JP6668754B2 - Composition, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device - Google Patents

Description

  The present invention relates to a composition used for forming a polyimide film, a liquid crystal alignment agent used in manufacturing a liquid crystal display device, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display device using the liquid crystal alignment film. Things.

  A film made of an organic material such as a polymer material attracts attention for its ease of formation and insulating performance, and is widely used as an interlayer insulating film and a protective film in electronic devices. Above all, 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 elements have been widely used 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 used has become larger than before, and furthermore, the unevenness of the substrate step has become larger. Even in such a situation, it has been demanded that a liquid crystal alignment film be 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-based polymer (also referred to as resin) such as polyamic acid or solvent-soluble polyimide (also referred to as polyimide) is industrially applied. It is common to use a flexographic printing method or an inkjet coating method. At that time, the solvent of the liquid crystal alignment treatment agent includes 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). In addition to the above, ethylene glycol monobutyl ether or the like, which is a solvent having low resin solubility (also referred to as a poor solvent), is mixed in order to enhance the coatability of the liquid crystal alignment film (for example, see Patent Document 1).

JP-A-2-37324

  BACKGROUND ART A polyimide-based organic film (also referred to as a polyimide film) is widely used as an interlayer insulating film, a protective film, and the like in electronic devices, in addition to a liquid crystal alignment film. 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 solution of polyamic acid or polyimide as a polyimide precursor. Also, in other electronic devices, it is required to enhance the coating property of the polyimide film. That is, the improvement of the coating property of the polyimide film is effective for suppressing defects generated during the coating.

  In addition, a liquid crystal alignment treatment agent using a polyamic acid or a polyimide obtained using a diamine compound having a side chain has a tendency that the coating property of the liquid crystal alignment film is reduced due to high hydrophobicity of a side chain portion. . In particular, when uniform coating properties cannot be obtained, that is, when pinholes occur due to repelling, when the liquid crystal display element is used, the 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 and spreadability of the coating solution onto the substrate. However, poor solvents have poor ability to dissolve polyamic acids and polyimides, and therefore, when mixed in large amounts, there is a problem that resin precipitation occurs.

  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, to bond the substrates between the liquid crystal display elements. Is present at a position close to the edge of the liquid crystal alignment film. Therefore, when the coating property of the edge of the liquid crystal alignment film is reduced, that is, when the edge of the liquid crystal alignment film is not linear, or when the edge is raised, the liquid crystal alignment film and the sealant The adhesion (also referred to as adhesion) effect is reduced, and the display characteristics and reliability of the liquid crystal display element are reduced.

  Further, in the case of a composition using a polyimide or a liquid crystal alignment treatment agent, since the boiling point of NMP or γ-BL, which is a solvent used for them, is high, a polyimide film and a liquid crystal alignment film such as an interlayer insulating film and a protective film are formed. In this case, firing at a high temperature is required. Therefore, from the viewpoint of reducing energy costs, firing 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 which can suppress the occurrence of pinholes due to repelling when forming a polyimide film, and which is excellent in coating properties at the end. In that case, it is also an object to obtain a composition capable of forming a polyimide film even when firing at a low temperature.

  Further, in the liquid crystal alignment treating 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 repelling, and furthermore, to the coating properties of the end portion It is to provide an excellent liquid crystal alignment treatment agent. In particular, it is an object of the present invention to provide a liquid crystal alignment treatment agent having excellent properties even with a liquid crystal alignment treatment agent using a polyamic acid or a polyimide obtained by using a diamine compound having a side chain. It is still another object of the present invention to provide a liquid crystal alignment treatment agent which is excellent in electric characteristics of a liquid crystal display element, particularly, voltage holding ratio (also referred to as VHR) 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 agent, and a liquid crystal display device having the liquid crystal alignment film.

  The present inventor has conducted intensive studies and found that a composition containing a solvent having a specific structure and at least one polymer selected from polyimide precursors or polyimides is extremely effective for achieving the above object. The inventors have found that the present invention has been completed.

  That is, the present invention has the following gist.

（式中、Ｘ^１およびＸ^２は、それぞれ独立して、炭素数１〜３のアルキル基を示し、Ｘ^３およびＸ^４は、それぞれ独立して、炭素数１〜３のアルキル基を示す）で示される溶媒；および
（Ｂ）成分：ポリイミド前駆体およびポリイミドから選ばれる少なくとも１種の重合体
を含有する組成物。(1) Component (A): The following formula [A]:

(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 a component (B): a composition containing at least one polymer selected from a polyimide precursor and a polyimide.

で示される溶媒である、上記（１）に記載の組成物。(2) The solvent of the component (A) is represented by the following formula [A-1]:

The composition according to the above (1), which is a solvent represented by the formula:

（式中、Ｙ^１は、単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＣＯＯ−および−ＯＣＯ−から選ばれる少なくとも１種の結合基を示し、Ｙ^２は、単結合または−（ＣＨ_２）_ｂ−（ｂは１〜１５の整数である）を示し、Ｙ^３は、単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−および−ＯＣＯ−から選ばれる少なくとも１種の結合基を示し、Ｙ^４は、ベンゼン環、シクロヘキサン環および複素環から選ばれる少なくとも１種の環の２価の環状基、またはステロイド骨格を有する炭素数１７〜５１の２価の有機基を示し、前記環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基またはフッ素原子で置換されていてもよく、Ｙ^５は、ベンゼン環、シクロヘキサン環および複素環から選ばれる少なくとも１種の環の２価の環状基を示し、これらの環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基またはフッ素原子で置換されていてもよく、ｎは、０〜４の整数を示し、Ｙ^６は、炭素数１〜２２のアルキル基、炭素数２〜２２のアルケニル基、炭素数１〜２２のフッ素含有アルキル基、炭素数１〜２２のアルコキシル基および炭素数１〜２２のフッ素含有アルコキシル基から選ばれる少なくとも１種を示す）；

（式中、Ｙ^７は、単結合、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＣＯＯ−および−ＯＣＯ−から選ばれる少なくとも１種の結合基を示し、Ｙ^８は、炭素数８〜２２のアルキル基または炭素数６〜１８のフッ素含有アルキル基を示す）
で示される構造から選ばれる少なくとも１種の構造を有するジアミン化合物を原料の一部に用いたポリイミド前駆体およびポリイミドから選ばれる少なくとも１種の重合体である、上記（１）または上記（２）に記載の組成物。(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. _{(CH 3) -, - N} (CH 3) CO -, - COO- and -OCO- represents at least one bond group selected from, ^{Y 2} is a single bond or _{- (CH 2) b - (} b Represents an integer of 1 to 15), and Y ³ represents a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO. - represents at least one bond group selected from and -OCO-, Y ⁴ is a benzene ring, a carbon having at least one divalent cyclic group ring or steroid skeleton, chosen from the cyclohexane ring and heterocyclic ring A bivalent organic group represented by the formulas 17 to 51, wherein any hydrogen atom on the cyclic group is Number 1-3 alkyl group, an alkoxyl group having 1 to 3 carbon atoms, a 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 any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, 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. Contained 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 Represents at least one kind of a binding 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), which is at least one polymer selected from a polyimide precursor and a polyimide using a diamine compound having at least one structure selected from the following structures as a part of the raw material: A composition according to claim 1.

（式中、Ｙは、前記式［１−１］および式［１−２］で示される構造から選ばれる少なくとも１種の構造を示し、ｍは、１〜４の整数を示す）
で示されるジアミン化合物である、上記（３）に記載の組成物。(4) A diamine compound having a structure represented by the formulas [1-1] and [1-2] is represented by the following formula [1a]:

(Wherein, Y represents at least one kind of 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 according to the above (3), which is a diamine compound represented by the formula:

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

｛式中、Ａは、下記の式［２−１］および式［２−２］：

（式［２−１］中、ａは、０〜４の整数を示し、式［２−２］中、ｂは、０〜４の整数を示す）から選ばれる少なくとも１つの構造の置換基を示し、ｍは、１〜４の整数を示す｝
で示されるジアミン化合物である、上記（５）に記載の組成物。(6) The diamine compound having a carboxyl group and a hydroxyl group is represented by the following formula [2a]:

Ａ In the formula, A is 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.) And m represents an integer of 1 to 4
The composition according to the above (5), which is a diamine compound represented by the formula:

（式中、Ｂ^１は、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−および−Ｎ（ＣＨ_３）ＣＯ−から選ばれる少なくとも１種の結合基を示し、Ｂ^２は、単結合、炭素数１〜２０の脂肪族炭化水素の２価の基、非芳香族環式炭化水素の２価の基および芳香族炭化水素の２価の基から選ばれる少なくとも１種を示し、Ｂ^３は、単結合、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−および−Ｏ（ＣＨ_２）_ｍ−（ｍは１〜５の整数である）から選ばれる少なくとも１種の結合基を示し、Ｂ^４は、窒素含有複素環基を示し、ｎは、１〜４の整数を示す）で示されるジアミン化合物を原料の一部に用いたポリイミド前駆体およびポリイミドから選ばれる少なくとも１種の重合体である、上記（１）〜上記（６）のいずれかに記載の組成物。(7) The polymer of the component (B) is represented by the following formula [3a]:

(In the formula, B ¹ represents —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ) — and —N (CH ₃ ) CO— represents at least one kind of a bonding group, and B ² represents a single bond, a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a non-aromatic cyclic hydrocarbon. of represents at least one selected from divalent groups of the divalent group and an aromatic hydrocarbon, ^{B 3} represents a single _{bond, -O -, - NH -,} - N (CH 3) -, - CONH- , -NHCO -, - COO -, - OCO -, - CON (CH 3) -, - from (m is an integer of 1 to 5) - _{N (CH} 3) CO- and -O _{(CH 2)} m And B ⁴ represents a nitrogen-containing heterocyclic group, and n represents an integer of 1 to 4. The composition according to any one of the above (1) to (6), which is at least one polymer selected from a polyimide precursor and a polyimide using a diamine compound as a part of a raw material.

(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 the above (7), which is a diamine compound wherein n is 1.

｛式中、Ｚは、下記の式［４ａ］〜式［４ｋ］：

（式［４ａ］中、Ｚ^１〜Ｚ^４は、それぞれ独立して、水素原子、メチル基、塩素原子またはフェニル基を示し、式［４ｇ］中、Ｚ^５およびＺ^６は、それぞれ独立して、水素原子またはメチル基を示す）から選ばれる少なくとも１種の構造の基を示す｝
で示されるテトラカルボン酸化合物を原料の一部に用いたポリイミド前駆体およびポリイミドから選ばれる少なくとも１種の重合体である、上記（１）〜上記（８）のいずれかに記載の組成物。(9) The polymer of the component (B) is represented by the following formula [4]:

ＺIn the formula, Z is 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 each independently represent , A hydrogen atom or a methyl group).
The composition according to any one of the above (1) to (8), wherein the composition is at least one polymer selected from a polyimide precursor and a polyimide obtained by using a tetracarboxylic acid compound represented by the following formula as a part of the raw material.

