WO2015053394A1

WO2015053394A1 - Composition, treatment agent for liquid crystal alignment, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: WO2015053394A1
Application number: PCT/JP2014/077219
Authority: WO
Inventors: 徳俊三木; 橋本　淳; 暁子若林; 保坂　和義
Original assignee: 日産化学工業株式会社
Priority date: 2013-10-10
Filing date: 2014-10-10
Publication date: 2015-04-16
Also published as: JPWO2015053394A1; KR20160070777A; TWI649362B; CN105814141B; JP6668754B2; TW201529659A; KR102259997B1; CN105814141A

Abstract

The present invention provides a composition that contains: a component (A) that is a solvent that is represented by formula [A] (in the formula, X¹ and X² each independently represent an alkyl group having 1-3 carbon atoms and X³ and X⁴ each independently represent an alkyl group having 1-3 carbon atoms); and a component (B) that is at least one polymer selected from among polyimide precursors and polyimides.

Description

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

The present invention relates to a composition used for forming a polyimide film, a liquid crystal alignment treatment agent used in the production of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film. Is.

A film made of an organic material such as a polymer material is widely used as an interlayer insulating film, a protective film, and the like in electronic devices because of its ease of formation and insulation performance. Among them, in a liquid crystal display element well known as a display device, an organic film made of an organic material is used as a liquid crystal alignment film.

In recent years, liquid crystal display devices have been widely put into practical use for large-screen liquid crystal televisions and high-definition mobile applications (display portions of digital cameras and mobile phones). Along with this, the size of the substrate to be used is increased compared to the conventional one, and the unevenness of the step of the substrate has become larger. Even in such a situation, it has been demanded that the liquid crystal alignment film is uniformly coated on a large substrate or a step from the viewpoint of display characteristics. In the process of producing the liquid crystal alignment film, when a liquid crystal alignment treatment agent using a polyimide polymer (also referred to as resin) such as polyamic acid or solvent-soluble polyimide (also referred to as polyimide) is applied to a substrate, industrially In general, the flexographic printing method or the ink jet coating method is used. At that time, as a solvent for the liquid crystal alignment treatment agent, N-methyl-2-pyrrolidone (also referred to as NMP) or γ-butyrolactone (also referred to as γ-BL), which is a solvent having excellent resin solubility (also referred to as a good solvent), is used. In addition to the above, in order to improve the coating properties of the liquid crystal alignment film, ethylene glycol monobutyl ether, which is a solvent having low resin solubility (also referred to as a poor solvent), or the like is mixed (for example, see Patent Document 1).

Japanese Unexamined Patent Publication No. 2-37324

Polyimide-based organic films (also referred to as polyimide films) are widely used as interlayer insulating films and protective films in electronic devices in addition to liquid crystal alignment films. As in the case of the liquid crystal alignment film, it can be formed from a composition (also referred to as a coating solution) containing a polyamic acid or polyimide solution that is a polyimide precursor. And also in other electronic devices, it is calculated | required to improve the coating property of a polyimide film. That is, the improvement of the coating property of the polyimide film is effective for suppressing defects that occur with application.

Moreover, the liquid crystal aligning agent using the polyamic acid and polyimide obtained by using the diamine compound which has a side chain has the tendency for the coating property of a liquid crystal aligning film to fall because the hydrophobicity of a side chain site | part is high. . In particular, when uniform coating properties cannot be obtained, that is, when pinholes accompanying repelling occur, when the liquid crystal display element is formed, that portion becomes a display defect. Therefore, in order to obtain uniform coating properties, it is necessary to increase the mixing amount of a poor solvent having high wettability of the coating solution to the substrate. However, since a poor solvent is inferior in the ability to dissolve a polyamic acid or a polyimide, there exists a problem that resin precipitation will occur when it mixes in large quantities.

In addition, in recent years, liquid crystal display elements have been used for mobile applications such as smartphones and mobile phones. In these applications, in order to secure as many display surfaces as possible, the substrates of the liquid crystal display elements are bonded together. The sealant used in is present at a position close to the end of the liquid crystal alignment film. Therefore, when the coating 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 a straight line, or when the end portion is raised, the liquid crystal alignment film and the sealing agent Adhesive (also referred to as adhesion) effect is reduced, and the display characteristics and reliability of the liquid crystal display element are lowered.

Furthermore, in the composition or the liquid crystal alignment treatment agent using polyimide, since the boiling point of NMP and γ-BL which are the solvents used for them is high, a polyimide film such as an interlayer insulating film and a protective film and a liquid crystal alignment film are produced. In this case, firing at a high temperature is required. Therefore, from the viewpoint of reducing energy costs, baking at a low temperature is required when producing these polyimide films and liquid crystal alignment films.

Therefore, an object of the present invention is to provide a composition having the above characteristics. That is, an object of the present invention is to provide a composition that can suppress the occurrence of pinholes accompanying repelling when forming a polyimide film and is excellent in the coating properties at the end. In that case, it aims also at becoming the composition which can produce a polyimide film also by baking at low temperature.

In addition, in the liquid crystal alignment treatment agent using the composition of the present invention, when forming a liquid crystal alignment film, it is possible to suppress the occurrence of pinholes due to repellency, and also to the coating properties at the end. It is to provide an excellent liquid crystal alignment treatment agent. In particular, an object of the present invention is to provide a liquid crystal aligning agent excellent in these characteristics even when it is a liquid crystal aligning agent using a polyamic acid or polyimide obtained by using a diamine compound having a side chain. It is another object of the present invention to provide a liquid crystal alignment treatment agent which is excellent in electrical characteristics, particularly voltage holding ratio (also referred to as VHR) in a liquid crystal display element even when firing at the time of producing a liquid crystal alignment film is at a low temperature.

In addition, another object is to provide a polyimide film obtained from the composition, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display device having the liquid crystal alignment film.

As a result of diligent research, the present inventors have found that a composition containing a solvent having a specific structure and at least one polymer selected from a polyimide precursor or a polyimide is extremely effective for achieving the above object. As a result, the present invention has been completed.

That is, the present invention has the following gist.

(1) Component (A): Formula [A] below:

(Wherein, X ¹ and X ² each independently represent an alkyl group having 1 to 3 carbon atoms, and X ³ and X ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms) And (B) component: a composition containing at least one polymer selected from polyimide precursors and polyimides.

(2) The solvent of the component (A) is represented by the following formula [A-1]:

The composition as described in said (1) which is a solvent shown by these.

(3) The component (B) is represented by the following formula [1-1] and formula [1-2]:

Wherein Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON At least one linking group selected from (CH ₃ ) —, —N (CH ₃ ) CO—, —COO— and —OCO—, wherein Y ² represents a single bond or — (CH ₂ ) _b — (b Is an integer of 1 to 15, and Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO Y represents at least one linking group selected from — and —OCO—, and Y ⁴ represents a carbon having a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a steroid skeleton A divalent organic group of formula 17 to 51, wherein any hydrogen atom on the cyclic group is a carbon atom Alkyl group having 1 to 3, an alkoxyl group having 1 to 3 carbon atoms, fluorine-containing alkyl group having 1 to 3 carbon atoms may be substituted with a fluorine-containing alkoxyl group or a fluorine atom having 1 to 3 carbon atoms, Y ⁵ represents a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, and n represents an integer of 0 to 4 Y ⁶ represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, an alkoxyl group having 1 to 22 carbon atoms, and fluorine having 1 to 22 carbon atoms. Contains At least one selected from alkoxyl groups);

Wherein Y ⁷ is a single bond, —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —COO— and At least one linking group selected from —OCO—, and Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms)
(1) or (2) above, which is at least one polymer selected from polyimide precursors and polyimides using a diamine compound having at least one structure selected from the structure represented by A composition according to 1.

(4) A diamine compound having a structure represented by the formula [1-1] and the formula [1-2] is represented by the following formula [1a]:

(Wherein Y represents at least one structure selected from the structures represented by the formulas [1-1] and [1-2], and m represents an integer of 1 to 4)
The composition as described in said (3) which is a diamine compound shown by these.

(5) A polyimide precursor in which the polymer of the component (B) uses a diamine compound having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group) as a part of the raw material. The composition according to any one of (1) to (4) above, which is at least one polymer selected from the group consisting of polyimide and polyimide.

(6) The diamine compound having a carboxyl group and a hydroxyl group is represented by the following formula [2a]:

{In the formula, A represents the following formula [2-1] and formula [2-2]:

(In the formula [2-1], a represents an integer of 0 to 4, and in the formula [2-2], b represents an integer of 0 to 4). M represents an integer of 1 to 4}
The composition according to (5) above, which is a diamine compound represented by:

(7) The polymer of the component (B) is represented by the following formula [3a]:

Wherein B ¹ is —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ) — and Represents at least one linking group selected from —N (CH ₃ ) CO—, wherein B ² is a single bond, a divalent group of an aliphatic hydrocarbon having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon; And B ³ is a single bond, —O—, —NH—, —N (CH ₃ ) —, —CONH—. , —NHCO—, —COO—, —OCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO— and —O (CH ₂ ) _m — (m is an integer of 1 to 5) At least one selected linking group, B ⁴ represents a nitrogen-containing heterocyclic group, and n represents an integer of 1 to 4. The composition according to any one of (1) to (6) above, which is at least one polymer selected from a polyimide precursor using a diamine compound as part of a raw material and a polyimide.

(8) In the formula [3a], B ¹ represents —CONH—, B ² represents an alkylene group having 1 to 5 carbon atoms, B ³ represents a single bond, and B ⁴ represents an imidazolyl group or a pyridyl group. The composition according to (7) above, wherein n is a diamine compound wherein 1.

(9) The polymer of the component (B) is represented by the following formula [4]:

{In the formula, Z represents the following formula [4a] to formula [4k]:

(In formula [4a], Z ¹ to Z ⁴ each independently represent a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, and in formula [4g], Z ⁵ and Z ⁶ are each independently Represents a hydrogen atom or a methyl group) and represents a group having at least one structure selected from
The composition according to any one of the above (1) to (8), which is at least one polymer selected from a polyimide precursor and a polyimide using a tetracarboxylic acid compound represented by the formula:

(10) The composition according to any one of (1) to (9) above, wherein the polymer of the component (B) is at least one polymer selected from polyamic acid alkyl ester and polyimide.

(11) The components (1) to (10) above containing at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone as component (C) A composition according to any one of the above.

(12) As component (D), 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether and the following formula [D -1] to formula [D-3]:

(In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms. In the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms. -3], D ³ represents an alkyl group having 1 to 4 carbon atoms)
The composition according to any one of (1) to (11) above, which contains at least one solvent selected from the solvents represented by:

(13) In the composition, at least one substituent selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. The composition according to any one of (1) to (12) above, comprising at least one crosslinkable compound selected from a crosslinkable compound having a polymerizable unsaturated bond and a crosslinkable compound having a polymerizable unsaturated bond.

(14) The composition according to any one of (1) to (13) above, wherein the component (A) is 5 to 70% by mass of the total solvent contained in the composition.

(15) The composition according to any one of (11) to (14) above, wherein the component (C) is 40 to 80% by mass of the total solvent contained in the composition.

(16) The composition according to any one of (12) to (15) above, wherein the component (D) is 1 to 50% by mass of the total solvent contained in the composition.

(17) The composition according to any one of (1) to (16) above, wherein the component (B) is 0.1% by mass to 30% by mass in the composition.

(18) A polyimide film obtained from the composition according to any one of (1) to (17) above.

(19) A liquid crystal aligning agent obtained from the composition according to any one of (1) to (17).

(20) A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to (19).

(21) A liquid crystal alignment film obtained by an ink jet method using the liquid crystal alignment treatment agent according to (19).

(22) A liquid crystal display device having the liquid crystal alignment film according to (20) or (21).

(23) A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal alignment film according to (20) or (21), wherein the liquid crystal alignment film is used for a liquid crystal display device produced through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.

(24) A liquid crystal display device comprising the liquid crystal alignment film according to (23).

(25) A liquid crystal alignment film having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group that is 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 (20) or (21), wherein the liquid crystal alignment film is used for a liquid crystal display device produced through a step of polymerizing the polymerizable group while applying a voltage between the electrodes.

(26) A liquid crystal display element comprising the liquid crystal alignment film according to (25).

The composition containing a solvent having a specific structure of the present invention and at least one polymer selected from polyimide precursors or polyimides can suppress the generation of pinholes accompanying repelling when forming a polyimide film. The polyimide film which is excellent also in the coating property of the edge part can be produced. At that time, the polyimide film can be formed by baking at a low temperature.

