TWI681986B - Liquid crystal alignment treatment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

The invention provides a liquid crystal alignment treatment agent, which can obtain stable vertical stability even after long-term exposure to high temperature and light irradiation, voltage retention reduction is suppressed, rapid accumulation of residual charge is reduced, and ODF can be reduced The following liquid crystal alignment film with uneven liquid crystal alignment.

A liquid crystal alignment treatment agent containing the following components (A), (B) and (C).

(A) Component: a polyimide precursor obtained by reacting a diamine component containing a diamine having the following formula [1] and a diamine having the following formula [2] and a tetracarboxylic acid component Or the polyimide which is the imidized precursor of the polyimide.

(B) Component: a polyimide precursor obtained by the reaction of a diamine component containing a diamine having the structure of the following formula [2] and a tetracarboxylic acid component or the polyimide precursor is compounded The imidized polyimide.

(C): Polyimide obtained by reacting a diamine component containing a diamine having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group) and a tetracarboxylic acid component Precursor or the polyimide precursor Amidimated polyimide.

The definition of the symbol in the formula is as described in the specification.

Description

Liquid crystal alignment treatment agent, liquid crystal alignment film and liquid crystal display element

The present invention relates to a liquid crystal alignment treatment agent, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film.

As a thin and light-weight display device, liquid crystal display elements are now widely used. Generally, a liquid crystal alignment film for determining the state of liquid crystal alignment is used in this liquid crystal display element.

As one of the characteristics required for the liquid crystal alignment film, there is control to maintain the alignment tilt angle of the liquid crystal molecules relative to the substrate surface at an arbitrary value, so-called liquid crystal pretilt angle. It is known that the size of this pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film. In the technology of controlling the pretilt angle by the structure of polyimide, the method of using a diamine compound having a side chain as a part of the raw material of polyimide can control the pretilt angle according to the proportion of the diamine compound used. It is easier to obtain the intended pretilt angle, so it is useful as a means to increase the pretilt angle (see Patent Document 1). In addition, the diamine compound used to increase the pretilt angle of the liquid crystal in this way has also been discussed in terms of the structure for improving the stability or process dependence of the pretilt angle. As a side chain structure used here, a ring structure including a phenyl group, a cyclohexyl group, or the like has been proposed (see Patent Document 2).

In the production of the liquid crystal display element, there must be a step of filling the liquid crystal between two substrates (lattice gap) on which the liquid crystal alignment film has been formed. So far, liquid crystal filling is a vacuum injection method in which liquid crystal is filled between two substrates by using the pressure difference between atmospheric pressure and vacuum. However, in this case, since the liquid crystal injection port is provided only on one side of the substrate, it takes a long time to fill the liquid crystal, and it is difficult to simplify the manufacturing steps of the liquid crystal display element. In particular, in the manufacture of liquid crystal TVs or large screens that have been put into practical use in recent years, this subject has become a big problem.

Therefore, in order to solve the above problems in the vacuum injection method, a liquid crystal dropping method (ODF (One Drop Filling) method) has been developed. This method is a method of filling liquid crystal by dripping liquid crystal on a substrate on which a liquid crystal alignment film has been formed, bonding the other substrate in a vacuum, and then curing the sealing material by UV. On the other hand, as the definition of liquid crystal display elements becomes higher, it becomes necessary to suppress display unevenness. In the liquid crystal dropping method, it has been solved by optimizing the manufacturing steps to reduce the influence of adsorbed water or impurities by reducing the dropping amount of liquid crystal or increasing the vacuum degree during bonding. However, with the enlargement of the production lines of liquid crystal display devices, the optimization of the current manufacturing steps alone has gradually become unable to suppress display unevenness, so a liquid crystal alignment film that can reduce the alignment unevenness more than in the past is required.

In addition, as liquid crystal display elements become more sophisticated, from the viewpoint of suppressing the decrease in contrast of the liquid crystal display elements or reducing the afterimage phenomenon, even Among the liquid crystal alignment films used here, characteristics such as a high voltage retention rate, a small accumulated charge when a DC voltage is applied, or a rapid relaxation of the charge accumulated due to a DC voltage also gradually become important.

In the liquid crystal alignment film of the polyimide system, as the time until the afterimage caused by the DC voltage disappears, it is known to use polyamic acid or polyimide acid containing an imido group, And those containing a liquid crystal alignment treatment agent containing a tertiary amine with a specific structure (see Patent Document 3), and those using a soluble polyimide containing a specific diamine compound having a pyridine skeleton as a raw material (Refer to Patent Document 4).

In addition, as the high voltage retention rate and the time until the afterimage caused by the DC voltage disappears is short, it is known to use a polar electrode other than polyamic acid or its imidized polymer. A liquid crystal alignment treatment agent containing a small amount of a compound selected from a compound containing a carboxylic acid group in the molecule, a compound containing a carboxylic acid anhydride group in the molecule, and a compound containing a tertiary amine group in the molecule (see Patent Literature) 5).

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-282726

[Patent Document 2] Japanese Patent Laid-Open No. 9-278724

[Patent Document 3] Japanese Patent Laid-Open No. 9-316200

[Patent Document 4] Japanese Patent Laid-Open No. 10-104633

[Patent Document 5] Japanese Patent Laid-Open No. 8-76128

[Summary of the invention]

In order to control the liquid crystal angle with respect to the substrate, that is, to control the liquid crystal pretilt angle, the liquid crystal alignment film is still subject to users. In particular, in the VA mode or PSA mode, etc., since the liquid crystal must be vertically aligned, the liquid crystal alignment film is required to be capable of vertically aligning the liquid crystal (also known as vertical alignment or high pretilt angle). In addition, for the liquid crystal alignment film, not only high vertical alignment becomes important, but also its stability is gradually becoming important. In particular, in order to obtain high brightness, a liquid crystal display element that uses a large amount of heat and a large amount of light-illuminated backlight, such as a car navigation system or a large TV, may be used or placed for a long time under high temperature and light irradiation. Under such severe conditions, it may cause a decrease in vertical alignment, failure to obtain initial display characteristics, or problems such as uneven display.

In addition, in the ODF method, the liquid crystal is directly dropped on the alignment film. Therefore, when the liquid crystal is dropped, physical pressure is caused on the alignment film, or it is necessary to fill the entire area of the panel with liquid crystal, and it is necessary to increase the liquid crystal. Dripping point. Therefore, in the liquid crystal dropping part or the part where the liquid crystal droplets are in contact with the adjacent liquid droplets, there will be dripping traces or uneven grids, that is, the so-called uneven alignment, and when this is made into a liquid crystal display element, there are The problem of uneven display due to uneven alignment occurs. This uneven alignment is considered to be due to the adsorption of water or impurities adhering to the surface of the liquid crystal alignment film formed on the substrate, which was concentrated by the dripping of the liquid crystal in the ODF step. The liquid crystal dropping portion or the liquid crystal droplets are connected to each other due to different amounts of adsorbed water or impurities.

In addition, the voltage retention rate, which is one of the electrical characteristics of the liquid crystal display element, is also required to have high stability under severe conditions as described above. That is, if the voltage retention rate decreases due to light irradiation from the backlight, it may cause burn-in failure (also known as line burn-in), which is one of the display defects of the liquid crystal display element, and the liquid crystal with high reliability cannot be obtained Display element. Therefore, the liquid crystal alignment film is required not only to have good initial characteristics but also to have a low voltage retention rate even after being exposed to light irradiation for a long time. Furthermore, for another type of poor burn-in, that is, surface burn-in, it also requires a liquid crystal alignment film that is irradiated with light from the backlight and the residual charge accumulated by the DC voltage is relaxed more quickly.

Therefore, the object of the present invention is to provide a liquid crystal alignment film which exhibits stable vertical stability even after being exposed to high temperature and light irradiation for a long time, suppresses the decrease in voltage retention rate, and quickly alleviates the accumulation of residual DC voltage Charge, in addition, can reduce the uneven alignment of the liquid crystal generated in the ODF mode. In addition, the present invention provides a liquid crystal alignment treatment agent for obtaining the liquid crystal alignment film, and a liquid crystal display element provided with the liquid crystal alignment film.

As a result of careful research by the present inventors, it has been found that a liquid crystal alignment treatment agent containing three kinds of polymers having a specific structure is extremely effective in achieving the above-mentioned object, and then completed the present invention. That is, the present invention has The following gist.

(1) A liquid crystal alignment treatment agent containing the following components (A), (B) and (C).

(A) Component: a polyimide precursor obtained by reacting a diamine component containing a diamine having the structure of the following formula [1] and a diamine having the structure of the following formula [2] with a tetracarboxylic acid component Or the polyimide which is the imidized precursor of the polyimide.

(B) Component: a polyimide precursor obtained by reacting a diamine component of a diamine having the structure of the following formula [2] with a tetracarboxylic acid component, or the polyimide precursor is compounded Aminated polyimide.

(C): Polyimide obtained by reacting a diamine component containing a diamine having at least one substituent selected from the group consisting of a carboxyl group (COOH group) and a hydroxyl group (OH group) with a tetracarboxylic acid component The precursor or the polyimide which has been imidized by the polyimide precursor.

(X¹表示選自由單鍵、-(CH₂)_a-(a為1~15之整數)、-O-、-CH₂O-、-CONH-、-NHCO-、-CON(CH₃)-、-N(CH₃)CO-、-COO-及-OCO-所成群之至少一種結合基。X²表示單鍵或-(CH₂)_b-(b為1~15之整數)。X³表示選自由單鍵、-(CH₂)_c-(c為1~15之整數)、-O-、-CH₂O-、-COO-及-OCO-所成群之至少一種。X⁴表示選自由苯環、環己烷環及雜環所成群之至少一種2價環狀基，或具有類固醇骨 架之碳數17~51之2價有機基，且前述環狀基上之任意氫原子可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子所取代。X⁵表示選自由苯環、環己烷環及雜環所成群之至少一種環狀基，且此等環狀基上之任意氫原子可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子所取代。n表示0~4之整數。X⁶表示選自由碳數1~18之烷基、碳數2~18之烯基、碳數1~18之含氟烷基、碳數1~18之烷氧基及碳數1~18之含氟烷氧基所成群之至少一種)。

(X ¹ means selected from a single bond, -(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ ) -, -N(CH ₃ )CO-, -COO-, and -OCO- at least one binding group. X ² represents a single bond or -(CH ₂ ) _b -(b is an integer of 1-15). X ³ represents at least one selected from the group consisting of a single bond, -(CH ₂ ) _c- (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO-, and -OCO-. X ⁴ represents at least one divalent cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic ring, or a divalent organic group having a steroid skeleton and a carbon number of 17 to 51, and any of the aforementioned cyclic groups The hydrogen atom can be replaced by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom . X ⁵ represents at least one cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic ring, and any hydrogen atom on these cyclic groups may be 1 to 3 alkoxy groups, C 1 to 3 fluorine-containing alkyl groups, C 1 to 3 fluorine-containing alkoxy groups or fluorine atoms. n represents an integer of 0 to 4. X ⁶ represents a group selected from carbon Alkyl groups with 1 to 18 carbon atoms, alkenyl groups with 2 to 18 carbon atoms, fluoroalkyl groups with 1 to 18 carbon atoms, alkoxy groups with 1 to 18 carbon atoms and fluoroalkoxy groups with 1 to 18 carbon atoms At least one of the groups).

[Chem 2] -W ¹ -W ² -W ³ -W ⁴ [2] (W ¹ represents selected from -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-,- CH ₂ O-, -OCO-, -CON(CH ₃ )-, and -N(CH ₃ )CO- at least one kind of binding group. W ² represents a single bond, a carbon number of 1 to 20 alkylene At least one group consisting of a group, a non-aromatic ring and an aromatic ring. W ³ represents selected from a single bond, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-,- COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO- and -O(CH ₂ ) _m- (m represents an integer from 1 to 5) at least one group. W ⁴ Represents a nitrogen-containing aromatic heterocycle.

(2) The liquid crystal alignment treatment agent of (1) above, wherein the diamine having the structure of the aforementioned formula [1] is used only as the diamine component of the aforementioned (A) component.

(3) The liquid crystal alignment treatment agent according to (1) above, wherein the diamine component having the structure represented by the formula [1] in the aforementioned (A) component is used for the entire diamine component When the ratio (mol%) is set to 1.0, the use ratio (mol%) of the diamine having the structure shown in formula [1] to the entire diamine component in the component (B) is 0.01 to 0.8.

(4) The liquid crystal alignment treatment agent according to (1) or (3) above, wherein the use ratio of the diamine having the structure represented by the formula [1] to the entire diamine component in the component (A) (mol %) When set to 1.0, the use ratio (mol %) of the diamine to the entire diamine component having the structure shown in formula [1] in the component (C) is a ratio of 0.01 to 0.3.

(5) The liquid crystal alignment treatment agent according to any one of (1) to (4) above, wherein the aforementioned diamine system having at least one substituent selected from the group consisting of a carboxyl group (COOH group) and a hydroxyl group (OH group) Only used for the diamine component of the aforementioned (C) component.

(6) The liquid crystal alignment treatment agent according to any one of (1) to (5) above, wherein the diamine having the structure of formula [1] is represented by the following formula [1a].

(X表示前述式[1]之構造。n1表示1~4之整數)。

(X represents the structure of the aforementioned formula [1]. n1 represents an integer of 1 to 4).

(7) The liquid crystal alignment treatment agent according to any one of (1) to (6) above, wherein the diamine having the structure of formula [2] is represented by the following formula [2a].

(W表示前述式[2]之構造。p1表示1~4之整數)。

(W represents the structure of the aforementioned formula [2]. p1 represents an integer of 1 to 4).

(8) The liquid crystal alignment treatment agent according to any one of (1) to (7) above, wherein the diamine having at least one substituent selected from the group consisting of carboxyl groups and hydroxyl groups is represented by the following formula [3a] By.