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

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

（式［Ｄ−１］中、Ｄ^１は、炭素数１〜３のアルキル基を示し、式［Ｄ−２］中、Ｄ^２は、炭素数１〜３のアルキル基を示し、式［Ｄ−３］中、Ｄ^３は、炭素数１〜４のアルキル基を示す）
で示される溶媒から選ばれる少なくとも１種の溶媒を含有する、上記（１）〜上記（１１）のいずれかに記載の組成物。(12) As the 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 the above (1) to (11), comprising at least one solvent selected from the solvents represented by the following formula (1).

(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 a crosslinkable compound having at least one crosslinkable compound selected from a crosslinkable compound having a polymerizable unsaturated bond.

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

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

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

(17) The composition according to any one of the above (1) to (16), 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).

(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 inkjet 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 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 the above (20) or (21), which is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.

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

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

(26) A liquid crystal display device 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, when forming a polyimide film, can suppress the occurrence of pinholes due to repelling. Thus, a polyimide film having excellent coating properties at the end can be produced. At that time, a polyimide film can be produced even by firing at a low temperature.

  Further, in the liquid crystal alignment treating 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 repelling, and furthermore, to the coating properties of the end portion It is to provide an excellent liquid crystal alignment treatment agent. In particular, it is an object of the present invention to provide a liquid crystal alignment treatment agent having excellent properties even with a liquid crystal alignment treatment agent using a polyamic acid or a polyimide obtained by using a diamine compound having a side chain. It is still another object of the present invention to provide a liquid crystal alignment treatment agent which is excellent in electric characteristics of a liquid crystal display element, particularly, voltage holding ratio (VHR) 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 repelling, and to provide a liquid crystal alignment film having excellent coating properties at its edges. Can be. In particular, even with a liquid crystal alignment treatment agent using a polyamic acid or a polyimide obtained by using a diamine compound having a side chain, a liquid crystal alignment film excellent in these characteristics can be provided. Further, even if the firing at the time of manufacturing the liquid crystal alignment film is at a low temperature, a liquid crystal alignment film having excellent electric characteristics, particularly, voltage holding ratio (VHR) in a liquid crystal display element can be provided. Therefore, a liquid crystal display device having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and is used in a large-screen high-definition liquid crystal television, a small and medium-sized car navigation system, a smartphone, and the like. It can be suitably used.

FIG. 3 is a diagram illustrating the linearity of an end portion of a polyimide film applied to a glass substrate. FIG. 3 is a diagram showing a bulge at an end of a polyimide film applied to a glass substrate.

  Hereinafter, the present invention will be described in detail.

（式［Ａ］中、Ｘ^１およびＸ^２は、それぞれ独立して、炭素数１〜３のアルキル基を示し、Ｘ^３およびＸ^４は、それぞれ独立して、炭素数１〜３のアルキル基を示す）。The present invention provides a composition containing the following components (A) and (B), a liquid crystal alignment agent, a liquid crystal alignment film obtained by using the liquid crystal alignment 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 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. Is shown).

  Component (B): at least one polymer selected from a polyimide precursor and a 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-based polymer such as a polyimide precursor and a polyimide (also referred to as a good solvent), and further has a coating property of a polyimide film and a liquid crystal alignment film. It also has the effect of increasing That is, since the specific solvent of the present invention generally has a lower surface tension as a solvent than NMP used as a good solvent, a coating solution using the specific solvent is compared with a coating solution not using it. As a result, the spreading property of the coating solution on the substrate is improved. Thereby, the linearity of the edges of the polyimide film and the liquid crystal alignment film at the ends thereof becomes high. Furthermore, since the wet-spreading property of the coating solution on the substrate is increased, the occurrence of pinholes due to repelling can be suppressed.

  Furthermore, the specific solvent of the present invention has a lower boiling point than NMP and γ-BL which are usually used as good solvents. Therefore, baking at the time of producing the polyimide film and the 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 baking at the time of manufacturing the liquid crystal alignment film is at a low temperature.

（式［１−１］中、Ｙ^１は、単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＣＯＯ−および−ＯＣＯ−から選ばれる少なくとも１種の結合基を示し、Ｙ^２は、単結合または−（ＣＨ_２）_ｂ−（ｂは１〜１５の整数である）を示し、Ｙ^３は、単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−および−ＯＣＯ−から選ばれる少なくとも１種の結合基を示し、Ｙ^４は、ベンゼン環、シクロヘキサン環および複素環から選ばれる少なくとも１種の環の２価の環状基、またはステロイド骨格を有する炭素数１７〜５１の２価の有機基を示し、前記環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基またはフッ素原子で置換されていてもよく、Ｙ^５は、ベンゼン環、シクロヘキサン環および複素環から選ばれる少なくとも１種の環の２価の環状基を示し、これらの環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基またはフッ素原子で置換されていてもよく、ｎは、０〜４の整数を示し、Ｙ^６は、炭素数１〜２２のアルキル基、炭素数２〜２２のアルケニル基、炭素数１〜２２のフッ素含有アルキル基、炭素数１〜２２のアルコキシル基および炭素数１〜２２のフッ素含有アルコキシル基から選ばれる少なくとも１種を示す）。

（式［１−２］中、Ｙ^７は、単結合、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＣＯＯ−および−ＯＣＯ−から選ばれる少なくとも１種の結合基を示し、Ｙ^８は、炭素数８〜２２のアルキル基または炭素数６〜１８のフッ素含有アルキル基を示す）。In addition, the component (B) of the present invention is at least one polymer selected from a polyimide precursor or a polyimide. Among them, when a liquid crystal alignment film is produced using the composition of the present invention as a liquid crystal alignment treatment agent, at least one selected from the 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 a polyimide precursor or polyimide 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-,- _{NHCO -, - CON (CH 3} ) -, - N (CH 3) CO -, - COO- and -OCO- represents at least one bond group selected from, ^{Y 2} is a single bond or - (CH ₂ ) _b - indicates (b is an integer of 1 to 15), ^{Y 3} represents a single _{bond, - (CH 2) c -} (c is an integer of 1~15), - O -, - CH 2 O -, - COO- and -OCO- represents at least one bond group selected from, Y ⁴ is at least one divalent cyclic group ring selected from a benzene ring, cyclohexane ring and heterocyclic ring or, A divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms, and any hydrogen on the cyclic group Is substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, an 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 any hydrogen atom on these cyclic groups has 1 to 3 carbon atoms. 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 of At least one selected from a fluorine-containing alkoxyl group).

(In the formula [1-2], Y ⁷ is a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO- , -COO- and -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).

  Above all, the specific side chain structure represented by the formula [1-1] is a bivalent cyclic group having a benzene ring, a cyclohexyl ring or a heterocyclic ring in the side chain portion, or a C 2 -C 2 having a steroid skeleton. It has a valent organic group. Such a divalent cyclic group of a benzene ring, a cyclohexyl ring or a heterocyclic ring, or a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms has a rigid structure. Thereby, the stability of the side chain portion against heat is improved, the decomposition of the side chain portion due to baking when producing the liquid crystal alignment film is suppressed, and a liquid crystal alignment film excellent in VHR can be obtained.

  In view of the above, the composition containing the specific solvent of the present invention and at least one polymer selected from a polyimide precursor or a polyimide has excellent coatability, and can form a polyimide film even when fired at a low temperature. A composition that can be used.

  Further, the liquid crystal alignment treating agent obtained from the composition of the present invention can obtain a liquid crystal alignment film having excellent coating properties. Further, even if the firing at the time of manufacturing the liquid crystal alignment film is at a low temperature, a liquid crystal alignment film having excellent VHR in a liquid crystal display element can be obtained. Therefore, by using this liquid crystal alignment film, a highly reliable liquid crystal display element having excellent display characteristics can be provided.

  In addition, a liquid crystal alignment treatment obtained from a composition containing the specific solvent of the present invention and at least one polymer selected from a polyimide precursor or a polyimide having the specific side chain structure represented by the formula [1-1]. The agent can provide a liquid crystal alignment film excellent in VHR in a liquid crystal display element even if the above-mentioned effect, that is, the firing at the time of producing 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 an ethyl group. And 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. And 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 entire solvent contained in the composition and the liquid crystal alignment treatment agent, in order to further enhance the spreadability of the coating solution onto the substrate described above. Especially, 5 to 75 mass% is preferable. More preferably, it is 5 to 70% by mass, and still more preferably 10 to 60% by mass.

  Among the entire solvent in the composition and the liquid crystal alignment treatment agent, the greater the amount of the specific solvent of the present invention, the higher the effect of the present invention, that is, the higher the wet-spreading property 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 as 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-based polymer). Among them, the polyimide polymer of the present invention is preferably a polyimide precursor or a polyimide obtained by reacting a diamine component with a tetracarboxylic acid component.

（式［ａ］中、Ｒ^１は、４価の有機基であり、Ｒ^２は、２価の有機基であり、Ａ^１およびＡ^２は、それぞれ独立して、水素原子または炭素数１〜５のアルキル基を示し、Ａ^３およびＡ^４は、それぞれ独立して、水素原子、炭素数１〜５のアルキル基またはアセチル基を示し、ｎは正の整数を示す）。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 group having 1 to 1 carbon atoms. 5 represents an alkyl group, A ³ and A ⁴ each independently represent 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 a diamine compound having two primary or secondary amino groups in the molecule.

  Examples of the tetracarboxylic acid component include tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic dihalide compounds, tetracarboxylic dialkyl ester compounds and tetracarboxylic dialkyl ester dihalide compounds.

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 a tetracarboxylic acid compound 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 the formula [a] are alkyl groups having 1 to 5 carbon atoms, the diamine compound, a tetracarboxylic dihalide compound, a tetracarboxylic dialkyl ester compound or It can be obtained by reacting a tetracarboxylic 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 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 the polyimide precursor and the polyimide.

In the formula [1-1], Y ¹ is a bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —CONH—, and —NHCO—. _{, -CON (CH 3) -,} - N (CH 3) CO -, - COO- represents at least one linking group selected from and -OCO-. From the standpoint of ease of the availability of raw materials and synthetic, single _{bond, - (CH 2) a -} (a is an integer of 1~15), - 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 the formula [1-1], Y ² represents a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15). Among them, a single bond or _{- (CH 2) b - (} b is an integer of 1 to 10) are preferred.

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. -Represents at least one kind of bonding group selected from-. Among them, for ease of synthesis, a single _{bond, - (CH 2) c -} (c is an integer of 1~15), - O -, - CH 2 O- or -COO- are preferred. More preferred is a single _{bond, - (CH 2) c -} (c is an integer of 1 to _{10), - O -, - CH} 2 O- or -COO-.

In 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 any hydrogen atom on these cyclic groups is a carbon atom. 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. Further, Y ⁴ may be a divalent organic group selected from organic groups having a steroid skeleton and having 17 to 51 carbon atoms. Among them, a divalent cyclic group of a benzene ring or a cyclohexane ring or a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms is preferable from the viewpoint of ease of synthesis.

In the 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 a carbon atom. 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. Among them, a benzene ring or a cyclohexane ring is preferred.