In addition, in the liquid crystal alignment treatment agent using the composition of the present invention, when forming a liquid crystal alignment film, it is possible to suppress the occurrence of pinholes due to repellency, and also to the coating properties at the end. It is to provide an excellent liquid crystal alignment treatment agent. In particular, an object of the present invention is to provide a liquid crystal aligning agent excellent in these characteristics even when it is a liquid crystal aligning agent using a polyamic acid or polyimide obtained by using a diamine compound having a side chain. It is another object of the present invention to provide a liquid crystal alignment treatment agent that is excellent in electrical characteristics, particularly voltage holding ratio (VHR) in a liquid crystal display element even when firing at the time of producing a liquid crystal alignment film is at a low temperature.

In addition, by using the composition of the present invention as a liquid crystal alignment treatment agent, it is possible to suppress the occurrence of pinholes due to repellency, and to provide a liquid crystal alignment film having excellent coating properties at the end portions Can do. In particular, even if it is a liquid crystal aligning agent using the polyamic acid and polyimide obtained using the diamine compound which has a side chain, the liquid crystal aligning film which is excellent in these characteristics can be provided. Furthermore, even when baking at the time of producing a liquid crystal aligning film is low temperature, the liquid crystal aligning film which is excellent in the electrical property in a liquid crystal display element, especially a voltage holding ratio (VHR) can be provided. Therefore, the liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and is used for a large-screen high-definition liquid crystal television, a small-sized car navigation system, a smartphone, and the like. It can be suitably used.

It is a figure showing the linearity of the edge part of the polyimide film apply | coated to the glass substrate. It is a figure showing the swelling of the edge part of the polyimide film apply | coated to the glass substrate.

Hereinafter, the present invention will be described in detail.

The present invention provides a composition containing the following components (A) and (B), a liquid crystal alignment treatment agent, a liquid crystal alignment film obtained using the liquid crystal alignment treatment agent, and a liquid crystal having the liquid crystal alignment film It is a display element.
Component (A): A solvent represented by the following formula [A] (also referred to as a specific solvent).

(In the formula [A], X ¹ and X ² each independently represent an alkyl group having 1 to 3 carbon atoms, and X ³ and X ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms. Showing).

Component (B): at least one polymer selected from a polyimide precursor and polyimide (also referred to as a specific polymer).

The specific solvent of the present invention can be used as a solvent capable of dissolving a polyimide polymer such as a polyimide precursor and polyimide (also referred to as a good solvent), and further, coating properties of a polyimide film and a liquid crystal alignment film There is also an effect to increase. That is, the specific solvent of the present invention usually has a lower surface tension as a solvent than NMP that is used as a good solvent, so that a coating solution using the specific solvent is compared with a coating solution that does not use it. As a result, the spreadability of the coating solution on the substrate is increased. As a result, the linearity of the end portions of these films becomes high when the polyimide film and the liquid crystal alignment film are formed. Furthermore, since the wettability of the coating solution on the substrate is increased, the occurrence of pinholes accompanying repelling can be suppressed.

Furthermore, the specific solvent of the present invention has a lower boiling point than NMP or γ-BL, which is usually used as a good solvent. Therefore, baking at the time of producing a polyimide film and a liquid crystal alignment film can be performed at a low temperature. Therefore, a liquid crystal alignment film excellent in VHR in a liquid crystal display element can be obtained even when firing at the time of producing the liquid crystal alignment film is at a low temperature.

In addition, the component (B) of the present invention is at least one polymer selected from a polyimide precursor or a polyimide. In particular, when a liquid crystal alignment film is produced using the composition of the present invention as a liquid crystal alignment treatment agent, at least selected from structures represented by the following formulas [1-1] and [1-2]: It is preferable to use at least one polymer (also referred to as a specific polymer) selected from polyimide precursors or polyimides having one type of side chain (also referred to as a specific side chain structure).

(In the formula [1-1], Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —CONH—, — At least one linking group selected from NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO-, -COO- and -OCO-, and Y ² represents a single bond or-(CH ₂ ) _B — (b is an integer of 1 to 15), Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ Represents at least one linking group selected from O—, —COO— and —OCO—, and Y ⁴ represents a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or A divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, and any hydrogen on the cyclic group The child is 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 fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Y ⁵ represents a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups has 1 to 3 carbon atoms. It may be substituted with an alkyl group, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, and n is 0 to 4 Y ⁶ represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, an alkoxyl group having 1 to 22 carbon atoms, and 1 carbon atom. ~ 22 At least one selected from fluorine-containing alkoxyl groups).

(In Formula [1-2], Y ⁷ represents a single bond, —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO— , -COO- and -OCO-, Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms).

In particular, the specific side chain structure represented by the formula [1-1] has a carbon number of 17 to 51 having a benzene ring, a cyclohexyl ring or a heterocyclic divalent cyclic group, or a steroid skeleton in the side chain portion. Having a valent organic group. These divalent cyclic groups such as a benzene ring, a cyclohexyl ring or a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms and having a steroid skeleton have a rigid structure. Thereby, the stability with respect to the heat of a side chain site | part improves, decomposition | disassembly of the side chain site | part by baking at the time of producing a liquid crystal aligning film is suppressed, and the liquid crystal aligning film excellent in VHR can be obtained.

From the above points, the composition containing the specific solvent of the present invention and at least one polymer selected from polyimide precursors or polyimides is excellent in coating properties and forms a polyimide film even at low temperature firing. It becomes the composition which can be obtained.

Moreover, the liquid crystal aligning agent obtained from the composition of the present invention can provide a liquid crystal alignment film having excellent coating properties. Furthermore, a liquid crystal alignment film having excellent VHR in a liquid crystal display element can be obtained even when the baking for producing the liquid crystal alignment film is performed at a low temperature. Therefore, by using this liquid crystal alignment film, a highly reliable liquid crystal display element having excellent display characteristics can be provided.

In addition, the liquid crystal alignment treatment obtained from the composition containing the specific solvent of the present invention and the polyimide precursor having the specific side chain structure represented by the formula [1-1] or at least one polymer selected from polyimides The agent can obtain a liquid crystal alignment film having excellent VHR in the liquid crystal display element even when the above-described effects, that is, baking during the production of the liquid crystal alignment film is at a low temperature. Therefore, by using this liquid crystal alignment film, a highly reliable liquid crystal display element having more excellent display characteristics can be provided.

Hereinafter, embodiments of the present invention will be described in more detail.

<Specific solvent>
The specific solvent of the present invention is a solvent represented by the following formula [A].

In the formula [A], X ¹ and X ² each independently represent an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, a propyl group or an isopropyl group), preferably a methyl group or ethyl Group, particularly preferably a methyl group.

In the formula [A], X ³ and X ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, or an isopropyl group), preferably a methyl group or an ethyl group Group, particularly preferably a methyl group.

Specifically, those represented by the following formula [A-1] are preferable.

The amount of the specific solvent of the present invention is preferably 5 to 80% by mass of the total solvent contained in the composition and the liquid crystal aligning agent in order to further improve the wettability of the coating solution to the substrate described above. Among these, 5 to 75% by mass is preferable. A more preferred range is 5 to 70% by mass, and a further more preferred range is 10 to 60% by mass.

The greater the amount of the specific solvent of the present invention in the entire solvent in the composition and the liquid crystal alignment treatment agent, the higher the effect of the present invention, that is, the wettability of the coating solution on the substrate, and the better the coating properties. An excellent polyimide film and liquid crystal alignment film can be obtained.

<Specific polymer>
The specific polymer which is the component (B) of the present invention is at least one polymer selected from a polyimide precursor and a polyimide (also collectively referred to as a polyimide polymer). Especially, it is preferable that the polyimide-type polymer of this invention is a polyimide precursor or a polyimide obtained by making a diamine component and a tetracarboxylic acid component react.

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

(In the formula [a], R ¹ is a tetravalent organic group, R ² is a divalent organic group, and A ¹ and A ² are each independently a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group, and A ³ and A ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acetyl group, and n represents a positive integer).

Examples of the diamine component include diamine compounds having two primary or secondary amino groups in the molecule.

In addition, examples of the tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, and a tetracarboxylic acid dialkyl ester dihalide compound.

In order to obtain a polyamic acid in which A ¹ and A ² in the formula [a] are hydrogen atoms, a diamine compound having two primary or secondary amino groups in the molecule, a tetracarboxylic acid compound or tetra It can be obtained by reacting with a carboxylic anhydride.

In order to obtain a polyamic acid alkyl ester in which A ¹ and A ^{2 in} formula [a] are alkyl groups having 1 to 5 carbon atoms, the diamine compound, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or It can be obtained by reacting with a tetracarboxylic acid dialkyl ester dihalide compound. In addition, an alkyl group having 1 to 5 carbon atoms can be introduced into A ¹ and A ^{2 represented} by the formula [a] in the polyamic acid obtained by the above method.

The polyimide polymer of the present invention uses a diamine compound having at least one specific side chain structure selected from the structures represented by the following formulas [1-1] and [1-2] as a part of the raw material. It is preferably at least one polymer selected from polyimide precursors and polyimides.

In Formula [1-1], Y ¹ is a bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —CONH—, —NHCO—. , —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —COO— and —OCO—. Among these, from the viewpoint of availability of raw materials and ease of synthesis, a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O— or —COO -Is preferred. More preferred is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 10), —O—, —CH ₂ O— or —COO—.

In formula [1-1], Y ² represents a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15). Among these, a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 10) is preferable.

In the formula [1-1], Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— and —OCO. At least one linking group selected from-; Of these, a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O— or —COO— is preferable from the viewpoint of ease of synthesis. More preferred is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O— or —COO—.

In the formula [1-1], Y ⁴ is a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is a carbon It 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 fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Furthermore, Y ⁴ may be a divalent organic group selected from organic groups having 17 to 51 carbon atoms and having a steroid skeleton. Among these, from the viewpoint of easy synthesis, a divalent cyclic group of a benzene ring or a cyclohexane ring, or a divalent organic group having 17 to 51 carbon atoms and having a steroid skeleton is preferable.

In Formula [1-1], Y ⁵ represents a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups is carbon It 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 fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Of these, a benzene ring or a cyclohexane ring is preferable.

In the formula [1-1], n represents an integer of 0 to 4. Among these, 0 to 3 are preferable from the viewpoint of availability of raw materials and ease of synthesis. More preferred is 0-2.

In the formula [1-1], Y ⁶ represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, an alkoxyl group having 1 to 22 carbon atoms, and At least one selected from fluorine-containing alkoxyl groups having 1 to 22 carbon atoms is shown. Among them, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl having 1 to 10 carbon atoms. Groups are preferred. More preferably, it is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

Preferred combinations of Y ¹ to Y ⁶ and n in the formula [1-1] are listed in Tables 6 to 47 on pages 13 to 34 of International Publication No. 2011/132751 (published 2011.10.27). (2-1) to (2-629) are the same combinations. In each table of the International Publication, Y ¹ to Y ⁶ in the present invention are shown as Y ¹ to Y ⁶ , but Y ¹ to Y ⁶ are read as Y ¹ to Y ⁶ . Further, in (2-605) to (2-629) listed in each table of the International Publication, the organic group having 17 to 51 carbon atoms having a steroid skeleton in the present invention has 12 to 20 carbon atoms having a steroid skeleton. An organic group having 12 to 25 carbon atoms having a steroid skeleton is to be read as an organic group having 17 to 51 carbon atoms having a steroid skeleton.

In the formula [1-2], Y ⁷ represents a single bond, —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, — It represents at least one linking group selected from COO— and —OCO—. Of these, a single bond, —O—, —CH ₂ O—, —CONH—, —CON (CH ₃ ) — or —COO— is preferable. More preferably, they are a single bond, —O—, —CONH— or —COO—.

In formula [1-2], Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms. Of these, an alkyl group having 8 to 18 carbon atoms is preferable.

As the specific side chain structure of the present invention, it is preferable to use a structure represented by the formula [1-1] from the viewpoint that a high and stable liquid crystal vertical alignment can be obtained.

The method for introducing the specific side chain structure of the present invention into the specific polymer is not particularly limited, but a diamine compound having a specific side chain structure is preferably used for the diamine component.

Specifically, it is preferable to use a diamine compound (also referred to as a specific side chain diamine compound) represented by the following formula [1a]. In that case, the diamine compound whose amino group in following formula [1a] is a secondary amino group can also be used.

In Formula [1a], Y represents at least one structure selected from the structures represented by Formula [1-1] and Formula [1-2]. A preferable combination of Y ¹ to Y ⁶ and n when Y in the formula [1a] represents the formula [1-1] is as described above.

In the formula [1a], m represents an integer of 1 to 4. Of these, 1 is preferable.
Specific examples of the specific side chain type diamine compound of the present invention include, for example, diamine compounds represented by the following formulas [1a-1] to [1a-34], and these amino groups are secondary amino groups. A certain diamine compound is mentioned.