(Y表示下述式[3-1]或式[3-2]之構造。m1表示1~4之整數)。

(Y represents the structure of the following formula [3-1] or formula [3-2]. m1 represents an integer of 1 to 4).

(a及b係各自表示0~4之整數)。

(a and b are each an integer from 0 to 4).

(9) The liquid crystal alignment treatment agent according to any one of (1) to (8) above, wherein the tetracarboxylic acid component of the aforementioned (A) component, (B) component and (C) component includes the following formula [ 4] The tetracarboxylic dianhydride.

(Z表示選自由下述式[4a]~式[4k]之構造所成群之至少一種之構造)。

(Z represents at least one structure selected from the group consisting of the following formula [4a] to formula [4k]).

(Z¹~Z⁴係各自獨立表示選自由氫原子、甲基、氯原子及苯環所成群之至少一種。Z⁵及Z⁶係各自獨立表示氫原子或甲基)。

(Z ¹ to Z ⁴ each independently represent at least one selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom, and a benzene ring. Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group).

(10) The liquid crystal alignment treatment agent according to any one of (1) to (9) above, which contains a member selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ- At least one solvent grouped by butyrolactone.

(11) The liquid crystal alignment treatment agent according to any one of (1) to (10) above, which contains a compound selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, and propylene glycol At least one solvent grouped by monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, and solvents of the following formula [D1] to formula [D3].

(D¹表示碳數1~3之烷基。D²表示碳數1~3之烷基。D³表示碳數1~4之烷基)。

(D ¹ represents an alkyl group having 1 to 3 carbon atoms. D ² represents an alkyl group having 1 to 3 carbon atoms. D ³ represents an alkyl group having 1 to 4 carbon atoms).

(12) The liquid crystal alignment treatment agent according to any one of (1) to (11) above, wherein the liquid crystal alignment treatment agent contains a compound selected from the group consisting of an epoxy group, an isocyanate group, a propylene oxide group, and a cyclocarbonate group A crosslinkable compound of at least one group of groups, having a crosslinkable compound of at least one group selected from the group consisting of hydroxy, hydroxyalkyl, and lower alkoxyalkyl groups, or having a polymerizable unsaturated bond group Of cross-linking compounds.

(13) A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of (1) to (12) above.

(14) A liquid crystal alignment film obtained by applying the liquid crystal alignment treatment agent according to any one of (1) to (12) above by an inkjet method.

(15) A liquid crystal display device having the liquid crystal alignment film as described in (13) or (14) above.

(16) The liquid crystal alignment film as described in (13) or (14) above, which is used for a liquid crystal display element which has a liquid crystal layer between a pair of substrates provided with electrodes, and is A liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between a pair of substrates, and a voltage is applied between the electrodes to polymerize the polymerizable compound.

(17) A liquid crystal display device having the liquid crystal alignment film as described in (16) above.

(18) The liquid crystal alignment film of (13) or (14) above, which is used in a liquid crystal display element having a liquid crystal layer between a pair of substrates provided with electrodes, and A liquid crystal formulation including polymer groups polymerized by at least one of active energy rays and heat is disposed between the substrates It is manufactured by the step of applying a voltage to the film to polymerize the polymerizable group.

(19) A liquid crystal display device having the liquid crystal alignment film as described in (18) above.

The liquid crystal alignment treatment agent of the present invention can obtain a liquid crystal alignment film that shows stable vertical alignment even after long-term exposure to high temperature and light irradiation. In addition, a liquid crystal alignment film that can reduce the liquid crystal alignment unevenness generated in the ODF method can be obtained. Moreover, even after long-term exposure to light irradiation, a drop in the voltage retention rate is suppressed, and a liquid crystal alignment film that quickly relaxes the residual charge accumulated by the DC voltage can be obtained.

The reason why the liquid crystal display device having the above-mentioned excellent characteristics can be obtained according to the present invention is not very clear, but several reasons can be speculated as the following reasons.

The specific structure (1) in the specific polymer (A) contains a benzene ring, a cyclohexane ring, a heterocyclic ring, or a divalent organic group having a steroid skeleton and a carbon number of 17 to 51. Compared with the long-chain alkyl group of the prior art that vertically aligns the liquid crystal, the side chain structure of these rings and organic groups is more rigid, and the structure is more stable to light such as ultraviolet rays. Therefore, compared with the prior art, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent having a specific structure (1) shows high vertical alignment, and even if it is exposed to light irradiation for a long time, the change in vertical alignment can be suppressed . In addition, even when exposed to light irradiation, the voltage retention rate is not reduced, and side chains that accumulate residual charge due to DC voltage can be suppressed Decomposition of ingredients.

In addition, since the specific structure (1) is a highly water-based structure, it is possible to suppress the generated adsorbed water or impurities from adhering to the surface of the liquid crystal alignment film during the manufacturing process of the liquid crystal display element. Therefore, the liquid crystal alignment unevenness generated in the ODF method can be reduced.

In addition, the nitrogen-containing heterocyclic ring included in the specific structure (2) in the specific polymers (A) and (B) and the carboxyl group or hydroxyl group in the specific polymer (C) are electrostatically interacted with each other by a salt formation or hydrogen bonding. It is combined by action, so it becomes easy to cause the charge to move between the nitrogen-containing aromatic heterocycle and the carboxyl group or hydroxyl group. By this, the moved charges can efficiently move within and between the molecules of the polyimide-based polymer, so that the residual charge accumulated by the DC voltage can be quickly relaxed. Therefore, a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is one with excellent reliability.

In the present invention, "parts" and "%" mean "mass parts" and "mass %", respectively, unless otherwise defined.

<Specific structure (1)‧Specific diamine (1)>

The specific diamine (1) in the present invention has a specific structure (1) of the following formula [1].

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and n are as defined above, but X ^{1 is} a single bond, -(CH ₂ ) _{a from} the viewpoint of availability of raw materials or ease of synthesis -(a is an integer from 1 to 15), -O-, -CH ₂ O- or -COO- is preferred. Preferably, it is a single bond, -(CH ₂ ) _a- (a is an integer from 1 to 10), -O-, -CH ₂ O-, or -COO-.

X ² is preferably a single bond or -(CH ₂ ) _b- (b is an integer from 1 to 10).

X ^{3 is} preferably a single bond, -(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ O-, or -COO- from the viewpoint of ease of synthesis. It is preferably a single bond, -(CH ₂ ) _c- (c is an integer from 1 to 10), -O-, -CH ₂ O- or -COO-.

From the viewpoint of ease of synthesis, X ^{4 is} preferably a benzene ring, a cyclohexane ring, or an organic group having 17 to 51 carbon atoms having a steroid skeleton.

X ⁵ series is preferably a benzene ring or a cyclohexane ring.

X ⁶ is composed of an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or one containing 1 to 10 carbon atoms. Fluoroalkoxy is preferred. It is preferably an alkyl group having 1 to 12 carbons, an alkenyl group having 2 to 18 carbons or an alkoxy group having 1 to 12 carbons. Particularly preferred are alkyl groups having 1 to 9 carbons, alkenyl groups having 2 to 12 carbons or alkoxy groups having 1 to 9 carbons.

n is preferably 0~3 from the viewpoint of availability of raw materials or ease of synthesis. It is preferably 0~2.

The ideal combination of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and n is listed in Table 6 on pages 13 to 34 of International Publication WO2011/132751 (published on 2011.10.27) ~The same combination of (2-1)~(2-629) contained in Table 47. In addition, in the tables of the International Publication, X ¹ to X ⁶ in the present invention are marked as Y1 to Y6, so Y1 to Y6 should be read as X ¹ to X ⁶ . In addition, in (2-605) to (2-629) contained in the tables of the International Publication, the organic groups having carbon numbers 17 to 51 having a steroid skeleton in the present invention are marked as carbon numbers 12 having a steroid skeleton The organic group of ~25, so the organic group with carbon number 12~25 with steroid skeleton should be read into the organic group with carbon number 17~51 with steroid skeleton.

Among them, also (2-25)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-268)~(2-315 ), (2-364)~(2-387), (2-436)~(2-483) or (2-603)~(2-615) combination is better. The best combination is (2-49)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-603)~(2-606 ), (2-607)~(2-609), (2-611), (2-612) or (2-624).

The specific diamine (1) is particularly preferably a diamine using the following formula [1a].

X represents the structure of the aforementioned formula [1]. In addition, the details and preferred combinations of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and n in the formula [1a] are as described in the aforementioned formula [1].

n1 represents an integer from 1 to 4. Among them, an integer of 1 is also preferred.

Specifically, the formula [2-1] to formula [2-6] and formula [2-9] to formula as described in pages 15 to 19 of International Publication WO2013/125595 (published on 2013.8.29) can be given. [2-31] Diamine. Yet, according to International Publication WO2013 / 125595 of the formula [2-1] to the formula [2-3], and R ₂ in the formula [2-4] to Formula [2-6] is selected from the group consisting of R ₄ represents At least one type of a C 1-18 alkyl group, a C 1-18 fluorine-containing alkyl group, a C 1-18 alkoxy group, and a C 1-18 fluorine-containing alkoxy group. In addition, A ₄ in formula [2-13] represents a linear or branched alkyl group having 3 to 18 carbon atoms. In addition, R _{3 in} Formula [2-4] to Formula [2-6] represents at least one selected from the group consisting of -O-, -CH ₂ O-, -COO-, and -OCO-.

Among them, from the viewpoint that it can exhibit a stable pretilt angle, can reduce the liquid crystal alignment unevenness generated in the ODF method, and suppress the reduction of the voltage retention rate after long-term exposure to light irradiation, the ideal diamine is as follows According to the formula [2-1] to formula [2-6], formula [2-9] to formula [2-13] or formula [2-22] to formula [2-31] described in International Publication WO2013/125595 Diamine.

From the above viewpoint, the use ratio of the specific diamine (1) in the specific polymer (A) is preferably 10 to 70 mol% relative to the entire diamine component. It is preferably 15 to 70 mol%, and particularly preferably 20 to 60 mol%. In the specific polymer (B), it is preferably 0 to 40 mol% relative to the entire diamine component. It is preferably 0 to 30 mol%, and particularly preferably 0 to 25 mol%. In the specific polymer (C), 0-20 mole% is better. It is preferably 0 to 10 mol%.

In addition, depending on the solubility of the polyimide-based polymer in the solvent, the liquid crystal alignment property when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element, the specific diamine (1) can use one type or Two or more types are mixed for use.

<Specific Structure (2)‧Specific Diamine (2)>

The specific diamine (2) of the present invention has a specific structure of the following formula [2].

[化12] -W ¹ -W ² -W ³ -W ⁴ [2]

W ¹ , W ² , W ³ and W ⁴ are as defined above, but each of them is preferably the following.

W ¹ is preferably -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )-, or -N(CH ₃ )CO-. From the viewpoint of ease of synthesis, preferred is -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, or -CON(CH ₃ )-. Particularly preferred are -O-, -CONH- or -CH ₂ O-.

W ² represents at least one selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring, and an aromatic ring. The alkylene group having 1 to 20 carbon atoms may be linear or branched. In addition, it may have an unsaturated bond. From the viewpoint of ease of synthesis, alkylene having 1 to 10 carbon atoms is preferred.

Specific examples of the non-aromatic ring include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring Ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, Ring nineteen ring, ring eicosane ring, tricyclic eicosane ring, tricyclic behenane ring, fused ring heptane ring, decahydronaphthalene ring, norbornene ring and adamantane ring, etc. Among them, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornane ring or adamantane ring are also preferred.

Specific examples of the aromatic ring include benzene ring, naphthalene ring, tetrahydronaphthalene ring, molybdenum ring, indene ring, stilbene ring, anthracene ring, phenanthrene ring, and phlebo ring. Among them, benzene ring, naphthalene ring, tetrahydronaphthalene ring, stilbene ring or anthracene ring is also preferred.

W ² is a single bond, an alkylene group having a carbon number of 1 to 10, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, A benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a stilbene ring or an anthracene ring is preferred. From the point of view of ease of synthesis and from the point of view that the relaxation of the residual charge accumulated due to the DC voltage after long-term exposure to light irradiation becomes faster, among which are also single bonds, alkylene groups with 1 to 5 carbon atoms, Hexane ring or benzene ring is preferred.

W ³ is preferably a single bond, -O-, -COO-, -OCO- or -O(CH ₂ ) _m- (m represents an integer of 1 to 5). From the viewpoint of ease of synthesis, a single bond, -O-, -OCO-, or -O(CH ₂ ) _m- (m is 1 to 5) is preferred.

W ⁴ represents a nitrogen-containing aromatic heterocyclic ring, and contains at least one structure selected from the group consisting of the following formula [a], formula [b], and formula [c].

(Z表示碳數1~5之烷基)。

(Z represents an alkyl group having 1 to 5 carbon atoms).

More specifically, examples include a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an oxazoline ring, an isoquinoline ring, a carbazole ring, Purine ring, thiadiazole ring, triazine ring, pyazolidine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, cinnoline ring, morpholine Ring, indole ring, quinoxaline ring, benzothiazole ring, phenolthiazine ring, oxadiazole ring, acridine ring, etc. Among them, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a triazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring or a benzimidazole ring are also preferable. From the viewpoint that the relaxation of the residual charge accumulated by the direct current voltage after exposure to light for a long time becomes faster, the pyrrole ring, imidazole ring, pyrazole ring, pyridine ring or pyrimidine ring is preferred. Particularly preferred are imidazole ring or pyridine ring. In addition, W ³ in formula [2] is preferably bound to a substituent that is not adjacent to formula [a], formula [b], and formula [c] contained in W ⁴ .

The ideal combinations of W ¹ , W ² , W ³ and W ⁴ are shown in Table 1 to Table 31.

