the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (BI). &lt;Comparative Example 1〇2&gt; Preparation of Liquid Crystal Aligning Agent (B-II) 6.34 g of the polylysine (B-2) solution obtained in Comparative Synthesis Example 102 was placed in a 50 mL conical flask equipped with a stirrer, and NMP 2.34 was added. After g and BCS 2.1 7 g, the liquid crystal alignment agent (Β-Π) was obtained by stirring for 30 minutes using a magnetic stirrer. &lt;Comparative Example 1〇3&gt; Preparation of Liquid Crystal Aligning Agent (B-III) 6.47 g of the polylysine (B-3) solution obtained in Comparative Synthesis Example 103 was placed in a 5 〇 mL conical flask equipped with a stir bar, and added. NMP 1.85g and -78- 201041848 BCS 2.10g after 'mixing with a magnetic stirrer for 3 minutes to obtain a liquid crystal alignment agent (B-III). &lt;Example 1〇6&gt; The liquid crystal alignment agent (A-Ι) obtained in Example 1 was filtered using a filter of 1. ημηι, and then spin-coated on a glass substrate and placed on a hot plate of 8 〇〇c. After drying for 5 minutes, it was then calcined at 230 ° C for 30 minutes (baking condition 1) or at 250 ° C for 30 minutes (baking condition 2) to obtain a polyimide film having a film thickness of 10 nm. A 254 nm ultraviolet ray was irradiated onto the surface of the coating film with a polarizing plate at a density of 1 〇 J/cm 2 to obtain a liquid crystal alignment film. The anisotropy of the obtained liquid crystal alignment film with respect to the alignment direction was measured. Further, the imidization ratio of oxime under each calcination condition was measured by IR. The results of measurement of the anisotropy size and the ruthenium imidization ratio are shown in the following tables. &lt;Example 1 〇7&gt; In addition to the use of the liquid crystal alignment agent (A-II) obtained in Example 102, the liquid crystal alignment film was produced in the same manner as in Example 106, and the anisotropy with respect to the alignment direction was measured. Amination rate. The results of the anisotropy and the yttrium imidization rate are as follows. &lt;Example 108 &gt; In addition to using the liquid crystal alignment agent (A-III) obtained in Example 103, after the liquid crystal alignment film was produced in the same manner as in Example 106, the anisotropy size and the quinone imine with respect to the alignment direction were measured. Rate. The results of the measurement of the anisotropy size and the oxime imidization ratio -79-201041848 are shown in the following table. &lt;Example 1〇9&gt; The liquid crystal alignment agent (A-IV) obtained in Example 1 04 was filtered using a filter of 1·0 μηι, and then spin-coated on a glass substrate, and then placed on a hot plate of 8 (rc). After a minute, it was calcined at 203 for 3 〇 minutes (calcination condition 丨) to obtain a polyimide film having a film thickness of 100 nm, and ultraviolet rays of 254 nm were irradiated with a polarizing plate at 1.0 〇 J/cm 2 . On the surface of the coating film, a liquid crystal alignment film was obtained. The anisotropy of the obtained liquid crystal alignment film with respect to the alignment direction was measured, and the imidization ratio of each of the calcination conditions was measured by IR. The anisotropy size and the imidization ratio were determined. The measurement results are shown in the following table. <Example 1 1 〇> In addition to the use of the liquid crystal alignment agent (AV) obtained in Example 156, a liquid crystal alignment film was produced in the same manner as in Example 109, and the measurement was performed with respect to the alignment direction. The results of the measurement of the anisotropy size and the ruthenium imidization ratio, the anisotropy size, and the oxime imidization ratio are shown in the following table. <Comparative Example 1 0 4 &gt; The liquid crystal alignment agent obtained in Comparative Example 1 0 1 was used. (B -1 ), after the liquid crystal alignment film was produced in the same manner as in Example 1 0 6 , the measurement was made with respect to the alignment direction. The results of the measurement of the anisotropy size and the ruthenium imidization ratio, the anisotropy size and the ruthenium iodide ratio are shown in the following table. -80 - 201041848 &lt;Comparative Example 1 〇5 &gt; In addition to the liquid crystal obtained in Comparative Example 102 The alignment agent (Β-Π) was used to prepare a liquid crystal alignment film in the same manner as in Example 106, and the anisotropy size and the oxime imidization ratio with respect to the alignment direction were measured. The measurement results of the anisotropy size and the ruthenium imidization ratio were as follows. The following table is shown. <Comparative Example 1 〇6 &gt; Using the liquid crystal alignment agent obtained in Comparative Example 103, a liquid crystal alignment film was produced in the same manner as in Example 106, and then the directions with respect to the alignment direction were measured. The results of the measurement of the anisotropy size and the ruthenium imidization ratio are shown in the following table. Example 1 06 to 1 1 0 and Comparative Example 1 04 