WO2015033922A1

WO2015033922A1 - Liquid-crystal orientation treatment agent, liquid-crystal orientation film, and liquid-crystal display element

Info

Publication number: WO2015033922A1
Application number: PCT/JP2014/073041
Authority: WO
Inventors: 徳俊三木; 雅章片山; 幸司巴; 奈穂国見; 保坂　和義
Original assignee: 日産化学工業株式会社
Priority date: 2013-09-03
Filing date: 2014-09-02
Publication date: 2015-03-12
Also published as: KR102234876B1; JPWO2015033922A1; KR20160052632A; JP6561834B2; TW201514248A; CN105683829A; CN105683829B; TWI628232B

Abstract

Provided are: a liquid-crystal orientation treatment agent from which a liquid-crystal orientation film can be obtained which, even after being exposed to light and high temperatures for a long period of time, exhibits a stable pretilt angle, suppresses a decline in voltage retention rate, and quickly reduces an accumulated residual charge; a liquid-crystal orientation film; and a liquid-crystal display element. This liquid-crystal orientation treatment agent contains an (A) component and a (B) component. (A) component: a polyimide precursor obtained by reacting a tetracarboxylic acid component and a diamine component containing a diamine compound having a sidechain structure represented by formula (1); and a polymer containing one or more of the polyimides. (B) component: a polyimide precursor obtained by reacting a tetracarboxylic acid component and a diamine component not containing a diamine compound having a sidechain structure represented by formula (1); and a polymer containing one or more of the polyimides. (Y¹, Y² and Y³ represent a single bond, an alkylene, etc.; Y⁴ and Y⁵ represent a divalent cyclic group such as a benzene ring; n is an integer of 0-4; and Y⁶ represents a C1-18 alkyl group, etc.)

Description

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

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element used for a liquid crystal display element.

Liquid crystal display elements are now widely used as display devices that are thin and light. Usually, a liquid crystal alignment film is used in a liquid crystal display element in order to determine the alignment state of the liquid crystal.

As one of the characteristics required for the liquid crystal alignment film, there is control of the so-called pre-tilt angle of the liquid crystal, which maintains the alignment tilt angle of the liquid crystal molecules with respect to the substrate surface at an arbitrary value. It is known that the size of the pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film. Even in the technique of controlling the pretilt angle depending on the structure of the polyimide, the method using a diamine having a side chain as a part of the polyimide raw material can control the pretilt angle according to the use ratio of the diamine, so that the desired pretilt angle can be obtained. It is relatively easy and is useful as a means for increasing the pretilt angle (see, for example, Patent Document 1). In addition, the diamine component for increasing the pretilt angle of the liquid crystal has been studied for improving the stability and process dependency of the pretilt angle, and its side chain structure includes a phenyl group and a cyclohexyl group. The thing containing a ring structure is proposed (for example, refer to patent documents 2).

In addition, as the liquid crystal display elements have become higher in definition, the liquid crystal alignment film used has a higher voltage holding ratio and a direct current voltage is applied from the viewpoint of suppressing the decrease in contrast of the liquid crystal display elements and reducing the afterimage phenomenon. The characteristic that the accumulated charge at the time is small or the charge accumulated by the DC voltage is quickly relaxed is becoming increasingly important.

In a polyimide-based liquid crystal alignment film, a liquid crystal alignment treatment agent containing a tertiary amine with a specific structure in addition to polyamic acid or imide group-containing polyamic acid is used as a short time until the afterimage generated by direct current voltage disappears. (For example, see Patent Document 3) and those using a liquid crystal alignment treatment agent containing a soluble polyimide using a specific diamine having a pyridine skeleton as a raw material (for example, see Patent Document 4). Yes. In addition to polyamic acid and its imidized polymer, a compound containing one carboxylic acid group in the molecule, assuming that the voltage holding ratio is high and the time until the afterimage generated by direct current voltage disappears is short , Using a liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing one carboxylic anhydride group in the molecule and a compound containing one tertiary amino group in the molecule (for example, Patent Document 5) is known.

JP-A-2-282726 JP-A-9-278724 JP-A-9-316200 JP-A-10-104633 JP-A-8-76128

The liquid crystal alignment film is also used for controlling the angle of the liquid crystal with respect to the substrate, that is, the pretilt angle of the liquid crystal. Especially in the VA (Vertical Alignment) mode and PSA (Polymer Sustained Alignment) mode, etc., it is necessary to align the liquid crystal vertically, so the liquid crystal alignment film has the ability to align the liquid crystal vertically (vertical alignment and high pretilt). Called corners). Furthermore, the liquid crystal alignment film has become important not only for high vertical alignment but also for its stability. In particular, liquid crystal display elements that use backlights that generate a large amount of heat and have a large amount of light to obtain high brightness, such as car navigation systems and large televisions, are exposed to high temperatures and light irradiation for long periods of time. May be used or left under. Under such severe conditions, when the vertical alignment property is lowered, problems such as inability to obtain initial display characteristics or occurrence of unevenness in display occur.

Furthermore, regarding the voltage holding ratio which is one of the electrical characteristics of the liquid crystal display element, high stability under the above severe conditions is also required. That is, if the voltage holding ratio is reduced by light irradiation from the backlight, a burn-in defect (also referred to as line burn-in), which is one of display defects of the liquid crystal display element, is likely to occur. A high liquid crystal display element cannot be obtained. Accordingly, the liquid crystal alignment film is required not only to have good initial characteristics, but also to have a low voltage holding ratio even after being exposed to light irradiation for a long time. Furthermore, there is a need for a liquid crystal alignment film that can quickly relieve residual charges accumulated by a direct current voltage by light irradiation from a backlight, even for another surface burn-in, which is another burn-in defect.

Therefore, the present invention can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time, and additionally suppresses a decrease in voltage holding ratio even after being exposed to light irradiation for a long time. And it aims at providing the liquid-crystal aligning agent from which the liquid crystal aligning film in which the residual electric charge accumulate | stored with a DC voltage is quick is obtained.
In addition, an object of the present invention is to provide a liquid crystal alignment film having the above characteristics and a liquid crystal display device including the liquid crystal alignment film.

As a result of intensive studies, the present inventor has found that a liquid crystal alignment treatment agent having two polymers having a specific structure is extremely effective for achieving the above object, and completes the present invention. It came.

That is, the present invention has the following gist.
1. The liquid crystal aligning agent characterized by containing the following (A) component and (B) component.
Component (A): at least one selected from the group consisting of a polyimide precursor obtained by reacting a diamine component containing a diamine having a structure represented by the following formula [1] and a tetracarboxylic acid component and a polyimide. Polymer.
(B) component: At least 1 sort (s) chosen from the group which consists of the polyimide precursor obtained by making the diamine component and tetracarboxylic acid component which do not contain the diamine which has a structure shown by following formula [1] react, and a polyimide. Polymer.

(Y ¹ represents a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or OCO—, where Y ² represents a single bond. Or (CH ₂ ) _b — (b is an integer of 1 to 15) Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or OCO— Y ⁴ represents a divalent organic group having a carbon number of 17 to 51 having a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a steroid skeleton. Any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine atom having 1 to 3 carbon atoms optionally substituted with-containing alkoxyl group or a fluorine atom .Y ⁵ is a benzene ring, cyclohexenone A divalent cyclic group selected from an aromatic ring and a heterocyclic ring, and any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms. 3 may be substituted with a fluorine-containing alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, n represents an integer of 0 to 4. Y ⁶ is an alkyl group having 1 to 18 carbon atoms, A fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms).
2. 2. The liquid crystal aligning agent according to 1 above, wherein the diamine having the structure represented by the formula [1] is represented by the following formula [1a]. Formula (1a) (in the formula, Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , n, Y ⁶ and m represent the same meaning as described above.

3. The polyimide precursor 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) with a tetracarboxylic acid component. 3. The liquid crystal aligning agent according to 1 or 2 above, which is at least one polymer selected from the group consisting of a body and polyimide.
4). The component (A) is a polymer used for a diamine component further comprising a diamine having a diamine having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group). 3. The liquid crystal aligning agent according to 3.
5. The liquid crystal aligning agent according to 3 or 4 above, wherein the diamine having at least one substituent selected from the carboxyl group and the hydroxyl group is represented by the following formula [2a].

(A ¹ represents at least one substituent selected from the following formulas [2a-1] and [2a-2], and m1 represents an integer of 1 to 4).

(D represents an integer of 0 to 4, and e represents an integer of 0 to 4).
6). 6. The liquid crystal alignment treatment according to any one of 1 to 5, wherein the polymer of the component (A) and the component (B) is a polymer using a diamine represented by the following formula [3a] as a diamine component. Agent.

(B ¹ is —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ) — or N (CH ₃ ) CO— B ² represents a single bond, alkylene having 1 to 20 carbon atoms, non-aromatic ring or aromatic ring B ³ represents a single bond, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH ₃ ) —, N (CH ₃ ) CO—, or —O (CH ₂ ) _m2 — (where m2 is 1 to 5) B ⁴ represents a nitrogen-containing heterocyclic ring, n1 represents an integer of 1 to 4, and when n1 is 2 or more, -B ¹ -B ² -B ³ -B ⁴ are the same as each other But it may be different).
7). The B ¹ in the formula [3a] is —O—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCO— or CON (CH ₃ ) —. Liquid crystal aligning agent.
8). 8. The liquid crystal aligning agent according to 6 or 7 above, wherein B ² in the formula [3a] is a single bond, alkylene having 1 to 5 carbon atoms, cyclohexane ring or benzene ring.
9. Any one of 6 to 8 above, wherein B ³ in the formula [3a] is a single bond, —O—, —OCO— or O (CH ₂ ) ₂ — (m2 is an integer of 1 to 5). The liquid crystal aligning agent according to item.
10. 10. The liquid crystal aligning agent according to any one of 6 to 9, wherein B ⁴ in the formula [3a] is a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring or pyrimidine ring.
11. B ¹ in the formula [3a] represents —CONH—, B ² represents alkylene having 1 to 5 carbon atoms, B ³ represents a single bond, B ⁴ represents an imidazole ring or a pyridine ring, and n 1 7. The liquid crystal aligning agent according to 6, wherein 1 is 1.
12 The liquid crystal according to any one of 1 to 11 above, wherein the tetracarboxylic acid component in at least one of the component (A) and the component (B) contains a tetracarboxylic dianhydride represented by the following formula [4]. Alignment treatment agent.

(Z ¹ is a group selected from the following formulas [4a] to [4k]).

(Z ² to Z ⁵ each independently represents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and Z ⁶ and Z ⁷ each independently represents a hydrogen atom or a methyl group.)
13. 13. The liquid crystal aligning agent according to any one of 1 to 12 above, which contains at least one solvent among N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone.
14 14. The liquid crystal aligning agent according to any one of 1 to 13, which contains at least one solvent selected from the following formulas [D-1] to [D-3].

(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).
15. The above 1 containing at least one solvent selected from 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether 15. The liquid crystal aligning agent according to any one of 1 to 14.
16. The liquid crystal aligning agent has at least one substituent selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. 16. The liquid crystal aligning agent according to any one of the above 1 to 15, comprising at least one crosslinkable compound selected from a crosslinkable compound and a crosslinkable compound having a polymerizable unsaturated bond.
17. A liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of 1 to 16 above.
18. A liquid crystal alignment film obtained by printing the liquid crystal aligning agent according to any one of the above 1 to 16 by an inkjet method.
19. 19. A liquid crystal display device having the liquid crystal alignment film as described in 17 or 18 above.
20. A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and between the electrodes 19. The liquid crystal alignment film as described in 17 or 18 above, which is used in a liquid crystal display device produced through a step of polymerizing the polymerizable compound while applying a voltage.
21. A liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates; 19. The liquid crystal alignment film as described in 17 or 18 above, which is used for a liquid crystal display device produced through a step of polymerizing the polymerizable group while applying a voltage therebetween.
22. 22. A liquid crystal display device having the liquid crystal alignment film as described in 20 or 21 above.