(In the formulas [1a-1] to [1a-3], R ¹ , R ³ and R ⁵ are each independently —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ — Or —CH ₂ OCO—, wherein R ² , R ⁴ and R ⁶ are each independently linear or branched having 1 to 22 carbon atoms in the formulas [1a-1] to [1a-3] And a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 22 carbon atoms).

(In the formulas [1a-4] to [1a-6], R ¹ , R ³ and R ⁵ are each independently —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ — or —CH ₂ —, in which R ² , R ⁴ and R ⁶ are represented by the formulas [1a-4] to [1a-6] Each independently containing a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, or a linear or branched fluorine group having 1 to 22 carbon atoms An alkyl group or a fluorine-containing alkoxyl group having 1 to 22 carbon atoms).

(In the formulas [1a-7] and [1a-8], R ¹ and R ³ are each independently —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, — CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, —CH ₂ —, —O— or —NH—, wherein R ² and R ⁴ are each independently fluorine, cyano, trifluoro A methyl group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group).

(In the formulas [1a-9] and [1a-10], R ¹ and R ² each independently represents a linear or branched alkyl group having 3 to 12 carbon atoms, and 1,4-cyclohexene The cis-trans isomerism of silene is the trans isomer, respectively).

(In the formulas [1a-11] and [1a-12], R ¹ and R ² each independently represents a linear or branched alkyl group having 3 to 12 carbon atoms, and represents 1,4-cyclohexene. The cis-trans isomerism of silene is the trans isomer, respectively).

(In the formula [1a-13], A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A ₃ is a 1,4-cyclohexylene group or A ₂ -phenylene group, A ₂ is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A ₃ ), and A ₁ is an oxygen atom or —COO— * (However, the bond marked with “*” binds to (CH ₂ ) a ₂ )). A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1.

(In the formulas [1a-32] to [1a-35], A ¹ to A ⁴ each independently represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

Of the formulas [1a-1] to [1a-21] and [1a-24] to [1a-35], the particularly preferred side chain type diamine compounds having the particularly preferred structures are those represented by the formulas [1a-1] to [1a- 6], formula [1a-9] to formula [1a-13] or formula [1a-24] to formula [1a-31].

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

The specific side chain type diamine compound of the present invention includes the solubility of the specific polymer of the present invention in a solvent, the coating properties of the composition and the liquid crystal alignment agent, the alignment property of liquid crystal when used as a liquid crystal alignment film, and the voltage holding ratio. Depending on the characteristics such as accumulated charge, one kind or a mixture of two or more kinds may be used.

The specific polymer of the present invention is preferably a polymer using, as a diamine component, a diamine compound having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group).

Specifically, it is preferable to use a diamine compound represented by the following formula [2a]. In that case, the diamine compound whose amino group in following formula [2a] is a secondary amino group can also be used.

In the formula [2a], A represents a substituent having at least one structure selected from the following formulas [2-1] and [2-2].

In the formula [2-1], a represents an integer of 0 to 4.

In the formula [2-2], b represents an integer of 0 to 4.

In the formula [2a], m represents an integer of 1 to 4.

More specifically, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid. Of these, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid is preferable.

Further, diamine compounds represented by the following formulas [2a-1] to [2a-4] and diamine compounds in which these amino groups are secondary amino groups can also be used.

(In the formula [2a-1], A ¹ 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 And represents at least one linking group selected from (CH ₃ ) — and —N (CH ₃ ) CO—, each of m ¹ and m ² independently represents an integer of 0 to 4, and m ¹ + m ² represents an integer of 1 to 4, and in formula [2a-2], m ³ and m ⁴ each independently represent an integer of 1 to 5, and in formula [2a-3], A ² represents represents a linear or branched alkyl group having 1 to 5 carbon atoms, ^{m 5} is an integer of 1 to 5, wherein [2a-4], ^{a 3} and ^{a 4,} respectively Standing 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 ) — and —N ( CH ₃ ) represents at least one linking group selected from CO—, and m ⁶ represents an integer of 1 to 4.

The diamine compound having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group) in the specific polymer of the present invention is 10 mol% or more and 80 mol% or less of the entire diamine component. Is preferred. Particularly preferred is 10 mol% or more and 70 mol% or less.

The diamine compound having at least one substituent selected from the carboxyl group (COOH group) and hydroxyl group (OH group) of the present invention is soluble in the solvent of the specific polymer of the present invention, composition and liquid crystal alignment treatment. One type or a mixture of two or more types can be used depending on the properties such as the coating property of the agent, the orientation of the liquid crystal in the case of the liquid crystal alignment film, the voltage holding ratio, and the accumulated charge.

For the specific polymer of the present invention, it is preferable to use a diamine compound having a nitrogen-containing heterocyclic ring represented by the following formula [3a] and a diamine compound in which these amino groups are secondary amino groups.

In the formula [3a], B ¹ represents —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ). And at least one linking group selected from — and —N (CH ₃ ) CO—. Among them, —O—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ) — or —N (CH ₃ ) CO— represents a diamine compound. It is preferable because it is easy to synthesize. More preferred is —O—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCO— or —CON (CH ₃ ) —. Particularly preferred is —O—, —CONH— or —CH ₂ O—.

In the formula [3a], B ² is a single bond, a divalent group of an aliphatic hydrocarbon having 1 to 20 carbon atoms, a divalent group of a non-aromatic cyclic hydrocarbon, or a divalent group of an aromatic hydrocarbon. At least one selected from the group is shown. The divalent group of the aliphatic hydrocarbon having 1 to 20 carbon atoms may be linear or branched. Moreover, you may have an unsaturated bond. Of these, an alkylene group having 1 to 10 carbon atoms is preferable. Specific examples of the non-aromatic hydrocarbon include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, a cyclo Tridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene And a ring, a norbornene ring, an adamantane ring, and the like. Of these, a cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring or adamantane ring is preferred. Specific examples of the aromatic hydrocarbon group include a benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring or phenalene ring. Of these, a benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring or anthracene ring is preferred.

Preferred B ² in the formula [3a] is a single bond, an alkylene group having 1 to 10 carbon atoms, or a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, or a benzene ring. , A divalent group of at least one ring selected from a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring, and an anthracene ring. Of these, a single bond, an alkylene group having 1 to 5 carbon atoms, or a divalent group of a cyclohexane ring or a benzene ring is preferable.

In the formula [3a], B ³ represents a single bond, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO— and —O (CH ₂ ) _m — (m is an integer of 1 to 5). Among these, a single bond, —O—, —COO—, —OCO— or —O (CH ₂ ) _m — (m is an integer of 1 to 5) is preferable. More preferred is a single bond, —O—, —OCO— or —O (CH ₂ ) _m — (m is an integer of 1 to 5).

In the formula [3a], B ⁴ is a nitrogen-containing heterocyclic group, and contains at least one structure selected from the following formulas [3a-1], [3a-2] and [3a-3] Heterocyclic group.

(In the formula [3a-3], Z ¹¹ represents an alkyl group having 1 to 5 carbon atoms).

More specifically, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring , Triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring or acridine ring. Among these, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, or a benzimidazole ring is preferable. More preferred are a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring. Also, ^{B 3} in the formula [3a] are expressions included in the ^{B 4} [3a-1], that is bonded to the structure and not adjacent ring atoms of the formula [3a-2] and the formula [3a-3] Is preferred.

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

Particularly preferred combinations of B ¹ to B ⁴ and n in the formula [3a] are as follows: B ¹ represents —CONH—, B ² represents an alkylene group having 1 to 5 carbon atoms, B ³ represents a single bond, ⁴ is a diamine compound in which ⁴ represents an imidazole ring or a pyridine ring and n represents 1.

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

positions

2, 4 or 2, 5 are more preferable.

The diamine compound having a nitrogen-containing heterocycle represented by the formula [3a] in the specific polymer of the present invention is preferably 10 mol% or more and 80 mol% or less of the entire diamine component. Particularly preferred is 10 mol% or more and 70 mol% or less.

The diamine compound having a nitrogen-containing heterocyclic ring represented by the above formula [3a] of the present invention is soluble in the solvent of the specific polymer of the present invention, the coating property of the composition and the liquid crystal aligning agent, and the liquid crystal alignment film. Depending on the liquid crystal orientation, voltage holding ratio, accumulated charge, etc., one kind or a mixture of two or more kinds can be used.

As long as the effects of the present invention are not impaired, the specific polymer of the present invention includes diamine compounds represented by the following formulas [a-1] to [a-13] and amino groups thereof as other diamine compounds. A diamine compound which is a secondary amino group can also be used.

(In the formula [a-1], A ¹ and A ³ each independently represent —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— and Represents at least one linking group selected from —NH—, and A ² represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine group having 1 to 22 carbon atoms. In formula [a-2], A ⁴ and A ⁶ are each independently —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—. , —CO— and —NH—, wherein A ⁵ represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear group having 1 to 22 carbon atoms. Or a branched fluorine-containing alkyl group).

(In the formula [a-3], A ¹ and A ³ each independently represent —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— and Represents at least one linking group selected from —NH—, and A ² represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine group having 1 to 22 carbon atoms. In formula [a-4], A ⁴ and A ⁶ are each independently —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—. , —CO— and —NH—, wherein A ⁵ represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear group having 1 to 22 carbon atoms. Or a branched fluorine-containing alkyl group).

(In the formula [a-5], A ¹ and A ³ each independently represent —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— and Represents at least one linking group selected from —NH—, and A ² represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine group having 1 to 22 carbon atoms. In the formula [a-6], A ⁴ and A ⁶ each independently represent —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—. , —CO— and —NH—, wherein A ⁵ represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear group having 1 to 22 carbon atoms. Or a branched fluorine-containing alkyl group).

(In the formula [a-7], p represents an integer of 1 to 10).

(In the formula [a-12], R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and in the formula [a-13], n represents an integer of 1 to 10).

Furthermore, as other diamine compounds, the following diamine compounds and diamine compounds in which these amino groups are secondary amino groups can also be used.

Specifically, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m- Phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4 '-Diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl 3,3′-trifluoromethyl-4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3 ' -Diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyl Dianiline, 3,3′-sulfonyldianiline, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) Silane, 4,4'-thiodia Phosphorus, 3,3′-thiodianiline, 4,4′-diaminodiphenylamine, 3,3′-diaminodiphenylamine, 3,4′-diaminodiphenylamine, 2,2′-diaminodiphenylamine, 2,3′-diaminodiphenylamine, N -Methyl (4,4'-diaminodiphenyl) amine, N-methyl (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'- Diaminodiphenyl) amine, N-methyl (2,3′-diaminodiphenyl) amine, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5 -Diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8- Diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3- Aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4- Bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3 -Bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 '-[1,4-phenylenebis (methylene) )] Dianiline, 4,4 ′-[1,3-phenylenebis (methylene)] dianiline, 3,4 ′-[1,4-phenylenebis (methylene)] dianiline, 3,4 ′-[1,3- Phenylenebis (methylene)] dianiline, 3,3 ′-[1,4-phenylenebis (methylene)] dianiline, 3,3 ′-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1, -Phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate) ), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) Isophthalate, N, N ′-(1,4-phenylene) bis (4-aminobenzamide), N, N ′-(1,3-phenylene) bis (4-aminobenzamide), N, N ′-(1 , 4-phenylene) bis (3-aminobenzamide), N, N ′-(1,3-phenylene) bis (3-aminobenze) Amide), N, N′-bis (4-aminophenyl) terephthalamide, N, N′-bis (3-aminophenyl) terephthalamide, N, N′-bis (4-aminophenyl) isophthalamide, N, N′-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4′-bis (4-aminophenoxy) diphenylsulfone, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2,2′-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2′-bis (4-aminophenyl) hexafluoropropane, 2,2 '-Bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane 2,2′-bis (4-aminophenyl) propane, 2,2′-bis (3-aminophenyl) propane, 2,2′-bis (3-amino-4-methylphenyl) propane, 1,3 -Bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, , 5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) Hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3 Aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3- Aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) ) Aromatic diamine compounds such as dodecane, alicyclic diamine compounds such as bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane, 1,4-diamino Butane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-dia Nookutan, 1,9-diaminononane, 1,10-diaminodecane, 1,11-di-aminoundecanoic, 1,12 aliphatic diamine compounds such as diamino dodecane.

The other diamine compound of the present invention includes the solubility of the specific polymer of the present invention in a solvent, the coating property of the composition and the liquid crystal alignment treatment agent, the alignment property of the liquid crystal when used as a liquid crystal alignment film, the voltage holding ratio, and the accumulated charge. Depending on the characteristics, one kind or a mixture of two or more kinds can be used.

