TWI805573B - Liquid crystal alignment agent, liquid crystal alignment film and manufacturing method thereof, liquid crystal element and polymer - Google Patents

Abstract

When obtaining a liquid crystal alignment film by the photo-alignment method, the liquid crystal element excellent in AC afterimage characteristic and long-term heat resistance is obtained. The liquid crystal alignment agent contains a polymer (P) having at least one selected from the group consisting of partial structures represented by formula (1) and partial structures represented by formula (2). In the formula, X ^is a tetravalent organic group having a cyclobutane ring structure, and has at least one substituent on the ring portion of the cyclobutane ring. ^X2 is a divalent organic group having a specific structure having at least any one of a chain hydrocarbon structure and an alicyclic hydrocarbon structure. R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms.

Description

Liquid crystal alignment agent, liquid crystal alignment film and manufacturing method thereof, liquid crystal Components and Polymers

The disclosure relates to a liquid crystal alignment agent, a liquid crystal alignment film and a manufacturing method thereof, a liquid crystal element, a polymer and a compound.

[Cross-reference of related application]

This application is based on Japanese Patent Application No. 2017-74659 filed on April 4, 2017, the contents of which are described here.

Liquid crystal elements are widely used in televisions, mobile devices, various monitors, and the like. Moreover, in a liquid crystal element, a liquid crystal alignment film is used in order to control the alignment of the liquid crystal molecule in a liquid crystal cell. As a method of obtaining an organic film having liquid crystal alignment confinement force, a method of rubbing an organic film, a method of obliquely vapor-depositing silicon oxide, a method of forming a monomolecular film with a long-chain alkyl group, and A method of irradiating a photosensitive organic film with light (photo-alignment method), etc.

The photo-alignment method can suppress the generation of static electricity or dust while imparting uniform liquid crystal alignment to the photosensitive organic film, and can also precisely control the alignment direction of the liquid crystal. Therefore, various studies have been carried out in recent years (for example, refer to patent Literature 1). Patent Document 1 discloses that a liquid crystal alignment film is formed by irradiating polarized radiation on a film obtained by applying a liquid crystal alignment agent containing a polyamic acid having a cyclobutane ring structure in its main chain on a substrate and calcining it. [Prior Art Documents] [Patent Documents]

[Patent Document 1] International Publication No. 2012/176822

[Problems to be Solved by the Invention] In the case of obtaining a liquid crystal alignment film by photo-alignment treatment, there is a tendency that the alignment restriction force of liquid crystal molecules is not sufficient compared with rubbing treatment, and it is easy to cause a phenomenon known as alternating current (alternating current, AC) Afterimages of afterimages. The AC afterimage is an afterimage generated when the direction of the initial alignment deviates from the original direction of the liquid crystal element due to long-term driving of the liquid crystal element. An effective method for reducing AC afterimages in liquid crystal elements is to improve the alignment order of the liquid crystal alignment film. As a liquid crystal element, it is desired to sufficiently reduce AC afterimages in order to meet demands for further performance enhancement in recent years.

In addition, in recent years, liquid crystal elements have been used in a wide range of devices and applications ranging from large-screen liquid crystal televisions to small display devices such as smartphones and tablet personal computers (PCs). With such multi-purpose use, it is assumed that the liquid crystal element is placed or installed in a place where the temperature may become high, such as inside a car or outdoors, or is driven for a long time and used under severer temperature conditions than before. Therefore, as a liquid crystal element, high reliability with respect to heat resistance is required. However, when a liquid crystal alignment film is obtained by photo-alignment treatment using a liquid crystal alignment agent containing a polyimide-based polymer having a cyclobutane ring structure on the main chain, there is a concern that by performing When the obtained liquid crystal element is exposed to a high-temperature environment for a long time due to the generated decomposition products by irradiation with light, tiny bright spots are likely to be generated, and the reliability of heat resistance (especially long-term heat resistance) is poor.

This disclosure is made in view of the above situation, and one object thereof is to provide a liquid crystal alignment agent that can obtain a liquid crystal element having excellent AC afterimage characteristics and long-term heat resistance when a liquid crystal alignment film is obtained by a photo-alignment method . [Means to solve the problem]

In order to solve the above-mentioned problems, this disclosure adopts the following means.

（式（1）及式（2）中，X¹ 為具有環丁烷環結構的4價有機基，且於環丁烷環的環部分具有至少一個取代基。X² 為下述式（4）或下述式（5）表示的2價有機基。R⁵ 及R⁶ 分別獨立地為氫原子或碳數1～6的1價有機基） [化2]

（式（4）及式（5）中，A¹ 及A² 為2價芳香環基，且亦可於環部分具有取代基。其中，A¹ 與A² 相同。Y¹ 及Y² 分別獨立地為單鍵、氧原子、硫原子、或｢-NR⁷ -｣（R⁷ 為氫原子或1價有機基）。其中，Y¹ 與Y² 互不相同。B¹ 為下述式（7）或式（8）表示的2價雜環基。Y³ 為氧原子、或｢-NR⁹ -｣（R⁹ 為氫原子或1價有機基）。Z¹ 為具有鏈狀烴結構及脂環式烴結構中的至少任一者的碳數1～15的2價有機基，Z² 為單鍵、或者具有鏈狀烴結構及脂環式烴結構中的至少任一者的碳數1～15的2價有機基。其中，在Y¹ 及Y² 中的一者為硫原子且另一者為單鍵的情況下，Z¹ 的碳數為2以上。｢*｣表示結合鍵） [化3]

（式（7）及式（8）中，R⁸ 為取代基。r為0～3的整數，m為0～（r+2）的整數。｢*｣表示結合鍵） ＜2＞ 一種液晶配向膜，其是使用所述＜1＞的液晶配向劑而形成。 ＜3＞ 一種液晶配向膜的製造方法，其包括如下光配向步驟：使用所述＜1＞的液晶配向劑形成塗膜，對所述塗膜實施光照射處理而賦予液晶配向能力。 ＜4＞ 一種液晶元件，其具備所述＜2＞的液晶配向膜。 ＜5＞ 一種聚合物，其具有選自由所述式（1）表示的部分結構及所述式（2）表示的部分結構所組成的群組中的至少一種。 ＜6＞ 一種化合物，其由下述式（16）表示。 [化4]

（式（16）中，A³ 及A⁴ 為自苯環（Benzene ring）、吡啶環（Pyridine ring）或嘧啶環（Pyrimidine ring）的環部分去除2個氫原子而成的2價基團，且亦可於環部分具有取代基。其中，A³ 與A⁴ 相同。R¹³ 為氫原子或1價有機基，Y⁸ 為氧原子或硫原子。n為1～5的整數） [發明的效果]<1> A liquid crystal alignment agent comprising a polymer (P) having a partial structure selected from a partial structure represented by the following formula (1) and a partial structure represented by the following formula (2): at least one of the group. [chemical 1]

(In formula (1) and formula (2), X ¹ is a tetravalent organic group having a cyclobutane ring structure, and has at least one substituent on the ring part of the cyclobutane ring. X ² is the following formula (4 ) or a divalent organic group represented by the following formula (5). R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent organic group with 1 to 6 carbon atoms) [Chemical 2]

(In formula (4) and formula (5), A ¹ and A ² are divalent aromatic ring groups, and may have substituents on the ring part. Among them, A ¹ and A ² are the same. ^{Y 1} and Y ² are independently is a single bond, an oxygen atom, a sulfur atom, or "-NR ⁷ -" (R ⁷ is a hydrogen atom or a monovalent organic group). Among them, Y ¹ and Y ² are different from each other. ^{B 1} is the following formula (7 ) or a divalent heterocyclic group represented by formula (8). Y ³ is an oxygen atom, or "-NR ⁹ -" (R ⁹ is a hydrogen atom or a monovalent organic group). ^{Z 1} is a A divalent organic group having 1 to 15 carbon atoms in at least any one of the cyclic hydrocarbon structure, Z ² is a single bond, or a carbon number 1 of at least any one of the chain hydrocarbon structure and the alicyclic hydrocarbon structure ~15 divalent organic groups. However, when one of ^Y1 and ^Y2 is a sulfur atom and the other is a single bond, the carbon number of ^Z1 is 2 or more. "*" indicates a bond) [Chem 3]

(In formulas (7) and (8), R ⁸ is a substituent. r is an integer from 0 to 3, and m is an integer from 0 to (r+2). "*" represents a bonding bond) <2> A liquid crystal The alignment film is formed by using the liquid crystal alignment agent of <1>. <3> A method for producing a liquid crystal alignment film, comprising a photo-alignment step of forming a coating film using the liquid crystal alignment agent of <1>, and subjecting the coating film to light irradiation treatment to impart liquid crystal alignment capability. <4> A liquid crystal element including the liquid crystal alignment film of the above <2>. <5> A polymer having at least one selected from the group consisting of the partial structure represented by the formula (1) and the partial structure represented by the formula (2). <6> A compound represented by the following formula (16). [chemical 4]

(In formula (16), A ³ and A ⁴ are divalent groups obtained by removing two hydrogen atoms from the ring portion of a Benzene ring, a Pyridine ring, or a Pyrimidine ring, And also may have a substituent in the ring part. Wherein, A ³ is the same as A ^4. R ¹³ is a hydrogen atom or a monovalent organic group, Y ⁸ is an oxygen atom or a sulfur atom. n is an integer of 1 to 5) [invented Effect]

According to the liquid crystal alignment agent disclosed herein, when a liquid crystal alignment film is obtained by a photo-alignment method, a liquid crystal element having excellent long-term heat resistance and reduced AC afterimages can be obtained.

Hereinafter, the components prepared in the liquid crystal alignment agent of the present disclosure, and other components arbitrarily prepared as needed will be described.

<<Polymer (P)>> The liquid crystal alignment agent disclosed herein contains a polymer (P) having a partial structure selected from the formula (1) and the formula (2). At least one of the group consisting of partial structures of . In the formulas (1) and (2), X ¹ is a tetravalent organic group having a cyclobutane ring structure, and has at least one substituent on the ring portion of the cyclobutane ring. As a substituent which a cyclobutane ring has, a halogen atom, an alkyl group, a halogenated alkyl group, an alkoxyl group, an alkenyl group, an alkynyl group etc. are mentioned, for example. The number of substituents is not particularly limited, but is preferably 1-4.

（式（3）中，R¹ ～R³ 分別獨立地為氫原子、鹵素原子、碳數1～6的烷基、碳數1～6的鹵化烷基、碳數1～6的烷氧基、碳數1～6的硫代烷基、碳數2～6的烯基、碳數2～6的炔基、或｢-COR²⁰ ｣（其中，R²⁰ 為碳數1～6的烷基、含氟烷基、烷氧基或含氟烷氧基）。R⁴ 為鹵素原子、碳數1～6的烷基、碳數1～6的鹵化烷基、碳數1～6的烷氧基、碳數1～6的硫代烷基、碳數2～6的烯基、碳數2～6的炔基、或｢-COR²⁰ ｣。其中，R¹ ～R⁴ 中鄰接的基團彼此亦可鍵結而形成環結構。在式中存在多個R²⁰ 的情況下，多個R²⁰ 可彼此相同亦可不同。｢*｣表示結合鍵）X ¹ is preferably a group represented by the following formula (3). [chemical 5]

(In formula (3), R ¹ to R ³ are independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbons, a halogenated alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons , a thioalkyl group with 1 to 6 carbons, an alkenyl group with 2 to 6 carbons, an alkynyl group with 2 to 6 carbons, or “-COR ²⁰ ” (wherein, R ²⁰ is an alkyl group with 1 to 6 carbons , fluorine-containing alkyl, alkoxy or fluorine-containing alkoxy). ^R4 is a halogen atom, an alkyl group with 1 to 6 carbons, a halogenated alkyl group with 1 to 6 carbons, or an alkoxy group with 1 to 6 carbons group, thioalkyl group with 1 to 6 carbons, alkenyl group with 2 to 6 carbons, alkynyl group with 2 to 6 carbons, or “-COR ²⁰ ”. Among them, the adjacent groups among R ¹ to R ⁴ They can also be bonded to each other to form a ring structure. When there are multiple R ^20s in the formula, the multiple R ^20s can be the same or different from each other. "*" means a bond)

（式（1-A）及式（1-B）中，X² 、R⁵ 及R⁶ 分別與所述式（1）中的X² 、R⁵ 及R⁶ 為相同含義。R¹ ～R⁴ 分別與所述式（3）中的R¹ ～R⁴ 為相同含義） [化7]

（式（2-A）中，X² 與所述式（1）中的X² 為相同含義。R¹ ～R⁴ 分別與所述式（3）中的R¹ ～R⁴ 為相同含義）Furthermore, in the case where ^X in the formula (1) is a group represented by the formula (3), the formula (1) is represented by the following formula (1-A) or formula (1-B) ), the formula (2) is represented by the following formula (2-A). [chemical 6]

(In formula (1-A) and formula (1-B), X ² , R ⁵ and R ⁶ have the same meanings as X ² , R ⁵ and R ⁶ in formula (1). R ¹ to R ⁴ have the same meaning as R ¹ to R ⁴ in the formula (3), respectively) [Chem. 7]

(In formula (2-A), X ² has the same meaning as X ² in formula (1). ^{R 1} to R ⁴ have the same meaning as R ¹ to R ⁴ in formula (3).)