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

In the formula [1-1], Y ⁶ is 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 It shows at least one selected from fluorine-containing alkoxyl groups having 1 to 22 carbon atoms. 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 described in Tables 6 to 47 on pages 13 to 34 of WO 2011/132751 (published on 2011.10.27). (2-1) to (2-629). In addition, 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 should be read as Y ^{1 to} Y ⁶ . In addition, in (2-605) to (2-629) described in each table of International Publication, the organic group having 17 to 51 carbon atoms having a steroid skeleton in the present invention is a compound having 12 to 12 carbon atoms having a steroid skeleton. Although shown as an organic group having 25, an organic group having a steroid skeleton and having 12 to 25 carbon atoms is to be read as an organic group having a steroid skeleton and having 17 to 51 carbon atoms.

In the formula [1-2], Y ⁷ is a single bond, —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, It represents at least one type of bonding group selected from COO- and -OCO-. Among them, a single _{bond, -O -, - CH 2 O} -, - CONH -, - CON (CH 3) - or -COO- are preferred. More preferably, it is 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. Among them, 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 high and stable vertical alignment of liquid crystal can be obtained.

  The method for introducing the specific side chain structure into the specific polymer of the present invention is not particularly limited, but it is preferable to use a diamine compound having the specific side chain structure as the diamine component.

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

In the formula [1a], Y represents at least one kind of structure selected from the structures represented by the formulas [1-1] and [1-2]. In addition, when Y in Formula [1a] represents Formula [1-1], preferred combinations of Y ¹ to Y ⁶ and n are as described above.

（式［１ａ−１］〜式［１ａ−３］中、Ｒ^１、Ｒ^３およびＲ^５は、それぞれ独立して、−Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−または−ＣＨ_２ＯＣＯ−を示し、式［１ａ−１］〜式［１ａ−３］中、Ｒ^２、Ｒ^４およびＲ^６は、それぞれ独立して、炭素数１〜２２の直鎖状または分岐状アルキル基、炭素数１〜２２の直鎖状または分岐状アルコキシル基、炭素数１〜２２の直鎖状または分岐状フッ素含有アルキル基または炭素数１〜２２のフッ素含有アルコキシル基を示す）。

（式［１ａ−４］〜式［１ａ−６］中、Ｒ^１、Ｒ^３およびＲ^５は、それぞれ独立して、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−または−ＣＨ_２−を示し、式［１ａ−４］〜式［１ａ−６］中、Ｒ^２、Ｒ^４およびＲ^６は、それぞれ独立して、炭素数１〜２２の直鎖状または分岐状アルキル基、炭素数１〜２２の直鎖状または分岐状アルコキシル基、炭素数１〜２２の直鎖状または分岐状フッ素含有アルキル基または炭素数１〜２２のフッ素含有アルコキシル基を示す）。

（式［１ａ−７］および式［１ａ−８］中、Ｒ^１およびＲ^３は、それぞれ独立して、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ_２−、−Ｏ−または−ＮＨ−を示し、Ｒ^２およびＲ^４はそれぞれ独立して、フッ素基、シアノ基、トリフルオロメチル基、ニトロ基、アゾ基、ホルミル基、アセチル基、アセトキシ基または水酸基を示す）。

（式［１ａ−９］および式［１ａ−１０］中、Ｒ^１およびＲ^２は、それぞれ独立して、炭素数３〜１２の直鎖状または分岐状アルキル基を示し、１，４-シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体である）。

（式［１ａ−１１］および式［１ａ−１２］中、Ｒ^１およびＲ^２は、それぞれ独立して、炭素数３〜１２の直鎖状または分岐状アルキル基を示し、１，４-シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体である）。

（式［１ａ−１３］中、Ａ_４はフッ素原子で置換されていてもよい炭素数３〜２０の直鎖状または分岐状アルキル基であり、Ａ_３は１，４−シクロへキシレン基または１，４−フェニレン基であり、Ａ_２は酸素原子または−ＣＯＯ−＊（ただし、「＊」を付した結合手がＡ_３と結合する）であり、Ａ_１は酸素原子または−ＣＯＯ−＊（ただし、「＊」を付した結合手が（ＣＨ_２）ａ_２）と結合する）である。また、ａ_１は０または１の整数であり、ａ_２は２〜１０の整数であり、ａ_３は０または１の整数である）。

（式［１ａ−３２］〜式［１ａ−３５］中、Ａ^１〜Ａ^４はそれぞれ独立して、炭素数１〜２２のアルキル基またはフッ素含有アルキル基を示す）。In the formula [1a], m represents an integer of 1 to 4. Especially, 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 further, these amino groups are secondary amino groups. Certain diamine compounds are 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 indicates _-CH 2 OCO-, wherein [1a-1] ~ formula ^{[1a-3], R 2} , R 4 and ^{R 6} are each independently a linear or branched C1-22 An alkyl group, 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 —, wherein R ² , R ⁴ and R ⁶ in the formulas [1a-4] to [1a-6] Each independently represents 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).

(Wherein [1a-7] and the formula [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 a fluorine group, a cyano group, a trifluoro group, 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 represent a linear or branched alkyl group having 3 to 12 carbon atoms, and 1,4-cyclohexyl The cis-trans isomers of silene are each trans isomers).

(In the formulas [1a-11] and [1a-12], R ¹ and R ² each independently represent a linear or branched alkyl group having 3 to 12 carbon atoms, and The cis-trans isomers of silene are each trans isomers).

(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 ₁ is a 1,4-phenylene group, A ₂ is an oxygen atom or —COO- * (however, a bond with “*” is bonded to A ₃ ), and A ₁ is an oxygen atom or —COO- * (However, the bond with “*” is bonded to (CH ₂ ) a ₂ ). Also, _{a 1} is an integer of 0 or 1, _{a 2} is an integer of 2 to 10, _{a 3} is an integer of 0 or 1).

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

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

  The specific side chain type diamine compound in the specific polymer of the present invention is preferably from 10 mol% to 80 mol% 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 has the solubility of the specific polymer of the present invention in a solvent, the applicability of the composition and the liquid crystal aligning agent, the alignment of the liquid crystal when formed into a liquid crystal alignment film, and the voltage holding ratio. One type or a mixture of two or more types can be used depending on characteristics such as accumulated charge.

  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 this case, a diamine compound in which the amino group in the following formula [2a] is a secondary amino group may 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 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. Among them, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid is preferred.

（式［２ａ−１］中、Ａ^１は、単結合、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）_２−、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−および−Ｎ（ＣＨ_３）ＣＯ−から選ばれる少なくとも１種の結合基を示し、ｍ^１およびｍ^２は、それぞれ独立して、０〜４の整数を示し、かつｍ^１＋ｍ^２は、１〜４の整数を示し、式［２ａ−２］中、ｍ^３およびｍ^４は、それぞれ独立して、１〜５の整数を示し、式［２ａ−３］中、Ａ^２は、炭素数１〜５の直鎖または分岐アルキル基を示し、ｍ^５は、１〜５の整数を示し、式［２ａ−４］中、Ａ^３およびＡ^４は、それぞれ独立して、単結合、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）_２−、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−および−Ｎ（ＣＨ_３）ＣＯ−から選ばれる少なくとも１種の結合基を示し、ｍ^６は、１〜４の整数を示す）。Also, 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 be used.

(Wherein ^{[2a-1], A} 1 is a single _{bond, -CH 2 -, - C 2} H 4 -, - C (CH 3) 2 -, - CF 2 -, - C (CF 3) 2 - _{, -O -, - CO -,} - NH -, - N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CON (CH ₃ ) — and —N (CH ₃ ) CO— represent at least one kind of a binding group, m ¹ and m ² each independently represent an integer of 0 to 4, and m ¹ + m ² represents an integer of 1 to 4, and in the formula [2a-2], m ³ and m ⁴ each independently represent an integer of 1 to 5, and in the formula [2a-3], A ² represents represents a linear or branched alkyl group having 1 to 5 carbon atoms, ^{m 5} represents 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 kind of a binding 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 from 10 mol% to 80 mol% 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 a carboxyl group (COOH group) and a hydroxyl group (OH group) according to the present invention is capable of dissolving the specific polymer of the present invention in a solvent, a composition, and a liquid crystal alignment treatment. One type or a mixture of two or more types can be used according to the properties such as the coating properties of the agent, the orientation of the liquid crystal when forming a liquid crystal alignment film, the voltage holding ratio, and the accumulated charge.

As the specific polymer of the present invention, it is preferable to use a diamine compound having a nitrogen-containing heterocycle 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 -N _(CH 3) exhibits at least one bond group selected from CO-. Among them, -O -, - NH -, - CONH -, - NHCO -, - CH 2 O -, - OCO -, - CON (CH 3) - or -N _(CH 3) CO- is a diamine compound It is preferable because it can be easily synthesized. More preferred, -O -, - NH -, - CONH -, - NHCO -, - CH 2 O -, - OCO- or -CON (CH ₃₎ - is. Particularly preferred is, -O -, - CONH- or _-CH 2 is 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 and a divalent group of an aromatic hydrocarbon. And at least one selected from groups. The divalent group of the aliphatic hydrocarbon having 1 to 20 carbon atoms may be linear or branched. Further, it may have an unsaturated bond. Among them, 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, Tridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene Ring, norbornene ring or adamantane ring. Among them, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring or an adamantane ring is preferred. Specific examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring and a phenalene ring. Among them, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring or an anthracene ring is preferred.

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

Wherein [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 denotes at least one bond group selected from an a) an integer from 1 to 5. Among them, a single bond, -O -, - COO -, - OCO- or _{-O (CH 2) m - (} m is an integer of 1 to 5) is preferred. More preferred is a single bond, -O -, - OCO- or -O _{(CH 2)} m - is (m is an integer of 1 to 5).

（式［３ａ−３］中、Ｚ^１１は炭素数１〜５のアルキル基を示す）。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]. It is a heterocyclic group.

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

More specifically, a 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 them, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring or a benzimidazole ring are preferable. More preferred are a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring. In addition, B ³ in the formula [3a] is bonded to a ring atom that is not adjacent to the structures of the formulas [3a-1], [3a-2], and [3a-3] included in B ⁴ Is preferred.

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

Particularly preferred combinations of B ^{1 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 an imidazole ring or a pyridine ring, and n is 1;

The bonding position of the two amino groups (—NH ₂ ) in the formula [3a] is not limited. Specifically, with respect to the bonding group (-B ^1- ) on the side chain, positions 2, 3, 2, 4, 2, 5, 2, 6, 3, The position 4 or the position 3 or 5 can be mentioned. Among them, the 2,4 position, the 2,5 position, or the 3,5 position are preferred from the viewpoint of reactivity when synthesizing the polyamic acid. Taking into account the ease of synthesizing the diamine compound, the 2,4 position or the 2,5 position is more preferable.

  The diamine compound having a nitrogen-containing heterocycle represented by the formula [3a] in the specific polymer of the present invention preferably accounts for 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 heterocycle represented by the formula [3a] of the present invention is used as a solvent for the specific polymer of the present invention in a solvent, applicability of a composition and a liquid crystal aligning agent, and a liquid crystal alignment film. One type or a mixture of two or more types can be used according to the characteristics of the liquid crystal, such as the orientation, the voltage holding ratio, and the accumulated charge.