As the specific polymer of the present invention, that is, the tetracarboxylic acid component for producing these polyimide polymers, it is preferable to use a tetracarboxylic dianhydride represented by the following formula [4]. At that time, not only the tetracarboxylic dianhydride represented by the formula [4] but also the tetracarboxylic acid derivative tetracarboxylic acid, tetracarboxylic acid dihalide compound, tetracarboxylic acid dialkyl ester compound or tetracarboxylic acid dialkyl ester di Halide compounds can also be used (the tetracarboxylic dianhydride represented by the formula [4] and its derivatives are collectively referred to as a specific tetracarboxylic acid component).

(In Formula [4], Z represents at least one structure selected from structures represented by Formula [4a] to Formula [4k] below).

In the formula [4a], Z ¹ to Z ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a phenyl group.

In the formula [4g], Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group.

Among Z in formula [4], from the viewpoint of ease of synthesis and ease of polymerization reactivity in producing a polymer, formula [4a], formula [4c] to formula [4g] or formula [4k] ] The tetracarboxylic dianhydride of the structure shown by these and its tetracarboxylic acid derivative are preferable. More preferable is the structure represented by the formula [4a] or the formula [4e] to the formula [4g]. Particularly preferred are tetracarboxylic dianhydrides and their tetracarboxylic acid derivatives having the structure represented by [4a], formula [4e] or formula [4f].

The specific tetracarboxylic acid component in the specific polymer of the present invention is preferably 1 mol% to 100 mol% in 100 mol% of all tetracarboxylic acid components. Of these, 5 mol% to 95 mol% is preferable. More preferred is 20 mol% to 80 mol%.
The specific tetracarboxylic acid component of the present invention includes the solubility of the specific polymer of the present invention in a solvent, the coating properties of the composition and the liquid crystal alignment treatment agent, the alignment of liquid crystals when used as a liquid crystal alignment film, the voltage holding ratio, One type or a mixture of two or more types can be used depending on characteristics such as accumulated charge.

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

That is, other tetracarboxylic acid components include 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic 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 ′ -Benzophenone tetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1, 1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ′, 4,4 Examples include '-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

The other tetracarboxylic acid components of the present invention are the solubility of the specific polymer of the present invention in a solvent, the coating properties of the composition and the liquid crystal aligning agent, the orientation of the liquid crystal when used as a liquid crystal alignment film, and the voltage holding ratio. Depending on the characteristics such as accumulated charge, one kind or a mixture of two or more kinds may be used.

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

In order to obtain a polyamic acid alkyl ester, a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group with a primary or secondary diamine compound, a tetracarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group, and A method of polycondensation with a primary or secondary diamine compound or a method of converting a carboxyl group of a polyamic acid into an ester is used.

In order to obtain polyimide, a method is used in which the polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in a solvent with the diamine component and the tetracarboxylic acid component. The solvent used in that case may be the specific solvent of the present invention, but is not particularly limited as long as the produced polyimide precursor is dissolved. Although the specific example of the solvent used for reaction below is given, it is not limited to these examples.

Examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolidinone. It is done. When the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3] The indicated solvents can be used.

(In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and the formula [D-3 In the formula, D ³ represents an alkyl group having 1 to 4 carbon atoms).

These solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not melt | dissolve a polyimide precursor, you may mix and use it for the said solvent in the range which the produced | generated polyimide precursor does not precipitate. Moreover, since water in the solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, it is preferable to use a dehydrated and dried solvent.

When the diamine component and the tetracarboxylic acid component are reacted in a solvent, the solution in which the diamine component is dispersed or dissolved in the solvent is stirred, and the tetracarboxylic acid component is added as it is or dispersed or dissolved in the solvent. Methods, conversely, a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in a solvent, a method of alternately adding a diamine component and a tetracarboxylic acid component, etc., and any of these methods May be used. In addition, when reacting using a plurality of diamine components or tetracarboxylic acid components, they may be reacted in a premixed state, individually or sequentially, or further individually reacted low molecular weight substances. May be mixed and reacted to form a polymer. In this case, the polymerization temperature can be selected from -20 ° C to 150 ° C, but is preferably in the range of -5 ° C to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. It becomes. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial reaction can be carried out at a high concentration, and then a solvent can be added.

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

The polyimide of the present invention is a polyimide obtained by ring closure of the polyimide precursor, and in this polyimide, the ring closure rate of the amic acid group (also referred to as imidization rate) is not necessarily 100%. It can be arbitrarily adjusted according to the purpose.

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

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

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

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

<Composition / Liquid crystal aligning agent>
The composition of the present invention and the liquid crystal alignment treatment agent using the composition are coating solutions for forming a polyimide film and a liquid crystal alignment film (also collectively referred to as a resin film), and contain a specific solvent and a specific polymer. A coating solution for forming a resin film.

The specific polymer of the present invention may be any polyimide polymer such as polyamic acid, polyamic acid alkyl ester and polyimide. Of these, polyamic acid alkyl ester or polyimide is preferable. More preferably, it is a polyimide.

All the polymer components in the composition and the liquid crystal aligning agent of the present invention may all be the specific polymer of the present invention. In that case, you may use 2 or more types of specific polymers of this invention in mixture. In addition, other polymers may be mixed with the specific polymer. Examples of other polymers include cellulosic polymers, acrylic polymers, methacrylic polymers, polystyrene, polyamides, and polysiloxanes. At that time, the content of the other polymer is 0.5 to 30 parts by mass with respect to 100 parts by mass of the specific polymer of the present invention. Of these, 1 to 20 parts by mass is preferable.

In the case of forming a liquid crystal alignment film using the composition of the present invention as a liquid crystal aligning agent, the specific polymer has a specific side chain structure represented by the formula [1-1] of the present invention. Is preferably used. Among these, it is preferable to use a specific polymer using the specific side chain diamine compound represented by the formula [1a] having the specific side chain structure represented by the formula [1-1]. In particular, a liquid crystal alignment film for a mode that requires a pretilt angle of liquid crystal, such as a TN (twisted nematic) mode or a VA (vertical alignment) mode, may be a specific polymer using a specific side chain type diamine compound. good. In this case, a specific polymer using a specific side chain diamine compound and a specific polymer not using a specific side chain diamine compound may be mixed and used. In this case, the content of the specific polymer not using the specific side chain diamine compound is 10 to 300 parts by mass with respect to 100 parts by mass of the specific polymer using the specific side chain diamine compound. preferable. Of these, 20 to 200 parts by mass is preferable.

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

In addition, as the solvent at that time, all may be the specific solvent of the present invention, but a solvent for dissolving the specific polymer of the present invention, that is, a good solvent may be used at the same time. Although the specific example of a good solvent is given to the following, it is not limited to these examples.

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

Of these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyllactone (also referred to as component (C) above) is preferably used.

These components (C) are preferably 1 to 70% by mass of the entire solvent contained in the composition and the liquid crystal aligning agent. Among these, 5 to 65% by mass is preferable. A more preferred range is 5 to 60% by mass, and a further more preferred range is 10 to 60% by mass.

The good solvent may be used alone or in combination of two or more depending on the solubility of the specific polymer of the present invention in the solvent and the applicability of the composition and the liquid crystal alignment treatment agent.

Unless the effects of the present invention are impaired, the composition of the present invention and the liquid crystal aligning agent are organic solvents that improve the coating properties and surface smoothness of the resin film when the composition and the liquid crystal aligning agent are applied, That is, it is also preferable to use a poor solvent. Although the specific example of a poor solvent is given to the following, it is not limited to these examples.

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

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether or the above formulas [D-1] to [D -3] (also referred to as component (D) above) is preferably used.

These components (D) are preferably 10 to 80% by mass of the total solvent contained in the composition and the liquid crystal aligning agent. Among these, 10 to 70% by mass is preferable. A more preferred range is 20 to 70% by mass, and a further more preferred range is 20 to 60% by mass.

The poor solvent may be used alone or in combination of two or more depending on the solubility of the specific polymer of the present invention in the solvent and the applicability of the composition and the liquid crystal alignment treatment agent.

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

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

Specifically, crosslinkable compounds represented by the formulas [4a] to [4k] described in the 58th to 59th items of International Publication No. 2011/132751 (published 2011.10.27) can be mentioned.

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

Specifically, the crosslinkable compounds represented by the formulas [5-1] to [5-42] described in the paragraphs 76 to 82 of International Publication No. 2012/014898 (published in 2012.2.2) Can be mentioned.

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, a urea resin, a guanamine resin, and a glycoluril. -Formaldehyde resin, succinilamide-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, a melamine derivative, a benzoguanamine derivative, or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group or an alkoxymethyl group or both can be used. The melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.

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

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

More specifically, the crosslinkability represented by the formulas [6-1] to [6-48] described on pages 62 to 66 of International Publication No. 2011/132751 (published 2011.10.27). Compounds.

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

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

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

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

The content of the crosslinkable compound in the composition and the liquid crystal aligning 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. Among these, in order for the crosslinking reaction to proceed and to exhibit the desired effect, the amount is preferably 0.1 parts by mass to 100 parts by mass with respect to 100 parts by mass of all the polymer components. More preferred is 1 to 50 parts by mass.

Unless the effects of the present invention are impaired, the composition and liquid crystal alignment treatment agent of the present invention improve the uniformity of the film thickness and surface smoothness of the resin film when the composition and the liquid crystal alignment treatment agent are applied. Can be used.

Examples of the compound that improves the uniformity of the film thickness and the surface smoothness of the resin coating include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

More specifically, for example, F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink), Florard FC430, FC431 (or more) And Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.).

The ratio of these surfactants to be used is preferably 0.01 parts by mass to 2 parts by mass, and more preferably 0.00 parts by mass with respect to 100 parts by mass of all the polymer components contained in the composition and the liquid crystal aligning agent. 01 parts by mass to 1 part by mass.

Furthermore, in the composition and the liquid crystal alignment treatment agent of the present invention, International Publication No. 2011/132751 (2011.10.27) is disclosed as a compound that promotes charge transfer in the resin film and promotes charge release of the device. The nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156], which are listed on pages 69 to 73, can also be added. This amine compound may be added directly to the composition and the liquid crystal alignment treatment agent, but it is made into a solution having a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass with an appropriate solvent. It is preferable to add from the above. The solvent is not particularly limited as long as it is a solvent that dissolves the above-described specific polymer.

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

<Polyimide film>
The composition of the present invention can be used as a polyimide film after coating and baking on a substrate. As a substrate used at this time, a plastic substrate such as a glass substrate, a silicon wafer, an acrylic substrate, a polycarbonate substrate, or a PET (polyethylene terephthalate) substrate can be used depending on a target device. Moreover, a polyimide film can also be used as a film substrate as it is. The coating method of the composition is not particularly limited, but industrially, there are methods such as a dipping method, a roll coater method, a slit coater method, a spinner method, a spray method, screen printing, offset printing, flexographic printing, or an inkjet method. It is common. You may use these according to the objective.

After the composition is applied onto the substrate, the solvent is evaporated at 50 to 300 ° C., preferably 80 to 250 ° C. by a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven, and the polyimide film and can do. In the case of the composition using the specific solvent of the present invention, the polyimide film can be produced even at a temperature of 200 ° C. or lower. The thickness of the polyimide film after firing can be adjusted to 0.01 to 100 μm depending on the purpose.

<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal alignment treatment agent using the composition of the present invention can be used as a liquid crystal alignment film by applying alignment treatment by rubbing treatment or light irradiation after coating and baking on a substrate. In the case of vertical alignment applications such as VA mode, it can be used as a liquid crystal alignment film without alignment treatment. The substrate used in this case is not particularly limited as long as it is a highly transparent substrate. In addition to a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or a PET (polyethylene terephthalate) substrate can also be used. From the viewpoint of simplifying the process, it is preferable to use a substrate on which an ITO (indium tin oxide) electrode or the like for driving a liquid crystal is formed. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.

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

After applying the liquid crystal aligning agent on the substrate, it is preferably 30 to 300 ° C., depending on the solvent used for the liquid crystal aligning agent, by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven. The liquid crystal alignment film can be obtained by evaporating the solvent at a temperature of 30 to 250 ° C. In the case of the liquid crystal aligning agent using the specific solvent of this invention, a liquid crystal aligning film can be produced also at the temperature of 200 degrees C or less. If the thickness of the liquid crystal alignment film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 10 to 150 nm. When the liquid crystal is horizontally aligned or tilted, the fired liquid crystal alignment film is treated by rubbing or irradiation with polarized ultraviolet rays.

The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the above-described method, and then preparing a liquid crystal cell by a known method.

As a method for manufacturing a liquid crystal cell, prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and place the other side of the liquid crystal alignment film on the other side. And a method of sealing the substrate by injecting liquid crystal under reduced pressure, or a method of bonding the substrate after dropping the liquid crystal on the surface of the liquid crystal alignment film on which the spacers are dispersed, and the like.