X ² in the formula (1) and formula (2) is a divalent organic group represented by the formula (4) or formula (5). In the formulas (4) and (5), A ¹ and A ² are groups obtained by removing two hydrogen atoms from the ring portion of the aromatic ring, and may have a substituent on the ring portion. Examples of the aromatic ring include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a biphenyl ring; a pyridine ring, a pyrazine ring, and a pyrimidine ring; ring, pyridazine ring (Pyridazine ring) and other nitrogen-containing heterocycles, etc. As a substituent which an aromatic ring may have, the alkyl group etc. which have 1-6 carbon atoms are mentioned, for example. Among them, ^A1 is the same as ^A2 . In the case where ^A1 and ^A2 are the same, the monomers used to obtain the polymer (P) can be easily synthesized, and the effects of reducing AC afterimages and improving long-term heat resistance are high. better. A ¹ and A ² are preferably selected from benzene rings, biphenyl rings, and pyridine rings which may have substituents, in terms of obtaining a liquid crystal device with better liquid crystal alignment and AC afterimage characteristics. Or a group obtained by removing two hydrogen atoms from the ring portion of the pyrimidine ring.

Y ¹ and Y ² in the formula (4) are each independently a single bond, an oxygen atom, a sulfur atom, or "-NR ⁷ -" (R ⁷ is a hydrogen atom or a monovalent organic group). Wherein, Y ¹ and Y ² are different from each other. Among them, an oxygen atom and a sulfur atom are preferable in that the sensitivity of the polymer (P) to light can be increased, and the effect of improving the liquid crystal alignment and AC afterimage characteristics of the obtained liquid crystal element is higher. , or "-NR ⁷ -", more preferably an oxygen atom or "-NR ⁷ -". Furthermore, it is considered that since Y ¹ and Y ² are different from each other, X ² in the formula (1) becomes an asymmetric structure, so the solubility of the polymer can be improved, and the crystallinity of the photodecomposed product decreases, Therefore, the occurrence of tiny bright spots can be reduced. The monovalent organic group of R ⁷ includes, for example, an alkyl group having 1 to 6 carbon atoms, a protecting group, and the like. The protecting group is preferably a group detached by heat, and examples thereof include a carbamate-based protecting group, an amide-based protecting group, an imide-based protecting group, a sulfonamide-based protecting group, and the like. Among these, the protecting group is preferably a tert-butoxycarbonyl group in terms of high detachability by heat or in terms of reducing the remaining amount of the deprotected moiety in the film. ^R7 is preferably a hydrogen atom, an alkyl group with 1 to 3 carbons, or a protecting group, and is more preferably a carbon number from the viewpoint of further reducing the occurrence of tiny bright spots and improving the permeability of the liquid crystal alignment film. 1 to 3 alkyl groups. Y ³ in the formula (5) is an oxygen atom or "-NR ⁹ -". Regarding specific examples and preferable examples of R ⁹ , the description of R ⁷ in the aforementioned "-NR ⁷ -" can be applied.

^Z1 is a divalent organic group having 1 to 15 carbon atoms having at least any one of a chain hydrocarbon structure and an alicyclic hydrocarbon structure, and ^Z2 is a single bond, or has a chain hydrocarbon structure or an alicyclic hydrocarbon structure At least any one of divalent organic groups having 1 to 15 carbon atoms. However, when one of Y ¹ and Y ² is a sulfur atom and the other is a single bond, the carbon number of Z ¹ is an integer of 2 to 15. Here, in this specification, a "chain hydrocarbon structure" refers to a linear hydrocarbon structure and a branched hydrocarbon structure including only a chain structure without a ring structure. Wherein, the chain hydrocarbon structure may be saturated or unsaturated. The "alicyclic hydrocarbon structure" refers to a hydrocarbon structure including only an alicyclic hydrocarbon structure as a ring structure and not containing an aromatic ring structure. However, the alicyclic hydrocarbon structure does not need to include only the alicyclic hydrocarbon structure, but also includes those having a chain structure in a part thereof. Z ¹ is preferably a divalent chain hydrocarbon group, or has an oxygen atom, a sulfur atom or "-NR ¹² -" between the carbon-carbon bonds of the chain hydrocarbon group (R ¹² is a hydrogen atom or a monovalent organic group) group. Z ² is preferably a single bond, a divalent chain hydrocarbon group, or a group having an oxygen atom, a sulfur atom, or "-NR ¹² -" between the carbon-carbon bonds of the chain hydrocarbon group.

（式（6）中，R¹⁰ 及R¹¹ 分別獨立地為烷二基，R¹⁰ 及R¹¹ 的合計碳數為1～15。Y⁴ 為氧原子、硫原子、或｢-NR¹² -｣（R¹² 為氫原子或1價有機基）。p為0～4的整數。在p為2以上的情況下，多個R¹⁰ 、Y⁴ 可彼此相同亦可不同。其中，在所述式（4）中的Y¹ 及Y² 中的一者為硫原子且另一者為單鍵的情況下，R¹⁰ 及R¹¹ 的合計碳數為2以上）The divalent organic groups of Z ¹ and Z ² are preferably divalent organic groups represented by the following formula (6) in terms of further reducing the occurrence of fine bright spots caused by photodecomposed products. [chemical 8]

(In formula (6), R ¹⁰ and R ¹¹ are independently alkanediyl groups, and the total carbon number of R ¹⁰ and R ¹¹ is 1 to 15. ^{Y 4} is an oxygen atom, a sulfur atom, or "-NR ¹² -" (R ¹² is a hydrogen atom or a monovalent organic group). p is an integer of 0 to 4. When p is 2 or more, a plurality of R ¹⁰ and Y ⁴ may be the same or different from each other. Wherein, in the formula (4) When one of Y ¹ and Y ² is a sulfur atom and the other is a single bond, the total carbon number of R ¹⁰ and R ¹¹ is 2 or more)

In the above-mentioned formula (6), R ¹⁰ and R ¹¹ may be linear or branched, but in terms of improving the effect of suppressing the generation of tiny bright spots in the liquid crystal element, preferably straight chain. Specifically, the groups represented by the formula (6) (ie, Z ¹ and Z ² ) are preferably alkanediyl groups, or have oxygen atoms, sulfur atoms or The "-NR ⁸ -" group is more preferably an alkanediyl group, or a group having an oxygen atom between the carbon-carbon bonds of the alkanediyl group, and is still more preferably an alkanediyl group. Regarding specific examples and preferable examples of R ¹² , the description of R ⁷ in "-NR ⁷ -" above can be applied. p is preferably 0-2.

In the case where Z ¹ in the formula (4) is a divalent group represented by the formula (6), in terms of promoting the re-alignment of molecular chains by heating in the manufacture of liquid crystal alignment films, and The total carbon number of R ¹⁰ and R ¹¹ (when p is 2 or more, the total carbon number of a plurality of R ¹⁰ and R ¹¹ ) is preferable in terms of further reducing the generation of tiny bright spots in the liquid crystal element It is 2 or more carbon atoms, more preferably 3 or more carbon atoms. Y ⁴ is preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom. When Z ² in the formula (5) is a divalent group represented by the formula (6), R ¹¹ is preferably methylene in terms of further enhancing the effect of reducing AC afterimages. basis, and p=0. Z ² is preferably a single bond or methylene.

B ¹ of the formula (5) is a nitrogen-containing heterocyclic group represented by the formula (7) or formula (8). In the formula (7) and formula (8), the substituent of R ⁸ includes, for example, an alkyl group having 1 to 6 carbon atoms. r is preferably 1 or 2, more preferably 2, from the viewpoint of liquid crystal alignment. Among these, ^B1 is preferably substituted or unsubstituted piperidine-1,4-diyl or substituted or unsubstituted piperazine from the viewpoint of liquid crystal alignment and AC afterimage characteristics. -1,4-diyl, especially substituted or unsubstituted piperidine-1,4-diyl.

（式（4A）中，A³ 及A⁴ 為自苯環、吡啶環或嘧啶環的環部分去除2個氫原子而成的2價基團，且亦可於環部分具有取代基。其中，A³ 與A⁴ 相同。Y⁵ 及Y⁶ 分別獨立地為單鍵、氧原子、硫原子、或｢-NR¹³ -｣（R¹³ 為氫原子或1價有機基）。其中，Y⁵ 與Y⁶ 互不相同。n為1～5的整數。其中，在Y⁵ 及Y⁶ 中的一者為硫原子且另一者為單鍵的情況下，n為2以上。｢*｣表示結合鍵）The above-mentioned formula (4) is particularly preferably a group represented by the following formula (4A) in terms of improving liquid crystal alignment, AC afterimage characteristics, and long-term heat resistance. [chemical 9]

(In formula (4A), A ³ and A ⁴ are divalent groups obtained by removing two hydrogen atoms from the ring part of the benzene ring, pyridine ring, or pyrimidine ring, and may have a substituent on the ring part. Among them, A ³ is the same as A ^4. Y ⁵ and Y ⁶ are each independently a single bond, an oxygen atom, a sulfur atom, or "-NR ¹³ -" (R ¹³ is a hydrogen atom or a monovalent organic group). Among them, Y ⁵ and Y ⁶ are different from each other. n is an integer of 1 to 5. However, when one of Y ⁵ and Y ⁶ is a sulfur atom and the other is a single bond, n is 2 or more. "*" indicates a combination key)

（式（4C）中，Y⁵¹ 及Y⁶¹ 分別獨立地為單鍵、氧原子或硫原子。其中，Y⁵¹ 與Y⁶¹ 互不相同。n為1～5的整數。其中，在Y⁵¹ 及Y⁶¹ 中的一者為硫原子且另一者為單鍵的情況下，n為2以上。A³ 及A⁴ 與所述式（4A）為相同含義。｢*｣表示結合鍵）Examples of substituents that ^A3 and ^A4 may have include alkyl groups having 1 to 6 carbon atoms, and the like. Regarding specific examples and preferable examples of the monovalent organic group of R ¹³ , the description of R ⁷ above can be applied. In the case where Y ⁵ and Y ⁶ of the group represented by the formula (4A) are a single bond, an oxygen atom or a sulfur atom (wherein Y ⁵ and Y ⁶ are different from each other), it is highly sensitive to light, Moreover, it is preferable at the point that the yield can be increased in the synthesis of polyamic acid ester. In this case, X ² is represented by the following formula (4C). In the following formula (4C), it is particularly preferable that one of Y ⁵¹ and Y ⁶¹ is an oxygen atom and the other is a single bond. [chemical 10]