（式［ａ−１］中、Ａ^１およびＡ^３は、それぞれ独立して、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−および−ＮＨ−から選ばれる少なくとも１種の結合基を示し、Ａ^２は、炭素数１〜２２の直鎖状もしくは分岐状のアルキル基、または炭素数１〜２２の直鎖状もしくは分岐状のフッ素含有アルキル基を示し、式［ａ−２］中、Ａ^４およびＡ^６は、それぞれ独立して、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−および−ＮＨ−から選ばれる少なくとも１種の結合基を示し、Ａ^５は、炭素数１〜２２の直鎖状もしくは分岐状のアルキル基、または炭素数１〜２２の直鎖状もしくは分岐状のフッ素含有アルキル基を示す）。

（式［ａ−３］中、Ａ^１およびＡ^３は、それぞれ独立して、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−および−ＮＨ−から選ばれる少なくとも１種の結合基を示し、Ａ^２は、炭素数１〜２２の直鎖状もしくは分岐状のアルキル基、または炭素数１〜２２の直鎖状もしくは分岐状のフッ素含有アルキル基を示し、式［ａ−４］中、Ａ^４およびＡ^６は、それぞれ独立して、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−および−ＮＨ−から選ばれる少なくとも１種の結合基を示し、Ａ^５は、炭素数１〜２２の直鎖状もしくは分岐状のアルキル基、または炭素数１〜２２の直鎖状もしくは分岐状のフッ素含有アルキル基を示す）。

（式［ａ−５］中、Ａ^１およびＡ^３は、それぞれ独立して、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−および−ＮＨ−から選ばれる少なくとも１種の結合基を示し、Ａ^２は、炭素数１〜２２の直鎖状もしくは分岐状のアルキル基、または炭素数１〜２２の直鎖状もしくは分岐状のフッ素含有アルキル基を示し、式［ａ−６］中、Ａ^４およびＡ^６は、それぞれ独立して、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−および−ＮＨ−から選ばれる少なくとも１種の結合基を示し、Ａ^５は、炭素数１〜２２の直鎖状もしくは分岐状のアルキル基、または炭素数１〜２２の直鎖状もしくは分岐状のフッ素含有アルキル基を示す）。

（式［ａ−７］中、ｐは１〜１０の整数を示す）。

（式［ａ−１２］中、Ｒ^１は水素原子または炭素数１〜５のアルキル基を示し、式［ａ−１３］中、ｎは１〜１０の整数を示す）。In the specific polymer of the present invention, as long as the effects of the present invention are not impaired, other diamine compounds include diamine compounds represented by the following formulas [a-1] to [a-13] and amino groups thereof. A diamine compound which is a secondary amino group can also be used.

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

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

(In the formula [a-5], A ¹ and A ³ are each independently —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— and 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. indicates containing alkyl group, wherein [a-6], ^{a 4} and ^{a 6} are each independently, -COO -, - OCO -, - CONH -, - NHCO -, - CH 2 -, - O- , -CO- represents at least one bond group selected from and -NH-, ^{a 5} is a linear or branched alkyl group having 1 to 22 carbon atoms or straight-chain 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.).

  Further, 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'-diaminodiphenylether, 3,3'-diaminodiphenylether, 3,4'-diaminodiphenylether, 2,2'-diaminodiphenylether, 2,3'-diaminodiphenylether, 4,4'-sulfonyldi Aniline, 3,3'-sulfonyldianiline, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane , 4,4'-thiodiani 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-diamino Naphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-amino Phenyl) 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-phenylene Bis (methylene)] dianiline, 3,3 ′-[1,4-phenylenebis (methylene)] dianiline, 3,3 ′-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [ (4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3 Phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4-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) iso Phthalate, 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-aminobenz) 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, 1, 5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) Xan, 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3- Minophenoxy) 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-diamine Octane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-di-aminoundecanoic, 1,12 aliphatic diamine compounds such as diamino dodecane.

  Other diamine compounds of the present invention, the solubility of the specific polymer of the present invention in a solvent, the applicability of the composition and the liquid crystal alignment treatment agent, the liquid crystal alignment in the case of a liquid crystal alignment film, voltage holding ratio, accumulated charge Depending on the characteristics such as the above, one kind or a mixture of two or more kinds can be used.

（式［４］中、Ｚは、下記の式［４ａ］〜式［４ｋ］で示される構造から選ばれる少なくとも１種の構造を示す）。

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 a tetracarboxylic acid derivative thereof such as tetracarboxylic acid, tetracarboxylic dihalide compound, tetracarboxylic dialkyl ester compound or tetracarboxylic dialkyl ester dialkyl ester A halide compound can also be used (the tetracarboxylic dianhydride and its derivative represented by the formula [4] are collectively referred to as a specific tetracarboxylic acid component).

(In the formula [4], Z represents at least one structure selected from the structures represented by the following formulas [4a] to [4k]).

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 the formula [4], from the viewpoint of easiness of synthesis and easiness of polymerization reactivity when producing a polymer, the formulas [4a], [4c] to [4g] or [4k] The tetracarboxylic dianhydride of the structure shown by these] and its tetracarboxylic acid derivative are preferable. More preferred are those represented by the formulas [4a] or [4e] to [4g]. Particularly preferred are tetracarboxylic dianhydrides having the structure represented by [4a], [4e] or [4f] and tetracarboxylic acid derivatives thereof.

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 the tetracarboxylic acid components. Especially, 5 mol%-95 mol% are preferable. More preferably, it is 20 mol% to 80 mol%.
The specific tetracarboxylic acid component of the present invention, 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 the liquid crystal when a liquid crystal alignment film, the voltage holding ratio, One type or a mixture of two or more types can be used according to the characteristics such as the accumulated charge.

  As 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. Other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic dihalide compounds, tetracarboxylic dialkyl ester compounds or tetracarboxylic dialkyl ester dihalide compounds.

  That is, as other tetracarboxylic acid components, 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 ′ -Benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1, 1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ′, 4,4 ′ -Diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

  Other tetracarboxylic acid components of the present invention include the solubility of the specific polymer of the present invention in a solvent, the applicability of the composition and the liquid crystal aligning agent, the alignment of the liquid crystal when formed into a liquid crystal alignment film, and the voltage holding ratio. One type or a mixture of two or more types can be used depending on characteristics such as accumulated charge.

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

  In order to obtain a polyamic acid alkyl ester, a method of polycondensing a tetracarboxylic acid in which a carboxylic acid group is dialkylesterified with a primary or secondary diamine compound, a method in which a tetracarboxylic acid dihalide in which a carboxylic acid group is dialkylesterified is used. A method of polycondensing 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 a polyimide, a method is used in which the above-mentioned polyamic acid or polyamic acid alkyl ester is closed to form a polyimide.

  The reaction between the diamine component and the tetracarboxylic acid component is usually performed in a solvent with the diamine component and the tetracarboxylic acid component. The solvent used in this case may be the specific solvent of the present invention, but is not particularly limited as long as the produced polyimide precursor is dissolved. Specific examples of the solvent used in the reaction are shown below, but are not limited to these examples.

（式［Ｄ−１］中、Ｄ^１は炭素数１〜３のアルキル基を示し、式［Ｄ−２］中、Ｄ^２は炭素数１〜３のアルキル基を示し、式［Ｄ−３］中、Ｄ^３は炭素数１〜４のアルキル基を示す）。For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide or 1,3-dimethyl-imidazolidinone. Can be Further, 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 solvents indicated can be used.

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

  These solvents may be used alone or as a mixture. Furthermore, even if the solvent does not dissolve the polyimide precursor, it may be mixed with the solvent as long as the generated polyimide precursor does not precipitate. Further, since water in the solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, it is preferable to use a solvent that has been dehydrated and dried.

  When reacting a diamine component and a tetracarboxylic acid component in a solvent, a 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. Method, 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, and the like, and any of these methods May be used. When a plurality of diamine components or tetracarboxylic acid components are used for the reaction, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. May be mixed to form a polymer. The polymerization temperature at that time can be selected from any temperature in the range of -20 ° C to 150 ° C, but is preferably in the range of -5 ° C to 100 ° C. In addition, the reaction can be performed 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. Becomes Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, after which a solvent can be added.

  In the polymerization reaction of the polyimide precursor, the ratio of the total mole number of the diamine component to the total mole number of the tetracarboxylic acid component is preferably 0.8 to 1.2. As in the ordinary polycondensation reaction, the molecular weight of the generated polyimide precursor increases as the molar ratio approaches 1.0.

  The polyimide of the present invention is a polyimide obtained by ring-closing the above-mentioned polyimide precursor. In this polyimide, the ring-closure rate of amic acid groups (also referred to as imidation rate) does not necessarily need to be 100%, It can be adjusted arbitrarily according to the purpose.

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

  The temperature at which the polyimide precursor is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to perform the process while removing water generated by the imidization reaction out of the system.

  Catalytic imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor, 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 to 30 times, preferably 2 to 20 times the mole of the amic acid group, and the amount of the acid anhydride is 1 to 50 times the mole of the amic acid group. Preferably it is 3 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 causing the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferred because purification after the reaction is easy. The imidation rate by the catalytic imidization can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

  When recovering the generated polyimide precursor or polyimide from the polyimide precursor or polyimide reaction solution, the reaction solution may be put into a solvent to precipitate. 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, water and the like. After the polymer that has been put into the solvent and precipitated is collected by filtration, it can be dried at normal temperature or under reduced pressure at normal temperature or under normal pressure. Further, by repeating the operation of re-dissolving the precipitated and recovered polymer in a solvent and re-precipitating and recovering it two to ten times, impurities in the polymer can be reduced. Examples of the solvent at this time include alcohols, ketones, and hydrocarbons. It is preferable to use three or more solvents selected from these, because purification efficiency is further increased.

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

  As the specific polymer of the present invention, any polyimide-based polymer of polyamic acid, polyamic acid alkyl ester and polyimide may be used. Of these, polyamic acid alkyl esters or polyimides are preferred. More preferably, it is a polyimide.

  All polymer components in the composition and the liquid crystal alignment treatment agent of the present invention may be all the specific polymer of the present invention. At that time, two or more kinds of the specific polymers of the present invention may be mixed and used. Further, another polymer may be mixed with the specific polymer. Other polymers include cellulosic polymers, acrylic polymers, methacrylic polymers, polystyrene, polyamide or polysiloxane. At that time, the content of the other polymer is 0.5 to 30 parts by mass based on 100 parts by mass of the specific polymer of the present invention. Especially, 1 mass part-20 mass parts are preferable.

  When a liquid crystal alignment film is formed using the composition of the present invention as a liquid crystal alignment treatment agent, the specific polymer includes the specific polymer having a specific side chain structure represented by the formula [1-1] of the present invention. It is preferable to use Above all, it is preferable to use a specific polymer using a specific side chain type diamine compound represented by the formula [1a] having a specific side chain structure represented by the formula [1-1]. In particular, for a liquid crystal alignment film for a mode requiring a pretilt angle of a liquid crystal, such as a TN (Twisted Nematic) mode or a VA (Vertical Alignment) mode, a specific polymer using a specific side chain type diamine compound may be used. good. In that case, the specific polymer using the specific side chain type diamine compound and the specific polymer not using the specific side chain type diamine compound may be used as a mixture. In that case, the content of the specific polymer not using the specific side chain type diamine compound is 10 parts by mass to 300 parts by mass with respect to 100 parts by mass of the specific polymer using the specific side chain type diamine compound. preferable. Especially, 20 mass parts-200 mass parts are preferable.