Among them, (a-43)~(a-49), (a-57)~(a-63), (a-218)~(a-224), (a-232)~(a-238) , (A-323)~(a-329), (a-337)~(a-343), (a-428)~(a-434) or (a-442)~(a-448) combination Better. From the viewpoint that the relaxation of the residual charge accumulated by the DC voltage becomes faster after being exposed to light for a long time, the preferred ones are (a-44), (a-45), (a-58) or (a -59) combination.

The specific diamine (2) is particularly preferably a diamine using the following formula [2a].

W represents the structure of the aforementioned formula [2]. The details and ideal combinations of W ¹ , W ² , W ³ , and W ⁴ are as described in the aforementioned formula [2]. p1 represents an integer from 1 to 4. From the viewpoint of ease of synthesis, 1 is preferable.

From the above viewpoint, the specific diamine (2) is preferably used in the following ratio. In the specific polymer (A), it is preferably 1 to 60 mol% relative to the entire diamine component. The better one is 5~50 mol%, and the best one is 10~50 mol%. In the specific polymer (B), it is preferably 5 to 100 mol% relative to the entire diamine component. The better is 10 to 95 mol%, and the particularly good is 15 to 95 mol%. In the specific polymer (C), 0-20 mole% is preferable. The better one is 0~10 mol%, and the best one is 0 mol%.

In addition, depending on the solubility of the polyimide-based polymer in the solvent, the liquid crystal alignment property when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element, the specific diamine (2) can use one type or Two or more types are mixed for use.

<Specific diamine (3)>

The specific diamine (3) in the present invention has at least one substituent selected from the group consisting of a carboxyl group (COOH group) and a hydroxyl group (OH group).

Specifically, it is preferable to use the diamine of the following formula [3a].

Y represents the structure of the following formula [3-1] or formula [3-2].

m1 represents an integer from 1 to 4.

a represents an integer from 0 to 4. From the viewpoint of availability of raw materials or ease of synthesis, an integer of 0 or 1 is also preferable.

In formula [3-2], b represents an integer of 0~4. From the viewpoint of availability of raw materials or ease of synthesis, an integer of 0 or 1 is also preferable.

More specifically, examples include 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, and 4 ,6-Diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid, etc.

From the viewpoint of suppressing the decrease in the voltage retention rate after prolonged exposure to light irradiation, and the relaxation of the residual charge accumulated by the DC voltage becomes faster, among which 2,4-diaminophenol, 3,5 -Diaminophenol, 3,5-diaminobenzyl alcohol or 3,5-diaminobenzoic acid is preferred.

From the above viewpoint, the specific diamine (3) is preferably used in the following ratio. In the specific polymer (A), it is preferably 0 to 20 mol% relative to the entire diamine component. The better one is 0~10 mol%, and the best one is 0 mol%. In the specific polymer (B), relative to the diamine The whole composition is preferably 0-20 mole %. The better one is 0~10 mol%, and the best one is 0 mol%. In the specific polymer (C), 40 to 100 mole% is preferable. The better one is 50~100 mol%, and the best one is 60~100 mol%.

In addition, according to the characteristics of the solubility of the polyimide-based polymer in the solvent, the liquid crystal alignment when forming the liquid crystal alignment film, and the optical characteristics of the liquid crystal display element, the specific diamine (3) can use one type or Two or more types are mixed for use.

<Specific polymer (A)~Specific polymer (C)>

The specific polymers (A), (B), and (C) in the present invention mean the aforementioned (A) component, (B) component, and (C) component, respectively, and are polyimide precursors or polyimides Imines (also collectively referred to as polyimide-based polymers). These are preferably a polyimide precursor or polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

The polyimide precursor has the structure of the following formula [A].

(R¹表示4價之有機基。R²表示2價之有機基。A¹及A²係各自獨立表示氫原子或碳數1~8之烷基。A³及A⁴係各自獨立表示氫原子、碳數1~5之烷基或乙醯基。nA表示正之整數)。

(R ¹ represents a tetravalent organic group. R ² represents a divalent organic group. A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. A ³ and A ⁴ each independently represent hydrogen Atom, alkyl or acetyl group with 1 to 5 carbon atoms. nA represents a positive integer).

Examples of the aforementioned diamine component include diamines having two primary or secondary amine groups in the molecule. Examples of the tetracarboxylic acid component include tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds or tetracarboxylic acid dialkyl ester dihalide compounds.

The polyimide-based polymer uses tetracarboxylic dianhydride of the following formula [B] and diamine of the following formula [C] as raw materials. It is more easily obtained from the reason that the following formula [D ] The polyamic acid formed by the structural formula of the repeating unit or the polyimide made by the imidization of the polyamic acid is preferred. From the viewpoint of the physical and chemical stability of the liquid crystal alignment film, polyimide is also preferred.

(R¹及R²係與式[A]中所定義者相同)。

(R ¹ and R ² are the same as defined in formula [A]).

(R¹、R²及nA係與前述式[A]中所定義者相同)。

(R ¹ , R ² and nA are the same as defined in the aforementioned formula [A]).

In addition, the polymer of formula [D] obtained above can be introduced into the alkyl group of 1 to 8 carbon atoms of A ¹ and A ² in formula [A] and into formula [A] by the usual synthetic method A ³ and A ^{4 have} a carbon number of 1 to 5 alkyl or acetyl.

As long as the effects of the present invention are not impaired, in the specific polymers (A), (B) and (C) of the present invention, in addition to the aforementioned specific diamines, other diamines (also known as other Diamine).

Specifically, the diamine shown by following formula [D1]-formula [D6] is mentioned.

In addition, other diamines as described in pages 19 to 23 of International Publication WO2013/125595 (published on 2013.8.29), and formulas [DA1] to [DA12] described in pages 23 to 24 of the publication and The diamine represented by formula [DA15] to formula [DA20], and the diamine represented by formula [DA27] and formula [DA28] described on page 26 of the same publication.

Other diamines can be used for any specific polymer of specific polymers (A), (B) and (C), and can be used for all of these specific polymers, or any One specific polymer two Amine components.

In addition, according to the characteristics of the solubility of the polyimide-based polymer in the solvent, the liquid crystal alignment when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element, other diamine systems can use one type or two types The above are mixed.

The tetracarboxylic acid component in at least any one of the specific polymers (A), (B), and (C) is a tetracarboxylic dianhydride (also called specific tetracarboxylic acid) of the following formula [4] Acid component) is preferred. Preferably, all specific polymers use specific tetracarboxylic acid components.

Z represents at least one structure selected from the group consisting of the structures of the aforementioned formula [4a] to formula [4k]. From the viewpoint of ease of synthesis or ease of polymerization reactivity when manufacturing a polymer, Z is represented by formula [4a], formula [4c], formula [4d], formula [4e], formula [4f], and formula [4g] Or type [4k] is better. Preferably, it is formula [4a], formula [4e], formula [4f], formula [4g] or formula [4k]. Particularly preferred are formula [4e], formula [4f], formula [4g] or formula [4k].

The use ratio of the specific tetracarboxylic acid component is preferably 1 mol% or more relative to the total tetracarboxylic acid component. The better is 5 mol%. The most preferable one is 10 mol% or more. From the viewpoint of suppressing the decrease in the voltage retention rate after prolonged exposure to light irradiation, the best one is 10 to 90 mol%.

In addition, when the tetracarboxylic acid component having the structure of the above formula [4e], formula [4f], formula [4g] or formula [4k] is used, the amount of the tetracarboxylic acid component is 20 mole% of the total tetracarboxylic acid component Above, you can get the desired effect. It is preferably 30 mol% or more. Furthermore, all of the tetracarboxylic acid components may be tetracarboxylic acid components having the structure of formula [4e], formula [4f], formula [4g] or formula [4k].

As long as the effect of the present invention is not impaired, other tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used in all specific polymers.

Specifically, there can be mentioned other tetracarboxylic acid components as described in pages 27 to 28 of International Publication WO2013/125595 (published on 2013.8.29). In addition, depending on various characteristics, the specific tetracarboxylic acid component and other tetracarboxylic acid component systems can be used alone or in combination of two or more.

The specific polymer (A) is a polyimide precursor obtained by reacting a diamine component containing a specific diamine (1) and a specific diamine (2) with a tetracarboxylic acid component or the polyimide The precursor is polyimide which is imidized.

On this occasion, the specific diamine (1) and the use ratio of the specific diamine are as follows. That is, the specific diamine (1) is preferably 10 to 70 mol% relative to the entire diamine component. The better is 15 to 70 mol%, and the particularly good is 20 to 60 mol%. In addition, the specific diamine (2) is preferably 1 to 60 mol% relative to the entire diamine component. The better one is 5~50 mol%, and the best one is 10~50 mol%. In addition, in the specific diamine (3), from the viewpoint of reducing the unevenness of liquid crystal alignment generated in the ODF method, the specific diamine (3) is preferably 0 to 20 mol% relative to the entire diamine component. The better one is 0~10 Molar%, especially the best is 0 mol%, that is, no specific diamine is used (3).

The specific polymer (B) is a polyimide precursor obtained by reacting a diamine component containing a specific diamine (2) with a tetracarboxylic acid component or the polyimide precursor is imidate The polyimide. On this occasion, the specific use ratio of the diamine (2) is as follows. That is, the specific diamine (2) system is preferably 5 to 100 mol% relative to the entire diamine component. The better is 10 to 95 mol%, and the particularly good is 15 to 95 mol%. In addition, in the specific diamine (1), it is preferably 0 to 40 mol% relative to the entire diamine component. The better one is 0~30 mol%, and the best one is 0~25 mol%.

However, the use ratio of specific diamine (1) in the specific polymer (B) to the entire diamine component (mol %), when the use ratio of the specific diamine (1) in the specific polymer (A) (Mohr%) is set to 1.0, the ratio is the use ratio (Mohr%) less than 1.0. On this occasion, when the ratio is 0, that is, when the diamine component of the specific polymer (B) is not used for the specific diamine (1), the voltage retention rate after suppressing the exposure to light for a long period of time decreases , And the viewpoint that the relaxation of the residual charge accumulated by the DC voltage becomes faster is preferable. When the specific polymer (B) uses the specific diamine (1), the aforementioned ratio is preferably 0.01 to 0.9. The better one is 0.01~0.8, and the best one is 0.05~0.7.

In addition, in the specific diamine (3), it is preferably 0 to 20 mol% relative to the entire diamine component. The preferred value is 0 to 10 mol %. From the viewpoint of reducing the unevenness of liquid crystal alignment generated by the ODF method, the most preferred value is 0 mol %, that is, the diamine component of the specific polymer (B) is not used. Specific diamine (3).

The specific polymer (C) is a diamine containing a specific diamine (3) The polyimide precursor obtained by reacting the component with the tetracarboxylic acid component or the polyimide obtained by subjecting the polyimide precursor to imidization. On this occasion, the use ratio of the specific diamine (3) is as described below. That is, the specific diamine (3) is preferably 40 to 100 mol% relative to the entire diamine component. The better one is 50~100 mol%, and the best one is 60~100 mol%. In addition, in the specific diamine (1), it is preferably 0 to 20 mol% relative to the entire diamine component. The better one is 0~10 mol%. However, the use ratio of the specific diamine (1) in the specific polymer (C) to the entire diamine component (mol %), when using the specific diamine (1) in the specific polymer (A) ( When the mole %) is set to 1.0, the ratio is less than 1.0 (Mohr %). At this time, when the ratio is 0, that is, when the specific diamine component (C) of the specific polymer (C) does not use the specific diamine (1), the reduction in the voltage retention rate after long-term exposure to light irradiation is suppressed , And the viewpoint that the relaxation of the residual charge accumulated by the DC voltage becomes faster is preferable. When the specific polymer (C) does not use the specific diamine (1), the aforementioned ratio is preferably 0.01 to 0.4. The better one is 0.01~0.3, and the best one is 0.01~0.2.

In addition, the specific diamine (3) is preferably 0 to 20 mol% relative to the entire diamine component. It is preferably 0 to 10 mol %. From the viewpoint of suppressing the decrease in the voltage retention rate after prolonged exposure to light irradiation, and the relaxation and increase in the residual charge accumulated by the DC voltage, the most preferred is 0 Molar %, that is, the specific diamine (3) is not used for the diamine component of the specific polymer (C).

In the present invention, the method for producing all the specific polymers, that is, the method for producing these polyimide-based polymers is not particularly limited. It is usually obtained by reacting a diamine component and a tetracarboxylic acid component. Generally speaking, It is obtained by reacting at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydride and its derivatives with a diamine component consisting of one or more diamines. Polyamide method. Specifically, the method of polycondensing a tetracarboxylic dianhydride and a 1st or 2nd diamine by polycondensation, and the dehydration condensation polymerization reaction of a tetracarboxylic acid and a 1st or 2nd diamine can be used. A method of obtaining polyamic acid, or a method of reacting tetracarboxylic acid dihalide with level 1 or level 2 diamine to obtain polyamic acid.

To obtain polyalkyl amides, a method of polycondensation of a tetracarboxylic acid obtained by esterifying a carboxylic acid group with a dialkyl group and a 1st or 2nd stage diamine can be used. The method of reacting the tetracarboxylic acid dihalide formed by alkyl esterification with the 1st or 2nd level diamine, or the method of converting the carboxyl group of the polyamic acid into an ester.

To obtain polyimide, a method of forming a polyimide by ring-closing the aforementioned polyamic acid or polyalkylamino acid can be used.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out by allowing the diamine component and the tetracarboxylic acid component in an organic solvent. The organic solvent used at this time is not particularly limited as long as it dissolves the produced polyimide precursor. Specific examples of organic solvents used in the reaction are given below, but not limited to these examples.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethyl Ethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolidinone, etc. In addition, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula can be used: D-1]~Form [D- 3] The solvent.