Liquid crystal alignment having two polymers of at least one polymer selected from polyimide precursors and polyimides containing a specific structure of the present invention and at least one polymer selected from polyimide precursors and polyimides not containing a specific structure The treatment agent can provide a liquid crystal alignment film that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. In addition, it is possible to obtain a liquid crystal alignment film that suppresses the decrease in the voltage holding ratio even after being exposed to light irradiation for a long period of time and quickly relaxes the residual charges accumulated by the DC voltage. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen high-definition liquid crystal television.

The liquid-crystal aligning agent of this invention contains the following (A) component and (B) component.
(A) component: a polyimide precursor obtained by reacting a diamine component containing a diamine compound having a side chain structure (also referred to as a specific side chain structure) represented by the above formula [1] with a tetracarboxylic acid component; A polymer containing at least one selected from polyimide (also referred to as a specific polymer (A)).
Component (B): At least one selected from a polyimide precursor obtained by reacting a diamine component not containing a diamine compound having a side chain structure represented by the above formula [1] and a tetracarboxylic acid component, and a polyimide. Containing a polymer (also referred to as a specific polymer (B)).
Especially the liquid-crystal aligning agent of this invention contains the following (A) component and (B) component. In that case, it is preferable to use the diamine compound which has a specific side chain structure only for (A) component.
(A) Component: A polymer containing at least one selected from a polyimide precursor and a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.
(B) Component: A polymer containing at least one selected from a polyimide precursor and a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

The specific side chain structure represented by the formula [1] contained in the specific polymer (A) of the present invention has at least one group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring at the side chain site, or a steroid skeleton. It has a divalent organic group having 17 to 51 carbon atoms. The side chain structure of these rings and organic groups shows a rigid structure as compared with the side chain structure of long-chain alkyl groups, which is a conventional technique for vertically aligning liquid crystals. As a result, the liquid crystal alignment film obtained from the liquid crystal aligning agent having a specific side chain structure can obtain a higher and more stable vertical alignment of liquid crystal than the conventional long chain alkyl group side chain structure. it can.
Further, the specific side chain structure is more stable to light such as ultraviolet rays than the conventional side chain structure of a long-chain alkyl group. Therefore, even if the specific side chain structure is exposed to light irradiation for a long time, it is possible to reduce a voltage holding ratio and to suppress a decomposition product of a side chain component that accumulates residual charges by a DC voltage.

In addition, the liquid crystal aligning agent of this invention is a liquid crystal aligning agent which has a specific polymer (A) and a specific polymer (B), and a specific polymer (B) does not contain a specific side chain structure. Therefore, in the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention, the amount of side chain components that increase the volume resistance of the liquid crystal alignment film is reduced, so that accumulation of residual charges due to DC voltage can be suppressed. .
Thus, according to the liquid crystal alignment treatment agent of the present invention, it is possible to obtain a liquid crystal alignment film that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. In addition, it is possible to obtain a liquid crystal alignment film that suppresses the decrease in the voltage holding ratio even after being exposed to light irradiation for a long period of time and quickly relaxes the residual charges accumulated by the DC voltage.
<Specific side chain structure>

The specific polymer (A) of the present invention includes a polyimide precursor and a polyimide obtained by reacting a diamine component containing a diamine compound having a specific side chain structure represented by the following formula [1] with a tetracarboxylic acid component. It is a polymer containing at least one selected from.

(In formula [1], the definitions of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , and n are as described above.)

In the formula [1], Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O, from the viewpoint of availability of raw materials and ease of synthesis. —, —CH ₂ O— or COO— is preferred. More preferred is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 10), —O—, —CH ₂ O— or COO—. Among them, Y ² is preferably a single bond or (CH ₂ ) _b — (b is an integer of 1 to 10). Y 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. preferable. More preferred is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O— or COO—. Among these, Y ⁴ is preferably an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton from the viewpoint of ease of synthesis. Among them, Y ⁵ is preferably a benzene ring or a cyclohexane ring. In particular, n is preferably 0 to 3 from the viewpoint of availability of raw materials and ease of synthesis. More preferred is 0-2. Y ⁶ is preferably an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

As a preferable combination of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [1], pages 13 to 34 of International Publication No. WO2011 / 132751 (published 2011.10.27). The same combinations as (2-1) to (2-629) listed in Tables 6 to 47 of the above are listed. In each table of the International Publication, Y ¹ to Y ⁶ in the present invention are shown as Y ¹ to Y ⁶ , but Y ¹ to Y ⁶ are read as Y ¹ to Y ⁶ . Further, in (2-605) to (2-629) listed in each table of the International Publication, the organic group having 17 to 51 carbon atoms having a steroid skeleton in the present invention has 12 to 20 carbon atoms having a steroid skeleton. An organic group having 12 to 25 carbon atoms having a steroid skeleton is to be read as an organic group having 17 to 51 carbon atoms having a steroid skeleton.

Among them, (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) to (2-315) , (2-364) to (2-387), (2-436) to (2-483), or (2-603) to (2-615) are preferred. Particularly preferred combinations are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-603) to (2- 606), (2-607) to (2-609), (2-611), (2-612) or (2-624).

<Specific polymer (A) / Specific polymer (B)>
The specific polymer (A) and the specific polymer (B) are at least selected from a polyimide precursor obtained by reacting a diamine component and a tetracarboxylic acid component and a polyimide (also collectively referred to as a polyimide polymer). It is a polymer containing either one.
The polyimide precursor has a structure represented by the following formula [A].

(R ¹ is a tetravalent organic group, R ² is a divalent organic group, A ¹ and A ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, which may be the same or different. A ³ and A ^{4 each} represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acetyl group, which may be the same or different, and n2 represents a positive integer.)

The diamine component is a diamine compound having two primary or secondary amino groups in the molecule, and the tetracarboxylic acid component is a tetracarboxylic acid compound, tetracarboxylic dianhydride, or tetracarboxylic acid dihalide compound. , Tetracarboxylic acid dialkyl ester compounds or tetracarboxylic acid dialkyl ester dihalide compounds.

The polyimide polymer of the present invention can be obtained relatively easily by using a tetracarboxylic dianhydride represented by the following formula [B] and a diamine compound represented by the following formula [C] as raw materials. Therefore, a polyamic acid having a structural formula of a repeating unit represented by the following formula [D] or a polyimide obtained by imidizing the polyamic acid is preferable. Especially, it is preferable to use a polyimide for a specific polymer (A) and a specific polymer (B) from the point of the physical and chemical stability of a liquid crystal aligning film.

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

(R ¹ , R ² and n2 are the same as defined in formula [A].)

In addition, the polymer of the formula [D] obtained above by the usual synthesis method is added to the alkyl group having 1 to 8 carbon atoms of A ¹ and A ^{2 represented by} the formula [A] and the formula [A]. It is also possible to introduce an alkyl group having 1 to 5 carbon atoms or an acetyl group of A ³ and A ⁴ shown.

The specific polymer (A) is a polyimide polymer obtained by using a diamine component containing a diamine compound having a specific side chain structure. At that time, as a diamine compound having a specific side chain structure, it is preferable to use a diamine compound represented by the following formula [1a] (also referred to as a specific side chain diamine compound).

In the formula [1a], Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , and n are the same as the respective definitions in the above formula [1], and the respective preferable definitions are also the same. .
Also, preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n are the same as described for the above formula [1]. Note that m is an integer of 1 to 4. Preferably, it is an integer of 1.

Specific examples include structures represented by the following formulas [1a-1] to [1a-31].

(R ¹ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ — or CH ₂ OCO—, and R ² represents a linear or branched alkyl group having 1 to 22 carbon atoms, carbon A linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkyl group or a fluorine-containing alkoxyl group having 1 to 22 carbon atoms.)

(R ³ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ — or CH ₂ —, ⁴ is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, or fluorine. Containing alkoxyl groups.)

(R ⁵ is —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, —CH ₂ —, —O -Represents NH-, and R ⁶ represents a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group.

(R ⁷ is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.)

(R ⁸ is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.)

(A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A ₃ is a 1,4-cyclohexylene group or a 1,4-phenylene group. , A ₂ is an oxygen atom or COO- * (positive, a bond with “*” is bonded to A ₃ ), and A ₁ is an oxygen atom or COO— * (where “*” is a bond) The hand binds to (CH ₂ ) a ₂ ). A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1. )

Among the above formulas [1a-1] to [1a-31], diamine compounds having particularly preferred structures are represented by the formulas [1a-1] to [1a-6] and the formulas [1a-9] to [1a-13]. Or they are the formulas [1a-22] to [1a-31].

The specific side chain diamine compound in the specific polymer (A) is preferably 10 mol% or more and 80 mol% or less of the entire diamine component. Particularly preferred is 10 mol% or more and 70 mol% or less.

The specific side chain diamine compound has characteristics such as the solubility of the specific polymer (A) in the solvent, the coating property of the liquid crystal alignment treatment agent, the liquid crystal alignment property, the voltage holding ratio, and the accumulated charge when the liquid crystal alignment film is used. Depending on the situation, one kind or a mixture of two or more kinds may be used.

As the diamine component in producing the specific polymer (A) and the specific polymer (B), it is preferable to use another diamine compound (also referred to as a specific second diamine compound) together with the specific side chain diamine compound. .

Among these, it is preferable to use a diamine compound having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group).
Specifically, it is preferable to use a diamine compound represented by the following formula [2a].

In formula [2a], A ¹ represents a substituent having at least one structure selected from the following formula [2a-1] and formula [2a-2]. Among these, a substituent having a structure represented by the formula [2a-1] is preferable.

In the formula [2a], m1 represents an integer of 1 to 4. Of these, 1 is preferable.

In the formula [2a-1], d represents an integer of 0 to 4. Of these, 0 or 1 is preferable.
In the formula [2a-2], e represents an integer of 0 to 4. Of these, 0 or 1 is preferable.

More specifically, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid. Of these, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid is preferable.
As the specific second diamine compound, diamine compounds represented by the following formulas [2b-1] to [2b-4] can also be used.

(A ¹ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, —O—, —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ ) — or N (CH ₃ ) CO—, wherein m ¹ and m ² each represent an integer of 0 to 4, and m ¹ + m ² represents an integer of 1 to 4, and in formula [2b-2], m ³ and m ⁴ are Each represents an integer of 1 to 5, and in formula [2b-3], A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms, m ⁵ represents an integer of 1 to 5, and formula [2b- 4], A ³ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, —O—, — CO-, _{NH -, - N (CH 3} ) -, - CONH -, - NHCO -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CON (CH 3) - or N (CH ₃ ) Represents CO—, and m ⁶ represents an integer of 1 to 4.
The specific second diamine compound may be used for the diamine component of either the specific polymer (A) or the specific polymer (B) and the specific polymer (A) and the specific polymer (B). It can also be used for the diamine component of both of the specific polymers. Especially, it is preferable to use only for the diamine component of a specific polymer (A), or to use only for the diamine component of a specific polymer (B).

The specific second diamine compound is preferably 10 mol% or more of the entire diamine component. Especially, 20 mol% or more is preferable and 30 mol% or more is especially preferable.

The specific second diamine compound is the solubility of the specific polymer (A) and the specific polymer (B) in the solvent, the coating property of the liquid crystal aligning agent, the liquid crystal alignment property when the liquid crystal alignment film is used, and the voltage holding. One type or a mixture of two or more types can be used depending on the characteristics such as rate and accumulated charge.

As a diamine component of the specific polymer (A) and the specific polymer (B) of the present invention, a diamine compound represented by the following formula [3a] (specific) together with a specific side chain diamine compound and a specific second diamine compound It is preferable to use a third diamine compound).