  The solvent in the composition of the present invention and the liquid crystal alignment treatment agent preferably has a solvent content of 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 intended thickness of the polyimide film and the liquid crystal alignment film.

  As the solvent at that time, all may be the specific solvent of the present invention, or a solvent that dissolves the specific polymer of the present invention, that is, a good solvent may be used at the same time. Specific examples of the good solvent are described below, but the present invention 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.

  Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyl lactone (also referred to as the component (C)).

  The component (C) preferably accounts for 1 to 70% by mass of the entire solvent contained in the composition and the liquid crystal alignment treatment agent. Especially, 5 to 65 mass% is preferable. More preferably, it is 5 to 60% by mass, and still more preferably, 10 to 60% by mass.

  The good solvent may be used singly or as a mixture 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 alignment treatment agent of the present invention, as long as the effects of the present invention are not impaired, an organic solvent that improves the coatability and surface smoothness of the resin film when the composition and the liquid crystal alignment treatment agent are applied, That is, it is also preferable to use a poor solvent. Specific examples of the poor solvent are described below, but the present invention 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- Etangi Diol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentane Diol, 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 monoacetate Tart, 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, vinegar Methyl, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Propionic 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] to A solvent represented by the formula [D-3] can be mentioned.

  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] It is preferred to use a solvent represented by the following formula (3):

  The component (D) preferably accounts for 10 to 80% by mass of the entire solvent contained in the composition and the liquid crystal alignment treatment agent. Especially, 10-70 mass% is preferable. More preferably, it is 20 to 70% by mass, and still more preferably, 20 to 60% by mass.

  The poor solvent may be used singly or as a mixture 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 alignment treatment agent of the present invention include at least one kind of substitution selected from a crosslinking 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. These substituents and polymerizable unsaturated bonds need to be two or more in the crosslinkable compound.

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

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

  Specific examples include crosslinkable compounds represented by formulas [4a] to [4k] described in paragraphs 58 to 59 of International Publication No. 2011/132751 (published on 2011.10.27).

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 paragraphs 76 to 82 of WO2012 / 014898 (published on 2012.2.2) are described. No.

  Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include, for example, an amino resin having a hydroxyl group or an alkoxyl group, for example, a melamine resin, a urea resin, a guanamine resin, and a glycoluril. -Formaldehyde resin, succinylamide-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 a melamine derivative or benzoguanamine derivative include MX-750, which is a commercially available product and has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5.000 methoxymethyl groups per triazine ring. Eight-substituted methoxymethylated melamines such as MW-30 (above, manufactured by Sanwa Chemical Co., Ltd.) and Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236 Methoxymethylated butoxymethylated melamine, such as Cymel 506, 238, 253, 254, Cymer 506, 508, etc., carboxyl group-containing methoxymethylated isobutoxymethylated melamine, such as Cymel 1141, and Cymel 1123. Methoxymethylated ethoxy Methylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxy-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 (Mitsui Cyanamid). 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, and 1,4-bis ( sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p-tert-butylphenol.

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

  Examples of the crosslinkable compound having a polymerizable unsaturated bond include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxy trimethylol. Crosslinkable compounds having three polymerizable unsaturated groups in the molecule, such as propane or glycerin polyglycidyl ether poly (meth) acrylate, and ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol 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, diglycidyl phthalate di (meth) acrylate, or neohydroxypivalate A crosslinkable compound having two polymerizable unsaturated groups in the molecule, such as pentyl glycol di (meth) acrylate, and 2-hydroxyethyl (meth) acryle G, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropylphthalate, 3-chloro -2-Hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate or N-methylol (meth) acrylamide has one polymerizable unsaturated group in the molecule. Crosslinkable compounds and the like can be mentioned.

（式［７Ａ］中、Ｅ^１はシクロヘキサン環、ビシクロヘキサン環、ベンゼン環、ビフェニル環、ターフェニル環、ナフタレン環、フルオレン環、アントラセン環およびフェナントレン環から選ばれる少なくとも１種を示し、Ｅ^２は下記の式［７ａ］または式［７ｂ］から選ばれる基を示し、ｎは１〜４の整数を示す）。

In addition, a compound represented by the following formula [7A] can 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 A group selected from the following formula [7a] or [7b], and n is an integer of 1 to 4).

  The above compound is an example of a crosslinkable compound and is not limited thereto. Further, the crosslinkable compound used in the composition and the liquid crystal alignment treatment agent of the present invention may be one kind or a combination of two or more kinds.

  The content of the crosslinkable compound in the composition of the present invention and the liquid crystal alignment treatment agent is preferably 0.1 part by mass to 150 parts by mass with respect to 100 parts by mass of all the polymer components. Among them, in order for the cross-linking reaction to proceed and achieve the desired effect, the amount is preferably from 0.1 to 100 parts by mass based on 100 parts by mass of all the polymer components. More preferred is 1 to 50 parts by mass.

  The composition and the liquid crystal alignment agent of the present invention are compounds that improve the uniformity of the film thickness of the resin film and the surface smoothness when the composition and the liquid crystal alignment agent are applied, as long as the effects of the present invention are not impaired. Can be used.

  Examples of the compound that improves the uniformity of the thickness of the resin film and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant.

  More specifically, for example, F-top EF301, EF303, EF352 (all manufactured by Tochem Products), Megafac F171, F173, R-30 (all manufactured by Dainippon Ink), Florad FC430, FC431 (all) And Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (all manufactured by Asahi Glass Co., Ltd.) and the like.

  The use ratio of these surfactants is preferably from 0.01 to 2 parts by mass, more preferably from 0.1 to 2 parts by mass, based on 100 parts by mass of all polymer components contained in the composition and the liquid crystal alignment treatment agent. It is from 01 parts by mass to 1 part by mass.

  Further, the composition and the liquid crystal alignment treatment agent of the present invention include compounds that promote charge transfer in a resin film and promote charge removal of an element, as disclosed in WO2011 / 132751 (2011.10.27). And the nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156], which are described on pages 69 to 73 of the above. This amine compound may be directly added to the composition and the liquid crystal alignment treatment agent, but it is prepared as 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. Is preferably added. The solvent is not particularly limited as long as the solvent dissolves the above-mentioned specific polymer.

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

<Polyimide film>
The composition of the present invention can be used as a polyimide film after being applied and baked on a substrate. As the substrate used at this time, a glass substrate, a silicon wafer, an acrylic substrate, a polycarbonate substrate, a plastic substrate such as a PET (polyethylene terephthalate) substrate, or the like can be used depending on a target device. Further, a polyimide film can be used as it is as a film substrate. The method of applying the composition is not particularly limited, but industrially, a method performed by a dip method, a roll coater method, a slit coater method, a spinner method, a spray method, screen printing, offset printing, flexographic printing, an inkjet method, or the like. General. These may be used depending on the purpose.

  After applying the composition on 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 circulating oven or an IR (infrared) oven to form a polyimide film. can do. In the case of the composition using the specific solvent of the present invention, a polyimide film can be produced even at a temperature of 200 ° C. or less. The thickness of the fired polyimide film can be adjusted to 0.01 to 100 μm depending on the purpose.

<Liquid crystal alignment film and liquid crystal display device>
The liquid crystal aligning agent using the composition of the present invention can be used as a liquid crystal aligning film after being applied and baked on a substrate, and then subjected to an alignment treatment by rubbing treatment or light irradiation. Further, in the case of a vertical alignment application such as a VA mode, it can be used as a liquid crystal alignment film without an alignment treatment. The substrate used at this time is not particularly limited as long as it is a substrate having high transparency. In addition to a glass substrate, an acrylic substrate, a polycarbonate substrate, or a plastic substrate such as a PET (polyethylene terephthalate) substrate can be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO (indium tin oxide) electrode for driving a liquid crystal is formed. In the case of a reflection type liquid crystal display device, an opaque substrate such as a silicon wafer can be used if only one substrate is used. In this case, a material that reflects light such as aluminum can be used as an electrode.

  The method for applying the liquid crystal alignment treatment agent is not particularly limited, but is industrially generally performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method, and a spray method, and these may be used according to the purpose.

  After applying the liquid crystal alignment treatment agent on the substrate, it is preferably 30 to 300 ° C., preferably by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven, depending on the solvent used for the liquid crystal alignment treatment agent. Can evaporate the solvent at a temperature of 30 to 250 ° C. to form a liquid crystal alignment film. In the case of the liquid crystal alignment treating agent using the specific solvent of the present invention, a liquid crystal alignment film can be produced even at a temperature of 200 ° C. or lower. If the thickness of the liquid crystal alignment film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if too thin, the reliability of the liquid crystal display element may be reduced. Is 10 to 150 nm. In the case where the liquid crystal is horizontally or tilted, the baked liquid crystal alignment film is treated by rubbing or irradiation with polarized ultraviolet rays.

  The liquid crystal display device of the present invention is obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-mentioned method, and then manufacturing a liquid crystal cell by a known method to obtain a liquid crystal display device.

  As a method for manufacturing a liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers are scattered on the liquid crystal alignment film of one substrate so that the liquid crystal alignment film surface is on the inside, and the other is provided. And a method of sealing by injecting liquid crystal under reduced pressure, or a method of dropping liquid crystal on the surface of the liquid crystal alignment film on which spacers are scattered, and then bonding the substrates to seal.

  Furthermore, the liquid crystal alignment treatment agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable compound polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display device manufactured through a step of arranging a liquid crystal composition containing the compound and applying a voltage between the electrodes while polymerizing the polymerizable compound by at least one of irradiation with active energy rays and heating. Here, ultraviolet rays are preferable as the active energy rays. The ultraviolet light has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, the ultraviolet ray and the heating may be performed simultaneously.

  The liquid crystal display element controls the pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, an ultraviolet ray is applied to the photopolymerizable compound while a predetermined voltage is applied to the liquid crystal layer. Then, the pretilt of the liquid crystal molecules is controlled by the generated polymer. Since the alignment state of the liquid crystal molecules when the polymer is generated 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. Further, the PSA method does not require a rubbing treatment, and thus is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by the rubbing treatment.

  That is, the liquid crystal display element of the present invention obtains a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method, then prepares a liquid crystal cell, and irradiates the polymerizable compound with at least one of ultraviolet irradiation and heating. The orientation of liquid crystal molecules can be controlled by polymerization.

  To give an example of producing a PSA-type liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers are scattered on the liquid crystal alignment film of one of the substrates so that the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded and sealed by injecting liquid crystal under reduced pressure, or a method of bonding the substrate after dropping liquid crystal on the surface of the liquid crystal alignment film on which spacers are scattered, and performing sealing. No.