(D¹表示碳數1~3之烷基。D²表示碳數1~3之烷基。D³表示碳數1~4之烷基)。

(D ¹ represents an alkyl group having 1 to 3 carbon atoms. D ² represents an alkyl group having 1 to 3 carbon atoms. D ³ represents an alkyl group having 1 to 4 carbon atoms).

These systems can be used alone or in combination. Moreover, even if it is a solvent which does not dissolve the polyimide precursor, it can be mixed and used in the above-mentioned solvent as long as the polyimide precursor produced does not precipitate. In addition, since the water in the organic solvent may hinder the polymerization reaction and cause the polyimide precursor to be hydrolyzed, the organic solvent is preferably a dehydrated and dried one.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, for example, a solution obtained by stirring to disperse or dissolve the diamine component in an organic solvent, and the tetracarboxylic acid component is directly added or dispersed or The method of dissolving in an organic solvent and adding; conversely, the method of adding a diamine component to a solution of dispersing or dissolving a tetracarboxylic acid component in an organic solvent; the method of alternately adding a diamine component and a tetracarboxylic acid component, etc., use this Either method is acceptable. In addition, when a plurality of diamine components and tetracarboxylic acid components are used for the reaction, the reaction may be carried out in a mixed state in advance, or the reaction may be carried out sequentially in sequence, or the individual low molecular weight bodies may be mixed to make It reacts to make a polymer. The polymerization temperature at this time can be selected from -20℃~ Any temperature of 150°C is preferably in the range of -5°C to 100°C. In addition, the reaction system can be carried out at an arbitrary concentration, but when the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and when the concentration is too high, the viscosity of the reaction solution becomes too high, making it difficult to uniformly stir. Therefore, it is preferably 1-50%, preferably 5-30%. It is also possible to proceed at a high concentration in the initial stage of the polymerization reaction, and then add an organic solvent thereafter.

In the polymerization reaction of the polyimide precursor, the ratio of the total molar number of the diamine component to the total molar number of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to the normal polymerization reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyimide precursor produced.

Polyimide is a polyimide obtained by ring-closing the aforementioned polyimide precursor. The ring-closing rate of the amino acid group (also known as the rate of imidization) does not necessarily need to be 100%. It can be arbitrarily adjusted for its use or purpose. Among them, in the present invention, all the specific polymers are preferably polyimide which is imidized by the polyimide precursor. In this case, the rate of acyl imidization is preferably as described below. That is, the specific polymer (A) is preferably 50 to 90%. The better one is 55~90%, and the best one is 60~90%. The specific polymer (B) is preferably 50-95%. The better is 55~95%, the particularly good is 60~95%, and the specific polymer (C) is preferably 50~90%. The better one is 60~90%, and the best one is 60~80%.

As a method for subjecting the polyimide precursor to imidization, there may be mentioned, for example, directly heating the thermal imidization of the polyimide precursor solution, or adding a catalyst to the polyimide precursor solution. The medium is imidized. The temperature at which the polyimide precursor is thermally imidized in the solution is 100°C to 400°C, preferably 120°C to 250°C, but it is preferable to exclude the water generated by the amide imidization reaction from the system and proceed simultaneously.

The catalyst of the polyimide precursor can be added to the polyimide precursor solution with an alkaline catalyst and anhydride, by stirring at -20~250℃, preferably 0~180℃ To implement. The amount of the alkaline catalyst is 0.5 to 30 mole times of the amide acid group, preferably 2 to 20 mole times, and the amount of the acid anhydride is 1 to 50 mole times of the amide acid group, preferably 3 to 30 mole times. Examples of the alkaline catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has a moderate basicity required for the reaction to proceed. Examples of the acid anhydride include anhydrous acetic acid, anhydrous trimellitic acid, anhydrous pyromellitic acid, and the like. Among them, if anhydrous acetic acid is used, purification after completion of the reaction becomes easy, which is preferable. The imidization rate formed by catalyst imidization can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.

When recovering the generated polyimide precursor or polyimide from the reaction solution of the polyimide precursor or polyimide, it is only necessary to put the reaction solution in a solvent to precipitate it. As the solvent used for precipitation, for example, methanol, ethanol, isopropyl alcohol, acetone, hexane, butylcellulose, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene or Water etc. After the polymer precipitated after being put in the solvent is filtered and recovered, it can be dried at normal pressure or under normal temperature or heating. In addition, the polymer recovered by precipitation is redissolved in an organic solvent, and the operation of reprecipitation and recovery is repeated 2 to 10 times to reduce impurities in the polymer. Examples of the solvent at this time include alcohols, ketones, and hydrocarbons. If three or more solvents selected from these are used, It is better because it can further improve the efficiency of purification.

The weight average molecular weight of the polyimide-based polymer is measured by the GPC (Gel Permeation Chromatography) method when considering the strength of the liquid crystal alignment film obtained therefrom, the workability at the time of forming the liquid crystal alignment film, and the coating film performance It is preferably 5,000~1,000,000. Among them, 10,000~150,000 is better.

As mentioned previously, all the specific polymers in the present invention can show stable vertical stability even after long-term exposure to high temperature and light irradiation, and even after long-term exposure to light irradiation, voltage retention can be suppressed From the viewpoint of reduction of the rate, the polyimide obtained by subjecting the above-mentioned polyimide precursor to catalyst imidization is preferred. At this time, the rate of acyl imidization is preferably within the above range.

<Liquid crystal alignment treatment agent>

The use ratio of the specific polymers (A), (B) and (C) in the liquid crystal alignment treatment agent is 30 to 300 parts relative to 100 parts of the specific polymer (A) The specific polymer (C) is preferably 60 to 500 parts. Preferably, the specific polymer (B) is 50 to 250 parts, the specific polymer (C) is 100 to 350 parts, and the particularly preferred is the specific polymer (B) is 50 to 200 parts, the specific polymer (C) For 100~300 copies.

All the polymer components in the liquid crystal alignment treatment agent may be all specific polymers or may be mixed with other polymers. At this time, the content of other polymers is preferably 0.5 to 15 parts relative to 100 parts of all specific polymers. Preferably, it is 1~10 servings. Make Examples of other polymers than those mentioned above include cellulose-based polymers, acrylic polymers, methacrylic polymers, polystyrene, polyamide, and polysiloxane.

The solvent in the liquid crystal alignment treatment agent is preferably 70 to 99.9% from the viewpoint of forming a uniform liquid crystal alignment film by coating. This content can be suitably changed according to the film thickness of the liquid crystal alignment film as the objective.

The solvent used in the liquid crystal alignment treatment agent of the present invention is not particularly limited as long as it dissolves all specific polymers (also referred to as good solvents). Specific examples of good solvents are given below, but not limited to these.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, di Methylene sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone, etc. .

Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is also preferably used.

In addition, when the solubility of the specific polymer in the solvent is high, it is preferable to use the solvent of the aforementioned formula [D-1] to formula [D-3].

The good solvent in the liquid crystal alignment treatment agent is preferably 10 to 100% of the total solvent contained in the liquid crystal alignment treatment agent. The better is 20~90%. The best is 30~80%.

The liquid crystal alignment treatment agent can also be used to improve the coating properties of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied, without impairing the effects of the present invention. Solvent for surface smoothness (also called lean solvent). Specific examples of the poor solvent are given below, but not limited to these.

Specific examples include the poor solvents described in pages 35 to 37 of International Publication WO2013/125595 (published on August 29, 2013).

Among them, 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether or the aforementioned formula are also used [D-1]~The solvent of formula [D-3] is good.

These poor solvents preferably account for 1 to 70% of the total solvent contained in the liquid crystal alignment treatment agent. The better is 1~60%. The best is 5~60%.

Within the scope of not detracting from the effects of the present invention, by introducing a crosslinkable compound having a group selected from an epoxy group, an isocyanate group, a glycidyl group, and a cyclic carbonate group into the liquid crystal alignment treatment agent, it has Cross-linkable compounds selected from the group consisting of hydroxy, hydroxyalkyl, and lower alkoxyalkyl groups, or cross-linkable compounds with a polymerizable unsaturated bond group (also collectively referred to as specific cross-linkable compounds) are preferred . In this case, it is necessary to have two or more of these groups in the compound.

As an example of the crosslinkable compound having an epoxy group or an isocyanate group, specific examples include those having an epoxy group or an isocyanate group as described in pages 37 to 38 of International Publication WO2013/125595 (published on 2013.8.29) on pages 37 to 38. Crosslinkable compounds.

Specific examples of the crosslinkable compound having a propylene oxide group include the crosslinkable compounds represented by Formula [4a] to Formula [4k] described in pages 58 to 59 of International Publication WO2011/132751.

As a crosslinkable compound having a cyclic carbonate group, specifically Examples of the cross-linkable compounds are represented by formula [5-1] to formula [5-42] described in pages 76 to 82 of International Publication WO2012/014898.

Examples of the cross-linkable compound having at least one group selected from the group consisting of hydroxy, hydroxyalkyl, and lower alkoxyalkyl include International Publication Gazette 2013/125595 (published on 2013.8.29), page 39. The melamine derivative or benzoguanamine derivative described on page ~40, and the formula [6-1] to formula [6-48] described on pages 62 to 66 of the International Publication WO2011/132751 (published on October 27, 2011) The cross-linking compound shown.

As the crosslinkable compound having a polymerizable unsaturated bond, specifically, a crosslinkable compound having a polymerizable unsaturated bond as described in pages 40 to 41 of International Publication WO2013/125595 (published on 2013.8.29) is described. .

The content of the specific crosslinkable compound in the liquid crystal alignment treatment agent is preferably 0.1 to 100 parts relative to 100 parts of the total polymer component. In order to allow the cross-linking reaction to proceed and to exhibit the desired effect, it is preferably 0.1 to 50 parts. The best ones are 1~30 copies.

In the liquid crystal alignment treatment agent of the present invention, in order to promote the charge movement in the liquid crystal alignment film and promote the charge loss of the device, the formula described in pages 69 to 73 of International Publication WO2011/132751 (published on 2011.10.27) can be added [ M1]~ Nitrogen-containing heterocyclic amine of formula [M156]. Even if this amine is directly added to the liquid crystal alignment treatment agent, it is okay, but it is better to use an appropriate solvent as a solution with a concentration of 0.1 to 10%, preferably 1 to 7%, and then add it. The solvent is not particularly limited as long as it is an organic solvent that can dissolve a specific polymer.

As long as the effect of the present invention is not compromised, the liquid crystal alignment As the physical agent, a compound that enhances the uniformity of the thickness of the liquid crystal alignment film or the surface smoothness when the liquid crystal alignment treatment agent is applied can be used. In addition, a compound that enhances the adhesion between the liquid crystal alignment film and the substrate can be used.

Examples of the compound that improves the film thickness uniformity or surface smoothness of the liquid crystal alignment film include fluorine-based surfactants, polysiloxane-based surfactants, and nonionic surfactants. Specific examples include surfactants described on pages 42 to 43 of International Publication WO2013/125595 (published on 2013.8.29).

The use amount of these surfactants is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass relative to 100 parts by mass of all polymer components contained in the liquid crystal alignment treatment agent.

As a specific example of the compound that enhances the adhesion between the liquid crystal alignment film and the substrate, there may be mentioned a compound containing a functional silane or a compound containing an epoxy group. Specifically, the compounds described on pages 43 to 44 of International Publication WO2013/125595 (published on 2013.8.29) can be mentioned.

The use ratio of the compound adhering to the substrate is preferably 0.1 to 30 parts, and preferably 1 to 20 parts relative to 100 parts of all polymer components contained in the liquid crystal alignment treatment agent. If it is less than 0.1 part, the effect of improving the adhesiveness cannot be expected, and if it exceeds 30 parts, the storage stability of the liquid crystal alignment treatment agent may be deteriorated.

Within the scope of the effects of the present invention, compounds other than the above may be added to the liquid crystal alignment treatment agent, and a dielectric or conductive material may be added for the purpose of changing the electrical characteristics such as the dielectric constant or conductivity of the liquid crystal alignment film. substance.

<Liquid crystal alignment film‧Liquid crystal display element>

The liquid crystal alignment treatment agent of the present invention is applied to a substrate and fired, and then subjected to alignment treatment by rubbing treatment or light irradiation, and can be used as a liquid crystal alignment film. Furthermore, in the case of vertical alignment applications, etc., even if no alignment treatment is applied, it can be used as a liquid crystal alignment film. The substrate used at this time is not particularly limited as long as it is a highly transparent substrate. In addition to a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used. From the viewpoint of simplification of the manufacturing process, it is preferable to use a substrate on which ITO electrodes for liquid crystal driving have been formed. In addition, in the reflective liquid crystal display element, if only a single-sided substrate is used, an opaque substrate such as a silicon wafer can also be used. As an electrode at this time, a material that reflects light such as aluminum can also be used.

The coating method of the liquid crystal alignment treatment agent is not particularly limited, and the industry generally adopts screen printing, offset printing, flexographic printing, or inkjet method. As other coating methods, there are a dipping method, a roll coating method, a slit coating method, a spin coating method, or a spray method, etc., and these may be used depending on the purpose.

After the liquid crystal alignment treatment agent is coated on the substrate, by heating means such as a hot plate, a thermal cycle oven or an IR (infrared) type oven, and according to the solvent used by the liquid crystal alignment treatment agent, at 30 to 300°C, Preferably, the solvent is evaporated at a temperature of 30 to 250°C to form a liquid crystal alignment film. If the thickness of the liquid crystal alignment film after firing is too thick, it will be unfavorable on the power consumption surface of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element may be reduced, so it is 5~ 300 nm is preferred, preferably 10-100 nm. When aligning the liquid crystal horizontally or obliquely, rub or polarize purple Treatment of the liquid crystal alignment film after firing with external radiation, etc.

