KR20140059219A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

Provided is a liquid crystal alignment treatment agent which is free from a change in the pretilt angle even at a high temperature and light irradiation for a long time and has a high wetting and diffusing property with respect to a substrate, thereby obtaining a liquid crystal alignment film excellent in uniform film property and end film property. N-ethyl-2-pyrrolidone, and a polyimide precursor having side chains of the following formula [1] and a polyimide. (Provided that X ₁ , X ₂ , X ₃ Are independently a single bond or the like, and X ₄ , X ₅ Is independently a benzene ring or the like, and X ₆ Is an alkyl group having 1 to 18 carbon atoms, and the like, and n is an integer of 0 to 4.)

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 used in manufacturing a liquid crystal alignment film and a liquid crystal display element using the same.

At present, many characteristics are required for a liquid crystal alignment film used for a liquid crystal display element. One of the characteristics of this is control of the so-called liquid crystal pretilt angle, in which the alignment tilt angle of the liquid crystal molecules with respect to the substrate surface is maintained at an arbitrary value. It is known that the size of the pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film. Among techniques for controlling the pretilt angle by the structure of polyimide, in the method of using a diamine compound having a side chain as a part of the polyimide raw material, the pretilt angle can be controlled according to the use ratio of the diamine compound. Therefore, it is relatively easy to obtain a target pretilt angle, and this is useful as means for increasing the pretilt angle. As a side chain structure of a diamine compound which increases the pretilt angle of a liquid crystal, it has been proposed that a cyclic structure such as a long chain alkyl group or a fluoroalkyl group (see, for example, Patent Document 1), a phenyl group or a cyclohexyl group (See, for example, Patent Documents 2 and 3).

2. Description of the Related Art In recent years, liquid crystal display devices have been widely used for liquid crystal televisions and large-scale mobile applications (display portions of digital cameras and cellular phones) in large-screen liquid crystal televisions. have. Even in such a situation, from the viewpoint of display characteristics, it is required that a liquid crystal alignment film is uniformly formed on a large substrate or a step. When a liquid crystal alignment treatment agent (also referred to as a coating solution) of a polyamic acid or a solvent-soluble polyimide (also referred to as a resin) is applied to a substrate in the production process of the liquid crystal alignment film, a flexographic printing method, Coating method or the like. At this time, in order to improve the film uniformity of the liquid crystal alignment film, in addition to N-methyl-2-pyrrolidone or? -Butyrolactone, which is a solvent excellent in solubility of the resin (also referred to as good solvent) Butylcellosolve, which is a low-solubility solvent (also referred to as a poor solvent), and the like (see, for example, Patent Document 4).

Japanese Patent Application Laid-Open No. 2-282726 Japanese Patent Application Laid-Open No. 9-278724 International Publication No. 2004/52962 pamphlet Japanese Unexamined Patent Application Publication No. 2-37324

The liquid crystal alignment film is also used for controlling the angle of the liquid crystal with respect to the substrate, that is, the control of the pretilt angle of the liquid crystal. However, as the liquid crystal display element is made high performance and its use range is enlarged year by year, The stability of the pretilt angle is becoming more important.

In the manufacturing process of a liquid crystal display element, in order to enhance the alignment uniformity of the liquid crystal, there is a case where the liquid crystal is enclosed and then subjected to heat treatment to make the liquid crystal isotropic once. However, when the stability of the pretilt angle is low, there arises a problem that the pretilt angle of the desired size is not obtained after the isotropic process, or a deviation occurs in the pretilt angle. Particularly, in a liquid crystal display device using a backlight having a large amount of heat for obtaining a high brightness and having a large amount of light irradiation, for example, in a car navigation system or a large TV, it is used or left in an environment exposed to high temperature and light for a long time There is a case. In such a severe condition, when the pretilt angle is gradually changed, initial display characteristics are not obtained, or there arises a problem such as display unevenness.

In addition, a liquid crystal alignment treatment agent using a polyamic acid or a solvent-soluble polyimide obtained by using a diamine compound having a side chain tends to lower the film uniformity of the liquid crystal alignment film. Particularly, when a uniform film property can not be obtained, that is, when cratering or pinholes are generated, this portion becomes a display defect when used as a liquid crystal display element. For this reason, it is necessary to increase the mixing amount of the poor solvent having a high wetting and diffusing property of the coating solution on the substrate. However, since the poor solvent has poor ability to dissolve the polyamic acid or the solvent soluble polyimide, There is a problem that precipitation of the resin occurs.

In recent years, liquid crystal display devices have been used for mobile applications such as smart phones and mobile phones. In these applications, a sealant used for bonding substrates between liquid crystal display elements exists at a position close to the end of the liquid crystal alignment film in order to secure as much display surface as possible. Therefore, when the film property of the end portion of the liquid crystal alignment film is lowered, that is, when the end portion of the liquid crystal alignment film is not straight or the end portion is swollen, the sealing effect of the sealant between the substrates is lowered, The display characteristics and reliability of the display element are deteriorated.

The present invention has been made in view of the above circumstances. That is, a problem to be solved by the present invention is to provide a liquid crystal alignment film in which the pretilt angle does not change even when exposed to high temperature and light irradiation for a long time. In addition, even in the case of a liquid crystal alignment treatment agent using a polyamic acid or a solvent-soluble polyimide obtained by using a diamine compound having a side chain, the wetting and spreading property of the coating solution on the substrate is high and a uniform coating film is obtained, Which is also excellent in the film property of the end portion of the liquid crystal alignment film. Furthermore, it is another object of the present invention to provide a liquid crystal display element having the liquid crystal alignment film and a liquid crystal alignment treatment agent capable of providing the liquid crystal alignment film.

As a result of intensive studies, the inventors of the present invention have found that a liquid crystal alignment treatment agent containing a solvent having a specific structure and a polymer having a side chain of a specific structure is very effective for achieving the above object. It came.

That is, the present invention has the following points.

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

Component (A): N-ethyl-2-pyrrolidone.

Component (B): at least one polymer selected from the group consisting of a polyimide precursor having a side chain represented by the following formula [1] and a polyimide obtained by imidizing a polyimide precursor.

[Chemical Formula 1]

(Formula [1], X ₁ is a single _{bond, - (CH 2) a -} (a is an integer of 1 ~ 15), -O-, -NH- , -N (CH 3) -, -CONH- _{, -NHCO-, -CH 2 O-, -COO-} , -OCO-, -CON (CH 3) -. or -N (CH _{3) 2} X is CO- Is a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 15). X ₃ is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH ₃ ) - or -N (CH ₃ ) CO-. X ₄ Is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring (any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine atom having 1 to 3 carbon atoms Containing alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom). X ₅ Is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring (any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine atom having 1 to 3 carbon atoms Containing alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom). X ₆ Is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms, and n is an integer of 0 to 4.)

(2) the component (B) is at least one selected from the group consisting of a polyimide precursor using a diamine compound having a side chain represented by the above formula [1] as a part of the starting material and a polyimide obtained by imidizing a polyimide precursor The liquid crystal alignment treatment agent according to the above (1), which is a polymer of the general formula (1).

(3) The liquid crystal alignment treating agent according to (2), wherein the diamine compound having a side chain represented by the formula [1] is a diamine compound represented by the following formula [1a].

(2)

(Formula [1a] of the, X ₁ is a single _{bond, - (CH 2) a -} (a is an integer of 1 ~ 15), -O-, -NH- , -N (CH 3) -, -CONH- _{, -NHCO-, -CH 2 O-, -COO-} , -OCO-, -CON (CH 3) -. or -N (CH _{3) 2} X is CO- Is a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 15). X ₃ is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH ₃ ) - or -N (CH ₃ ) CO-. X ₄ Is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring (any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine atom having 1 to 3 carbon atoms Containing alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom). X ₅ Is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring (any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine atom having 1 to 3 carbon atoms Containing alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom). X ₆ Is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluoro-containing alkoxyl group having 1 to 18 carbon atoms. n is an integer of 0 to 4, and m is an integer of 1 to 4.)

(4) The liquid crystal alignment treatment agent according to (2) or (3), wherein the diamine represented by the above formula [1a] is used in an amount of 5 to 80 mol% of the diamine component of the raw material.

(5) The liquid crystal alignment treating agent according to any one of (1) to (4), wherein the component (B) is a polymer using a tetracarboxylic acid dianhydride represented by the following formula [2].

(3)

(In the formula [2], Y ₁ is a tetravalent organic group having 4 to 13 carbon atoms and further contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms.)

6, the Y ₁ Is the group represented by the following formulas [2a] to [2j].

[Chemical Formula 4]

(In the formula [2a], Y ₂ to Y ₅ Is a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different, and Y ₆ and Y ₇ Are each a hydrogen atom or a methyl group, and may be the same or different.

(7) The liquid crystal alignment treatment agent according to any one of (1) to (6), wherein the polymer as the component (B) is a polyamic acid.

(8) The liquid crystal alignment treating agent according to any one of (1) to (6) above, wherein the polymer as the component (B) is a polyimide obtained by dehydrating and ring closure of a polyamic acid.

(9) The liquid crystal alignment treatment agent according to any one of (1) to (8), wherein the component (C) contains N-methyl-2-pyrrolidone or? -Butyrolactone.

(10) The positive resist composition as described in any one of (1) to (6) above, wherein the component (D) is at least one compound selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethanediol, At least one member selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monobutyl ether The liquid crystal alignment treating agent according to any one of (1) to (9) above.

(11) The liquid crystal alignment treatment agent according to any one of (1) to (10), wherein the component (A) is 10 to 100 mass% of the total organic solvent contained in the liquid crystal alignment treatment agent.

(12) The liquid crystal alignment treatment agent according to any one of (9) to (11), wherein the component (C) accounts for 0.1 to 50 mass% of the total organic solvent contained in the liquid crystal alignment treatment agent.

(13) The liquid crystal alignment treatment agent according to any one of (10) to (12), wherein the component (D) accounts for 5 to 80 mass% of the total organic solvent contained in the liquid crystal alignment treatment agent.

(14) The liquid crystal alignment treatment agent according to any one of (1) to (13), wherein the amount of the component (B) in the liquid crystal alignment treatment agent is 0.1 to 15 mass%.

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

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

(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 containing a polymerizable compound polymerized by at least one of an active energy ray and a heat is disposed between the pair of substrates The liquid crystal alignment film according to (15) or (16) above, which is used for a liquid crystal display device manufactured through a step 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).

(20) A liquid crystal device comprising a liquid crystal layer between a pair of electrodes including an electrode and the liquid crystal alignment layer, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat between the pair of substrates A liquid crystal display element according to the above item (19), wherein the liquid crystal display element is produced by arranging a composition and polymerizing the polymerizable compound while applying a voltage between the electrodes.

(21) A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes, wherein a liquid crystal alignment film containing a polymerizable group polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, The liquid crystal alignment film according to (15) or (16) above, wherein the liquid crystal alignment film is used for a liquid crystal display device manufactured through a process of polymerizing the polymerizable group while applying a voltage between the electrodes.

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

(23) A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes, wherein a liquid crystal alignment film containing a polymerizable group polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, The liquid crystal display element according to (22), wherein the polymerizable group is polymerized while applying a voltage between the electrodes.

According to the liquid crystal alignment treatment agent of the present invention, it is possible to obtain a liquid crystal alignment film in which the pretilt angle does not change even when exposed to a long period of high temperature or light irradiation, and the wet diffusion property of the solution to the substrate is high, , A liquid crystal alignment film having excellent film uniformity can be obtained. By using such a liquid crystal alignment film, it is possible to provide a liquid crystal display device having excellent display characteristics and high reliability.