(In formula (4C), Y ⁵¹ and Y ⁶¹ are each independently a single bond, an oxygen atom or a sulfur atom. Among them, Y ⁵¹ and Y ⁶¹ are different from each other. n is an integer from 1 to 5. Among them, in Y ⁵¹ and When one of Y ⁶¹ is a sulfur atom and the other is a single bond, n is 2 or more. A ³ and A ⁴ have the same meaning as the above-mentioned formula (4A). "*" indicates a bond)

（式（4A-1）中，Q¹ 及Q² 分別獨立地為｢CH｣或氮原子。R¹³ 、Y⁵ 、Y⁶ 及n與所述式（4A）為相同含義。｢*｣表示結合鍵）From the perspective of liquid crystal alignment and AC afterimage characteristics, the bonding sites on the benzene ring, pyridine ring or pyrimidine ring of ^A3 and ^A4 in ^Y5 and ^Y6 in the formula (4A) It is preferably in the para position with respect to the nitrogen atom bonded to X ² in the above-mentioned formula (1) and the above-mentioned formula (2). The group represented by the formula (4A) is particularly preferably a group represented by the following formula (4A-1). [chemical 11]

(In formula (4A-1), Q ¹ and Q ² are independently "CH" or a nitrogen atom. R ¹³ , Y ⁵ , Y ⁶ and n have the same meanings as in formula (4A). "*" means bond)

（式（5A）中，A⁵ 及A⁶ 為自苯環、吡啶環或嘧啶環的環部分去除2個氫原子而成的2價基團，且亦可於環部分具有取代基。其中，A⁵ 與A⁶ 相同。B^２ 為經取代或未經取代的哌啶-1,4-二基、或者經取代或未經取代的哌嗪-1,4-二基。Y⁷ 為氧原子、或｢-NR⁹ -｣（R⁹ 為氫原子或1價有機基）。k為0～5的整數。｢*｣表示結合鍵）The formula (5) is preferably a divalent organic group represented by the following formula (5A). It is preferable that k in Formula (5) is 0-3, More preferably, it is 0 or 1. [chemical 12]

(In formula (5A), A ⁵ and A ⁶ are divalent groups obtained by removing two hydrogen atoms from the ring part of the benzene ring, pyridine ring, or pyrimidine ring, and may have a substituent on the ring part. Among them, A ⁵ is the same as A ^6. B ² is substituted or unsubstituted piperidine-1,4-diyl, or substituted or unsubstituted piperazine-1,4-diyl. Y ⁷ is an oxygen atom , or "-NR ⁹ -" (R ⁹ is a hydrogen atom or a monovalent organic group). k is an integer from 0 to 5. "*" means a bond)

The polymer (P) is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide. The polymer (P) has a partial structure derived from a tetracarboxylic acid derivative having a cyclobutane ring structure having at least one substituent in a ring portion, and a partial structure derived from a diamine compound, The diamine compound has a divalent organic group represented by the formula (4) or formula (5). The synthesis method of such a polymer (P) is not specifically limited, It can obtain by combining the general method of organic chemistry suitably. In addition, in this specification, the meaning of "tetracarboxylic acid derivative" includes tetracarboxylic dianhydride, tetracarboxylic diester, and tetracarboxylic diester dihalide.

(Polyamic acid) When the polymer (P) is polyamic acid, this polyamic acid (hereinafter also referred to as "polyamic acid (P)") can be obtained, for example, by making tetracarboxylic acid di Tetracarboxylic dianhydrides obtained by reacting anhydrides with diamine compounds including tetracarboxylic dianhydrides having a cyclobutane ring structure having at least one substituent on the ring portion (hereinafter also referred to as "specific acid dianhydrides") , the diamine compound includes a diamine compound having a divalent organic group represented by the formula (4) or formula (5) (hereinafter also referred to as "specific diamine").

(Specific acid dianhydride) As a specific acid dianhydride, the tetracarboxylic dianhydride which has the partial structure represented by said formula (3) is mentioned. As a specific example of a specific acid dianhydride, the compound etc. which are each represented by following formula (TA-1-1) - a formula (TA-1-15) are mentioned, for example. [chemical 13]

As the specific acid dianhydride, among these, compounds represented by the formulas (TA-1-1) to (TA-1-12) are preferred, and 1,3-dimethyl-1, 2,3,4-Cyclobutanetetracarboxylic dianhydride (the compound represented by the above formula (TA-1-2)). In addition, specific acid dianhydride can be used individually by 1 type or in combination of 2 or more types.

When synthesizing polyamic acid (P), you may use specific acid dianhydride together with other tetracarboxylic dianhydrides other than a specific acid dianhydride as tetracarboxylic dianhydride. Other tetracarboxylic dianhydrides will not be particularly limited as long as they do not have a cyclobutane ring structure having at least one substituent in a ring portion. As specific examples of other tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides include, for example, ethylenediaminetetraacetic dianhydride, etc.;

Examples of alicyclic tetracarboxylic dianhydride include: 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5 -Dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran -3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetra Hydrogen-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5 :6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclohexanetetracarboxylic dianhydride, cyclopentanetetracarboxylic acid dianhydride, etc.; examples of aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)bisphthalic anhydride, p-phenylene bis(partial trimellitic acid monoester anhydride), ethylene glycol bis(trimellitic anhydride ester), 1,3-propanediol bis(trimellitic anhydride ester), 3,3',4,4'-benzophenone tetracarboxylic dianhydride, etc. , Tetracarboxylic dianhydride described in JP 2010-97188 A can be used.

As other tetracarboxylic dianhydrides, in terms of further improving the effect of reducing microspots, among them, those selected from ethylenediaminetetraacetic dianhydride, 1,2,3,4-cyclobutane Composed of alkane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, pyromellitic dianhydride and 3,3',4,4'-benzophenone tetracarboxylic dianhydride At least one of the group as a copolymerization component. In addition, when synthesizing a polymer (P), as another tetracarboxylic dianhydride, it can use individually by 1 type or in combination of 2 or more types.

When synthesizing polyamic acid (P), from the viewpoint of sufficiently obtaining the effect of the present disclosure, the use ratio of the specific acid dianhydride is preferably set to More than 30 mol%. More preferably, it is at least 50 mol%, and still more preferably at least 80 mol%. When other tetracarboxylic dianhydrides are used, the usage ratio is preferably 5 mol % to 70 mol %, more preferably 10 mol%~50 mol%.

(specific diamine)

Specific diamine is a compound represented by following formula (14) or following formula (15).

[Chem. 14] H ₂ NA ¹ -Y ¹ -Z ¹ -Y ² -A ² -NH ₂ (14) H ₂ NA ¹ -B ¹ -Z ² -Y ³ -A ² -NH ₂ (15)

(In formula (14) and formula (15), A ¹ , A ² , B ¹ , Y ¹ , Y ² , Y ³ , Z ¹ and Z ² have the same meaning as the formula (4) and formula (5) )

The descriptions of A ¹ , A ² , B ¹ , Y ¹ , Y ² , Y ³ , Z ¹ and Z ² in the formula (14) and formula (15) respectively apply to the formula (4), formula (5 )instruction of. Among these, the compound represented by the formula (14) is preferably a compound represented by the following formula (4B), and the compound represented by the formula (15) is preferably a compound represented by the following formula (5B).

（式（4B）中，A³ 、A⁴ 、Y⁵ 、Y⁶ 及n與所述式（4A）中的A³ 、A⁴ 、Y⁵ 、Y⁶ 及n為相同含義） [化16]

（式（5B）中，A⁵ 、A⁶ 、B² 、Y⁷ 及k與所述式（5A）中的A⁵ 、A⁶ 、B² 、Y⁷ 及k為相同含義）[chemical 15]

(In formula (4B), A ³ , A ⁴ , Y ⁵ , Y ⁶ and n have the same meaning as A ³ , A ⁴ , Y ⁵ , Y ⁶ and n in formula (4A) above) [Chem. 16]

(In formula (5B), A ⁵ , A ⁶ , B ² , Y ⁷ and k have the same meanings as A ⁵ , A ⁶ , B ² , Y ⁷ and k in formula (5A) above.)

The primary amine groups in the formula (4B) and formula (5B) are preferably other groups relative to the rings (benzene ring, pyridine ring or pyrimidine ring) bonded to A ³ , A ⁴ , A ⁵ and A ⁶ The group is the counterpoint. Concrete examples and comparisons of A ³ , A ⁴ , Y ⁵ , Y ⁶ and n in the formula (4B), and A ⁵ , A ⁶ , B ² , Y ⁷ and k in the formula (5B). For the best example, apply the description.

[化18]

[化19]

[化20]

As a specific example of a specific diamine, the compound etc. which are each represented by following formula (d-1) - a formula (d-54) are mentioned, for example. Specific diamines can be synthesized by appropriate general methods of combinatorial organic chemistry. In addition, specific diamine may be used individually by 1 type, or may use it in combination of 2 or more types. "Boc" in the following formula represents t-Butyloxy carbonyl (t-Butyloxy carbonyl). [chemical 17]

[chemical 18]

[chemical 19]

[chemical 20]

When synthesizing polyamic acid (P), only specific diamine may be used as a diamine compound, but specific diamine may be used together with other diamines other than specific diamine. Other diamines will not be specifically limited as long as it does not correspond to a specific diamine, For example, aliphatic diamine, alicyclic diamine, aromatic diamine, diaminoorganosiloxane, etc. are mentioned. As specific examples of these, aliphatic diamines include, for example, m-xylylenediamine, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, hexamethylenediamine, etc.; Examples of diamines of the formula include: p-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), etc.;

（式（E-1）中，XI及XII分別獨立地為單鍵、-O-、-COO-或-OCO-，R^I 為碳數1～3的烷二基，R^II 為單鍵或碳數1～3的烷二基，a為0或1，b為0～2的整數，c為1～20的整數，d為0或1。其中，a及b不會同時成為0） 表示的化合物等側鏈型二胺： 對苯二胺、4,4'-二胺基二苯基甲烷、4,4'-伸乙基二苯胺、4,4'-二胺基二苯基胺、4,4'-二胺基二苯基硫醚、4-胺基苯基-4'-胺基苯甲酸酯、4,4'-二胺基偶氮苯、3,5-二胺基苯甲酸、1,2-雙(4-胺基苯氧基)乙烷、1,5-雙(4-胺基苯氧基)戊烷、N,N'-二(4-胺基苯基)-N,N'-二甲基乙二胺、雙[2-(4-胺基苯基)乙基]己二酸、雙(4-胺基苯基)胺、N,N-雙(4-胺基苯基)甲基胺、1,4-雙(4-胺基苯基)-哌嗪、N,N'-雙(4-胺基苯基)-聯苯胺、2,2'-二甲基-4,4'-二胺基聯苯、2,2'-雙(三氟甲基)-4,4'-二胺基聯苯、4,4'-二胺基二苯基醚、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、4,4'-(伸苯基二亞異丙基)雙苯胺、1,4-雙(4-胺基苯氧基)苯、4-(4-胺基苯氧基羰基)-1-(4-胺基苯基)哌啶、4,4'-[4,4'-丙烷-1,3-二基雙(哌啶-1,4-二基)]二苯胺等非側鏈型二胺； 二胺基有機矽氧烷例如可列舉：1,3-雙(3-胺基丙基)-四甲基二矽氧烷等，此外，可使用日本專利特開2010-97188號公報中記載的二胺化合物。Examples of aromatic diamines include dodecyloxydiaminobenzene, hexadecyloxydiaminobenzene, octadecyloxydiaminobenzene, cholesteryloxydiaminobenzene, cholesteryloxydiaminobenzene, Alkenyloxydiaminobenzene, cholestyl diaminobenzoate, cholestenyl diaminobenzoate, lanostyl diaminobenzoate, 3,6-bis(4-amine benzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 1,1-bis(4-((aminophenyl)methyl)phenyl) -4-butylcyclohexane, 2,5-diamino-N,N-diallylaniline, the following formula (E-1) [Chem. 21]

(In formula (E-1), XI and XII are independently a single bond, -O-, -COO- or -OCO-, R ^I is an alkanediyl group with 1 to 3 carbons, R ^II is a single bond or An alkanediyl group with 1 to 3 carbons, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1. Among them, a and b will not be 0 at the same time) Compounds such as side-chain diamines: p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-ethylenediphenylamine, 4,4'-diaminodiphenylamine , 4,4'-diaminodiphenyl sulfide, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminoazobenzene, 3,5-diamine benzoic acid, 1,2-bis(4-aminophenoxy)ethane, 1,5-bis(4-aminophenoxy)pentane, N,N'-bis(4-aminophenoxy) base)-N,N'-dimethylethylenediamine, bis[2-(4-aminophenyl)ethyl]adipic acid, bis(4-aminophenyl)amine, N,N-bis (4-aminophenyl)methylamine, 1,4-bis(4-aminophenyl)-piperazine, N,N'-bis(4-aminophenyl)-benzidine, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-diaminobiphenyl Phenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-(phenylenediisopropylidene)bisaniline, 1,4-bis( 4-aminophenoxy)benzene, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, 4,4'-[4,4'-propane-1 ,3-diylbis(piperidine-1,4-diyl)]diphenylamine and other non-side-chain diamines; diaminoorganosiloxanes include, for example: 1,3-bis(3-aminopropane base)-tetramethyldisiloxane, etc., and diamine compounds described in JP-A-2010-97188 can be used.