The liquid crystal display element of the present invention is obtained by obtaining the substrate with the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention by the above-mentioned method, using a known method to produce a liquid crystal cell, and then forming a liquid crystal display element.

As a method for manufacturing the liquid crystal cell, for example, a pair of substrates having a liquid crystal alignment film formed thereon, and a spacer is spread on the liquid crystal alignment film of a single substrate, so that the liquid crystal alignment film surface is bonded to the other substrate toward the inside, reducing The method of pressure injection of liquid crystals for sealing; or the method of dropping liquid crystals on the liquid crystal alignment film surface of the dispersed spacers, bonding the substrate and sealing (ODF method), etc.

The liquid crystal alignment treatment agent of the present invention is also ideally used in a crystal display element, and the liquid crystal display element is formed by having a liquid crystal layer between a pair of substrates provided with electrodes, and is arranged between the pair of substrates A liquid crystal composition of a polymerizable compound polymerized by at least one of an active energy ray and heat is manufactured by applying a voltage between the electrodes to polymerize the polymerizable compound. Here, the active energy rays are suitably ultraviolet rays. The wavelength of ultraviolet rays is 300~400nm, preferably 310~360nm. When the polymerization is performed by heating, the heating temperature is 40 to 120°C, preferably 60 to 80°C. In addition, ultraviolet rays and heating may be performed simultaneously.

The above liquid crystal display device controls the pretilt of liquid crystal molecules by the PSA method. In the PSA method, a small amount of photopolymerizable compound, such as a photopolymerizable monomer, is mixed in the liquid crystal material in advance to form a liquid crystal cell, and then the photopolymerizable compound is irradiated with ultraviolet rays while applying a predetermined voltage to the liquid crystal layer. The pretilt of liquid crystal molecules is controlled by the resulting polymer. polymerization The alignment state of the liquid crystal molecules at the time of object generation is still remembered after the voltage is removed, so the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer. In addition, since the PSA method does not require rubbing treatment, it is suitable for the formation of a vertical alignment type liquid crystal layer whose pretilt is difficult to control by rubbing treatment. That is, the liquid crystal display element of the present invention is to obtain a substrate with a liquid crystal alignment film obtained by a liquid crystal alignment treatment agent by the above-mentioned method, and then produce a liquid crystal cell, and polymerize by irradiating at least one of ultraviolet rays and heating Sexual compounds polymerize and can be made to control the alignment of liquid crystal molecules.

An example of the production of a liquid crystal cell under the PSA method is as follows. That is, the liquid crystal cell is produced using the above production method. The liquid crystal at this time is mixed with a polymerizable compound polymerized by heat or ultraviolet radiation. Examples of the polymerizable compound include compounds having one or more polymerizable unsaturated groups such as acrylate group or methacrylate group in the molecule. At this time, the polymerizable compound is preferably 0.01 to 10 parts relative to 100 parts of the liquid crystal component, preferably 0.1 to 5 parts. If the polymerizable compound is less than 0.01 part, the polymerizable compound will not polymerize and the liquid crystal alignment will not be controlled. If it is more than 10 parts, the unreacted polymerizable compound will increase, which will result in the deterioration of the burn-in characteristics of the liquid crystal display element . After the liquid crystal cell is fabricated, an AC or DC voltage is applied to the liquid crystal cell, and heat or ultraviolet rays are simultaneously applied to polymerize the polymerizable compound. In this way, the alignment of the liquid crystal molecules can be controlled.

Furthermore, the liquid crystal alignment treatment agent of the present invention can also be used for a liquid crystal display element, and the liquid crystal display element is formed by having a liquid crystal layer between a pair of substrates having electrodes, A liquid crystal alignment film including a polymer group polymerized by at least one of active energy rays and heat is disposed between the plates, and a voltage is applied between the electrodes to polymerize the polymerizable group, that is, Used in SC-PVA mode. Here, the active energy rays are suitably ultraviolet rays. The wavelength of ultraviolet rays is 300~400nm, preferably 310~360nm. When the polymerization is performed by heating, the heating temperature is 40 to 120°C, preferably 60 to 80°C. In addition, ultraviolet rays and heating may be performed simultaneously.

In order to obtain a liquid crystal alignment film containing a polymerizable group polymerized by at least one of active energy rays and heat, a method of adding the compound containing a polymerizable group to a liquid crystal alignment treatment agent, or using Method of polymer component based polymer component.

As an example of producing an SC-PVA mode liquid crystal cell, for example, the following will be described. That is, the liquid crystal cell is produced using the above production method. Thereafter, the voltage of AC or DC is applied to the liquid crystal cell, and heat or ultraviolet radiation is simultaneously applied to control the alignment of the liquid crystal molecules.

[Example]

The following examples illustrate the present invention in more detail, but the present invention is not limited by these and is to be interpreted. The abbreviations used below are shown below.

(Specific diamine (1))

A1: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxy]benzene

A2: 1,3-diamino-5-[4-(trans-4-n-heptylcyclohexyl)phenoxymethyl Benzene

A3: 1,3-Diamino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene

A4: Diamine of the following formula [A4]

(Specific diamine (2))

(Specific diamine (3))

(Other diamines)

D1: p-phenylene diamine, D2: m-phenylene diamine

D3: 1,3-diamino-4-octadecyloxybenzene

(Specific tetracarboxylic dianhydride)

E1: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

E2: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

E3: tetracarboxylic dianhydride of the following formula [E3]

E4: tetracarboxylic dianhydride of the following formula [E4]

E5: tetracarboxylic dianhydride of the following formula [E5]

(Crosslinkable compound)

(Solvent)

NMP: N-methyl-2-pyrrolidone, NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone, BCS: ethylene glycol monobutyl ether, PB: propylene glycol monobutyl ether, DME: dipropylene glycol dimethyl ether, DPM: dipropylene glycol monomethyl ether

"Molecular weight measurement of polyimide polymer"

Using a room temperature gel permeation chromatography (GPC) device (GPC-101, manufactured by Showa Denko Co., Ltd.) and a column (KD-803, KD-805, manufactured by Shodex), the measurement was performed by the following operation.

Column temperature: 50℃

Eluate: N,N'-dimethylformamide (as additive, lithium bromide-hydrate (LiBr‧H ₂ O) is 30mmol/L (liter)), phosphoric acid‧ anhydrous crystal (o-phosphoric acid) is 30mmol/ (L, tetrahydrofuran (THF) is 10ml/L)

Flow rate: 1.0ml/min

Standard sample for making calibration line: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000, Tosoh Corporation System) and polyethylene glycol (molecular weight: approximately 12,000, 4,000, and 1,000, manufactured by Polymer Laboratories).

"Measurement of Amidation Rate of Polyimide-based Polymers"

5(草野科學公司製))，添加氘化二甲亞碸(DMSO-d6，0.05%TMS(四甲基矽烷)混合品)(0.53ml)，施加超音波使其完全溶解。在NMR測量機(JNW-ECA500、日本電子資料公司製)中，測量此溶液之500MHz之質子NMR。醯亞胺化率係將源自醯亞胺化前後並未變化之構造之質子決定當作基準質子，使用此質子之波峰累算值，與源自出現在9.5ppm~10.0ppm附近之醯胺酸之NH基之質子波峰累算值，藉由以下之式而求得者。 Put 20 mg of polyimide powder in the NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard,

5 (manufactured by Kusano Science Corporation)), deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixed product) (0.53 ml) was added, and ultrasonic waves were applied to completely dissolve it. In a NMR measuring machine (JNW-ECA500, manufactured by Nippon Electronics Data Corporation), the 500 MHz proton NMR of this solution was measured. The rate of amide imidization is based on the determination of protons derived from the structure that has not changed before and after amide imidization as the reference protons, and the cumulative value of the peak of this proton is used, which is derived from the amides appearing in the vicinity of 9.5 ppm to 10.0 ppm. The cumulative value of the proton peak of the NH group of the acid is obtained by the following formula.

Acetylimidization rate (%) = (1-α‧x/y) × 100 (x is the cumulative value of the proton peak derived from the NH group of amide acid, y is the cumulative value of the peak of the reference proton, and α is the poly In the case of amide acid (acid imidization rate is 0%), the ratio of the reference proton to the number of NH matrix protons of amide acid is one).

"Synthesis of Polyimide Polymers"

<Synthesis Example 1>

Mix E2 (2.17g, 8.67mmol), A1 (2.67g, 7.02mmol), B1 (1.28g, 5.28mmol) and D1 (0.57g, 5.27mmol) in NMP (16.8g), and react at 80°C for 5 After hours, add E1 (1.70g, 8.67mmol) and NMP (8.39g) were reacted at 40°C for 6 hours, and the concentration (representing the resin solid content concentration. The following examples are all the same) was 25% polyamic acid solution.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting it to 6%, anhydrous acetic acid (4.50 g) and pyridine (3.30 g) were added as an amide imidization catalyst, and the reaction was carried out at 80° C. for 4 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100°C to obtain polyimide powder (1). The polyimide had an imidization rate of 80%, a number average molecular weight (Mn) of 17,400, and a weight average molecular weight (Mw) of 47,500.

<Synthesis Example 2>

Mix E2 (0.89g, 3.56mmol), A3 (2.35g, 5.43mmol), B1 (1.75g, 7.22mmol) and D1 (0.59g, 5.46mmol) in NMP (16.8g), and react at 80°C for 5 After 1 hour, E1 (2.80 g, 14.3 mmol) and NMP (8.38 g) were added and reacted at 40° C. for 6 hours to obtain a 25%-concentrated polyamic acid solution.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting it to 6%, anhydrous acetic acid (4.50 g) and pyridine (3.30 g) were added as an amide imidization catalyst, and the reaction was carried out at 80° C. for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100°C to obtain polyimide powder (2). The polyimide has an imidization rate of 75%, Mn of 16,100, and Mw of 44,400.

<Synthesis Example 3>

E2 (3.06g, 12.2mmol), A2 (2.61g, 6.61mmol), B1 (1.20g, 4.95mmol) and D1 (0.54g, 4.99mmol) were mixed in NEP (16.4g), and reacted at 80°C for 5 After 1 hour, E1 (0.80 g, 4.08 mmol) and NEP (8.21 g) were added and reacted at 40° C. for 6 hours to obtain a polyamic acid solution with a concentration of 25%.

After adding NEP to the obtained polyamic acid solution (30.0 g) and diluting it to 6%, anhydrous acetic acid (4.50 g) and pyridine (3.30 g) were added as an amide imidization catalyst, and the reaction was carried out at 80° C. for 3 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100°C to obtain polyimide powder (3). The polyimide has an imidization rate of 70%, Mn of 17,800, and Mw of 47,600.

<Synthesis Example 4>

Mix N2 (17.0g) with E2 (2.17g, 8.67mmol), A4 (2.16g, 4.38mmol), B1 (1.91g, 7.88mmol) and D1 (0.57g, 5.27mmol), and react at 80°C for 5 After 1 hour, E1 (1.70 g, 8.67 mmol) and NMP (8.52 g) were added and reacted at 40° C. for 6 hours to obtain a polyamic acid solution with a concentration of 25%.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting it to 6%, anhydrous acetic acid (4.50 g) and pyridine (3.30 g) were added as an amide imidization catalyst, and the reaction was carried out at 80° C. for 2.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100°C to obtain polyimide powder (4). Polyimide The imidate ratio was 65%, Mn was 15,300, and Mw was 42,100.

<Synthesis Example 5>

Mix E3 (3.80g, 17.0mmol), A2 (2.03g, 5.14mmol), B1 (1.66g, 6.85mmol) and D2 (0.56g, 5.18mmol) in NEP (24.2g), and react at 40°C for 8 Hours to obtain a 25% concentration of polyamic acid solution.

After adding NEP to the obtained polyamic acid solution (30.0 g) and diluting it to 6%, anhydrous acetic acid (4.50 g) and pyridine (3.30 g) were added as an amide imidization catalyst, and the reaction was carried out at 80° C. for 3 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100°C to obtain polyimide powder (5). The polyimide has an imidization rate of 70%, Mn of 18,600, and Mw of 48,800.

<Synthesis Example 6>

E4 (2.60g, 8.66mmol), A2 (2.08g, 5.27mmol), B1 (1.70g, 7.02mmol) and D1 (0.57g, 5.27mmol) were mixed in NMP (17.3g), and reacted at 80°C for 5 After 1 hour, E1 (1.70 g, 8.67 mmol) and NMP (8.65 g) were added and reacted at 40° C. for 6 hours to obtain a 25%-concentrated polyamic acid solution.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting it to 6%, anhydrous acetic acid (4.50 g) and pyridine (3.30 g) were added as an amide imidization catalyst, and the reaction was carried out at 80° C. for 4 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Wash this precipitate with methanol, It was dried under reduced pressure at 100°C to obtain polyimide powder (6). The polyimide has an imidization rate of 80%, Mn of 16,300, and Mw of 45,400.

<Synthesis Example 7>

Mix N2 (16.7g) with E2 (0.89g, 3.56mmol), A1 (2.75g, 7.23mmol), B1 (1.31g, 5.41mmol) and D2 (0.59g, 5.46mmol), and react at 80°C for 5 After 1 hour, E1 (2.80 g, 14.3 mmol) and NMP (8.35 g) were added and reacted at 40° C. for 6 hours to obtain a polyamic acid solution with a concentration of 25%.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting it to 6%, anhydrous acetic acid (4.50 g) and pyridine (3.30 g) were added as an amide imidization catalyst, and the reaction was carried out at 80° C. for 3 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100°C to obtain polyimide powder (7). The polyimide has an imidization rate of 70%, Mn of 17,100, and Mw of 45,900.

