KR20170101277A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

A liquid crystal alignment film capable of suppressing a decrease in voltage holding ratio and not causing display irregularities in the vicinity of a frame of a liquid crystal display element, a liquid crystal display device having the liquid crystal alignment film, and a liquid crystal alignment treatment agent capable of forming the liquid crystal alignment film. A liquid crystal alignment treatment agent comprising the following components (A), (B) and (C). (A): A polyimide precursor obtained by the reaction of a diamine having a structure represented by the following formula [1] and a diamine component containing a diamine having a structure represented by the following formula [2] with a tetracarboxylic acid component or A polyimide obtained by imidizing the polyimide precursor. Component (B): A polyimide precursor obtained by the reaction of a diamine component containing a diamine having a structure represented by the following formula [2] with a tetracarboxylic acid component, or a polyimide precursor obtained by imidizing the polyimide precursor. (C): a polyimide precursor obtained by the reaction of a diamine component containing a diamine having at least one substituent selected from the group consisting of a carboxy group (COOH group) and a hydroxyl group (OH group) and a tetracarboxylic acid component Or a polyimide obtained by imidizing the polyimide precursor. (X ¹ is a single bond, etc., X ² is a single bond, etc., X ² is a single bond, etc., X ⁴ is a benzene ring, X ⁵ is a benzene ring, n is an integer of 0 ~ 4, X ⁶ is C 1 -C (W ¹ represents -O-, W ² represents a single bond, W ³ represents a single bond, and W ⁴ represents a nitrogen-containing aromatic heterocyclic ring.)

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element,

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

BACKGROUND ART [0002] Liquid crystal display devices are widely used today as display devices that realize thinness and light weight. A liquid crystal alignment film is usually used in this liquid crystal display element to determine the alignment state of the liquid crystal.

The liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal. However, with the high definition of liquid crystal display elements, there has been a demand for suppressing the display defects accompanying the contrast of liquid crystal display elements or long-term use. As opposed to these, there is proposed a liquid crystal alignment film using a liquid crystal alignment treatment agent to which an alkoxysilane compound is added as a method for enhancing the liquid crystal alignment property and making display defects less likely to occur in the periphery of the liquid crystal display screen in the liquid crystal alignment film using polyimide Patent Documents 1 and 2).

In addition, from the viewpoints of suppressing the lowering of the contrast of the liquid crystal display element and reducing the afterimage phenomenon as the liquid crystal display element is made more precise, the liquid crystal alignment film used therein has a higher voltage holding ratio and a higher DC voltage The charge accumulation at the time when the DC voltage is reduced or the characteristic that the charge accumulated by the DC voltage is fast is becoming increasingly important.

In the polyimide-based liquid crystal alignment film, a liquid crystal alignment treatment agent containing a tertiary amine having a specific structure, in addition to a polyamic acid or an imide group-containing polyamic acid, has a short time until the after- (See, for example, Patent Document 3), and a liquid crystal alignment treatment agent containing a soluble polyimide in which a specific diamine having a pyridine skeleton or the like is used as a raw material (see Patent Document 4).

It is also possible to use a compound having one carboxylic acid group in the molecule in addition to the polyamic acid and its imidized polymer, such as a compound having a high voltage holding ratio and a short time until the afterimage caused by the DC voltage disappears, There is known a liquid crystal alignment treatment agent containing a carboxylic acid anhydride group-containing compound and a compound selected from compounds containing one tertiary amino group in the molecule in a very small amount (see Patent Document 5).

Japanese Patent Application Laid-Open No. 61-171762 Japanese Patent Application Laid-Open No. 11-119226 Japanese Patent Application Laid-Open No. 9-316200 Japanese Patent Application Laid-Open No. 10-104633 Japanese Patent Application Laid-Open No. 8-76128

2. Description of the Related Art Recently, liquid crystal display devices have been used for mobile applications such as smart phones and cellular phones. In these applications, it is necessary to narrow the width of the sealant used for bonding the substrates of the liquid crystal display elements to each other in order to secure as much display surface as possible. For the reasons described above, it is also required to position the sealing agent at the position where the sealant is in contact with the end portion of the liquid crystal alignment film having poor adhesiveness to the sealant or the liquid crystal alignment film. In such a case, the use under high temperature and high humidity conditions tends to cause water to be mixed between the sealant and the liquid crystal alignment film, resulting in display irregularities near the frame of the liquid crystal display element. Therefore, it is required to increase the adhesion between the sealing agent and the liquid crystal alignment film, and to suppress the defective display unevenness.

In addition, with respect to the voltage holding ratio, which is one of the electric characteristics of the liquid crystal display element, high stability under such a severe condition is also required. That is, if the voltage holding ratio is lowered by the light irradiation from the backlight, an exposure failure (also referred to as line exposure), which is one of the display defects of the liquid crystal display element, tends to occur and a highly reliable liquid crystal display element is obtained I can not. Therefore, in addition to good initial characteristics, it is required that the liquid crystal alignment film is hard to lower the voltage holding ratio even after exposure to light for a long time, for example. In addition, a liquid crystal alignment film that is capable of alleviating the residual charges accumulated by the direct current voltage by irradiation of light from the backlight is also required for another surface exposure which is an exposure failure.

Therefore, it is an object of the present invention to provide a liquid crystal alignment film having the above characteristics. That is, an object of the present invention is to provide a liquid crystal alignment film capable of enhancing adhesion between a sealant and a liquid crystal alignment film, and suppressing occurrence of display unevenness in the vicinity of a frame of the liquid crystal display element under high temperature and high humidity conditions . It is another object of the present invention to provide a liquid crystal alignment film capable of suppressing a decrease in the voltage holding ratio even after exposure to light for a long time and also alleviating the residual charges accumulated by the direct current voltage.

It is another object of the present invention to provide a liquid crystal display element having the above liquid crystal alignment film and a liquid crystal alignment treatment agent capable of providing the above liquid crystal alignment film.

As a result of intensive studies, the inventors of the present invention have found that a liquid crystal alignment treating agent comprising three polymers having a specific structure is very effective for achieving the above object, and has completed the present invention.

That is, the present invention has the following points.

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

(A): A polyimide precursor obtained by the reaction of a diamine having a structure of the following formula [1] and a diamine component containing a diamine having a structure of the following formula [2] and a tetracarboxylic acid component, Polyimide imidized precursor.

Component (B): A polyimide precursor obtained by the reaction of a diamine component containing a diamine having the structure represented by the following formula [2] with a tetracarboxylic acid component, or a polyimide precursor obtained by imidizing the polyimide precursor.

(C): a polyimide precursor obtained by the reaction of a diamine component containing a diamine having at least one substituent selected from the group consisting of a carboxy group (COOH group) and a hydroxyl group (OH group) and a tetracarboxylic acid component Or a polyimide obtained by imidizing the polyimide precursor.

However, the diamine component in at least one of the components (A), (B) and (C) contains a diamine having the structure of the following formula [4].

[Chemical Formula 1]

(X ¹ is at least one selected from the group consisting of a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- and -OCO- It shows a longitudinal coupler of X ² is a single bond or _{-. (CH 2) b -} . represents a (b is an integer of 1 to 15) X ³ is a single _{bond, - (CH 2) c -} (c is 1 to -O-, -CH ₂ O-, -COO- and -OCO-, X ⁴ represents a group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring , Or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, and any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms the alkoxy group, the number of carbon atoms may be substituted one to three fluorine-containing alkyl group, fluorine-containing alkoxy group or a fluorine atom of 1 to 3 carbon atoms in. X ⁵ is a benzene ring, An alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom, n is an integer of 0 to 4. X ⁶ is an alkyl group having 1 to 18 carbon atoms, An alkyl group, an alkoxy group having 1 to 18 carbon atoms, and a fluorine-containing alkoxy group having 1 to 18 carbon atoms.

(2)

(W ¹ is -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ ) ₃ ) CO-, and W ² represents at least one member selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring and an aromatic ring. W ³ is a single bond, -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH ₃ ) -, -N ₃ ) CO- and -O (CH ₂ ) _m - (m represents an integer of 1 to 5), and W ⁴ represents a nitrogen-containing aromatic heterocyclic ring.

(3)

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

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

(4) The use of the diamine represented by the formula (1) in the component (C) in the component (A), wherein the use ratio (mol%) of the diamine having the structure represented by the formula The liquid crystal alignment treating agent according to the above (1) or (3), wherein the usage ratio (mol%) of the diamine having the structure represented by [1] to the whole diamine component is in the range of 0.01 to 0.3.

(5) The positive resist composition as described in (1) above, wherein the diamine having at least one substituent selected from the group consisting of the carboxyl group (COOH group) and the hydroxyl group (OH group) is used only for the diamine component in the component (C) To (4) above.

(6) The liquid crystal alignment treating agent according to any one of (1) to (5) above, wherein the diamine having the structure of the formula [4] is used only for the diamine component in the component (A).

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

[Chemical Formula 4]

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

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

[Chemical Formula 5]

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

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

[Chemical Formula 6]

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

(7)

(a and b each represent an integer of 0 to 4).

(10) The liquid crystal alignment treating agent according to any one of (1) to (9), wherein the diamine having the structure of the formula [4] is represented by the following formula [4a-1].

[Chemical Formula 8]

(q1 represents an integer of 1 to 8).

(11) The composition according to any one of (1) to (10) above, wherein the tetracarboxylic acid component in the component (A), component (B) and component (C) comprises a tetracarboxylic acid dianhydride represented by the following formula [ ) Of the liquid crystal alignment treatment agent.

[Chemical Formula 9]

(Wherein Z represents at least one structure selected from the group consisting of the following formulas [5a] to [5k]).

[Chemical formula 10]

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

(12) The liquid crystal composition according to any one of (1) to (11) above, which contains at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N- Wherein the liquid crystal alignment treatment agent is a liquid crystal alignment agent.

(13) A process for producing a polyether polyol as described in any one of (1) to (13), which comprises reacting 1-hexanol, cyclohexanol, 1,2-ethanediol, The liquid crystal alignment treatment agent according to any one of (1) to (12) above, which contains at least one solvent selected from the group consisting of a solvent of the formula [D3].

(11)

(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.)

(14) a crosslinkable compound having at least one group selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group and a cyclocarbonate group, at least one member selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group (1) to (13), wherein the liquid crystal alignment treatment agent contains a crosslinkable compound having a group of a polymerizable unsaturated bond group or a crosslinkable compound having a polymerizable unsaturated bonding group.

(15) A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of (1) to (14).

(16) A liquid crystal alignment film obtained by applying the liquid crystal alignment treatment agent according to any one of (1) to (14) by an ink jet method.

(17) A liquid crystal display element having the liquid crystal alignment film according to (15) or (16) above.

(18) A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes, and comprising a polymerizable compound polymerized by at least one of active energy rays and heat between the pair of substrates, (15) or (16), wherein the liquid crystal alignment film is used for a liquid crystal display device manufactured by a process of polymerizing the polymerizable compound while applying a voltage between the electrodes.

(19) A liquid crystal display element having the liquid crystal alignment film according to (18) above.

(20) A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes, and comprising a polymerizable group polymerized by at least one of active energy rays and heat between the pair of substrates (15) or (16), which is used for a liquid crystal display element manufactured through a step of disposing a polymerizable group and polymerizing the polymerizable group while applying a voltage between the electrodes.

(21) A liquid crystal display element having the liquid crystal alignment film according to (20) above.

The liquid crystal alignment treatment agent of the present invention can improve the adhesion between the sealant and the liquid crystal alignment film and obtain a liquid crystal alignment film capable of suppressing occurrence of display unevenness in the vicinity of the frame of the liquid crystal display element under high temperature and high humidity conditions. It is also possible to obtain a liquid crystal alignment film which is capable of suppressing a decrease in the voltage holding ratio and also alleviating the residual charges accumulated by the direct current voltage even after exposure to light for a long time.

The mechanism by which the liquid crystal display element having the excellent characteristics described above can be obtained by the present invention is presumed to be as follows, though not necessarily clear.