In the formula [3a], B ¹ represents —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ) —. Or N (CH ₃ ) CO—. Among them, —O—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ) — or N (CH ₃ ) CO— synthesize diamine compounds. Since it is easy to do, it is preferable. Particularly preferred is —O—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCO— or CON (CH ₃ ) —. More preferred is —O—, —CONH— or CH ₂ O—.

In the formula [3a], B ² represents a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring or an aromatic ring.

The alkylene group having 1 to 20 carbon atoms may be linear or branched. Moreover, you may have an unsaturated bond. In particular, an alkylene group having 1 to 10 carbon atoms is preferable.

Specific examples of the non-aromatic ring include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, and cyclotridecane ring. , Cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosan ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring, norbornene And a ring or an adamantane ring. Among these, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, or an adamantane ring is preferable.

Specific examples of the aromatic ring include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring or phenalene ring. Of these, a benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring or anthracene ring is preferred.

Preferred B ² in the formula [3a] is a single bond, an alkylene group having 1 to 10 carbon atoms, 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 fluorene ring or an anthracene ring; Of these, a single bond, an alkylene group having 1 to 5 carbon atoms, a cyclohexane ring or a benzene ring is preferable.

In the formula [3a], B ³ is a single bond, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH ₃ ). — Or N (CH ₃ ) CO—, —O (CH ₂ ) _m2 — (m2 is an integer of 1 to 5). Among these, a single bond, —O—, —COO—, —OCO— or O (CH ₂ ) _m2 — (m2 is an integer of 1 to 5) is preferable, and a single bond, —O— is particularly preferable. , —OCO— or O (CH ₂ ) _m2 — (m2 is an integer of 1 to 5).
In formula [3a], B ⁴ is a nitrogen-containing heterocycle, which is a heterocycle containing at least one structure selected from the following formula [a], formula [b] and formula [c].

(In the formula [c], Z represents an alkyl group having 1 to 5 carbon atoms.)
More specifically, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring , Triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, cinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring or acridine ring be able to. Among these, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring or a benzimidazole ring are preferable, and a pyrrole ring or an imidazole ring is particularly preferable. , A pyrazole ring, a pyridine ring or a pyrimidine ring.

Also, B ³ in the formula [3a] are expressions included in the B ⁴ [a], is preferably bonded with a substituent nonadjacent the formula [b] and the formula [c].
Preferred combinations of B ¹ , B ² , B ³ and B ^{4 in} the formula [3a] are as shown in Tables 1 to 31 below. In Tables 1 to 31, X ¹ , X ² , X ³ and X ⁴ are to be read as B ¹ , B ² , B ³ and B ⁴ , respectively.

In the formula [3a], n1 is an integer of 1 to 4, and is preferably 1 or 2 from the viewpoint of reactivity with the tetracarboxylic acid component.

Particularly preferred combinations of B ¹ , B ² , B ³ , B ⁴ and n1 in the formula [3a] are such that B ¹ represents —CONH—, B ² represents an alkyl group having 1 to 5 carbon atoms, and B ³ represents A diamine compound which represents a single bond, B ⁴ represents an imidazole ring or a pyridine ring, and n 1 represents 1.

The bonding position of the two amino groups (—NH ₂ ) in the formula [3a] is not limited. Specifically, with respect to the linking group (B ¹ ) of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring Position or 3, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, the 2,4 position, the 2,5 position, or the 3,5 position is preferable. Considering the ease in synthesizing the diamine compound, the positions 2, 4 or 2, 5 are more preferable.

The specific third diamine compound may be used for the diamine component of the polyimide polymer of either the specific polymer (A) or the specific polymer (B). The specific polymer (A) and the specific polymer (B) It can also be used for the diamine component of both of the specific polymers. Especially, when a specific 2nd diamine compound is used for a specific polymer (A) for a diamine component, it is preferable to use a specific 3rd diamine compound for a diamine component of a specific polymer (B). Moreover, when using a specific 2nd diamine compound for a specific polymer (B) for a diamine component, it is preferable to use a specific 3rd diamine compound for the diamine component of a specific polymer (A). That is, it is preferable to use a specific 2nd diamine compound and a specific 3rd diamine compound for a diamine component separately with respect to each specific polymer.

The specific third diamine compound is preferably 5 mol% or more of the entire diamine component. Especially, 10 mol% or more is preferable and 15 mol% or more is especially preferable.

The specific third diamine compound is the solubility of the specific polymer (A) and the specific polymer (B) in the solvent, the coating property of the liquid crystal aligning agent, the alignment property of the liquid crystal when the liquid crystal alignment film is used, and the voltage holding. One type or a mixture of two or more types can be used depending on the characteristics such as rate and accumulated charge.

As a diamine component of the specific polymer (A) and the specific polymer (B), the specific side chain type diamine compound, the specific second diamine compound and the specific third diamine compound are used as long as the effects of the present invention are not impaired. Other diamine compounds (also referred to as other diamine compounds) can be used.

Specific examples of other diamine compounds include 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminobiphenyl, 3,3. '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy- 4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3 '-Diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3 -Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diamino Diphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis (4-aminophenyl) silane, bis (3-amino Phenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4′-thiodianiline, 3,3′-thiodianiline, 4,4′-diaminodiphenylamine, 3, 3'-Diaminodiphenyla 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3,3'-diamino) Diphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4 ' -Diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene 2,2-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3 -Aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4aminophenyl) butane, 1,4-bis ( 3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenyl) Noxy) benzene, 4,4 '-[1,4-phenylenebis (methylene)] dianiline, 4,4'-[1,3-phenylenebis (methylene)] dianiline, 3,4 '-[1,4- Phenylenebis (methylene)] dianiline, 3,4 ′-[1,3-phenylenebis (methylene)] dianiline, 3,3 ′-[1,4-phenylenebis (methylene)] dianiline, 3,3 ′-[ 1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1, -Phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-amino Phenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N ′-(1,4-phenylene) bis (4-aminobenzamide), N, N ′-( 1,3-phenylene) bis (4-aminobenzamide), N, N ′-(1,4-phenylene) bis (3-aminobenzamide), N, N ′-(1,3-phenylene) bis (3- Aminobenzamide), N, N′-bis (4-aminophenyl) terephthalamide, N, N′-bis (3-aminophenyl) terephthalate Luamide, N, N′-bis (4-aminophenyl) isophthalamide, N, N′-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4′- Bis (4-aminophenoxy) diphenylsulfone, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2,2′-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2′-bis (4-aminophenyl) hexafluoropropane, 2,2′-bis (3-aminophenyl) hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) hexafluoro Propane, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis 3-amino-4-methylphenyl) propane, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) Hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7-bis (3-aminophenoxy) heptane, 1,8-bis (4 -Aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminopheno) C) Nonane, 1,10-bis (4-aminophenoxy) decane, 1,10-bis (3-aminophenoxy) decane, 1,11-bis (4-aminophenoxy) undecane, 1,11-bis (3 -Aminophenoxy) undecane, 1,12-bis (4-aminophenoxy) dodecane, 1,12-bis (3-aminophenoxy) dodecane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methyl) (Cyclohexyl) methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9 -Diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, etc. It is.

Further, as other diamine compounds, diamine compounds represented by the following formulas [D1] to [DA25] can also be used.

(A ¹ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.)

(A ¹ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— or NH—, and A ² is a straight chain having 1 to 22 carbon atoms. Alternatively, it represents a branched alkyl group or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.)

(P represents an integer of 1 to 10)

(M represents an integer of 0 to 3, and n represents an integer of 1 to 5.)

Other diamine compounds may be used for the diamine component of either the specific polymer (A) or the specific polymer (B), and both the specific polymer (A) and the specific polymer (B). It can also be used for the diamine component of the specific polymer.

Other diamine compounds include the solubility of the specific polymer (A) and the specific polymer (B) in the solvent, the coating property of the liquid crystal aligning agent, and the liquid crystal alignment property and voltage holding ratio when used as a liquid crystal alignment film. Depending on the characteristics such as accumulated charge, one kind or a mixture of two or more kinds may be used.

As the tetracarboxylic acid component for producing the specific polymer (A) and the specific polymer (B), that is, these polyimide-based polymers, a tetracarboxylic dianhydride represented by the following formula [4] ( It is preferable to use a specific tetracarboxylic dianhydride. At that time, not only the specific tetracarboxylic dianhydride represented by the formula [4] but also the tetracarboxylic acid derivative tetracarboxylic acid, tetracarboxylic dihalide compound, tetracarboxylic dialkyl ester compound or tetracarboxylic dialkyl ester Dihalide compounds can also be used.

(Z ¹ is a group having a structure selected from the following formulas [4a] to [4k].)

In the formula [4a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.
In the formula [4g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group, and may be the same or different.
Among Z ¹ in the formula [4], from the viewpoint of easy synthesis and ease of polymerization reactivity when producing a polymer, the formula [4a], the formula [4c], the formula [4d], the formula [4] 4e], a formula [4f], a formula [4g] or a tetracarboxylic dianhydride having a structure represented by the formula [4k] and a tetracarboxylic acid derivative thereof are preferable. More preferred is a structure represented by the formula [4a], the formula [4e], the formula [4f], the formula [4g] or the formula [4k], and particularly preferred is the formula [4e], the formula [4]. 4f], formula [4g] or formula [4k].

As long as the effects of the present invention are not impaired, other tetracarboxylic acid components other than the specific tetracarboxylic dianhydride can also be used for the polyimide polymer of the present invention.
Examples of other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds, and tetracarboxylic acid dialkyl ester dihalide compounds.

That is, other tetracarboxylic acid components include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalene. Tetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ', 4'-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2 2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetra Carboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, or 1, Examples include 3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

In the tetracarboxylic acid component in the specific polymer (A) and the specific polymer (B), the specific tetracarboxylic dianhydride in each specific polymer is preferably 10 mol% or more of the tetracarboxylic acid component. Especially, 20 mol% or more is preferable and 30 mol% or more is especially preferable. All of the tetracarboxylic acid components may be a specific tetracarboxylic dianhydride.
When the specific tetracarboxylic dianhydride and other tetracarboxylic acid components are used as the solubility of the specific polymer (A) and the specific polymer (B) in the solvent, the coating property of the liquid crystal aligning agent, and the liquid crystal alignment film One type or a mixture of two or more types can be used according to the characteristics such as the orientation of the liquid crystal, the voltage holding ratio, and the accumulated charge.

<The manufacturing method of a specific polymer (A) and a specific polymer (B)>
The specific polymer (A) in the present invention is obtained from a polyimide precursor and a polyimide obtained by reacting a diamine component containing a diamine compound having a specific side chain structure represented by the formula [1] with a tetracarboxylic acid component. At least one polymer selected from the group consisting of: At that time, as the diamine compound having a specific side chain structure, it is preferable to use the specific side chain diamine compound represented by the formula [1a].
The specific polymer (A) includes a specific side chain diamine compound, a diamine compound having at least one substituent selected from a carboxyl group and a hydroxyl group, and / or a specific compound represented by the formula [3a]. A third diamine compound may be used in combination. At that time, the specific second diamine compound represented by the formula [2a] is preferably used for the diamine compound having at least one substituent selected from a carboxyl group and a hydroxyl group.
When the specific second diamine compound is used in combination, the use ratio is 10 to 80 mol% for the specific side chain diamine compound and 10 to 90 mol for the specific second diamine compound with respect to 100 mol% of the total diamine component. Mole% is preferred. More preferably, the specific side chain diamine compound is 10 to 80 mol%, and the specific second diamine compound is 20 to 70 mol%.