to 1 06 with respect to the alignment direction The results of the anisotropy measurement are shown in the following Table 8. [Table 8] Liquid crystal alignment agent baking condition 1 Calcination condition 2 Example 106 A - I 0.275 0.402 Example 107 Α-ΙΙ 0.290 0.485 Example 108 Α-ΙΙΙ 0.411 0.498 Implementation Example 109 A-IV 0.867 - Example 110 AV 0.688 - Comparative Example 104 Β - Ϊ 0.103 0.111 Comparative Example 105 Β - II 0.384 0.443 Comparative Example 106 Β - ΠΙ 0.373 0.373 测定 Examples 106 to 110 and Comparative Examples 104 to 106 The measurement results of the ruthenium amide ratio are as follows Table 9 shows. -81 - 201041848 [Table 9] Liquid crystal alignment agent baking condition 1 Calcination condition 2 Example 106 Α - I 38.9% 61.3% Example 107 A-II 51.9% 74.0% Example 108 A-III 53.1% 82.2% Example 109 A-IV 93.3% _ Example 110 A-V 98.7% _ Comparative Example 104 B-I 80.4% 86.4% Comparative Example 105 B-II 75.0% 86.4% Comparative Example 106 B-III 79.0% 87.2% Confirmed use of the above The liquid crystal alignment agent of the invention has a ruthenium imidization ratio of the liquid crystal alignment film produced by photo-alignment treatment, and can be equal to or higher than the liquid crystal alignment film of the comparative example formed of poly-proline. To the opposite sex. &lt;Example 1 1 1 &gt; The liquid crystal alignment agent (Α-Ι) obtained in Example 1 was filtered using a filter of 1.0 μm, and then spin-coated on a glass substrate with a transparent electrode, and placed at 80 t. The hot plate was dried for 5 minutes, and then baked at 23 ° C for 20 minutes to obtain a polyimide film having a film thickness of 100 nm. A 254 nm ultraviolet ray was irradiated onto the surface of the coating film with a polarizing plate at 1.0 OJ/cm2 to obtain a substrate with a liquid crystal alignment film. After preparing two substrates with the liquid crystal alignment film, a 4 μm distance adjuster is spread on the liquid crystal alignment film surface of one of the substrates, and then two substrates are combined by the parallel twisting of 85 degrees in the alignment direction, and thereafter The residual liquid crystal injection port is further sealed around, and an empty cell having a cell gap of 4 μηα is fabricated. Liquid crystal (MLC-2 04 1, manufactured by Mercury Co., Ltd.) was vacuum-injected into the empty cell at room temperature, and the inlet was sealed to twist the nematic liquid crystal cell. The alignment state of the liquid crystal cell was observed using a polarizing microscope, and as a result, it was confirmed that -82-201041848 was found to have no defect uniformity. The voltage of the liquid crystal cell was measured, and the ion density was measured. As a result, the voltage holding ratio was 97.2% at 23 ° C and 98 ° C, and the ion density was 23 p: 79 pC/cm 2 , 5 84 pC/cm 2 . &lt;Comparative Example 1〇7&gt; In addition to the use of the liquid crystal alignment agent obtained in Comparative Example 1 〇1 (BO, the twisted nematic liquid crystal cell was produced in the same manner as in Example η1. The alignment state of the liquid crystal cell was observed using a polarizing microscope, and it was considered that the defect was uniform. Alignment. The voltage of the liquid crystal cell was measured, and the ion density was measured. As a result, the voltage holding ratio was 96.4% at 98 ° C at 23 ° C, and the ion density was 247 pC/cm 2 ' 1160 pC/cm 2 at 23 ° C. The liquid crystal germanium liquid crystal element produced by the method of the present invention can have excellent liquid crystal alignment, and has high voltage retention and low ion density even at high temperatures. [Industrial Applicability] The tetracarboxylic acid dioxane of the present invention The base ester or bis(chlorocarbonyl) is used as a raw material monomer such as polyamine, polyimine, polyester, etc. The liquid crystal alignment agent of the present invention is suitable for use in a photo-alignment treatment® alignment film. The liquid crystal crucible 1 produced by the method is used for the production of various liquid crystal elements. The Japanese patent application rate applied for on February 12, 2009 is 5% &gt; 60 60. (: I), the result is indeed After the rate of .4% 60 6 0t is a film of the film, and can be used as a liquid crystal to the film; 2009-83-201041848 030285 and Japanese Patent Application No. 2009-03-02 No. 92, filed on Feb. 12, 2009 The scope, the graph and the summary contents are included in the disclosure of the present specification. [Simplified illustration of the drawing] Fig. 1 is an ORTEP diagram of the single crystal X-ray analysis result of the compound (1-1). Fig. 2 is a compound (2) - 1) ORTEP diagram of single crystal X-ray analysis results. -84-

Claims (1)