The specific structure (1) in a specific polymer (A) has a benzene ring, a cyclohexane ring, a divalent organic group having 17 to 51 carbon atoms having a heterocyclic or steroid skeleton. The side chain structure of these rings and organic groups is stricter than the long chain alkyl group of the prior art for orienting the liquid crystal vertically and is a structure stable to light such as ultraviolet rays. Therefore, a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent having a specific side chain structure has a lower decomposition rate of the decomposition product of the side chain component for lowering the voltage holding ratio and accumulating the residual charge by the direct voltage even when exposed to light, Can be suppressed.

In the specific structure (4) in the specific diamine (4), radicals are generated by irradiation of ultraviolet rays. Therefore, radicals promoting the curing of the sealant also occur in the liquid crystal alignment film due to the sealant curing process, that is, the ultraviolet irradiation process, when the liquid crystal display device is manufactured, and the curing of the sealant, It is believed that the adhesiveness of the substrate can be enhanced.

The nitrogen-containing heterocyclic ring of the specific structure (2) in the specific polymer (A) and the specific polymer (B) can be obtained by reacting a carboxyl group or a hydroxy group in the specific polymer (C) with an electrostatic As a result of the interaction, the charge easily migrates between the nitrogen-containing aromatic heterocyclic ring and the carboxyl group or the hydroxyl group. Thereby, the transferred charge can efficiently move within the molecule and between the molecules of the polyimide polymer, and the relaxation of the residual charge accumulated by the DC voltage can be accelerated. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is excellent in reliability.

In the present invention, "part" and "%" mean "part by mass" and "% by mass", respectively, unless otherwise specified.

<Specific diamine (1)>

The specific diamine (1) is a diamine having a specific structure of the following formula [1].

[Chemical Formula 12]

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and n are as defined above, and among them, the following are preferable.

X ¹ is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, or -COO-, in the point of availability of raw materials or ease of synthesis. . More preferably, it is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

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

X ³ is preferably a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- from the viewpoint of easiness of synthesis. More preferably, it is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

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

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

X ⁶ is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 10 carbon atoms. More preferably an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. Particularly preferably an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkoxy group having 1 to 9 carbon atoms.

n is preferably 0 to 3 in view of the availability of raw materials and ease of synthesis. More preferred is 0 to 2.

Preferred combinations of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and n are described in International Patent Publication WO2011 / 132751 (published on October 27, 2011) (2-1) to (2-629) shown in FIG. In each table of the International Publication, X ¹ to X ⁶ in the present invention are represented as Y ¹ to Y ⁶ , and Y ¹ to Y ⁶ are read in replacement with X ¹ to X ⁶ . In (2-605) to (2-629) listed in the tables of International Publication, the organic group having a steroid skeleton and having a carbon number of 17 to 51 in the present invention is an organic group having a steroid skeleton and having a carbon number of 12 to 25 The organic group having 12 to 25 carbon atoms and having a steroid skeleton is replaced with 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) , (2-364) to (2-387), (2-436) to (2-483), (2-603) to (2-615), or (2-624). Particularly preferable combinations are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-603) 606), (2-607) to (2-609), (2-611), (2-612), or (2-624).

The specific diamine (1) is preferably a diamine represented by the following formula [1a].

[Chemical Formula 13]

X represents the structure represented by the above formula [1]. Details and preferable combinations of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and n in the formula [1a] are as described in the above formula [1].

n1 represents an integer of 1 to 4; Among them, an integer of 1 is preferable.

Specifically, the compounds represented by formulas [2-1] to [2-6], formula [2-9] to formula [2-6] described in pages 15-19 of International Publication WO2013 / 125595 2-31]. Further, in the description of International Publication No. WO2013 / 125595, formula [2-1] - formula [2-3] in R ₂ and the formula [2-4] - formula [2-6] in R ₄ is C 1 At least one member selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a fluorinated alkoxy group having 1 to 18 carbon atoms. In addition, A ₄ in the formula [2-13] represents a linear or branched alkyl group having 3 to 18 carbon atoms. In addition, R ₃ in formulas [2-4] to [2-6] represents at least one kind selected from the group consisting of -O-, -CH ₂ O-, -COO- and -OCO-.

Among them, preferred diamines are capable of exhibiting a stable pretilt angle, reducing the liquid crystal alignment irregularity occurring in the ODF method, and exhibiting a high effect of suppressing a decrease in the voltage holding ratio after exposure to long-time light irradiation 2-9] to Formula [2-13] or Formula [2-22] to Formula [2-23] described in International Publication WO2013 / 125595, -31] diamine.

The use ratio of the specific diamine (1) is preferably the following ratio in view of the above. In the specific polymer (A), 10 to 70 mol% is preferable for the entire diamine component. , More preferably 15 to 70 mol%, and particularly preferably 20 to 60 mol%. In the specific polymer (B), 0 to 40 mol% is preferable for the entire diamine component. , More preferably 0 to 30 mol%, and particularly preferably 0 to 25 mol%. In the case of the specific polymer (C), 0 to 20 mol% is preferable. More preferred is 0 to 10 mol%.

The specific diamine (1) may be used alone or in combination of two or more, depending on the solubility of the polyimide polymer in a solvent, the liquid crystal alignability when used as a liquid crystal alignment film, and furthermore, Can be mixed and used.

<Specific diamine (2)>

The specific diamine (2) in the present invention is a diamine having the specific structure (2) represented by the following formula [2].

[Chemical Formula 14]

W ¹ , W ² , W ³ and W ⁴ are as defined above, and among them, the following are preferable.

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

W ² represents at least one member selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring and an aromatic ring.

The alkylene group having 1 to 20 carbon atoms may be linear or branched. It may also have an unsaturated bond. Among them, an alkylene group having 1 to 10 carbon atoms is preferable from the viewpoint of easiness of synthesis.

Specific examples of the non-aromatic ring include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecan ring, cyclododecane ring, A cyclododecane ring, a cyclohexadecane ring, a cyclododecane ring, a cyclododecane ring, a cyclododecane ring, a tridecane ring, a cyclotetradecane ring, a cyclopentadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, , A bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring and an adamantane ring. Among them, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring or an adamantane ring are preferable.

Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring and a phenrenylene ring. Among them, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring or an anthracene ring is preferable.

W ^{2 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 tetrahydronaphthalene ring, a fluorene ring or an anthracene ring are preferable. Among them, a single bond, an alkylene group having 1 to 5 carbon atoms, a cyclohexane ring, or a benzene ring is preferable in that the ease of synthesis and the alleviation of the residual charge accumulated by the direct current voltage after exposure to long- A ring is preferred.

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

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

[Chemical Formula 15]

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

More specifically, examples include a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, A pyrazoline ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a benzimidazole ring, a cinnoline ring, a phenanthroline ring, an indole ring, A quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring and an acridine ring. Among them, 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 is preferable. More preferred is a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, or pyrimidine ring in that the relaxation of the residual charge accumulated by the DC voltage after exposure to light for a long time is accelerated. Particularly preferred are imidazole rings or pyridine rings.

It is preferable that W ³ in the formula [2] is bonded to a substituent which is not adjacent to the formula [a], the formula [b] and the formula [c] contained in W ⁴ .

Preferable combinations of W ¹ , W ² , W ³ and W ^{4 in} the formula [2a] are as shown in Tables 1 to 31 below.

b: an alkylene group having 1 to 5 carbon atoms

b: an alkylene group having 1 to 5 carbon atoms

b: an alkylene group having 1 to 5 carbon atoms

b: an alkylene group having 1 to 5 carbon atoms

b: an alkylene group having 1 to 5 carbon atoms

b: an alkylene group having 1 to 5 carbon atoms

b: an alkylene group having 1 to 5 carbon atoms

b: an alkylene group having 1 to 5 carbon atoms

b: an alkylene group having 1 to 5 carbon atoms, c: -O (CH ₂ ) _m - (m is an integer of 1 to 5)

b: an alkylene group having 1 to 5 carbon atoms, c: -O (CH ₂ ) _m - (m is an integer of 1 to 5)

b: an alkylene group having 1 to 5 carbon atoms, c: -O (CH ₂ ) _m - (m is an integer of 1 to 5)

c: -O (CH ₂ ) _m - (m is an integer of 1 to 5)

c: -O (CH ₂ ) _m - (m is an integer of 1 to 5)

c: -O (CH ₂ ) _m - (m is an integer of 1 to 5)

c: -O (CH ₂ ) _m - (m is an integer of 1 to 5)

c: -O (CH ₂ ) _m - (m is an integer of 1 to 5)

c: -O (CH ₂ ) _m - (m is an integer of 1 to 5)

Among them, (a-43) to (a-49), (a-57) to (a-63), (a- (a-323) to (a-329), a-337 to a-343, . More preferably, (a-44), (a-45), (a-58) or (a- 59).

As the specific diamine (2), it is particularly preferable to use a diamine represented by the following formula [2a].

[Chemical Formula 16]

In the formula [2a], W represents a structure represented by the above formula [2]. Details and preferable combinations of W ¹ , W ² , W ³ and W ^{4 in} the formula [2a] are as described in the above formula [2]. p1 represents an integer of 1 to 4; Among them, 1 is preferable from the viewpoint of easiness of synthesis.

The use ratio of the specific diamine (2) is preferably the following ratio in view of the above. In the specific polymer (A), 1 to 60 mol% is preferable for the entire diamine component. , More preferably 5 to 50 mol%, and particularly preferably 10 to 50 mol%. In the specific polymer (B), 5 to 100 mol% is preferable for the entire diamine component. , More preferably 10 to 95 mol%, and particularly preferably 15 to 95 mol%. In the case of the specific polymer (C), 0 to 20 mol% is preferable. More preferably, it is 0 to 10 mol%, particularly preferably 0 mol%.

The specific diamine (2) may be used alone or in combination of two or more, depending on the solubility of the polyimide-based polymer in a solvent, the liquid crystal alignability when used as a liquid crystal alignment film, and furthermore, Can be mixed and used.

<Specific diamine (3)>

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

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

[Chemical Formula 17]

In formula [3a], Y represents a structure represented by the following formula [3-1] or formula [3-2].

m1 represents an integer of 1 to 4;

[Chemical Formula 18]

In the formula [3-1], a represents an integer of 0 to 4. Of these, an integer of 0 or 1 is preferable in view of availability of raw materials and ease of synthesis.

In the formula [3-2], b represents an integer of 0 to 4. Of these, an integer of 0 or 1 is preferable in view of availability of raw materials and ease of synthesis.

More specifically, for example, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6- Ricinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, and the like.

Among them, 2,4-diaminophenol, 3,5-diamine, 2,4-diaminophenol, 3,5-diaminophenol and 3,5-diaminophenol are preferred because they suppress the decrease in the voltage holding ratio after exposure to long-time light irradiation and further alleviate the residual charge accumulated by the direct- Minophenol, 3,5-diaminobenzyl alcohol or 3,5-diaminobenzoic acid is preferable.

The use ratio of the specific diamine (3) is preferably the following ratio in view of the above. In the specific polymer (A), 0 to 20 mol% is preferable for the entire diamine component. More preferably, it is 0 to 10 mol%, particularly preferably 0 mol%. In the specific polymer (B), 0 to 20 mol% is preferable for the entire diamine component. More preferably, it is 0 to 10 mol%, particularly preferably 0 mol%. In the case of the specific polymer (C), 40 to 100 mol% is preferable. More preferably, it is from 50 to 100 mol%, particularly preferably from 60 to 100 mol%.

The specific diamine (3) may be used alone or in combination of two or more kinds, depending on the solubility of the polyimide polymer in a solvent, the liquid crystal alignment property when used as a liquid crystal alignment film, and furthermore, Can be mixed and used.

<Specific diamine (4)>

The specific diamine (4) in the present invention is a diamine having the specific structure (4) represented by the following formula [4].

[Chemical Formula 19]

More specifically, it is preferable to use a diamine represented by the following formula [4a-1].