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

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

That is, in the liquid crystal display element of the present invention, after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above method, a liquid crystal cell is prepared, and a polymerizable compound is applied by at least one of ultraviolet irradiation and heating. Polymerization can control the orientation of liquid crystal molecules.

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

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

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

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

In order to obtain a liquid crystal alignment film containing a polymerizable group that polymerizes from at least one of active energy rays and heat, a method of adding a compound containing this polymerizable group to a liquid crystal aligning agent, A method using a coalescing component may be mentioned.

To give an example of SC-PVA mode liquid crystal cell preparation, a pair of substrates on which the liquid crystal alignment film of the present invention is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is prepared. The other substrate is bonded so that the inner side is on the inside and the liquid crystal is injected under reduced pressure to seal, or the liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed and then the substrate is bonded and sealed The method of performing etc. is mentioned.

After the liquid crystal cell is produced, the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.

As described above, the liquid crystal aligning agent of the present invention becomes a liquid crystal alignment film having excellent coating properties, and furthermore, even when firing at the time of producing the liquid crystal alignment film is at a low temperature, It becomes a liquid crystal alignment film excellent in VHR which is a characteristic. Therefore, the liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and is used for a large-screen high-definition liquid crystal television, a small-sized car navigation system, a smartphone, and the like. It can be suitably used.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

"Abbreviations used in the synthesis examples, examples and comparative examples of the present invention"
Abbreviations used in the synthesis examples, examples and comparative examples are as follows.

<Monomer for producing the polyimide polymer of the present invention>
(Specific side chain diamine compound of the present invention)
A1: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene (specific side chain having a specific side chain structure represented by the formula [1-1] of the present invention) Type diamine compound)
A2: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxymethyl] benzene (specific side having a specific side chain structure represented by the formula [1-1] of the present invention) Chain-type diamine compounds)
A3: 1,3-diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene (shown by the formula [1-1] of the present invention) Specific side chain type diamine compound having specific side chain structure)
A4: a diamine compound represented by the following formula [A4] (a specific side chain diamine compound having a specific side chain structure represented by the formula [1-1] of the present invention)
A5: 1,3-diamino-4-octadecyloxybenzene (a specific side chain diamine compound having a specific side chain structure represented by the formula [1-2] of the present invention)

(Diamine compound represented by the formula [2a] of the present invention)
B1: 3,5-diaminobenzoic acid (diamine compound having a carboxyl group (COOH group) represented by the formula [2a] of the present invention)

(Diamine compound represented by the formula [3a] of the present invention)
C1: A diamine compound represented by the following formula [C1] (a diamine compound having a nitrogen-containing heterocycle represented by the formula [3a] of the present invention)
C2: a diamine compound represented by the following formula [C2] (a diamine compound having a nitrogen-containing heterocycle represented by the formula [3a] of the present invention)

(Other diamine compounds)
D1: p-phenylenediamine D2: m-phenylenediamine

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

<Crosslinkable compound used in the present invention>
K1: Crosslinkable compound represented by the following formula [K1]

<Specific solvent of the present invention>
S1: Solvent represented by the following formula [S1] (specific solvent represented by the formula [A-1] of the present invention)

<Other solvents>
NMP: N-methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone γ-BL: γ-butyrolactone BCS: ethylene glycol monobutyl ether PB: propylene glycol monobutyl ether EC: diethylene glycol monoethyl ether DME: dipropylene glycol dimethyl ether

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

"Measurement of imidization ratio of polyimide of the present invention"
The imidation ratio of polyimide in the synthesis example was measured as follows. 20 mg of polyimide powder was put into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku)), and deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05 mass% TMS (tetramethylsilane). ) Mixture) (0.53 ml) was added and completely dissolved by sonication. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Datum). The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid that appear in the vicinity of 9.5 ppm to 10.0 ppm. Using the integrated value, the following formula was used.
Imidization rate (%) = (1−α · x / y) × 100

In the above formula, x is a proton peak integrated value derived from NH group of amic acid, y is a peak integrated value of reference proton, α is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.

"Synthesis of polyimide polymer of the present invention"
<Synthesis Example 1>
E1 (5.21 g, 26.6 mmol), A1 (5.12 g, 13.5 mmol) and B1 (2.05 g, 13.5 mmol) were mixed in S1 (37.1 g) and reacted at 40 ° C. for 8 hours. To obtain a polyamic acid solution (1) having a resin solid content concentration of 25% by mass. The number average molecular weight of this polyamic acid was 25,800, and the weight average molecular weight was 86,900.

<Synthesis Example 2>
E2 (3.40 g, 13.6 mmol), B1 (4.19 g, 27.6 mmol) and D1 (0.74 g, 6.89 mmol) were mixed in S1 (24.7 g) and reacted at 80 ° C. for 5 hours. After that, E1 (4.00 g, 20.4 mmol) and S1 (12.3 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25 mass%. . The number average molecular weight of this polyamic acid was 26,200, and the weight average molecular weight was 86,400.

<Synthesis Example 3>
After adding NMP to the polyamic acid solution (2) (30.0 g) obtained by the synthesis method of Synthesis Example 2 and diluting to 6% by mass, acetic anhydride (3.95 g) and pyridine (2. 50 g) was added and reacted at 60 ° C. for 2 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (3). The imidation ratio of this polyimide was 53%, the number average molecular weight was 22,100, and the weight average molecular weight was 60,900.

<Synthesis Example 4>
E2 (3.96 g, 15.8 mmol), B1 (4.14 g, 27.2 mmol), C1 (0.39 g, 1.60 mmol) and D2 (0.35 g, 3.20 mmol) NEP (24.2 g) After mixing at 80 ° C. for 5 hours, E1 (3.10 g, 15.8 mmol) and NEP (12.1 g) were added and reacted at 40 ° C. for 6 hours to give a resin solid content concentration of 25 mass. % Polyamic acid solution was obtained.

NEP was added to the obtained polyamic acid solution (30.0 g), diluted to 6% by mass, acetic anhydride (4.40 g) and pyridine (3.30 g) were added as an imidization catalyst, and 3.80 ° C. was added. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (4). The imidation ratio of this polyimide was 80%, the number average molecular weight was 19,900, and the weight average molecular weight was 55,100.

<Synthesis Example 5>
E2 (3.22 g, 12.9 mmol), A2 (4.62 g, 11.7 mmol), B1 (1.78 g, 11.7 mmol) and D1 (0.28 g, 2.60 mmol) into S1 (24.8 g) After mixing at 80 ° C. for 5 hours, E1 (2.52 g, 12.9 mmol) and S1 (12.4 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. % Polyamic acid solution (5) was obtained. The number average molecular weight of this polyamic acid was 20,900, and the weight average molecular weight was 72,100.

<Synthesis Example 6>
NMP was added to the polyamic acid solution (5) (30.0 g) obtained by the synthesis method of Synthesis Example 5 and diluted to 6% by mass, and then acetic anhydride (3.95 g) and pyridine (2. 40 g) was added and reacted at 70 ° C. for 3.5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (6). The imidation ratio of this polyimide was 73%, the number average molecular weight was 19,900, and the weight average molecular weight was 53,900.

<Synthesis Example 7>
E2 (1.31 g, 5.23 mmol), A3 (3.44 g, 7.94 mmol), C1 (2.57 g, 10.6 mmol) and D2 (0.86 g, 7.94 mmol) to NMP (24.5 g) After mixing at 80 ° C. for 5 hours, E1 (4.10 g, 20.9 mmol) and NMP (12.3 g) were added and reacted at 40 ° C. for 6 hours to give a resin solid concentration of 25 mass. % Polyamic acid solution was obtained.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst, and 3. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (7). The imidation ratio of this polyimide was 80%, the number average molecular weight was 15,900, and the weight average molecular weight was 43,800.

<Synthesis Example 8>
E2 (1.23 g, 4.91 mmol), A2 (3.92 g, 9.94 mmol), C2 (2.58 g, 9.94 mmol) and D2 (0.54 g, 4.97 mmol) to NMP (24.2 g) After mixing at 80 ° C. for 5 hours, E1 (3.85 g, 19.6 mmol) and NMP (12.1 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. % Polyamic acid solution was obtained.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (3.85 g) and pyridine (2.50 g) were added as imidization catalysts, and the mixture was heated at 60 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (8). The imidation ratio of this polyimide was 55%, the number average molecular weight was 16,900, and the weight average molecular weight was 46,900.

<Synthesis Example 9>
E2 (2.55 g, 10.2 mmol), A4 (2.55 g, 5.17 mmol), B1 (0.39 g, 2.58 mmol), C2 (3.35 g, 12.9 mmol) and D2 (0.56 g, 5.17 mmol) was mixed in NEP (24.8 g) and reacted at 80 ° C. for 5 hours, then E1 (3.00 g, 15.3 mmol) and NEP (12.4 g) were added, and 6 ° C. The reaction was carried out for a time to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

To the obtained polyamic acid solution (30.5 g), NEP was added to dilute to 6% by mass, then acetic anhydride (3.95 g) and pyridine (2.55 g) were added as an imidization catalyst, and the mixture was heated at 60 ° C. for 3 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (9). The imidation ratio of this polyimide was 61%, the number average molecular weight was 16,000, and the weight average molecular weight was 44,800.

<Synthesis Example 10>
E2 (1.20 g, 4.78 mmol), A5 (3.65 g, 9.69 mmol), C2 (2.51 g, 9.69 mmol) and D2 (0.52 g, 4.84 mmol) were combined with NMP (23.3 g). After mixing at 80 ° C. for 5 hours, E1 (3.75 g, 19.1 mmol) and NMP (11.6 g) were added and reacted at 40 ° C. for 6 hours to give a resin solid content concentration of 25 mass. % Polyamic acid solution was obtained.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (3.80 g) and pyridine (2.55 g) were added as imidization catalysts, and the mixture was heated at 60 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (10). The imidation ratio of this polyimide was 56%, the number average molecular weight was 16,200, and the weight average molecular weight was 48,100.

<Synthesis Example 11>
E3 (7.50 g, 33.5 mmol), B1 (3.61 g, 23.7 mmol), C1 (0.41 g, 1.69 mmol) and D1 (0.92 g, 8.47 mmol) to NMP (37.3 g) Then, the mixture was reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.20 g) and pyridine (3.10 g) were added as an imidization catalyst, and 2. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (11). The imidation ratio of this polyimide was 75%, the number average molecular weight was 19,800, and the weight average molecular weight was 53,900.

<Synthesis Example 12>
E3 (5.90 g, 26.3 mmol), A2 (4.21 g, 10.7 mmol), B1 (0.41 g, 2.67 mmol) and D2 (1.44 g, 13.3 mmol) were added to NMP (35.9 g). Then, the mixture was reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.35 g) were added as an imidization catalyst, and 3. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (12). The imidation ratio of this polyimide was 81%, the number average molecular weight was 18,200, and the weight average molecular weight was 51,600.

<Synthesis Example 13>
E3 (5.50 g, 24.5 mmol), A4 (2.45 g, 4.97 mmol), B1 (0.19 g, 1.24 mmol), C2 (3.54 g, 13.7 mmol) and D2 (0.54 g, 4.97 mmol) was mixed in NMP (36.7 g) and reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

After adding NMP to the obtained polyamic acid solution (30.5 g) and diluting to 6% by mass, acetic anhydride (3.90 g) and pyridine (2.60 g) were added as an imidization catalyst, and 3. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (13). The imidation ratio of this polyimide was 65%, the number average molecular weight was 18,500, and the weight average molecular weight was 50,200.

<Synthesis Example 14>
E4 (5.21 g, 17.3 mmol), A1 (4.60 g, 12.1 mmol), B1 (0.67 g, 4.39 mmol) and D1 (0.59 g, 5.49 mmol) to NEP (23.8 g) After mixing at 80 ° C. for 6 hours, E1 (0.85 g, 4.33 mmol) and NEP (11.9 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. % Polyamic acid solution was obtained.

To the obtained polyamic acid solution (30.0 g), NEP was added and diluted to 6% by mass, and then acetic anhydride (3.80 g) and pyridine (2.50 g) were added as an imidization catalyst, and the mixture was heated at 60 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (14). The imidation ratio of this polyimide was 55%, the number average molecular weight was 16,800, and the weight average molecular weight was 45,300.

<Synthesis Example 15>
E4 (3.29 g, 11.0 mmol), A2 (3.51 g, 8.88 mmol), C1 (1.61 g, 6.66 mmol), C2 (1.15 g, 4.44 mmol) and D2 (0.24 g, 2.22 mmol) was mixed in NMP (23.9 g) and reacted at 80 ° C. for 6 hours, and then E1 (2.15 g, 11.0 mmol) and NMP (12.0 g) were added. The reaction was carried out for a time to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After adding NMP to the obtained polyamic acid solution (30.1 g) and diluting to 6% by mass, acetic anhydride (4.20 g) and pyridine (3.15 g) were added as an imidization catalyst, and 2. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (15). The imidation ratio of this polyimide was 73%, the number average molecular weight was 15,900, and the weight average molecular weight was 43,800.

