JP2019007988A - Liquid crystal aligning agent for forming liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element using the same - Google Patents

Abstract

To provide a liquid crystal aligning agent showing high solubility and causing no in-plane unevenness when a coating film for a liquid crystal alignment film is printed by an inkjet process, and to provide a liquid crystal alignment film formed by using the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal alignment film.SOLUTION: The liquid crystal aligning agent comprises at least one polymer selected from the group of a polyamic acid and its derivatives, and a solvent, in which the solvent comprises 4-methyl-2-pentanol.SELECTED DRAWING: None

Description

The present invention relates to a liquid crystal alignment agent containing polyamic acid or a derivative thereof and a specific compound, a liquid crystal alignment film formed using the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.

Various display devices such as personal computer monitors, LCD TVs, video camera viewfinders, and projection displays, as well as optoelectronic devices such as optical printer heads, optical Fourier transform elements, and light valves, have been commercialized today. Generally used liquid crystal display elements are display elements using nematic liquid crystals. As a display system of the nematic liquid crystal display element, a TN (Twisted Nematic) mode and an STN (Super Twisted Nematic) mode are well known. In recent years, in order to improve the narrow viewing angle, which is one of the problems of these modes, a TN liquid crystal display device using an optical compensation film, MVA (Multi -domain Vertical Alignment) mode, IPS (In-Plane Switching) mode of horizontal electric field method, FFS (Fringe Field Switching) mode, etc. have been proposed and put to practical use.

The development of the technology of the liquid crystal display element is achieved not only by simply improving these driving methods and element structures but also by improving the components used in the elements. Among the components used in liquid crystal display elements, the liquid crystal alignment film is one of important materials related to display quality, and the performance of the alignment film can be improved with the improvement in quality of the liquid crystal display element. It is becoming important.

The liquid crystal alignment film is formed from a liquid crystal aligning agent. The liquid crystal aligning agent mainly used at present is a solution (varnish) in which polyamic acid, polyamic acid ester, polyimide, or the like is dissolved in an organic solvent. After this solution is applied to the substrate, the polyimide liquid crystal alignment film is formed by film formation by means such as heating. After film formation, an orientation treatment suitable for the above-described display mode is performed as necessary.

Industrially, a rubbing method that is simple and capable of high-speed processing of a large area is widely used as an alignment processing method. The rubbing method is a process of rubbing the surface of the liquid crystal alignment film in one direction using a cloth in which fibers of nylon, rayon, polyester, or the like are planted, and this makes it possible to obtain uniform alignment of liquid crystal molecules. However, problems such as dust generation by static rubbing and generation of static electricity have been pointed out. Although the alignment treatment method by rubbing is still used in the manufacturing process of liquid crystal display elements, development of an alignment treatment method that replaces this has been actively conducted in recent years.

A photo alignment treatment method in which alignment treatment is performed by irradiating light is attracting attention as an alignment treatment method replacing the rubbing method. Many alignment mechanisms such as a photodecomposition method, a photoisomerization method, a photodimerization method, and a photocrosslinking method have been proposed for the photoalignment treatment method (see, for example, Non-Patent Document 1, Patent Documents 1 and 2). The photo-alignment method has higher uniformity of alignment than the rubbing method, and it is a non-contact alignment method, so the film is not damaged and causes the display defects of liquid crystal display elements such as dust generation and static electricity. There are advantages such as reduction.

On the other hand, in order to apply a liquid crystal aligning agent (varnish) on a substrate, an industrial printing method is used. Examples of the printing method of the liquid crystal aligning agent include flexographic printing and inkjet printing. Ink jet printing is becoming mainstream for printing on large-area substrates of the sixth generation or higher.

However, when the varnish is ejected as droplets onto the substrate using the ink jet method to form a coating film, there may be a problem that unevenness occurs in the surface along the scanning direction of the outlet (nozzle). The causes of this in-plane unevenness are as follows: (1) The droplets are not sufficiently spread and spread on the substrate, (2) the leveling properties of the discharged droplets are poor, and the solute component (solid content) is unevenly distributed. It is conceivable that (3) the solvent having good wettability is quickly dried and the solution applied during drying is degenerated (see, for example, Patent Document 3).

Under these circumstances, the use of diisobutyl ketone that imparts a low surface tension is disclosed as a solvent used for inkjet printing in order to solve in-plane unevenness (see, for example, Patent Document 4).

However, since the solubility of the polymer in diisobutyl ketone is low, white turbidity and solid content are likely to occur. Such white turbidity and solid content precipitation cause clogging of the nozzles of the ejection head.

JP-A-9-297313 JP-A-10-251646 JP2009-063797 International Publication 2009/107406

Liquid Crystal, Vol. 3, No. 4, 262 pages, 1999

An object of the present invention is to provide a liquid crystal aligning agent that is used when printing a coating film for a liquid crystal alignment film by an ink jet method and that does not cause polymer solids to precipitate and does not cause in-plane unevenness in the coating film. is there. Another object of the present invention is to provide a liquid crystal alignment film formed using the liquid crystal alignment agent, and further a liquid crystal display element having the liquid crystal alignment film.

As a result of intensive studies, the inventors of the present invention have a high solubility of a polymer that forms an alignment film, which will be described later, a good wet spread, and a solvent that can prevent in-plane unevenness of the coating film “4-methyl-2-pentanol” The present invention was completed.

The present invention comprises the following.
[1] A liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyamic acid and derivatives thereof and a solvent, wherein the solvent contains 4-methyl-2-pentanol.

[2] The liquid crystal aligning agent according to the item [1], wherein the proportion of 4-methyl-2-pentanol in the solvent is 0.1 to 20% by weight.

[3] At least one selected from the group consisting of N-methyl-2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone as a good solvent in the solvent. The liquid crystal aligning agent as described in the item [1] or [2].

[4] The solvent contains at least one selected from the group consisting of butyl cellosolve, 1-butoxy-2-propanol, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol butyl methyl ether as a poor solvent. ] The liquid crystal aligning agent of any one of [3].

[5] Any one of [1] to [4], wherein the proportion of the good solvent in the solvent is 20 to 89% by weight, and the proportion of the poor solvent is 10 to 60% by weight with respect to the total solvent weight. A liquid crystal aligning agent according to item.

[6] A method for forming a liquid crystal alignment film, comprising a step of applying the liquid crystal aligning agent according to any one of [1] to [5] to a substrate by an inkjet method.

[7] A method for producing a liquid crystal alignment film, comprising: a step of applying the liquid crystal alignment agent according to any one of [1] to [5]; and a step of irradiating the coating film with ultraviolet rays.

[8] A pair of opposed substrates, an electrode group formed on one or both of the opposed surfaces of each of the pair of substrates, a plurality of active elements connected to the electrode group, In a method for manufacturing a liquid crystal display element, comprising: a liquid crystal alignment film formed on opposing surfaces of each of the pair of substrates; and a liquid crystal layer formed between the pair of substrates.
The said liquid crystal aligning film is a manufacturing method of the liquid crystal display element formed by the method as described in the item [6] or [7].

The liquid crystal aligning agent using a solvent containing 4-methyl-2-pentanol having high polymer solubility can improve the wetting spread and prevent in-plane unevenness of the coating film. The liquid crystal aligning agent of the present invention is particularly suitable for inkjet printing applications.

The main component of the present invention is a liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyamic acid and derivatives thereof and a solvent, wherein the solvent contains 4-methyl-2-pentanol. It is a liquid crystal aligning agent. The solvent used for the liquid crystal aligning agent of this invention is divided into the following three groups, the good solvent, the poor solvent, and the 3rd solvent.

The good solvent is selected from the group of polar organic solvents in which the polymer forming the alignment film has high solubility.

Specific examples of such polar organic solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N, N-dimethylacetamide, Lactones such as dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide, and γ-butyrolactone.