[Chemical Formula 20]

(q1 represents an integer of 1 to 8).

The use ratio of the specific diamine (4) is preferably such that the use ratio of the specific diamine (4) is in the range of 1: 1 to 1: 1, in that the adhesion ratio between the sealant and the liquid crystal alignment film is increased, and occurrence of display unevenness in the vicinity of the frame of the liquid crystal display element is suppressed under high- desirable. In the specific polymer (A), 1 to 50 mol% is preferable for the entire diamine component. , More preferably 5 to 40 mol%, and particularly preferably 5 to 30 mol%. In the specific polymer (B), 0 to 20 mol% is preferable for the entire diamine component. More preferably, it is 0 to 10 mol%, particularly preferably 0 mol%. In the case of the specific polymer (C), 0 to 20 mol% is preferable. More preferably, it is 0 to 10 mol%, particularly preferably 0 mol%.

The specific diamine (4) may be used alone or in combination of two or more, depending on the solubility of the polyimide polymer in a solvent, the liquid crystal alignment property when used as a liquid crystal alignment film, and furthermore, Can be mixed and used.

&Lt; Specific polymer (A) to specific polymer (C) &gt;

Specific polymer (A), specific polymer (B) and specific polymer (C) in the present invention refer to the above-mentioned components (A), (B) and (C) (Also collectively referred to as a polyimide-based polymer). They are polyimide precursors or polyimides obtained by reacting a diamine component and a tetracarboxylic acid component.

The polyimide precursor has a structure represented by the following formula [A].

[Chemical Formula 21]

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

Examples of the diamine component include diamines having two primary or secondary amino groups in the molecule. Examples of the tetracarboxylic acid component include a tetracarboxylic acid, a tetracarboxylic acid dianhydride, a tetracarboxylic acid dihalide, a tetracarboxylic acid dialkyl ester or a tetracarboxylic acid dialkyl ester dihalide.

The polyimide polymer is preferably a polyimide polymer obtained by reacting a tetracarboxylic acid dianhydride represented by the following formula [B] with a diamine represented by the following formula [C] as a raw material, A polyamic acid comprising a structural formula or a polyimide obtained by imidizing the polyamic acid is preferable. Among them, the polyimide polymer is preferably polyimide in view of the physical and chemical stability of the liquid crystal alignment film.

[Chemical Formula 22]

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

(23)

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

In addition, the polymers of the usual synthesis techniques, equation [D] obtained in the above-mentioned formula [A] represented by A ¹ and A carbon number of alkyl group of 1-8 of Figure ^2, and the equation [A] represented by A ³ and A ⁴ An alkyl group having 1 to 5 carbon atoms or an acetyl group may be introduced.

Other diamines may be used in the specific polymers (A), (B) and (C), as long as they do not impair the effects of the present invention.

Specifically, diamines represented by the following formulas [D1] to [D6] can be mentioned.

&Lt; EMI ID =

(25)

Further, other diamines described on pages 19 to 23 of WO2013 / 125595 (published on Mar. 29, 201, 2013), diazonium salts represented by the formulas [DA1] to [DA12] described on pages 23 to 24 of the same publication Diamines represented by the formulas [DA15] to [DA20], and diamines represented by the formulas [DA27] and [DA28] described in page 26 of the same publication.

The other diamine may be used as a diamine component of any one of the specific polymers (A), (B) and (C), and may be used as a diamine component of any specific polymer or as a diamine component of any specific polymer.

The other diamine may be used alone or in combination of two or more kinds depending on the solubility of the polyimide polymer in a solvent, the liquid crystal alignability when used as a liquid crystal alignment film, and further, the optical characteristics of the liquid crystal display device Can be used.

The tetracarboxylic acid component in the polymer of at least one of the specific polymers (A), (B) and (C) is preferably a tetracarboxylic acid dianhydride represented by the following formula [5] (also referred to as a specific tetracarboxylic acid component ) Is preferably used. More preferably, the specific tetracarboxylic acid component is used for all the specific polymers.

(26)

In the formula [5], Z represents at least one structure selected from the group consisting of the structures represented by the above formulas [5a] to [5k].

The Z in the formula [5] can be represented by the formula [5a], the formula [5c], the formula [5d], the formula [5e], and the formula [5f], from the viewpoints of ease of synthesis and ease of polymerization reactivity in the production of the polymer. , The formula [5g] or the formula [5k] is preferable. More preferred is a structure represented by formula [5a], formula [5e], formula [5f], formula [5g] or formula [5k]. Especially preferred is a structure represented by the formula [5e], the formula [5f], the formula [5g] or the formula [5k].

The use ratio of the specific tetracarboxylic acid component is preferably 1 mol% or more with respect to the total tetracarboxylic acid component. More preferred is 5 mol% or more. Particularly preferably, it is 10 mol% or more, and most preferably 10 to 90 mol% from the viewpoint of suppressing a decrease in voltage holding ratio after exposure to long-time light irradiation.

When the tetracarboxylic acid component having the structure represented by the formula [5e], the formula [5f], the formula [5g] or the formula [5k] is used, the amount of the tetracarboxylic acid component is preferably 20 mol% Or more, a desired effect can be obtained. Preferably, it is at least 30 mol%. All of the tetracarboxylic acid component may be a tetracarboxylic acid component having a structure represented by formula [5e], formula [5f], formula [5g] or formula [5k].

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

Specific examples include other tetracarboxylic acid components described on pages 27 to 28 of International Publication WO2013 / 125595 (published on Mar. 29, 2013). The specific tetracarboxylic acid component and the other tetracarboxylic acid component may be used alone or in combination of two or more, depending on the respective properties.

The specific polymer (A) of the present invention is obtained by imidizing a polyimide precursor or its polyimide precursor obtained by the reaction of a diamine component containing a specific diamine (1) and a specific diamine (2) with a tetracarboxylic acid component It is a polyimide.

At this time, the use (content) ratio of the specific diamine (1) and the specific diamine (2) in the whole diamine component is as follows. That is, the specific diamine (1) is preferably from 10 to 70 mol% with respect to the whole diamine component. , More preferably 15 to 70 mol%, and particularly preferably 20 to 60 mol%. The specific diamine (2) is preferably 1 to 60 mol% based on the entire diamine component. , More preferably 5 to 50 mol%, and particularly preferably 10 to 50 mol%. Further, the specific diamine (3) can improve the adhesion between the sealant and the liquid crystal alignment film and suppress the occurrence of display unevenness in the vicinity of the frame of the liquid crystal display element under high temperature and high humidity conditions, 0 to 20 mol% is preferable. More preferably, it is 0 to 10 mol%, particularly preferably 0 mol%, that is, the specific diamine (3) is not used.

The specific polymer (B) is a polyimide precursor obtained by the reaction of a diamine component containing a specific diamine (2) and a tetracarboxylic acid component, or a polyimide obtained by imidizing the polyimide precursor. At this time, the use ratio (mol%) of the specific diamine (2) in the whole diamine component is as follows. That is, the specific diamine (2) is preferably 5 to 100 mol% based on the total amount of the diamine component. , More preferably 10 to 95 mol%, and particularly preferably 15 to 95 mol%. The specific diamine (1) is preferably 0 to 40 mol% with respect to the whole diamine component. , More preferably 0 to 30 mol%, and particularly preferably 0 to 25 mol%. However, the use ratio (mol%) of the specific diamine (1) to the total diamine component in the specific polymer (B) is not particularly limited so long as the use ratio (mol%) of the specific diamine (1) (Mol%) at which the ratio becomes less than 1.0. At that time, when the ratio is 0, that is, when the specific diamine (1) is not used for the diamine component of the specific polymer (B), the decrease in the voltage holding ratio after exposure to long time light irradiation is suppressed , And also that the residual charge accumulated by the DC voltage is alleviated more quickly. When a specific diamine (1) is used for the specific polymer (B), the above ratio is preferably 0.01 to 0.9. More preferably, it is from 0.01 to 0.8, and particularly preferably from 0.05 to 0.7.

The specific diamine (3) is preferably 0 to 20 mol% based on the entire diamine component. More preferably, it is 0 to 10 mol%. Particularly preferably, from the viewpoint of enhancing the adhesion between the sealant and the liquid crystal alignment film and suppressing occurrence of display unevenness in the vicinity of the frame of the liquid crystal display element under high temperature and high humidity conditions, 0 mol%, that is, the specific diamine (3) is not used for the diamine component of the specific polymer (B).

The specific polymer (C) is a polyimide precursor obtained by the reaction of a diamine component containing a specific diamine (3) and a tetracarboxylic acid component, or a polyimide obtained by imidizing the polyimide precursor. At this time, the use ratio (mol%) of the specific diamine (3) in the whole diamine component is as follows. That is, the specific diamine (3) is preferably from 40 to 100 mol% with respect to the whole diamine component. More preferably, it is from 50 to 100 mol%, particularly preferably from 60 to 100 mol%. In the specific diamine (1), 0 to 20 mol% is preferable for the entire diamine component. More preferred is 0 to 10 mol%. The use ratio (mol%) of the specific diamine (1) to the total diamine component in the specific polymer (C) is preferably set such that the use ratio (mol%) of the specific diamine (1) in the specific polymer (Mol%) at which the ratio becomes less than 1.0. At that time, when the ratio is 0, that is, when the specific diamine (1) is not used for the diamine component of the specific polymer (C), the decrease in the voltage holding ratio after exposure to long-time light irradiation is suppressed , And also that the residual charge accumulated by the DC voltage is alleviated more quickly. When a specific diamine (1) is used for a specific polymer (C), the above ratio is preferably 0.01 to 0.4. More preferably, it is from 0.01 to 0.3, and particularly preferably from 0.01 to 0.2.

The specific diamine (3) is preferably 0 to 20 mol% based on the entire diamine component. More preferably, it is 0 to 10 mol%, particularly preferably 0 to 10 mol% from the viewpoint of suppressing a decrease in the voltage holding ratio after exposure to long-time light irradiation and further alleviating the residual charge accumulated by the direct- Mol%, that is, the specific diamine (3) is not used for the diamine component of the specific polymer (C).

In the present invention, the diamine component in the polymer of at least one of the specific polymers (A), (B) and (C) contains a specific diamine (4). The diamine at that time is preferably a diamine represented by the above formula [4a-1]. The specific diamine (4) is used for the specific polymer (A) because it can improve the adhesion between the sealing agent and the liquid crystal alignment film and suppress the occurrence of display unevenness in the vicinity of the frame of the liquid crystal display element under high temperature and high humidity conditions. . At this time, the proportion of the specific diamine (4) in the specific polymer (A) is preferably 1 to 50 mol% based on the total amount of the diamine component. , More preferably 5 to 40 mol%, and particularly preferably 5 to 30 mol%. When it is used in a specific polymer (B), it is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, based on the entire diamine component. When used for a specific polymer (C), it is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, based on the entire diamine component.

Specific polymers (A), (B) and (C) of the present invention are usually obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, a tetracarboxylic acid dianhydride and a derivative of the tetracarboxylic acid are reacted with at least one tetracarboxylic acid component and one or more diamine diamine components to form a poly Amide acid can be obtained. Specifically, there are a method of polycondensing a tetracarboxylic acid dianhydride and a primary or secondary diamine to obtain a polyamic acid, a method of dehydrating and polycondensating a tetracarboxylic acid and a primary or secondary diamine to form a polyamic acid Or a method of reacting a tetracarboxylic acid dihalide with a primary or secondary diamine to obtain a polyamic acid is used.

The polyamide acid alkyl ester can be obtained by polycondensation of a tetracarboxylic acid having a carboxylic acid group with a dialkyl ester group and a primary or secondary diamine, a method of polycondensation of a tetracarboxylic acid dihalide having a carboxylic acid group with a dialkyl ester, A method of reacting a primary or secondary diamine or a method of converting a carboxyl group of a polyamic acid into an ester is used.