When the specific third diamine compound is used in combination, the use ratio is 10 to 80 mol% for the specific side chain type diamine compound and 10 to 90 for the specific third diamine compound with respect to 100 mol% of the total diamine component. Mole% is preferred. More preferably, the specific side chain diamine compound is 10 to 80 mol%, and the specific third diamine compound is 20 to 70 mol%.
When the specific second diamine compound and the specific third diamine compound are used in combination, the specific side chain type diamine compound is used in an amount of 10 to 80 mol% with respect to the total diamine component of 100 mol%. The diamine compound is preferably 10 to 80 mol%, and the specific third diamine compound is preferably 10 to 80 mol%. More preferably, the specific side chain type diamine compound is 10 to 80 mol%, the specific second diamine compound is 20 to 70 mol%, and the specific third diamine compound is 20 to 70 mol%. In the present invention, it is preferable to use a specific third diamine compound in combination with the specific polymer (A).

The specific polymer (B) in the present invention is selected from the group consisting of a polyimide precursor obtained by reacting a diamine component not containing a diamine compound having a specific side chain structure with a tetracarboxylic acid component and a polyimide. At least one polymer. At that time, it is preferable to use a diamine compound having at least one substituent selected from a carboxyl group and a hydroxyl group for the specific polymer (B). More preferable is the specific second diamine compound represented by the formula [2a].

As described above, the use ratio of the specific second diamine compound is preferably 10 mol% or more with respect to 100 mol% of the entire diamine component. More preferred is 20 mol% or more, and particularly preferred is 30 mol% or more.
Moreover, a specific 2nd diamine compound and a specific 3rd diamine compound can also be used together for a specific polymer (B). In this case, it is preferable that the specific second diamine compound is 10 to 80 mol% and the specific third diamine compound is 10 to 80 mol% with respect to 100 mol% of the entire diamine component. More preferably, the specific second diamine compound is 20 to 70 mol%, and the specific third diamine compound is 20 to 70 mol%.

In the present invention, the specific polymer (A) and the specific polymer (B), that is, a method for producing these polyimide polymers is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. In general, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydride and its derivatives is reacted with a diamine component consisting of one or more diamine compounds. And a method of obtaining a polyamic acid. Specifically, a method of obtaining polyamic acid by polycondensation of tetracarboxylic dianhydride and primary or secondary diamine compound, dehydration polycondensation reaction of tetracarboxylic acid and primary or secondary diamine compound Or a method of obtaining a polyamic acid by reacting a tetracarboxylic acid dihalide with a primary or secondary diamine compound.

To obtain the polyamic acid alkyl ester, a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group with a primary or secondary diamine compound, a tetracarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group and 1 A method of reacting with a secondary or secondary diamine compound or a method of converting a carboxyl group of a polyamic acid into an ester is used.
In order to obtain polyimide, a method is used in which the polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.

The reaction between the diamine component and the tetracarboxylic acid component is usually performed in an organic solvent with the diamine component and the tetracarboxylic acid component. The organic solvent used at that time is not particularly limited as long as the produced polyimide precursor is dissolved. Although the specific example of the organic solvent used for reaction below is given, it is not limited to these examples.
Examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolidinone. It is done.

When the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3] The indicated solvents can be used.

(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).

These may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use the said solvent in the range which the produced | generated polyimide precursor does not precipitate. Moreover, since the water | moisture content in an organic solvent inhibits a polymerization reaction, and also causes the produced polyimide precursor to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic acid component is dispersed or dissolved in the organic solvent as it is. And a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent, a method of alternately adding a diamine component and a tetracarboxylic acid component, etc. Any of these methods may be used. Moreover, when making it react with each using multiple types of diamine component or tetracarboxylic acid component, you may make it react in the state mixed beforehand, may make it react separately one by one, and it is further made to react individually. May be mixed and reacted to form a polymer. In this case, the polymerization temperature can be selected from -20 ° C to 150 ° C, but is preferably in the range of -5 ° C to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. It becomes. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor produced increases as the molar ratio approaches 1.0.

The polyimide of the present invention is a polyimide obtained by ring closure of the polyimide precursor, and in this polyimide, the ring closure rate of the amic acid group (also referred to as imidization rate) is not necessarily 100%. It can be arbitrarily adjusted according to the purpose. Among these, in the present invention, the specific polymer (A) is 30 to 100% of the specific polymer because it can suppress a decrease in the voltage holding ratio after being exposed to light irradiation for a long time. (B) is preferably 30 to 100%. More preferably, the specific polymer (A) is 40 to 90%, and the specific polymer (B) is 40 to 90%. Particularly preferably, the specific polymer (A) is 50 to 85%, and the specific polymer (B) is 50 to 85%.

Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalytic imidization in which a catalyst is added to the polyimide precursor solution.

When the polyimide precursor is thermally imidized in a solution, the temperature is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.

The catalyst imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

When recovering the produced polyimide precursor or polyimide from the polyimide precursor or polyimide reaction solution, the reaction solution may be poured into a solvent and precipitated. Examples of the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated in the solvent can be collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating. In addition, when the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the solvent at this time include alcohols, ketones, and hydrocarbons, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further increased.

The molecular weight of the polyimide polymer of the present invention is a weight average measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the liquid crystal alignment film obtained therefrom, workability at the time of forming the liquid crystal alignment film, and coating properties. The molecular weight is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

<Liquid crystal alignment agent>
The liquid crystal aligning agent of the present invention is a coating solution for forming a liquid crystal alignment film (also referred to as a resin film), and a liquid crystal alignment film containing a specific polymer (A), a specific polymer (B) and a solvent. It is a coating solution for forming.
The ratio of the specific polymer (A) and the specific polymer (B) in the liquid crystal aligning agent is 10 to 900 parts by mass of the specific polymer (B) with respect to 100 parts by mass of the specific polymer (A). It is preferable that The specific polymer (B) is more preferably 20 to 800 parts by mass. The specific polymer (B) is particularly preferably 30 to 700 parts by mass.

All of the polymer components in the liquid crystal aligning agent of the present invention may be the specific polymer (A) and the specific polymer (B) of the present invention, and other polymers are mixed. May be. At that time, the content of the other polymer is 0.5 to 15 parts by mass, preferably 100 parts by mass of the specific polymer (A) and the specific polymer (B). Is 1 to 10 parts by mass. Examples of the other polymer include a cellulose polymer, an acrylic polymer, a methacrylic polymer, polystyrene, polyamide, or polysiloxane.

The solvent in the liquid crystal aligning agent of the present invention is preferably 70 to 99.9% by mass of the solvent in the liquid crystal aligning agent from the viewpoint of forming a uniform liquid crystal aligning film by coating. This content can be appropriately changed depending on the film thickness of the target liquid crystal alignment film.

The solvent used for the liquid crystal aligning agent of the present invention is not particularly limited as long as it is a solvent (also referred to as a good solvent) that dissolves the specific polymer (A) and the specific polymer (B). Although the specific example of a good solvent is given to the following, it is not limited to these examples.

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

Of these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are preferably used.

Furthermore, when the solubility of the specific polymer (A) and the specific polymer (B) in the solvent is high, it is preferable to use the solvents represented by the formulas [D-1] to [D-3].

The good solvent in the liquid crystal aligning agent of the present invention is preferably 10 to 100% by mass of the total solvent contained in the liquid crystal aligning agent. Of these, 20 to 90% by mass is preferable. More preferred is 30 to 80% by mass.

The liquid crystal aligning agent of the present invention uses a solvent (also referred to as a poor solvent) that improves the coating properties and surface smoothness of the liquid crystal aligning film when the liquid crystal aligning agent is applied unless the effects of the present invention are impaired. be able to. Although the specific example of a poor solvent is given to the following, it is not limited to these examples.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Ethane All, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1 , 2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, -Heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene Carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1 -(Butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol , Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol mono Acetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene Glycol monoethyl ether, Methyl acetate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxy Ethyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, lactate n-propyl ester, lactate n-butyl ester, Examples thereof include isoamyl lactate and solvents represented by the above formulas [D-1] to [D-3].

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, or the above-mentioned formula [D-1] to formula It is preferable to use a solvent represented by [D-3].

These poor solvents are preferably 1 to 70% by mass of the whole solvent contained in the liquid crystal aligning agent. Among these, 1 to 60% by mass is preferable. More preferred is 5 to 60% by mass.

The liquid crystal alignment treatment agent of the present invention has at least one substitution selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. It is preferable to introduce a crosslinkable compound having a group or a crosslinkable compound having a polymerizable unsaturated bond. It is necessary to have two or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl Triglycidyl-p-aminophenol, tetraglycidylmetaxylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-epoxy) Propoxy) phenyl) ethyl) phenyl) propane or 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2,3 -Epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4A].

Specifically, the crosslinkable compounds represented by the formulas [4a] to [4k] described in the paragraphs 58 to 59 of the international publication WO2011 / 132751 (published 2011.10.27) can be mentioned.

The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5A].

Specifically, crosslinkable compounds represented by the formulas [5-1] to [5-42] described in the paragraphs 76 to 82 of International Publication No. WO2012 / 014898 (published in 2012.2.2) are listed. It is done.

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include, for example, an amino resin having at least one substituent selected from a hydroxyl group and an alkoxyl group, such as a melamine resin. And urea resin, guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, and ethyleneurea-formaldehyde resin. Specifically, a melamine derivative, a benzoguanamine derivative, or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both can be used. The melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.

Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring. Eight-substituted MW-30 (Sanwa Chemical Co., Ltd.) and Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and other methoxymethylated melamines, Cymel 235, 236 Methoxymethylated butoxymethylated melamine such as 238, 212, 253, 254, butoxymethylated melamine such as Cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, Cymel 1123 and the like Methoxymethylated etoxy Methylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 Cyanamide). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powderlink 1174.

Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p-tert-butylphenol.

More specifically, International Publication No. WO2011-132751. (2011.10.27), pages 62 to 66, and crosslinkable compounds represented by the formulas [6-1] to [6-48].

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxytrimethylol. Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as propane or glycerin polyglycidyl ether poly (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Rudi (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin Di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate or hydroxypivalic acid neo Crosslinkable compounds having two polymerizable unsaturated groups in the molecule, such as pentyl glycol di (meth) acrylate, in addition, 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2 Crosslinkability having one polymerizable unsaturated group in the molecule such as hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate ester or N-methylol (meth) acrylamide Compounds.

In addition, a compound represented by the following formula [7A] can also be used.

(In the formula [7A], E ₁ represents a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring and a phenanthrene ring; ₂ represents a group selected from the following formulas [7a] and [7b], and n represents an integer of 1 to 4.

The above compound is an example of a crosslinkable compound and is not limited thereto. Moreover, the crosslinkable compound used for the liquid-crystal aligning agent of this invention may be 1 type, and may be combined 2 or more types.

In the liquid crystal aligning agent of the present invention, the content of the crosslinkable compound is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all the polymer components. In order for the crosslinking reaction to proceed and to achieve the desired effect, the amount is more preferably 0.1 to 100 parts by weight, and most preferably 1 to 50 parts by weight, based on 100 parts by weight of all polymer components.

For the liquid crystal alignment treatment agent of the present invention, a compound that improves the uniformity of the film thickness and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used as long as the effects of the present invention are not impaired.

Examples of compounds that improve the film thickness uniformity and surface smoothness of the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

More specifically, for example, F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink), Florard FC430, FC431 (or more) And Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.). The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent. It is.

Furthermore, in the liquid crystal alignment treatment agent of the present invention, as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge loss of the element, page 69 of International Publication No. WO2011 / 132751 (published 2011.10.20). It is also possible to add nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156], which are listed on page 73. This amine compound may be added directly to the liquid crystal aligning agent, but it is added after a solution having a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass with an appropriate solvent. It is preferable. The solvent is not particularly limited as long as it is an organic solvent that dissolves the specific polymer (A) and the specific polymer (B) described above.