Among these solvents, the solvents in which the polymer has particularly high solubility are N-methyl-2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, and N-ethyl-2-pyrrolidone. .

The poor solvent is characterized by low solubility of the polymer but relatively low surface energy of less than 30 mN / m and good paintability to the substrate. Specific examples include alcohols and ethers.

Specific examples of alcohols include butyl cellosolve (ethylene glycol monobutyl ether), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, 1- Butoxy-2-propanol, ethyl lactate, methyl lactate, propyl lactate.

Specific examples of ethers are ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol ethyl propyl ether, diethylene glycol butyl methyl ether, diethylene glycol propyl methyl ether, diethylene glycol butyl ethyl ether, propylene glycol. Monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl acetate Le acetate, propylene glycol monomethyl ether propionate.

Among these, butyl cellosolve, 1-butoxy-2-propanol, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol butyl methyl ether are solvents having a relatively small surface energy and good wettability to the substrate.

The third solvent is a solvent that improves the spreadability of the solution. By mixing this solvent, it is possible to prevent uneven coating.

Specific examples of such a solvent include diisobutyl ketone, 4-methyl-2-pentanol, and dipentyl ether. Among these, diisobutyl ketone and 4-methyl-2-pentanol are solvents that are more excellent in solution spreading. Furthermore, considering the solubility of the polymer, 4-methyl-2-pentanol is particularly preferable.

Since these three types of solvents have different characteristics, it is important to have the constituent ratios described below.

The ratio of the good solvent to the total solvent is 20 to 89% by weight, the preferable ratio is 30 to 84% by weight, and the more preferable ratio is 45 to 75% by weight.

The good solvent is used in a proportion of 20% by weight or more with respect to the total solvent in order to prevent the precipitation of the polymer in the solution, clogging of the nozzles and heads of the ink jet apparatus, and the occurrence of in-plane unevenness of the coating film. On the contrary, in order to prevent deterioration of printability due to a decrease in the amount of the poor solvent, it is used at a ratio of 89% by weight or less with respect to the total solvent.

The ratio of the poor solvent to the total solvent is 10 to 60% by weight, the preferable ratio is 15 to 50% by weight, and the more preferable ratio is 20 to 45% by weight.

The poor solvent is used in a proportion of 10% by weight or more based on the total solvent weight in order to prevent the occurrence of liquid shrinkage due to printing failure or evaporation from the edge portion. Conversely, in order to prevent polymer precipitation in the solution as the proportion of the good solvent decreases, the resulting clogging of the nozzles and heads of the ink jet device, and the occurrence of in-plane unevenness of the coating film, It is used in a proportion of 60% by weight or less based on the solvent weight.

A ratio of the third solvent to the total solvent weight is 0.1 to 20% by weight, a preferable ratio is 0.1 to 18% by weight, and a more preferable ratio is 0.1 to 15% by weight.

The third solvent is used in a proportion of 0.1% by weight or more with respect to the total solvent in order to prevent deterioration of the liquid spreading property and generation of unevenness in the head running direction. On the contrary, in order to prevent the edge linearity from deteriorating due to excessive spreading of the liquid, it is used at a ratio of 20% by weight or less based on the total solvent.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of this invention is a reaction product of at least 1 chosen from tetracarboxylic dianhydride and its derivative (s), and diamine. The derivative of tetracarboxylic dianhydride is tetracarboxylic acid diester or tetracarboxylic acid diester dichloride. A polyamic acid derivative is a component that dissolves in a solvent when a liquid crystal aligning agent described later containing a solvent is used. When the liquid crystal aligning agent is used as a liquid crystal aligning film, a liquid crystal aligning film containing polyimide as a main component. Is a component capable of forming Examples of such polyamic acid derivatives include soluble polyimides, polyamic acid esters, and polyamic acid amides. More specifically, 1) polyimide in which all amino acids and carboxyls of polyamic acid are subjected to a dehydration ring-closing reaction, 2) Partially dehydrated ring-closing partial polyimide, 3) Polyamic acid ester in which carboxyl of polyamic acid is converted to ester, 4) Part of acid dianhydride contained in tetracarboxylic dianhydride compound is organic dicarboxylic Examples thereof include polyamic acid-polyamide copolymers obtained by reacting with an acid, and 5) polyamideimide obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closing reaction. One type of polymer may be sufficient as the said polyamic acid and its derivative (s), and 2 or more types may be sufficient as it. The polyamic acid and its derivative may be a polymer having a structure of a reaction product of tetracarboxylic dianhydride and diamine, and other raw materials may be used except for the reaction of tetracarboxylic dianhydride and diamine. It may contain reaction products from other reactions.

The polyamic acid ester can be synthesized by reacting the above-mentioned polyamic acid with a hydroxyl group-containing compound, halide, epoxy group-containing compound or the like, or a tetracarboxylic acid diester or tetracarboxylic acid derived from tetracarboxylic dianhydride. It can synthesize | combine by the method of synthesize | combining by making acid diester dichloride and diamine react. Tetracarboxylic acid diesters derived from tetracarboxylic dianhydride can be obtained, for example, by reacting tetracarboxylic dianhydride with 2 equivalents of alcohol to cause ring opening. Tetracarboxylic acid diester dichloride is obtained by reacting with tetracarboxylic acid diester. It can be obtained by reacting a diester with 2 equivalents of a chlorinating agent (for example, thionyl chloride). The polyamic acid ester may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist.

The tetracarboxylic dianhydride used for producing the polyamic acid and its derivative contained in the liquid crystal aligning agent of the present invention will be described. The tetracarboxylic dianhydride used in the present invention can be selected without limitation from known tetracarboxylic dianhydrides. Such tetracarboxylic dianhydrides include aromatic systems (including heteroaromatic ring systems) in which dicarboxylic acid anhydrides are directly bonded to aromatic rings, and aliphatic groups in which dicarboxylic acid anhydrides are not directly bonded to aromatic rings. It may belong to any group of systems (including heterocyclic ring systems). Tetracarboxylic dianhydride may react one compound with diamine, or may mix two or more compounds and react with diamine. As used herein, “tetracarboxylic dianhydride” refers not only to one compound, but may also include a mixture of two or more compounds in its meaning.

Tetracarboxylic dianhydrides can be broadly classified into tetracarboxylic dianhydrides having a photoreactive structure and tetracarboxylic dianhydrides having no photoreactive structure.

As a suitable example of the tetracarboxylic dianhydride having no photoreactive structure, from the viewpoint of easy availability of raw materials, ease of polymer polymerization, and electrical properties of the film, the formula (AN-I) to And tetracarboxylic dianhydride represented by (AN-VII).

In the formulas (AN-I), (AN-IV) and (AN-V), X is independently a single bond or —CH ₂ —. In Formula (AN-II), G is a single bond, alkylene having 1 to 20 carbons, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or —C. (CF ₃ ) ₂ —. In the formulas (AN-II) to (AN-IV), Y is independently one selected from the following group of trivalent groups, and the bond is connected to any carbon. At least one hydrogen may be replaced with methyl, ethyl or phenyl.

In the formulas (AN-III) to (AN-V), the ring A ¹⁰ is a monocyclic hydrocarbon group having 3 to ¹⁰ carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms. At least one hydrogen of the group may be replaced by methyl, ethyl or phenyl, and the bond on the ring is connected to any carbon constituting the ring, and the two bonds are the same carbon You may connect to. In the formula (AN-VI), X ¹⁰ is independently alkylene having 2 to 6 carbon atoms, Me represents methyl, and Ph represents phenyl. In the formula (AN-VII), G ¹⁰ is independently —O—, —COO— or —OCO—, and r is independently 0 or 1.

More specifically, tetracarboxylic dianhydrides represented by the following formulas (AN-1) and (AN-3) to (AN-16-15) can be mentioned.