1 is an example of a coating film image of an optical microscope used for evaluating the linearity of an end portion of a liquid crystal alignment film.
2 is an example of a coating film image of an optical microscope used for evaluating mounting of an end portion of a liquid crystal alignment film.

The liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment treatment agent of the present invention which contains N-ethyl-2-pyrrolidone (also referred to as a specific solvent) as the component (A) and the side chain represented by the above formula [1] (Also referred to as a specific polymer) selected from the group consisting of a polyimide precursor having a polyimide precursor and a polyimide precursor having a polyimide precursor imidized therein.

The specific solvent in the present invention is a good solvent having excellent solubility of polyamic acid or soluble polyimide. In addition, surface tension as a solvent is lower than that of commonly used N-methyl-2-pyrrolidone or? -Butyrolactone. Therefore, the liquid crystal alignment treatment agent using a specific solvent has a higher wetting and spreading property of the coating solution on the substrate, compared with a liquid crystal alignment treatment agent that does not use the liquid crystal alignment treatment agent. Therefore, even if a poor solvent having low solubility in resin is not used, This excellent liquid crystal alignment film can be obtained. Further, since the wetting and diffusing property of the coating solution is enhanced, the linearity of the end portion of the liquid crystal alignment film is enhanced.

In addition, since such a specific solvent has a higher boiling point than N-methyl-2-pyrrolidone or? -Butyrolactone which is commonly used, the liquid crystal aligning agent using a specific solvent is a liquid crystal alignment film, The mounting of the end portion can be suppressed.

The specific side chain structure in the present invention has a benzene ring, a cyclohexyl ring or a heterocyclic ring in the side chain portion. These benzene rings, cyclohexyl rings or heterocyclic rings exhibit a rigid structure in comparison with the long chain alkyl groups of the prior art. This improves the stability of the side chain region against heat and ultraviolet rays, and provides a liquid crystal alignment film having a stable pretilt angle with respect to heat or light. These benzene rings, cyclohexyl rings, or heterocyclic rings exhibit a rigid structure, but have higher solubility in organic solvent of the polymer as compared with cyclic groups formed by the conventional steroid skeleton. Therefore, the liquid crystal alignment treatment agent having the specific side chain structure of the present invention has higher uniformity of coating on the substrate as compared with the liquid crystal alignment treatment agent having a cyclic group comprising the conventional steroid skeleton.

In view of the above, according to the liquid crystal alignment treatment agent containing the specific solvent of the present invention and the polymer having the specific side chain structure, even when exposed to high temperature and light irradiation for a long time, the pretilt angle does not change, A liquid crystal alignment film can be obtained. By using this liquid crystal alignment film, a liquid crystal display device having excellent display characteristics and high reliability can be obtained.

<Specific solvent>

A specific solvent of the present invention is N-ethyl-2-pyrrolidone. N-ethyl-2-pyrrolidone is preferably 10 to 100% by mass based on the total amount of the organic solvent contained in the liquid crystal alignment treatment agent, so as to have an effect of improving the wettability of the coating solution to the substrate. Among them, it is preferably 15 to 100 mass%, more preferably 20 to 100 mass%, and still more preferably 25 to 100 mass% of the entire organic solvent.

The effect of the present invention, that is, the wetting and diffusing property of the coating solution on the substrate, becomes higher as the amount of the specific solvent of the present invention in the whole of the organic solvent in the liquid crystal alignment treatment agent is increased, and a liquid crystal alignment film excellent in film film uniformity can be obtained .

<Specific side chain structure>

The specific polymer of the present invention, that is, at least one selected from the group consisting of a polyimide precursor and a polyimide imidized with a polyimide precursor, has a specific side chain structure represented by the following formula [1].

[Chemical Formula 5]

In formula [1], X ₁ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH ₃ ) - or -N (CH ₃ ) CO-. Among them, a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CONH-, -CH ₂ O- or -COO- Therefore, it is preferable. More preferably, it is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CONH-, -CH ₂ O- or -COO-. 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 a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 15). Among them, a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 10) is preferable.

X ₃ - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O -, -COO-, -OCO-, -CON (CH ₃ ) - or -N (CH ₃ ) CO-. Among them, a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- is preferable since it is easy to synthesize. More preferably, it is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO- or -OCO-.

X ₄ Is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring. The arbitrary hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom . Among them, as the bivalent cyclic group, a benzene ring or a cyclohexyl ring is preferable.

X ₅ Is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring. Any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluoro-containing alkoxyl group having 1 to 3 carbon atoms, do. Among them, as the bivalent cyclic group, a benzene ring or a cyclohexane ring is preferable.

n is an integer of 0 to 4, preferably 0 to 2.

X ₆ Is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluoro-containing alkoxyl group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

Preferable combinations of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and n in the formula [1] are described in International Patent Publication No. WO2011 / 132751 (published on October 27, 2011) (2-1) to (2-600) listed in Tables 6 to 45 of the page. In addition, in each table of the International Publication, X ₁ to X ₆ This, as is shown, but Y1 ~ Y6, Y1 ~ Y6 is assumed to change the reading X ₁ ~ X _6.

&Lt; Specific side chain type diamine compound &gt;

As a method for introducing the specific side chain structure represented by the formula [1] into at least one selected from the group consisting of the specific polymer of the present invention, that is, the polyimide precursor and the polyimide obtained by imidizing the polyimide precursor, It is preferable to use a diamine compound having a structure as a part of the raw material. In particular, it is preferable to use a diamine compound represented by the following formula [1a] (also referred to as a specific side chain type diamine compound).

[Chemical Formula 6]

X ₁ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH ₃ ) - or -N (CH ₃ ) CO-. Among them, a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CONH-, -CH ₂ O- or -COO- Therefore, it is preferable. More preferably, it is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CONH-, -CH ₂ O- or -COO-. 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 a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 15). Among them, a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 10) is preferable.

X ₃ - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O -, -COO-, -OCO-, -CON (CH ₃ ) - or -N (CH ₃ ) CO-. Among them, a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- is preferable since it is easy to synthesize. More preferably, it is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO- or -OCO-.

X ₄ Is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring. The arbitrary hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom . Among them, as the bivalent cyclic group, a benzene ring or a cyclohexyl ring is preferable.

X ₅ Is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring. Any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluoro-containing alkoxyl group having 1 to 3 carbon atoms, do. Among them, as the bivalent cyclic group, a benzene ring or a cyclohexyl ring is preferable.

n is an integer of 0 to 4, preferably 0 to 2.

X ₆ Is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluoro-containing alkoxyl group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

A preferable combination of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and n in the formula [1a] is the same as that of the formula [1].

In the combination of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and n in the formula [1], a more preferable combination is 1-25 to 1-96, 168, 1-217 to 1-240, 1-268 to 1-315, 1-364 to 1-387, 1-436 to 1-483, etc. Especially preferred combinations are 1-49 to 1-96, -145 to 1-168, 1-217 to 1-240, and the like.

In the formula [1a], m is an integer of 1 to 4, preferably 1.

Specifically, the formula [1a] is a structure represented by the following formulas [1-1] to [1-13], for example.

(7)

(In the formulas [1-1] to [1-3], R ₁ is -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or CH ₂ OCO- and R ₂ Is an alkyl group having 1 to 22 carbon atoms, an alkoxyl group having 1 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 22 carbon atoms.

[Chemical Formula 8]

(Of the formulas [1-4] to [1-6], R ₃ -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or -CH ₂ - and R ₄ Is an alkyl group having 1 to 22 carbon atoms, an alkoxyl group having 1 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 22 carbon atoms.

[Chemical Formula 9]

(Of the formulas [1-7] and [1-8], R ₅ Is, -COO-, -OCO-, -CONH-, -NHCO- , -COOCH 2 -, -CH 2 OCO-, -CH 2 O-, -OCH 2 -, -CH 2 -, -O- or - NH-, and R &lt; ₆ &gt; Is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group.

[Chemical formula 10]

(Of the formulas [1-9] and [1-10], R ₇ Is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer.

(11)

(Of the formulas [1-11] and [1-12], R ₈ Is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer.

[Chemical Formula 12]

(In the formula [1-13], A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A ₃ is a 1,4-cyclohexylene group or 1,4-phenyl And A ₂ is an oxygen atom or COO- * (provided that the bonding hand to which &quot; * &quot; is bonded is bonded to A ₃ ), A ₁ is an oxygen atom or COO- * (CH ₂ ) a ₂ ).

A ₁ is 0 or 1, a ₂ Is an integer of 2 to 10, and a ₃ Is 0 or 1.)

Of the above-mentioned formulas [1-1] to [1-13], particularly preferred diamine compounds are those represented by formulas [1-1] to [1-6], formulas [1-9] to be.

The above-mentioned specific side chain type diamine compound may be used alone or in combination of two or more kinds thereof, depending on the properties such as liquid crystal alignment property, voltage holding ratio, and accumulated charge when the liquid crystal alignment film is used.

&Lt; Other diamine compounds &gt;

In the present invention, as long as the effect of the present invention is not impaired, other diamine compounds (other diamine compounds) other than the specific side chain diamine compound can be used as the diamine component of the starting material. Specific examples thereof are given below.

p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- Diaminodiphenol, 3,5-diaminophenol, 3,5-diaminobenzyl, 2,4-diaminophenol, 3,5-diaminophenol, Alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, Dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diamino Biphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'- diaminobiphenyl, Diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl Methane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diamino Phenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, Bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl- bis (3-aminophenyl) silane, Aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'- Diaminodiphenylamine, 2,3-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3, (2,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl Diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2 ' - diaminobenzophenone, 2,3'-diaminobenzophenone, Diaminonaphthalene, 1,6-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,6-diaminonaphthalene, Bis (4-aminophenyl) ethane, 1, 3-bis (4-aminophenyl) ) Propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4- Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3- Phenylene bis (methylene)] dianiline, 3, 4 '- [1,3-phenylenebis (methylene)] dianiline, 3,4' - [ 4 '- [1,3-phenylenebis (methylene)] dianiline, 3,3' - [1,4-phenylenebis )]] Dianiline, 3,3 '- [1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [ [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone] Phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), 1,3-phenylenebis Aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N (3-aminophenyl) terephthalate, bis N, N '- (1,4-phenylene) bis (4-aminobenzamide) (Phenylene) bis (3-aminobenzamide), N, N '- (1,3-phenylene) N, N'-bis (3-aminophenyl) Amide, N, N'-bis (4-aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, 9,10- Bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [4- Bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'- Bis (3-aminophenyl) propane, 2,2'-bis (3-amino- Bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, Bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) Aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hex Heptane, 1,7-bis (4-aminophenoxy) heptane, 1,7-bis (Aminophenoxy) octane, 1,9-bis (3-aminophenoxy) nonane, 1,9-bis , 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) decane, Aromatic diamine compounds such as undecane, 1,12- (4-aminophenoxy) dodecane and 1,12- (3-aminophenoxy) dodecane; aromatic diamine compounds such as bis (4-aminocyclohexyl) methane, bis 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1, 7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,1-diaminoundecane, 1,12-diaminododecane, etc. Aliphatic diamine compounds.

In addition, as long as the effect of the present invention is not impaired, a diamine compound having an alkyl group or a fluorine-containing alkyl group in the diamine side chain can be used.

Specifically, for example, diamine compounds represented by the following formulas [DA1] to [DA12] can be exemplified.