<Synthesis Example 8>

Mix E2 (3.06g, 12.2mmol), A1 (3.15g, 8.28mmol), B2 (0.64g, 2.47mmol) and D2 (0.63g, 5.83mmol) in NEP (16.6g), and react at 80°C for 5 After 1 hour, E1 (0.80 g, 4.08 mmol) and NEP (8.28 g) were added and reacted at 40° C. for 6 hours to obtain a 25%-concentrated polyamic acid solution.

After adding NEP to the obtained polyamic acid solution (30.0g) and diluting it to 6%, anhydrous acetic acid (4.50g) and pyridine (3.30g) were added as the amide imidization contact The medium was reacted at 80°C for 3 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100°C to obtain polyimide powder (8). The polyimide has an imidization rate of 70%, Mn of 15,800, and Mw of 42,100.

<Synthesis Example 9>

Mix E2 (0.89g, 3.56mmol), B1 (1.75g, 7.22mmol), D1 (0.59g, 5.46mmol) and D3 (2.04g, 5.42mmol) in NMP (16.2g), and react at 80°C for 5 After 1 hour, E1 (2.80 g, 14.3 mmol) and NMP (8.28 g) were added and reacted at 40° C. for 6 hours to obtain a polyamic acid solution having a concentration of 25%.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting it to 6%, anhydrous acetic acid (4.50 g) and pyridine (3.30 g) were added as an amide imidization catalyst, and the reaction was carried out at 80° C. for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100°C to obtain polyimide powder (9). The polyimide has an imidization rate of 75%, Mn of 16,500, and Mw of 43,300.

<Synthesis Example 10>

E2 (0.89g, 3.56mmol), A1 (1.38g, 3.63mmol) and B1 (3.50g, 14.4mmol) were mixed with NMP (17.2g), and after reacting at 80°C for 5 hours, E1 (2.80g, 14.3mmol) and NMP (8.57g) were reacted at 40°C for 6 hours to obtain a polyamic acid solution with a concentration of 25%.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting it to 6%, anhydrous acetic acid (4.50 g) and pyridine (3.30 g) were added as an amide imidization catalyst, and the reaction was carried out at 80° C. for 5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100°C to obtain polyimide powder (10). The polyimide had an imidization rate of 90%, Mn of 17,800, and Mw of 46,900.

<Synthesis Example 11>

Mix E2 (0.96g, 3.84mmol), A1 (1.47g, 3.86mmol), B1 (1.88g, 7.76mmol) and D1 (0.84g, 7.77mmol) in NMP (16.3g), and react at 80°C for 5 After 1 hour, E1 (3.00 g, 15.3 mmol) and NMP (8.15 g) were added and reacted at 40° C. for 6 hours to obtain a polyamic acid solution with a concentration of 25%.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting it to 6%, anhydrous acetic acid (4.50 g) and pyridine (3.30 g) were added as an amide imidization catalyst, and the reaction was carried out at 80° C. for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100°C to obtain polyimide powder (11). The polyimide has an imidization rate of 75%, Mn of 18,600, and Mw of 48,300.

<Synthesis Example 12>

E2 (2.30 g, 9.19 mmol), B1 (4.05 g, 16.7 mmol) and D2 (0.20 g, 1.85 mmol) were mixed with NMP (16.7 g), and after reacting at 80°C for 5 hours, E1 (1.80 g, 9.18mmol) and NMP (8.35g), The reaction was carried out at 40°C for 6 hours to obtain a solution of polyamide with a concentration of 25%.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting it to 6%, anhydrous acetic acid (4.50 g) and pyridine (3.30 g) were added as an amide imidization catalyst, and the reaction was carried out at 80° C. for 2.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (12). The polyimide has an imidization rate of 65%, Mn of 22,100, and Mw of 53,400.

<Synthesis Example 13>

Mix N2 (17.1g) with E2 (2.55g, 10.2mmol), A1 (1.57g, 4.13mmol), B1 (1.07g, 4.13mmol) and D2 (1.34g, 12.4mmol), and react at 80°C for 5 After 1 hour, E1 (2.00 g, 10.2 mmol) and NMP (8.54 g) were added and reacted at 40° C. for 6 hours to obtain a 25%-concentrated polyamic acid solution.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting it to 6%, anhydrous acetic acid (4.50 g) and pyridine (3.30 g) were added as an amide imidization catalyst, and the reaction was carried out at 80° C. for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100°C to obtain polyimide powder (13). The polyimide had an imidization rate of 75%, Mn of 17,900, and Mw of 46,500.

<Synthesis Example 14>

Mix E2 (2.81g, 11.2mmol) and C1 in NMP (16.9g) (3.46g, 22.7mmol), after reacting at 80°C for 5 hours, E1 (2.20g, 11.2mmol) and NMP (8.46g) were added and reacted at 40°C for 6 hours to obtain a 25% concentration of polyamide Acid solution.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting it to 6%, anhydrous acetic acid (4.50 g) and pyridine (3.30 g) were added as an amide imidization catalyst, and the reaction was carried out at 80° C. for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100°C to obtain polyimide powder (14). The polyimide has an imidization rate of 75%, Mn of 21,800, and Mw of 52,100.

<Synthesis Example 15>

E2 (2.81g, 11.2mmol), C1 (2.94g, 19.3mmol) and D2 (0.37g, 3.42mmol) were mixed in NMP (16.6g), and after reacting at 80°C for 5 hours, E1 (2.20g, 11.2mmol) and NMP (8.31g) were reacted at 40°C for 6 hours to obtain a polyamic acid solution with a concentration of 25%.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting it to 6%, anhydrous acetic acid (4.50 g) and pyridine (3.30 g) were added as an amide imidization catalyst, and the reaction was carried out at 80° C. for 3 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100°C to obtain polyimide powder (15). The polyimide has an imidization rate of 70%, Mn of 23,200, and Mw of 54,200.

<Synthesis Example 16>

E5 (2.30g, 10.8mmol), C1 (2.84g, 18.7mmol) and D2 (0.36g, 3.33mmol) were mixed with NEP (16.4g), and after reacting at 80°C for 5 hours, E1 (2.30g, 10.8 mmol) and NEP (8.21g) were reacted at 40°C for 6 hours to obtain a polyamic acid solution with a concentration of 25%.

After adding NEP to the obtained polyamic acid solution (30.0 g) and diluting it to 6%, anhydrous acetic acid (4.50 g) and pyridine (3.30 g) were added as an amide imidization catalyst, and the reaction was carried out at 80° C. for 3 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100°C to obtain polyimide powder (16). The polyimide had an imidization rate of 70%, Mn of 20,500, and Mw of 51,800.

<Synthesis Example 17>

Mix E2 (2.17g, 8.67mmol), A1 (2.67g, 7.02mmol), B1 (1.28g, 5.28mmol) and C1 (0.80g, 5.26mmol) in NMP (17.2g), and react at 80°C for 5 After 1 hour, E1 (1.70 g, 8.67 mmol) and NMP (8.62 g) were added and reacted at 40° C. for 6 hours to obtain a polyamic acid solution with a concentration of 25%.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting it to 6%, anhydrous acetic acid (4.50 g) and pyridine (3.30 g) were added as an amide imidization catalyst, and the reaction was carried out at 80° C. for 4 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (17). The polyimide has an imidization rate of 80%, Mn of 16,300, and Mw of 46,300.

The details of the polyimide-based polymers obtained in each synthesis example are shown in Table 32 and Table 33.

"Evaluation of Inkjet Coating Property of Liquid Crystal Alignment Treatment Agent"

The liquid crystal alignment treatment agents obtained in the post-operative Example 3 and Example 8 were used to evaluate inkjet coatability. Specifically, these liquid crystal alignment treatment agents are pressure-filtered using a membrane filter with a pore size of 1 μm, and the ITO (indium tin oxide) electrode substrate (length 100 mm×) that has been washed with pure water and IPA (isopropyl alcohol). 100 mm wide and 0.7 mm thick), the coating area was 70×70 mm, nozzle pitch 0.423 mm, scanning pitch 0.5 mm, and coating speed 40 mm/sec. In this case, HIS-200 (manufactured by Hitachi Industrial Equipment Technology Co., Ltd.) was used as the inkjet coater. Again, by coating The time until the temporary drying was 60 seconds. The temporary drying was performed on a hot plate at 70°C for 5 minutes.

The evaluation of the coatability was carried out by visually observing the coating film surface of the substrate with a liquid crystal alignment film obtained above. Specifically, the coating film surface was visually observed under a sodium lamp to confirm the presence or absence of pinholes. As a result, no pinholes were found on the coating film surface of the liquid crystal alignment film obtained in any of the examples, that is, a liquid crystal alignment film having excellent coating properties was obtained.

"Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)"

Using the liquid crystal alignment treatment agents obtained in Examples and Comparative Examples described later, the preparation of liquid crystal cells and evaluation of the pretilt angle were performed. Specifically, these liquid crystal alignment treatment agents are pressure-filtered using a membrane filter with a pore size of 1 μm, and spin-coated on ITO electrode substrates (length 40 mm × width 30 mm, thickness 0.7 mm) washed with pure water and IPA On the surface, it was heat-treated at 100°C for 5 minutes on a hot plate, and heat-treated at 230°C for 30 minutes in a heat-circulating dust-free oven to obtain an ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm. Furthermore, the liquid crystal alignment treatment agent of Example 3 and Example 8 was produced under the same conditions as the above "evaluation of the inkjet coatability of the liquid crystal alignment treatment agent", and then was subjected to 230 Heat treatment at ℃ for 30 minutes to prepare an ITO substrate with a liquid crystal alignment film with a film thickness of 100 nm.

Next, using a rubbing device with a roller diameter of 120 mm, using a rayon cloth, the coating surface of the substrate was rubbed at a roller rotation speed of 1000 rpm, a roller speed of 50 mm/sec, and a plunging amount of 0.1 mm. Management.

After that, two substrates after the rubbing treatment were prepared, with the coating film surface facing inward, a 6 μm spacer was sandwiched and combined, and the surrounding was sealed with a sealant to form an empty cell. MLC-6608 (manufactured by Merck) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell.

Use the obtained liquid crystal cell to measure the pretilt angle. Specifically, the liquid crystal cell after the liquid crystal cell was subjected to a homogenous treatment (heat treatment at 95°C for 5 minutes) and this heat treatment (heat treatment at 120°C for 5 hours) were used for measurement.

Furthermore, the liquid crystal cell produced by subjecting the liquid crystal cell produced under the same conditions as above to the isotropic treatment and then irradiated with ultraviolet rays of 10 J/cm ^{2 in terms} of 365 nm was also measured. In addition, the pretilt angle system was measured at room temperature using PAS-301 (manufactured by ELSICON). In addition, ultraviolet irradiation is implemented using a desktop UV curing device (HCT3B28HEX-1) (manufactured by Senlight).

The evaluation is based on the change of the pretilt angle with respect to the liquid crystal after the normal treatment (also called the initial stage), after the heat treatment (also called the high temperature treatment) and after the ultraviolet irradiation (also called the ultraviolet irradiation) The smaller one is regarded as the better the evaluation. Table 37 to Table 39 show the values of each pretilt angle.

"Evaluation of uneven alignment of liquid crystals generated under the ODF method"

Using the liquid crystal alignment treatment agents obtained in the Examples and Comparative Examples described later, the liquid crystal alignment unevenness produced by the ODF method was evaluated. Specifically, a membrane filter with a pore size of 1 μm is used to pressure-filter these liquid crystal alignments The physic agent is spin-coated on the ITO surface of the ITO electrode substrate (100mm long x 100mm wide and 0.7mm thick) washed with pure water and IPA, heat-treated on a hot plate at 100°C for 5 minutes, and thermally cycled In a dust-free oven at 230°C for 30 minutes, an ITO substrate with a liquid crystal alignment film with a film thickness of 100 nm was obtained. Furthermore, the liquid crystal alignment treatment agent of Example 3 and Example 8 was produced under the same conditions as the above "evaluation of the inkjet coatability of the liquid crystal alignment treatment agent", and then was subjected to 230 Heat treatment at ℃ for 30 minutes to prepare an ITO substrate with a liquid crystal alignment film with a film thickness of 100 nm.

Next, using a rubbing device with a roller diameter of 120 mm, using a rayon cloth, the coating film surface of this substrate was subjected to a rubbing treatment under the conditions of a roller rotation speed of 1000 rpm, a roller speed of 50 mm/sec, and a plunging amount of 0.1 mm.

After that, two substrates that have been subjected to the above rubbing treatment to two substrates that have not been processed are prepared, and a spacer of 6 μm is spread on the coating film surface of the untreated substrate. After that, an ultraviolet-curable sealant was drawn around the substrate, and using the ODF method, 6 points of nematic liquid crystal (MLC-6608, manufactured by Merck Japan) toward the inside of the sealant were dropped at 6 points (2 points in length) ×3 points horizontally, and the interval between each point is made up, down, left, and right 10 mm), and the substrate subjected to the rubbing treatment is bonded to obtain a liquid crystal cell. Afterwards, due to the hardening of the sealant, a metal halogen lamp with an illuminance of 60mW was used to shield the wavelength below 310nm, and the liquid crystal cell was irradiated with ultraviolet rays of 5J/cm ^{2 in terms} of 365nm conversion, and the temperature was 120 in a thermal cycle type dust-free oven. The liquid crystal cell was obtained by heat treatment at ℃ for 60 minutes.

Using the obtained liquid crystal cell, it was confirmed that the liquid crystal dripping traces were uneven, that is, the liquid crystal alignment unevenness was confirmed. Specifically, an AC (alternating current drive) voltage of 5V was applied to the liquid crystal cell, and a polarizing plate and a backlight were used to visually confirm whether or not the liquid crystal alignment is uneven on the area where the liquid crystal is dropped.

In this evaluation, those who did not find liquid crystal alignment unevenness as described above were evaluated as excellent (marked well in Table 37 to Table 39).