  The liquid crystal is mixed with a polymerizable compound which is polymerized by heat or ultraviolet irradiation. Examples of the polymerizable compound include compounds having one or more polymerizable unsaturated groups such as an acrylate group and a methacrylate group in a molecule. At that time, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 part by mass, the orientation of the liquid crystal cannot be controlled because the polymerizable compound is not polymerized. The image sticking characteristics are reduced.

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

  In order to obtain a liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of active energy rays and heat, a method of adding a compound containing the polymerizable group to a liquid crystal alignment treatment agent, a method of adding a compound containing a polymerizable group, A method using a coalesced component is exemplified.

  To give an example of manufacturing a liquid crystal cell of SC-PVA mode, a pair of substrates on which a liquid crystal alignment film of the present invention is formed is prepared, and spacers are scattered on the liquid crystal alignment film of one of the substrates. The other side of the substrate is bonded and the liquid crystal is injected under reduced pressure and sealed, or the liquid crystal is dropped on the surface of the liquid crystal alignment film where spacers are scattered and the substrate is bonded and sealed. And the like.

  After manufacturing the liquid crystal cell, the alignment 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 alignment treatment agent of the present invention becomes a liquid crystal alignment film having excellent coatability, and furthermore, the liquid crystal alignment element can be used in a liquid crystal display element even when firing at a low temperature. It becomes a liquid crystal alignment film excellent in VHR which is a characteristic. Therefore, a liquid crystal display device having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and is used in a large-screen high-definition liquid crystal television, a small and medium-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 it should not be construed that the invention is limited thereto.

"Abbreviations used in Synthesis Examples, Examples and Comparative Examples of the present invention"
Abbreviations used in Synthesis Examples, Examples and Comparative Examples are as follows.

<Monomer for producing polyimide-based polymer of the present invention>
(Specific side chain type 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 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 compound)
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: Diamine compound represented by the following formula [A4] (specific side chain type diamine compound having a specific side chain structure represented by formula [1-1] of the present invention)
A5: 1,3-diamino-4-octadecyloxybenzene (specific side chain type diamine compound having a specific side chain structure represented by formula [1-2] of the present invention)

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

(Diamine compound represented by formula [3a] of the present invention)
C1: Diamine compound represented by the following formula [C1] (diamine compound having a nitrogen-containing heterocycle represented by formula [3a] of the present invention)
C2: Diamine compound represented by the following formula [C2] (diamine compound having a nitrogen-containing heterocycle represented by 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: a 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 the molecular weight of the polyimide polymer of the present invention"
The molecular weights of the polyimide precursor and the polyimide in the synthesis examples were measured 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). And measured as follows.
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as an additive, lithium bromide hydrate (LiBr.H ₂ O): 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid): 30 mmol / L 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 imidation ratio of polyimide of the present invention"
The imidation ratio of the polyimide in the synthesis example was measured as follows. 20 mg of the polyimide powder is placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Science), and deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% by mass TMS (tetramethylsilane) ) Mixture (0.53 ml) was added and sonicated to completely dissolve. The solution was subjected to proton NMR measurement at 500 MHz using an NMR measuring device (JNW-ECA500) (manufactured by JEOL Datum). The imidation rate is determined based on a proton derived from a structure that does not change before and after imidation as a reference proton, and a peak integrated value of the proton and a proton peak derived from an NH group of amic acid appearing around 9.5 ppm to 10.0 ppm. It was determined by the following equation using the integrated value.
Imidation ratio (%) = (1−α · x / y) × 100

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

"Synthesis of the 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) are mixed in S1 (37.1 g) and reacted at 40 ° C. for 8 hours. Thus, a polyamic acid solution (1) having a resin solid content concentration of 25% by mass was obtained. 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% by 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>
NMP was added to the polyamic acid solution (2) (30.0 g) obtained by the synthesis method of Synthesis Example 2 to dilute to 6% by mass, and then acetic anhydride (3.95 g) and pyridine (2. 50 g) and reacted at 60 ° C. for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a 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) were converted to NEP (24.2 g). And reacted at 80 ° C. for 5 hours. Then, E1 (3.10 g, 15.8 mmol) and NEP (12.1 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. % Polyamic acid solution was obtained.

  After adding NEP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.40 g) and pyridine (3.30 g) were added as imidation catalysts, and the mixture was added at 80 ° C. for 3 hours. The reaction was performed for 5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried at 100 ° C. under reduced pressure to obtain a 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) were converted to 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 to dilute it to 6% by mass, and then acetic anhydride (3.95 g) and pyridine (2. 40 g) and reacted at 70 ° C. for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a 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) were converted 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 the mixture was reacted at 40 ° C. for 6 hours. % Polyamic acid solution was obtained.

  NMP was added to the obtained polyamic acid solution (30.0 g) to dilute the solution to 6% by mass, and then acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidation catalysts. The reaction was performed for 5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried at 100 ° C. under reduced pressure to obtain a polyimide powder (7). The 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) were converted to NMP (24.2 g). And then reacted at 80 ° C. for 5 hours. Then, 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.

  NMP was added to the obtained polyamic acid solution (30.0 g) to dilute it to 6% by mass, and then acetic anhydride (3.85 g) and pyridine (2.50 g) were added as imidation catalysts, and the mixture was heated at 60 ° C. for 2 hours. Reacted. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried at 100 ° C. under reduced pressure to obtain a 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 the mixture was added at 40 ° C. for 6 hours. The reaction was carried out for a time to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

  NEP was added to the obtained polyamic acid solution (30.5 g) to dilute it to 6% by mass, and then acetic anhydride (3.95 g) and pyridine (2.55 g) were added as imidation catalysts, and the mixture was heated at 60 ° C. for 3 hours. Reacted. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a 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 converted to 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 the mixture was reacted at 40 ° C. for 6 hours. % Polyamic acid solution was obtained.

  NMP was added to the obtained polyamic acid solution (30.0 g) to dilute the solution to 6% by mass, and then acetic anhydride (3.80 g) and pyridine (2.55 g) were added as imidation catalysts, and the mixture was heated at 60 ° C. for 2 hours. Reacted. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried at 100 ° C. under reduced pressure to obtain a 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) were converted to NMP (37.3 g). And reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution having a resin solid content of 25% by mass.

  After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting it to 6% by mass, acetic anhydride (4.20 g) and pyridine (3.10 g) were added as imidation catalysts. The reaction was performed for 5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a 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 converted to NMP (35.9 g). And reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution having a resin solid content 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 imidation catalysts, and the mixture was added at 80 ° C. for 3 hours. The reaction was performed for 5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a 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% by 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 imidation catalysts, and the mixture was added at 60 ° C. for 3 hours. The reaction was performed for 5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried at 100 ° C. under reduced pressure to obtain a 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) were converted 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.

  After adding NEP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (3.80 g) and pyridine (2.50 g) were added as imidation catalysts, and the mixture was heated at 60 ° C. for 2 hours. Reacted. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried at 100 ° C. under reduced pressure to obtain a 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) were mixed in NMP (23.9 g) and reacted at 80 ° C. for 6 hours. E1 (2.15 g, 11.0 mmol) and NMP (12.0 g) were added, and the mixture was added at 40 ° C. for 6 hours. The reaction was carried out for a time to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

  NMP was added to the obtained polyamic acid solution (30.1 g) to dilute the solution to 6% by mass, and then acetic anhydride (4.20 g) and pyridine (3.15 g) were added as imidation catalysts. The reaction was performed for 5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried at 100 ° C. under reduced pressure to obtain a polyimide powder (15). The 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) were converted to 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 the mixture was reacted at 40 ° C. for 6 hours. % Polyamic acid solution was obtained.

  After NMP was added to the obtained polyamic acid solution (30.0 g) to dilute the solution to 6% by mass, acetic anhydride (3.85 g) and pyridine (2.40 g) were added as imidation catalysts, and the mixture was added at 60 ° C. for 2 hours. Reacted. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried at 100 ° C. under reduced pressure to obtain a polyimide powder (16). The 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 solids concentration of 25% by mass.

  NMP was added to the obtained polyamic acid solution (30.0 g) to dilute the solution to 6% by mass, and then acetic anhydride (4.20 g) and pyridine (3.20 g) were added as imidation catalysts. The reaction was performed for 5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried at 100 ° C. under reduced pressure to obtain a polyimide powder (17). The 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) and reacted at 80 ° C. for 6 hours, and then E2 (2.32 g, 9.27 mmol) and NEP ( 11.9 g) was added thereto and reacted at 80 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

  NMP was added to the obtained polyamic acid solution (30.0 g) to dilute the solution to 6% by mass, and then acetic anhydride (4.20 g) and pyridine (3.20 g) were added as imidation catalysts, and the mixture was heated at 80 ° C. for 2 hours. Reacted. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried at 100 ° C. under reduced pressure to obtain a 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% by 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) were converted to NMP (24.2 g). And reacted at 80 ° C. for 5 hours. Then, E1 (2.45 g, 12.5 mmol) and NMP (12.1 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. % 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 the composition of the present invention and a liquid crystal alignment treatment agent"
In the following Examples 1 to 20 and Comparative Examples 1 to 4, production examples of the composition are described. These compositions are also used for evaluating a liquid crystal alignment treatment agent.

  Tables 3 to 5 show the composition and the liquid crystal alignment treatment agent of the present invention.

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

"Evaluation of Printability of Composition and Liquid Crystal Alignment Agent (Evaluation of Pinhole)"
The pinholes of the polyimide film were evaluated using the compositions obtained by the methods of the examples and comparative examples of the present invention. Specifically, these compositions were subjected to pressure filtration with a membrane filter having a pore diameter of 1 μm, and printing was performed on an unwashed Cr-deposited substrate (length 100 mm × width 100 mm, thickness 1.0 mm). As a printing machine, a simple printing machine S15 type (manufactured by Nissha Printing Co., Ltd.) was used. The time until the drying was 90 seconds, the preliminary drying was performed on a hot plate at 70 ° C. for 5 minutes, and the main baking was performed in a thermal circulation clean oven at 160 ° C. for 15 minutes.

  Thereafter, the number of pinholes in the obtained substrate with a polyimide film was confirmed. Specifically, the substrate with the polyimide film was visually observed under a sodium lamp, and the number of pinholes on the polyimide film was counted. It should be noted that the smaller the number of pinholes, the smaller the precipitates in the composition and the better the evaluation.

  Tables 6 to 8 show the number of pinholes obtained in Examples and Comparative Examples.

  The compositions obtained in Examples and Comparative Examples of the present invention can be used for a liquid crystal alignment treatment agent. Therefore, the evaluation of the pinholes of the polyimide films of the compositions obtained in the examples and the comparative examples of the present invention was also made the evaluation of the pinholes of the liquid crystal alignment film.

"Evaluation of printability of composition and liquid crystal alignment treatment agent (evaluation of coating film edge)"
Using the substrate with a polyimide film obtained in the above “Evaluation of printability of composition and liquid crystal alignment treatment agent (Evaluation of pinhole)”, evaluation of the coating film edge of polyimide film, ie, polyimide film edge Of the polyimide film (also referred to as evaluation of linearity) and the rise of the polyimide film end portion (also referred to as rise evaluation).