The liquid crystal alignment treatment agent of the present invention includes, in addition to the above poor solvent, crosslinkable compound, resin film or compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film, and a compound that promotes charge removal, As long as the effects of the present invention are not impaired, a dielectric or conductive material for changing the electrical characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film may be added.
<Liquid crystal alignment film and liquid crystal display element>

The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate, and then subjected to alignment treatment by rubbing treatment or light irradiation. In the case of vertical alignment, etc., it can be used as a liquid crystal alignment film without alignment treatment. 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 also be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode for driving a liquid crystal is formed. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.

The application method of the liquid crystal alignment treatment agent is not particularly limited, but industrially, a method performed by screen printing, offset printing, flexographic printing, an inkjet method or the like is common. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, or a spray method, and these may be used depending on the purpose.

After the liquid crystal alignment treatment agent is applied on the substrate, it is preferably 30 to 300 ° C., depending on the solvent used for the liquid crystal alignment treatment agent, by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven. The liquid crystal alignment film can be obtained by evaporating the solvent at a temperature of 30 to 250 ° C. If the thickness of the liquid crystal alignment film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 10 to 100 nm. When the liquid crystal is horizontally aligned or tilted, the fired liquid crystal alignment film is treated by rubbing or irradiation with polarized ultraviolet rays.

The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
As a method for manufacturing a liquid crystal cell, prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and place the other side of the liquid crystal alignment film on the other side. And a method of sealing the substrate by injecting liquid crystal under reduced pressure, or a method of sealing the substrate by bonding the liquid crystal after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed.

Furthermore, the liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board | substrates provided with the electrode, The polymeric compound superposed | polymerized by at least one of an active energy ray and a heat | fever between a pair of board | substrates. The liquid crystal composition is also preferably used for a liquid crystal display element produced through a step of polymerizing a polymerizable compound by at least one of irradiation with active energy rays and heating while applying a voltage between electrodes. Here, ultraviolet rays are suitable as the active energy ray. The wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.

The above liquid crystal display element controls the pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, a predetermined voltage is applied to the liquid crystal layer and an ultraviolet ray is applied to the photopolymerizable compound. The pretilt of the liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer. The PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by the rubbing process.

That is, in the liquid crystal display element of the present invention, after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent by the above-described method, a liquid crystal cell is prepared, and a polymerizable compound is polymerized by at least one of ultraviolet irradiation and heating. Thus, the alignment of liquid crystal molecules can be controlled.

To give an example of manufacturing a PSA type liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded and the liquid crystal is injected under reduced pressure and sealed, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed and then the substrate is bonded and sealed. Can be mentioned.

In the liquid crystal, a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed. Examples of the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. In that case, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component. When the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled. The seizure characteristics of the steel deteriorate.

After producing the liquid crystal cell, the polymerizable compound is polymerized by irradiating with heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell. Thereby, the alignment of the liquid crystal molecules can be controlled.

In addition, the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferable to use it for a liquid crystal display element manufactured through a step of arranging a liquid crystal alignment film containing a group and applying a voltage between electrodes, that is, an SC-PVA mode. Here, ultraviolet rays are suitable as the active energy ray. The wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.

In order to obtain a liquid crystal alignment film containing a polymerizable group that is polymerized from at least one of active energy rays and heat, a method of adding a compound containing this polymerizable group to the liquid crystal aligning agent, A method using a coalescing component may be mentioned.
To give an example of SC-PVA mode liquid crystal cell preparation, a pair of substrates on which the liquid crystal alignment film of the present invention is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is prepared. The other substrate is bonded so that the inner side is inside, the liquid crystal is injected under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed The method of performing etc. is mentioned.
After the liquid crystal cell is manufactured, the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.

As described above, by using the liquid crystal alignment treatment agent of the present invention, it is possible to provide a liquid crystal alignment film that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. In addition, it is possible to obtain a liquid crystal alignment film that suppresses a decrease in the voltage holding ratio and quickly relaxes a residual charge accumulated by a DC voltage even after being exposed to high temperature and light irradiation for a long time. In particular, the liquid crystal alignment treatment agent of the present invention is useful for a liquid crystal alignment film of a liquid crystal display element using a PSA mode or an SC-PVA mode. Therefore, the liquid crystal display element manufactured using the liquid crystal aligning agent of the present invention has excellent reliability, and can be suitably used for large liquid crystal televisions, small and medium car navigation systems, smartphones, and the like. .

The present invention will be described in more detail with reference to the following examples, but is not limited thereto. The abbreviations used below are as follows.
(Specific side chain diamine compounds)
A1: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene A2: 1,3-diamino-5- [4- (trans-4-n-heptylcyclo) Hexyl) phenoxymethyl] benzene A3: 1,3-diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene A4: Diamine compound represented by A4]

(Specific second diamine compound)
B1: 3,5-diaminobenzoic acid (a specific second diamine compound having a carboxyl group (COOH group))

(Specific third diamine compound)
C1: Diamine compound represented by the following formula [C1] C2: Diamine compound represented by the following formula [C2]

(Other diamine compounds)
D1: p-phenylenediamine D2: m-phenylenediamine D3: 1,3-diamino-4-octadecyloxybenzene

(Specific tetracarboxylic dianhydride)
E1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride E2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride E3: the following formula [E3 E4: tetracarboxylic dianhydride represented by the following formula [E4] E5: tetracarboxylic dianhydride represented by the following formula [E5]

<Crosslinkable compound to be introduced into the liquid crystal aligning agent>
M1: Crosslinkable compound represented by the following formula [M1]

<Solvent used in the present invention>
NMP: N-methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone γ-BL: γ-butyrolactone BCS: ethylene glycol monobutyl ether PB: propylene glycol monobutyl ether EC: diethylene glycol monoethyl ether
DME: Dipropylene glycol dimethyl ether

"Measurement of molecular weight of polyimide polymer"
The molecular weights of the polyimide precursor and the polyimide in the synthesis example were determined using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK) and a column (KD-803, KD-805) (manufactured by Shodex). The measurement was performed as follows.
Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additive, lithium bromide-hydrate (LiBr · H ₂ O) 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol) / L, 10 ml / L of tetrahydrofuran (THF))
Flow rate: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).

"Measurement of imidization ratio of polyimide"
The imidation ratio of polyimide in the synthesis example was measured as follows. 20 mg of polyimide powder was put into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane)). (Mixed product) (0.53 ml) was added and completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Datum). The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid that appear in the vicinity of 9.5 ppm to 10.0 ppm. Using the integrated value, the following formula was used.
Imidization rate (%) = (1−α · x / y) × 100
In the above formula, x is a proton peak integrated value derived from NH group of amic acid, y is a peak integrated value of reference proton, α is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.

"Synthesis of polyimide polymers"
<Synthesis Example 1>
E1 (5.21 g, 26.6 mmol), A1 (5.12 g, 13.5 mmol) and B1 (2.05 g, 13.5 mmol) were mixed in NEP (37.1 g) and reacted at 40 ° C. for 8 hours. To obtain a polyamic acid solution (1) having a resin solid content concentration of 25% by mass. Mn (number average molecular weight) of this polyamic acid was 25,800, and Mw (weight average molecular weight) was 86,900.

<Synthesis Example 2>
E2 (3.22 g, 12.9 mmol), A2 (4.62 g, 11.7 mmol), B1 (1.78 g, 11.7 mmol) and D1 (0.28 g, 2.60 mmol) with NEP (24.8 g) After mixing at 80 ° C. for 5 hours, E1 (2.52 g, 12.9 mmol) and NEP (12.4 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. % Polyamic acid solution (2) was obtained. Mn of this polyamic acid was 23,100 and Mw was 76,400.

<Synthesis Example 3>
After adding NEP to the polyamic acid solution (2) (30.0 g) obtained in Synthesis Example 2 and diluting to 6% by mass, acetic anhydride (3.95 g) and pyridine (2.40 g) were used as imidization catalysts. In addition, the mixture was reacted at 70 ° C. for 3.5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (3). The imidation ratio of this polyimide was 75%, Mn was 21,100, and Mw was 57,500.

<Synthesis Example 4>
E2 (1.31 g, 5.23 mmol), A3 (3.44 g, 7.94 mmol), C1 (2.57 g, 10.6 mmol) and D2 (0.86 g, 7.94 mmol) NMP (24.5 g) After mixing at 80 ° C. for 5 hours, E1 (4.10 g, 20.9 mmol) and NMP (12.3 g) were added and reacted at 40 ° C. for 6 hours to give a resin solid concentration of 25 mass. % Polyamic acid solution was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidation catalyst, and 3. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (4). The imidation ratio of this polyimide was 80%, Mn was 15,900, and Mw was 43,800.

<Synthesis Example 5>
E2 (1.23 g, 4.91 mmol), A2 (3.92 g, 9.94 mmol), C2 (2.58 g, 9.94 mmol) and D2 (0.54 g, 4.97 mmol) to NMP (24.2 g) After mixing at 80 ° C. for 5 hours, E1 (3.85 g, 19.6 mmol) and NMP (12.1 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. % Polyamic acid solution was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (3.85 g) and pyridine (2.50 g) were added as imidization catalysts, and the mixture was heated at 60 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (5). The imidation ratio of this polyimide was 55%, Mn was 16,900, and Mw was 46,900.

<Synthesis Example 6>
E2 (2.55 g, 10.2 mmol), A4 (2.55 g, 5.17 mmol), B1 (0.39 g, 2.58 mmol), C2 (3.35 g, 12.9 mmol) and D2 (0.56 g, 5.17 mmol) was mixed in NEP (24.8 g) and reacted at 80 ° C. for 5 hours, then E1 (3.00 g, 15.3 mmol) and NEP (12.4 g) were added, and 6 ° C. The reaction was carried out for a time to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.
To the obtained polyamic acid solution (30.5 g), NEP was added to dilute to 6% by mass, then acetic anhydride (3.95 g) and pyridine (2.55 g) were added as an imidization catalyst, and the mixture was heated at 60 ° C. for 3 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (6). The imidation ratio of this polyimide was 61%, Mn was 16,000, and Mw was 44,800.

<Synthesis Example 7>
E2 (3.40 g, 13.6 mmol), B1 (4.19 g, 27.6 mmol) and D1 (0.74 g, 6.89 mmol) were mixed in NEP (24.7 g) and reacted at 80 ° C. for 5 hours. After that, E1 (4.00 g, 20.4 mmol) and NEP (12.3 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (7) having a resin solid content concentration of 25 mass%. . Mn of this polyamic acid was 27,500, and Mw was 90,100.

<Synthesis Example 8>
After adding NEP to the polyamic acid solution (7) (30.0 g) obtained in Synthesis Example 7 and diluting to 6% by mass, acetic anhydride (4.40 g) and pyridine (3.30 g) were used as imidization catalysts. In addition, it was reacted at 80 ° C. for 3.5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (8). The imidation ratio of this polyimide was 80%, Mn was 23,400, and Mw was 64,500.

<Synthesis Example 9>
E2 (3.96 g, 15.8 mmol), B1 (4.14 g, 27.2 mmol), C1 (0.39 g, 1.60 mmol) and D2 (0.35 g, 3.20 mmol) NEP (24.2 g) After mixing at 80 ° C. for 5 hours, E1 (3.10 g, 15.8 mmol) and NEP (12.1 g) were added and reacted at 40 ° C. for 6 hours to give a resin solid content concentration of 25 mass. % Polyamic acid solution was obtained.
After adding NEP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.00 g) and pyridine (2.50 g) were added as imidization catalysts, and the mixture was heated at 60 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (9). The imidation ratio of this polyimide was 53%, Mn was 19,900, and Mw was 55,100.

<Synthesis Example 10>
E3 (5.90 g, 26.3 mmol), A2 (4.21 g, 10.7 mmol), B1 (0.41 g, 2.67 mmol) and D2 (1.44 g, 13.3 mmol) were added to NMP (35.9 g). Then, the mixture was reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.35 g) were added as an imidization catalyst, and 3. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (10). The imidation ratio of this polyimide was 81%, Mn was 18,200, and Mw was 51,600.