式（ＡＮ−１）において、Ｇ^１１は単結合、炭素数１〜１２のアルキレン、１，４−フェニレン、または１，４−シクロヘキシレンである。Ｘ^１１は独立して単結合または−ＣＨ_２−である。Ｇ^１２は独立して下記の３価の基のどちらかである。

Ｇ^１２が＞ＣＨ−であるとき、＞ＣＨ−の水素は−ＣＨ_３に置き換えられてもよい。Ｇ^１２が＞Ｎ−であるとき、Ｇ^１１が単結合および−ＣＨ_２−であることはなく、Ｘ^１１は単結合であることはない。そしてＲ^１１は独立して水素または−ＣＨ_３である。 [Tetracarboxylic dianhydride represented by the formula (AN-1)]

In the formula (AN-1), G ¹¹ is a single bond, alkylene having 1 to 12 carbons, 1,4-phenylene, or 1,4-cyclohexylene. X ¹¹ is independently a single bond or —CH ₂ —. G ¹² is independently one of the following trivalent groups.

When G ¹² is> CH—, the hydrogen of> CH— may be replaced with —CH ₃ . When G ¹² is> N—, G ¹¹ is not a single bond and —CH ₂ —, and X ¹¹ is not a single bond. R ¹¹ is independently hydrogen or —CH ₃ .

式（ＡＮ−１−２）および（ＡＮ−１−１４）において、ｍは１〜１２の整数である。 Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formula.

In the formulas (AN-1-2) and (AN-1-14), m is an integer of 1 to 12.

式（ＡＮ−３）において、環Ａ^１１はシクロヘキサン環またはベンゼン環である。 [Tetracarboxylic dianhydride represented by the formula (AN-3)]

In the formula (AN-3), the ring A ¹¹ is a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include compounds represented by the following formula.

式（ＡＮ−４）において、Ｇ^１３は単結合、−（ＣＨ_２）_ｍ−、−Ｏ−、−Ｓ−、−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−ＣＯ−、−Ｃ（ＣＦ_３）_２−、または下記の式（Ｇ１３−１）で表される２価の基であり、ｍは１〜１２の整数である。環Ａ^１１は独立してシクロヘキサン環またはベンゼン環である。Ｇ^１３は環Ａ^１１の任意の位置に結合してよい。

式（Ｇ１３−１）において、Ｇ^１３ａおよびＧ^１３ｂは独立して、単結合、−Ｏ−または−ＮＨＣＯ−で表される２価の基である。フェニレンは、１，４−フェニレンおよび１，３−フェニレンが好ましい。 [Tetracarboxylic dianhydride represented by the formula (AN-4)]

In the formula (AN-4), G ¹³ is a single bond, — (CH ₂ ) _m —, —O—, —S—, —C (CH ₃ ) ₂ —, —SO ₂ —, —CO—, —C. (CF ₃ ) ₂ — or a divalent group represented by the following formula (G13-1), and m is an integer of 1 to 12. Ring A ¹¹ is independently a cyclohexane ring or a benzene ring. G ¹³ may be bonded to any position of ring A ¹¹ .

In the formula (G13-1), G ^13a and G ^13b are each independently a single bond, a divalent group represented by —O— or —NHCO—. The phenylene is preferably 1,4-phenylene and 1,3-phenylene.

式（ＡＮ−４−１７）において、ｍは１〜１２の整数である。

Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formula.

In formula (AN-4-17), m is an integer of 1-12.

式（ＡＮ−５）において、Ｒ^１１は独立して水素、または−ＣＨ_３である。ベンゼン環を構成する炭素原子に結合位置が固定されていないＲ^１１は、ベンゼン環における結合位置が任意であることを示す。 [Tetracarboxylic dianhydride represented by the formula (AN-5)]

In formula (AN-5), R ¹¹ is independently hydrogen or —CH ₃ . R ¹¹ whose bond position is not fixed to the carbon atom constituting the benzene ring indicates that the bond position in the benzene ring is arbitrary.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-5) include compounds represented by the following formula.

式（ＡＮ−６）において、Ｘ^１１は独立して単結合または−ＣＨ_２−である。Ｘ^１２は独立して−ＣＨ_２−、−ＣＨ_２ＣＨ_２−または−ＣＨ＝ＣＨ−である。ｎは１または２である。 [Tetracarboxylic dianhydride represented by the formula (AN-6)]

In the formula (AN-6), X ¹¹ is independently a single bond or —CH ₂ —. X ¹² is independently —CH ₂ —, —CH ₂ CH ₂ — or —CH═CH—. n is 1 or 2.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-6) include compounds represented by the following formula.

式（ＡＮ−７）において、Ｘ^１１は単結合または−ＣＨ_２−である。 [Tetracarboxylic dianhydride represented by the formula (AN-7)]

In the formula (AN-7), X ¹¹ is a single bond or —CH ₂ —.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-7) include compounds represented by the following formula.

式（ＡＮ−８）において、Ｘ^１１は単結合または−ＣＨ_２−である。Ｒ^１２は水素、−ＣＨ_３、−ＣＨ_２ＣＨ_３、またはフェニルであり、環Ａ^１２はシクロヘキサン環またはシクロヘキセン環である。 [Tetracarboxylic dianhydride represented by the formula (AN-8)]

In the formula (AN-8), X ¹¹ is a single bond or —CH ₂ —. R ¹² is hydrogen, —CH ₃ , —CH ₂ CH ₃ , or phenyl, and ring A ¹² is a cyclohexane ring or a cyclohexene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-8) include compounds represented by the following formula.

式（ＡＮ−９）において、ｒは独立して０または１である。 [Tetracarboxylic dianhydride represented by the formula (AN-9)]

In the formula (AN-9), r is independently 0 or 1.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-9) include compounds represented by the following formula.

[Tetracarboxylic dianhydrides represented by formula (AN-10-1) and formula (AN-10-2)]

式（ＡＮ−１１）において、環Ａ^１１は独立してシクロヘキサン環またはベンゼン環である。 [Tetracarboxylic dianhydride represented by the formula (AN-11)]

In the formula (AN-11), ring A ¹¹ is independently a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-11) include compounds represented by the following formula.

式（ＡＮ−１２）において、環Ａ^１１は独立してシクロヘキサン環またはベンゼン環である。 [Tetracarboxylic dianhydride represented by the formula (AN-12)]

In the formula (AN-12), ring A ¹¹ is independently a cyclohexane ring or a benzene ring.

As an example of the tetracarboxylic dianhydride represented by a formula (AN-12), the compound represented by a following formula can be mentioned.

式（ＡＮ−１３）において、Ｘ^１３は独立して炭素数２〜６のアルキレンであり、Ｐｈはフェニルを表す。 [Tetracarboxylic dianhydride represented by the formula (AN-13)]

In the formula (AN-13), X ¹³ is independently an alkylene having 2 to 6 carbon atoms, and Ph represents phenyl.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-13) include compounds represented by the following formula.

式（ＡＮ−１４）において、Ｇ^１４は独立して−Ｏ−、−ＣＯＯ−または−ＯＣＯ−であり、ｒは独立して０または１である。 [Tetracarboxylic dianhydride represented by the formula (AN-14)]

In the formula (AN-14), G ¹⁴ is independently —O—, —COO— or —OCO—, and r is independently 0 or 1.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-14) include compounds represented by the following formula.

式（ＡＮ−１５）において、ｗは１〜１０の整数である。 [Tetracarboxylic dianhydride represented by the formula (AN-15)]

In formula (AN-15), w is an integer of 1-10.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-15) include compounds represented by the following formula.

Examples of tetracarboxylic dianhydrides other than the above include the following compounds.

In the tetracarboxylic dianhydride having no photoreactive structure, suitable materials for improving each characteristic will be described.

When importance is attached to improving the orientation of the liquid crystal, compounds represented by the formulas (AN-1), (AN-3), and (AN-4) are preferred, and the formula (AN-1-2) , (AN-1-13), (AN-3-2), (AN-4-5), (AN-4-17) and (AN-4-29) are particularly preferred, In the formula (AN-1-2), m = 4 or 8 is preferable, and in the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is particularly preferable.