To obtain the polyimide, a method of converting the polyamide acid or polyamide acid alkyl ester into a polyimide by ring closure is used.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in an organic solvent with the diamine component and the tetracarboxylic acid component. The organic solvent to be used at this time is not particularly limited as long as the resulting polyimide precursor dissolves. Specific examples of the organic solvent to be used in the reaction include, but are not limited to, the following examples.

For example, there may be mentioned N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone,? -Butyrolactone, N, N-dimethylformamide, 1,3-dimethyl-imidazolidinone, and the like. When the solvent solubility of the polyimide precursor is high, it is preferable to use methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formulas [D- -3] can be used.

(27)

(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. In addition, a solvent that does not dissolve the polyimide precursor may be used in combination with the organic solvent insofar as the resultant polyimide precursor does not precipitate. In addition, water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the resulting polyimide precursor, and therefore, the organic solvent is preferably dehydrated and dried.

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 an organic solvent is stirred to add the tetracarboxylic acid component as it is, or dispersed or dissolved in an organic solvent A method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent, a method of alternately adding a diamine component and a tetracarboxylic acid component, and the like. Method may be used. When a plurality of the diamine component and the tetracarboxylic acid component are used in the reaction, they may be reacted in a preliminarily mixed state, or they may be sequentially reacted individually, or the low molecular weight compounds reacted individually may be mixed and reacted, .

The polymerization temperature at that time may be any temperature within the range of -20 to 150 ° C, preferably -5 to 100 ° C. The reaction can be carried out at an arbitrary concentration, but if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes too high, and uniform stirring becomes difficult. Therefore, it is preferably 1 to 50%, more preferably 5 to 30%. The initial stage of the polymerization reaction may be carried out at a high concentration, and then an organic solvent may 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 the moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. As with the conventional polymerization reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

The polyimide is a polyimide obtained by ring closure of the above polyimide precursor. The closed conversion rate (also referred to as imidization rate) of the amidic acid group is not necessarily 100%, and can be arbitrarily adjusted depending on the purpose and purpose. Among them, in the present invention, all the specific polymers are preferably polyimides obtained by imidizing a polyimide precursor.

The imidization rate at that time is preferably as follows. That is, the specific polymer (A) is preferably 50 to 90%. , More preferably 55 to 90%, and particularly preferably 60 to 90%. The specific polymer (B) is preferably 50 to 95%. , More preferably 55 to 95%, and particularly preferably 60 to 95%. The specific polymer (C) is preferably 50 to 90%. , More preferably 60 to 90%, and particularly preferably 60 to 80%.

Examples of the method of imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is directly heated, or catalyst imidation in which the catalyst is added to the solution of the polyimide precursor. The temperature at which the polyimide precursor is thermally imidized in the solution is 100 to 400 ° C, preferably 120 to 250 ° C, and it is preferable to carry out the removal while removing the water generated by the imidization reaction out of the system.

The catalyst imidation of the polyimide precursor can be carried out 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 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group.

Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferable since it has a suitable basicity for promoting the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Above all, use of acetic anhydride is preferable since purification after completion of the reaction becomes easy. The imidization rate by the catalyst imidization can be controlled by controlling the amount of catalyst, the reaction temperature and the reaction time.

When the polyimide precursor or the polyimide is recovered from the polyimide precursor or polyimide reaction solution, the reaction solution may be put into a solvent and precipitated. Examples of the solvent used in the precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene and water. The polymer precipitated by charging into a solvent can be recovered by filtration and then dried at normal temperature or under reduced pressure or by heating. In addition, by repeating the operation of re-dissolving and recovering the precipitated and recovered polymer in an organic solvent for 2 to 10 times, impurities in the polymer can be reduced. As the solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be exemplified, and when three or more kinds of solvents selected from these solvents are used, the purification efficiency is further improved, which is preferable.

The molecular weight of the polyimide polymer is preferably from 5,000 to 1,000,000 in terms of weight average molecular weight measured by GPC (Gel Permeation Chromatography) when the strength of the liquid crystal alignment film obtained therefrom, the workability in forming the liquid crystal alignment film, . Among these, 10,000 to 150,000 are preferable.

As described above, all the specific polymers of the present invention exhibit stable vertical stability even after exposure to high temperature and light irradiation for a long time, and the decrease in the voltage holding ratio can be suppressed even after exposure to light for a long time, It is preferable that the polyimide precursor is the polyimide obtained by catalytic imidization of the above-mentioned polyimide precursor. The imidization rate at that time is preferably in the above-described range.

&Lt; Liquid crystal alignment treatment agent &

The liquid crystal alignment treatment agent of the present invention is a coating solution for forming a liquid crystal alignment film (also referred to as a resin film), and is a coating solution for forming a liquid crystal alignment film containing specific polymers (A), (B), (C) to be.

The use (content) ratios of the specific polymers (A), (B) and (C) in the liquid crystal alignment treatment agent are preferably as follows. That is, 30 to 300 parts of the specific polymer (B) and 60 to 500 parts of the specific polymer (C) are preferable for 100 parts of the specific polymer (A). More preferably, 50 to 250 parts of the specific polymer (B) and 100 to 350 parts of the specific polymer (C) are used. Particularly preferably, 50 to 200 parts of the specific polymer (B) Is 100 to 300 parts.

All of the polymer components in the liquid crystal alignment treatment agent may be a specific polymer or may be mixed with other polymers. At that time, the content of the other polymer is preferably 0.5 to 15 parts with respect to 100 parts of all the specific polymers. More preferred is 1 to 10 parts. Examples of other polymers include cellulose polymers, acrylic polymers, methacrylic polymers, polystyrenes, polyamides, polysiloxanes, and the like.

The solvent in the liquid crystal alignment treatment agent preferably has a content of the solvent in the liquid crystal alignment treatment agent of 70 to 99.9% in view of forming a uniform liquid crystal alignment film by coating. This content can be appropriately changed depending on the film thickness of the intended liquid crystal alignment film.

The solvent used in the liquid crystal alignment treatment agent is not particularly limited as long as it is a solvent (also referred to as a good solvent) dissolving all the specific polymers. Specific examples of the good solvent include, but are not limited to, the following.

Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N- 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, and 4-hydroxy-4-methyl-2-pentanone.

Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or? -Butyrolactone.

When the solubility of a specific polymer in a solvent is high, it is preferable to use a solvent represented by the above formula [D-1] to [D-3].

The amount of the both solvents in the liquid crystal alignment treatment agent is preferably 10 to 100% of the total solvent contained in the liquid crystal alignment treatment agent. More preferably, it is 20 to 90%. Especially preferred is 30 to 80%.

As the liquid crystal alignment treatment agent, it is possible to use a solvent (also referred to as a poor solvent) for improving the film property and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied, so long as the effect of the present invention is not impaired. Specific examples of the poor solvent include, but are not limited to, the following.

Specifically, there may be mentioned the poor solvent described on pages 35 to 37 of International Publication No. WO2013 / 125595 (published on Mar. 8, 2013).

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, ] To [D-3] is preferably used.

These poor solvents are preferably 1 to 70% of the total solvent contained in the liquid crystal alignment treatment agent. More preferred is 1 to 60%. Especially preferred is 5 to 60%.

The liquid crystal alignment treatment agent may contain a crosslinking compound selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group and a cyclocarbonate group, a group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group , Or a crosslinkable compound having a polymerizable unsaturated bonding group (collectively referred to as a specific crosslinkable compound) is preferably introduced. At this time, these groups need to have two or more of the compounds.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include a crosslinkable compound having an epoxy group or an isocyanate group described in International Patent Publication WO2013 / 125595 (published on Mar. 23, 201, 2013), pages 37 to 38 .

Specific examples of the crosslinkable compound having an oxetane group include crosslinkable compounds represented by the formulas [4a] to [4k] shown on pages 58 to 59 of WO2011 / 132751.

Specific examples of the crosslinkable compound having a cyclocarbonate group include crosslinkable compounds represented by the formulas [5-1] to [5-42] listed on pages 76 to 82 of WO2012 / 014898 .

Specific examples of the crosslinkable compound having at least one group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group include those described in International Publication No. 2013/125595 (published on September 29, 2013) (6-1) to (6-), which are listed on page 62 of the International Patent Publication WO2011 / 132751 (published on October 27, 2011), and melamine derivatives or benzoguanamine derivatives described on page 40, 48].

Specific examples of the crosslinkable compound having a polymerizable unsaturated bond include crosslinkable compounds having a polymerizable unsaturated bond described in pages 40 to 41 of WO2013 / 125595 (published on Mar. 29, 201, 2013) have.

The content of the specific crosslinkable compound in the liquid crystal alignment treatment agent is preferably 0.1 to 100 parts based on 100 parts of all the polymer components. More preferably, it is 0.1 to 50 parts in order to proceed the crosslinking reaction and to manifest the intended effect. Particularly preferred is 1 to 30 parts.

The liquid crystal alignment treatment agent of the present invention includes a liquid crystal alignment treatment agent as disclosed in International Publication No. WO2011 / 132751 (published on October 27, 2011) on pages 69 to 73 in order to promote charge transfer in the liquid crystal alignment film, Nitrogen-containing heterocyclic amines represented by the formulas [M1] to [M156] may also be added. This amine may be directly added to the liquid crystal alignment treatment agent, but it is preferably added after the solution is adjusted to a concentration of 0.1 to 10%, preferably 1 to 7% by using a suitable solvent. This solvent is not particularly limited as long as it is an organic solvent capable of dissolving a specific polymer.

As long as the effect of the present invention is not impaired, a compound that improves the uniformity of the thickness of the liquid crystal alignment film and the surface smoothness when the liquid crystal alignment treatment agent is applied can be used for the liquid crystal alignment treatment agent. Further, a compound or the like which improves the adhesion between the liquid crystal alignment film and the substrate may be used.

Examples of the compound that improves the uniformity of the thickness of the liquid crystal alignment film and the surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent. Specific examples include the surfactants described on pages 42 to 43 of International Publication No. WO2013 / 125595 (published on Mar. 29, 2013).

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

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include a functional silane-containing compound and an epoxy group-containing compound. Specifically, there may be mentioned the compounds described on pages 43 to 44 of WO2013 / 125595 (published on September 29, 2013).

It is preferable that the ratio of the compound used in close contact with these substrates is 0.1 to 30 parts based on 100 parts of all the polymer components contained in the liquid crystal alignment treatment agent. More preferred is 1 to 20 parts. If the amount is less than 0.1 part, the effect of improving the adhesion can not be expected, and if it exceeds 30 parts, the storage stability of the liquid crystal alignment treatment agent may be deteriorated.

The liquid crystal alignment treatment agent may contain a dielectric material or a conductive material for the purpose of changing electric characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film, as long as the effect of the present invention is not impaired, in addition to the above-mentioned other compounds.

<Liquid Crystal Alignment Film / Liquid Crystal Display Device>

The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being applied on a substrate and baked and subjected to an orientation treatment by rubbing treatment, light irradiation, or the like. Further, in the case of vertical alignment application, etc., it can be used as a liquid crystal alignment film without alignment treatment. The substrate to be used at this time is not particularly limited as long as it is a substrate having high transparency. In addition to the glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplifying the process, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode for liquid crystal driving is formed. In a reflective liquid crystal display device, an opaque substrate such as a silicon wafer can be used as long as it is a substrate on only one side. As the electrode in this case, a material that reflects light such as aluminum can also be used.

The method of applying the liquid crystal alignment treatment agent is not particularly limited, but screen printing, offset printing, flexographic printing, inkjet printing, and the like are generally used industrially. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spraying method, and they may be used depending on the purpose.

After the liquid crystal alignment treatment agent is applied onto the substrate, it is heated at 30 to 300 占 폚, preferably at 30 to 300 占 폚, depending on the solvent used for the liquid crystal alignment treatment agent, by heating means such as a hot plate, a heat circulation type oven and an IR The liquid crystal alignment layer can be formed by evaporating the solvent at a temperature of 30 to 250 ° C. When the thickness of the liquid crystal alignment film after firing is too large, the power consumption of the liquid crystal display element is disadvantageously deteriorated. When too thin, the reliability of the liquid crystal display element may deteriorate, so that the thickness is preferably 5 to 300 nm, 10 to 100 nm. When the liquid crystal is horizontally aligned or tilted, the fired liquid crystal alignment film is subjected to rubbing, polarized ultraviolet irradiation, or the like.