<Synthesis Example 11>
E3 (5.50 g, 24.5 mmol), A4 (2.45 g, 4.97 mmol), B1 (0.19 g, 1.24 mmol), C2 (3.54 g, 13.7 mmol) and D2 (0.54 g, 4.97 mmol) was mixed in NMP (36.7 g) and reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.
After adding NMP to the obtained polyamic acid solution (30.5 g) and diluting to 6% by mass, acetic anhydride (3.90 g) and pyridine (2.60 g) were added as an imidization catalyst, and 3. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (11). The imidation ratio of this polyimide was 65%, Mn was 18,500, and Mw was 50,200.

<Synthesis Example 12>
E3 (7.50 g, 33.5 mmol), B1 (3.61 g, 23.7 mmol), C1 (0.41 g, 1.69 mmol) and D1 (0.92 g, 8.47 mmol) to NMP (37.3 g) Then, the mixture was reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.20 g) and pyridine (3.10 g) were added as an imidization catalyst, and 2. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (12). The imidation ratio of this polyimide was 75%, Mn was 19,800, and Mw was 53,900.

<Synthesis Example 13>
E4 (5.21 g, 17.3 mmol), A1 (4.60 g, 12.1 mmol), B1 (0.67 g, 4.39 mmol) and D1 (0.59 g, 5.49 mmol) to NEP (23.8 g) After mixing at 80 ° C. for 6 hours, E1 (0.85 g, 4.33 mmol) and NEP (11.9 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. % Polyamic acid solution was obtained.
To the obtained polyamic acid solution (30.0 g), NEP was added and diluted to 6% by mass, and then acetic anhydride (3.80 g) and pyridine (2.50 g) were added as an imidization catalyst, and the mixture was heated at 60 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (13). The imidation ratio of this polyimide was 55%, Mn was 16,800, and Mw was 45,300.

<Synthesis Example 14>
E4 (3.29 g, 11.0 mmol), A2 (3.51 g, 8.88 mmol), C1 (1.61 g, 6.66 mmol), C2 (1.15 g, 4.44 mmol) and D2 (0.24 g, 2.22 mmol) was mixed in NMP (23.9 g) and reacted at 80 ° C. for 6 hours, and then E1 (2.15 g, 11.0 mmol) and NMP (12.0 g) were added. The reaction was carried out for a time to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.
After adding NMP to the obtained polyamic acid solution (30.1 g) and diluting to 6% by mass, acetic anhydride (4.20 g) and pyridine (3.15 g) were added as an imidization catalyst, and 2. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (14). The imidation ratio of this polyimide was 73%, Mn was 15,900, and Mw was 43,800.

<Synthesis Example 15>
E5 (4.30 g, 20.3 mmol), A3 (3.89 g, 8.98 mmol), C2 (1.33 g, 5.13 mmol) and D2 (1.25 g, 11.6 mmol) NMP (23.5 g) After mixing at 80 ° C. for 6 hours, E1 (0.99 g, 5.07 mmol) and NMP (11.8 g) were added and reacted at 40 ° C. for 6 hours. The resin solid content concentration was 25 mass. % Polyamic acid solution was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (3.85 g) and pyridine (2.40 g) were added as an imidization catalyst, and the mixture was heated at 60 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (15). The imidation ratio of this polyimide was 51%, Mn was 15,700, and Mw was 44,500.

<Synthesis Example 16>
E5 (2.95 g, 13.9 mmol), A2 (3.71 g, 9.39 mmol), B1 (0.36 g, 2.35 mmol), C1 (1.14 g, 4.70 mmol), C2 (1.22 g, 4.70 mmol) and D1 (0.25 g, 2.35 mmol) were mixed in NEP (23.9 g), reacted at 80 ° C. for 6 hours, and then E2 (2.32 g, 9.27 mmol) and NEP ( 11.9 g) was added and reacted at 80 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.20 g) and pyridine (3.20 g) were added as imidization catalysts, and the mixture was heated at 80 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (16). The imidation ratio of this polyimide was 68%, Mn was 15,500, and Mw was 45,100.

<Synthesis Example 17>
E5 (4.10 g, 19.3 mmol), B1 (4.47 g, 29.4 mmol) and D2 (0.35 g, 3.26 mmol) were mixed in NMP (24.3 g) and reacted at 80 ° C. for 6 hours. After that, E2 (3.22 g, 12.9 mmol) and NMP (12.1 g) were added and reacted at 80 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.
After adding NMP to the obtained polyamic-acid solution (30.0g) and diluting to 6 mass%, acetic anhydride (4.20g) and a pyridine (3.20g) are added as an imidation catalyst, and 2. at 80 degreeC. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (17). The imidation ratio of this polyimide was 73%, Mn was 16,200, and Mw was 48,100.

<Synthesis Example 18>
E2 (2.85 g, 11.4 mmol), A1 (2.20 g, 5.77 mmol) and B1 (3.51 g, 23.1 mmol) were mixed in NEP (23.8 g) and reacted at 80 ° C. for 5 hours. After that, E1 (3.35 g, 17.1 mmol) and NEP (11.9 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (18) having a resin solid content concentration of 25 mass%. . Mn of this polyamic acid was 24,800, and Mw was 80,200.

<Synthesis Example 19>
After adding NEP to the polyamic acid solution (18) (30.0 g) obtained in Synthesis Example 18 and diluting to 6% by mass, acetic anhydride (4.40 g) and pyridine (3.35 g) were used as imidization catalysts. In addition, it was reacted at 80 ° C. for 3.5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (19). The imidation ratio of this polyimide was 79%, Mn was 18,400, and Mw was 47,200.

<Synthesis Example 20>
E2 (3.25 g, 13.0 mmol), B1 (1.80 g, 11.9 mmol), D1 (0.28 g, 2.60 mmol) and D3 (4.46 g, 11.9 mmol) were added to NMP (24.7 g). After mixing at 80 ° C. for 5 hours, E1 (2.55 g, 13.0 mmol) and NMP (12.4 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. % Polyamic acid solution was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.20 g) and pyridine (3.20 g) were added as an imidization catalyst, and the mixture was heated at 80 ° C. for 3 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (20). The imidation ratio of this polyimide was 75%, Mn was 14,600, and Mw was 41,200.
Tables 32 to 34 show the polyimide polymers.

* 1: Polyamic acid.

* 2: Polyamic acid.

* 3: Polyamic acid.

"Manufacture of liquid crystal alignment treatment agent"
In Examples 1 to 20 and Comparative Examples 1 to 7 described below, production examples of liquid crystal aligning agents are described. Moreover, this liquid crystal aligning agent was used also for evaluation.
The obtained liquid crystal aligning agents are shown in Table 35 to Table 37. In Tables 35 to 37, the following * 1 to * 5 represent the following meanings, respectively.
* 1: An introduction amount (parts by mass) of the specific polymer (A) with respect to 100 parts by mass of all polymers.
* 2: An introduction amount (parts by mass) of the specific polymer (B) with respect to 100 parts by mass of all polymers.
* 3: Indicates the introduction amount (parts by mass) of each solvent with respect to 100 parts by mass of all the solvents.
* 4: Indicates the ratio of all the polymers in the liquid crystal aligning agent.
* 5: Indicates the proportion of all polymers in the liquid crystal alignment treatment agent.

Using the liquid crystal alignment treatment agents obtained in Examples and Comparative Examples, “Evaluation of Ink-jet Coating Properties of Liquid Crystal Alignment Treatment Agents”, “Preparation of Liquid Crystal Cell and Evaluation of Pretilt Angle (Normal Cell)” “Evaluation of voltage holding ratio (normal cell)”, “Evaluation of relaxation of residual charge (normal cell)” and “Preparation of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell)” were performed.
"Evaluation of inkjet coating properties of liquid crystal alignment treatment agents"
Liquid crystal aligning agent (4) obtained in Example 4, liquid crystal aligning agent (7) obtained in Example 7, liquid crystal aligning agent (10) obtained in Example 10, obtained in Example 13 The obtained liquid crystal aligning agent (13) and the liquid crystal aligning agent (18) obtained in Example 18 were subjected to pressure filtration with a membrane filter having a pore diameter of 1 μm, and ink jet coatability was evaluated. As the ink jet coater, HIS-200 (manufactured by Hitachi Plant Technology) was used. Application is on an ITO (indium tin oxide) vapor-deposited substrate cleaned with pure water and IPA, the application area is 70 × 70 mm, the nozzle pitch is 0.423 mm, the scan pitch is 0.5 mm, and the application speed is 40 mm / Second, the time from application to provisional drying was 60 seconds, and provisional drying was performed on a hot plate at 70 ° C. for 5 minutes.
The coating properties of the obtained substrate with a liquid crystal alignment film were confirmed. Specifically, the coating film was visually observed under a sodium lamp to confirm the presence or absence of pinholes. As a result, in any of the liquid crystal alignment films obtained in any of the examples, no pinhole was found on the coating film, and a liquid crystal alignment film having excellent coating properties was obtained.

"Production of liquid crystal cell and evaluation of pretilt angle (normal cell)"
The liquid crystal aligning agents obtained in the examples and comparative examples were filtered under pressure through a membrane filter having a pore diameter of 1 μm to prepare a liquid crystal cell (normal cell). This solution was spin-coated on the ITO surface of a substrate with 100 × 100 mm ITO electrodes (length 100 mm × width 100 mm, thickness 0.7 mm) washed with pure water and IPA, and then on a hot plate at 100 ° C. for 5 minutes. Then, heat treatment was performed at 230 ° C. for 30 minutes in a heat circulation clean oven to obtain an ITO substrate with a polyimide liquid crystal alignment film having a film thickness of 100 nm. In addition, the liquid crystal aligning agent (4) obtained in Example 4, the liquid crystal aligning agent (7) obtained in Example 10, the liquid crystal aligning agent (10) obtained in Example 10, and Example 13 The liquid crystal alignment treatment agent (13) obtained in the above and the liquid crystal alignment treatment agent (18) obtained in Example 18 were subjected to liquid crystal alignment under the same conditions as in the above-mentioned “Evaluation of Ink-jet Coating Properties of Liquid Crystal Alignment Treatment Agent”. A substrate with a film was prepared, and then heat-treated at 230 ° C. for 30 minutes in a thermal circulation clean oven to obtain an ITO substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm.
The surface of the ITO substrate was rubbed using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.1 mm.
Two ITO substrates with the obtained liquid crystal alignment film were prepared, combined with a 6 μm spacer sandwiched with the liquid crystal alignment film surface on the inside, and the periphery was adhered with a sealant to prepare an empty cell. MLC-6608 (manufactured by Merck Japan) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell (ordinary cell).
Next, the pretilt angle of this liquid crystal cell (normal cell) was measured. The pretilt angle was measured after the liquid crystal cell was subjected to isotropic treatment (heat treatment at 95 ° C. for 5 minutes) and then heat treatment (heat treatment at 120 ° C. for 5 hours).
Furthermore, after the isotropic treatment was performed on the liquid crystal cell produced under the same conditions as described above, the liquid crystal cell after being irradiated with ultraviolet rays of 10 J / cm ^{2 in} terms of 365 nm was also measured. The pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON). Furthermore, ultraviolet irradiation was performed using a tabletop UV curing device (HCT3B28HEX-1) (manufactured by Senlite).
Evaluation is performed with respect to the pretilt angle after the liquid crystal isotropic treatment (also referred to after the Iso treatment) and after the heat treatment (also referred to as the high temperature treatment) and after the ultraviolet irradiation (also referred to as the ultraviolet irradiation). The smaller the change in angle, the better. (Tables 38 to 40 show pretilt angle values after Iso treatment, after high temperature treatment and after ultraviolet irradiation).
Tables 38 to 40 show the results obtained in the examples and comparative examples.