When importance is attached to improving the transmittance of the liquid crystal display element, among the above tetracarboxylic dianhydrides, the formulas (AN-1-1), (AN-1-2), (AN-3-) 1), (AN-4-17), (AN-4-30), (AN-5-1), (AN-7-2), (AN-10-1), (AN-16-3) And compounds represented by (AN-16-4) are preferred, and in formula (AN-1-2), m = 4 or 8 is preferred, and in formula (AN-4-17), m = 4 or 8 is preferred, and m = 8 is particularly preferred.

In the case where importance is attached to improving the VHR of the liquid crystal display element, among the above tetracarboxylic dianhydrides, the formulas (AN-1-1), (AN-1-2), (AN-3-1) ), (AN-4-17), (AN-4-30), (AN-7-2), (AN-10-1), (AN-16-1), (AN-16-3), And in the formula (AN-1-2), m = 4 or 8 is preferable, and in the formula (AN-4-17), m = 4. Or 8 is preferred, and m = 8 is particularly preferred.

Increasing the relaxation rate of residual charges (residual DC) in the alignment film by reducing the volume resistance value of the liquid crystal alignment film is an effective method for preventing burn-in. When importance is attached to this purpose, among the above tetracarboxylic dianhydrides, the formulas (AN-1-13), (AN-3-2), (AN-4-21), (AN-4- 29) and compounds represented by (AN-11-3) are preferred.

The diamine and dihydrazide used for producing the polyamic acid and derivatives thereof contained in the liquid crystal aligning agent of the present invention will be described. The diamine and dihydrazide used in the present invention can be selected without limitation from known diamines and dihydrazides. Diamine may react one compound with tetracarboxylic dianhydride, or may mix two or more compounds and react with tetracarboxylic dianhydride. As used herein, “diamine” refers not only to one compound but also to a mixture of two or more compounds. In the present specification, dihydrazide is also handled as “diamine”.

Similarly to tetracarboxylic dianhydrides, diamine compounds can be broadly classified into diamine compounds having a photoreactive structure and diamine compounds having no photoreactive structure. Diamines having no photoreactive structure can be classified into two types depending on the structure. That is, when a skeleton connecting two amino groups is viewed as a main chain, a group branched from the main chain, that is, a diamine having a side chain group and a diamine having no side chain group. This side chain group is a group having an effect of increasing the pretilt angle. The side chain group having such an effect needs to be a group having 3 or more carbon atoms. Specific examples include alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms, alkoxyalkyl having 3 or more carbon atoms, and A group having a steroid skeleton can be exemplified. A group having one or more rings, wherein the terminal ring has any one of alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms and alkoxyalkyl having 2 or more carbon atoms as a substituent; It has an effect as a side chain group. In the following description, a diamine having such a side chain group may be referred to as a side chain diamine. Such a diamine having no side chain group may be referred to as a non-side chain diamine.

By properly using the non-side chain diamine and the side chain diamine, it is possible to cope with the pretilt angle required for each. The side chain diamine is preferably used in combination so as not to impair the properties of the present invention. The side chain diamine and the non-side chain diamine are preferably selected and used for the purpose of improving the vertical alignment with respect to the liquid crystal, the voltage holding ratio, the image sticking property, and the alignment.

The non-side chain diamine will be described. Examples of diamines having no known side chain include diamines of the following formulas (DI-1) to (DI-16).

In the above formula (DI-1), G ²⁰ is —CH ₂ —, at least one —CH ₂ — may be replaced by —NH—, —O—, and m is an integer of 1-12. And at least one hydrogen of the alkylene may be replaced by -OH. In Formula (DI-3) and Formula (DI-5) to Formula (DI-7), G ²¹ is independently a single bond, —NH—, —NCH ₃ —, —O—, —S—, —S. _{-S -, - SO 2 -,} - CO -, - COO -, - CONCH 3 -, - CONH -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m _{-, - O- (CH 2)} m -O -, - N (CH 3) - (CH 2) k -N (CH 3) -, - (O-C 2 H 4) m -O -, - O —CH ₂ —C (CF ₃ ) ₂ —CH ₂ —O—, —O—CO— (CH ₂ ) _m —CO—O—, —CO—O— (CH ₂ ) _m —O—CO—, — _{(CH 2) m -NH- (CH} 2) m -, - CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m) k -NH -, - CO -C ₃ H _{6 - (NH-C 3 H 6} ) n -CO-, or -S- _{(CH 2)} a m -S-, m is an integer from 1 to 12 independently, k is independently 1-5 And n is 1 or 2. In formula (DI-4), s is an integer of 0-2 independently. In the formula (DI-6) and the formula (DI-7), G ²² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) _2- , -NH-, or alkylene having 1 to 10 carbon atoms. At least one hydrogen of the cyclohexane ring and the benzene ring in the formula (DI-2) to the formula (DI-7) is —F, —Cl, alkyl having 1 to 3 carbon atoms, —OCH ₃ , —OH, —CF. ₃ , —CO ₂ H, —CONH ₂ , —NHC ₆ H ₅ , phenyl, or benzyl, and in Formula (DI-4), at least one hydrogen of the cyclohexane ring and the benzene ring is It may be replaced with one selected from the group of groups represented by the following formula (DI-4-a) to formula (DI-4-e). A group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. The bonding position of —NH ₂ to the cyclohexane ring or the benzene ring is an arbitrary position excluding the bonding position of G ²¹ or G ²² .

式（ＤＩ−４−ａ）および式（ＤＩ−４−ｂ）において、Ｒ^２０は独立して水素または−ＣＨ_３である。

In Formula (DI-4-a) and Formula (DI-4-b), R ²⁰ is independently hydrogen or —CH ₃ .

式（ＤＩ−１１）において、ｒは０または１である。式（ＤＩ−８）〜式（ＤＩ−１１）において、環に結合する−ＮＨ_２の結合位置は、任意の位置である。

In the formula (DI-11), r is 0 or 1. In Formula (DI-8) to Formula (DI-11), the bonding position of —NH ₂ bonded to the ring is an arbitrary position.

In formula (DI-12), R ²¹ and R ²² are independently alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms. And w is an integer of 1-10. In the formula (DI-13), R ²³ is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or —Cl, p is independently an integer of 0 to 3, and q is It is an integer of 0-4. In formula (DI-14), ring B is monocyclic heteroaromatic, R ²⁴ is hydrogen, —F, —Cl, alkyl having 1 to 6 carbons, alkoxy, vinyl, alkynyl, and q is independently It is an integer of 0-4. In formula (DI-15), ring C is a monocycle containing a heteroatom. In the formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, and r is 0 or 1. A group whose bond position is not fixed to the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary. In Formula (DI-13) to Formula (DI-16), the bonding position of —NH ₂ bonded to the ring is an arbitrary position.

Specific examples of the following formulas (DI-1-1) to (DI-16-1) include diamines having no side chain of the above formula (DI-1) to formula (DI-16). it can.

式（ＤＩ−１−７）および式（ＤＩ−１−８）において、ｋは独立して、１〜３の整数である。 Examples of the diamine represented by the formula (DI-1) are shown below.

In Formula (DI-1-7) and Formula (DI-1-8), k is independently an integer of 1 to 3.

Examples of diamines represented by formula (DI-2) and formula (DI-3) are shown below.

Examples of the diamine represented by the formula (DI-4) are shown below.

式（ＤＩ−５−１）において、ｍは１〜１２の整数である。

式（ＤＩ−５−１）、式（ＤＩ−５−１２）および式（ＤＩ−５−１３）において、ｍは１〜１２の整数である。

式（ＤＩ−５−１６）において、ｖは１〜６の整数である。

式（ＤＩ−５−３０）において、ｋは１〜５の整数である。

式（ＤＩ−５−３５）〜式（ＤＩ−５−３７）、および式（ＤＩ−５−３９）において、ｍは独立して１〜１２の整数であり、式（ＤＩ−５−３８）および式（ＤＩ−５−３９）において、ｋは独立して１〜５の整数であり、式（ＤＩ−５−４０）において、ｎは１または２の整数である。 Examples of the diamine represented by the formula (DI-5) are shown below.