[Chemical Formula 13]

(Wherein [DA1] ~ [DA5] of, A ₁ is a linear or branched fluorine-containing alkyl group having 1 to 22 linear or branched alkyl group or carbon number of 1 to 22).

[Chemical Formula 14]

(In the formulas [DA6] to [DA11], A ₂ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, A ₃ represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.)

[Chemical Formula 15]

(In the formula [DA12], p is an integer of 1 to 10.)

As long as the effect of the present invention is not impaired, diamine compounds represented by the following formulas [DA13] to [DA20] may be used.

[Chemical Formula 16]

(In the formula [DA17], m is an integer of 0 to 3. In the formula [DA20], n is an integer of 1 to 5.)

In addition, as long as the effect of the present invention is not impaired, a diamine compound having a carboxyl group in the molecule represented by the following formulas [DA21] to [DA24] may be used.

[Chemical Formula 17]

(In the formula [DA21], m ₁ is an integer of 1 to 4.

Formula [DA22] of, A ₄ represents a single _{bond, -CH 2 -, -C 2 H} 4 -, -C (CH 3) 2 -, -CF 2 -, -C (CF 3) 2 -, -O- , -CO-, -NH-, -N (CH 3) -, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CON (CH 3) - or -N (CH ₃ ) CO-, m ₂ and m ₃ are each an integer of 0 to 4, and m ₂ + m ₃ is an integer of 1 to 4.

In the formula [DA23], m ₄ and m ₅ are integers of 1 to 5, respectively. In the formula [DA24], A ₅ is a linear or branched alkyl group having 1 to 5 carbon atoms, and m ₆ is an integer of 1 to 5.

Wherein [DA25], A ₆ represents a single _{bond, -CH 2 -, -C 2 H} 4 -, -C (CH 3) 2 -, -CF 2 -, -C (CF 3) 2 -, -O- , -CO-, -NH-, -N (CH 3) -, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CON (CH 3) - or -N, and (CH ₃₎ CO-, ₇ m is an integer from 1 to 4).

In addition, as long as the effect of the present invention is not impaired, a diamine compound represented by the following formula [DA26] may be used.

[Chemical Formula 18]

(In formula [DA26], A ₁ represents -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ ) - or -N (CH ₃₎ is a divalent organic group selected from CO-, a ₂ is a single bond, an aliphatic hydrocarbon group, non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group of a carbon number of 1 ~ 20 a ₃ represents a single -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH ₃ ) -, -N (CH ₃ ) Or -O (CH ₂ ) _m - (m is an integer of 1 to 5), A ₄ is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4.)

In addition, as long as the effect of the present invention is not impaired, a diamine compound having a steroid skeleton represented by the following formulas [DA27] to [DA46] may be used.

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

&Lt; EMI ID =

The other diamine compounds may be used alone or in combination of two or more thereof, depending on the properties such as liquid crystal alignability, voltage retention rate, and accumulated charge when used as a liquid crystal alignment film.

&Lt; Specific tetracarboxylic acid dianhydride &gt;

In order to obtain the specific polymer of the present invention, it is preferable to use a tetracarboxylic acid dianhydride (also referred to as a specific tetracarboxylic acid dianhydride) represented by the following formula [2] as a part of the starting material.

(25)

In the formula [2], Y ₁ is a tetravalent organic group having 4 to 13 carbon atoms, and further contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms.

Specifically, Y ₁ in the formula [2] is, for example, a tetravalent group represented by the following formulas [2a] to [2j].

(26)

In formula [2a], Y ₂ to Y ₅ Is a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.

In the formula [2g], Y ₆ and Y ₇ Is a hydrogen atom or a methyl group and may be the same or different.

Particularly preferred structures of Y ₁ in formula [2] are those of formula [2a], formula [2c], formula [2d], formula [2e], formula [2f] or formula [2g ]to be. Among them, the formula [2a], the formula [2e], the formula [2f] or the formula [2g] is preferable.

&Lt; Other tetracarboxylic acid dianhydrides &gt;

In the present invention, other tetracarboxylic acid dianhydrides (other tetracarboxylic acid dianhydrides) other than the specific tetracarboxylic acid dianhydrides may be used as long as the effects of the present invention are not impaired . As other tetracarboxylic acid dianhydrides, tetracarboxylic acid dianhydrides of the following tetracarboxylic acids may be mentioned.

Naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, Anthracene tetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4- Biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, bis (3,4- Dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2- Dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridine tetracarboxylic acid, 2 , 6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid.

The above-mentioned specific tetracarboxylic acid dianhydrides and other tetracarboxylic acid dianhydrides may be used singly or in combination of two or more kinds depending on the properties such as liquid crystal aligning property, voltage holding ratio, and accumulated charge when the liquid crystal alignment film is used It is possible.

&Lt; Specific polymer &

The specific polymer of the present invention is at least one polymer selected from the group consisting of a polyimide precursor having a side chain shown by the above formula [1] and a polyimide obtained by imidizing a polyimide precursor.

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

(27)

(In the formula [A], R ₁ is a tetravalent organic group and R ₂ Is a divalent organic group, and A ₁ and A ₂ are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, which may be the same or different, and n is a positive integer.

The specific polymer of the present invention can be obtained by the following formula [D] because it is comparatively easily obtained by using the diamine component represented by the following formula [B] and the tetracarboxylic acid dianhydride represented by the following formula [C] And a polyimide obtained by imidizing the polyamic acid is preferable.

(28)

(Of the formulas [B] and [C], R ₁ and R ₂ Is the same as defined in Equation [A]).

[Chemical Formula 29]

(In the formula [D], R ₁ and R ₂ Is the same as defined in Equation [A]).

In the present invention, a method of synthesizing a specific polymer is not particularly limited. It is usually obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, a polyamic acid is obtained by reacting at least one tetracarboxylic acid component selected from the group consisting of a tetracarboxylic acid and a derivative thereof and a diamine component composed of one or more kinds of diamine compounds. Specifically, there are a method of polycondensation of a tetracarboxylic acid dianhydride and a diamine component to obtain a polyamic acid, a method of obtaining a polyamic acid by dehydration polycondensation reaction of a tetracarboxylic acid and a diamine component or a method in which a tetracarboxylic acid dihalide and a diamine To obtain a polyamic acid.

To obtain the polyamide acid alkyl ester, a method of polycondensation of a tetracarboxylic acid having a carboxylic acid group with a dialkyl ester and a diamine component, a method of polycondensation of a diamine component with a tetracarboxylic dihalide obtained by dialkyl esterifying a carboxylic acid group 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 above polyamic acid or polyamide acid alkyl ester into a polyimide by ring closure is used.

The liquid crystal alignment film obtained by using the specific polymer of the present invention has such a tendency that as the content ratio of the specific side chain structure represented by the formula [1] in the diamine component increases, the hydrophilicity of the liquid crystal alignment film as a liquid crystal alignment film, The angle can be increased. At this time, as the diamine component, it is preferable to use the specific side chain type diamine compound represented by the above formula [1a]. Particularly preferably, at least one kind selected from the group consisting of the specific side chain type diamine compounds represented by the above-mentioned formulas [1-1] to [1-6] and the formulas [1-9] to [1-13] . Among them, it is preferable to use at least one kind selected from the group consisting of the specific side chain type diamine compounds represented by the formulas [1-1] to [1-6] or the formulas [1-9] to [1-12] Do. For the purpose of enhancing this property, it is preferable that 5 mol% or more and 80 mol% or less of the diamine component is a specific side chain type diamine compound. Of these, from the viewpoint of coating properties of the liquid crystal alignment treatment agent and electric characteristics as a liquid crystal alignment film, it is preferable that 5 mol% or more and 60 mol% or less of the diamine component is a specific side chain type diamine compound. More preferably, it is 10 mol% or more and 60 mol% or less of the diamine component.

In order to obtain the specific polymer of the present invention, it is preferable to use the specific tetracarboxylic acid dianhydride represented by the above formula [2] as the tetracarboxylic acid component. In particular, Y ₁ in formula [2] It is preferable to use a tetracarboxylic acid dianhydride which is a group of the structure represented by the above formulas [2a] to [2j]. At this time, it is preferable that 1 mol% or more of the tetracarboxylic acid component is a specific tetracarboxylic acid dianhydride, more preferably 5 mol% or more, and still more preferably 10 mol% or more. In addition, 100 mol% of the tetracarboxylic acid component may be a specific tetracarboxylic acid dianhydride.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in an organic solvent. The organic solvent to be used at this time is not particularly limited as long as it is a specific solvent of the present invention and the resulting polyimide precursor is dissolved. Specific examples thereof are given below.

Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, , Methyl ethyl ketone, cyclohexanone, cyclopentanone, and 4-hydroxy-4-methyl-2-pentanone.

These may be used alone or in combination. Further, the solvent may be a solvent that does not dissolve the polyimide precursor, or may be mixed with the solvent to the extent that the resulting 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, a method in which a solution in which a diamine component is dispersed or dissolved in an organic solvent is stirred and a tetracarboxylic acid component is added 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 tetracarboxylic acid component and a diamine component, and the like. May be used. When a plurality of diamine components or tetracarboxylic acid components are used to carry out 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 It may be a polymer. The polymerization temperature at that time may be any temperature within the range of -20 to 150 ° C, preferably -5 to 100 ° C. If the concentration is too low, it becomes difficult to obtain a specific polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes too high, and it becomes difficult to perform uniform stirring. Therefore, the content is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction is carried out at a high concentration in the initial stage, and then an organic solvent can be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total molar number of the diamine component to the total molar number of the tetracarboxylic acid component is preferably 0.8 to 1.2. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

The polyimide of the present invention is a polyimide obtained by ring-closing the above polyimide precursor, and is useful as a polymer for obtaining a liquid crystal alignment film.

In the polyimide of the present invention, the closed rate (also referred to as the imidization rate) of the amidic acid group does not necessarily have to be 100%, and can be arbitrarily adjusted depending on the purpose and purpose.

Examples of the method of imidizing the polyimide precursor include heat imidization for directly heating the solution of the polyimide precursor or catalyst imidization for adding a catalyst to a solution of the polyimide precursor.

The temperature when the polyimide precursor is thermally imidized in a solution is 100 to 400 캜, preferably 120 to 250 캜.

The thermal imidation reaction is preferably carried out while removing the produced water from 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. Of these, pyridine is preferred because it has a suitable basicity for promoting the reaction.

As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be given. Among them, acetic anhydride is preferable because the purification after completion of the reaction becomes easy. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, 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 the solvent can be recovered by filtration and then dried under normal pressure or reduced pressure at room temperature or by heating. In addition, when the polymer recovered by precipitation is redissolved in an organic solvent, and the operation of re-precipitation and recovery is repeated 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 mentioned, and it is preferable to use three or more kinds of solvents selected from these because the purification efficiency is further increased.

The molecular weight of the specific polymer of the present invention is preferably 5,000 to 1,000,000 in terms of weight average molecular weight measured by GPC (Gel Permeation Chromatography) in consideration of the strength of the obtained polymer film, the workability in forming the polymer film, and the uniformity of the polymer film , And more preferably from 10,000 to 150,000.

&Lt; Liquid crystal alignment treatment agent &

The liquid crystal alignment treatment agent of the present invention is a coating liquid for forming a liquid crystal alignment film, and is a coating liquid for forming a resin film containing a specific solvent and a specific polymer.