  The linearity of the end of the polyimide film was evaluated by observing the polyimide film on the right end in the printing direction with an optical microscope. More specifically, the difference between (1) and (2) in FIG. 1 of the polyimide film image obtained by observing the optical microscope at a magnification of 25 times, that is, the length of A in FIG. 1 was measured. did. At that time, images of all the 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 in the printing direction with an optical microscope. Specifically, the length B in FIG. 2 of the polyimide film image obtained by observing the optical microscope at a magnification of 25 was measured. At that time, all the polyimide film images were obtained at the same magnification. The shorter the length of B, the better the bulge at the end of the polyimide film.

  Tables 6 to 8 show the lengths A and B obtained in Examples and Comparative Examples.

  The compositions obtained in Examples and Comparative Examples of the present invention can be used for a liquid crystal alignment treatment agent. Therefore, the evaluation of the edge of the coating film of the polyimide film obtained in this example and the comparative example was also the evaluation of the edge of the coating film of the liquid crystal alignment film.

"Evaluation of voltage holding ratio (VHR) (normal cell)"
The voltage holding ratio (VHR) was evaluated using the liquid crystal alignment treating agents obtained in Examples and Comparative Examples of the present invention. Specifically, a substrate with an ITO electrode (length 40 mm × width 30 mm, thickness: 30 mm, thickness: 1 mm) was filtered under pressure through a membrane filter having a pore diameter of 1 μm, and washed with pure water and IPA (isopropyl alcohol). 0.7mm) spin-coated on an ITO surface, and heat-treated at 80 ° C for 3 minutes on a hot plate and at 160 ° C for 15 minutes in a heat-circulating clean oven to provide a liquid crystal alignment film with a thickness of 100nm. Was obtained. The coating surface of the ITO substrate is rubbed with a rubbing device having a roll diameter of 120 mm using a rayon cloth under the conditions of a roll rotation speed of 300 rpm, a roll advancing speed of 20 mm / sec, and a pushing amount of 0.4 mm. Was.

Two ITO substrates with a liquid crystal alignment film obtained were prepared, combined with a 6 μm spacer sandwiched with the liquid crystal alignment film surface inside, and an ultraviolet-curable sealant was printed. Next, after the other substrate and the liquid crystal alignment film were bonded together so as to face each other, a treatment for curing the ultraviolet-curable sealant was performed to obtain an empty cell. Specifically, using a metal halide lamp with an illuminance of 60 mW, a wavelength of 310 nm or less is cut and irradiated with ultraviolet rays of 5 J / cm ^{2 in} terms of 365 nm, and thereafter, at 120 ° C. for 60 minutes in a heat circulation type clean oven. An empty cell was obtained by heat treatment. A nematic liquid crystal was injected into the empty cell by a vacuum injection method to obtain a liquid crystal cell (normal cell).

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

  In addition, MLC-6608 (manufactured by Merck Japan) was used for the liquid crystal in the liquid crystal cells using the liquid crystal alignment treatment agents obtained in 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 could be held was calculated as a voltage holding ratio (VHR). The measurement was performed using a voltage holding ratio measuring device (VHR-1) (manufactured by Toyo Corporation) at a setting of Voltage: ± 1 V, Pulse Width: 60 μs, and Frame Period: 50 ms.

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

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

  Tables 9 to 11 show values of the voltage holding ratio (VHR) obtained in Examples and Comparative Examples.

"Evaluation of inkjet coating properties of liquid crystal alignment agent"
The liquid crystal alignment agent (4) obtained by the method of Example 4 of the present invention, the liquid crystal alignment agent (7) obtained by the method of Example 7, and the liquid crystal alignment agent obtained by the method of Example 15 Using (15), the applicability of ink jet was evaluated. Specifically, these liquid crystal alignment treatment agents are filtered under pressure through a membrane filter having a pore diameter of 1 μm, and washed with pure water and IPA using an HIS-200 (manufactured by Hitachi Plant Technologies) in an ink jet coating machine. On the ITO (indium tin oxide) deposited substrate, the application area is 70 × 70 mm, the nozzle pitch is 0.423 mm, the scan pitch is 0.5 mm, the application speed is 40 mm / sec, and the time from application to temporary drying is 60. For 2 seconds, pre-drying was performed on a hot plate at 70 ° C. for 5 minutes, and main baking was performed at 160 ° C. for 15 minutes in a heat circulation type clean oven.

  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. There were less than five. In each of the examples, a liquid crystal alignment film having excellent coating film uniformity was obtained.

  Further, using the obtained substrate with a liquid crystal alignment film, the evaluation of VHR (normal cell) was performed under the condition of “Evaluation of voltage holding ratio (VHR) (normal cell)”.

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

These substrates with a liquid crystal alignment film were combined with the liquid crystal alignment film surface inside, with a 6 μm spacer interposed therebetween, and the periphery was adhered with a sealant to produce an empty cell. The polymerizable compound (1) represented by the following formula was added to the nematic liquid crystal (MLC-6608) (manufactured by Merck Japan) by 100% by mass of the nematic liquid crystal (MLC-6608) by a vacuum injection method into the empty cell. Then, a liquid crystal in which the polymerizable compound (1) was mixed at 0.3% by mass was injected, and the injection port was sealed to obtain a liquid crystal cell.

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

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

  Since the response speed of the liquid crystal cell after irradiation with ultraviolet light was faster in the PSA cells obtained in any of the examples than in the liquid crystal cell before irradiation with ultraviolet light, it was confirmed that the orientation direction of the liquid crystal was controlled. . In addition, in each of the liquid crystal cells, it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) that the liquid crystals were uniformly oriented.

"Production of liquid crystal cell and evaluation of liquid crystal orientation (SC-PVA cell)"
The liquid crystal alignment agent (6) obtained by the method of Example 6 of the present invention, the liquid crystal alignment agent (9) obtained by the method of Example 9, and the liquid crystal alignment 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 alignment treatment agents at 2% by mass relative to 100% by mass of all polymer components in the liquid crystal alignment treatment agents, and the mixture is added at 25 ° C. for 4 hours. Stirred. Thereafter, the obtained liquid crystal alignment treatment agent was filtered under pressure through a membrane filter having a pore size of 1 μm, and washed with pure water and IPA. A substrate with an ITO electrode having a 10 × 10 mm pattern interval of 20 μm (length 40 mm × width 30 mm) , 0.7 mm in thickness) and spin-coated on the ITO surface of a substrate with 40 × 40 mm ITO electrodes (length 40 mm × width 30 mm, thickness 0.7 mm) at the center, and 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 thickness of 100 nm.

  These substrates with a liquid crystal alignment film were combined with the liquid crystal alignment film surface inside, with a 6 μm spacer interposed therebetween, and the periphery was adhered with a sealant to produce an empty cell. Nematic liquid crystal (MLC-6608) (manufactured by Merck Japan) was injected into the empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell.

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

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

  The SC-PVA cell obtained in any of the examples has a higher response speed of the liquid crystal cell after irradiation with ultraviolet light than the liquid crystal cell before irradiation with ultraviolet light, indicating that the alignment direction of the liquid crystal is controlled. confirmed. In addition, in each of the liquid crystal cells, it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) that the liquid crystals were uniformly oriented.

<Example 1>
S1 (8.17 g), K1 (0.18 g), NEP (3.92 g) were added to the polyamic acid solution (1) (10.0 g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 1. ) And PB (19.6 g) were added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a composition (1). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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 alignment agent (1), “evaluation of printability of composition and liquid crystal alignment agent (evaluation of pinhole)”, “evaluation of composition and liquid crystal alignment agent” Evaluation of printability (evaluation of coating film edge) "and" Evaluation of voltage holding ratio (VHR) (normal cell) ".

<Example 2>
S1 (16.8 g) and BCS (16.4 g) were added to a 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 the mixture was heated at 25 ° C. The mixture was stirred for 4 hours to obtain a composition (2). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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 alignment agent (2), “evaluation of printability of composition and liquid crystal alignment agent (evaluation of pinhole)”, “evaluation of composition and liquid crystal alignment agent” Evaluation of printability (evaluation of coating film edge) "and" Evaluation of voltage holding ratio (VHR) (normal cell) ".

<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 the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (3). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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 alignment agent (3), “evaluation of printability of composition and liquid crystal alignment agent (evaluation of pinhole)”, “evaluation of composition and liquid crystal alignment agent” Evaluation of printability (evaluation of coating film edge) "and" Evaluation of voltage holding ratio (VHR) (normal cell) ".

<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 the mixture was stirred at 70 ° C. for 24 hours to be dissolved. 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). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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 (evaluation of pinhole)" and "evaluation of voltage holding ratio (VHR)" (Normal cell) "and" Evaluation of inkjet coating properties of liquid crystal alignment treatment 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% by mass obtained by the synthesis method of Synthesis Example 5, and the mixture was heated at 25 ° C. The mixture was stirred for 4 hours to obtain a composition (5). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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 the liquid crystal alignment agent (5), “evaluation of printability of composition and liquid crystal alignment agent (evaluation of pinhole)”, “composition and liquid crystal alignment agent” Evaluation of printability (evaluation of coating film edge) "and" Evaluation of voltage holding ratio (VHR) (normal cell) ".

<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. BCS (12.0 g) was added to this solution, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (6). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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)", "evaluation of composition and liquid crystal aligning agent" "Evaluation of printability (evaluation of coating film edge)", "Evaluation of voltage holding ratio (VHR) (normal cell)", "Evaluation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)" and "Evaluation of liquid crystal cell" Production and Evaluation of Liquid Crystal Alignment (SC-PVA Cell) ".

<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 the mixture was stirred at 70 ° C. for 24 hours to be dissolved. To this solution was added PB (22.8 g), and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (7). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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 (evaluation of pinhole)" and "evaluation of voltage holding ratio (VHR)" (Normal cell) "and" Evaluation of inkjet coating properties of liquid crystal alignment treatment 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 the mixture was stirred at 70 ° C. for 24 hours to be dissolved. 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). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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)", "evaluation of composition and liquid crystal aligning agent" Evaluation of printability (evaluation of coating film edge) "and" Evaluation of voltage holding ratio (VHR) (normal cell) ".

<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 the mixture was stirred at 70 ° C. for 24 hours to be dissolved. To this solution, PB (10.0 g) and DME (2.51 g) were added, and the mixture was stirred at 40 ° C. for 5 hours to obtain a composition (9). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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 alignment agent (9), “evaluation of printability of composition and liquid crystal alignment agent (evaluation of pinhole)”, “composition and liquid crystal alignment agent” "Evaluation of printability (evaluation of coating film edge)", "Evaluation of voltage holding ratio (VHR) (normal cell)", "Evaluation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)" and "Evaluation of liquid crystal cell" Production and Evaluation of Liquid Crystal Alignment (SC-PVA Cell) ".

<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 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). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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 aligning agent (10), “evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)”, “evaluation of composition and liquid crystal aligning agent” Evaluation of printability (evaluation of coating film edge) "and" Evaluation of voltage holding ratio (VHR) (normal cell) ".