In formula (DI-5-1), m is an integer of 1-12.

In Formula (DI-5-1), Formula (DI-5-12), and Formula (DI-5-13), m is an integer of 1-12.

In the formula (DI-5-16), v is an integer of 1 to 6.

In the formula (DI-5-30), k is an integer of 1 to 5.

In formula (DI-5-35) to formula (DI-5-37) and formula (DI-5-39), m is independently an integer of 1 to 12, and formula (DI-5-38) In the formula (DI-5-39), k is independently an integer of 1 to 5, and in the formula (DI-5-40), n is an integer of 1 or 2.

Examples of the diamine represented by the formula (DI-6) are shown below.

式（ＤＩ−７−３）および式（ＤＩ−７−４）において、ｍは独立して１〜１２の整数であり、ｎは独立して１または２である。

式（ＤＩ−７−１２）において、ｍは１〜１２の整数である。 Examples of the diamine represented by the formula (DI-7) are shown below.

In formula (DI-7-3) and formula (DI-7-4), m is independently an integer of 1 to 12, and n is independently 1 or 2.

In formula (DI-7-12), m is an integer of 1-12.

Examples of the diamine represented by the formula (DI-8) are shown below.

Examples of the diamine represented by the formula (DI-9) are shown below.

Examples of the diamine represented by the formula (DI-10) are shown below.

Examples of the diamine represented by the formula (DI-11) are shown below.

Examples of the diamine represented by the formula (DI-12) are shown below.

Examples of the diamine represented by the formula (DI-13) are shown below.

Examples of the diamine represented by the formula (DI-14) are shown below.

Examples of the diamine represented by the formula (DI-15) are shown below.

Examples of the diamine represented by the formula (DI-16) are shown below.

Dihydrazide will be described. Examples of the dihydrazide having no known side chain include the following formulas (DIH-1) to (DIH-3).

In the formula (DIH-1), G ²⁵ represents a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or — C (CF ₃ ) ₂ —. In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of this ring may be replaced with methyl, ethyl, or phenyl. In formula (DIH-3), ring E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of the ring may be replaced by methyl, ethyl, or phenyl, and Y is a single bond, carbon C 1 -C 20 alkylene, -CO -, - O -, - S -, - SO 2 -, - C (CH 3) 2 -, or -C _{(CF 3) 2} - a. In Formula (DIH-2) and Formula (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is an arbitrary position.

式（ＤＩＨ−１−２）において、ｍは１〜１２の整数である。

Examples of formulas (DIH-1) to (DIH-3) are shown below.

In formula (DIH-1-2), m is an integer of 1-12.

Such non-side chain diamines and dihydrazides have the effect of improving electrical characteristics, such as reducing the ion density of liquid crystal display elements. When a non-side chain diamine and / or dihydrazide is used as the diamine used for producing the liquid crystal aligning agent comprising the polyamic acid, polyamic acid ester or polyimide used in the liquid crystal aligning agent of the present invention, the total amount of diamine and dihydrazide The proportion is preferably 0 to 90 mol%, more preferably 0 to 50 mol%.

The side chain type diamine will be described. Examples of the side chain group of the side chain type diamine include the following groups.

As a side group, first, alkyl, alkyloxy, alkyloxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkenylcarbonyloxy, alkenyloxycarbonyl, alkenylaminocarbonyl, Alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylaminocarbonyl and the like can be mentioned. Alkyl, alkenyl and alkynyl in these groups are all groups having 3 or more carbon atoms. However, in alkyloxyalkyl, it is sufficient if the entire group has 3 or more carbon atoms. These groups may be linear or branched.

Next, phenyl, phenylalkyl, phenylalkyloxy, phenyloxy, provided that the terminal ring has alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms or alkoxyalkyl having 2 or more carbon atoms as a substituent. Phenylcarbonyl, phenylcarbonyloxy, phenyloxycarbonyl, phenylaminocarbonyl, phenylcyclohexyloxy, cycloalkyl having 3 or more carbon atoms, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexylphenyloxy, bis ( Cyclohexyl) oxy, bis (cyclohexyl) alkyl, bis (cyclohexyl) phenyl, bis (cyclohexyl) phenylalkyl, bis ( Kurohekishiru) oxycarbonyl, and bis (cyclohexyl) phenyloxycarbonyl and cyclohexyl bis (phenyl) group of a ring structure, such as oxycarbonyl,.

Further, a group having two or more benzene rings, a group having two or more cyclohexane rings, or two or more groups composed of a benzene ring and a cyclohexane ring, wherein the bonding groups are independently a single bond, -O-, -COO-, -OCO-, -CONH-, or alkylene having 1 to 3 carbon atoms, and the terminal ring is alkyl having 1 or more carbon atoms as a substituent, fluorine-substituted alkyl having 1 or more carbon atoms, carbon A ring assembly group having an alkoxy of several or more or an alkoxyalkyl having two or more carbons can be given. A group having a steroid skeleton is also effective as a side chain group.

式（ＤＩ−３１）において、Ｇ^２６は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−（ＣＨ_２）_ｍ’−であり、ｍ’は１〜１２の整数である。Ｇ^２６の好ましい例は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、および炭素数１〜３のアルキレンであり、特に好ましい例は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＣＨ_２−および−ＣＨ_２ＣＨ_２−である。Ｒ^２５は炭素数３〜３０のアルキル、フェニル、ステロイド骨格を有する基、または下記の式（ＤＩ−３１−ａ）で表される基である。このアルキルにおいて、少なくとも１つの水素は−Ｆで置き換えられてもよく、そして少なくとも１つの−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよい。このフェニルの水素は、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、炭素数３〜３０のアルキルまたは炭素数３〜３０のアルコキシで置き換えられていてもよい。ベンゼン環に結合する−ＮＨ_２の結合位置はその環において任意の位置であることを示すが、その結合位置はメタまたはパラであることが好ましい。即ち、基「Ｒ^２５−Ｇ^２６−」の結合位置を１位としたとき、２つの結合位置は３位と５位、または２位と５位であることが好ましい。 Examples of the diamine having a side chain include compounds represented by the following formula (DI-31) to formula (DI-35).

In the formula (DI-31), G ²⁶ represents a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—. , —OCF ₂ —, or — (CH ₂ ) _{m ′} —, and m ′ is an integer of 1 to 12. Preferred examples of G ²⁶ include a single bond, —O—, —COO—, —OCO—, —CH ₂ O—, and alkylene having 1 to 3 carbon atoms, and particularly preferred examples include a single bond, —O—, — _{COO -, - OCO -, -} CH 2 O -, - CH 2 - and _-CH 2 CH ₂ -. R ²⁵ is a group having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In the alkyl, at least one hydrogen may be replaced by -F, and at least one -CH ₂ - is -O -, - CH = CH- or may be replaced by -C≡C-. Hydrogen which _{phenyl, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, be replaced by an alkoxy alkyl or 3 to 30 carbon atoms having 3 to 30 carbon atoms Also good. The bonding position of —NH ₂ bonded to the benzene ring indicates an arbitrary position in the ring, but the bonding position is preferably meta or para. That is, when the bonding position of the group “R ²⁵ -G ²⁶ —” is the first position, the two bonding positions are preferably the third position and the fifth position, or the second position and the fifth position.