As other diamines used in the synthesis of polyamic acid (P), it is preferable to include diamines selected from the group consisting of O,O'-bis(4-amine) in terms of the high effect of reducing microscopic bright spots generated in liquid crystal elements. At least one of the group consisting of phenyl)-ethylene glycol and N,N'-bis(4-aminophenyl)-N,N'-dimethylethylenediamine can obtain liquid crystal In terms of a liquid crystal device with good alignment and AC afterimage characteristics, it is preferable to contain a liquid crystal element selected from p-phenylenediamine, 1,4-bis(4-aminophenyl)-piperidine, and 2,2'- At least one of the group consisting of dimethyl-4,4'-diaminobiphenyl. In addition, when synthesizing polyamic acid (P), other diamines can be used individually by 1 type or in combination of 2 or more types.

From the viewpoint of sufficiently obtaining the effects of the present disclosure, the usage ratio of the specific diamine is preferably 20 mol % or more relative to the total amount of diamine compounds used for synthesizing polyamic acid (P). More preferably, it is at least 40 mol%, and still more preferably at least 60 mol%. When other diamines are used, the usage ratio is preferably from 5 mol% to 80 mol%, more preferably from 10 mol% to the total amount of diamine compounds used for synthesis. 60 mole %.

(Synthesis of polyamic acid) Polyamic acid (P) can be obtained by mixing tetracarboxylic dianhydride and diamine compound as described above with a molecular weight regulator (for example, acid monoanhydride, monoamine compound, Monoisocyanate compounds, etc.) are obtained by reacting together. The usage ratio of the tetracarboxylic dianhydride and the diamine compound used in the synthesis reaction of polyamic acid (P) is preferably such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 per equivalent of the amine group of the diamine compound. The ratio of equivalent to 2 equivalents.

The synthesis reaction of polyamide acid (P) is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20°C to 150°C, and the reaction time is preferably 0.1 hour to 24 hours. Examples of the organic solvent used for the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. A preferred organic solvent is selected from N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butylene One or more of the group consisting of lactone, tetramethylurea, hexamethylphosphoryltriamine, m-cresol, xylenol, and halogenated phenol as a solvent, or more than one of these with other organic solvents ( For example, mixtures of butyl cellosolve, diethylene glycol diethyl ether, etc.). It is preferable that the usage-amount of an organic solvent shall be the quantity which becomes 0.1 mass % - 50 mass % with respect to the total amount of a reaction solution with respect to the total amount of a tetracarboxylic dianhydride and a diamine compound. The reaction solution obtained by dissolving the polyamic acid (P) may be directly used for the preparation of the liquid crystal alignment agent, or may be used for the preparation of the liquid crystal alignment agent after separating the polyamic acid (P) contained in the reaction solution.

(Polyamide ester) The polyamide ester as the polymer (P) is 1 having at least one of R ⁵ and R ⁶ in the partial structure represented by the above formula (1) having 1 to 6 carbon atoms. Polymers of structural units of valent organic groups. Specific examples of ^R5 and ^R6 include, for example, straight-chain or branched alkyl groups having 1 to 6 carbons, straight-chain or branched alkenyl groups having 2 to 6 carbons, cyclohexyl, phenyl, etc. . The polyamic acid ester can be obtained, for example, by the following method: [I] making the polyamic acid (P) obtained above and an esterifying agent (such as methanol or ethanol, N,N-dimethylformamide amine diethyl acetal, etc.), [II] making a tetracarboxylic acid diester containing a tetracarboxylic acid diester having a partial structure represented by the above formula (3) and a diamine compound containing a specific diamine Preferably in an organic medium and in a suitable dehydration catalyst (e.g., halogenated 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholine , carbonyl imidazolyl, phosphorus-based condensing agent, etc.) in the presence of the method of reacting, [III] making tetracarboxylic acid diester containing tetracarboxylic acid diester dihalide having the partial structure represented by the above formula (3) Dihalides and diamine compounds containing specific diamines are preferably in an organic solvent and in a suitable base (for example, pyridine, triethylamine and other tertiary amines, or sodium hydride, potassium hydride, sodium hydroxide, hydroxide A method in which the reaction is carried out in the presence of alkali metals such as potassium, sodium, and potassium).

The tetracarboxylic diester used in [II] above can be obtained by ring-opening a specific acid dianhydride or another tetracarboxylic dianhydride with alcohol or the like. The tetracarboxylic-acid diester dihalide used in said [III] can be obtained by making the tetracarboxylic-acid diester obtained as mentioned above react with an appropriate chlorinating agent, such as thionyl chloride. The polyamic acid ester may have only an uric acid ester structure, or may be a partially esterified product in which an uric acid ester structure and an uric acid ester structure coexist. When the polyamide ester is obtained as a solution by the above reaction, the solution may be directly used in the preparation of a liquid crystal alignment agent, or the polyamide ester contained in the reaction solution may be separated and used in a liquid crystal. Preparation of alignment agent.

(Polyimide) The polyimide as the polymer (P) is a polymer having a partial structure represented by the formula (2). The polyimide can be obtained, for example, by dehydrating and ring-closing the polyamic acid (P) synthesized as described above, and imidizing it. The polyimide may be a complete imide formed by dehydrating and ring-closing the entire amide acid structure of the polyamic acid (P) as its precursor, or it may be a part of the amide acid structure. Partial imide compound with dehydration ring closure and coexistence of amide acid structure and amide imide ring structure. The polyimide preferably has an imidization rate of 40% to 100%, more preferably 60% to 90%. The imidization rate represents the ratio of the number of imide ring structures to the sum of the number of amide acid structures and the number of imide ring structures of polyimide in percentage. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of polyamic acid (P) is preferably carried out by the following method: dissolving polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating if necessary. As the dehydrating agent, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used, for example. It is preferable that the usage-amount of a dehydrating agent shall be 0.01 mol - 20 mol with respect to 1 mol of the amide acid structure of polyamic acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. The amount of the dehydration ring-closing catalyst used is preferably 0.01 mol to 10 mol with respect to 1 mol of the dehydrating agent used. Examples of the organic solvent used include the organic solvents exemplified as those used in the synthesis of polyamic acid (P). The reaction temperature of the dehydration ring-closing reaction is preferably 0° C. to 180° C., and the reaction time is preferably 1.0 hour to 120 hours. The reaction solution containing polyimide obtained in this way can be directly used in the preparation of liquid crystal alignment agent, and can also be used in the preparation of liquid crystal alignment agent after separating polyimide. Furthermore, polyimide can also be obtained by imidation by the dehydration ring-closure reaction of polyamic acid ester.

When made into a solution with a concentration of 10% by mass, the solution viscosity of the polymer (P) is preferably a solution viscosity of 10 mPa·s to 800 mPa·s, more preferably a solution viscosity of 15 mPa·s to 500 mPa·s solution viscosity. Furthermore, the solution viscosity (mPa·s) is a concentration of 10% by mass prepared for a good solvent (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) using the polymer (P). The polymer solution is a value measured at 25° C. using an E-type rotational viscometer. The polystyrene conversion weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) of a polymer (P) becomes like this. Preferably it is 1,000-500,000, More preferably, it is 5,000-100,000. The molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. In addition, the polymer (P) contained in a liquid crystal alignment agent may be only 1 type, or may combine 2 or more types.

<<Other Components>> The liquid crystal alignment agent disclosed herein may contain other components than the polymer (P). Examples of such other components include: polymers (hereinafter also referred to as "other polymers") that do not have any of the partial structure represented by the above-mentioned formula (1) and the partial structure represented by the above-mentioned formula (2), Compounds having at least one epoxy group in the molecule, functional silane compounds, antioxidants, metal chelate compounds, hardening accelerators, surfactants, fillers, dispersants, photosensitizers, acid generators, base generators agents, free radical generators, etc. These compounding ratios can be suitably selected according to each compound in the range which does not impair the effect of this indication.

A liquid crystal alignment agent is preferable at the point which can increase the effect of suppressing the generation|occurrence|production of a micro bright spot by containing another polymer. The main skeleton of other polymers is not particularly limited, for example, polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, cellulose derivatives, polyacetal, poly Styrene derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylates, and other main-skeleton polymers. Among these, other polymers are preferably at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide in terms of suppressing the formation of fine bright spots. A sort of. In the case of blending other polymers into the liquid crystal alignment agent, the blending ratio is preferably 1% by mass to 90% by mass, more preferably 10% by mass to 80% by mass relative to the total amount of polymers in the liquid crystal alignment agent %, and more preferably 20% by mass to 70% by mass.

The liquid crystal alignment agent disclosed herein is prepared as a liquid composition preferably obtained by dispersing or dissolving the polymer (P) and optional components in an appropriate solvent. Examples of the organic solvent used include: N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolinone, γ-butyl Lactone, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol mono Methyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol- Isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate ester, diisoamyl ether, ethyl carbonate, propylene carbonate, etc. These can be used individually or in mixture of 2 or more types.

The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, etc., and is preferably 1% by mass to 10% by mass. mass % range. That is, the liquid crystal alignment agent is coated on the surface of the substrate as described later, and preferably heated to form a coating film as a liquid crystal alignment film or a coating film as a liquid crystal alignment film. At this time, when the solid content concentration is less than 1% by mass, the film thickness of the coating film becomes too small, making it difficult to obtain a favorable liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, there is a tendency that the film thickness of the coating film becomes too large, making it difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases and the coating becomes difficult. reduced sex.

The content ratio of the polymer (P) in the liquid crystal alignment agent is preferably at least 10 parts by mass, more preferably 20 parts by mass, based on a total of 100 parts by mass of the solid content (components other than the solvent) in the liquid crystal alignment agent. or more, and more preferably 30 parts by mass or more.

<<Liquid Crystal Alignment Film and Liquid Crystal Element>> The liquid crystal alignment film disclosed herein can be formed by using the liquid crystal alignment agent prepared as described above. In particular, the liquid crystal alignment film of the present disclosure is preferably produced by a method including a photo-alignment step, which is to use the liquid crystal alignment agent to form a coating film, and to perform light irradiation treatment on the coating film to impart Liquid crystal alignment capability. Moreover, the liquid crystal element of this disclosure is equipped with the liquid crystal alignment film formed using the liquid crystal alignment agent demonstrated above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited, for example, it can be applied to twisted nematic (Twisted Nematic, TN) type, super twisted nematic (Super Twisted Nematic, STN) type, vertical alignment (Vertical Alignment, VA) type (including vertical alignment-multi-domain vertical alignment (Vertical Alignment-Multi-domain Vertical Alignment, VA-MVA) type, vertical alignment-patterned vertical alignment (Vertical Alignment-Patterned Vertical Alignment, VA-PVA) type, etc.), coplanar switching (In-Plane Switching, IPS) type, Fringe Field Switching (Fringe Field Switching, FFS) type, Optically Compensated Bend (Optically Compensated Bend, OCB) type and other modes. A liquid crystal element can be manufactured by the method including the following steps 1-3, for example. The substrate used in step 1 differs depending on the required operation mode. All operation modes in step 2 and step 3 are common.