In the liquid crystal display element of the present invention, a substrate on which a liquid crystal alignment film is formed from the liquid crystal alignment treatment agent of the present invention is formed by the above-mentioned technique, and then a liquid crystal cell is produced by a known method to form a liquid crystal display element.

As a manufacturing method of the liquid crystal cell, for example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer is dispersed on the liquid crystal alignment film of the substrate of the single chamber so that the liquid crystal alignment film surface is inward, A method in which liquid crystal is injected under reduced pressure, or a method in which a liquid crystal is dropped on the surface of a liquid crystal alignment film on which a spacer is dispersed, and then a substrate is bonded and sealed.

The liquid crystal alignment treatment agent of the present invention comprises a liquid crystal layer between a pair of substrates provided with electrodes and includes a polymerizable compound polymerized by at least one of active energy rays and heat between a pair of substrates And then polymerizing the polymerizable compound by at least one of irradiation of an active energy ray and heating, while applying a voltage between electrodes, is preferably used for a liquid crystal display device. As the active energy ray, ultraviolet ray is preferable. The ultraviolet ray has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 占 폚, preferably 60 to 80 占 폚. In addition, ultraviolet rays and heating may be simultaneously performed.

The liquid crystal display element described above controls the pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA system, a small amount of a photopolymerizable compound such as a photopolymerizable monomer is mixed in a liquid crystal material, and after a liquid crystal cell is assembled, a predetermined voltage is applied to the liquid crystal layer, And controls the pretilt of the liquid crystal molecules by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is produced is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed on the liquid crystal layer. In the PSA method, since the rubbing treatment is not required, it is suitable for forming a vertical alignment type liquid crystal layer which is difficult to control the pretilt by the rubbing treatment. That is, the liquid crystal display element of the present invention can be obtained by obtaining a substrate on which a liquid crystal alignment film is formed from a liquid crystal alignment treatment agent by the above-mentioned technique, preparing a liquid crystal cell, and polymerizing the polymerizable compound by at least one of irradiation with ultraviolet rays and heating The orientation of the liquid crystal molecules can be controlled.

An example of manufacturing a PSA-type liquid crystal cell is as follows. That is, a polymerizable compound that is polymerized by heat or irradiation with ultraviolet light is mixed with the liquid crystal when the liquid crystal cell is manufactured by the above-described manufacturing method. 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. At that time, the polymerizable compound is preferably 0.01 to 10 parts, more preferably 0.1 to 5 parts, per 100 parts of the liquid crystal component. If the amount of the polymerizable compound is less than 0.01 part, the polymerization of the polymerizable compound is not polymerized and the alignment of the liquid crystal can not be controlled. If more than 10 parts, the unreacted polymerizable compound increases and the exposure property of the liquid crystal display element deteriorates . After the liquid crystal cell is manufactured, the polymerizable compound is polymerized by applying heat or ultraviolet rays while applying alternating current or direct current voltage to the liquid crystal cell. Thereby, the orientation of the liquid crystal molecules can be controlled.

The liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment treatment agent comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group which is polymerized by at least one of active energy rays and heat between the pair of substrates And a liquid crystal display element manufactured through a process of applying a voltage between the electrodes, that is, the SC-PVA mode. As the active energy ray, ultraviolet ray is preferable. As ultraviolet rays, the wavelength is from 300 to 400 nm, and more preferably from 310 to 360 nm. In the case of polymerization by heating, the heating temperature is from 40 to 120 캜, more preferably from 60 to 80 캜. In addition, ultraviolet rays and heating may be simultaneously performed.

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

An example of manufacturing a liquid crystal cell in the SC-PVA mode is as follows, for example. That is, the liquid crystal cell is fabricated by the manufacturing method described above. Thereafter, alignment of liquid crystal molecules can be controlled by applying heat or ultraviolet rays while applying alternating current or direct current voltage to the liquid crystal cell.

By using the liquid crystal alignment treatment agent of the present invention as described above, it is possible to improve the adhesion between the sealant and the liquid crystal alignment film, and to provide a liquid crystal alignment film capable of suppressing occurrence of display unevenness near the frame of the liquid crystal display element under high temperature and high humidity conditions . It is also possible to provide a liquid crystal alignment film which suppresses a decrease in the voltage holding ratio even after exposure to light for a long period of time and can alleviate the residual charges accumulated by the DC voltage. Therefore, the liquid crystal display device manufactured using the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be preferably used for a large liquid crystal television, a small-sized car navigation system, a smart phone, and the like. 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 VA mode, a PSA mode and an SC-PVA mode.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples. The abbreviations of the compounds used below are as follows.

(Specific diamine (1))

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

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

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

(28)

(Specific diamine (2))

[Chemical Formula 29]

(Specific diamine (3))

C1: 3,5-diaminobenzoic acid

(30)

(Specific diamine (4))

(31)

(Other diamines)

E1: p-phenylenediamine, E2: m-phenylenediamine

E3: 1,3-Diamino-4-octadecyloxybenzene

(32)

(Specific tetracarboxylic acid dianhydride)

F1: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

F2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride

(33)

(Crosslinkable compound)

(34)

(menstruum)

NMP: N-methyl-2-pyrrolidone, NEP: N-ethyl-2-pyrrolidone,? -BL:? -Butyrolactone, BCS: ethylene glycol monobutyl ether, PB: propylene glycol monobutyl ether, DME: dipropylene glycol dimethyl ether, DPM: dipropylene glycol monomethyl ether

&Quot; Molecular weight measurement of polyimide polymer &quot;

(KD-803, KD-805, manufactured by Shodex) at room temperature gel permeation chromatography (GPC-101, manufactured by Showa Denko K.K.).

Column temperature: 50 ° C

Eluent: 30 mmol / l (liter) of lithium bromide-hydrate (LiBr.H ₂ O), 30 mmol / l of phosphoric anhydride crystal (o-phosphoric acid) as an additive, N, N'-dimethylformamide 10 ml / l of hydrofuran (THF)

Flow rate: 1.0 ml / min

Standard samples 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 Laboratories).

&Quot; Measurement of imidization rate of polyimide polymer &quot;

(DMSO-d6, 0.05% TMS (tetramethylsilane) mixed product) (0.53 ml) was placed in an NMR sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific Co., Ltd.), 20 mg of polyimide powder, Was added, and completely dissolved by applying ultrasonic waves. This solution was subjected to proton NMR measurement at 500 MHz with an NMR measuring instrument (JNW-ECA500, manufactured by Nippon Denshoku). A proton originating from a structure which is not changed before and after imidation is defined as a reference proton and the proton peak integrated value derived from the NH group of the amide acid appearing in the vicinity of 9.5 to 10.0 ppm By using the following equation.

Imidization ratio (%) = (1 -? X / y) x 100

(x is the proton peak integrated value derived from the NH group of the amide acid, y is the peak integrated value of the reference proton, and? is one of the NH group protons of the amide acid in the case of polyamic acid (the imidization rate is 0% The ratio of the number of reference protons to the number of protons.

&Quot; Synthesis of polyimide polymer &quot;

&Lt; Synthesis Example 1 &

NMP (16.5 g) was added to F2 (2.04 g, 8.15 mmol), A1 (2.52 g, 6.62 mmol), B1 (1.20 g, 4.95 mmol), D1 (0.55 g, 1.66 mmol) (1.60 g, 8.16 mmol) and NMP (8.26 g) were added and reacted at 40 占 폚 for 6 hours to give a concentration (concentration of resin solid content). The same is true) was 25%.

To the obtained polyamic acid solution (30.0 g) was added NMP and diluted to 6%. Acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidation catalyst and reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (1). The polyimide had an imidization rate of 80%, a number average molecular weight (Mn) of 16,200 and a weight average molecular weight (Mw) of 45,300.

&Lt; Synthesis Example 2 &

NMP (16.9 g) was added to F2 (2.04 g, 8.15 mmol), A3 (2.15 g, 4.97 mmol), B1 (1.20 g, 4.95 mmol), D1 (1.09 g, 3.30 mmol) (1.60 g, 8.16 mmol) and NMP (8.44 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a concentration of 25% .

To the resulting polyamic acid solution (30.0 g) was added NMP and diluted to 6%. Acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst and reacted at 80 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (2). The imidization rate of the polyimide was 75%, Mn was 15,800 and Mw was 43,700.

&Lt; Synthesis Example 3 &

N2P (16.3 g) was added to F2 (0.83 g, 3.32 mmol), A2 (2.32 g, 5.88 mmol), B1 (1.22 g, 5.04 mmol) (2.60 g, 13.3 mmol) and NEP (8.16 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a concentration of 25% .

NEP was added to the obtained polyamic acid solution (30.0 g) to dilute it to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidation catalyst and reacted at 80 ° C for 3 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (3). The imidization ratio of the polyimide was 70%, Mn was 15,900, and Mw was 43,800.

&Lt; Synthesis Example 4 &

NMP (16.2 g) was added to F2 (2.04 g, 8.15 mmol), A4 (1.60 g, 3.25 mmol), B1 (1.40 g, 5.78 mmol), D1 (1.09 g, 3.30 mmol) (1.60 g, 8.16 mmol) and NMP (8.12 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a concentration of 25% .

NMP was added to the resultant polyamic acid solution (30.0 g) to dilute it to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidation catalysts and reacted at 80 ° C for 2.5 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (4). The imidization ratio of the polyimide was 65%, Mn was 14,500, and Mw was 40,900.

&Lt; Synthesis Example 5 &

N1 (25.1 g) was added to a solution of F3 (3.50 g, 15.6 mmol), A2 (2.50 g, 6.34 mmol), B1 (1.15 g, 4.75 mmol), D1 (1.05 g, 3.18 mmol) And the mixture was reacted at 40 DEG C for 8 hours to obtain a polyamic acid solution having a concentration of 25%.

NEP was added to the obtained polyamic acid solution (30.0 g) to dilute it to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidation catalyst and reacted at 80 ° C for 3 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (5). The imidization ratio of the polyimide was 70%, Mn was 18,300, and Mw was 49,400.

&Lt; Synthesis Example 6 &

NMP (17.2 g) was added to F4 (2.45 g, 8.16 mmol), A2 (1.96 g, 4.97 mmol), B1 (1.40 g, 5.78 mmol), D1 (0.82 g, 2.48 mmol) (1.60 g, 8.16 mmol) and NMP (8.58 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a concentration of 25% .

To the resulting polyamic acid solution (30.0 g) was added NMP and diluted to 6%. Acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst and reacted at 80 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (6). The imidization ratio of this polyimide was 75%, Mn was 15,600 and Mw was 43,200.

&Lt; Synthesis Example 7 &

NMP (16.3 g) was added to F2 (0.83 g, 3.32 mmol), A1 (2.56 g, 6.73 mmol), B1 (1.22 g, 5.04 mmol), D1 (0.55 g, 1.66 mmol) (2.60 g, 13.3 mmol) and NMP (8.12 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a concentration of 25% .

To the resulting polyamic acid solution (30.0 g) was added NMP and diluted to 6%. Acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst and reacted at 80 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (7). The imidization rate of this polyimide was 75%, Mn was 17,000, and Mw was 44,200.

&Lt; Synthesis Example 8 &

(0.64 g, 2.47 mmol), D1 (0.55 g, 1.66 mmol) and E2 (0.63 g, 5.83 mmol) were dissolved in NEP (16.4 g) (0.80 g, 4.08 mmol) and NEP (8.19 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a concentration of 25% .

NEP was added to the obtained polyamic acid solution (30.0 g) to dilute to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidation catalyst and reacted at 80 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (8). The imidization ratio of this polyimide was 75%, Mn was 16,300, and Mw was 44,300.