式（ＤＩ−３１−ａ）において、Ｇ^２７、Ｇ^２８およびＧ^２９は結合基であり、これらは独立して単結合、または炭素数１〜１２のアルキレンであり、このアルキレンの１以上の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−で置き換えられていてもよい。環Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４は独立して１，４−フェニレン、１，４−シクロへキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ピペリジン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−２，７−ジイルまたはアントラセン−９，１０−ジイルであり、環Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４において、少なくとも１つの水素は−Ｆまたは−ＣＨ_３で置き換えられてもよく、ｓ、ｔおよびｕは独立して０〜２の整数であって、これらの合計は０〜５であり、ｓ、ｔまたはｕが２であるとき、各々の括弧内の２つの結合基は同じであっても異なってもよく、そして、２つの環は同じであっても異なっていてもよい。Ｒ^２６は水素、−Ｆ、−ＯＨ、炭素数１〜３０のアルキル、炭素数１〜３０のフッ素置換アルキル、炭素数１〜３０のアルコキシ、−ＣＮ、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、または−ＯＣＦ_３であり、この炭素数１〜３０のアルキルの少なくとも１つの−ＣＨ_２−は下記式（ＤＩ−３１−ｂ）で表される２価の基で置き換えられていてもよい。

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are bonding groups, and these are each independently a single bond or alkylene having 1 to 12 carbons, and one or more — CH ₂ — may be replaced by —O—, —COO—, —OCO—, —CONH—, —CH═CH—. Ring B ²¹ , Ring B ²² , Ring B ²³ and Ring B ²⁴ are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5. -Diyl, pyridine-2,5-diyl, piperidine-1,4-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, ring B ²¹ , ring In B ²² , Ring B ²³ and Ring B ²⁴ , at least one hydrogen may be replaced with —F or —CH ₃ , s, t and u are each independently an integer from 0 to 2, The sum is 0-5, when s, t or u are 2, the two linking groups in each bracket may be the same or different and the two rings may be the same May be different. R ²⁶ is hydrogen, —F, —OH, alkyl having 1 to 30 carbons, fluorine-substituted alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —CN, —OCH ₂ F, —OCHF ₂ , or —OCF ₃ and at least one —CH ₂ — of the alkyl having 1 to 30 carbon atoms may be replaced by a divalent group represented by the following formula (DI-31-b).

式（ＤＩ−３１−ｂ）において、Ｒ^２７およびＲ^２８は独立して炭素数１〜３のアルキルであり、ｖは１〜６の整数である。Ｒ^２６の好ましい例は炭素数１〜３０のアルキルおよび炭素数１〜３０のアルコキシである。

In the formula (DI-31-b), R ²⁷ and R ²⁸ are each independently alkyl having 1 to 3 carbon atoms, and v is an integer of 1 to 6. Preferred examples of R ²⁶ are alkyl having 1 to 30 carbons and alkoxy having 1 to 30 carbons.

In the formula (DI-32) and the formula (DI-33), G ³⁰ is independently a single bond, —CO— or —CH ₂ —, R ²⁹ is independently hydrogen or —CH ₃ , R 30 ³⁰ is hydrogen, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons. At least one hydrogen of the benzene ring in formula (DI-32) and formula (DI-33) may be replaced with alkyl having 1 to 20 carbons or phenyl. A group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. One of the two groups “-phenylene-G ³⁰ —O—” in formula (DI-32) is preferably bonded to the 3-position of the steroid nucleus and the other is bonded to the 6-position of the steroid nucleus. The bonding position of the two groups “-phenylene-G ³⁰ —O—” in formula (DI-33) to the benzene ring is preferably a meta position or a para position, respectively, with respect to the bonding position of the steroid nucleus. In formula (DI-32) and formula (DI-33), -NH ₂ bonded to the benzene ring indicates that the binding position in the ring is optional.

In Formula (DI-34) and Formula (DI-35), G ³¹ is independently —O—, —NH—, or alkylene having 1 to 6 carbons, and G ³² is a single bond or 1 to 3 carbons. Of alkylene. R ³¹ is hydrogen or alkyl having 1 to 20 carbons, and at least one —CH ₂ — of the alkyl may be replaced by —O—, —CH═CH— or —C≡C—. R ³² is alkyl having 6 to 22 carbon atoms, and R ³³ is hydrogen or alkyl having 1 to 22 carbon atoms. Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1. And although -NH ₂ bonded to the benzene ring indicates that the binding position in the ring is optional, it is preferable independently a meta or para position with respect to the binding position of the G ^31.

Specific examples of the side chain diamine are illustrated below. Examples of the diamine having a side chain of the above formula (DI-31) to formula (DI-35) include compounds represented by the following formula (DI-31-1) to formula (DI-35-3). it can.

Examples of the compound represented by the formula (DI-31) are shown below.

In the formula (DI-31-1) to the formula (DI-31-11), R ³⁴ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl having 5 to 25 carbons or Alkoxy having 5 to 25 carbon atoms. R ³⁵ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl having 3 to 25 carbons or alkoxy having 3 to 25 carbons.

式（ＤＩ−３１−１２）〜式（ＤＩ−３１−１７）において、Ｒ^３６は炭素数４〜３０のアルキルであり、好ましくは炭素数６〜２５のアルキルである。Ｒ^３７は炭素数６〜３０のアルキルであり、好ましくは炭素数８〜２５のアルキルである。

In Formula (DI-31-12) to Formula (DI-31-17), R ³⁶ is alkyl having 4 to 30 carbons, and preferably alkyl having 6 to 25 carbons. R ³⁷ is alkyl having 6 to 30 carbon atoms, preferably alkyl having 8 to 25 carbon atoms.

式（ＤＩ−３１−１８）〜式（ＤＩ−３１−４３）において、Ｒ^３８は炭素数１〜２０のアルキルまたは炭素数１〜２０のアルコキシであり、好ましくは炭素数３〜２０のアルキルまたは炭素数３〜２０のアルコキシである。Ｒ^３９は水素、−Ｆ、炭素数１〜３０のアルキル、炭素数１〜３０のアルコキシ、−ＣＮ、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２または−ＯＣＦ_３であり、好ましくは炭素数３〜２５のアルキル、または炭素数３〜２５のアルコキシである。そしてＧ^３３は炭素数１〜２０のアルキレンである。

In formula (DI-31-18) to formula (DI-31-43), R ³⁸ is alkyl having 1 to 20 carbons or alkoxy having 1 to 20 carbons, preferably alkyl having 3 to 20 carbons or It is C3-C20 alkoxy. R ³⁹ is hydrogen, —F, alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —CN, —OCH ₂ F, —OCHF ₂ or —OCF ₃ , preferably ₃ to 25 carbons. Alkyl or alkoxy having 3 to 25 carbon atoms. G ³³ is alkylene having 1 to 20 carbon atoms.

Examples of the compound represented by the formula (DI-32) are shown below.

Examples of the compound represented by the formula (DI-33) are shown below.

式（ＤＩ−３４−１）〜式（ＤＩ−３４−１４）において、Ｒ^４０は水素または炭素数１〜２０のアルキル、好ましくは水素または炭素数１〜１０のアルキルであり、そしてＲ^４１は水素または炭素数１〜１２のアルキルである。 Examples of the compound represented by the formula (DI-34) are shown below.

In Formula (DI-34-1) to Formula (DI-34-14), R ⁴⁰ is hydrogen or alkyl having 1 to 20 carbons, preferably hydrogen or alkyl having 1 to 10 carbons, and R ⁴¹ is Hydrogen or alkyl having 1 to 12 carbons.

式（ＤＩ−３５−１）〜式（ＤＩ−３５−３）において、Ｒ^３７は炭素数６〜３０のアルキルであり、Ｒ^４１は水素または炭素数１〜１２のアルキルである。 Examples of the compound represented by the formula (DI-35) are shown below.

In formula (DI-35-1) ~ formula ^{(DI-35-3), R 37} is alkyl of 6 to 30 carbon ^{atoms, R 41} is hydrogen or alkyl having 1 to 12 carbon atoms.