(Step 1: Formation of Coating Film) First, the liquid crystal alignment agent is coated on the substrate, preferably by heating the coated surface, thereby forming a coating film on the substrate. As the substrate, for example, glass such as float glass and soda glass can be used; polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly(alicyclic olefin) and other plastic transparent substrates. As the transparent conductive film provided on one side of the substrate, Nesser (NESA) film (registered trademark of PPG Corporation of the United States) containing tin oxide (SnO ₂ ), a film containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) Indium tin oxide (Indium tin oxide, ITO) film, etc. In the case of manufacturing a TN-type, STN-type, or VA-type liquid crystal element, two substrates provided with patterned transparent conductive films are used. On the other hand, when manufacturing an IPS or FFS liquid crystal element, a substrate provided with electrodes including a comb-shaped transparent conductive film or a metal film and a counter substrate provided with no electrodes are used. As the metal film, for example, a film containing metal such as chromium can be used. The coating of the liquid crystal alignment agent on the substrate is preferably carried out on the electrode formation surface by lithographic printing, flexographic printing, spin coating, roll coater or inkjet.

After applying the liquid crystal alignment agent, it is preferable to perform preheating (prebaking) for the purpose of preventing the applied liquid crystal alignment agent from running and the like. The pre-baking temperature is preferably 30° C. to 200° C., and the pre-baking time is preferably 0.25 minutes to 10 minutes. Thereafter, the solvent is completely removed, and if necessary, a calcination (post-baking) step is performed for the purpose of thermal imidization of the amic acid structure present in the polymer. The calcination temperature (post-baking temperature) at this time is preferably 80° C. to 300° C., and the post-baking time is preferably 5 minutes to 200 minutes. The film thickness of the film formed in this way is preferably 0.001 μm to 1 μm. After coating the liquid crystal alignment agent on the substrate, the organic solvent is removed to form a liquid crystal alignment film or a coating film of the liquid crystal alignment film.

(Step 2: Alignment Treatment) When producing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal element, a treatment (alignment treatment) for imparting liquid crystal alignment ability to the coating film formed in the above step 1 is performed. Thereby, the alignment ability of a liquid crystal molecule is given to a coating film, and it becomes a liquid crystal alignment film. As the alignment treatment, rubbing treatment by rubbing in a certain direction with a roller wound with cloth can also be used, but the polymer (P) has high photosensitivity, and even a small amount of exposure can make the coating film exhibit various In terms of anisotropy, photo-alignment treatment for imparting liquid crystal alignment ability to a coating film formed on a substrate by irradiating light to the coating film is preferably used. On the other hand, in the case of producing a vertical alignment type liquid crystal element, the coating film formed in the above step 1 can be used as a liquid crystal alignment film as it is, but the coating film can also be subjected to an alignment treatment.

Light irradiation in the photo-alignment treatment can be performed by methods such as a method of irradiating the coating film after the post-baking step, a method of irradiating the coating film after the pre-baking step and before the post-baking step, A method of irradiating the coating film during heating of the coating film in at least any one of the pre-baking step and the post-baking step. In the photo-alignment process, as the radiation irradiated to the coating film, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used. Ultraviolet rays including light having a wavelength of 200 nm to 400 nm are preferable. In the case where the radiation is polarized, it may be either linearly polarized or partially polarized. In addition, when the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, may be performed from an oblique direction, or may be performed in combination. In the case of irradiating non-polarized radiation, the irradiation direction is set to be an oblique direction.

As the light source used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. The dose of radiation exposure is preferably from 400 J/m ² to 20,000 J/m ² , more preferably from 1,000 J/m ² to 5,000 J/m ² . In order to improve the reactivity, the coating film may be irradiated with light while heating the coating film.

When manufacturing the liquid crystal alignment film, a step of contacting the coating film subjected to the light irradiation treatment with water, a water-soluble organic solvent, or a mixed solvent of water and a water-soluble organic solvent may be further included. By performing such a contact process, the decomposition product generated by the photo-alignment treatment can be removed from the film, and it is preferable in terms of further suppressing the generation of minute bright spots in the obtained liquid crystal element. Here, examples of water-soluble organic solvents include methanol, ethanol, 1-propanol, isopropanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, acetone, methyl Ethyl ketone, methyl isobutyl ketone, cyclohexanone. Among these, the solvent used in the contacting step is preferably water, isopropanol and a mixture thereof.

As a method of contacting the coating film and the solvent, there may be mentioned, for example, spray (spray) treatment, shower treatment, immersion treatment, flooding treatment, etc., but the method is not limited thereto. The contact time between the coating film and the solvent is not particularly limited, and is, for example, 5 seconds to 15 minutes.

When manufacturing the liquid crystal alignment film, it is also possible to further perform a heating step: in at least one of the contact step before and after the contact step, the coating that has been subjected to light irradiation treatment is subjected to a light irradiation treatment within a temperature range of 120° C. to 280° C. The film is heated. By performing such a heating process, liquid crystal alignment is further improved, and it is preferable at the point which can obtain the liquid crystal element which reduced AC afterimage further. In the heating step, the heating temperature is preferably 140°C or higher, more preferably 150°C to 250°C, from the viewpoint of promoting molecular chain reorientation by heating. The heating time is preferably from 5 minutes to 200 minutes, more preferably from 10 minutes to 60 minutes.

(Step 3: Construction of Liquid Crystal Cell) Two substrates on which the liquid crystal alignment film was formed as described above were prepared, and liquid crystal was arranged between the two substrates facing each other to manufacture a liquid crystal cell. Examples of manufacturing a liquid crystal cell include: (1) Arranging two substrates facing each other through a gap (spacer) so that the liquid crystal alignment films face each other, and bonding the peripheral parts of the two substrates together with a sealant , inject and fill the liquid crystal into the cell gap divided by the surface of the substrate and the sealant, and then seal the injection hole, (2) apply the sealant to a specified position on one of the substrates on which the liquid crystal alignment film is formed , and then drop the liquid crystal on several prescribed places on the surface of the liquid crystal alignment film, then attach another substrate in such a way that the liquid crystal alignment film faces each other, and spread the liquid crystal over the entire surface of the substrate (liquid crystal dropping ( one drop filling, ODF) method), etc. It is desirable to further heat the manufactured liquid crystal cell up to the temperature at which the liquid crystal used becomes an isotropic phase, and then slowly cool it to room temperature to remove the flow alignment at the time of liquid crystal filling.

As the sealing agent, for example, an epoxy resin containing a curing agent and alumina balls as spacers can be used. As the spacer, a photo spacer, a beads spacer, or the like can be used. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferable, and for example, Schiff base liquid crystals, azoxy liquid crystals, and biphenyl liquid crystals can be used. , Phenylcyclohexane-based liquid crystals, ester-based liquid crystals, terphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, and cubane-based liquid crystals wait. In addition, these liquid crystals may be used by adding, for example, cholesteric liquid crystals, chiral reagents, ferroelectric liquid crystals, and the like.

Next, if necessary, a polarizing plate is bonded to the outer surface of the liquid crystal cell. Examples of the polarizing plate include a polarizing plate in which a polarizing film called “H film” is interposed between protective films of cellulose acetate, or a polarizing plate including the H film itself. Vinyl alcohol is stretched and aligned on one side to absorb iodine. Thereby, a liquid crystal element is obtained.

In addition, the reason why a liquid crystal element excellent in AC afterimage characteristics and long-term heat resistance is obtained by a liquid crystal alignment agent containing a polymer (P) is not certain, but it is considered as follows. The polymer (P) has a structural unit including an asymmetric structure as a diamine-derived structural unit. Therefore, it is presumed that the crystallinity of the photodecomposed product generated when the coating film containing the polymer (P) is irradiated with light is low, and the generation of fine bright spots is suppressed. In addition, it is presumed that the decrease in the crystallinity of the photodecomposed product due to the chain hydrocarbon structure and alicyclic hydrocarbon structure of ^X2 is also one of the reasons for obtaining a liquid crystal element with less occurrence of tiny bright spots. Furthermore, it is speculated that the structural part derived from diamine promotes photoinduced electron transfer from the diamine skeleton to the substituted cyclobutane ring (electron transfer sensitization reaction) by polymerizing the bonding group (amine group) and the electron-donating group, Thereby, the photodecomposition by the reverse [2+2] reaction of the cyclobutane ring is promoted, and as a result, the degree of alignment order of the liquid crystal is improved, and the reduction of AC afterimage is realized.

The disclosed liquid crystal element can be effectively applied to various purposes, for example, it can be used in clocks, portable game machines, word processors, notebook personal computers, car navigation systems, camcorders, personal digital assistants (Personal Digital Assistant, PDA), Digital cameras, mobile phones, smart phones, various monitors, LCD TVs, information displays and other display devices, or light-adjustable films, etc. In addition, the liquid crystal element formed by using the liquid crystal alignment agent of the present disclosure can also be applied to a retardation film.

[Example]

Hereinafter, the present disclosure will be further specifically described through examples, but the present disclosure is not limited to these examples.

The structures and abbreviations of the main compounds used in the following examples are as follows.

(tetracarboxylic acid derivatives)

TA-1: (1R,2R,3S,4S)-1,3-Dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride

TB-2: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

TB-3: 2,3,5-Tricarboxycyclopentylacetic dianhydride

TC-4: Dimethylallyl (2r,4r)-2,4-bis(chlorocarbonyl)-2,4-dimethylcyclobutane-1,3-dicarboxylate

(Specific diamine) DA-1: N,O-bis(4-aminophenyl)-N-methylethanolamine DA-2: N,O-bis(4-aminophenyl)-N-third Butoxycarbonylethanolamine DA-3: N,O-bis(4-aminophenyl)-ethanolamine DA-4: N,O-bis(4-aminophenyl)-4-hydroxypiperidine DA-5 : N,O-bis(4-aminophenyl)-4-piperidinemethanol DA-6: N,N'-bis(4-aminophenyl)-N-methyl-4-aminopiperidine DA-7: N,S-bis(4-aminophenyl)-2-aminoethanedithiol DA-8: N,O-bis(5-amino-2-pyridyl)-N-methyl Ethanolamine DA-9: N,O-bis(5-amino-2-pyridyl)-4-hydroxypiperidine DA-10: 4,4'-diaminobenzyl phenyl ether

[化24]

(Other diamines) DB-1: O,O'-bis(4-aminophenyl)-ethylene glycol DB-2: N,N'-bis(4-aminophenyl)-N,N' -Dimethylethylenediamine DB-3: 4,4'-Ethylenediphenylamine DB-4: N,N'-bis(4-aminophenyl)-piperazine DB-5: N,N' -bis(5-amino-2-pyridyl)-piperazine DB-6: p-phenylenediamine DB-7: 2,2'-dimethyl-4,4'-diaminobiphenyl [Chem. 23 ]

[chem 24]