"Evaluation of voltage retention rate (usually unit cell)"

Using the liquid crystal cell produced under the same conditions as the above-mentioned "Preparation of Liquid Crystal Cell and Evaluation of Pretilt Angle (Normal Cell)", the voltage retention rate was evaluated. Specifically, the liquid crystal cell obtained by the above method is applied with a voltage of 1 V for 60 μs at a temperature of 80° C. The voltage after 50 ms is measured, and the period during which the voltage can be maintained is calculated as the voltage retention rate (also referred to as VHR). In addition, the measurement was performed using a voltage retention measurement device (VHR-1, manufactured by Toyo Technology Co., Ltd.) under the settings of Voltage: ±1 V, Pulse Width: 60 μs, and Flame Period: 50 ms.

Furthermore, using a desktop UV curing device (HCT3B28HEX-1, manufactured by Senlight), the above-mentioned liquid crystal cell having measured the voltage retention rate immediately after the production of the liquid crystal cell was irradiated at 365nm and converted to 50J/cm ² For ultraviolet rays, the voltage retention rate was measured under the same conditions as above.

In this evaluation, the value of the voltage retention ratio immediately after fabrication of the liquid crystal cell is high, and the value after ultraviolet irradiation (also known as the initial stage) is relative to the value of the voltage retention ratio immediately after fabrication of the liquid crystal cell (also known as the initial stage). After UV irradiation) The lower the number, the less the evaluation is excellent. The values of each VHR are shown in Table 40 to Table 42.

"Evaluation of the relaxation of residual charge (usually unit cell)"

Using the liquid crystal cell produced under the same conditions as the aforementioned "Preparation of Liquid Crystal Cell and Evaluation of Pretilt Angle (Normal Cell)", the evaluation of the relaxation of residual charge was performed. Specifically, after applying a DC voltage of 10 V to the liquid crystal cell for 30 minutes and short-circuiting it for 1 second, the potential generated in the liquid crystal cell was measured for 1800 seconds. Among them, the value of the residual charge after 50 seconds is used as an evaluation of the relaxation of the residual charge. In addition, the measurement system uses a 6254-type liquid crystal physical property evaluation device (manufactured by Toyo Technology Co., Ltd.).

Furthermore, using a desktop UV curing device (HCT3B28HEX-1, manufactured by Senlight), the liquid crystal cell that has completed the measurement of the residual charge immediately after the production of the liquid crystal cell is irradiated with ultraviolet rays of 30J/cm ^{2 in} 365nm conversion The residual charge is measured under the same conditions as above.

In this evaluation, the smaller the value immediately after preparation of the liquid crystal cell (also referred to as the initial stage) and the value of the residual charge after ultraviolet irradiation (also referred to as after ultraviolet irradiation), the smaller the evaluation is, the superior. The values of each residual charge are shown in Table 40 to Table 42.

"Fabrication of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)"

The liquid crystal alignment treatment agents obtained in Example 3 and Example 9 described later were used to prepare the liquid crystal cell and evaluate the liquid crystal alignment (PSA cell). Specifically, pressure filtration is performed using a membrane filter with a pore size of 1 μm These liquid crystal alignment treatment agents were spin-coated on substrates with ITO and electrodes (40mm in length×30mm in width and 0.7 in thickness) which were washed with pure water and IPA and had ITO with 10×10mm pattern spacing of 20μm in the center. mm) and the ITO surface of the substrate with ITO and electrodes with an ITO of 10×40mm in the center (40mm in length×30mm in width and 0.7mm in thickness), and then heat-treated at 100°C for 5 minutes on a hot plate. In a dust-free oven, heat treatment was performed at 230°C for 30 minutes to obtain an ITO substrate with a liquid crystal alignment film with a film thickness of 100 nm. Furthermore, the liquid crystal alignment treatment agent of Example 3 was produced under the same conditions as the above "evaluation of the inkjet coatability of the liquid crystal alignment treatment agent", and then heat-treated at 230°C for 30 in a heat-circulating dust-free oven. In minutes, an ITO substrate with a liquid crystal alignment film with a film thickness of 100 nm is prepared.

Next, the two substrates were combined with a 6 μm spacer sandwiched with the coating film surface facing inward, and then sealed with a sealant to form an empty cell. A mixed liquid crystal was injected into this empty cell by a decompression injection method. The mixed liquid crystal was a nematic liquid crystal (MLC-6608, manufactured by Merck Co., Ltd.). The polymerizable compound (1) of the following formula was mixed with respect to the nematic For 100% of the liquid crystal, 0.3% of the polymerizable compound (1) of the following formula was mixed, and then the injection port was sealed to obtain a liquid crystal cell.

Apply a voltage of AC5V to the obtained liquid crystal cell, and use a metal halogen lamp with an illuminance of 60mW to shield the wavelength below 350nm and perform ultraviolet irradiation of 20J/cm ² under the conversion of 365nm, and then obtain a liquid crystal crystal whose alignment direction of the liquid crystal is controlled Cell. The temperature in the irradiation device when irradiating the liquid crystal cell with ultraviolet rays was 50°C.

Thereafter, the response speed of the liquid crystal of the liquid crystal cell before and after ultraviolet irradiation was measured. The response speed is measured from T90→T10 from 90% penetration rate to 10% penetration rate.

In the liquid crystal cell obtained in any embodiment, since the response speed of the liquid crystal cell after ultraviolet irradiation is faster than that of the liquid crystal cell before ultraviolet irradiation, it can be confirmed that the alignment direction of the liquid crystal is controlled. Moreover, any liquid crystal cell was observed under a polarizing microscope (ECLIPSE E600WPOL, manufactured by Nikon), and it was confirmed that the liquid crystal was uniformly aligned.

<Example 1>

NEP (3.92 g) was added to the polyimide powder (1) (0.50 g) obtained in Synthesis Example 1, and stirred at 70° C. for 24 hours to dissolve. BCS (3.92g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

On the other hand, NEP (5.88 g) was added to the polyimide powder (10) (0.75 g) obtained in Synthesis Example 10, and stirred at 70° C. for 24 hours to dissolve. BCS (5.88g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

Furthermore, NEP (9.79 g) was added to the polyimide powder (14) (1.25 g) obtained in Synthesis Example 14, and stirred at 70° C. for 24 hours to dissolve. Correct BCS (9.79g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed and stirred at 40°C for 4 hours to obtain a liquid crystal alignment treatment agent (1). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Example 2>

NEP (3.92 g) was added to the polyimide powder (2) (0.50 g) obtained in Synthesis Example 2, and stirred at 70° C. for 24 hours to dissolve. BCS (2.35g) and PB (1.57g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

On the other hand, NEP (5.88 g) was added to the polyimide powder (10) (0.75 g) obtained in Synthesis Example 10, and stirred at 70° C. for 24 hours to dissolve. BCS (3.53g) and PB (2.35g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

Furthermore, NEP (9.79 g) was added to the polyimide powder (14) (1.25 g) obtained in Synthesis Example 14, and stirred at 70° C. for 24 hours to dissolve. BCS (5.88g) and PB (3.92g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed and stirred at 40°C for 4 hours to obtain a liquid crystal alignment treatment agent (2). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Example 3>

For the polyimide powder (3) (0.30 g) obtained in Synthesis Example 3, the polyimide powder (10) (0.45 g) obtained in Synthesis Example 10, and the polyimide powder obtained in Synthesis Example 14 (14) (0.75g) NEP (16.5g) and γ-BL (4.18g) were added, and stirred at 70°C for 24 hours to dissolve. BCS (8.27g), PB (8.27g) and DME (4.14g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (3). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Example 4>

NMP (6.27 g) was added to the polyimide powder (4) (0.80 g) obtained in Synthesis Example 4, and stirred at 70° C. for 24 hours to dissolve. BCS (5.02g) and DME (1.25g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

On the other hand, NMP (6.27 g) was added to the polyimide powder (12) (0.80 g) obtained in Synthesis Example 12, and stirred at 70° C. for 24 hours to dissolve. BCS (5.02g) and DME (1.25g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

Furthermore, NMP (8.36 g) was added to the polyimide powder (14) (1.07 g) obtained in Synthesis Example 14, and stirred at 70° C. for 24 hours to dissolve. BCS (6.68g) and DME (1.67g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed and stirred at 40°C for 4 hours to obtain a liquid crystal alignment treatment agent (4). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Example 5>

NEP (7.52 g) was added to the polyimide powder (5) (0.80 g) obtained in Synthesis Example 5, and stirred at 70° C. for 24 hours to dissolve. BCS (2.51g) and PB (2.51g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

On the other hand, NEP (7.52 g) was added to the polyimide powder (10) (0.80 g) obtained in Synthesis Example 10, and stirred at 70° C. for 24 hours to dissolve. BCS (2.51g) and PB (2.51g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

Furthermore, NEP (10.0 g) was added to the polyimide powder (14) (1.07 g) obtained in Synthesis Example 14, and stirred at 70° C. for 24 hours to dissolve. BCS (3.34g) and PB (3.34g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed and stirred at 40°C for 4 hours to obtain a liquid crystal alignment treatment agent (5). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Example 6>

For the polyimide powder (6) (0.50 g) obtained in Synthesis Example 6, the polyimide powder (10) (0.75 g) obtained in Synthesis Example 10, and the polyimide powder obtained in Synthesis Example 14 (14) (1.25g) NEP (21.5g) was added, and it stirred for 24 hours and made it melt|dissolve at 70 degreeC. PB (17.6g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (6). This LCD is equipped with No abnormality such as turbidity or precipitation was found in the treatment agent, and it was confirmed to be a homogeneous solution.

<Example 7>

NMP (3.76 g) and NEP (3.76 g) were added to the polyimide powder (7) (0.80 g) obtained in Synthesis Example 7, and stirred at 70° C. for 24 hours to dissolve. BCS (2.51g) and PB (2.51g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

On the other hand, NMP (3.76 g) and NEP (3.76 g) were added to the polyimide powder (10) (0.80 g) obtained in Synthesis Example 10, and stirred at 70° C. for 24 hours to dissolve. BCS (2.51g) and PB (2.51g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

Furthermore, NMP (5.02 g) and NEP (5.02 g) were added to the polyimide powder (14) (1.07 g) obtained in Synthesis Example 14, and stirred at 70° C. for 24 hours to dissolve. BCS (3.34g) and PB (3.34g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed and stirred at 40°C for 4 hours to obtain a liquid crystal alignment treatment agent (7). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Example 8>

For the polyimide powder (8) (0.30 g) obtained in Synthesis Example 8, the polyimide powder (10) (0.45 g) obtained in Synthesis Example 10, and the polyimide powder obtained in Synthesis Example 14 (14) (0.75g) Add NEP (12.4g) and γ-BL (6.21g), stirred at 70°C for 24 hours to dissolve. BCS (8.27g) and PB (14.5g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (8). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Example 9>

NEP (5.09 g) was added to the polyimide powder (1) (0.50 g) obtained in Synthesis Example 1, and stirred at 70° C. for 24 hours to dissolve. BCS (1.18g) and PB (1.57g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

On the other hand, NEP (7.64 g) was added to the polyimide powder (11) (0.75 g) obtained in Synthesis Example 11, and stirred at 70° C. for 24 hours to dissolve. BCS (1.76g) and PB (2.35g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

Furthermore, NEP (12.7 g) was added to the polyimide powder (14) (1.25 g) obtained in Synthesis Example 14, and stirred at 70° C. for 24 hours to dissolve. BCS (2.94g) and PB (3.92g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed and stirred at 40°C for 4 hours to obtain a liquid crystal alignment treatment agent (9). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Example 10>

Add to the polyimide powder (5) (0.50g) obtained in Synthesis Example 5 NEP (4.70g) was stirred at 70°C for 24 hours to dissolve. PB (3.13g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

On the other hand, NEP (7.05 g) was added to the polyimide powder (12) (0.75 g) obtained in Synthesis Example 12, and stirred at 70° C. for 24 hours to dissolve. PB (4.70g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

Furthermore, NEP (11.8 g) was added to the polyimide powder (14) (1.25 g) obtained in Synthesis Example 14, and stirred at 70° C. for 24 hours to dissolve. PB (7.83g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed and stirred at 40°C for 4 hours to obtain a liquid crystal alignment treatment agent (10). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Example 11>

NEP (4.70 g) was added to the polyimide powder (1) (0.50 g) obtained in Synthesis Example 1, and stirred at 70° C. for 24 hours to dissolve. BCS (0.78g) and PB (2.35g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

On the other hand, NEP (7.05 g) was added to the polyimide powder (13) (0.75 g) obtained in Synthesis Example 13, and stirred at 70° C. for 24 hours to dissolve. BCS (1.18g) and PB (3.53g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

In addition, the polyimide powder (14) obtained in Synthesis Example 14 (1.25) g) Add NEP (11.8g) and stir at 70°C for 24 hours to dissolve. BCS (1.96g) and PB (5.88g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed and stirred at 40°C for 4 hours to obtain a liquid crystal alignment treatment agent (11). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Example 12>

NMP (6.27 g) was added to the polyimide powder (1) (0.80 g) obtained in Synthesis Example 1, and stirred at 70° C. for 24 hours to dissolve. BCS (2.51g) and PB (3.76g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

On the other hand, NMP (4.18 g) was added to the polyimide powder (10) (0.53 g) obtained in Synthesis Example 10, and stirred at 70° C. for 24 hours to dissolve. BCS (1.67g) and PB (2.51g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

Furthermore, NMP (10.4 g) was added to the polyimide powder (15) (1.33 g) obtained in Synthesis Example 15, and stirred at 70° C. for 24 hours to dissolve. BCS (4.18g) and PB (6.27g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed, and M1 (0.19 g) was added, and stirred at 40°C for 6 hours to obtain a liquid crystal alignment treatment agent (12). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Example 13>

For the polyimide powder (1) (0.80 g) obtained in Synthesis Example 1, the polyimide powder (10) (0.80 g) obtained in Synthesis Example 10, and the polyimide powder obtained in Synthesis Example 16 (16) (1.07g) NEP (20.9g) was added and stirred at 70°C for 24 hours to dissolve. BCS (8.36g) and PB (12.5g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (13). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Example 14>

For the polyimide powder (1) (0.80 g) obtained in Synthesis Example 1, the polyimide powder (10) (0.80 g) obtained in Synthesis Example 10, and the polyimide powder obtained in Synthesis Example 16 (16) (1.07g) NEP (20.9g) was added and stirred at 70°C for 24 hours to dissolve. PB (12.5g) and DPM (8.36g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (22). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Comparative Example 1>

NEP (19.6 g) was added to the polyimide powder (1) (2.50 g) obtained in Synthesis Example 1, and stirred at 70° C. for 24 hours to dissolve. BCS (19.6g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (14). The liquid crystal alignment treatment agent did not find turbidity or precipitation, etc. Abnormal and confirmed as a homogeneous solution.