<Synthesis Example 16>
E5 (4.30 g, 20.3 mmol), A3 (3.89 g, 8.98 mmol), C2 (1.33 g, 5.13 mmol) and D2 (1.25 g, 11.6 mmol) NMP (23.5 g) After mixing at 80 ° C. for 6 hours, E1 (0.99 g, 5.07 mmol) and NMP (11.8 g) were added and reacted at 40 ° C. for 6 hours. The resin solid content concentration was 25 mass. % Polyamic acid solution was obtained.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (3.85 g) and pyridine (2.40 g) were added as an imidization catalyst, and the mixture was heated at 60 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (16). The imidation ratio of this polyimide was 51%, the number average molecular weight was 15,700, and the weight average molecular weight was 44,500.

<Synthesis Example 17>
E5 (4.10 g, 19.3 mmol), B1 (4.47 g, 29.4 mmol) and D2 (0.35 g, 3.26 mmol) were mixed in NMP (24.3 g) and reacted at 80 ° C. for 6 hours. After that, E2 (3.22 g, 12.9 mmol) and NMP (12.1 g) were added and reacted at 80 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.20 g) and pyridine (3.20 g) were added as an imidization catalyst, and 2. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (17). The imidation ratio of this polyimide was 73%, the number average molecular weight was 16,200, and the weight average molecular weight was 48,100.

<Synthesis Example 18>
E5 (2.95 g, 13.9 mmol), A2 (3.71 g, 9.39 mmol), B1 (0.36 g, 2.35 mmol), C1 (1.14 g, 4.70 mmol), C2 (1.22 g, 4.70 mmol) and D1 (0.25 g, 2.35 mmol) were mixed in NEP (23.9 g), reacted at 80 ° C. for 6 hours, and then E2 (2.32 g, 9.27 mmol) and NEP ( 11.9 g) was added and reacted at 80 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.20 g) and pyridine (3.20 g) were added as an imidization catalyst, and the mixture was heated at 80 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (18). The imidation ratio of this polyimide was 68%, the number average molecular weight was 15,500, and the weight average molecular weight was 45,100.

<Synthesis Example 19>
E2 (3.10 g, 12.4 mmol), B1 (3.82 g, 25.1 mmol) and D1 (0.68 g, 6.28 mmol) were mixed in NMP (22.5 g) and reacted at 80 ° C. for 5 hours. After that, E1 (3.65 g, 18.6 mmol) and NMP (11.3 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (19) having a resin solid content concentration of 25 mass%. . The number average molecular weight of this polyamic acid was 27,900, and the weight average molecular weight was 88,900.

<Synthesis Example 20>
E2 (3.13 g, 12.5 mmol), A2 (4.49 g, 11.4 mmol), B1 (1.73 g, 11.4 mmol) and D1 (0.27 g, 2.53 mmol) to NMP (24.2 g) After mixing at 80 ° C. for 5 hours, E1 (2.45 g, 12.5 mmol) and NMP (12.1 g) were added and reacted at 40 ° C. for 6 hours to give a resin solid content concentration of 25 mass. % Polyamic acid solution (20) was obtained. The number average molecular weight of this polyamic acid was 22,200, and the weight average molecular weight was 76,900.

Tables 1 and 2 show the polyimide polymers of the present invention.

“Production of Composition and Liquid Crystal Alignment Treatment Agent of the Present Invention”
In Examples 1 to 20 and Comparative Examples 1 to 4 described below, production examples of the composition will be described. These compositions are also used for evaluation of liquid crystal aligning agents.

Tables 3 to 5 show the compositions and liquid crystal aligning agents of the present invention.

“Evaluation of printability of composition and liquid crystal alignment treatment agent (pinhole evaluation)”, “Composition and liquid crystal alignment treatment” using the compositions and liquid crystal alignment treatment agents obtained in Examples and Comparative Examples of the present invention "Evaluation of printability of coating agent (evaluation of coating film edge)", "Evaluation of voltage holding ratio (VHR) (ordinary cell)", "Evaluation of inkjet coating property of liquid crystal alignment treatment agent", "Preparation of liquid crystal cell and Evaluation of liquid crystal alignment (PSA cell) ”and“ Preparation of liquid crystal cell and evaluation of liquid crystal alignment (SC-PVA cell) ”were performed.

"Evaluation of printability of composition and liquid crystal aligning agent (Evaluation of pinhole)"
Using the compositions obtained by the methods of Examples and Comparative Examples of the present invention, pinholes of polyimide films were evaluated. Specifically, these compositions were subjected to pressure filtration with a membrane filter having a pore diameter of 1 μm, and printed on an unwashed Cr vapor deposition substrate (length 100 mm × width 100 mm, thickness 1.0 mm). A simple printing machine S15 type (made by Nissha Printing Co., Ltd.) was used as the printing machine. The printing area was in the range of 80 × 80 mm with respect to the center of the substrate, the printing pressure was 0.2 mm, the number of discarded substrates was 5, and printing was temporarily performed. The time until drying was 90 seconds, temporary drying was performed on a hot plate at 70 ° C. for 5 minutes, and main firing was performed in a heat-circulating clean oven at 160 ° C. for 15 minutes.

Thereafter, the number of pinholes in the obtained substrate with the polyimide film was confirmed. Specifically, this polyimide film-coated substrate was visually observed under a sodium lamp, and the number of pinholes on the polyimide film was counted. The smaller the number of pinholes, the fewer the precipitates in the composition, and the better the evaluation.

Tables 6 to 8 show the number of pinholes obtained in the examples and comparative examples.

The compositions obtained in the examples and comparative examples of the present invention can be used for liquid crystal alignment treatment agents. Therefore, the evaluation of pinholes in the polyimide film of the compositions obtained in the examples and comparative examples of the present invention was also evaluated as pinholes in the liquid crystal alignment film.

"Evaluation of printability of composition and liquid crystal aligning agent (evaluation of coating film edge)"
Using the polyimide film-coated substrate obtained in the above-mentioned “evaluation of printability of composition and liquid crystal alignment treatment agent (pinhole evaluation)”, evaluation of the coating film end of the polyimide film, that is, polyimide film end Evaluation of linearity (also referred to as evaluation of linearity) and swell of the polyimide film end (also referred to as evaluation of swell) were performed.

Evaluation of the linearity of the end of the polyimide film was performed by observing the polyimide film at the right end with respect to the printing direction using an optical microscope. More specifically, the difference between (1) and (2) in FIG. 1 of the polyimide film image obtained by observing at an optical microscope magnification of 25 times, that is, the length of A in FIG. did. At that time, images of all polyimide films were obtained at the same magnification. The shorter the length of A, the better the linearity of the end of the polyimide film.

The evaluation of the bulge at the end of the polyimide film was performed by observing the polyimide film at the right end with respect to the printing direction with an optical microscope. Specifically, the length of B in FIG. 2 of the polyimide film image obtained by observing at an optical microscope magnification of 25 was measured. At that time, all polyimide film images were obtained at the same magnification. The shorter the length of B, the better the rise of the end of the polyimide film.

Tables 6 to 8 show the lengths A and B obtained in the examples and comparative examples.

The compositions obtained in the examples and comparative examples of the present invention can be used for liquid crystal alignment treatment agents. Therefore, evaluation of the coating film edge part of the polyimide film obtained by the present Example and the comparative example was also made evaluation of the coating film edge part of a liquid crystal aligning film.

"Evaluation of voltage holding ratio (VHR) (normal cell)"
The voltage holding ratio (VHR) was evaluated using the liquid crystal aligning agents obtained in the examples and comparative examples of the present invention. Specifically, these liquid crystal alignment treatment agents were pressure filtered through a membrane filter having a pore size of 1 μm and washed with pure water and IPA (isopropyl alcohol) (40 mm long × 30 mm wide, thickness) 0.7mm)) is spin-coated on the ITO surface and heat-treated on a hot plate at 80 ° C. for 3 minutes and in a heat-circulating clean oven at 160 ° C. for 15 minutes with a liquid crystal alignment film with a thickness of 100 nm An ITO substrate was obtained. A rubbing apparatus having a roll diameter of 120 mm is used to rub the coated surface of this ITO substrate under the conditions of roll rotation speed: 300 rpm, roll progression speed: 20 mm / sec, push-in amount: 0.4 mm. It was.

Two obtained ITO substrates with a liquid crystal alignment film were prepared, combined with a 6 μm spacer sandwiched with the liquid crystal alignment film surface inside, and an ultraviolet curable sealant was printed. Subsequently, after bonding together so that the other board | substrate and the liquid crystal aligning film surface might face each other, the process for hardening an ultraviolet curing sealing agent was performed, and the empty cell was obtained. Specifically, using a metal halide lamp with an illuminance of 60 mW, the wavelength of 310 nm or less is cut and irradiated with ultraviolet rays of 5 J / cm ^{2 in} terms of 365 nm, and then in a heat-circulating clean oven at 120 ° C. for 60 minutes. An empty cell was obtained by heat treatment. A nematic liquid crystal was injected into this empty cell by a reduced pressure injection method to obtain a liquid crystal cell (ordinary cell).

In addition, the liquid crystal aligning agent (2) to the liquid crystal aligning agent (4) obtained by the methods of Examples 2 to 4, the liquid crystal aligning agent (12) obtained by the method of Example 12, and the examples The liquid crystal aligning agent (19) obtained by 19 methods, the liquid crystal aligning agent (21) obtained by the method of Comparative Example 1 and the liquid crystal aligning agent (22) obtained by the method of Comparative Example 2 were used. The liquid crystal cell used was MLC-2003 (manufactured by Merck Japan) as the liquid crystal.

Further, MLC-6608 (manufactured by Merck Japan) was used for the liquid crystal in the liquid crystal cell using the liquid crystal aligning agent obtained in the examples and comparative examples other than the above.

A voltage of 1 V was applied to the obtained liquid crystal cell at a temperature of 80 ° C. for 60 μs, the voltage after 50 ms was measured, and how much the voltage was held was calculated as a voltage holding ratio (VHR). The measurement was carried out using a voltage holding ratio measuring device (VHR-1) (manufactured by Toyo Technica Co., Ltd.) with settings of Voltage: ± 1 V, Pulse Width: 60 μs, and Frame Period: 50 ms.

Furthermore, the liquid crystal cell in which the measurement of VHR was completed was stored in a high-temperature bath at a temperature of 80 ° C. for 720 hours, and VHR was measured again (also referred to after storage in a high-temperature bath) under the same conditions as described above.

In addition to the VHR value immediately after production of the liquid crystal cell, the evaluation was made better as the decrease in the VHR value after storage in the high-temperature bath was smaller than the VHR value immediately after production of the liquid crystal cell.

Tables 9 to 11 show the voltage holding ratio (VHR) values obtained in the examples and comparative examples.

"Evaluation of inkjet coating properties of liquid crystal alignment treatment agents"
Liquid crystal aligning agent (4) obtained by the method of Example 4 of the present invention, Liquid crystal aligning agent (7) obtained by the method of Example 7 and Liquid crystal aligning agent obtained by the method of Example 15 (15) was used to evaluate ink jet coatability. Specifically, these liquid crystal alignment treatment agents are pressure filtered through a membrane filter having a pore size of 1 μm, and washed with pure water and IPA using an HIS-200 (manufactured by Hitachi Plant Technology) as an inkjet coating machine. On the ITO (Indium Tin Oxide) vapor deposition substrate, the coating area is 70 × 70 mm, the nozzle pitch is 0.423 mm, the scan pitch is 0.5 mm, the coating speed is 40 mm / second, and the time from coating to temporary drying is 60 Second, preliminary drying was performed on a hot plate at 70 ° C. for 5 minutes, and main baking was performed in a heat circulation type clean oven at 160 ° C. for 15 minutes.

The obtained substrate with a liquid crystal alignment film was visually observed under a sodium lamp and the number of pinholes on the liquid crystal alignment film was counted. It was less than 5. Moreover, the liquid crystal aligning film excellent in the coating-film uniformity was obtained in any Example.

Furthermore, using the obtained substrate with a liquid crystal alignment film, VHR (normal cell) was evaluated under the conditions of “evaluation of voltage holding ratio (VHR) (normal cell)”.