The polymer component in the liquid crystal alignment treatment agent of the present invention may be all the specific polymer of the present invention, and the polymer other than the specific polymer of the present invention may be mixed. At this time, the content of the other polymer in the polymer component is 0.5 to 15 mass%, preferably 1 to 10 mass%.

As other polymers other than these, a polyimide precursor obtained from a tetracarboxylic acid component containing no diamine component containing no specific side chain diamine compound and a specific tetracarboxylic acid dianhydride, and a polyimide precursor obtained by imidizing a polyimide precursor And at least one kind of polymer selected from the group consisting of amines. Further, polymers other than polyimide precursors and polyimides, specifically acrylic polymers, methacrylic polymers, polystyrenes, polyamides, siloxane polymers, and the like can be given.

The organic solvent in the liquid crystal alignment treatment agent of the present invention preferably has an organic solvent content of 70 to 99 mass% in the liquid crystal alignment treatment agent from the viewpoint of forming a uniform film by coating. The content of the organic solvent can be appropriately changed according to the thickness of the intended liquid crystal alignment film.

As the organic solvent, it is preferable to use the specific solvent of the present invention. At this time, as long as the organic solvent dissolves the specific polymer, in addition to the specific solvent, the following solvents may be used. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, , Methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone.

Among them, it is preferable to use N-methyl-2-pyrrolidone,? -Butyrolactone and the like (these are also referred to as component (C)).

The amount of the component (C) to be used is preferably 0.1 to 70 mass% of the total amount of the organic solvent contained in the liquid crystal alignment treatment agent. In particular, it is preferably 1 to 60% by mass. More preferably from 1 to 50% by mass, and still more preferably from 3 to 40% by mass.

As long as the effect of the present invention is not impaired, the liquid crystal alignment treatment agent of the present invention can use an organic solvent, that is, a poor solvent, which improves the film uniformity and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied . Specific examples of the poor solvent for improving the film uniformity and surface smoothness of the liquid crystal alignment film are described below.

Butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-propanediol, Butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, Ethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4- Ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-ethylhexyl acetoacetate, 2-ethylhexyl acetate, (Methoxymethoxy) ethanol, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl Propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl Diethylene glycol, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, acetic acid (such as methyl acetate, ethyl acetate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3- ethylhexyl methoxypropionate, A low surface tension organic acid such as methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, Solvent.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether and the like (these are also referred to as component (D)).

The amount of the poor solvent (component (D)) to be used is preferably 1 to 80 mass% of the total amount of the organic solvent contained in the liquid crystal alignment treatment agent. In particular, it is preferably from 5 to 70% by mass. And more preferably 10 to 70 mass%.

Preferred combinations of the organic solvents in the liquid crystal alignment treatment agent of the present invention are shown in Tables 1 to 3.

In Table 1 to 3, NEP represents N-ethyl-2-pyrrolidone, NMP represents N-methyl-2-pyrrolidone,? -BL represents? -Butyrolactone, BCS represents ethylene glycol mono Butyl ether, ECS represents ethylene glycol monoethyl ether, MC represents diethylene glycol monomethyl ether, EC represents diethylene glycol monoethyl ether, and PGME represents propylene glycol monomethyl ether.

Among these combinations of organic solvents, 2-1 to 2-10, 2-14 to 2-17, 2-19 to 2-25, 2-29 to 2-32, 2-34 to 2-40, or 2-44 To 2-46 is preferred. More preferred are combinations of 2-1 to 2-10, 2-14 to 2-17, 2-19 to 2-2-25, 2-32 or 2-38-2-40. Particularly preferred is a combination of 2-2, 2-8 to 2-10, 2-17, 2-23 to 2-25, 2-32 or 2-38 to 2-40.

The liquid crystal alignment treatment agent of the present invention may contain a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group, as long as the effect of the present invention is not impaired Or a crosslinkable compound having at least one kind of substituent selected from the group consisting of a polymerizable unsaturated bond and a crosslinkable compound having a polymerizable unsaturated bond. It is preferable that two or more of these substituents and polymerizable unsaturated bonds are contained in the crosslinkable compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolak epoxy resin, cresol novolak epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, (Aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetate di Glycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4- 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4-methylphenyl) Phenyl) propane, 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) ) Phenyl) -1- (4- (1- ( 4- (2,3-epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [3].

(30)

Specifically, it is a crosslinkable compound represented by the following formulas [3-1] to [3-11].

(31)

(32)

(33)

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

(34)

Specifically, it is a crosslinkable compound represented by the following formulas [4-1] to [4-37].

(35)

(36)

(37)

(38)

[Chemical Formula 39]

(40)

(41)

(42)

(4-24), n is an integer of 1 to 5. In the formula [4-25], n is an integer of 1 to 5. In the formula [4-36], n is an integer of 1 to 100 In formula [4-37], n is an integer of 1 to 10.)

Also, a polysiloxane having at least one structure represented by the following formulas [4-38] to [4-40] may be used.

(43)

(In formulas [4-38] to [4-40], R ₁ , R ₂ , R ₃ , R ₄ and R ₅ Each independently represent a structure represented by the formula [4], a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aliphatic ring or an aromatic ring, and at least one of them is a structure represented by the formula [4].

More specifically, the compounds of the following formulas [4-41] and [4-42] can be mentioned.

(44)

(In the formula [4-42], n is an integer of 1 to 10.)

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

Examples of such melamine derivatives or benzoguanamine derivatives include MX-750 in which a methoxymethyl group is substituted on average 3.7 per 1 triazine ring of a commercial product, MW- Methomethylated melamines such as Cymel 235, 236, 238, 212, 253, and 254 (manufactured by Sansui Chemical Co., Ltd.) or Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, Methoxymethylated butoxymethylated melamines such as Cymel 506 and 508, carboxyl-containing methoxymethylated isobutoxymethylated melamines such as Cymel 1141, and methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1123, Methoxymethylated butoxymethylated benzoguanamines such as Cymel 1123-10, butoxymethylated benzoguanamines such as Cymel 1128, carboxyl-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80, Anamin (manufactured by Mitsui Cyanamid), and the like. Examples of the glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylol glycoluril such as Cymel 1172, methoxymethylolglycoluril such as Powderlink 1174, and the like.

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

Specific examples thereof include crosslinkable compounds represented by the formulas [6-1] to [6-48], which are listed on pages 62 to 66 of International Publication No. WO2011 / 132751 (published on October 27, 2011).

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) A crosslinkable compound having three polymerizable unsaturated groups such as acryloyloxyethoxy trimethylol propane and glycerin polyglycidyl ether poly (meth) acrylate in the molecule, ethylene glycol di (meth) acrylate, diethylene glycol di (Meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di ) Acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide (Meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, pentaerythritol di (Meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, and hydroxypivalic neopentyl glycol di (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2 Hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- 2- (meth) acryloyloxy And crosslinkable compounds having one polymerizable unsaturated group such as methyl ethyl phosphate, N-methylol (meth) acrylamide and the like in the molecule.

The compound represented by the following formula [6] may also be used.

[Chemical Formula 45]

In formula [6], E ₁ is a group selected from the group consisting of cyclohexane ring, bicyclohexane ring, benzene ring, biphenyl ring, terphenyl ring, naphthalene ring, fluorene ring, anthracene ring and phenanthrene ring , E ₂ Is a group selected from the following formulas [6a] and [6b], and n is an integer of 1 to 4.

(46)

The above compound is an example of a crosslinkable compound, but is not limited thereto.

The crosslinkable compound contained in the liquid crystal alignment treatment agent of the present invention may be one kind or two or more kinds.

The content of the crosslinkable compound in the liquid crystal alignment treatment agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all the polymer components. More preferably from 0.1 to 100 parts by mass, and most preferably from 1 to 50 parts by mass, per 100 parts by mass of all the polymer components, in order that the crosslinking reaction proceeds to exhibit the intended effect and not to deteriorate the orientation properties of the liquid crystal.

As a compound for promoting the charge transfer in the liquid crystal alignment film formed by using the liquid crystal alignment treatment agent of the present invention and promoting the charge leakage of the liquid crystal cell using the liquid crystal alignment film is disclosed in International Publication WO2011 / 132751 (published on October 27, 2011) Nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156], which are listed on pages 69 to 73 of JP-A- These amine compounds may be directly added to a solution of a specific polymer, but it is preferable to add the amine compound in an appropriate solvent at a concentration of 0.1 to 10 mass%, preferably 1 to 7 mass%. The solvent is not particularly limited as long as it is an organic solvent capable of dissolving the above-mentioned specific polymer.

As long as the effect of the present invention is not impaired, the liquid crystal alignment treatment agent of the present invention can use a compound that improves the film thickness uniformity and surface smoothness of the polymer film when the liquid crystal alignment treatment agent is applied. 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 film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent.

More specifically, it is possible to use, for example, EFTOP EF301, EF303, EF352 (manufactured by TOKEM PRODUCTS CO., LTD.), Megafac F171, F173, R-30 (manufactured by Dainippon Ink and Chemicals Inc.), FLORAD FC430 and FC431 (manufactured by Sumitomo 3M Ltd.) ), Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.). The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment treatment agent.

Specific examples of the compound improving the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (3-aminopropyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 Tetraglycidyl-2,4-hexanediol, N, N, N ', N', -tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N', -tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

In the case of using a compound for improving adhesion with a substrate, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment treatment agent. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected, and if it is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

The liquid crystal alignment treatment agent of the present invention may contain the above-mentioned poor solvent, the crosslinkable compound, the compound which improves the uniformity of the film thickness and the surface smoothness, and the compound which adheres to the substrate in a satisfactory manner, A dielectric material or a conductive material may be added for the purpose of changing electrical characteristics such as dielectric constant and conductivity of the alignment film.

<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 and baked on a substrate and subjected to an orientation treatment by rubbing treatment, light irradiation, or the like. Further, in the case of vertical alignment applications, 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 simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like 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 generally, screen printing, offset printing, flexographic printing, inkjet printing, and the like are common. 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, the solvent is evaporated at a temperature of 50 to 300 ° C, preferably 80 to 250 ° C by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) It can be made into a film. When the thickness of the polymer film after firing is too large, the power consumption of the liquid crystal display element is deteriorated. When the thickness of the polymer film is too thin, the reliability of the liquid crystal display element may be deteriorated. Therefore, the thickness is preferably 5 to 300 nm, 10 to 100 nm.

When the liquid crystal is horizontally aligned or tilted, the polymer film after firing 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 method for manufacturing a liquid crystal cell, a pair of substrates on which liquid crystal alignment films are formed are prepared, spacers are spread on the liquid crystal alignment films of the substrates, and the substrates of the other substrates are bonded to each other, A method in which a liquid crystal is injected under reduced pressure and sealed, a method in which a liquid crystal is dropped on the surface of a liquid crystal alignment film on which a spacer is spread, and then the substrate is bonded and sealed.

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 containing 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 with an active energy ray and heating, while applying a voltage between the electrodes, is preferably used for a liquid crystal display device. The active energy ray is preferably ultraviolet ray.

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 into a liquid crystal material, and a liquid crystal cell is assembled. Then, 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 the liquid crystal alignment treatment agent of the present invention by the above-mentioned technique, preparing a liquid crystal cell, The orientation of the liquid crystal molecules can be controlled.

For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer is spread on the liquid crystal alignment film of the substrate of the single chamber, and the liquid crystal alignment film surface is inward, A method in which a liquid crystal is injected under reduced pressure and sealed, a method in which a liquid crystal is dropped on the surface of a liquid crystal alignment film on which a spacer is spread, and then a substrate is bonded and sealed.