<Example 11>
To the polyimide powder (10) (1.60 g) obtained by the synthesis method of Synthesis Example 10, S1 (3.76 g) and NEP (10.0 g) were added 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). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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 obtained composition (11) and liquid crystal aligning agent (11), “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) ".

<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 the mixture was stirred at 70 ° C. for 24 hours to be dissolved. Was. BCS (7.99 g) was added to this solution, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (12). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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)”, “evaluation of composition and liquid crystal aligning agent” Evaluation of printability (evaluation of coating film edge) "and" Evaluation of voltage holding ratio (VHR) (normal cell) ".

<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 the mixture was stirred at 70 ° C. for 24 hours to be dissolved. BCS (5.17 g) and PB (7.76 g) were added to this solution, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (13). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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 aligning agent (13), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "evaluation of composition and liquid crystal aligning agent" Evaluation of printability (evaluation of coating film edge) "and" Evaluation of voltage holding ratio (VHR) (normal cell) ".

<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 the mixture was dissolved by stirring at 70 ° C. for 24 hours. PB (12.5 g) was added to this solution, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (14). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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)", "evaluation of composition and liquid crystal aligning agent" "Evaluation of printability (evaluation of coating film edge)", "Evaluation of voltage holding ratio (VHR) (normal cell)", "Evaluation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)" and "Evaluation of liquid crystal cell" Production and Evaluation of Liquid Crystal Alignment (SC-PVA Cell) ".

<Example 15>
To the polyimide powder (13) (1.70 g) obtained by the synthesis method of Synthesis Example 13, S1 (4.69 g) and γ-BL (18.8 g) were added and dissolved by stirring at 70 ° C. for 24 hours. Was. 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 (15). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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 alignment agent (15), "evaluation of printability of composition and liquid crystal alignment agent (evaluation of pinhole)", and evaluation of voltage holding ratio (VHR) (Normal cell) "and" Evaluation of inkjet coating properties of liquid crystal alignment treatment 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 the mixture was stirred at 70 ° C. for 24 hours to be dissolved. K1 (0.08 g) and BCS (10.0 g) were added to this solution, and the mixture was stirred at 40 ° C. for 5 hours to obtain a composition (16). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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 aligning agent (16), “evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)”, “evaluation of composition and liquid crystal aligning agent” Evaluation of printability (evaluation of coating film edge) "and" Evaluation of voltage holding ratio (VHR) (normal cell) ".

<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 the mixture was dissolved by stirring at 70 ° C. for 24 hours. Was. To this solution, K1 (0.08 g), BCS (2.51 g) and PB (5.01 g) were added, and the mixture was stirred at 40 ° C. for 5 hours to obtain a composition (17). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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)”, “evaluation of composition and liquid crystal aligning agent” Evaluation of printability (evaluation of coating film edge) "and" Evaluation of voltage holding ratio (VHR) (normal cell) ".

<Example 18>
To the polyimide powder (16) (1.70 g) obtained by the synthesis method of Synthesis Example 16, S1 (2.66 g) and NEP (10.7 g) were added and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (5.33 g) and PB (7.99 g) were added, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (18). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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)”, “evaluation of composition and liquid crystal aligning agent” Evaluation of printability (evaluation of coating film edge) "and" Evaluation of voltage holding ratio (VHR) (normal cell) ".

<Example 19>
To the polyimide powder (17) (1.60 g) obtained by the synthesis method of Synthesis Example 17, S1 (8.77 g) and NMP (5.01 g) were added and dissolved by stirring at 70 ° C. for 24 hours. BCS (8.77 g) and EC (2.51 g) were added to this solution, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (19). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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)”, “evaluation of composition and liquid crystal aligning agent” Evaluation of printability (evaluation of coating film edge) "and" Evaluation of voltage holding ratio (VHR) (normal cell) ".

<Example 20>
To the polyimide powder (18) (1.60 g) obtained by the synthesis method of Synthesis Example 18, S1 (10.0 g) and NEP (3.76 g) were added 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). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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)", "Evaluation of composition and liquid crystal aligning agent" Evaluation of printability (evaluation of coating film edge) "and" Evaluation of voltage holding ratio (VHR) (normal cell) ".

<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% by mass obtained by the synthesis method of Synthesis Example 19, and the mixture was heated at 25 ° C. The mixture was stirred for 4 hours to obtain a composition (21). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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)”, “evaluation of composition and liquid crystal aligning agent” Evaluation of printability (evaluation of coating film edge) "and" Evaluation of voltage holding ratio (VHR) (normal cell) ".

<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. BCS (12.0 g) was added to this solution, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (22). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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)”, “evaluation of composition and liquid crystal aligning agent” Evaluation of printability (evaluation of coating film edge) "and" Evaluation of voltage holding ratio (VHR) (normal cell) ".

<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% by mass obtained by the synthesis method of Synthesis Example 20. The mixture was stirred for 4 hours to obtain a composition (23). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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)", "evaluation of composition and liquid crystal aligning agent" Evaluation of printability (evaluation of coating film edge) "and" Evaluation of voltage holding ratio (VHR) (normal cell) ".

<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 (11.6 g) was added to this solution, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (24). No abnormalities such as turbidity and generation of precipitates were observed in this composition, 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)”, “evaluation of composition and liquid crystal aligning agent” Evaluation of printability (evaluation of coating film edge) "and" Evaluation of voltage holding ratio (VHR) (normal cell) ".

  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 in which pinholes are not generated as compared with the polyimide film obtained from the composition of the comparative example. In addition, the linearity of the end of the polyimide film was high, and the rise of the end was small. Specifically, a comparison between a composition using the specific solvent as the component (A) of the present invention and a composition not using the specific solvent, that is, a comparison between Example 2 and Comparative Example 1, and Example 3 And Comparative Example 2; Example 5 and Comparative Example 3; and Example 6 and Comparative Example 4. In these comparative examples, as compared with the corresponding examples, the number of pinholes on the polyimide film was larger, and further, the coating property of the coating film edge of the polyimide film was poor. Further, since the compositions of these examples were also used for evaluation as a liquid crystal alignment treatment agent, the results of the examples using these compositions were regarded as the results of the liquid crystal alignment treatment agent.

  In addition, the liquid crystal alignment film obtained from the liquid crystal alignment agent using the composition of the present invention is compared with the liquid crystal alignment film obtained from the liquid crystal alignment agent of the comparative example, and has a higher firing property when producing the liquid crystal alignment film. Even at a low temperature, a result excellent in the voltage holding ratio (also referred to as VHR) in the liquid crystal display element was obtained. Specifically, a comparison between a liquid crystal alignment treatment agent using a specific solvent as the component (A) of the present invention and a liquid crystal alignment treatment 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 a high-temperature bath was low, that is, the decrease in VHR due to high temperature was large.

  The composition of the present invention can suppress the occurrence of pinholes due to repelling when forming a polyimide film, and can obtain a polyimide film having excellent coating properties at the end. At this time, a polyimide film can be produced even by firing at a low temperature.

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

Claims (20)

Component (A): The following formula [A]:

(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) A solvent represented by :
( B) component: at least one polymer selected from a polyimide precursor and a polyimide ;
and
A composition containing, as the component (C), at least one solvent selected from N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone , wherein the component (A) is included in the composition. A composition that accounts for 5 to 70% by mass of the entire solvent (unless the component (A) accounts for 60 mol% or more of the entire solvent contained in the composition). The solvent of the component (A) has the following formula [A-1]:

The composition according to claim 1, which is a solvent represented by the formula: 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. _{(CH 3) -, - N} (CH 3) CO -, - COO- and -OCO- represents at least one bond group selected from, ^{Y 2} is a single bond or _{- (CH 2) b - (} b Represents an integer of 1 to 15), and Y ³ represents a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO. - represents at least one bond group selected from and -OCO-, Y ⁴ is a benzene ring, a carbon having at least one divalent cyclic group ring or steroid skeleton, chosen from the cyclohexane ring and heterocyclic ring A bivalent organic group represented by the formulas 17 to 51, wherein any hydrogen atom on the cyclic group is Number 1-3 alkyl group, an alkoxyl group having 1 to 3 carbon atoms, a 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 any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, 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. Contained 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 Represents at least one kind of a binding 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)
3. A polyimide precursor obtained by using a diamine compound having at least one kind of structure selected from the following structures as a part of a raw material, and at least one kind of polymer selected from polyimide. Composition. A diamine compound having a structure represented by the formulas [1-1] and [1-2] is represented by the following formula [1a]:

(Wherein, Y represents at least one kind of 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 according to claim 3, which is a diamine compound represented by the formula:   The polymer of the component (B) is a polyimide precursor or a polyimide obtained by using 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 a 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]:

Ａ In the formula, A is 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.) The composition according to claim 5, wherein m is a diamine compound represented by｝, which is an integer of 1 to 4. The polymer of the component (B) is represented by the following formula [3a]:

(In the formula, B ¹ represents —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ) — and —N (CH ₃ ) CO— represents at least one kind of a bonding group, and B ² represents a single bond, a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a non-aromatic cyclic hydrocarbon. of represents at least one selected from divalent groups of the divalent group and an aromatic hydrocarbon, ^{B 3} represents a single _{bond, -O -, - NH -,} - N (CH 3) -, - CONH- , -NHCO -, - COO -, - OCO -, - CON (CH 3) -, - from (m is an integer of 1 to 5) - _{N (CH} 3) CO- and -O _{(CH 2)} m 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, wherein the composition is at least one polymer selected from a polyimide precursor and a polyimide using a diamine compound represented by the formula (1) as a part of the raw material. In 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, and n The composition according to claim 7, wherein is a diamine compound showing 1. The polymer of the component (B) is represented by the following formula [4]:

ＺIn the formula, Z is 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 each independently represent , A hydrogen atom or a methyl group)
Represents a group having at least one structure selected from
The composition according to any one of claims 1 to 8, wherein the composition is at least one polymer selected from a polyimide precursor and a polyimide using a tetracarboxylic acid component represented by the following formula as a part of the 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 esters and polyimides. As the 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, and in the formula [D-2], D ² Represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-3], D ³ Represents an alkyl group having 1 to 4 carbon atoms)
The composition according to any one of claims 1 to 10, comprising at least one solvent selected from solvents represented by the following formula: In the composition, a crosslinkable compound 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 The composition according to any one of claims 1 to 11, comprising a compound and at least one crosslinkable compound selected from crosslinkable compounds having a polymerizable unsaturated bond. The composition according to claim 1, wherein the component (C) accounts for 40 to 80% by mass of the entire solvent contained in the composition. The composition according to any one of claims 11 to 13, wherein the component (D) accounts for 1 to 50% by mass of the entire solvent contained in the composition.   The composition according to any one of claims 1 to 14, wherein the component (B) accounts for 0.1% to 30% by mass of the composition. A polyimide film obtained from the composition according to claim 1. A liquid crystal alignment treating agent obtained from the composition according to claim 1. A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to claim 17. A liquid crystal alignment film obtained by an inkjet method using the liquid crystal alignment treatment agent according to claim 17. A liquid crystal display device comprising the liquid crystal alignment film according to claim 18.

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