式（ＤＩ−３６−１）〜式（ＤＩ−３６−８）において、Ｒ^４２は独立して炭素数３〜３０のアルキル基を表す。 As the diamine in the present invention, the formula (DI-1-1) to the formula (DI-16-1), the formula (DIH-1-1) to the formula (DIH-3-6), and the formula (DI-31-1). ) To diamines other than the diamines represented by formula (DI-35-3) can also be used. Examples of such diamines include compounds represented by the following formulas (DI-36-1) to (DI-36-13).

In formula (DI-36-1) ~ formula ^{(DI-36-8), R 42} represents an alkyl group having 3 to 30 carbon atoms independently.

式（ＤＩ−３６−９）〜式（ＤＩ−３６−１１）において、ｅは独立して２〜１０の整数であり、式（ＤＩ−３６−１２）中、Ｒ^４３は独立して水素、−ＮＨＢｏｃまたは−Ｎ（Ｂｏｃ）_２であり、Ｒ^４３の少なくとも１つは−ＮＨＢｏｃまたは−Ｎ（Ｂｏｃ）_２であり、式（ＤＩ−３６−１３）において、Ｒ^４４は−ＮＨＢｏｃまたは−Ｎ（Ｂｏｃ）_２であり、ｍは１〜１２の整数であり、そして、式（ＤＩ−３６−１４）において、ｋは１〜５の整数である。ここで、Ｂｏｃはｔ−ブトキシカルボニル基である。

In Formula (DI-36-9) to Formula (DI-36-11), e is independently an integer of 2 to 10, and in Formula (DI-36-12), R ⁴³ is independently hydrogen, —NHBoc or —N (Boc) ₂ , at least one of R ⁴³ is —NHBoc or —N (Boc) ₂ , and in formula (DI-36-13), R ⁴⁴ is —NHBoc or —N ( Boc) ₂ , m is an integer of 1-12, and in formula (DI-36-14), k is an integer of 1-5. Here, Boc is a t-butoxycarbonyl group.

In the diamine and dihydrazide, suitable materials for improving each characteristic will be described.

When importance is attached to further improving the orientation of the liquid crystal, among the above diamines and dihydrazides, the formula (DI-1-3), formula (DI-4-1), formula (DI-5-1) , Formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-29), formula (DI- 6-7), a compound represented by formula (DI-7-3) and a formula (DI-11-2) are preferably used. Diamines represented by formula (DI-4-1), formula (DI-5-1), formula (DI-5-12), formula (DI-5-13), and formula (DI-7-3) More preferred. In the formula (DI-5-1), m = 2, 4 or 6 is preferable, and m = 4 is more preferable. In formula (DI-5-12), m = 2 to 6 is preferable, and m = 5 is more preferable. In formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is more preferable. In the formula (DI-7-3), m = 2, 3, n = 1, or 2 is preferable, and m = 1 is more preferable.

When importance is attached to improving the transmittance, among the above diamines and dihydrazides, the formula (DI-1-3), the formula (DI-2-1), the formula (DI-5-1), the formula ( It is preferable to use a compound represented by DI-5-5), formula (DI-5-17), and formula (DI-7-3), and a diamine represented by (DI-2-1) is more preferable. preferable. In formula (DI-5-1), m = 2, 4 or 6 is preferable, and m = 4 is more preferable. In the formula (DI-7-3), m = 2, 3, n = 1, or 2 is preferable, and m = 1 is more preferable.

When importance is attached to improving the VHR of the liquid crystal display element, among the above diamines and dihydrazides, the formula (DI-2-1), formula (DI-4-1), formula (DI-4-2) , Formula (DI-4-10), Formula (DI-4-15), Formula (DI-5-1), Formula (DI-5-28), Formula (DI-5-30), Formula (DI- 13-1), a formula (DI-31-56), and a compound represented by the formula (DI-36-14) are preferably used, and the formula (DI-2-1) and the formula (DI-5-1) are preferably used. ), Formula (DI-13-1), formula (DI-31-56), and formula (DI-36-14) are more preferred. In the formula (DI-5-1), m = 1 is preferable. In the formula (DI-5-30), k = 2 is preferable. In the formula (DI-36-14), k = 3 is preferable.

Increasing the relaxation rate of residual charges (residual DC) in the alignment film by reducing the volume resistance value of the liquid crystal alignment film is an effective method for preventing burn-in. When emphasizing this purpose, among the above diamines and dihydrazides, formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4- 15), Formula (DI-5-1), Formula (DI-5-12), Formula (DI-5-13), Formula (DI-5-28), and Formula (DI-16-1) It is preferable to use a compound represented by formula (DI-4-1), formula (DI-5-1), and a compound represented by formula (DI-5-13). In the formula (DI-5-1), m = 2, 4 or 6 is preferable, and m = 4 is more preferable. In formula (DI-5-12), m = 2 to 6 is preferable, and m = 5 is more preferable. In formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is more preferable.

In each diamine, the ratio of the monoamine to the diamine may be 40 mol% or less, and a part of the diamine may be replaced with the monoamine. Such replacement can cause termination of the polymerization reaction when the polyamic acid is produced, and further progress of the polymerization reaction can be suppressed. For this reason, the molecular weight of the obtained polymer (polyamic acid, polyamic acid ester or polyimide) can be easily controlled by such replacement, for example, the coating characteristics of the liquid crystal aligning agent without impairing the effects of the present invention. Can be improved. As long as the effect of the present invention is not impaired, one or more diamines may be substituted for the monoamine. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n- Undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-eicosylamine Is mentioned.

The polyamic acid and derivative thereof of the present invention may further contain a monoisocyanate compound in the monomer. By including the monoisocyanate compound in the monomer, the terminal of the resulting polyamic acid or derivative thereof is modified, and the molecular weight is adjusted. By using this terminal-modified polyamic acid or a derivative thereof, for example, the coating properties of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. It is preferable from said viewpoint that content of the monoisocyanate compound in a monomer is 1-10 mol% with respect to the total amount of the diamine and tetracarboxylic dianhydride in a monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

In the present invention, polyamic acid having a photoreactive structure and derivatives thereof can be preferably used. Examples of the photoreactive structure include a photoisomerization structure that causes isomerization by ultraviolet irradiation, a photolysis structure that causes decomposition, a photodimerization structure that causes dimerization, and the like.

式（Ｐ−１）中、Ｒ^６１は独立して、水素原子、炭素数１〜５のアルキル基、またはフェニル基である。 The polyamic acid having a photoreactive structure and its derivative are referred to as a polymer (a). In the polymer (a), a diamine having a photoreactive structure or a tetracarboxylic dianhydride having a photoreactive structure and a derivative thereof can be used as a raw material. A diamine having a photoreactive structure and a photoreactive structure The tetracarboxylic dianhydride and derivatives thereof may be used in combination. Examples of the photoreactive structure include structures represented by the following formulas (P-1) to (P-7).

In formula (P-1), R ⁶¹ is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

式（ＰＡ−３）〜式（ＰＡ−６）において、Ｒ^６２は独立して、炭素数１〜５のアルキル基である。 Examples of the compound having a photoreactive structure causing photolysis represented by the formula (P-1) include compounds represented by the following formulas (PA-1) to (PA-6).

In Formula (PA-3) to Formula (PA-6), ^R62 is independently an alkyl group having 1 to 5 carbon atoms.

Among the compounds represented by formula (P-1), the above formula (PA-1), formula (PA-2) and formula (PA-5) are preferably used.

The compounds represented by the formulas (PA-1) to (PA-6) are a liquid crystal aligning agent using liquid crystal aligning ability based on photoisomerization reaction, a liquid crystal aligning agent using liquid crystal aligning ability based on photodimerization, or When used as a material for a rubbing liquid crystal aligning agent, it is used as a tetracarboxylic dianhydride having no photoreactive structure.