The liquid crystal is mixed with a polymerizable compound which is polymerized by irradiation with heat or ultraviolet rays. 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 by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal can not be controlled. When the amount is larger than 10 parts by mass, unreacted polymerizable compound increases, .

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.

Further, 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 containing a polymerizable group polymerized by at least one of active energy rays and heat between the pair of substrates And a liquid crystal display device manufactured by a process of applying a voltage between electrodes. The active energy ray is preferably ultraviolet ray.

In order to obtain a liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and a 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 Method. Since the liquid crystal alignment treatment agent of the present invention contains a specific compound having a double bonding site that reacts by irradiation with heat or ultraviolet rays, the orientation of the liquid crystal molecules can be controlled by at least one of irradiation of ultraviolet rays and heating have.

One example of manufacturing a liquid crystal cell is to prepare a pair of substrates on which a liquid crystal alignment film is formed by spraying a spacer 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 a liquid crystal is injected under reduced pressure, a method in which a liquid crystal is dropped on a surface of a liquid crystal alignment film on which a spacer is spread, and a substrate is bonded to the substrate by sealing.

After the liquid crystal cell is fabricated, the alignment of the 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.

As described above, the liquid crystal display element manufactured by using the liquid crystal alignment treatment agent of the present invention has excellent reliability and can be preferably used for a liquid crystal television of high precision on a large screen.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not construed as being limited thereto. The abbreviations of the compounds used in Examples and Comparative Examples are as follows.

(Tetracarboxylic acid dianhydride)

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

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

TCA: tetracarboxylic acid dianhydride represented by the following formula

TDA: tetracarboxylic acid dianhydride represented by the following formula

(47)

(Specific side chain type diamine compound)

PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

PBCH5DAB: 1,3-diamino-4- {trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy}

m-PBCH5DABz: 1,3-diamino-5- {4- [4- (trans-4-n-pentylcyclohexyl) phenyl] phenoxymethyl}

(48)

(Other diamine compounds)

p-PDA: p-phenylenediamine

m-PDA: m-Phenylenediamine

DBA: 3,5-diaminobenzoic acid

AP18: 1,3-Diamino-4-octadecyloxybenzene

ColDAB: diamine compound represented by the following formula

(49)

(Organic solvent)

NEP: N-ethyl-2-pyrrolidone

NMP: N-methyl-2-pyrrolidone

? -BL:? -butyrolactone

BCS: ethylene glycol monobutyl ether

ECS: ethylene glycol monoethyl ether

MC: diethylene glycol monomethyl ether

EC: diethylene glycol monoethyl ether

PGME: Propylene glycol monomethyl ether

The physical properties such as molecular weight and imidization ratio of the polyimide precursor and polyimide were measured or evaluated as follows.

(Measurement of molecular weight of polyimide precursor and polyimide)

The molecular weight of the polyimide in Synthesis Example was measured using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko K.K.), a column (KD-803, KD-805) And measured as follows.

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 calibration curves: 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).

(Measurement of imidization rate)

The imidization rate of the polyimide in the synthesis example was measured in the following manner. (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixed product) was added in an NMR sample tube (NMR sampling tube standard 5 (manufactured by Kusano Scientific Co., Ltd.) 20 mg of polyimide powder 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 does not change before and after imidization 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

In the above formula, 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 the NH of the amide acid in the case of the polyamic acid (the imidization rate is 0% The ratio of the number of reference protons to one protopertone.

[Synthesis of polyimide and polyimide acid]

&Lt; Synthesis Example 1 &

PDA (2.13 g, 19.7 mmol) were mixed in NEP (32.5 g) and reacted at 40 占 폚 for 6 hours to obtain a resin solid content concentration of 5.5 g, 28.0 mmol, PCH7DAB (3.20 g, 8.41 mmol) To obtain 25.0 mass% of a polyamic acid solution (1). This polyamic acid had a number average molecular weight of 25,100 and a weight average molecular weight of 74,800.

&Lt; Synthesis Example 2 &

BODA (10.2 g, 40.8 mmol), PCH7DAB (9.70 g, 25.5 mmol) and DBA (3.88 g, 25.5 mmol) were mixed in NEP (42.6 g) and reacted at 80 ° C for 5 hours. Thereafter, CBDA (2.00 g, 10.2 mmol) and NEP (34.8 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25.0 mass%. The polyamic acid had a number average molecular weight of 24,200 and a weight average molecular weight of 64,000.

&Lt; Synthesis Example 3 &

To polyamic acid solution (2) (90.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 2, NEP was added and diluted to 6% by mass, acetic anhydride (11.6 g) Pyridine (8.56 g), and the mixture was reacted at 80 DEG C for 4 hours. This reaction solution was poured into methanol (1800 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 (3). The imidization ratio of the polyimide was 57%, the number average molecular weight was 21,300, and the weight average molecular weight was 51,500.

&Lt; Synthesis Example 4 &

BODA (6.89 g, 27.5 mmol), PBCH5DAB (5.21 g, 12.0 mmol) and DBA (3.42 g, 22.5 mmol) were mixed in NEP (28.1 g) and reacted at 80 ° C for 5 hours. Thereafter, CBDA (1.35 g, 6.88 mmol) and NEP (22.4 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

Acetic anhydride (13.5 g) and pyridine (9.80 g) were added as imidation catalysts to the obtained polyamic acid solution (60.0 g) and diluted to 6 mass% . The reaction solution was poured into methanol (1500 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 polyimide had an imidization rate of 79%, a number average molecular weight of 19,200, and a weight average molecular weight of 48,200.

&Lt; Synthesis Example 5 &

PDA (2.57 g, 23.8 mmol) were mixed in NEP (25.0 g) and reacted at 80 ° C for 5 hours. Thereafter, CBDA (2.00 g, 10.2 mmol) and NEP (20.3 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

Acetic anhydride (12.3 g) and pyridine (9.11 g) were added as imidation catalysts to the obtained polyamic acid solution (55.0 g), diluted to 6 mass%, and reacted at 90 ° C for 3 hours . The reaction solution was poured into methanol (1500 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 80%, the number average molecular weight was 21,500, and the weight average molecular weight was 53,800.

&Lt; Synthesis Example 6 &

PDA (1.52 g, 14.1 mmol) were mixed in NEP (24.9 g) and reacted at 40 占 폚 for 6 hours to obtain a resin solid content concentration of 4.50 g, 20.1 mmol, PCH7DAB (2.29 g, 6.02 mmol) Of polyamic acid solution (6) of 25.0 mass%. This polyamic acid had a number average molecular weight of 25,100 and a weight average molecular weight of 71,900.

&Lt; Synthesis Example 7 &

The reaction was carried out at 40 占 폚 for 6 hours to obtain a resin solid content concentration of 25.0 占 TC, Mass% of a polyamic acid solution was obtained.

Acetic anhydride (6.05 g) and pyridine (4.73 g) as an imidation catalyst were added to the resulting polyamic acid solution (50.0 g) and diluted to 6 mass% . The reaction solution was poured into methanol (900 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 (7). The imidization ratio of the polyimide was 54%, the number average molecular weight was 21,800, and the weight average molecular weight was 56,200.

&Lt; Synthesis Example 8 &

TDA (2.98 g, 9.92 mmol), PCH7DAB (3.78 g, 9.93 mmol) and DBA (3.53 g, 23.2 mmol) were mixed in NEP (24.5 g) and reacted at 80 ° C for 5 hours. Thereafter, CBDA (4.55 g, 23.2 mmol) and NEP (20.1 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

Acetic anhydride (11.1 g) and pyridine (8.05 g) were added as imidation catalysts to the obtained polyamic acid solution (50.0 g), diluted to 6 mass% . The reaction solution was poured into methanol (1500 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 the polyimide was 76%, the number average molecular weight was 20,700, and the weight average molecular weight was 52,500.

&Lt; Synthesis Example 9 &

PDA (2.76 g, 25.5 mmol) were mixed in NEP (26.1 g) and reacted at 80 ° C for 5 hours. Thereafter, CBDA (5.01 g, 25.5 mmol) and NEP (21.3 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

Acetic anhydride (11.2 g) and pyridine (8.21 g) were added as imidation catalysts to the obtained polyamic acid solution (50.5 g), diluted to 6 mass% . The reaction solution was poured into methanol (1500 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 the polyimide was 80%, the number average molecular weight was 20,100, and the weight average molecular weight was 50,200.

&Lt; Synthesis Example 10 &

The mixture was stirred at 80 占 폚 for 5 hours. The reaction mixture was stirred at 80 占 폚 for 2 hours. The mixture was stirred at room temperature for 2 hours. Thereafter, CBDA (4.65 g, 23.7 mmol) and NEP (21.4 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

Acetic anhydride (11.2 g) and pyridine (8.24 g) were added as imidation catalysts to the obtained polyamic acid solution (50.0 g) and diluted to 6 mass% . The reaction solution was poured into methanol (1500 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 80%, the number average molecular weight was 20,500, and the weight average molecular weight was 52,900.

&Lt; Synthesis Example 11 &

BODA (5.21 g, 20.8 mmol), PCH7DAB (4.95 g, 13.0 mmol) and DBA (1.98 g, 13.0 mmol) were mixed in NMP (21.7 g) and reacted at 80 ° C for 5 hours. Thereafter, CBDA (1.02 g, 5.20 mmol) and NMP (17.8 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution 11 having a resin solid content concentration of 25.0 mass%. The polyamic acid had a number average molecular weight of 25,100 and a weight average molecular weight of 65,900.

&Lt; Synthesis Example 12 &

BODA (6.38 g, 25.5 mmol), AP18 (6.00 g, 15.9 mmol) and DBA (2.45 g, 16.1 mmol) were mixed in NMP (26.5 g) and reacted at 80 ° C for 5 hours. Thereafter, CBDA (1.25 g, 6.37 mmol) and NMP (21.7 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution 12 having a resin solid content concentration of 25.0 mass%. This polyamic acid had a number average molecular weight of 18,900 and a weight average molecular weight of 54,800.

&Lt; Synthesis Example 13 &

To the polyamic acid solution (12) (50.0 g) having a resin solid content concentration of 25.0 mass% obtained in Synthesis Example 12, NMP was added and diluted to 6 mass%, acetic anhydride (6.23 g) and Pyridine (4.65 g) was added, and the mixture was reacted at 80 DEG C for 4 hours. The reaction solution was poured into methanol (1000 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 (13). The imidization ratio of the polyimide was 58%, the number average molecular weight was 16,900, and the weight average molecular weight was 43,800.

&Lt; Synthesis Example 14 &

BODA (6.89 g, 27.5 mmol), ColDAB (5.40 g, 10.3 mmol) and DBA (3.68 g, 24.2 mmol) were mixed in NEP (28.6 g) and reacted at 80 ° C for 5.5 hours. Thereafter, CBDA (1.35 g, 6.88 mmol) and NEP (23.4 g) were added and reacted at 40 ° C for 7 hours to obtain a polyamic acid solution 14 having a resin solid content concentration of 25.0 mass%. The polyamic acid had a number average molecular weight of 20,100 and a weight average molecular weight of 59,800.

&Lt; Synthesis Example 15 &

BODA (6.74 g, 26.9 mmol), ColDAB (5.28 g, 10.1 mmol) and DBA (3.60 g, 23.7 mmol) were mixed in NMP (27.9 g) and reacted at 80 ° C for 5.5 hours. Thereafter, CBDA (1.32 g, 6.73 mmol) and NMP (22.9 g) were added and reacted at 40 占 폚 for 7 hours to obtain a polyamic acid solution 15 having a resin solid content concentration of 25.0 mass%. This polyamic acid had a number average molecular weight of 19,900 and a weight average molecular weight of 59,100.