(Solvent) NMP: N-methyl-2-pyrrolidone γBL: γ-butyrolactone BC: Butyl cellosolve

<Synthesis of Compound 1> [Synthesis Example 1] Potassium carbonate (34.55 g, 0.25 mol) was placed in a three-necked flask equipped with a reflux tube and a nitrogen gas introduction tube, nitrogen replacement was performed, and N-methylethanolamine (7.51 g, 0.10 mol), NMP (150 mL). While stirring the reaction solution under nitrogen, 4-fluoronitrobenzene (28.22 g, 0.20 mol) was added dropwise. The reaction solution was stirred at 150°C for 6 hours and the reaction was completed. After cooling, the reaction solution was poured into 300 mL of water and stirred to solidify the product. Add 150 mL of a mixed solvent of hexane:ethyl acetate=4:1 (volume ratio) to the water-coagulated dispersion, and stir at room temperature for 1 hour. The obtained dispersion was filtered and washed with water and ethyl acetate, respectively. The obtained precipitate was washed with heating and stirring in 150 mL of ethyl acetate, filtered after cooling, and vacuum-dried to obtain the nitro-form intermediate (29.51 g, yield 93%) as a yellow powder. Next, 2.4 g of palladium carbon was placed in a three-necked flask equipped with a reflux tube and a nitrogen gas introduction tube, and nitrogen substitution was performed. 120 mL of tetrahydrofuran degassed by nitrogen bubbling and 30 mL of ethanol were put thereinto, and a nitro intermediate (9.41 g, 0.03 mol) was added, followed by stirring to prepare a suspension solution. 10 mL of hydrazine monohydrate was slowly added dropwise to the reaction solution at room temperature. After the dropwise addition, the temperature was gradually raised to 60° C. and stirred for 4 hours. After diluting by adding 200 mL of ethyl acetate to the reaction solution and filtering it through diatomaceous earth (celite), liquid separation washing with 200 mL of water was repeated three times. The obtained organic layer was concentrated and vacuum-dried, whereby diamine (DA-1) (4.94 g, yield 64%) was obtained as a pale brown liquid. FIG. 1 shows the measurement results of ¹ H-NMR spectrum (dimethylsulfoxide (DMSO)-d ⁶ , 400 MHz) of diamine (DA-1). [chem 25]

[Synthesis Example 2] A nitro intermediate was obtained in the same manner as in Synthesis Example 1 except that N-methylethanolamine was changed to ethanolamine. Next, put the nitro-form intermediate (3.03 g, 0.010 mol) and N,N-dimethyl-4-aminopyridine (0.24 g, 0.002 mol) into a three-necked flask equipped with a reflux tube and a nitrogen gas inlet tube and Perform nitrogen replacement and place in tetrahydrofuran (60 mL). The reaction solution was heated to 50°C, and a mixed solution of di-tert-butyl dicarbonate (5.24 g, 0.024 mol) and tetrahydrofuran (5 mL) was added dropwise, and allowed to react for 24 hours. After the reaction solution was concentrated under reduced pressure, the obtained precipitate was recrystallized from toluene and vacuum-dried to obtain a Boc-protected nitro-form intermediate (3.43 g, yield 85%) as a yellow powder. The obtained Boc-protected nitro-body intermediate was reduced in the same manner as in Synthesis Example 1 to obtain diamine (DA-2) as light brown powder. [Synthesis Example 3] Diamine (DA-3) was obtained in the same manner as in Synthesis Example 1 except that N-methylethanolamine was changed to ethanolamine.

[Synthesis Example 4] Potassium carbonate (34.55 g, 0.25 mol) was put into a three-neck flask equipped with a reflux tube and a nitrogen gas introduction tube, and nitrogen replacement was carried out, and 4-hydroxypiperidine (10.12 g, 0.10 mol), NMP ( 150 mL). While stirring the reaction solution under nitrogen, 4-fluoronitrobenzene (28.22 g, 0.20 mol) was added dropwise. The reaction solution was stirred at 150°C for 6 hours and the reaction was completed. After cooling, the reaction solution was poured into 300 mL of water and stirred to solidify the product. Add 150 mL of a mixed solvent of hexane:ethyl acetate=4:1 (volume ratio) to the water-coagulated dispersion, and stir at room temperature for 1 hour. The obtained dispersion was filtered and washed with water and ethyl acetate, respectively. The obtained precipitate was washed by heating and stirring in 150 mL of ethyl acetate, filtered after cooling, and vacuum-dried to obtain the nitro-form intermediate product (29.87 g, yield 87%) of ocher powder. Next, 2.4 g of palladium carbon was placed in a three-necked flask equipped with a reflux tube and a nitrogen gas introduction tube, and nitrogen substitution was performed. 120 mL of tetrahydrofuran degassed by bubbling nitrogen gas and 30 mL of ethanol were put there, and a nitro-form intermediate (10.30 g, 0.03 mol) was added thereto, followed by stirring to prepare a suspension solution. 10 mL of hydrazine monohydrate was slowly added dropwise to the reaction solution at room temperature. After the dropwise addition, the temperature was gradually raised to 60° C. and stirred for 4 hours. After diluting by adding 200 mL of ethyl acetate to the reaction solution and filtering it through celite, liquid separation washing with 200 mL of water was repeated three times. The obtained organic layer was concentrated and recrystallized by ethyl acetate 100 mL. The obtained solid was filtered and vacuum-dried, whereby diamine (DA-4) (5.19 g, yield 61%) was obtained as pale pink solid. FIG. 2 shows the measurement results of ¹ H-NMR spectrum (DMSO-d ⁶ , 400 MHz) of diamine (DA-4). [chem 26]

[Synthesis Example 5] Diamine (DA-5) was obtained by synthesizing in the same manner as in Synthesis Example 4 except that 4-hydroxypiperidine was changed to 4-piperidinemethanol. [Synthesis Example 6] A nitro intermediate was obtained in the same manner as in Synthesis Example 4 except that 4-hydroxypiperidine was changed to 4-aminopiperidine. Next, put nitro-form intermediates (3.42 g, 0.010 mol) and potassium tert-butoxide (1.68 g, 0.015 mol) into a three-necked flask equipped with a reflux tube and a nitrogen gas introduction tube, and perform nitrogen replacement, and put tetrahydrofuran ( 100 mL). While stirring the reaction solution under nitrogen, methyl iodide (2.84 g, 0.020 mol) was added dropwise. The reaction solution was stirred at 40°C for 24 hours and the reaction was completed. After cooling, the reaction solution was poured into 300 mL of water and stirred to solidify the product. The obtained dispersion was filtered and washed with water. The obtained precipitate was recrystallized with tetrahydrofuran and vacuum-dried to obtain a yellow powder of N-methylated nitro intermediate (3.10 g, yield 87%). The obtained N-methylated nitro intermediate was reduced in the same manner as in Synthesis Example 4 to obtain a pink powder of diamine (DA-6).

[Synthesis Example 7] Diamine (DA-7) was obtained in the same manner as in Synthesis Example 1 except that N-methylethanolamine was changed to 2-aminoethanedithiol. [Synthesis Example 8] Diamine (DA-8) was obtained in the same manner as in Synthesis Example 1 except that 4-fluoronitrobenzene was changed to 2-fluoro-5-nitropyridine. [Synthesis Example 9] Diamine (DA-9) was obtained in the same manner as in Synthesis Example 4 except that 4-fluoronitrobenzene was changed to 2-fluoro-5-nitropyridine.

<Polymer Synthesis 1> [Synthesis Example 10] Diamine (DA-1) was dissolved in NMP, and 0.95 equivalent of tetracarboxylic dianhydride (TA-1) was added, and the reaction was carried out at room temperature for 6 hours. A 15% by mass solution of polyamic acid (PA-1) having a structural unit represented by the following formula (PA-1) was obtained. [chem 27]

[Synthesis Example 11 to Synthesis Example 26] The types and molar ratios of the tetracarboxylic dianhydride and the diamine compound were respectively changed as described in the following Table 1, and were obtained in the same manner as in Synthesis Example 10, respectively. Polyamide acid (PA-2～PA-17). In addition, about the numerical value in Table 1, for the tetracarboxylic dianhydride, it represents the use ratio (mol part) of each compound with respect to the total amount of tetracarboxylic dianhydride used for synthesis 100 mol parts, For the diamine compound, the use ratio (mol part) of each compound is shown with respect to 100 mol parts of the total amount of the diamine compound used for synthesis (it is the same for Table 3).

[Synthesis Example 27] The 15% by mass solution of polyamic acid (PA-1) obtained in Synthesis Example 10 was diluted to 10% by mass with NMP, and 0.8 equivalents of 1-methylpiperidine and acetic anhydride were added, It was heated at 60°C for 3 hours while stirring. The obtained solution was repeatedly concentrated under reduced pressure and diluted with NMP to obtain a 15% by mass solution of polyimide (PI-1) having a structural unit represented by the following formula (PI-1). Determination of ¹ H-NMR spectrum (DMSO-d ⁶ , 400 MHz) of polyimide (PI-1), by aromatic proton (δ6.0 ppm～9.0 ppm) and main chain amide proton (δ9.8 ppm to 10.3 ppm) and the integral ratio of acetyl-terminal amide protons (δ9.6 ppm to 9.8 ppm) to calculate the imidization rate. As a result, the imidization rate was 78%. [chem 28]

[Synthesis Example 28] Polyimide (PI-2) was obtained in the same manner as in Synthesis Example 27 except that polyamic acid (PA-1) was changed to polyamic acid (PA-10).

[Table 1]

[Example 1: Photoalignment FFS type liquid crystal display element] (1) Preparation of liquid crystal alignment agent Use the solution of polyamic acid (PA-1) obtained in Synthesis Example 10 and dilute it with NMP and BC to obtain a solid The component concentration was 4.0% by mass, and the solvent composition ratio was a solution of NMP:BC=80:20 (mass ratio). The liquid crystal alignment agent (R-1) was prepared by filtering the solution through a filter with a pore size of 0.2 μm.

(2) Formation of liquid crystal alignment film by photo-alignment method Use a spinner to apply the liquid crystal alignment agent (R-1) prepared in (1) on one side where a flat plate electrode, an insulating layer and a comb are sequentially laminated. The glass substrate of the tooth-shaped electrode and the opposite glass substrate without the electrode were heated (pre-baked) for 1 minute with a hot plate at 80°C, and then nitrogen was replaced in the chamber. Dry in an oven at 230°C for 30 minutes (post-baking) to form a coating film with an average film thickness of 0.1 μm. The surface of the coating film was irradiated with 3,000 J/m ² of ultraviolet light including a linearly polarized bright line of 254 nm from the normal direction of the substrate using a Hg-Xe lamp to perform photo-alignment treatment. The coating film subjected to photo-alignment treatment was heated in a clean oven at 230° C. for 30 minutes for heat treatment to form a liquid crystal alignment film.

(3) Manufacture of liquid crystal display element For the pair of substrates having the liquid crystal alignment film prepared in (2), the liquid crystal injection port was left on the edge of the surface on which the liquid crystal alignment film was formed, and a 5.5 μm diameter After coating the epoxy resin adhesive agent of alumina balls by screen printing, the substrates were stacked and pressure-bonded so that the projection direction of the polarization axis toward the substrate surface during light irradiation was antiparallel, and the adhesive was bonded at 150°C for 1 hour. agent heat hardening. Next, after filling nematic liquid crystal (MLC-7028 manufactured by Merck) between the pair of substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy-based adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, after heating at 120 degreeC, it cooled gradually to room temperature. Next, a polarizing plate was bonded to the outer both surfaces of the board|substrate, and the FFS type liquid crystal display element was manufactured.

(4) Evaluation of liquid crystal alignment When a voltage of 5 V is turned on and off (ON and OFF) (applied and released), the liquid crystal display element produced in the above (3) is observed with a microscope at a magnification of 50 times Presence or absence of an abnormal domain (domain) in the change of light and dark. About evaluation, the case where the abnormal domain was not observed was made into liquid crystal alignment "good", and the case where the abnormal domain was observed was made into "poor". As a result, it was evaluated as "good" in this Example.