&Lt; Synthesis Example 9 &

(1.28 g, 5.28 mmol) and E1 (0.57 g, 5.27 mmol) were mixed in NMP (16.8 g) and heated to 80 &lt; 0 &gt; C for 5 h After the reaction, F1 (1.70 g, 8.67 mmol) and NMP (8.39 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a concentration of 25%.

To the obtained polyamic acid solution (30.0 g) was added NMP and diluted to 6%. Acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidation catalyst and reacted at 80 ° C for 4 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (9). The imidization ratio of this polyimide was 80%, Mn was 17,500 and Mw was 47,200.

&Lt; Synthesis Example 10 &

(2.04 g, 8.15 mmol), B1 (1.20 g, 4.95 mmol), E1 (0.36 g, 3.33 mmol) and E3 (1.87 g, 4.97 mmol) were mixed in NMP (16.3 g) After the reaction, F1 (1.60 g, 8.16 mmol) and NMP (8.16 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a concentration of 25%.

To the resulting polyamic acid solution (30.0 g) was added NMP and diluted to 6%. Acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst and reacted at 80 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 占 폚 to obtain a polyimide powder (10). The imidization ratio of the polyimide was 75%, Mn was 15,800, and Mw was 42,500.

&Lt; Synthesis Example 11 &

(1.80 g, 3.63 mmol) and B1 (3.50 g, 14.4 mmol) were mixed in NMP (17.2 g) and reacted at 80 ° C for 5 hours. Then, F1 (2.80 g, 14.3 mmol) and NMP (8.57 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a concentration of 25%.

To the resulting polyamic acid solution (30.0 g) was added NMP and diluted to 6%. Acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidation catalysts and reacted at 80 ° C for 5 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (11). The imidization ratio of this polyimide was 90%, Mn was 17,800 and Mw was 46,900.

&Lt; Synthesis Example 12 &

(1.88 g, 7.76 mmol), B1 (1.88 g, 7.76 mmol) and E1 (0.84 g, 7.77 mmol) were mixed in NMP (16.3 g) After the reaction, F1 (3.00 g, 15.3 mmol) and NMP (8.15 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a concentration of 25%.

To the resulting polyamic acid solution (30.0 g) was added NMP and diluted to 6%. Acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst and reacted at 80 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (12). The imidization rate of this polyimide was 75%, Mn was 18,600 and Mw was 48,300.

&Lt; Synthesis Example 13 &

(1.80 g, 1.85 mmol) were mixed in NMP (16.7 g) and reacted at 80 ° C for 5 hours. 9.18 mmol) and NMP (8.35 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a concentration of 25%.

NMP was added to the resultant polyamic acid solution (30.0 g) to dilute it to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidation catalysts and reacted at 80 ° C for 2.5 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (13). The imidization ratio of the polyimide was 65%, Mn was 22,100, and Mw was 53,400.

&Lt; Synthesis Example 14 &

(1.7 g, 4.13 mmol), B1 (1.07 g, 4.13 mmol) and E2 (1.34 g, 12.4 mmol) were mixed in NMP (17.1 g) After the reaction, F1 (2.00 g, 10.2 mmol) and NMP (8.54 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a concentration of 25%.

To the resulting polyamic acid solution (30.0 g) was added NMP and diluted to 6%. Acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst and reacted at 80 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (14). The imidization rate of the polyimide was 75%, Mn was 17,900, and Mw was 46,500.

&Lt; Synthesis Example 15 &

(2.20 g, 11.2 mmol) and NMP (8.46 g) were added to the reaction mixture at 80 &lt; 0 &gt; C for 5 hours, And the mixture was reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a concentration of 25%.

To the resulting polyamic acid solution (30.0 g) was added NMP and diluted to 6%. Acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst and reacted at 80 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (15). The imidization rate of the polyimide was 75%, and the Mn was 21,800 and the Mw was 52,100.

&Lt; Synthesis Example 16 &

F2 (2.81 g, 11.2 mmol), C1 (2.94 g, 19.3 mmol) and E2 (0.37 g, 3.42 mmol) were mixed in NMP (16.6 g) 11.2 mmol) and NMP (8.31 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a concentration of 25%.

NEP was added to the obtained polyamic acid solution (30.0 g) to dilute it to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidation catalyst and reacted at 80 ° C for 3 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (16). The imidization ratio of the polyimide was 70%, Mn was 23,200, and Mw was 54,200.

&Lt; Synthesis Example 17 &

(2.30 g, 18.7 mmol) and E2 (0.36 g, 3.33 mmol) were mixed in NEP (16.4 g) and reacted at 80 ° C for 5 hours. 10.8 mmol) and NEP (8.21 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a concentration of 25%.

To the obtained polyamic acid solution (30.0 g) was added NMP and diluted to 6%. Acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst and reacted at 80 ° C for 3 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (17). The imidization ratio of the polyimide was 70%, Mn was 20,500, and Mw was 51,800.

&Lt; Synthesis Example 18 &

NMP (16.8 g) was added to F2 (2.04 g, 8.15 mmol), A1 (2.52 g, 6.62 mmol), B1 (1.20 g, 4.95 mmol), C1 (0.50 g, 3.29 mmol) (1.60 g, 8.16 mmol) and NMP (8.41 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a concentration of 25% .

To the obtained polyamic acid solution (30.0 g) was added NMP and diluted to 6%. Acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidation catalyst and reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (18). The imidization rate of the polyimide was 81%, Mn was 15,300 and Mw was 41,600.

The polyimide polymers obtained in the respective synthesis examples are shown in Tables 32 and 33.

Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot;

Using the liquid crystal alignment treatment agents obtained in the later-described Examples 3 and 8, evaluation of the ink-jet application properties was carried out. Specifically, these liquid crystal alignment treatment agents were pressure-filtered through a membrane filter having a pore diameter of 1 占 퐉, and thereafter the substrate was cleaned with pure water and IPA (isopropyl alcohol) 100 mm in width and 100 mm in width and 0.7 mm in thickness) was applied on the ITO surface under conditions of a coating area of 70 mm x 70 mm, a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm and a coating speed of 40 mm / sec. At that time, HIS-200 (manufactured by Hitachi Plant Technologies Co., Ltd.) was used for the ink jet applicator. The time from application to drying was 60 seconds, and the drying was carried out on a hot plate at 70 DEG C for 5 minutes.

Evaluation of coating properties was carried out by visually observing the coated film surface of the substrate on which the liquid crystal alignment film obtained above was formed. Specifically, the surface of the coated film was visually observed under a sodium lamp to confirm the presence or absence of pinholes. As a result, in the liquid crystal alignment film obtained in any of the examples, no pinhole was seen on the coated film surface, and a liquid crystal alignment film excellent in film property was obtained.

Evaluation of display non-uniformity characteristics in the vicinity of frame of liquid crystal cell (normal cell)

The liquid crystal alignment treatment agent obtained in the later-described Examples and Comparative Examples was pressure-filtered with a membrane filter having a pore diameter of 1 占 퐉 and cleaned with pure water and IPA, on which an ITO electrode was formed (40 mm long x 30 mm wide, ), And subjected to a heat treatment on a hot plate at 100 占 폚 for 5 minutes and a heat cycle type clean oven at 230 占 폚 for 30 minutes to obtain an ITO substrate on which a liquid crystal alignment film having a thickness of 100 nm was formed. The substrates of the liquid crystal alignment treatment agents of Examples 3 and 8 were prepared under the same conditions as those of the above-mentioned &quot; Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot;, and then subjected to heat treatment at 230 캜 for 30 minutes in a heat- To form an ITO substrate on which a liquid crystal alignment film having a thickness of 100 nm was formed.

Next, the coated surface of the substrate was subjected to rubbing treatment using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm under conditions of a roll rotation number of 1000 rpm, a roll progress speed of 50 mm / sec, and a press-in amount of 0.1 mm.

Thereafter, two substrates after the rubbing treatment were prepared, and 6 mu m spacers were put together with the coated film face inward, and the periphery was adhered with a sealant to prepare empty cells. MLC-6608 (manufactured by Merck Japan) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell.

Using the obtained liquid crystal cell, the display non-uniformity characteristics in the vicinity of the frame of the liquid crystal cell were evaluated. Specifically, the polarizing plate and the backlight were used to evaluate the liquid crystal alignability in the vicinity of the sealant by visual observation. As a result, all of the liquid crystal cells obtained in Examples and Comparative Examples exhibited uniform liquid crystal alignability.

Thereafter, the liquid crystal cell was stored in a constant-temperature and constant humidity chamber at a temperature of 80 캜 and a humidity of 90% RH for 144 hours, and the liquid crystal alignability near the sealant was evaluated under the same conditions as above.

The evaluation showed that, after storage in a constant temperature and humidity bath, no disturbance of liquid crystal alignability was observed near the sealant, the evaluation was excellent in this evaluation (good display in Tables 37 to 39).

Evaluation of voltage holding ratio (normal cell)

The voltage holding ratio was evaluated using a liquid crystal cell manufactured under the same conditions as those described above under &quot; evaluation of display non-uniformity characteristics in the vicinity of the frame of the liquid crystal cell (normal cell) &quot;. Specifically, a voltage of 1 V is applied to a liquid crystal cell obtained by the above method at a temperature of 80 캜 for 60 ㎲, and a voltage after 50 ms is measured to see how much the voltage is held is referred to as a voltage holding ratio (also referred to as VHR ). The measurement was performed by setting the voltage: ± 1 V, the pulse width: 60 μs, and the flame period: 50 ms by using a voltage sustaining ratio measuring device (VHR-1, manufactured by Toyotec Corporation).

Further, ultraviolet rays of 50 J / cm 2 in terms of 365 nm in terms of 365 nm were irradiated to the liquid crystal cell in which the voltage holding ratio was measured immediately after the liquid crystal cell was prepared, using a table type UV curing device (HCT3B28HEX-1, , And the voltage holding ratio was measured under the same conditions as described above.

In this evaluation, the value of the voltage holding ratio immediately after the fabrication of the liquid crystal cell is high and the value of the voltage holding ratio immediately after the fabrication of the liquid crystal cell (also referred to as the initial value) The better, the better. Tables 37 to 39 show values of each VHR.

Evaluation of relaxation of residual charge (normal cell)

Evaluation of relaxation of residual charges was carried out by using a liquid crystal cell produced under the same condition as the above-mentioned &quot; evaluation of display non-uniformity characteristics in the vicinity of a frame of a liquid crystal cell (normal cell) &quot;. Specifically, the liquid crystal cell was subjected to DC voltage 10 V for 30 minutes, shorted for 1 second, and then the potential generated in the liquid crystal cell was measured for 1,800 seconds. Among them, the value of the residual charge after 50 seconds was used to evaluate the relaxation of the residual charge. Further, a 6254-type liquid crystal physical property evaluation apparatus (manufactured by Toyo Technica Co., Ltd.) was used for measurement.

Further, ultraviolet rays of 30 J / cm &lt; 2 &gt; in terms of 365 nm were irradiated onto the liquid crystal cell after the measurement of the residual charge immediately after the liquid crystal cell was prepared, using a table type UV curing apparatus (HCT3B28HEX- And the residual charge was measured under the same conditions as described above.

In this evaluation, the smaller the values (immediately after initialization) and the residual charge values after ultraviolet irradiation (also referred to as ultraviolet irradiation) of the liquid crystal cell were, the better the evaluation was. In Table 37 to Table 39, values of each residual charge are shown.