&Lt; Synthesis Example 16 &

To polyamic acid solution (15) (55.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 15, NMP was added and diluted to 6% by mass, acetic anhydride (6.81 g) Pyridine (5.07 g) was added, and the reaction was allowed to proceed at 80 占 폚 for 4 hours. The reaction solution was poured into methanol (1100 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimide powder (16). The imidization ratio of the polyimide was 57%, the number average molecular weight was 15,900, and the weight average molecular weight was 45,100.

The polyamic acid and polyimide of the present invention are summarized in Table 4.

* 1: All polyamidic acid, imidization rate not measured.

[Preparation of liquid crystal alignment treatment agent]

The following Examples 1 to 34 and Comparative Examples 1 to 12 are examples of preparation of a liquid crystal alignment treatment agent, all of which are for evaluation of a liquid crystal alignment treatment agent.

The liquid crystal alignment treatment agents obtained in Examples and Comparative Examples were used to evaluate the printability of the liquid crystal alignment treatment agent, the evaluation of the inkjet application of the liquid crystal alignment treatment agent, the production of the liquid crystal cell (normal cell) Evaluation of pretilt angle (normal cell), production of liquid crystal cell (PSA cell), and evaluation of liquid crystal orientation (PSA cell).

(Printing property evaluation of liquid crystal alignment treatment agent)

Printing performance was evaluated using the liquid crystal alignment treatment agents obtained in Examples and Comparative Examples. For the printing press, a simple printer S15 type (manufactured by Nippon Photo Printing Co., Ltd.) was used. The printing was carried out on a cleaned chromium-deposited substrate with a printing area of 80 mm x 80 mm, a printing pressure of 0.2 mm, five sheets of waste substrates, a time from printing to drying of 90 seconds, For 5 minutes.

Evaluation of the pinhole of the obtained coating film, evaluation of the linearity of the end portion of the liquid crystal alignment film, and evaluation of the mounting of the end portion of the liquid crystal alignment film were carried out.

The evaluation of the pinhole was carried out by visually observing the coating film under a sodium lamp. Specifically, the number of pinholes identified on the liquid crystal alignment film was counted, and the smaller the number of pinholes, the better the applicability.

The linearity of the end portion of the liquid crystal alignment film was evaluated by observing the coating film at the right end portion with respect to the printing direction with an optical microscope (Nikon Corporation, ECLIPSE E600WPOL). Concretely, the magnification was observed with an optical microscope at a magnification of 25, and the difference between 3 and 4 in FIG. 1, that is, the length of A in FIG. 1, was measured. All coating film images were obtained at the same magnification. The shorter the length of A, the better the linearity of the end portion of the liquid crystal alignment film.

Mounting of the end portion of the liquid crystal alignment film was evaluated by observing the coating film at the right end portion with respect to the printing direction with an optical microscope. Specifically, the magnification was observed with an optical microscope at a magnification of 25, and the length of B in the obtained coating film image (FIG. 2) was measured. All coating film images were obtained at the same magnification. The shorter the length of B, the better the mounting 5 at the end of the liquid crystal alignment film.

Tables 8 to 10 show the number of pinholes, the length of A and the length of B in the liquid crystal alignment film obtained in Examples and Comparative Examples.

(Evaluation of inkjet application property of liquid crystal alignment treatment agent)

Evaluation of ink-jet applicability was carried out by using the liquid crystal alignment treatment agent (7) obtained in Example 7 and the liquid crystal alignment treatment agent (12) obtained in Example 12. For the ink-jet applicator, HIS-200 (manufactured by Hitachi Plant Technologies Co., Ltd.) was used. The coating was carried out on a cleaned ITO (indium tin oxide) -evaporated substrate with a coating area of 70 mm x 70 mm, a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm, a coating speed of 40 mm / sec, For 60 seconds, and drying on a hot plate at 70 DEG C for 5 minutes.

Evaluation of pinholes of the obtained coating film was carried out under the same conditions as &quot; evaluation of printability of liquid crystal alignment treatment agent &quot;. Table 8 shows the evaluation results of the pinholes in Examples 7 and 12.

(Fabrication of liquid crystal cell (normal cell))

The liquid crystal alignment treatment agent obtained in Examples and Comparative Examples was spin-coated on the ITO surface of a substrate having a 30 mm x 40 mm ITO electrode formed thereon and heated on a hot plate at 80 캜 for 5 minutes and at 220 캜 for 30 minutes at 220 캜 in a clean- Minute heat treatment to obtain an ITO substrate on which a polyimide liquid crystal alignment film having a film thickness of 100 nm was formed. The coated film surface of the ITO substrate was rubbed with rayon cloth with a rubbing apparatus having a roll diameter of 120 mm under the conditions of a roll rotation number of 1000 rpm, a roll progress speed of 50 mm / sec, and a press amount of 0.1 mm.

Two pieces of the ITO substrates on which the obtained liquid crystal alignment films were formed were prepared, and 6 mu m spacers were interposed therebetween with the liquid crystal alignment film surface on the inner side, and the periphery was adhered with a sealant to prepare blank 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 (ordinary cell).

(Evaluation of Liquid Crystal Orientation and Pretilt Angle (Normal Cell))

Using the liquid crystal cell obtained above, the liquid crystal alignability and the pretilt angle were evaluated. The liquid crystal alignability was observed by observing the liquid crystal cell with a polarizing microscope (ECLIPSE E600WPOL, manufactured by Nikon Corporation) to confirm the presence of alignment defects.

The pretilt angle was measured after heating the liquid crystal at 95 ° C for 5 minutes and then at 120 ° C for 5 hours. After the liquid crystal injection, the liquid crystal cell subjected to heat treatment at 95 캜 for 5 minutes was irradiated with ultraviolet rays of 10 J / cm 2 in 365 nm conversion, and then the pretilt angle was measured.

The smaller the change in the pretilt angle after the heat treatment at 120 ° C for 5 hours or after the irradiation with ultraviolet light, the smaller the stability of the pretilt angle with respect to heat or ultraviolet ray .

The pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON). The ultraviolet ray irradiation was carried out using a tabletop UV curing device (HCT3B28HEX-1) (manufactured by Sen Wright).

The liquid crystal alignability and the results of the pretilt angles of the liquid crystal cell obtained in the examples and comparative examples are shown in Tables 11 to 13.

(Production of liquid crystal cell (PSA cell))

The liquid crystal alignment treatment agent (5) obtained in Example 5, the liquid crystal alignment treatment agent (6) obtained in Example 6, the liquid crystal alignment treatment agent (11) obtained in Example 11, the liquid crystal alignment treatment agent (17) The liquid crystal alignment treatment agent 30 obtained in Example 30 was applied onto a substrate on which an ITO electrode having a pattern interval of 20 占 퐉 of 10 mm 占 10 mm was formed on the center and a ITO electrode of a 10 mm 占 40 mm substrate, Heat treatment was performed on a hot plate at 80 DEG C for 5 minutes and at 220 DEG C for 30 minutes in a thermocycling type clean oven to obtain a polyimide coating film having a thickness of 100 nm. The coated film surface was cleaned with pure water and then subjected to heat treatment at 100 캜 for 15 minutes in a thermocycling type clean oven to obtain a substrate having a liquid crystal alignment film formed thereon.

The substrate on which the liquid crystal alignment film was formed was assembled by interposing a spacer having a size of 6 mu m with the liquid crystal alignment film face inward and bonding the periphery with a sealant to prepare an empty cell. A polymerizable compound (1) represented by the following formula was added to this hollow cell by MLC-6608 (manufactured by Merck Japan Co., Ltd.) by a reduced pressure injection method and 0.3% by mass of a polymerizable compound based on 100% by mass of MLC- The mixed liquid crystal was injected and the injection port was sealed to obtain a liquid crystal cell.

(50)

A wavelength of 350 nm or less was cut using a metal halide lamp having an illuminance of 60 mW while applying an AC voltage of 5 V to the obtained liquid crystal cell and irradiated with ultraviolet rays of 20 J / cm 2 in terms of 365 nm, (PSA cell) in which the alignment direction 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.

(Evaluation of Liquid Crystal Alignment Property (PSA Cell))

The response speeds of the obtained liquid crystal cell before and after ultraviolet irradiation 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 PSA cell obtained in Examples and Comparative Examples had a higher response speed of the liquid crystal cell after ultraviolet irradiation than in the liquid crystal cell before irradiation with ultraviolet rays, so that the alignment direction of the liquid crystal was controlled.

It was confirmed that the liquid crystal was uniformly oriented by observation of a polarizing microscope in any of the liquid crystal cells.

Examples 1 to 34 and Comparative Examples 1 to 12 will be described in detail below. Conditions for preparing the liquid crystal alignment treatment agent in each example are summarized in Tables 5 to 7.

The liquid crystal alignment treatment agents obtained in Examples 1 to 34 and Comparative Examples 1 to 12 were used for evaluation of printability of liquid crystal alignment treatment agent, evaluation of inkjet application property of liquid crystal alignment treatment agent, (PSA cell) "and" evaluation of liquid crystal orientation (PSA cell) "were conducted on the results of the evaluation of the liquid crystal alignment and the pretilt angle (normal cell). The results are summarized in Tables 8 to 13.

&Lt; Example 1 &gt;

NEP (32.0 g) was added to polyamic acid solution (1) (10.1 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 1 and stirred at 25 占 폚 for 2 hours to obtain 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.

Using the obtained liquid crystal alignment treatment agent (1), production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 2 &gt;

NEP (12.1 g), BCS (11.8 g) and EC (7.84 g) were added to polyamic acid solution (1) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 1, Followed by stirring to obtain a liquid crystal alignment treating 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.

Using the obtained liquid crystal alignment treatment agent (2), cell preparation and various evaluations were carried out under the above-mentioned conditions.

&Lt; Example 3 &gt;

NEP (31.7 g) was added to the polyamide acid solution (2) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 2 and stirred at 25 占 폚 for 2 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.

Using the resultant liquid crystal alignment treatment agent (3), production of cells and various evaluations were carried out under the above-mentioned conditions.

<Example 4>

NEP (14.0 g) and BCS (17.6 g) were added to polyamic acid solution (2) (10.0 g) having a resin solid content concentration of 25.0 mass% obtained in Synthesis Example 2 and stirred at 25 占 폚 for 2 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.

Using the obtained liquid crystal alignment treatment agent (4), cell preparation and various evaluations were carried out under the above-described conditions.

&Lt; Example 5 &gt;

NEP (40.0 g) was added to the polyimide powder (3) (2.55 g) obtained in Synthesis Example 3 and stirred at 70 占 폚 for 24 hours to obtain a liquid crystal alignment treating 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.

Using the obtained liquid crystal alignment treatment agent (5), preparation of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 6 &gt;

NEP (14.6 g) was added to the polyimide powder (3) (2.54 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. NEP (7.30 g) and BCS (17.9 g) were added to this solution, and the mixture was stirred at 50 占 폚 for 10 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.

Using the obtained liquid crystal alignment treatment agent (6), production and various evaluations of cells were carried out under the above-described conditions.

&Lt; Example 7 &gt;

NEP (29.7 g) was added to the polyimide powder (3) (2.50 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. NEP (14.8 g) and BCS (36.4 g) were added to this solution and stirred at 50 占 폚 for 10 hours to obtain 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.