(5) Evaluation of AC afterimage characteristics An FFS type liquid crystal cell was fabricated by performing the same operation as in (3) above except that no polarizing plates were bonded to both outer surfaces of the substrate. After driving this FFS liquid crystal cell for 30 hours with an AC voltage of 10 V, the minimum relative transmittance represented by the following formula (2) was measured using a device with a polarizer and an analyzer disposed between the light source and the light quantity detector. Rate(%). Minimum relative transmittance (%) = ((β-B ₀ )/(B ₁₀₀ -B ₀ ))×100 ... (2) (In formula (2), B ₀ is blank and is orthogonal The amount of light transmitted under crossed nicols. B ₁₀₀ is blank, and is the amount of light transmitted under parallel nicols. β is crossed nicols under the polarizer and analyzer The liquid crystal unit is sandwiched between the devices and the light transmission becomes the minimum) The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal unit. In the FFS type liquid crystal unit, the smaller the black level in the dark state, the contrast ( contrast) the better. The minimum relative transmittance is less than 0.2% as "Excellent", 0.2% to less than 0.5% is "Good", 0.5% to 1.0% is "Acceptable", and 1.0 % or more is regarded as "bad". As a result, it was evaluated as "excellent" in this Example.

(6) Evaluation of long-term heat resistance (defective micro-spots) Micro-spots were evaluated by performing the same operation as in (3) above, except that polarizing plates were not attached to both sides of the outer sides of the substrate. After the manufactured liquid crystal cell was stored in a 100° C. thermostat for 21 days, the presence or absence of minute bright spots in the liquid crystal cell was observed with a microscope. It is known that in the case where decomposed products generated by light irradiation for photo-alignment processing remain in the film, by exposing the liquid crystal display element to a high-temperature environment for a long time, the decomposed products ooze out of the film surface, and at Gradually crystallizes in the liquid crystal and is observed as tiny bright spots. It should be noted that the observation area was 680 μm×680 μm, and the microscope magnification was 100 times. Regarding the evaluation, the case where no tiny bright spots were observed was rated as "excellent", the case where the number of tiny bright spots was 1 to 5 points was rated as "good", and the number of tiny bright spots was 6 or more to 10 points. The following cases were regarded as "acceptable", and the case of micro bright spots of 11 points or more was regarded as "poor". As a result, it was evaluated as "good" in this Example.

[Example 2-Example 12, Comparative Example 1-Comparative Example 6] In the above-mentioned Example 1, the polymer contained in the liquid crystal alignment agent was changed as shown in the following Table 2. In the same manner as in Example 1, a liquid crystal alignment agent was prepared and a liquid crystal alignment film was formed, and an FFS type liquid crystal display element and a liquid crystal unit were manufactured and various evaluations were performed. The evaluation results are shown in Table 2 below. Furthermore, in Example 11 and Example 12, two kinds of polymers (polymer 1 and polymer 2) were contained in in liquid crystal alignment agents.

[Example 13] In the above-mentioned Example 1, "(1) Preparation of liquid crystal alignment agent" and "(2) Formation of liquid crystal alignment film by photo-alignment method" are as follows (1a) and (2a) Except having generally changed, an FFS type liquid crystal display element and a liquid crystal cell were produced in the same manner as in Example 1, and various evaluations were performed. The evaluation results are shown in Table 2 below.

(1a) Preparation of liquid crystal alignment agent Using the solution of polyimide (PI-1) obtained in Synthesis Example 27 as a polymer, it was diluted with NMP and BC to obtain a solid content concentration of 4.0% by mass and a solvent composition ratio of Become a solution of NMP:BC=80:20 (mass ratio). The liquid crystal alignment agent (R-13) was prepared by filtering the solution through a filter with a pore size of 0.2 μm.

(2a) Formation of liquid crystal alignment film by photo-alignment method Apply the liquid crystal alignment agent (R-13) prepared in the above (1a) to a film thickness of 0.1 μm using a spinner to build up layers sequentially on one side A coating film was formed by drying (pre-baking) on a hot plate at 80°C for 1 minute on the surfaces of the glass substrate with the flat electrode, insulating layer, and comb-shaped electrode, and the facing glass substrate without electrodes. The surface of the coating film was irradiated with 3,000 J/m ² of ultraviolet light including a linearly polarized bright line of 254 nm from the normal direction of the substrate using a Hg-Xe lamp to perform photo-alignment treatment. The coating film subjected to the photo-alignment treatment was heated for 30 minutes in an oven at 230° C. in which the cavity was replaced with nitrogen (post-baking), thereby forming a liquid crystal alignment film.

[Example 14-Example 16] In the above-mentioned Example 13, except that the polymer contained in the liquid crystal alignment agent was changed as shown in the following Table 2, a liquid crystal was prepared in the same manner as in Example 13. Alignment agent and liquid crystal alignment film are formed, and FFS-type liquid crystal display elements and liquid crystal cells are manufactured and various evaluations are performed. The evaluation results are shown in Table 2 below. Furthermore, in Example 15 and Example 16, two kinds of polymers (polymer 1 and polymer 2) were contained in the compounding ratio of polymer 1:polymer 2=40:60 (mass ratio in terms of solid content) in liquid crystal alignment agents.

[Table 2]

The liquid crystal alignment was "good" in all of Examples 1 to 16. In addition, the AC afterimage characteristics were all "excellent" or "good" in Examples 1 to 16. These are considered to be caused by improvement in the photoreactivity of the liquid crystal alignment film. That is, the liquid crystal alignment agents of Examples 1 to 16 contain a polymer of substituted cyclobutanetetracarboxylic dianhydride and diamine. In addition, regarding diamines used in the synthesis of polymers, the aromatic rings to which the polymeric linking group (-NH ₂ ) is bonded are passed through an alkylamine group or a piperidine diyl group, an oxyalkylene group (-C _n H _2n - O-) and other electron-donating groups are substituted. The mechanism of high sensitivity to light is not certain, but it is speculated that photoinduced electron transfer (electron transfer sensitization reaction) from the diamine skeleton to the substituted cyclobutane ring by the electron-donating group promotes the conversion of the substituted ring Photolysis induced by the retro [2+2] reaction of the butane ring.

In addition, regarding the long-term heat resistance (reduction of micro-spot defects), all of Examples 1 to 16 were "excellent" or "good". The liquid crystal alignment agents of Examples 1 to 16 contain, as a polymer component, a polymer having a structural unit derived from a diamine having an asymmetric structure. The mechanism of long-term heat resistance improvement is not certain, but it is speculated that among diamines having an asymmetric structure, the photodecomposition product generated by the photo-alignment treatment step becomes an asymmetric structure, thereby reducing the crystallinity of the photodecomposition product, and Generation of tiny bright spots is suppressed.

Moreover, the polymer (P) contained in the liquid crystal aligning agent of Example 8-Example 10, Example 14, and Example 16 contains the compound which consists of multiple types of acid dianhydride components or diamine components. Therefore, it is presumed that the photodecomposition product contains various chemical structures, inhibits the crystallization of the photodecomposition product, and suppresses the generation of fine bright spots. Furthermore, in Example 11, Example 12, Example 15, and Example 16 (blending system), it is estimated that due to the small content ratio of the photodecomposed polymer (polymer 1), the resulting photodecomposed product The amount is small, whereby the generation of tiny bright spots is suppressed.

On the other hand, in Comparative Examples 1 to 5 using a polymer having no partial structure derived from a substituted cyclobutane ring and a specific diamine, the long-term heat resistance of the liquid crystal cell was "poor". The liquid crystal aligning agent of these comparative examples 1-5 contains the polymer which used only the diamine which has a symmetrical structure as a diamine component. In this case, it is presumed that the photodecomposition product generated by the photo-alignment treatment has a symmetrical structure, and the crystallinity of the photodecomposition product becomes high, thereby making it easy to generate tiny bright spots. In addition, in Comparative Example 6, the liquid crystal orientation and AC afterimage characteristics of the liquid crystal cell were "defective". Regarding the long-term heat resistance, the liquid crystal alignment of the liquid crystal cell was "poor", so it could not be evaluated.

<Synthesis of Compound 2> [Synthesis Example 29] 4-Nitrophenol (13.91 g, 0.10 mol), 4-nitrobenzyl bromide (21.60 g, 0.10 mol), potassium carbonate (16.59 g, 0.12 mol) and nitrogen replacement, put in acetone (200 mL). The reaction solution was stirred at 60° C. under nitrogen for 8 hours and the reaction was allowed to complete. After cooling, the reaction solution was poured into 300 mL of water and stirred to solidify the product. The product was filtered, washed with water, and then vacuum-dried to obtain a colorless crystalline nitro-body intermediate (26.70 g, 0.097 mol). Next, put nitro-form intermediates (8.22 g, 0.030 mol), zinc (39.2 g, 0.60 mol), and ammonium chloride (32.09 g, 0.60 mol) into a three-necked flask equipped with a reflux tube and a nitrogen gas introduction tube and carry out Nitrogen replacement. 120 mL of tetrahydrofuran degassed by bubbling nitrogen gas and 40 mL of ethanol were added thereto, and cooled to 5° C. to 10° C. in an ice-water bath while stirring. 16 mL of water was slowly added dropwise to the reaction solution, and stirred at room temperature for 8 hours to complete the reaction. 100 mL of water was added to the reaction solution to dilute, and the insoluble components were removed by Celite filtration, and the Celite was extracted and washed with 200 mL of ethyl acetate. The obtained filtrate was liquid-separated, and the organic layer was washed 5 times with water. The obtained organic layer was concentrated and recrystallized with 30 mL of a mixed solvent of ethyl acetate/ethanol=1/10. Diamine (DA-10) (4.50 g, yield 70%) was obtained as a pale yellow solid by filtering and vacuum-drying the obtained solid. FIG. 3 shows the measurement results of ¹ H-NMR spectrum (DMSO-d ⁶ , 400 MHz) of diamine (DA-10). [chem 29]

[合成例31～合成例34] 將四羧酸二酐及二胺化合物的種類和莫耳比分別如下述表3所記載般進行變更，除此以外，以與合成例30同樣的方式分別獲得聚醯胺酸（PA-19～PA-22）。再者，關於表3中的數值，對於四羧酸二酐而言，表示相對於用於合成的四羧酸二酐的合計量100莫耳份的各化合物的使用比例（莫耳份），對於二胺化合物而言，表示相對於用於合成的二胺化合物的合計量100 莫耳份的各化合物的使用比例（莫耳份）。<Polymer Synthesis 2> [Synthesis Example 30] Diamine (DA-10) was dissolved in NMP, and 0.95 equivalent of tetracarboxylic dianhydride (TA-1) was added, and the reaction was carried out at room temperature for 6 hours. A 15% by mass solution of polyamic acid (PA-18) having a structural unit represented by the following formula (PA-18) was obtained. [chem 30]

[Synthesis Example 31 to Synthesis Example 34] The types and molar ratios of the tetracarboxylic dianhydride and the diamine compound were respectively changed as described in the following Table 3, and were obtained in the same manner as in Synthesis Example 30, respectively. Polyamide acid (PA-19～PA-22). In addition, about the numerical value in Table 3, for the tetracarboxylic dianhydride, it represents the use ratio (mol part) of each compound with respect to the total amount of tetracarboxylic dianhydride used for synthesis 100 mol parts, The diamine compound represents the usage ratio (mol part) of each compound with respect to 100 mol parts of the total amount of the diamine compound used for synthesis.

[Synthesis Example 35] Tetracarboxylic acid derivative (TC-4) (8.11 g, 20.0 mmol), pyridine (3.80 g, 48.0 mmol), and γBL 20.4 g were placed in a 50 mL three-neck flask equipped with a nitrogen gas introduction tube and a thermometer , and 13.6 g of NMP, and cooled to about 10°C to prepare an acyl chloride solution. Here, a diamine solution prepared by dissolving diamine (DA-10) (3.86 g, 18.0 mmol) in 20.4 g of γBL in advance was added, and reacted at 10° C. for 4 hours under a nitrogen stream. The obtained polymerization solution was diluted with 70 g of methanol, and slowly poured into a mixed solvent of water/isopropanol=1/1 while stirring, and solidified. The precipitated solid was recovered, stirred and washed in water and isopropanol, and vacuum-dried at 60° C., thereby obtaining a white powder. The obtained powder was dissolved in γBL to obtain a 15% by mass solution of polyamide ester (PAE-1) having a structural unit represented by the following formula (PAE-1). [chem 31]

[Synthesis Example 36 to Synthesis Example 37] Except that the type and molar ratio of the diamine compound were changed as described in the following Table 3, polyamide esters were obtained in the same manner as Synthesis Example 35 ( PAE-2～PAE-3).