&Quot; Production of liquid crystal cell and evaluation of liquid crystal orientation property (PSA cell) &quot;

Using the liquid crystal alignment treatment agents obtained in the later-described Examples 3 and 9, the production of the liquid crystal cell and the evaluation of the liquid crystal alignment property (PSA cell) were carried out. Specifically, these liquid crystal alignment treatment agents were pressure-filtered with a membrane filter having a pore diameter of 1 占 퐉 and cleaned with pure water and IPA to obtain a substrate having an ITO-forming electrode on which ITO having a pattern interval of 20 占 퐉 of 10 占 10 mm was formed (40 mm in length x 30 mm in width, 0.7 mm in thickness) and ITO surface of a substrate (40 mm long x 30 mm wide, 0.7 mm thick) on which ITO forming electrodes having ITO formed at 10 x 40 mm in the center were formed, , And subjected to heat treatment at 100 캜 for 5 minutes on a hot plate and 230 캜 for 30 minutes in a thermocycling type clean oven to obtain an ITO substrate having a liquid crystal alignment film with a thickness of 100 nm formed. The substrate of the liquid crystal alignment treatment agent of Example 3 was prepared under the same conditions as the above-mentioned &quot; Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot;, and then heat treatment was performed at 230 DEG C for 30 minutes in a thermocycling type clean oven , And a liquid crystal alignment film having a thickness of 100 nm was formed.

Next, these two substrates were assembled by interposing a spacer having a size of 6 mu m with the coated film surface on the inner side, and adhered to the periphery with a sealant to prepare empty cells. The polymerizable compound (1) represented by the following formula was dissolved in a nematic liquid crystal (MLC-6608, manufactured by Merck Japan Co., Ltd.) into the empty cell by reduced pressure injection, ) Was injected, and then the injection port was sealed to obtain a liquid crystal cell.

(35)

A wavelength of 350 nm or less was cut using a metal halide lamp having an illuminance of 60 mW while a voltage of AC 5 V was applied to the obtained liquid crystal cell and irradiated with ultraviolet rays of 20 J / cm 2 in terms of 365 nm, Of the liquid crystal cell was controlled. The temperature in the irradiator when the liquid crystal cell was irradiated with ultraviolet rays was 50 占 폚.

Thereafter, the response speed of the liquid crystal before the ultraviolet ray irradiation and after the ultraviolet ray irradiation of the liquid crystal cell were measured. The response speed was measured from T90 to T10 from a transmittance of 90% to a transmittance of 10%.

It was confirmed that the alignment direction of the liquid crystal was controlled in that the response speed of the liquid crystal cell after ultraviolet irradiation was faster than that of the liquid crystal cell before ultraviolet irradiation in any liquid crystal cell. Further, it was confirmed that the liquid crystal was uniformly aligned by observation with a polarizing microscope (ECLIPSE E600WPOL, Nikon Corporation) of any liquid crystal cell.

&Lt; Example 1 &gt;

To polyimide powder (1) (0.50 g) obtained in Synthesis Example 1, NEP (3.92 g) was added and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (3.92 g) was added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NEP (5.88 g) was added to the polyimide powder (11) (0.75 g) obtained in Synthesis Example 11 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (5.88 g) was added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NEP (9.79 g) was added to the polyimide powder (15) (1.25 g) obtained in Synthesis Example 15 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (9.79 g) was added and stirred at 40 占 폚 for 4 hours to obtain a solution.

The three solutions obtained above were mixed and stirred at 40 캜 for 4 hours to obtain a liquid crystal alignment treatment agent (1). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 2 &gt;

To polyimide powder (2) (0.50 g) obtained in Synthesis Example 2, NEP (3.92 g) was added and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (2.35 g) and PB (1.57 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NEP (5.88 g) was added to the polyimide powder (11) (0.75 g) obtained in Synthesis Example 11 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (3.53 g) and PB (2.35 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NEP (9.79 g) was added to the polyimide powder (15) (1.25 g) obtained in Synthesis Example 15 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (5.88 g) and PB (3.92 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

The three solutions obtained above were mixed and stirred at 40 캜 for 4 hours to obtain a liquid crystal alignment treatment agent (2). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 3 &gt;

To the polyimide powder (3) (0.30 g) obtained in Synthesis Example 3, the polyimide powder (11) (0.45 g) obtained in Synthesis Example 11 and the polyimide powder (15) (0.75 g) obtained in Synthesis Example 15 were added NEP (16.5 g) and? -BL (4.18 g) were added and dissolved by stirring at 70 占 폚 for 24 hours. To this solution was added BCS (8.27 g), PB (8.27 g) and DME (4.14 g), and the mixture was stirred at 40 占 폚 for 4 hours to obtain a liquid crystal alignment treating agent (3). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

<Example 4>

NMP (6.27 g) was added to the polyimide powder (4) (0.80 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (5.02 g) and DME (1.25 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NMP (6.27 g) was added to the polyimide powder (13) (0.80 g) obtained in Synthesis Example 13 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (5.02 g) and DME (1.25 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NMP (8.36 g) was added to the polyimide powder (15) (1.07 g) obtained in Synthesis Example 15 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (6.68 g) and DME (1.67 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

The three solutions obtained above were mixed and stirred at 40 캜 for 4 hours to obtain a liquid crystal alignment treatment agent (4). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 5 &gt;

NEP (7.52 g) was added to the polyimide powder (5) (0.80 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (2.51 g) and PB (2.51 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NEP (7.52 g) was added to the polyimide powder (11) (0.80 g) obtained in Synthesis Example 11 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (2.51 g) and PB (2.51 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NEP (10.0 g) was added to the polyimide powder (15) (1.07 g) obtained in Synthesis Example 15 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (3.34 g) and PB (3.34 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

The three solutions obtained above were mixed and stirred at 40 캜 for 4 hours to obtain a liquid crystal alignment treatment agent (5). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 6 &gt;

To the polyimide powder (6) (0.50 g) obtained in Synthesis Example 6, the polyimide powder (11) (0.75 g) obtained in Synthesis Example 11 and the polyimide powder (15) (1.25 g) obtained in Synthesis Example 15 were added NEP (21.5 g) was added and dissolved by stirring at 70 DEG C for 24 hours. To this solution, PB (17.6 g) was added and stirred at 40 占 폚 for 4 hours to obtain a liquid crystal alignment treatment agent (6). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 7 &gt;

NMP (3.76 g) and NEP (3.76 g) were added to the polyimide powder (7) (0.80 g) obtained in Synthesis Example 7 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (2.51 g) and PB (2.51 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NMP (3.76 g) and NEP (3.76 g) were added to the polyimide powder (11) (0.80 g) obtained in Synthesis Example 11 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (2.51 g) and PB (2.51 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NMP (5.02 g) and NEP (5.02 g) were added to the polyimide powder (15) (1.07 g) obtained in Synthesis Example 15 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (3.34 g) and PB (3.34 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

The three solutions obtained above were mixed and stirred at 40 캜 for 4 hours to obtain a liquid crystal alignment treatment agent (7). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 8 &gt;

To the polyimide powder (8) (0.30 g) obtained in Synthesis Example 8, the polyimide powder (11) (0.45 g) obtained in Synthesis Example 11 and the polyimide powder (15) (0.75 g) obtained in Synthesis Example 15 were added NEP (12.4 g) and? -BL (6.21 g) were added and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (8.27 g) and PB (14.5 g) were added and stirred at 40 占 폚 for 4 hours to obtain a liquid crystal alignment treatment agent (8). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 9 &gt;

NEP (5.09 g) was added to the polyimide powder (1) (0.50 g) obtained in Synthesis Example 1 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (1.18 g) and PB (1.57 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NEP (7.64 g) was added to the polyimide powder (12) (0.75 g) obtained in Synthesis Example 12 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (1.76 g) and PB (2.35 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

Further, NEP (12.7 g) was added to the polyimide powder (15) (1.25 g) obtained in Synthesis Example 15 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (2.94 g) and PB (3.92 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

The three solutions obtained above were mixed and stirred at 40 캜 for 4 hours to obtain a liquid crystal alignment treatment agent (9). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 10 &gt;

NEP (4.70 g) was added to the polyimide powder (5) (0.50 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (3.13 g) was added and stirred at 40 占 폚 for 4 hours to obtain a solution.

Meanwhile, to the polyimide powder (13) (0.75 g) obtained in Synthesis Example 13, NEP (7.05 g) was added and dissolved by stirring at 70 캜 for 24 hours. To this solution, PB (4.70 g) was added and stirred at 40 占 폚 for 4 hours to obtain a solution.

Further, NEP (11.8 g) was added to the polyimide powder (15) (1.25 g) obtained in Synthesis Example 15 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (7.83 g) was added and stirred at 40 占 폚 for 4 hours to obtain a solution.

The three solutions obtained above were mixed and stirred at 40 캜 for 4 hours to obtain a liquid crystal alignment treatment agent (10). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 11 &gt;

NEP (4.70 g) was added to the polyimide powder (1) (0.50 g) obtained in Synthesis Example 1 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution was added BCS (0.78 g) and PB (2.35 g), and the mixture was stirred at 40 占 폚 for 4 hours to obtain a solution.

NEP (7.05 g) was added to polyimide powder (14) (0.75 g) obtained in Synthesis Example 14 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (1.18 g) and PB (3.53 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

Further, NEP (11.8 g) was added to the polyimide powder (15) (1.25 g) obtained in Synthesis Example 15 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (1.96 g) and PB (5.88 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

The three solutions obtained above were mixed and stirred at 40 占 폚 for 4 hours to obtain a liquid crystal alignment treatment agent (11). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 12 &gt;

NMP (6.27 g) was added to the polyimide powder (1) (0.80 g) obtained in Synthesis Example 1 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (2.51 g) and PB (3.76 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NMP (4.18 g) was added to the polyimide powder (11) (0.53 g) obtained in Synthesis Example 11 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (1.67 g) and PB (2.51 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NMP (10.4 g) was added to the polyimide powder (16) (1.33 g) obtained in Synthesis Example 16 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (4.18 g) and PB (6.27 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

The three solutions obtained above were mixed and further M1 (0.19 g) was added and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (12). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 13 &gt;

To the polyimide powder (1) (0.80 g) obtained in Synthesis Example 1, the polyimide powder (11) (0.80 g) obtained in Synthesis Example 11 and the polyimide powder (17) (1.07 g) obtained in Synthesis Example 17 were added NEP (20.9 g) was added and dissolved by stirring at 70 DEG C for 24 hours. To this solution, BCS (8.36 g) and PB (12.5 g) were added and stirred at 40 占 폚 for 4 hours to obtain a liquid crystal alignment treatment agent (13). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 14 &gt;

To the polyimide powder (1) (0.80 g) obtained in Synthesis Example 1, the polyimide powder (11) (0.80 g) obtained in Synthesis Example 11 and the polyimide powder (17) (1.07 g) obtained in Synthesis Example 17 were added NEP (20.9 g) was added and dissolved by stirring at 70 DEG C for 24 hours. To this solution, PB (12.5 g) and DPM (8.36 g) were added and stirred at 40 占 폚 for 4 hours to obtain a liquid crystal alignment treatment agent (23). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Comparative Example 1 &

NEP (19.6 g) was added to the polyimide powder (1) (2.50 g) obtained in Synthesis Example 1 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (19.6 g) was added and stirred at 40 占 폚 for 4 hours to obtain a liquid crystal alignment treatment agent (14). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Comparative Example 2 &

NEP (19.6 g) was added to the polyimide powder (11) (2.50 g) obtained in Synthesis Example 11 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (19.6 g) was added and stirred at 40 占 폚 for 4 hours to obtain a liquid crystal alignment treatment agent (15). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Comparative Example 3 &

NEP (19.6 g) was added to the polyimide powder (15) (2.50 g) obtained in Synthesis Example 15 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (19.6 g) was added and stirred at 40 占 폚 for 4 hours to obtain a liquid crystal alignment treatment agent (16). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Comparative Example 4 &

NEP (10.2 g) was added to the polyimide powder (1) (1.30 g) obtained in Synthesis Example 1 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (10.2 g) was added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NEP (10.2 g) was added to the polyimide powder (11) (1.30 g) obtained in Synthesis Example 11 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (10.2 g) was added and stirred at 40 占 폚 for 4 hours to obtain a solution.

The two solutions obtained above were mixed and stirred at 40 占 폚 for 4 hours to obtain a liquid crystal alignment treatment agent (17). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Comparative Example 5 &

NEP (10.2 g) was added to the polyimide powder (1) (1.30 g) obtained in Synthesis Example 1 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (10.2 g) was added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NEP (10.2 g) was added to the polyimide powder (15) (1.30 g) obtained in Synthesis Example 15 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (10.2 g) was added and stirred at 40 占 폚 for 4 hours to obtain a solution.