Using the obtained liquid crystal alignment treatment agent (7), &quot; Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot;

&Lt; Example 8 &gt;

NEP (17.3 g) was added to the polyimide powder (3) (2.55 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. NEP (8.71 g), BCS (8.01 g) and MC (6.00 g) were added to this solution and stirred at 50 占 폚 for 10 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.

Using the liquid crystal alignment treatment agent 8 thus obtained, cell preparation and various evaluations were carried out under the above-described conditions.

&Lt; Example 9 &gt;

NEP (18.7 g) was added to the polyimide powder (3) (2.56 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. NEP (9.40 g), BCS (6.00 g) and EC (6.00 g) were added to this solution, and the mixture was stirred at 50 占 폚 for 10 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.

Using the obtained liquid crystal alignment treatment agent (9), cell preparation and various evaluations were carried out under the above-described conditions.

&Lt; Example 10 &gt;

NEP (17.3 g) was added to the polyimide powder (3) (2.55 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. NEP (8.70 g) and PGME (14.0 g) were added to this solution, and the mixture was stirred at 50 占 폚 for 10 hours to obtain a liquid crystal alignment treating 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.

Using the obtained liquid crystal alignment treatment agent 10, production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 11 &gt;

NEP (16.0 g) was added to the polyimide powder (3) (2.55 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. NMP (6.02 g) and BCS (18.0 g) were added to the solution, and the mixture was stirred at 50 占 폚 for 10 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.

Using the obtained liquid crystal alignment treatment agent 11, production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 12 &gt;

NEP (27.6 g) was added to the polyimide powder (3) (2.50 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. NMP (10.3 g) and BCS (31.0 g) were added to this solution and stirred at 50 占 폚 for 10 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.

Using the obtained liquid crystal alignment treatment agent 12, &quot; Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot;

&Lt; Example 13 &gt;

NEP (16.0 g) was added to the polyimide powder (3) (2.55 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution,? -BL (4.02 g) and BCS (20.0 g) were added and stirred at 50 占 폚 for 10 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.

Using the obtained liquid crystal alignment treatment agent 13, production of cells and various evaluations were carried out under the above-mentioned conditions.

&Lt; Example 14 &gt;

NEP (12.0 g) was added to the polyimide powder (4) (2.55 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. NEP (6.02 g) and BCS (22.0 g) were added to the solution, and the mixture was stirred at 50 占 폚 for 10 hours to obtain a liquid crystal alignment treating 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.

Using the obtained liquid crystal alignment treatment agent 14, production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 15 &gt;

NEP (16.1 g) was added to the polyimide powder (4) (2.57 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. NEP (8.10 g) and ECS (16.1 g) were added to this solution and stirred at 50 占 폚 for 10 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.

Using the obtained liquid crystal alignment treatment agent 15, preparation of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 16 &gt;

NEP (18.5 g) was added to the polyimide powder (4) (2.53 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. NEP (9.20 g), BCS (7.93 g) and MC (3.97 g) were added to this solution and stirred at 50 占 폚 for 10 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.

Using the obtained liquid crystal alignment treatment agent 16, production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 17 &gt;

NEP (16.0 g) was added to the polyimide powder (4) (2.55 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. NMP (10.0 g) and BCS (14.1 g) were added to this solution and stirred at 50 占 폚 for 10 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.

Using the obtained liquid crystal alignment treatment agent 17, the production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 18 &gt;

NEP (20.0 g) was added to the polyimide powder (4) (2.55 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, γ-BL (4.00 g) and BCS (16.0 g) were added and stirred at 50 ° C. for 10 hours to obtain a 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.

Using the obtained liquid crystal alignment treatment agent 18, production of the cell and various evaluations were carried out under the above-described conditions.

&Lt; Example 19 &gt;

NEP (12.5 g) was added to the polyimide powder (5) (2.55 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. NEP (3.54 g) and BCS (24.0 g) were added to this solution and stirred at 50 占 폚 for 10 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.

Using the obtained liquid crystal alignment treatment agent 19, production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 20 &gt;

NEP (13.4 g) was added to the polyimide powder (5) (2.56 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. NEP (6.70 g), BCS (16.1 g) and MC (4.02 g) were added to this solution and stirred at 50 占 폚 for 10 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.

Using the obtained liquid crystal alignment treatment agent 20, preparation of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 21 &gt;

NEP (12.0 g) was added to the polyimide powder (5) (2.55 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. NMP (10.0 g) and BCS (18.1 g) were added to this solution and stirred at 50 占 폚 for 10 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.

Using the obtained liquid crystal alignment treatment agent 21, the production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 22 &gt;

NEP (17.8 g) was added to the polyimide powder (5) (2.55 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, γ-BL (2.00 g) and BCS (20.0 g) were added and stirred at 50 ° C. for 10 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.

Using the obtained liquid crystal alignment treatment agent 22, production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 23 &gt;

NEP (6.21 g) and BCS (25.5 g) were added to polyamic acid solution (6) (10.0 g) having a resin solid content concentration of 25.0 mass% obtained in Synthesis Example 6 and stirred at 25 占 폚 for 2 hours to prepare 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.

Using the obtained liquid crystal alignment treatment agent 23, production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 24 &gt;

NEP (16.0 g), BCS (7.87 g) and PGME (7.84 g) were added to the polyamic acid solution (6) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 6, Followed by stirring to obtain a liquid crystal alignment treatment agent (24). 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.

Using the obtained liquid crystal alignment treatment agent 24, the cell was produced and evaluated under various conditions as described above.

&Lt; Example 25 &gt;

NEP (15.9 g) was added to the polyimide powder (7) (2.54 g) obtained in Synthesis Example 7 and dissolved by stirring at 70 占 폚 for 24 hours. NEP (8.00 g) and ECS (15.9 g) were added to this solution and stirred at 50 占 폚 for 10 hours to obtain a liquid crystal alignment treatment agent (25). 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.

Using the liquid crystal alignment treatment agent 25 thus obtained, cell preparation and various evaluations were carried out under the above-described conditions.

&Lt; Example 26 &gt;

NEP (17.3 g) was added to the polyimide powder (7) (2.55 g) obtained in Synthesis Example 7 and dissolved by stirring at 70 占 폚 for 24 hours. NEP (8.71 g), BCS (8.01 g) and PGME (6.00 g) were added to this solution, and the mixture was stirred at 50 占 폚 for 10 hours to obtain a liquid crystal alignment treatment agent 26. 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.

Using the obtained liquid crystal alignment treatment agent 26, the production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 27 &gt;

NEP (20.0 g) was added to the polyimide powder (7) (2.55 g) obtained in Synthesis Example 7 and dissolved by stirring at 70 占 폚 for 24 hours. NMP (8.00 g), BCS (10.1 g) and EC (2.02 g) were added to this solution and stirred at 50 占 폚 for 10 hours to obtain a liquid crystal alignment treatment agent (27). 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.

Using the obtained liquid crystal alignment treatment agent 27, the production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 28 &gt;

NEP (18.1 g) was added to the polyimide powder (7) (2.55 g) obtained in Synthesis Example 7 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, γ-BL (2.00 g), BCS (12.0 g) and ECS (8.00 g) were added and stirred at 50 ° C. for 10 hours to obtain a liquid crystal alignment treatment agent 28. 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.

Using the resultant liquid crystal alignment treatment agent 28, production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 29 &gt;

NEP (21.3 g) was added to the polyimide powder (8) (2.55 g) obtained in Synthetic Example 8 and dissolved by stirring at 70 占 폚 for 24 hours. NEP (10.7 g) and BCS (8.01 g) were added to this solution, and the mixture was stirred at 50 占 폚 for 10 hours to obtain a liquid crystal alignment treatment agent (29). 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.

Using the liquid crystal alignment treatment agent 29 thus obtained, cell preparation and various evaluations were carried out under the above-described conditions.

&Lt; Example 30 &gt;

NEP (26.1 g) was added to the polyimide powder (8) (2.56 g) obtained in Synthesis Example 8 and dissolved by stirring at 70 占 폚 for 24 hours. NMP (8.00 g), BCS (4.00 g) and MC (2.00 g) were added to this solution and stirred at 50 占 폚 for 10 hours to obtain a liquid crystal alignment treating agent (30). 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.

Using the obtained liquid crystal alignment treatment agent 30, preparation of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 31 &gt;

NEP (16.0 g) was added to the polyimide powder (9) (2.55 g) obtained in Synthesis Example 9 and dissolved by stirring at 70 占 폚 for 24 hours. NMP (12.0 g) and BCS (12.1 g) were added to this solution and stirred at 50 占 폚 for 10 hours to obtain a liquid crystal alignment treatment agent (31). 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.

Using the obtained liquid crystal alignment treatment agent 31, production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 32 &gt;

NEP (20.0 g) was added to the polyimide powder (9) (2.55 g) obtained in Synthesis Example 9 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, γ-BL (4.00 g) and BCS (15.8 g) were added and stirred at 50 ° C. for 10 hours to obtain a liquid crystal alignment treatment agent 32. 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.

Using the obtained liquid crystal alignment treatment agent 32, production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 33 &gt;

NEP (32.2 g) was added to the polyimide powder (10) (2.55 g) obtained in Synthesis Example 10 and dissolved by stirring at 70 占 폚 for 24 hours. NMP (4.00 g), BCS (2.00 g) and EC (2.00 g) were added to this solution and stirred at 50 占 폚 for 10 hours to obtain a liquid crystal alignment treatment agent (33). 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.

Using the obtained liquid crystal alignment treatment agent (33), production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Example 34 &gt;

NEP (16.0 g) was added to the polyimide powder (10) (2.55 g) obtained in Synthesis Example 10 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, γ-BL (2.01 g), BCS (16.0 g) and MC (6.00 g) were added and stirred at 50 ° C. for 10 hours to obtain a liquid crystal alignment treatment agent (34). 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.

Using the obtained liquid crystal alignment treatment agent 34, the production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Comparative Example 1 &

NMP (14.5 g) was added to the polyimide powder (3) (2.52 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. NMP (7.21 g) and BCS (17.8 g) were added to this solution and stirred at 50 占 폚 for 10 hours to obtain a liquid crystal alignment treatment agent (35). 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.

Using the obtained liquid crystal alignment treatment agent 35, the production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Comparative Example 2 &

NMP (32.0 g) was added to polyamic acid solution (11) (10.1 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 11 and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent (36). 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.

Using the obtained liquid crystal alignment treatment agent 36, the production of the cells and various evaluations were carried out under the above-described conditions.

&Lt; Comparative Example 3 &

NMP (14.0 g) and BCS (17.6 g) were added to polyamic acid solution (11) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 11 and stirred at 25 캜 for 2 hours to prepare a liquid crystal alignment treatment agent 37). 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.

Using the obtained liquid crystal alignment treatment agent 37, production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Comparative Example 4 &

NMP (14.0 g) and BCS (17.4 g) were added to the polyamic acid solution (12) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 12 and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent 38). 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.

Using the obtained liquid crystal alignment treatment agent 38, the cell was produced and evaluated under various conditions as described above.

&Lt; Comparative Example 5 &

NMP (14.7 g) was added to the polyimide powder (13) (2.55 g) obtained in Synthesis Example 13 and dissolved by stirring at 70 占 폚 for 24 hours. NMP (7.28 g) and BCS (18.0 g) were added to this solution and stirred at 50 占 폚 for 10 hours to obtain a liquid crystal alignment treatment agent (39). 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.