[table 3]

[Example 17-Example 24, Comparative Example 7] In the above-mentioned Example 1, the polarized ultraviolet light exposure amount of the photo-alignment treatment was changed from 3,000 J/m ² to 5,000 J/m ² , and the liquid crystal alignment agent The polymer contained is changed as shown in the following Table 4, except that, a liquid crystal alignment agent is prepared in the same manner as in Example 1 to form a liquid crystal alignment film, and an FFS-type liquid crystal display element and a liquid crystal unit are manufactured and various evaluate. The evaluation results are shown in Table 4 below. Furthermore, in Example 20 and Example 24, two kinds of polymers (polymer 1 and polymer 2) were contained in the compounding ratio of polymer 1: polymer 2 = 40: 60 (mass ratio in terms of solid content) in liquid crystal alignment agents.

[Table 4]

In Examples 17 to 24, both the liquid crystal alignment property and the AC afterimage property were "excellent" or "good". Regarding these results, it is considered that the same reason as in Examples 1 to 16 is that the photoreactivity of the liquid crystal alignment film is improved by containing a polymer having a structural unit derived from a polymer bond A diamine in which the aromatic ring bonded by the knotting group (-NH ₂ ) is substituted by an electron-donating group ("-O-CH ₂ -" in diamine (DA-10)). In addition, the long-term heat resistance (reduction of micro-spot defects) was "excellent" in all of Examples 17 to 24. Regarding these results, it is considered that the same reason as in Examples 1 to 16 is due to the fact that the photodecomposition product generated by the photo-alignment treatment step has an asymmetric structure, so the crystallinity is lowered, and the generation of tiny bright spots is suppressed. .

This disclosure is described based on the embodiment, but it should be understood that the present disclosure is not limited to the above-mentioned embodiment or structure. This disclosure also includes various modified examples or modifications within an equivalent range. In addition, various combinations or forms, and further combinations or forms including only one element, more than one element, or less than one element among these also belong to the category or scope of thought of the present disclosure.

none

Fig. 1 is the ¹ H-nuclear magnetic resonance (nuclear magnetic resonance, NMR) spectrum of diamine (DA-1). Fig. 2 is the ¹ H-NMR spectrum of diamine (DA-4). Fig. 3 is the ¹ H-NMR spectrum of diamine (DA-10).

Claims (11)

A liquid crystal alignment agent, which contains a polymer (P), the polymer (P) has a partial structure represented by the following formula (1) and a partial structure represented by the following formula (2) in the group consisting of In the polymer (P), the diamine represented by the following formula (da-3), the diamine represented by the following formula (da-4), the diamine represented by the following formula (da-2) A polymer obtained by reacting diamine represented by the diamine represented by the following formula (da-31) with 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, Diamine represented by the following formula (da-6), diamine represented by the following formula (da-1), diamine represented by the following formula (da-12), and the following formula (da-31) A polymer obtained by reacting diamine and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, and a diamine represented by the following formula (da-5) Amines, diamines represented by the following formula (da-7), diamines represented by the following formula (da-3), diamines represented by the following formula (da-31) and 1,3-dimethyl Except for polymers formed by the reaction of -1,2,3,4-cyclobutane tetracarboxylic dianhydride;

In formula (1) and formula (2), X ¹ is a 4-valent organic group having a cyclobutane ring structure, and has at least one substituent in the ring part of the cyclobutane ring; X ² is the following formula (4) Or a divalent organic group represented by the following formula (5); R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent organic group with 1 to 6 carbons, *-A ¹ -Y ¹ -Z ¹ -Y ² -A ² -* (4) *-A ¹ -B ¹ -Z ² -Y ³ -A ² -* (5) In formula (4) and formula (5), A ¹ and A ² are divalent aromatic rings group, and may also have a substituent on the ring part; wherein, A ¹ and A ² are the same; Y ¹ is an oxygen atom, Y ² is a single bond, a sulfur atom, or "-NR ⁷ -", R ⁷ is a hydrogen atom or Monovalent organic group; B ¹ is a divalent heterocyclic group represented by the following formula (7) or formula (8); Y ³ is an oxygen atom, or "-NR ⁹ -", R ⁹ is a hydrogen atom or a monovalent organic group base; Z ¹ is a divalent organic group represented by the following formula (6); Z ² is a single bond or a divalent organic group represented by the following formula (6); "*" represents a bond,

In formula (7) and formula ( ⁸ ), R is a substituent; r is an integer of 0 to 3, and m is an integer of 0 to (r+2); "*" represents a bond,

In formula (6), R ¹⁰ and R ¹¹ are independently alkanediyl groups, and the total carbon number of R ¹⁰ and R ¹¹ is 1 to 15; Y ⁴ is an oxygen atom, a sulfur atom, or "-NR ¹² -", R ¹² is a hydrogen atom or a monovalent organic group; p is an integer of 0 to 4; when p is 2 or more, multiple R ¹⁰ and Y ⁴ may be the same or different from each other; "*" indicates a bond,

The liquid crystal alignment agent as described in Item 1 of the scope of the patent application, wherein the ^X is a tetravalent organic group represented by the following formula (3);

In formula (3), ^R1 ~ ^R3 are independently hydrogen atom, halogen atom, alkyl group with 1~6 carbon number, halogenated alkyl group with 1~6 carbon number, alkoxyl group with 1~6 carbon number, Thioalkyl with 1 to 6 carbons, alkenyl with 2 to 6 carbons, alkynyl with 2 to 6 carbons, or “-COR ²⁰ ”, where R ²⁰ is an alkyl with 1 to 6 carbons, fluorine-containing Alkyl, alkoxy or fluorine-containing alkoxy; ^R4 is a halogen atom, alkyl with 1 to 6 carbons, halogenated alkyl with 1 to 6 carbons, alkoxy with 1 to 6 carbons, or Thioalkyl with 1 to 6, alkenyl with 2 to 6 carbons, alkynyl with 2 to 6 carbons, or “-COR ²⁰ ”; among them, the adjacent groups in R ¹ to R ⁴ can also be bonded to each other Knot to form a ring structure; in the case of multiple ^R20s in the formula, multiple ^R20s may be the same or different from each other; "*" represents a bond. The liquid crystal alignment agent as described in item 1 or item 2 of the scope of the patent application, wherein the divalent organic group represented by the formula (4) is represented by the following formula (4A);

In formula (4A), A ³ and A ⁴ are divalent groups obtained by removing two hydrogen atoms from the ring part of the benzene ring, pyridine ring or pyrimidine ring, and may have substituents in the ring part; wherein, A ³ is the same as A ⁴ ; Y ⁵ is an oxygen atom, Y ⁶ is a single bond, a sulfur atom, or "-NR ¹³ -", R ¹³ is a hydrogen atom or a monovalent organic group; n is an integer from 1 to 5; "* ” means a bond. The liquid crystal alignment agent as described in item 1 or item 2 of the scope of the patent application, wherein the divalent organic group represented by the formula (5) is represented by the following formula (5A);

In formula (5A), A ⁵ and A ⁶ are divalent groups obtained by removing two hydrogen atoms from the ring part of the benzene ring, pyridine ring or pyrimidine ring, and may also have substituents in the ring part; wherein, A ⁵ is the same as A ⁶ ; B ² is a substituted or unsubstituted piperidine-1,4-diyl or a substituted or unsubstituted piperazine-1,4-diyl; Y ⁷ is an oxygen atom, Or "-NR ⁹ -", R ⁹ is a hydrogen atom or a monovalent organic group; k is an integer from 0 to 5; "*" indicates a bond. The liquid crystal alignment agent as described in item 1 or item 2 of the scope of the patent application, wherein, the ^R5 and ^R6 are each independently a monovalent organic group with 1 to 6 carbon atoms, and the ^X2 is the following formula (4C) a divalent organic group represented;

In formula (4C), A ³ and A ⁴ are divalent groups obtained by removing two hydrogen atoms from the ring part of the benzene ring, pyridine ring or pyrimidine ring, and may have substituents in the ring part; wherein, A ³ is the same as A ⁴ ; Y ⁵¹ is an oxygen atom, Y ⁶¹ is a single bond or a sulfur atom; n is an integer from 1 to 5; "*" represents a bond. A liquid crystal alignment film, which is formed by using the liquid crystal alignment agent described in any one of items 1 to 5 in the scope of the patent application. A method for manufacturing a liquid crystal alignment film, which includes the following steps of photoalignment: using the liquid crystal alignment agent described in any one of the first to fifth items of the scope of the patent application to form a coating film, and performing light irradiation treatment on the coating film And endow the liquid crystal with alignment ability. The method for manufacturing a liquid crystal alignment film as described in item 7 of the scope of the patent application, which further includes the following contact step: contacting the coating film subjected to light irradiation treatment with water, a water-soluble organic solvent, or water and a water-soluble organic solvent of mixed solvents. The method for manufacturing a liquid crystal alignment film as described in item 8 of the scope of the patent application, which further includes the following heating step: at least one of before the contact step and after the contact step, at 120°C or more and 280°C or less The coating film subjected to the light irradiation treatment is heated within a temperature range of . A liquid crystal element, which is provided with the liquid crystal alignment film described in item 6 of the scope of application. A polymer having at least one selected from the group consisting of a partial structure represented by the following formula (1) and a partial structure represented by the following formula (2); in the polymer, the following formula (da Diamine represented by -3), diamine represented by the following formula (da-4), diamine represented by the following formula (da-2), and diamine represented by the following formula (da-31) Polymer reacted with 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, diamine represented by the following formula (da-6), the following formula ( The diamine represented by da-1), the diamine represented by the following formula (da-12), the diamine represented by the following formula (da-31) and 1,3-dimethyl-1,2, A polymer obtained by reacting 3,4-cyclobutanetetracarboxylic dianhydride, a diamine represented by the following formula (da-5), a diamine represented by the following formula (da-7), the following Diamine represented by formula (da-3) and diamine represented by the following formula (da-31) and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride Except for reacted polymers;

In formula (1) and formula (2), X ¹ is a 4-valent organic group having a cyclobutane ring structure, and has at least one substituent in the ring part of the cyclobutane ring; X ² is the following formula (4) Or a divalent organic group represented by the following formula (5); R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent organic group with 1 to 6 carbons, *-A ¹ -Y ¹ -Z ¹ -Y ² -A ² -* (4) *-A ¹ -B ¹ -Z ² -Y ³ -A ² -* (5) In formula (4) and formula (5), A ¹ and A ² are divalent aromatic rings group, and may also have a substituent on the ring part; wherein, A ¹ and A ² are the same; Y ¹ is an oxygen atom, Y ² is a single bond, a sulfur atom, or "-NR ⁷ -", R ⁷ is a hydrogen atom or Monovalent organic group; B ¹ is a divalent heterocyclic group represented by the following formula (7) or formula (8); Y ³ is an oxygen atom, or "-NR ⁹ -", R ⁹ is a hydrogen atom or a monovalent organic group base; Z ¹ is a divalent organic group represented by the following formula (6); Z ² is a single bond or a divalent organic group represented by the following formula (6); "*" represents a bond,

In formula (7) and formula ( ⁸ ), R is a substituent; r is an integer of 0 to 3, and m is an integer of 0 to (r+2); "*" represents a bond,

In formula (6), R ¹⁰ and R ¹¹ are independently alkanediyl groups, and the total carbon number of R ¹⁰ and R ¹¹ is 1 to 15; Y ⁴ is an oxygen atom, a sulfur atom, or "-NR ¹² -", R ¹² is a hydrogen atom or a monovalent organic group; p is an integer of 0 to 4; when p is 2 or more, multiple R ¹⁰ and Y ⁴ may be the same or different from each other; "*" indicates a bond,

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