"Production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)"
Liquid crystal aligning agent (6) obtained by the method of Example 6 of the present invention, Liquid crystal aligning agent (9) obtained by the method of Example 9 and Liquid crystal aligning agent obtained by the method of Example 14 Using (14), production of a liquid crystal cell and evaluation of liquid crystal orientation (PSA cell) were performed. Specifically, these liquid crystal aligning agents were pressure filtered through a membrane filter having a pore size of 1 μm, washed with pure water and IPA, and a substrate with ITO electrodes (length: 40 mm × width) of 10 × 10 mm and a pattern spacing of 20 μm. 30mm, thickness 0.7mm) and spin coated on the ITO surface of the substrate with ITO electrode 10mm × 40mm in the center (length 40mm x width 30mm, thickness 0.7mm) and on hot plate at 80 ° C for 3 minutes Then, heat treatment was performed at 160 ° C. for 15 minutes in a heat-circulating clean oven to obtain a substrate with a liquid crystal alignment film having a film thickness of 100 nm.

These substrates with a liquid crystal alignment film were combined with a 6 μm spacer sandwiched with the liquid crystal alignment film surface on the inside, and the periphery was adhered with a sealant to produce an empty cell. A nematic liquid crystal (MLC-6608) (manufactured by Merck Japan) was added to the empty cell by a reduced pressure injection method, and a polymerizable compound (1) represented by the following formula was added to 100% by mass of the nematic liquid crystal (MLC-6608). Liquid crystal mixed with 0.3% by mass of the polymerizable compound (1) was injected, and the injection port was sealed to obtain a liquid crystal cell.

While applying an AC voltage of 5 V to the obtained liquid crystal cell, using a metal halide lamp with an illuminance of 60 mW, the wavelength of 350 nm or less was cut, and ultraviolet irradiation of 20 J / cm ^{2 in} terms of 365 nm was performed, and the alignment direction of the liquid crystal A liquid crystal cell (PSA cell) was controlled. The temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was 50 ° C.

The response speed of the liquid crystal before and after UV irradiation of this liquid crystal cell was measured. As the response speed, T90 → T10 from 90% transmittance to 10% transmittance was measured.

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

“Preparation of liquid crystal cell and evaluation of liquid crystal alignment (SC-PVA cell)”
Liquid crystal aligning agent (6) obtained by the method of Example 6 of the present invention, Liquid crystal aligning agent (9) obtained by the method of Example 9 and Liquid crystal aligning agent obtained by the method of Example 14 Using (14), production of a liquid crystal cell and evaluation of liquid crystal orientation (SC-PVA cell) were performed. Specifically, the polymerizable compound (1) shown above is added to these liquid crystal aligning agents in an amount of 2% by mass with respect to 100% by mass of the total polymer components in the liquid crystal aligning agent, and at 25 ° C. for 4 hours. Stir. Thereafter, the obtained liquid crystal aligning agent was pressure filtered through a membrane filter having a pore size of 1 μm, washed with pure water and IPA, and a 10 × 10 mm substrate with an ITO electrode having a pattern spacing of 20 μm (length 40 mm × width 30 mm). , Thickness 0.7mm) and the center of the 10x40mm ITO electrode substrate (length 40mm x width 30mm, thickness 0.7mm) on the ITO surface is spin-coated on a hot plate at 80 ° C for 3 minutes, A heat treatment was performed at 160 ° C. for 15 minutes in a heat circulation type clean oven to obtain a substrate with a liquid crystal alignment film having a film thickness of 100 nm.

These substrates with a liquid crystal alignment film were combined with a 6 μm spacer sandwiched with the liquid crystal alignment film surface inside, and an empty cell was prepared by adhering the periphery with a sealant. A nematic liquid crystal (MLC-6608) (manufactured by Merck Japan Ltd.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell.

While applying an AC voltage of 5 V to the obtained liquid crystal cell, using a metal halide lamp with an illuminance of 60 mW, the wavelength of 350 nm or less was cut, and ultraviolet irradiation of 20 J / cm ^{2 in} terms of 365 nm was performed, and the alignment direction of the liquid crystal A liquid crystal cell (SC-PVA cell) was controlled. The temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was 50 ° C.

In the SC-PVA cell obtained in any of the examples, the response speed of the liquid crystal cell after ultraviolet irradiation was higher than that of the liquid crystal cell before ultraviolet irradiation. confirmed. Further, in any liquid crystal cell, it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) that the liquid crystal was uniformly aligned.

<Example 1>
To the polyamic acid solution (1) (10.0 g) having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 1, S1 (8.17 g), K1 (0.18 g), NEP (3.92 g) ) And PB (19.6 g) were added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a composition (1). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (1) was used for evaluation also as a liquid-crystal aligning agent (1).

Using the obtained composition (1) and liquid crystal aligning agent (1), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

<Example 2>
S1 (16.8 g) and BCS (16.4 g) were added to the polyamic acid solution (2) (10.5 g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 2, and at 25 ° C. The mixture was stirred for 4 hours to obtain a composition (2). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (2) was used for evaluation also as a liquid-crystal aligning agent (2).

Using the obtained composition (2) and liquid crystal aligning agent (2), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

<Example 3>
S1 (13.8 g) was added to the polyimide powder (3) (1.60 g) obtained by the synthesis method of Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours. BCS (11.3 g) was added to this solution and stirred at 40 ° C. for 3 hours to obtain a composition (3). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (3) was used for evaluation also as a liquid-crystal aligning agent (3).

Using the obtained composition (3) and liquid crystal aligning agent (3), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

<Example 4>
S1 (14.1 g) and NEP (9.37 g) were added to the polyimide powder (4) (1.70 g) obtained by the synthesis method of Synthesis Example 4, and dissolved by stirring at 70 ° C. for 24 hours. BCS (9.37 g) and PB (14.1 g) were added to this solution, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (4). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (4) was used for evaluation as a liquid-crystal aligning agent (4).

Using the obtained composition (4) and liquid crystal aligning agent (4), "evaluation of printability of composition and liquid crystal aligning agent (pinhole evaluation)", "evaluation of voltage holding ratio (VHR)" (Normal cell) "and" Evaluation of ink-jet coating property of liquid crystal aligning agent ".

<Example 5>
S1 (14.0 g) and BCS (17.7 g) were added to a polyamic acid solution (5) (10.0 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 5, and the mixture was added at 25 ° C. The mixture was stirred for 4 hours to obtain a composition (5). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (5) was used for evaluation also as a liquid-crystal aligning agent (5).

Using the obtained composition (5) and liquid crystal aligning agent (5), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

<Example 6>
S1 (14.7 g) was added to the polyimide powder (6) (1.70 g) obtained by the synthesis method of Synthesis Example 6, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (12.0 g) was added and stirred at 40 ° C. for 3 hours to obtain a composition (6). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (6) was used for evaluation also as a liquid-crystal aligning agent (6).

Using the obtained composition (6) and liquid crystal aligning agent (6), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent "Evaluation of printability (evaluation of coating film edge)", "Evaluation of voltage holding ratio (VHR) (normal cell)", "Preparation of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell)" and "Liquid crystal cell Preparation and Evaluation of Liquid Crystal Orientation (SC-PVA Cell) ”were performed.

<Example 7>
S1 (9.10 g) and NEP (13.7 g) were added to the polyimide powder (6) (1.65 g) obtained by the synthesis method of Synthesis Example 6, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (22.8 g) was added and stirred at 40 ° C. for 3 hours to obtain a composition (7). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (7) was used for evaluation as a liquid-crystal aligning agent (7).

Using the obtained composition (7) and liquid crystal aligning agent (7), "evaluation of printability of composition and liquid crystal aligning agent (pinhole evaluation)" and "evaluation of voltage holding ratio (VHR)" (Normal cell) "and" Evaluation of ink-jet coating property of liquid crystal aligning agent ".

<Example 8>
S1 (6.27 g) and NEP (7.52 g) were added to the polyimide powder (7) (1.60 g) obtained by the synthesis method of Synthesis Example 7, and dissolved by stirring at 70 ° C. for 24 hours. BCS (2.51 g) and PB (8.77 g) were added to this solution, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (8). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (8) was used for evaluation also as a liquid-crystal aligning agent (8).

Using the obtained composition (8) and liquid crystal aligning agent (8), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

<Example 9>
S1 (7.52 g) and NMP (5.01 g) were added to the polyimide powder (8) (1.60 g) obtained by the synthesis method of Synthesis Example 8, and dissolved by stirring at 70 ° C. for 24 hours. PB (10.0 g) and DME (2.51 g) were added to this solution, and the mixture was stirred at 40 ° C. for 5 hours to obtain a composition (9). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (9) was used for evaluation also as a liquid-crystal aligning agent (9).

Using the obtained composition (9) and liquid crystal aligning agent (9), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent "Evaluation of printability (evaluation of coating film edge)", "Evaluation of voltage holding ratio (VHR) (normal cell)", "Preparation of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell)" and "Liquid crystal cell Preparation and Evaluation of Liquid Crystal Orientation (SC-PVA Cell) ”were performed.

<Example 10>
S1 (10.3 g) and NEP (7.76 g) were added to the polyimide powder (9) (1.65 g) obtained by the synthesis method of Synthesis Example 9, and the mixture was dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (6.46 g) and EC (1.29 g) were added, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (10). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (10) was used for evaluation also as a liquid-crystal aligning agent (10).

Using the obtained composition (10) and liquid crystal alignment treatment agent (10), "evaluation of printability of composition and liquid crystal alignment treatment agent (evaluation of pinhole)", "composition and liquid crystal alignment treatment agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

<Example 11>
S1 (3.76 g) and NEP (10.0 g) were added to the polyimide powder (10) (1.60 g) obtained by the synthesis method of Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours. BCS (11.3 g) was added to this solution, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (11). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (11) was used for evaluation also as a liquid-crystal aligning agent (11).

Using the composition (11) and the liquid crystal aligning agent (11) obtained, "Evaluation of printability of composition and liquid crystal aligning agent (pinhole evaluation)", "Composition and liquid crystal aligning agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

<Example 12>
S1 (5.33 g) and γ-BL (13.3 g) were added to the polyimide powder (11) (1.70 g) obtained by the synthesis method of Synthesis Example 11, and dissolved by stirring at 70 ° C. for 24 hours. It was. To this solution, BCS (7.9 g) was added and stirred at 40 ° C. for 3 hours to obtain a composition (12). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (12) was used for evaluation also as a liquid-crystal aligning agent (12).

Using the obtained composition (12) and liquid crystal aligning agent (12), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

<Example 13>
S1 (7.76 g) and NMP (5.17 g) were added to the polyimide powder (12) (1.65 g) obtained by the synthesis method of Synthesis Example 12, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (5.17 g) and PB (7.76 g) were added and stirred at 40 ° C. for 3 hours to obtain a composition (13). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (13) was used for evaluation also as a liquid-crystal aligning agent (13).

Using the obtained composition (13) and liquid crystal alignment treatment agent (13), "evaluation of printability of composition and liquid crystal alignment treatment agent (evaluation of pinhole)", "composition and liquid crystal alignment treatment agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

<Example 14>
S1 (5.01 g) and NEP (7.52 g) were added to the polyimide powder (13) (1.60 g) obtained by the synthesis method of Synthesis Example 13, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (12.5 g) was added and stirred at 40 ° C. for 3 hours to obtain a composition (14). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (14) was used for evaluation also as a liquid-crystal aligning agent (14).

Using the obtained composition (14) and liquid crystal aligning agent (14), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent "Evaluation of printability (evaluation of coating film edge)", "Evaluation of voltage holding ratio (VHR) (normal cell)", "Preparation of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell)" and "Liquid crystal cell Preparation and Evaluation of Liquid Crystal Orientation (SC-PVA Cell) ”were performed.

<Example 15>
S1 (4.69 g) and γ-BL (18.8 g) were added to the polyimide powder (13) (1.70 g) obtained by the synthesis method of Synthesis Example 13, and dissolved by stirring at 70 ° C. for 24 hours. It was. To this solution, BCS (9.37 g) and PB (14.1 g) were added and stirred at 40 ° C. for 3 hours to obtain a composition (15). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (15) was used for evaluation as a liquid-crystal aligning agent (15).

Using the obtained composition (15) and liquid crystal aligning agent (15), "evaluation of printability of composition and liquid crystal aligning agent (pinhole evaluation)", "evaluation of voltage holding ratio (VHR)" (Normal cell) "and" Evaluation of ink-jet coating property of liquid crystal aligning agent ".

<Example 16>
S1 (12.5 g) and NEP (2.51 g) were added to the polyimide powder (14) (1.60 g) obtained by the synthesis method of Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, K1 (0.08 g) and BCS (10.0 g) were added and stirred at 40 ° C. for 5 hours to obtain a composition (16). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (16) was used for evaluation also as a liquid-crystal aligning agent (16).