Using the obtained liquid crystal alignment treatment agent 39, production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Comparative Example 6 &gt;

NEP (14.7 g) was added to the polyimide powder (13) (2.55 g) obtained in Synthesis Example 13 and dissolved by stirring at 70 占 폚 for 24 hours. NEP (7.30 g) and BCS (18.0 g) were added to this solution and stirred at 50 占 폚 for 10 hours to obtain a liquid crystal alignment treatment agent (40). 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.

Using the obtained liquid crystal alignment treatment agent 40, the production and various evaluations of cells were carried out under the above-described conditions.

&Lt; Comparative Example 7 &

NEP (31.7 g) was added to the polyamic acid solution (14) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 14 and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent (41). 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.

Using the obtained liquid crystal alignment treatment agent 41, preparation of cells and various evaluations were carried out under the above-described conditions.

&Lt; Comparative Example 8 &gt;

NEP (14.1 g) and BCS (17.6 g) were added to polyamic acid solution (14) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 14 and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent 42). 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.

Using the obtained liquid crystal alignment treatment agent 42, production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Comparative Example 9 &

NMP (31.7 g) was added to polyamic acid solution 15 (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 15 and stirred at 25 占 폚 for 2 hours to obtain liquid crystal alignment treatment agent 43. 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.

Using the obtained liquid crystal alignment treatment agent 43, production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Comparative Example 10 &

NMP (14.0 g) and BCS (17.6 g) were added to the polyamic acid solution (15) (10.0 g) having a resin solid concentration of 25.0% by mass obtained in Synthesis Example 15 and stirred at 25 占 폚 for 2 hours to prepare a liquid crystal alignment treatment agent 44). 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.

Using the resultant liquid crystal alignment treatment agent 44, production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Comparative Example 11 &

NMP (14.7 g) was added to the polyimide powder (16) (2.55 g) obtained in Synthesis Example 16 and dissolved by stirring at 70 占 폚 for 24 hours. NMP (7.30 g) and BCS (18.2 g) were added to this solution, and the mixture was stirred at 50 占 폚 for 10 hours to obtain a liquid crystal alignment treatment agent (45). 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.

Using the obtained liquid crystal alignment treatment agent 45, production of cells and various evaluations were carried out under the above-described conditions.

&Lt; Comparative Example 12 &gt;

NEP (14.5 g) was added to the polyimide powder (16) (2.52 g) obtained in Synthesis Example 16 and dissolved by stirring at 70 占 폚 for 24 hours. NEP (7.21 g) and BCS (17.8 g) were added to this solution and stirred at 50 占 폚 for 10 hours to obtain a liquid crystal alignment treatment agent (46). 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.

Using the obtained liquid crystal alignment treatment agent 46, production of cells and various evaluations were carried out under the above-described conditions.

* 1: Ratio of the polymer in the liquid crystal alignment treatment agent.

* 2: Ratio of polymer in liquid crystal alignment treatment agent.

* 3: Ratio of the polymer in the liquid crystal alignment treatment agent.

* 4: More than 10 alignment defects due to pinholes were observed.

As can be seen from the above results, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the embodiment is superior to the liquid crystal alignment film obtained from the comparative liquid crystal alignment agent, An orientation film can be obtained.

Further, in the liquid crystal alignment treatment agent of the examples, a liquid crystal alignment film having a small change in the pretilt angle can be obtained, and a uniform film property can be obtained.

Further, in the same polyamic acid or polyimide, in the comparison between the example containing the specific solvent of the present invention and the comparative example containing no specific solvent, in the comparative example containing no specific solvent, the change of the pretilt angle But a lot of pinholes are generated, and the uniformity of the coating film at the end portion of the liquid crystal alignment film is poor. Specifically, the comparison between Example 3 and Comparative Example 2, the comparison between Example 4 and Comparative Example 3, and the comparison between Example 6 and Comparative Example 1 can be confirmed.

Further, in the comparison between the example using the diamine compound containing the specific side chain structure of the present invention and the comparative example using the diamine compound not containing the specific side chain structure, the comparison using the diamine compound containing no specific side chain structure In the example, the change of the pretilt angle is large, pinholes are generated a lot, and the film uniformity of the end portion of the liquid crystal alignment film is bad. Specifically, the comparison between Example 4 and Comparative Example 4, the comparison between Example 4 and Comparative Example 5, and the comparison between Example 4 and Comparative Example 6 can be confirmed. Particularly, in Comparative Example 6, although a specific solvent was used, many pinholes were generated, and the uniformity of the coating film on the end portion of the liquid crystal alignment film was poor.

In the comparison between the example using the diamine compound containing the specific side chain structure of the present invention and the comparative example using the diamine compound not containing the specific side chain structure, the comparison using the diamine compound containing no specific side chain structure In the example, although the change in the pretilt angle is small, many pinholes are generated, and the uniformity of the coating film at the end portion of the liquid crystal alignment film is poor. Specifically, the comparison between Example 3 and Comparative Example 7, the comparison between Example 3 and Comparative Example 9, the comparison between Example 4 and Comparative Example 8, the comparison between Example 4 and Comparative Example 10, the comparison between Example 4 and Comparative Example 11, and a comparison of Example 4 and Comparative Example 12.

Particularly, in Comparative Example 7, Comparative Example 8 and Comparative Example 12, although a specific solvent was used, many pinholes were generated, and the film uniformity of the end portion of the liquid crystal alignment film was poor.

Industrial availability

INDUSTRIAL APPLICABILITY The liquid crystal alignment treatment agent of the present invention is excellent in wetting and diffusing properties of a coating solution to a substrate and has a uniform film property and is excellent in the liquid crystal alignment properties of the liquid crystal alignment treatment agent which does not change the pretilt angle even when exposed to high temperature and light irradiation for a long time, A liquid crystal display element having such a liquid crystal alignment film can be preferably used for a liquid crystal television having excellent reliability and high precision on a large screen and can be suitably used for a TN device, an STN device, a TFT liquid crystal device, etc. And is useful for a vertically aligned liquid crystal display element.

The entire contents of the specification, claims, drawings and summary of Japanese Patent Application No. 2011-196320 filed on September 8, 2011 are hereby incorporated herein by reference and the disclosure of the specification of the present invention.

1: Liquid crystal alignment film
2: chromium deposition substrate
3: End of liquid crystal alignment film
4: end of the liquid crystal alignment film
5: Mounting of the end portion of the liquid crystal alignment film

Claims (23)

A liquid crystal alignment treatment agent characterized by containing the following components (A) and (B).
Component (A): N-ethyl-2-pyrrolidone.
Component (B): at least one polymer selected from the group consisting of a polyimide precursor having a side chain represented by the following formula [1] and a polyimide obtained by imidizing a polyimide precursor.
[Chemical Formula 1]

(Formula [1], X ₁ is a single _{bond, - (CH 2) a -} (a is an integer of 1 ~ 15), -O-, -NH- , -N (CH 3) -, -CONH- _{, -NHCO-, -CH 2 O-, -COO-} , -OCO-, -CON (CH 3) -. or -N (CH _{3) 2} X is CO- Is a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 15). X ₃ is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH ₃ ) - or -N (CH ₃ ) CO-. X ₄ Is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring (any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine atom having 1 to 3 carbon atoms Containing alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom). X ₅ Is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring (any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine atom having 1 to 3 carbon atoms Containing alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom). X ₆ Is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms, and n is an integer of 0 to 4.) The method according to claim 1,
Wherein the component (B) is at least one member selected from the group consisting of a polyimide precursor in which a diamine having a side chain represented by the formula [1] is used as a part of a diamine component of the starting material, and a polyimide in which a polyimide precursor is imidized By weight of the liquid crystal alignment treatment agent. 3. The method of claim 2,
Wherein the diamine having a side chain represented by the formula [1] is a diamine compound represented by the following formula [1a].
(2)

(Formula [1a] of the, X ₁ is a single _{bond, - (CH 2) a -} (a is an integer of 1 ~ 15), -O-, -NH- , -N (CH 3) -, -CONH- _{, -NHCO-, -CH 2 O-, -COO-} , -OCO-, -CON (CH 3) -. or -N (CH _{3) 2} X is CO- Is a single bond or (CH ₂ ) _b - (b is an integer of 1 to 15). X ₃ is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH ₃ ) - or -N (CH ₃ ) CO-. X ₄ Is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring (any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine atom having 1 to 3 carbon atoms Containing alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom). X ₅ Is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring (any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine atom having 1 to 3 carbon atoms Containing alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom). X ₆ Is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluoro-containing alkoxyl group having 1 to 18 carbon atoms. n is an integer of 0 to 4, and m is an integer of 1 to 4.) The method of claim 3,
The diamine represented by the above formula [1a] is used in an amount of 5 to 80 mol% of the diamine component of the raw material. 5. The method according to any one of claims 1 to 4,
Wherein the component (B) is a polymer using a tetracarboxylic acid dianhydride represented by the following formula [2].
(3)

(In the formula [2], Y ₁ is a tetravalent organic group having 4 to 13 carbon atoms and further contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms.) 6. The method of claim 5,
The Y ₁ Is a group of the structure represented by the following formulas [2a] to [2j].
[Chemical Formula 4]

(In the formula [2a], Y ₂ to Y ₅ Is a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different. In the formula [2g], Y ₆ and Y ₇ Are each a hydrogen atom or a methyl group, and may be the same or different. 7. The method according to any one of claims 1 to 6,
Wherein the polymer as the component (B) is a polyamide acid. 7. The method according to any one of claims 1 to 6,
Wherein the polymer as the component (B) is a polyimide obtained by dehydrating and ring closure of a polyamic acid. 9. The method according to any one of claims 1 to 8,
As the component (C), a liquid crystal alignment treatment agent containing N-methyl-2-pyrrolidone or? -Butyrolactone. 10. The method according to any one of claims 1 to 9,
As the component (D), there may be preferably used at least one member selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, A liquid crystal alignment treatment agent containing at least one member selected from the group consisting of monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monobutyl ether. . 11. The method according to any one of claims 1 to 10,
Wherein the component (A) is 10 to 100% by mass of the whole organic solvent contained in the liquid crystal alignment treatment agent. 12. The method according to any one of claims 9 to 11,
Wherein the component (C) is 0.1 to 70 mass% of the entire organic solvent contained in the liquid crystal alignment treatment agent. 13. The method according to any one of claims 10 to 12,
Wherein the component (D) is 5 to 80 mass% of the total organic solvent contained in the liquid crystal alignment treatment agent. 14. The method according to any one of claims 1 to 13,
Wherein the component (B) in the liquid crystal alignment treatment agent is 0.1 to 15 mass%. A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of claims 1 to 14. A liquid crystal alignment film obtained by the ink jet method using the liquid crystal alignment treatment agent according to any one of claims 1 to 14. 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 containing a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, And polymerizing the polymerizable compound while applying a voltage between the liquid crystal alignment layer and the liquid crystal alignment layer. A liquid crystal display element having the liquid crystal alignment film according to claim 18. 20. The method of claim 19,
A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and the liquid crystal alignment film and containing a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates And polymerizing the polymerizable compound while applying a voltage between the electrodes. 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 containing a polymerizable group polymerized 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, which is produced through a process of polymerizing the polymerizable group while applying a voltage. A liquid crystal display element having the liquid crystal alignment film according to claim 21. 23. The method of claim 22,
A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes and containing a polymerizable group polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, A liquid crystal display device produced through a process of polymerizing the polymerizable group while applying a voltage.

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