The two solutions obtained above were mixed and stirred at 40 캜 for 4 hours to obtain liquid crystal alignment treatment agent (18). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Comparative Example 6 &gt;

NEP (10.2 g) was added to the polyimide powder (11) (1.30 g) obtained in Synthesis Example 11 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (10.2 g) was added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NEP (10.2 g) was added to the polyimide powder (15) (1.30 g) obtained in Synthesis Example 15 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (10.2 g) was added and stirred at 40 占 폚 for 4 hours to obtain a solution.

The two solutions obtained above were mixed and stirred at 40 캜 for 4 hours to obtain a liquid crystal alignment treatment agent (19). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Comparative Example 7 &

To polyimide powder (9) (0.50 g) obtained in Synthesis Example 9, NEP (3.92 g) was added and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (3.92 g) was added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NEP (5.88 g) was added to the polyimide powder (11) (0.75 g) obtained in Synthesis Example 11 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (5.88 g) was added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NEP (9.79 g) was added to the polyimide powder (15) (1.25 g) obtained in Synthesis Example 15 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (9.79 g) was added and stirred at 40 占 폚 for 4 hours to obtain a solution.

The three solutions obtained above were mixed and stirred at 40 캜 for 4 hours to obtain a liquid crystal alignment treatment agent (20). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Comparative Example 8 &gt;

NMP (3.92 g) was added to the polyimide powder (10) (0.50 g) obtained in Synthesis Example 10 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (2.35 g) and PB (1.57 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NMP (5.88 g) was added to the polyimide powder (11) (0.75 g) obtained in Synthesis Example 11 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (3.53 g) and PB (2.35 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

NMP (9.79 g) was added to the polyimide powder (15) (1.25 g) obtained in Synthesis Example 15 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (5.88 g) and PB (3.92 g) were added and stirred at 40 占 폚 for 4 hours to obtain a solution.

The three solutions obtained above were mixed and stirred at 40 캜 for 4 hours to obtain a liquid crystal alignment treatment agent (21). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Comparative Example 9 &

NEP (19.6 g) was added to the polyimide powder (18) (2.50 g) obtained in Synthesis Example 18 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (19.6 g) was added and stirred at 40 占 폚 for 4 hours to obtain a liquid crystal alignment treatment agent (22). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Tables 34 to 36 collectively show the composition ratios of the liquid crystal alignment treating agent, the polyimide polymer used, and the solid content concentration (%) obtained in Examples and Comparative Examples.

In the table, * 1 is the content (parts) of the specific polymer (A) relative to 100 parts of all the polymers, * 2 is the content (parts) of the specific polymer (B) , The content (parts) of the specific polymer (C) relative to 100 parts of all the polymers, and * 4 indicate the content (parts) of other polymers relative to 100 parts of all the polymers.

* 5 represents the content ratio (solid content concentration) of all the polymers in the liquid crystal alignment treatment agent.

In the following Tables 37 to 39, * 1 indicates that liquid crystal orientation disturbance is observed in the vicinity of the sealant in the liquid crystal cell, * 2 indicates the liquid crystal orientation in the liquid crystal cell up to the width of 0.5 cm from the sealant (* 2) in which the disturbance of the liquid crystal orientation is seen from the sealant to the area of the width of 1.0 cm from the sealant (* 2) Indicating that the orientation disorder is widened).

As can be seen from the above results, in the liquid crystal alignment treatment agent of the Examples, even when the liquid crystal cell was stored in the high temperature and high humidity chamber for a long time, the liquid crystal alignment property was not disturbed in the vicinity of the sealant. In addition, even when the liquid crystal cell was irradiated with ultraviolet light, the reduction of the voltage holding ratio was suppressed and the residual charge accumulated by the direct current voltage was relaxed quickly.

That is, in the comparison between the examples using the three kinds of the specific polymers (A), (B) and (C) and the comparative example in which only one of them is used, the liquid crystal alignment treatment agent of the comparative example shows all the effects I could not satisfy them. Specifically, it is a comparison between Example 1 and Comparative Example 1, Comparative Example 2 or Comparative Example 3. The same was also true for the comparison between Example 1 and Comparative Example 4, Comparative Example 5, and Comparative Example 6. Further, in the comparison between Example 1 in which the specific diamine (4) was used and Comparative Example 7 in which the specific diamine (4) was not used, all the effects of the present invention could not be satisfied in the liquid crystal alignment treatment agent of the comparative example.

Further, in the comparison between Example 2 using a specific diamine (1) and Comparative Example 8 using a diamine having a side chain structure of a conventional alkyl group, the liquid crystal alignment treatment agent of the comparative example satisfies all the effects of the present invention I could not.

In the comparison of Example 1 and Comparative Example 9 using polyimide powder using all of the specific diamines (1), (2), (3) and (4), in the liquid crystal alignment treatment agent of Comparative Example, Could not satisfy all the effects of. Particularly, the occurrence of display unevenness in the vicinity of the frame of the liquid crystal cell and the residual charge after irradiation with ultraviolet light increased.

Industrial availability

The liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability and can be preferably used for a liquid crystal television with a high precision on a large screen and can be suitably used for TN devices, STN devices, TFT liquid crystal devices, Of the liquid crystal display element.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2014-262604 filed on December 25, 2014 are incorporated herein by reference and the disclosure of the specification of the present invention is hereby incorporated by reference.

Claims (21)

A liquid crystal alignment treatment agent comprising the following components (A), (B) and (C).
(A): a polyimide precursor obtained by a reaction between a diamine having a structure represented by the following formula [1] and a diamine component containing a diamine having a structure represented by the following formula [2] and a tetracarboxylic acid component; A polyimide obtained by imidizing a polyimide precursor.
Component (B): A polyimide precursor obtained by the reaction of a diamine component containing a diamine having a structure represented by the following formula [2] with a tetracarboxylic acid component, or a polyimide precursor obtained by imidizing the polyimide precursor.
(C): a polyimide precursor obtained by the reaction of a diamine component containing a diamine having at least one substituent selected from the group consisting of a carboxy group (COOH group) and a hydroxyl group (OH group) and a tetracarboxylic acid component Or a polyimide obtained by imidizing the polyimide precursor.
However, the diamine component in the polymer of at least one of the component (A), the component (B) and the component (C) contains a diamine having a structure represented by the following formula [4].
[Chemical Formula 1]

(X ¹ is at least one selected from the group consisting of a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- and -OCO- It shows a longitudinal coupler of X ² is a single bond or _{-. (CH 2) b -} . represents a (b is an integer of 1 to 15) X ³ is a single _{bond, - (CH 2) c -} (c is 1 to -O-, -CH ₂ O-, -COO- and -OCO-, X ⁴ represents a group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring , Or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, and any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms the alkoxy group, the number of carbon atoms may be substituted one to three fluorine-containing alkyl group, fluorine-containing alkoxy group or a fluorine atom of 1 to 3 carbon atoms in. X ⁵ is a benzene ring, An alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom, n is an integer of 0 to 4. X ⁶ is an alkyl group having 1 to 18 carbon atoms, An alkyl group, an alkoxy group having 1 to 18 carbon atoms, and a fluorine-containing alkoxy group having 1 to 18 carbon atoms.
(2)

(W ¹ is -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ ) ₃ ) CO-, W ² represents at least one member selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, and a non-aromatic ring and an aromatic ring W ³ is a single bond, -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH ₃ ) -, -N CH ₃ ) CO- and -O (CH ₂ ) _m - (m represents an integer of 1 to 5), and W ⁴ represents a nitrogen-containing aromatic heterocyclic ring.
(3)

The method according to claim 1,
A liquid crystal alignment treatment agent wherein the diamine having the structure represented by the formula (1) is used only for the diamine component in the component (A). The method according to claim 1,
(1) in the component (B), when the use ratio (mol%) of the diamine having the structure represented by the formula (1) to the total diamine component in the component (A) (Mol%) relative to the total diamine component of the diamine having a structure represented by the general formula (1) is in the range of 0.01 to 0.8. The method according to claim 1 or 3,
(1) in the component (C), when the use ratio (mol%) of the diamine having the structure represented by the formula (1) in the component (A) (Mol%) with respect to the total diamine component of the diamine having a structure represented by the formula (1) is in the range of 0.01 to 0.3. 5. The method according to any one of claims 1 to 4,
Wherein the diamine having at least one substituent selected from the group consisting of the carboxyl group (COOH group) and the hydroxyl group (OH group) is used only for the diamine component in the component (C). 6. The method according to any one of claims 1 to 5,
A liquid crystal alignment treatment agent wherein the diamine having the structure represented by the formula (4) is used only for the diamine component in the component (A). 7. The method according to any one of claims 1 to 6,
The liquid crystal alignment treatment agent represented by the following formula [1a], wherein the diamine having the structure represented by the above formula [1] is represented by the following formula [1a].
[Chemical Formula 4]

(X represents a structure represented by the above formula [1], and n1 represents an integer of 1 to 4.) 8. The method according to any one of claims 1 to 7,
The liquid crystal alignment treatment agent represented by the following formula [2a], wherein the diamine having the structure represented by the above formula [2] is represented by the following formula [2a].
[Chemical Formula 5]

(W represents a structure represented by the above formula [2], and p1 represents an integer of 1 to 4.) 9. The method according to any one of claims 1 to 8,
The diamine having at least one substituent selected from the group consisting of a carboxyl group and a hydroxyl group is represented by the following formula [3a].
[Chemical Formula 6]

(Y represents a structure represented by the following formula [3-1] or formula [3-2]: m1 represents an integer of 1 to 4)
(7)

(a and b each represent an integer of 0 to 4). 10. The method according to any one of claims 1 to 9,
The liquid crystal alignment treatment agent represented by the following formula [4a-1], wherein the diamine having the structure represented by the formula [4] is the following.
[Chemical Formula 8]

(q1 represents an integer of 1 to 8). 11. The method according to any one of claims 1 to 10,
Wherein the tetracarboxylic acid component in the components (A), (B) and (C) comprises a tetracarboxylic acid dianhydride represented by the following formula [5].
[Chemical Formula 9]

(Wherein Z represents at least one member selected from the group consisting of the structures represented by the following formulas [5a] to [5k]).
[Chemical formula 10]

(Z ¹ to Z ⁴ each independently represent at least one member selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom and a benzene ring.) Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group. ) 12. The method according to any one of claims 1 to 11,
At least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and? -Butyrolactone. 13. The method according to any one of claims 1 to 12,
Propylene diol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether and the following formula [D1] to formula [D3 And a solvent represented by the following general formula (1).
(11)

(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.) 14. The method according to any one of claims 1 to 13,
The liquid crystal alignment treating agent is selected from the group consisting of a crosslinking compound having at least one group selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group and a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group A liquid crystal alignment treatment agent comprising a crosslinkable compound having at least one kind of group or a crosslinkable compound having a polymerizable unsaturated bonding group. A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of claims 1 to 14. A liquid crystal alignment film obtained by applying the liquid crystal alignment treatment agent according to any one of claims 1 to 14 by an ink jet method. A liquid crystal display element having the liquid crystal alignment film according to claim 15 or 16. 17. The method according to claim 15 or 16,
A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and comprising a polymerizable compound capable of polymerizing by at least one of active energy rays and heat is disposed between the pair of substrates, A liquid crystal alignment film used in a liquid crystal display device manufactured through a process of polymerizing the polymerizable compound while applying a voltage between the electrodes. A liquid crystal display element having the liquid crystal alignment film according to claim 18. 17. The method according to claim 15 or 16,
A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes and comprising a polymerizable group capable of polymerizing by at least one of active energy rays and heat is disposed between the pair of substrates, A liquid crystal alignment film used in a liquid crystal display device manufactured through a process of polymerizing the polymerizable group while applying a voltage between the electrodes. A liquid crystal display element having the liquid crystal alignment film according to claim 20.