Using the obtained composition (16) and liquid crystal alignment treatment agent (16), "evaluation of printability of composition and liquid crystal alignment treatment agent (pinhole evaluation)", "composition and liquid crystal alignment treatment agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

<Example 17>
S1 (15.0 g) and γ-BL (2.51 g) were added to the polyimide powder (15) (1.60 g) obtained by the synthesis method of Synthesis Example 15, and dissolved by stirring at 70 ° C. for 24 hours. It was. To this solution, K1 (0.08 g), BCS (2.51 g) and PB (5.01 g) were added and stirred at 40 ° C. for 5 hours to obtain a composition (17). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (17) was used for evaluation also as a liquid-crystal aligning agent (17).

Using the obtained composition (17) and liquid crystal aligning agent (17), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

<Example 18>
S1 (2.66 g) and NEP (10.7 g) were added to the polyimide powder (16) (1.70 g) obtained by the synthesis method of Synthesis Example 16, and dissolved by stirring at 70 ° C. for 24 hours. To this solution were added BCS (5.33 g) and PB (7.99 g), and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (18). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (18) was used for evaluation also as a liquid-crystal aligning agent (18).

Using the obtained composition (18) and liquid crystal aligning agent (18), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

<Example 19>
S1 (8.77 g) and NMP (5.01 g) were added to the polyimide powder (17) (1.60 g) obtained by the synthesis method of Synthesis Example 17, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (8.77 g) and EC (2.51 g) were added, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (19). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (19) was used for evaluation also as a liquid-crystal aligning agent (19).

Using the obtained composition (19) and liquid crystal aligning agent (19), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

<Example 20>
S1 (10.0 g) and NEP (3.76 g) were added to the polyimide powder (18) (1.60 g) obtained by the synthesis method of Synthesis Example 18, and dissolved by stirring at 70 ° C. for 24 hours. BCS (3.76 g) and PB (7.52 g) were added to this solution, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (20). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (20) was used for evaluation also as a liquid-crystal aligning agent (20).

Using the obtained composition (20) and liquid crystal aligning agent (20), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

<Comparative Example 1>
NMP (16.0 g) and BCS (15.7 g) were added to a polyamic acid solution (19) (10.0 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 19, and the mixture was added at 25 ° C. The mixture was stirred for 4 hours to obtain a composition (21). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (21) was used for evaluation also as a liquid-crystal aligning agent (21).

Using the obtained composition (21) and liquid crystal aligning agent (21), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

<Comparative example 2>
NMP (14.7 g) was added to the polyimide powder (3) (1.70 g) obtained by the synthesis method of Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (12.0 g) was added and stirred at 40 ° C. for 3 hours to obtain a composition (22). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (22) was used for evaluation also as a liquid-crystal aligning agent (22).

Using the obtained composition (22) and liquid crystal aligning agent (22), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

<Comparative Example 3>
NMP (14.7 g) and BCS (18.5 g) were added to a polyamic acid solution (20) (10.5 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 20, and the mixture was added at 25 ° C. The mixture was stirred for 4 hours to obtain a composition (23). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (23) was used for evaluation also as a liquid-crystal aligning agent (23).

Using the obtained composition (23) and liquid crystal aligning agent (23), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

<Comparative example 4>
NMP (14.2 g) was added to the polyimide powder (6) (1.65 g) obtained by the synthesis method of Synthesis Example 6 and dissolved by stirring at 70 ° C. for 24 hours. BCS (11.6g) was added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (24). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (24) was used for evaluation also as a liquid-crystal aligning agent (24).

Using the obtained composition (24) and liquid crystal aligning agent (24), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.

As can be seen from the above results, the polyimide film obtained from the composition of the example of the present invention has a uniform coating property that does not generate pinholes compared to the polyimide film obtained from the composition of the comparative example. Furthermore, the linearity of the end portion of the polyimide film was high, and the rise of the end portion was small. Specifically, a comparison between the composition using the specific solvent which is the component (A) of the present invention and a composition not using it, that is, comparison between Example 2 and Comparative Example 1, Example 3 The comparison between Example 6 and Comparative Example 2, the comparison between Example 5 and Comparative Example 3, and the comparison between Example 6 and Comparative Example 4. In these comparative examples, the number of pinholes on the polyimide film was large as compared with the corresponding examples, and furthermore, the coating property at the coating film end portion of the polyimide film was also poor. Moreover, since the composition of these Examples was used also for evaluation as a liquid-crystal aligning agent, the result of the Example using these compositions was also made into the result of a liquid-crystal aligning agent.

Moreover, the liquid crystal aligning film obtained from the liquid crystal aligning agent using the composition of the present invention is fired when producing a liquid crystal aligning film as compared with the liquid crystal aligning film obtained from the liquid crystal aligning agent of the comparative example. Even when the temperature was low, a result of excellent voltage holding ratio (also referred to as VHR) in the liquid crystal display element was obtained. Specifically, a comparison between a liquid crystal aligning agent using a specific solvent which is the component (A) of the present invention and a liquid crystal aligning agent not using the same, that is, a comparison between Example 2 and Comparative Example 1. The comparison between Example 3 and Comparative Example 2, the comparison between Example 5 and Comparative Example 3, and the comparison between Example 6 and Comparative Example 4. In these comparative examples, the value of VHR was lower than in the corresponding examples. In particular, not only the value immediately after the production of the liquid crystal cell but also the value after storage in the high-temperature bath was low, that is, the VHR was greatly reduced with high temperature.

The composition of the present invention can suppress the generation of pinholes accompanying repelling when forming a polyimide film, and can provide a polyimide film having excellent coating properties at the edges. At that time, a polyimide film can be produced even by baking at a low temperature.

In addition, when the composition of the present invention is used for a liquid crystal alignment treatment agent, the generation of pinholes accompanying repelling can be suppressed, and a liquid crystal alignment film having excellent coating properties at the end can be obtained. Furthermore, even when the firing for producing the liquid crystal alignment film is performed at a low temperature, the liquid crystal alignment film has excellent electrical characteristics, particularly voltage holding ratio (also referred to as VHR). Therefore, the liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and is used for a large-screen high-definition liquid crystal television, a small-sized car navigation system, a smartphone, and the like. It can be suitably used, and is useful for a TN element, STN element, TFT liquid crystal element, particularly a vertical alignment type liquid crystal display element such as VA mode, PSA mode and SC-PVA mode.

Claims

Component (A): Formula [A] below:

(Wherein, X 1 and X 2 each independently represent an alkyl group having 1 to 3 carbon atoms, and X 3 and X 4 each independently represent an alkyl group having 1 to 3 carbon atoms) And (B) component: a composition containing at least one polymer selected from polyimide precursors and polyimides.
The solvent of the component (A) is represented by the following formula [A-1]:

The composition of Claim 1 which is a solvent shown by these.
The component (B) is represented by the following formula [1-1] and formula [1-2]:

Wherein Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —CONH—, —NHCO—, —CON At least one linking group selected from (CH 3 ) —, —N (CH 3 ) CO—, —COO— and —OCO—, wherein Y 2 represents a single bond or — (CH 2 ) b — (b Is an integer of 1 to 15, and Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO Y represents at least one linking group selected from — and —OCO—, and Y 4 represents a carbon having a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a steroid skeleton A divalent organic group of formula 17 to 51, wherein any hydrogen atom on the cyclic group is a carbon atom Alkyl group having 1 to 3, an alkoxyl group having 1 to 3 carbon atoms, fluorine-containing alkyl group having 1 to 3 carbon atoms may be substituted with a fluorine-containing alkoxyl group or a fluorine atom having 1 to 3 carbon atoms, Y 5 represents a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, and n represents an integer of 0 to 4 Y 6 represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, an alkoxyl group having 1 to 22 carbon atoms, and fluorine having 1 to 22 carbon atoms. Contains At least one selected from alkoxyl groups);

Wherein Y 7 is a single bond, —O—, —CH 2 O—, —CONH—, —NHCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, —COO— and At least one linking group selected from —OCO—, and Y 8 represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms)
The at least 1 type polymer selected from the polyimide precursor and polyimide which used the diamine compound which has at least 1 type of structure chosen from the structure shown by a part of raw material as described in any one of Claim 1 or Claim 2 Composition.
The diamine compound having the structure represented by the formula [1-1] and the formula [1-2] is represented by the following formula [1a]:

(Wherein Y represents at least one structure selected from the structures represented by the formulas [1-1] and [1-2], and m represents an integer of 1 to 4).
The composition of Claim 3 which is a diamine compound shown by these.
From the polyimide precursor and the polyimide in which the polymer of the component (B) is a diamine compound having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group) as a part of the raw material The composition according to any one of claims 1 to 4, which is at least one polymer selected.
The diamine compound having a carboxyl group and a hydroxyl group is represented by the following formula [2a]:

{In the formula, A represents the following formula [2-1] and formula [2-2]:

(In the formula [2-1], a represents an integer of 0 to 4, and in the formula [2-2], b represents an integer of 0 to 4). M represents an integer of 1 to 4}
The composition of Claim 5 which is a diamine compound shown by these.
The polymer of the component (B) is represented by the following formula [3a]:

Wherein B 1 is —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCO—, —CON (CH 3 ) — and Represents at least one linking group selected from —N (CH 3 ) CO—, wherein B 2 is a single bond, a divalent group of an aliphatic hydrocarbon having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon; And B 3 is a single bond, —O—, —NH—, —N (CH 3 ) —, —CONH—. , —NHCO—, —COO—, —OCO—, —CON (CH 3 ) —, —N (CH 3 ) CO— and —O (CH 2 ) m — (m is an integer of 1 to 5) At least one linking group selected, B 4 represents a nitrogen-containing heterocyclic group, and n represents an integer of 1 to 4)
The composition according to any one of claims 1 to 6, which is at least one polymer selected from a polyimide precursor and a polyimide obtained by using a diamine compound represented by the formula:
In the formula [3a], B 1 represents —CONH—, B 2 represents an alkylene group having 1 to 5 carbon atoms, B 3 represents a single bond, B 4 represents an imidazolyl group or a pyridyl group, n The composition according to claim 7, wherein is a diamine compound exhibiting 1.
The polymer of the component (B) is represented by the following formula [4]:

{In the formula, Z represents the following formula [4a] to formula [4k]:

(In formula [4a], Z 1 to Z 4 each independently represent a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, and in formula [4g], Z 5 and Z 6 are each independently Represents a hydrogen atom or a methyl group)
Represents a group of at least one structure selected from
The composition according to any one of claims 1 to 8, which is at least one polymer selected from polyimide precursors and polyimides using a tetracarboxylic acid component represented by formula (1) as part of a raw material.
The composition according to any one of claims 1 to 9, wherein the polymer of the component (B) is at least one polymer selected from polyamic acid alkyl ester and polyimide.
The component (C) contains at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone, according to any one of claims 1 to 10. The composition as described.
As component (D), 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether and the following formula [D-1] Formula [D-3]:

(In the formula [D-1], D 1 represents an alkyl group having 1 to 3 carbon atoms. In the formula [D-2], D 2 represents an alkyl group having 1 to 3 carbon atoms. -3], D 3 represents an alkyl group having 1 to 4 carbon atoms)
The composition according to any one of claims 1 to 11, comprising at least one solvent selected from the solvents represented by:
Crosslinkability having at least one substituent selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group in the composition The composition according to any one of claims 1 to 12, comprising a compound and at least one crosslinkable compound selected from crosslinkable compounds having a polymerizable unsaturated bond.
The composition according to any one of claims 1 to 13, wherein the component (A) is 5 to 70 mass% of the entire solvent contained in the composition.
The composition according to any one of claims 11 to 14, wherein the component (C) is 40 to 80% by mass of the total solvent contained in the composition.
The composition according to any one of claims 12 to 15, wherein the component (D) is 1 to 50% by mass of the whole solvent contained in the composition.
The composition according to any one of claims 1 to 16, wherein the component (B) is 0.1% by mass to 30% by mass in the composition.
A polyimide film obtained from the composition according to any one of claims 1 to 17.
A liquid crystal aligning agent obtained from the composition according to any one of claims 1 to 17.
A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to claim 19.
A liquid crystal alignment film obtained by an ink jet method using the liquid crystal aligning agent according to claim 19.
A liquid crystal display element comprising the liquid crystal alignment film according to claim 20 or claim 21.
A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and comprising a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and the electrodes The liquid crystal alignment film according to claim 20 or 21, wherein the liquid crystal alignment film is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable compound while applying a voltage therebetween.
24. A liquid crystal display element comprising the liquid crystal alignment film according to claim 23.
A liquid crystal layer comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates; The liquid crystal alignment film according to claim 20 or 21, wherein the liquid crystal alignment film is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable group while applying a voltage therebetween.
A liquid crystal display element comprising the liquid crystal alignment film according to claim 25.