"Evaluation of voltage holding ratio (normal cell)"
The voltage holding ratio was evaluated using a liquid crystal cell (ordinary cell) produced under the same conditions as the above-mentioned “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”. Specifically, a voltage of 1 V is applied to the liquid crystal cell (ordinary cell) obtained by the above method at a temperature of 80 ° C. for 60 μs, the voltage after 50 ms is measured, and how much the voltage is maintained. It was calculated as a voltage holding ratio (also referred to as VHR). The measurement was performed using a voltage holding ratio measuring device (VHR-1, manufactured by Toyo Technica Co., Ltd.) with settings of Voltage: ± 1 V, Pulse Width: 60 μs, and Frame Period: 50 ms.
Furthermore, the liquid crystal cell whose voltage holding ratio was measured immediately after the liquid crystal cell was manufactured was irradiated with ultraviolet rays of 50 J / cm ^{2 in} terms of 365 nm using a desktop UV curing device (HCT3B28HEX-1, manufactured by Senlite). The voltage holding ratio was measured under the same conditions as described above.
The value of the voltage holding ratio immediately after the production of the liquid crystal cell is high, and the smaller the decrease in the value after the ultraviolet irradiation with respect to the voltage holding ratio immediately after the production of the liquid crystal cell, the better (Table 41). Table 43 shows values of VHR immediately after the liquid crystal cell was produced and after UV irradiation. Tables 41 to 43 show the results obtained in Examples and Comparative Examples.

"Evaluation of residual charge relaxation (normal cell)"
Evaluation of relaxation of residual charges was performed using a liquid crystal cell (normal cell) manufactured under the same conditions as the above-mentioned “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”. Specifically, a DC voltage of 10 V was applied to the liquid crystal cell for 30 minutes and short-circuited for 1 second, and then the potential generated in the liquid crystal cell was measured for 1800 seconds. Among them, the value of the residual charge after 50 seconds was used to evaluate the relaxation of the residual charge. In addition, the measurement used the 6254 type liquid crystal physical-property evaluation apparatus (Toyo Technica company make).
Furthermore, the residual charge immediately after the above liquid crystal cell was measured was irradiated with 30 J / cm ² of UV converted to 365 nm using a desktop UV curing device (HCT3B28HEX-1) (manufactured by Senlite). Then, the residual charge was measured under the same conditions as described above.
In the evaluation, the smaller the value of the residual charge immediately after the production of the liquid crystal cell and after the ultraviolet irradiation, the better the results (Tables 41 to 43 show the VHR values immediately after the production of the liquid crystal cell and after the ultraviolet irradiation). Tables 41 to 43 show the results obtained in Examples and Comparative Examples.

"Production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)"
Liquid crystal aligning agent (2) obtained in Example 2, liquid crystal aligning agent (3) obtained in Example 3, liquid crystal aligning agent (9) obtained in Example 9, and obtained in Example 11 The obtained liquid crystal aligning agent (11) and the liquid crystal aligning agent (14) obtained in Example 14 were pressure filtered through a membrane filter having a pore diameter of 1 μm to prepare a liquid crystal cell and evaluate liquid crystal alignment (PSA cell). ) This solution was washed with pure water and IPA at the center with a 10 × 10 mm substrate with an ITO electrode having a pattern spacing of 20 μm (length 40 mm × width 30 mm, thickness 0.7 mm) and a substrate with an ITO electrode 10 × 40 mm at the center. Spin coated on ITO surface (length 40mm x width 30mm, thickness 0.7mm), heat-treated on a hot plate at 100 ° C for 5 minutes, and heat-circulating clean oven at 230 ° C for 30 minutes to form a film A polyimide coating film having a thickness of 100 nm was obtained.
This substrate with a liquid crystal alignment film was combined with a 6 μm spacer sandwiched with the liquid crystal alignment film surface inside, and the periphery was adhered with a sealant to produce an empty cell. A nematic liquid crystal (MLC-6608) (manufactured by Merck Japan) was added to the empty cell by a reduced pressure injection method, and a polymerizable compound (1) represented by the following formula was added to 100% by mass of the nematic liquid crystal (MLC-6608). Liquid crystal mixed with 0.3% by mass of the polymerizable compound (1) was injected, and the injection port was sealed to obtain a liquid crystal cell.

While applying an AC voltage of 5 V to the obtained liquid crystal cell, using a metal halide lamp with an illuminance of 60 mW, the wavelength of 350 nm or less was cut, and ultraviolet irradiation of 20 J / cm ^{2 in} terms of 365 nm was performed, and the alignment direction of the liquid crystal A liquid crystal cell (PSA cell) was controlled. The temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was 50 ° C.
The response speed of the liquid crystal before and after the ultraviolet irradiation of the liquid crystal cell was measured. As the response speed, T90 → T10 from 90% transmittance to 10% transmittance was measured.
The PSA cell obtained in any of the examples confirmed that the alignment direction of the liquid crystal was controlled because the response speed of the liquid crystal cell after ultraviolet irradiation was higher than that of the liquid crystal cell before ultraviolet irradiation. . Further, in any liquid crystal cell, it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) that the liquid crystal was uniformly aligned.

<Example 1>
Polyamic acid solution (1) (5.00 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 1 and a polyamic acid solution (7) (3) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 7 .30 g), NEP (13.3 g), BCS (9.80 g), EC (3.30 g) and M1 (0.21 g) were added and stirred at 25 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (1 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 2>
Polyamic acid solution (2) (6.50 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2 and a polyamic acid solution (7) (2) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 7 NEP (14.9 g) and BCS (14.5 g) were added to .80 g), and the mixture was stirred at 25 ° C. for 4 hours to obtain a liquid crystal aligning agent (2). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 3>
NEP (17.2 g) is added to the polyimide powder (3) (1.00 g) obtained in Synthesis Example 3 and the polyimide powder (8) (1.00 g) obtained in Synthesis Example 8, and 24 ° C. at 24 ° C. Stir for hours to dissolve. To this solution, PB (14.1 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (3). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 4>
NEP (19.2 g) is added to the polyimide powder (3) (0.65 g) obtained in Synthesis Example 3 and the polyimide powder (8) (0.65 g) obtained in Synthesis Example 8, and 24 ° C. at 24 ° C. Stir for hours to dissolve. To this solution, BCS (7.20 g) and PB (10.8 g) were added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (4). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 5>
NMP (18.5 g) is added to the polyimide powder (4) (1.65 g) obtained in Synthesis Example 4 and the polyimide powder (8) (0.71 g) obtained in Synthesis Example 8, and 24 ° C. at 24 ° C. Stir for hours to dissolve. BCS (18.5g) and M1 (0.12g) were added to this solution, and it stirred at 40 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (5). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 6>
NMP (2.96 g) and NEP (4.48 g) were added to the polyimide powder (5) (0.95 g) obtained in Synthesis Example 5, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (7.44 g) was added and stirred at 40 ° C. for 4 hours to obtain a solution.
On the other hand, NMP (4.44 g) and NEP (6.72 g) were added to the polyimide powder (9) (1.43 g) obtained in Synthesis Example 9, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (11.2 g) was added and stirred at 40 ° C. for 4 hours to obtain a solution.
The two solutions obtained above were mixed and stirred at 25 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (6). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 7>
NMP (4.10 g) and NEP (20.7 g) were added to the polyimide powder (5) (0.45 g) obtained in Synthesis Example 5 and the polyimide powder (9) (1.05 g) obtained in Synthesis Example 9. And dissolved by stirring at 70 ° C. for 24 hours. PB (16.5g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (7). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 8>
NMP (21.5 g) was added to the polyimide powder (5) (0.75 g) obtained in Synthesis Example 5 and the polyimide powder (17) (1.75 g) obtained in Synthesis Example 17, and 24 ° C. at 24 ° C. Stir for hours to dissolve. To this solution, BCS (13.7 g), DME (3.90 g) and M1 (0.25 g) were added and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (8). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 9>
NEP (11.8 g) was added to the polyimide powder (6) (1.25 g) obtained in Synthesis Example 6 and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (1.98 g) and PB (5.89 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
On the other hand, NEP (9.60 g) was added to the polyimide powder (12) (1.02 g) obtained in Synthesis Example 12, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (1.62 g) and PB (4.81 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
The two solutions obtained above were mixed, M1 (0.07 g) was added thereto, and the mixture was stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (9). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 10>
To the polyimide powder (6) (0.55 g) obtained in Synthesis Example 6 and the polyimide powder (12) (0.83 g) obtained in Synthesis Example 12, NMP (19.0 g) and γ-BL (3. 80 g) was added and dissolved by stirring at 70 ° C. for 24 hours. PB (15.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (10). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 11>
To the polyimide powder (10) (0.65 g) obtained in Synthesis Example 10 and the polyimide powder (8) (1.52 g) obtained in Synthesis Example 8, NMP (3.40 g) and NEP (17.0 g) And dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (3.40 g) and PB (10.2 g) were added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (11). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 12>
To the polyimide powder (11) (1.65 g) obtained in Synthesis Example 11 and the polyimide powder (12) (0.71 g) obtained in Synthesis Example 12, NEP (16.6 g) and γ-BL (3. 70 g) was added and dissolved by stirring at 70 ° C. for 24 hours. PB (16.6g) and M1 (0.24g) were added to this solution, and it stirred at 40 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (12). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 13>
NMP (3.90 g) and NEP (15.6 g) were added to the polyimide powder (11) (0.85 g) obtained in Synthesis Example 11 and the polyimide powder (12) (0.57 g) obtained in Synthesis Example 12. And dissolved by stirring at 70 ° C. for 24 hours. PB (19.5g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (13). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
went.