201041848 VII. Patent application scope: 1. A tetrabasic acid dialkyl ester, which is represented by the following formula or formula [2], 〇 (wherein 'R is an alkyl group having 1 to 5 carbon atoms, R2 is an alkyl group having 1 to 5 carbon atoms, and η is 1 to 4). 2. The dialkyl carboxylic acid according to the first aspect of the patent application, which is represented by the following formula Π-a], formula [2-a] or formula [2-b], [Chemical 2] (wherein R1 is an alkyl group having 1 to 5 carbon atoms, and R2 is a group having 1 to 5 carbon atoms). 3. A bis(chlorocarbonyl) compound which is represented by the following formula [3] or formula 14] Express '-85- 201041848 [化3] (wherein R 1 is an alkyl group having a carbon number of 1 $ 5 and R 2 is an alkyl group having a carbon number i to 4• A bis(chloro(tetra)) compound as claimed in item 3 of the patent application, which is represented by the following formula [3_a], formula [4_a] or formula [4-b], [Chemical 4] (wherein R1 is an alkyl group having 1 to 5 carbon atoms, and R2 is an alkyl group having 1 to 5 carbon atoms). 5. A method represented by the formula [1] or the formula [2] of the first aspect of the patent application. A method for producing a tetracarboxylic acid dialkyl vinegar, which is an acid dianhydride represented by the following formula [5], which is reacted with an alcohol having 1 to 5 carbon atoms, [Chemical 5] 15} -86- 201041848 (wherein R2 is the base of the carbon number 1 to 5, and η is 1 to 4). 6. A method for producing a tetracarboxylic acid dialkyl ester represented by the formula [1-a] or the formula [2-a] of the second aspect of the patent application, which is to give the following formula [5-a] The tetracarboxylic dianhydride represented is reacted with an alcohol having 1 to 5 carbon atoms. (wherein R2 is an alkyl group having 1 to 5 carbon atoms). (7) A method for producing a tetracarboxylic acid dialkyl ester represented by the formula [2-b] of the second aspect of the patent application, which is a tetracarboxylic acid represented by the following formula [5-b] Anhydride reacts with an alcohol having 1 to 5 carbons, (wherein R2 is an alkyl group having 1 to 5 carbon atoms). 8. The process according to any one of claims 5 to 7, wherein the tetrahydro acid dianhydride is reacted with an alcohol having 1 to 5 carbon atoms in the presence of an acidic compound or a basic compound. The manufacturing method according to any one of claims 5 to 7, wherein the tetracarboxylic acid disulfide is reacted with an alcohol of carbon^1 -87-anthracene, 201041848 to 5 in the presence of a basic compound. 1 〇. A method for producing a bis(chlorocarbonyl) compound represented by the formula [3] or the formula [4] of the scope of the patent application, which is to make the formula 1 of the scope of the patent application [1] Or the dialkyl tetracarboxylic acid represented by the formula [2] is reacted with a chlorinating agent. 11. A method for producing a bis(chlorocarbonyl) compound represented by the formula [3-a] of claim 4, which is represented by the formula [Ι-a] of the second aspect of the patent application; The dialkyl tetracarboxylate is reacted with a chlorinating agent. I2. A method for producing a bis(chlorocarbonyl) compound represented by the formula [4-a] of claim 4, which is represented by the formula [2-a] of the second aspect of the patent application. The dialkyl tetracarboxylate is reacted with a chlorinating agent. 1 3 _ a method for producing a bis(chlorocarbonyl) compound represented by the formula [4 - b ] of the fourth aspect of the patent application, which is made in the formula [2-b] of the second item of the patent application The represented dialkyl tetracarboxylate is reacted with a chlorinating agent. The manufacturing method of any one of claims 10 to 13 wherein the dialkyl tetracarboxylic acid is reacted with a chlorinating agent in the presence of a basic compound. The manufacturing method according to any one of claims 10 to 13, wherein the dialkyl tetracarboxylic acid is reacted with a chlorinating agent in the presence of pyridine. 16. A liquid crystal alignment agent characterized by containing 6 〇mol/. The above bis(chlorocarbonyl) compound and diamine of the acid chloride represented by the following formula (101) in which the cyclobutane ring is bonded to the chlorocarbonyl group at the 1,3 position and the alkyl ester group at the 2,4 position. Reactive polyglycolate, -88 - (101) 201041848 [Chemical 8] ^°ΊίΏτα ο ο (wherein, Ri is an alkyl group having 1 to 5 carbon atoms, and r2, r3, r4, and r5 ^ are a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, which may be related or different) 〇17. The liquid crystal alignment agent of claim 16, wherein the acid chloride is a structure represented by the following formula (102), [Chem. 9] I (102) 0 0 (wherein, Ri is an alkyl group having 1 to 5 carbon atoms, and R6 is a monovalent hydrocarbon group having 1 to 30 carbon atoms). 18. The liquid crystal alignment agent of claim 16, wherein the acid chloride is a structure represented by the following formula (103), -89- (103) (103) 201041848 [Chemical] (wherein, Ri is an alkyl group having 1 to 5 carbon atoms). A liquid crystal alignment film obtained by irradiating a polarized radiation onto a film obtained by baking a liquid crystal alignment agent according to any one of claims 16 to 19 of the patent application. A method for producing a liquid crystal alignment film which is obtained by irradiating a polarized radiation to a film obtained by baking a liquid crystal alignment agent according to any one of claims U to B. -90 -