<Comparative Example 2>

NEP (19.6 g) was added to the polyimide powder (10) (2.50 g) obtained in Synthesis Example 10, and stirred at 70° C. for 24 hours to dissolve. BCS (19.6g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (15). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Comparative Example 3>

NEP (19.6 g) was added to the polyimide powder (14) (2.50 g) obtained in Synthesis Example 14, and stirred at 70° C. for 24 hours to dissolve. BCS (19.6g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (16). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Comparative Example 4>

NEP (10.2 g) was added to the polyimide powder (1) (1.30 g) obtained in Synthesis Example 1, and stirred at 70° C. for 24 hours to dissolve. BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

On the other hand, NEP (10.2 g) was added to the polyimide powder (10) (1.30 g) obtained in Synthesis Example 10, and stirred at 70° C. for 24 hours to dissolve. BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The two solutions obtained above were mixed and stirred at 40°C for 4 hours to obtain a liquid crystal alignment treatment agent (17). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Comparative Example 5>

NEP (10.2 g) was added to the polyimide powder (1) (1.30 g) obtained in Synthesis Example 1, and stirred at 70° C. for 24 hours to dissolve. BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

On the other hand, NEP (10.2 g) was added to the polyimide powder (14) (1.30 g) obtained in Synthesis Example 14, and stirred at 70° C. for 24 hours to dissolve. BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The two solutions obtained above were mixed and stirred at 40°C for 4 hours to obtain a liquid crystal alignment treatment agent (18). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Comparative Example 6>

NEP (10.2 g) was added to the polyimide powder (10) (1.30 g) obtained in Synthesis Example 10, and stirred at 70° C. for 24 hours to dissolve. BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

On the other hand, NEP (10.2 g) was added to the polyimide powder (14) (1.30 g) obtained in Synthesis Example 14, and stirred at 70° C. for 24 hours to dissolve. BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The two solutions obtained above were mixed and stirred at 40°C for 4 hours to obtain a liquid crystal alignment treatment agent (19). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Comparative Example 7>

NEP (3.92 g) was added to the polyimide powder (9) (0.50 g) obtained in Synthesis Example 9, and stirred at 70° C. for 24 hours to dissolve. BCS (2.35g) and PB (1.57g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

On the other hand, NEP (5.88 g) was added to the polyimide powder (10) (0.75 g) obtained in Synthesis Example 10, and stirred at 70° C. for 24 hours to dissolve. BCS (3.53g) and PB (2.35g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

Furthermore, NEP (9.79 g) was added to the polyimide powder (14) (1.25 g) obtained in Synthesis Example 14, and stirred at 70° C. for 24 hours to dissolve. BCS (5.88g) and PB (3.92g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed and stirred at 40°C for 4 hours to obtain a liquid crystal alignment treatment agent (20). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

<Comparative Example 8>

NEP (19.6) was added to the polyimide powder (17) (2.50 g) obtained in Synthesis Example 17, and stirred at 70°C for 24 hours to dissolve. Add this solution BCS (19.6g) was added, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (21). The liquid crystal alignment treatment agent was not found to be abnormal such as turbidity or precipitation, and was confirmed to be a homogeneous solution.

The liquid crystal alignment treatment agents obtained in the above examples and comparative examples are shown in Table 34 to Table 36. In addition, the evaluation results of the liquid crystal display elements using these liquid crystal alignment treatment agents are shown in Tables 37 to 42.

In addition, in the table, *1 represents the introduction amount (minute) of the specific polymer (A) with respect to 100 parts of all polymers.

* 2 represents the introduction amount (part) of the specific polymer (B) with respect to 100 parts of all polymers, * 3 represents the introduction amount (part) of the specific polymer (C) with respect to 100 parts of all polymers, * 4 It shows the introduction amount (part) of other polymers with respect to 100 parts of all polymers. *5 shows the content ratio (solid content concentration) of all polymers in the liquid crystal alignment treatment agent.

It is clear from the above results that the liquid crystal alignment treatment agent of the comparative example and the liquid crystal alignment treatment agent of the example still exhibit a stable pretilt angle even if the liquid crystal cell is subjected to high temperature treatment and ultraviolet irradiation. In addition, it can reduce the uneven alignment of the liquid crystal generated under the ODF method. Furthermore, even if the liquid crystal cell is irradiated with ultraviolet rays, as a result, it is possible to suppress the decrease in the voltage retention rate and quickly alleviate the residual charge accumulated by the DC voltage.

That is, in the examples using the liquid crystal alignment treatment agents of the three specific polymers (A), (B) and (C), compared with the comparative examples using only one of these, none of the comparative examples can achieve the invention. The full effect. Specifically, it is as shown in the comparison between Example 1 and Comparative Examples 1, 2 or 3, and the comparison between Example 1 and Comparative Examples 4, 5 or 6.

In addition, in Example 2 using a specific diamine (1) and comparing with a comparative example using a diamine having an alkyl side chain structure in the past, the liquid crystal alignment treatment agent of Comparative Example 7 cannot achieve the cost of the invention. All effects.

In addition, in the comparison between Example 1 and Comparative Example 8 in which specific diamines (1), (2), and (3) are not used at all, the results of Comparative Example 8 are inferior to all the effects of the present invention, especially for the ODF method The occurrence of uneven alignment of the liquid crystal produced under the conditions and the reduction of the voltage retention rate after long-time exposure to light have both obtained poor results.

[Industry availability]

The liquid crystal alignment treatment agent of the present invention is very useful for liquid crystal display elements using VA mode, PSA mode and SC-PVA mode, especially TN element, STN element, TFT liquid crystal element, and especially vertical alignment type liquid crystal display element. The liquid crystal display device having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention can be suitably used in large-screen and high-definition LCD TVs, small and medium-sized car navigation systems, smart phones, and the like.

Not to mention, Japan will apply on December 25, 2014 The entire contents of the specification, patent application scope, drawings, and abstract of Patent Application No. 2014-262605 are hereby cited as the disclosure content of the specification of the present invention and incorporated.

Claims (18)

A liquid crystal alignment treatment agent characterized by containing the following (A) component, (B) component and (C) component; (A) component: by containing a diamine having the structure of the following formula [1] and having the following The polyimide precursor obtained by the reaction of the diamine component of the diamine of the structure [2] and the tetracarboxylic acid component or the polyimide obtained by subjecting the polyimide precursor to imidization; ( B) Component: a polyimide precursor obtained by the reaction of a diamine component containing a diamine having the structure of the following formula [2] and a tetracarboxylic acid component or the polyimide precursor is obtained Aminated polyimide; (C): by containing a diamine component and a tetracarboxylic acid component of a diamine having at least one substituent selected from the group consisting of a carboxyl group (COOH group) and a hydroxyl group (OH group) The polyimide precursor obtained by the reaction or the polyimide obtained by imidizing the polyimide precursor; however, the foregoing has a group selected from the group consisting of a carboxyl group (COOH group) and a hydroxyl group (OH group) The diamine of at least one substituent is only used for the diamine component of the aforementioned (C) component;

X ¹ represents selected from a single bond, -(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )- , -N(CH ₃ )CO-, -COO- and -OCO- at least one kind of binding group, X ² represents a single bond or -(CH ₂ ) _b -(b is an integer of 1~15), X ³ represents at least one selected from the group consisting of a single bond, -(CH ₂ ) _c- (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO-, and -OCO-, X ⁴ represents a divalent cyclic group selected from at least one group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring or a divalent organic group having a steroid skeleton and a carbon number of 17 to 51, and any of the aforementioned cyclic groups The hydrogen atom can be replaced by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom , X ⁵ represents at least one cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic ring, and any hydrogen atom on these cyclic groups may be Substituted by alkoxy groups of 1 to 3, fluorinated alkyl groups of 1 to 3 carbon atoms, fluorinated alkoxy groups of 1 to 3 carbon atoms or fluorine atoms, n represents an integer of 0 to 4, X ⁶ represents selected from C1-C18 alkyl, C2-C18 alkenyl, C1-C18 fluorine-containing alkyl, C1-C18 alkoxy and C1-C18 fluorine-containing alkoxy At least one of the groups; -W ¹ -W ² -W ³ -W ⁴ [2] W ¹ represents selected from -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO- , -CH ₂ O-, -OCO-, -CON(CH ₃ )- and -N(CH ₃ )CO-, at least one kind of binding group, W ² represents selected from a single bond, carbon number 1~20 At least one of alkylene group, non-aromatic ring and aromatic ring group, W ³ represents selected from single bond, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO -, -COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO- and -O(CH ₂ ) _m- (m represents an integer from 1 to 5) , W ⁴ represents a nitrogen-containing aromatic heterocyclic ring. The liquid crystal alignment treatment agent according to claim 1, which has the aforementioned formula [1] The diamine structure is used only for the diamine component of the aforementioned (A) component. The liquid crystal alignment treatment agent according to claim 1, wherein the use ratio (mol %) of the aforementioned diamine to the entire diamine component having the structure shown in formula [1] among the aforementioned (A) components is set to 1.0, (B) The use ratio (mol %) of the diamine to the whole diamine component which has the structure shown by Formula [1] among the components mentioned above is a ratio of 0.01 to 0.8. The liquid crystal alignment treatment agent according to claim 1 or 3, wherein the use ratio (mol %) of the diamine to the entire diamine component having the structure shown in the above formula [1] among the aforementioned (A) components is set to 1.0 In the (C) component, the use ratio (mol %) of the diamine having the structure represented by the formula [1] to the entire diamine component is 0.01 to 0.3. The liquid crystal alignment treatment agent according to any one of claims 1 to 3, wherein the aforementioned diamine having the structure of formula [1] is represented by the following formula [1a];

X represents the structure of the aforementioned formula [1], and n1 represents an integer of 1 to 4. The liquid crystal alignment treatment agent according to any one of claims 1 to 3, wherein the aforementioned diamine having the structure of formula [2] is represented by the following formula [2a];

W represents the structure of the aforementioned formula [2], and p1 represents an integer of 1 to 4. The liquid crystal alignment treatment agent according to any one of claims 1 to 3, wherein the aforementioned diamine having at least one substituent selected from the group consisting of carboxyl groups and hydroxyl groups is represented by the following formula [3a];

Y represents the structure of the following formula [3-1] or formula [3-2], m1 represents an integer of 1 to 4;

a and b represent integers from 0 to 4, respectively. The liquid crystal alignment treatment agent according to any one of claims 1 to 3, wherein the tetracarboxylic acid component of the aforementioned (A) component, (B) component and (C) component includes tetracarboxylic acid dicarboxylic acid of the following formula [4] anhydride;

Z represents at least one structure selected from the group consisting of the following formula [4a] to formula [4k];

Z ¹ to Z ⁴ each independently represent at least one selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom, and a benzene ring; Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group. The liquid crystal alignment treatment agent according to any one of claims 1 to 3, which contains a group selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone At least one solvent. The liquid crystal alignment treatment agent according to any one of claims 1 to 3, which contains a compound selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, and ethyl alcohol. Glycol monobutyl ether, dipropylene glycol dimethyl ether and at least one solvent grouped by the following formula [D1] to formula [D3];

D ¹ represents an alkyl group having 1 to 3 carbon atoms, D ² represents an alkyl group having 1 to 3 carbon atoms, and D ³ represents an alkyl group having 1 to 4 carbon atoms. The liquid crystal alignment treatment agent according to any one of claims 1 to 3, which contains a compound selected from the group consisting of epoxy group, isocyanate group, glycidyl group and ring A crosslinkable compound of at least one kind of group consisting of carbonate groups, a crosslinkable compound having at least one kind of group selected from the group consisting of hydroxyl groups, alkyl groups and lower alkoxyalkyl groups, or having a polymerization Cross-linking compounds with unsaturated bond groups. A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of claims 1 to 11. A liquid crystal alignment film obtained by applying the liquid crystal alignment treatment agent according to any one of claims 1 to 11 by an inkjet method. A liquid crystal display element having a liquid crystal alignment film as in claim 12 or 13. The liquid crystal alignment film according to claim 12 or 13, which is used for a liquid crystal display element which has a liquid crystal layer between a pair of substrates having electrodes and is arranged between the pair of substrates A liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat is manufactured by a step of applying a voltage between the electrodes to polymerize the polymerizable compound. A liquid crystal display element having the liquid crystal alignment film according to claim 15. The liquid crystal alignment film according to claim 12 or 13, which is used for a liquid crystal display element having a liquid crystal layer between a pair of substrates provided with electrodes and arranged between the pair of substrates A liquid crystal alignment film including a polymer group polymerized by at least one of active energy rays and heat, and a step of applying a voltage between the electrodes to polymerize the polymerizable group. A liquid crystal display element having the liquid crystal alignment film according to claim 17.