<Example 14>
NMP (7.50 g) and NEP (3.75 g) were added to the polyimide powder (13) (1.20 g) obtained in Synthesis Example 13, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (3.75 g) and DME (3.75 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
On the other hand, NMP (7.50 g) and NEP (3.75 g) were added to the polyimide powder (9) (1.20 g) obtained in Synthesis Example 9, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (3.75 g) and DME (3.75 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
The two solutions obtained above were mixed and stirred at 25 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (14). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 15>
NMP (5.70 g) and NEP (15.1 g) were added to the polyimide powder (14) (1.45 g) obtained in Synthesis Example 14 and the polyimide powder (8) (0.97 g) obtained in Synthesis Example 8. And dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (17.0 g) and M1 (0.07 g) were added and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (15). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 16>
NMP (6.90 g) and NEP (13.7 g) were added to the polyimide powder (15) (1.75 g) obtained in Synthesis Example 15 and the polyimide powder (9) (0.44 g) obtained in Synthesis Example 9. And dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (13.7 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (16). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 17>
NMP (11.9 g) and NEP (6.80 g) were added to the polyimide powder (16) (0.65 g) obtained in Synthesis Example 16 and the polyimide powder (17) (1.52 g) obtained in Synthesis Example 17. And dissolved by stirring at 70 ° C. for 24 hours. BCS (15.3 g) was added to this solution and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (17). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 18>
To the polyimide powder (16) (0.35 g) obtained in Synthesis Example 16 and the polyimide powder (17) (1.05 g) obtained in Synthesis Example 17, NEP (11.6 g) and γ-BL (5. 80 g) was added and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (21.2 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (18). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 19>
NMP (7.80 g) and NEP (13.7 g) were added to the polyimide powder (16) (0.75 g) obtained in Synthesis Example 16 and the polyimide powder (8) (1.75 g) obtained in Synthesis Example 8. And dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (13.7 g), EC (3.90 g) and M1 (0.13 g) were added and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (19). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 20>
To the polyamic acid solution (2) (1.88 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2 and the polyimide powder (17) (0.50 g) obtained in Synthesis Example 17, NEP (15. 7 g) was added and dissolved by stirring at 70 ° C. for 24 hours. BCS (7.40g) and PB (7.40g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (20). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Comparative Example 1>
NEP (15.2 g) and BCS (14.9 g) were added to the polyamic acid solution (2) (9.50 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2, and the mixture was stirred at 25 ° C. for 4 hours. And the liquid-crystal aligning agent (21) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Comparative example 2>
NEP (14.4 g) and BCS (14.1 g) were added to the polyamic acid solution (7) (9.00 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 7, and the mixture was stirred at 25 ° C. for 4 hours. As a result, a liquid crystal aligning agent (22) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Comparative Example 3>
NEP (19.4 g) was added to the polyimide powder (3) (2.25 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (15.9 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (23). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Comparative example 4>
NEP (19.0 g) was added to the polyimide powder (8) (2.20 g) obtained in Synthesis Example 8, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (15.5 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (24). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Comparative Example 5>
Polyamic acid solution (2) (7.00 g) with a resin solid content concentration of 25% by mass obtained in Synthesis Example 2 and a polyamic acid solution (18) (3) with a resin solid content concentration of 25% by mass obtained in Synthesis Example 18 NEP (16.0 g) and BCS (15.7 g) were added to 0.000 g), and the mixture was stirred at 25 ° C. for 4 hours to obtain a liquid crystal aligning agent (25). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Comparative Example 6>
NEP (18.1 g) is added to the polyimide powder (3) (1.05 g) obtained in Synthesis Example 3 and the polyimide powder (19) (1.05 g) obtained in Synthesis Example 19, and 24 ° C. at 24 ° C. Stir for hours to dissolve. To this solution, PB (14.8 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (26). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Comparative Example 7>
NEP (17.2 g) was added to the polyimide powder (20) (1.00 g) obtained in Synthesis Example 20 and the polyimide powder (8) (1.00 g) obtained in Synthesis Example 8, and 24 ° C. at 24 ° C. Stir for hours to dissolve. To this solution, PB (14.1 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (27). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
<Evaluation of liquid crystal aligning agent>
Using each liquid crystal alignment treatment agent obtained in each of Examples 1 to 20 and Comparative Examples 1 to 7, “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio ( "Normal cell)" and "Evaluation of relaxation of residual charge (normal cell)". In addition, about each liquid-crystal aligning agent obtained in Example 4, 7, 10, 13, 18, respectively, the inkjet applicability | paintability was also evaluated.
The results of these evaluations are summarized in Table 39 to Table 43 below.

* 1: The liquid crystal was not vertically aligned.

* 1: Measurement was not possible because the liquid crystal was not vertically aligned.

As can be seen from the above results, the liquid crystal alignment treatment agents of the examples showed a stable pretilt angle even when the liquid crystal cell was subjected to high temperature treatment and ultraviolet irradiation, as compared with the comparative example. Furthermore, even if ultraviolet irradiation is performed, the decrease in the voltage holding ratio is suppressed, and the residual charge accumulated by the DC voltage is quickly relaxed. That is, the liquid crystal composition treating agent of the present invention becomes a liquid crystal alignment film that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time, and in addition, has been exposed to light irradiation for a long time. Even after this, a liquid crystal alignment film is obtained in which the decrease in the voltage holding ratio is suppressed and the residual charge accumulated by the DC voltage is quickly relaxed.

Specifically, a comparison between an example of a liquid crystal aligning agent using a specific polymer (A) and a specific polymer (B) and an example of a liquid crystal aligning agent using only one of them. That is, a comparison between Example 2 and Comparative Example 1 or Comparative Example 2, and a comparison between Example 3 and Comparative Example 3 or Comparative Example 4. Comparative Example 1 and Comparative Example 3 using only these specific polymers (A) have a larger range of change in the pretilt angle after high temperature treatment and ultraviolet irradiation compared to the corresponding examples, and these treatments On the other hand, the voltage holding ratio was greatly reduced, and the residual charge value was also increased. In particular, the decrease in the voltage holding ratio was particularly large. In Comparative Examples 2 and 4, the liquid crystal was not aligned vertically.

Furthermore, Examples of liquid crystal alignment treatment agents using Example specific polymer (A) and specific polymer (B), specific polymer (A) and specific side chain structure represented by the above formula [1] Comparison with a comparative example of a liquid crystal aligning agent using a polymer using a specific side chain type diamine compound having a difference, that is, a comparison between Example 2 and Comparative Example 5, Example 3 and Comparative Example 6 It is a comparison. In these comparative examples, the change width of the pretilt angle after performing high temperature treatment and ultraviolet irradiation is larger than that of the corresponding examples, and the voltage holding ratio is greatly reduced with respect to these treatments. The charge value also increased. In particular, the decrease in voltage holding ratio and the value of residual charge were large.

In addition, an example of a liquid crystal aligning agent using the specific polymer (A) and the specific polymer (B), a polymer having a conventional side chain structure, and the specific polymer (B) were used. It is a comparison with a comparative example of a liquid crystal aligning agent, that is, a comparison between Example 3 and Comparative Example 7. Compared with Example 3, the comparative example 7 has a large change width of the pretilt angle after the high temperature treatment and the ultraviolet irradiation, and the voltage holding ratio is greatly reduced with respect to these treatments. The charge value also increased. In particular, the change width of the pretilt angle after the ultraviolet irradiation was large.

The liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. In addition, it is possible to provide a liquid crystal alignment film that suppresses a decrease in the voltage holding ratio even after being exposed to light irradiation for a long time and quickly relaxes residual charges accumulated by a DC voltage. In addition, the liquid crystal display element which has said liquid crystal aligning film, and the liquid-crystal aligning agent which can provide said liquid crystal aligning film can be provided.

Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has excellent reliability, and can be suitably used for a large-screen, high-definition liquid crystal television, etc. It is useful for a device, a TFT liquid crystal device, particularly a vertical alignment type liquid crystal display device.

Furthermore, the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is also useful for a liquid crystal display element that needs to be irradiated with ultraviolet rays when producing a liquid crystal display element. That is, a liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. A liquid crystal display element manufactured through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes, and further comprising a liquid crystal layer between a pair of substrates provided with electrodes, A liquid crystal produced through a step of placing a liquid crystal alignment film containing a polymerizable group that polymerizes at least one of active energy rays and heat between substrates and polymerizing the polymerizable group while applying a voltage between the electrodes. It is also useful for display elements.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2013-182352 filed on September 3, 2013 are incorporated herein as the disclosure of the specification of the present invention. It is.

Claims

The liquid crystal aligning agent characterized by containing the following (A) component and (B) component.
Component (A): at least one selected from the group consisting of a polyimide precursor obtained by reacting a diamine component containing a diamine having a structure represented by the following formula [1] and a tetracarboxylic acid component and a polyimide. Polymer.
(B) component: At least 1 sort (s) chosen from the group which consists of the polyimide precursor obtained by making the diamine component and tetracarboxylic acid component which do not contain the diamine which has a structure shown by following formula [1] react, and a polyimide. Polymer.

(Y 1 represents a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—, where Y 2 represents a single bond. Or (CH 2 ) b — (b is an integer of 1 to 15) Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO— Y 4 represents a divalent organic group having a carbon number of 17 to 51 having a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a steroid skeleton. Any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine atom having 1 to 3 carbon atoms optionally substituted with-containing alkoxyl group or a fluorine atom .Y 5 is a benzene ring, cyclohexenone A divalent cyclic group selected from an aromatic ring and a heterocyclic ring, and any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms. 3 may be substituted with a fluorine-containing alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, n represents an integer of 0 to 4. Y 6 is an alkyl group having 1 to 18 carbon atoms, A fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms).
The liquid crystal aligning agent according to claim 1, wherein the diamine having the structure represented by the formula [1] is represented by the following formula [1a].

(Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , n, Y 6 and m have the same meaning as described above).
The polyimide precursor 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) with a tetracarboxylic acid component. The liquid-crystal aligning agent of Claim 1 or 2 which is at least 1 sort (s) of polymer chosen from the group which consists of a body and a polyimide.
The polymer (A) is a polymer used for a diamine component further comprising a diamine having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group). Or the liquid-crystal aligning agent of 3.
The liquid crystal aligning agent according to claim 3 or 4, wherein the diamine having at least one substituent selected from the carboxyl group and the hydroxyl group is represented by the following formula [2a].

(A 1 represents at least one substituent selected from the following formulas [2a-1] and [2a-2], and m1 represents an integer of 1 to 4).

(D represents an integer of 0 to 4, and e represents an integer of 0 to 4).
6. The liquid crystal alignment according to claim 1, wherein the polymer of the component (A) and the component (B) is a polymer using a diamine represented by the following formula [3a] as a diamine component. Processing agent.

(B 1 is —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCO—, —CON (CH 3 ) — or N (CH 3 ) CO— B 2 represents a single bond, alkylene having 1 to 20 carbon atoms, non-aromatic ring or aromatic ring B 3 represents a single bond, —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH 3 ) —, N (CH 3 ) CO—, or —O (CH 2 ) m2 — (where m2 is 1 to 5) B 4 represents a nitrogen-containing heterocyclic ring, n1 represents an integer of 1 to 4, and when n1 is 2 or more, -B 1 -B 2 -B 3 -B 4 may be the same as each other May be different).
The B 1 in the formula [3a] is —O—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCO— or CON (CH 3 ) —. Liquid crystal alignment treatment agent.
The liquid crystal aligning agent according to claim 6 or 7, wherein B 2 in the formula [3a] is a single bond, an alkylene having 1 to 5 carbon atoms, a cyclohexane ring or a benzene ring.
B 3 in the formula [3a] is a single bond, —O—, —OCO—, or O (CH 2 ) 2 — (m2 is an integer of 1 to 5). The liquid crystal aligning agent according to one item.
The liquid crystal aligning agent according to any one of claims 6 to 9, wherein B 4 in the formula [3a] is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring.
B 1 in the formula [3a] represents —CONH—, B 2 represents alkylene having 1 to 5 carbon atoms, B 3 represents a single bond, B 4 represents an imidazole ring or a pyridine ring, and n 1 The liquid crystal aligning agent according to claim 6, wherein is 1.
The tetracarboxylic acid component in at least one of the component (A) and the component (B) contains a tetracarboxylic dianhydride represented by the following formula [4]. Liquid crystal aligning agent.

(Z 1 is a group selected from the following formulas [4a] to [4k]).

(Z 2 to Z 5 each independently represents an elementary atom, a methyl group, a chlorine atom or a benzene ring, and Z 6 and Z 7 each independently represents a hydrogen atom or a methyl group.)
The liquid crystal aligning agent according to any one of claims 1 to 12, comprising at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone.
The liquid crystal aligning agent according to any one of claims 1 to 13, comprising at least one solvent selected from the following formulas [D-1] to [D-3].

(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).
Containing at least one solvent selected from 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether; 14. The liquid crystal aligning agent as described in any one of 14.
The liquid crystal aligning agent has at least one substituent selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. The liquid crystal aligning agent according to any one of claims 1 to 15, comprising at least one crosslinkable compound selected from a crosslinkable compound and a crosslinkable compound having a polymerizable unsaturated bond.
A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of claims 1 to 16.
A liquid crystal alignment film obtained by printing the liquid crystal aligning agent according to any one of claims 1 to 16 by an ink jet method.
A liquid crystal display element having the liquid crystal alignment film according to claim 17 or 18.
A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and between the electrodes 19. The liquid crystal alignment film according to claim 17, wherein the liquid crystal alignment film is used in a liquid crystal display device manufactured through a step of polymerizing the polymerizable compound while applying a voltage.
A liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates; The liquid crystal alignment film according to claim 17 or 18, which is used for a liquid crystal display element produced through a step of polymerizing the polymerizable group while applying a voltage therebetween.
A liquid crystal display element having the liquid crystal alignment film according to claim 20 or 21.