上記各式において、環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し、式（Ｖ−２）において、Ｒ^６は独立して−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＣＯＯＣＨ_３であり、ａは０〜２の整数であり、式（Ｖ−３）において、環Ａおよび環Ｂは独立して、単環式炭化水素、縮合多環式炭化水素および複素環から選ばれる少なくとも１つであり、Ｒ^１１は、炭素数１〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−または−Ｎ（ＣＨ_３）ＣＯ−であり、Ｒ^１２は、炭素数１〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−または−Ｎ（ＣＨ_３）ＣＯ−であり、Ｒ^１１およびＲ^１２において、直鎖アルキレンの−ＣＨ_２−の１つまたは２つは−Ｏ−で置換されてもよく、Ｒ^７〜Ｒ^１０は、独立して、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＯＨであり、そして、ｂ〜ｅは、独立して、０〜４の整数である。 Examples of the compound having a photoreactive structure represented by Formula (P-2) to Formula (P-4) include tetracarboxylic dianhydrides represented by Formula (II-1) to Formula (VI-2) below. And diamine compounds.

In each of the above formulas, a group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary, and in formula (V-2), R ⁶ is independently -CH ₃ , -OCH ₃ , -CF ₃ , or -COOCH ₃ , a is an integer of 0 to 2, and in formula (V-3), ring A and ring B are each independently And at least one selected from a cyclic hydrocarbon, a condensed polycyclic hydrocarbon, and a heterocyclic ring, and R ¹¹ is a linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, or — N (CH ₃ ) CO—, R ¹² is a linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —NHCO— or —N (CH ₃ ) CO—, and R ¹¹ and in R ^12, a straight-chain alkylene -CH ₂ - 1 or 2 may be substituted with ^-O-, R 7 ^{to R 10} are _{independently,} -F, -CH _3, -OCH 3, a -CF ₃ or -OH,, and, b to e are independently integers of 0 to 4.

The compounds represented by the above formulas (V-1), (V-2) and (VI-2) can be particularly preferably used from the viewpoint of their photosensitivity. In the formulas (V-2) and (VI-2), the compound in which the amino group is bonded to the para-position, and in the formula (V-2), the compound in which a = 0 is selected from the viewpoint of the orientation. It can be used more suitably.

Tetracarboxylic dianhydrides or diamines having a structure capable of causing photoisomerization upon irradiation with ultraviolet rays represented by the formulas (II-1) to (VI-2) are represented by the following formulas (II-1-1) to (VI-2-). It can be specifically expressed by 3).

A liquid crystal aligning agent for photo-alignment that is more sensitive to ultraviolet irradiation by converting the formula (VI-1-1) to the formula (V-3-8) into a compound having a structure capable of causing isomerization by ultraviolet irradiation. Can be obtained. Formula (V-1-1), Formula (V-2-1), Formula (V-2-4) to Formula (V-2-11), and Formula (V-3-1) to Formula (V-3) By using -8) as a compound having a structure capable of causing isomerization by ultraviolet irradiation, a liquid crystal aligning agent for photoalignment capable of aligning liquid crystal molecules more uniformly can be obtained. A liquid crystal for photo-alignment in which the formed alignment film can be less colored by using the compounds of the formula (V-2-4) to the formula (V-3-8) having a structure capable of causing isomerization by ultraviolet irradiation. An alignment agent can be obtained.

Among these, since a larger anisotropy is exhibited when the liquid crystal alignment film is formed, the compound represented by the formula (V-2-1) can be used more suitably.

式（ＰＤＩ−１２）において、Ｒ^５４は炭素数１〜１０のアルキルまたはアルコキシであり、アルキルまたはアルコキシの少なくとも１つの水素はフッ素に置き換えられていてもよい。 Examples of the compound having a photoreactive structure represented by Formula (P-5) to Formula (P-7) include diamine compounds represented by Formula (PDI-9) to Formula (PDI-13) below. .

In the formula (PDI-12), R ⁵⁴ is alkyl or alkoxy having 1 to 10 carbons, and at least one hydrogen of alkyl or alkoxy may be replaced by fluorine.

The above formulas (PDI-9) and (PDI-11) can be preferably used.

In a mode in which a tetracarboxylic dianhydride having no photoreactive structure (non-photosensitive) and a (photosensitive) tetracarboxylic dianhydride having a photoreactive structure are used in combination, the sensitivity of the liquid crystal alignment film to light In order to prevent a decrease in the amount of photosensitive tetracarboxylic dianhydride, the total amount of tetracarboxylic dianhydride used as a raw material for producing the polyamic acid and derivatives thereof of the present invention is 0 to 70 mol%. Preferably, 0 to 50 mol% is particularly preferable. Further, two or more photosensitive tetracarboxylic dianhydrides may be used in combination in order to improve the above-described various characteristics such as sensitivity to light, electrical characteristics, and afterimage characteristics.

In an embodiment in which a diamine having no photoreactive structure (non-photosensitive) and a (photosensitive) diamine having a photoreactive structure are used in combination, the polyamic of the present invention is used to prevent a decrease in sensitivity of the alignment film to light. The photosensitive diamine is preferably from 20 to 100 mol%, particularly preferably from 50 to 100 mol%, based on the total amount of diamine used as a raw material for producing the acid and its derivative. Two or more photosensitive diamines may be used in combination in order to improve the above-described various characteristics such as sensitivity to light and afterimage characteristics. As described above, the embodiment of the present invention includes the case where the total amount of the tetracarboxylic dianhydride is occupied by the non-photosensitive tetracarboxylic dianhydride. Even in this case, at least 20 mol% of the total amount of the diamine is photosensitive. It is required to be a functional diamine.

In order to improve the above-described various characteristics such as sensitivity to light and afterimage characteristics, a photosensitive tetracarboxylic dianhydride and a photosensitive diamine may be used in combination, or two or more of each may be used in combination.

The polyamic acid and its derivative of the present invention can be obtained by reacting a mixture of the above tetracarboxylic dianhydride and a diamine in a solvent. In this synthesis reaction, no special conditions other than the selection of the raw materials are required, and the conditions for normal polyamic acid synthesis can be applied as they are. The solvent to be used will be described later.

The polymer contained in the liquid crystal aligning agent of the present invention may be one or may be used by blending two or more. In an embodiment in which two or more polymers are blended, at least one of the polymers is a polymer (a) obtained by reacting a raw material monomer in which at least one of a tetracarboxylic dianhydride and a diamine has a photoreactive structure. And at least one of the other polymers is at least selected from a polyamic acid obtained by reacting a tetracarboxylic dianhydride having no photoreactive structure and a diamine not having a photoreactive structure, and a derivative thereof. The case of one polymer (b) is included. Polymer (a) changes its structure when the photoreactive structure is isomerized, decomposed or dimerized by irradiation of ultraviolet energy energy, and the liquid crystal molecules in contact with the polymer film are aligned in a specific direction. (Photo-alignment) performance. Such polymers may be used in blends with other polymers that do not contain photoreactive structures.

The liquid crystal aligning agent of this invention may further contain other components other than polyamic acid or its derivative (s). The other component may be one type or two or more types. Examples of other components include other polymers and compounds described below.

When a plurality of polymers are blended and used in the liquid crystal aligning agent of the present invention, the structure and molecular weight of each polymer are controlled, and applied to a substrate and pre-dried as described later, for example, the above light The polymer (a) having an orientation function can be separated into the upper layer of the coating film, and the other polymer (b) can be separated into the lower layer of the coating film. This can be controlled by using a phenomenon in which a polymer having a small surface energy is separated into an upper layer and a polymer having a large surface energy is separated into a lower layer in a mixed polymer. Confirmation of the layer separation can be confirmed by confirming that the surface energy of the formed alignment film is the same as or close to the surface energy of the alignment film formed by the liquid crystal aligning agent containing only the polymer (a).

As tetracarboxylic dianhydride used for synthesizing the polymer (b), tetracarboxylic dianhydride used for synthesizing polyamic acid or a derivative thereof which is an essential component of the liquid crystal aligning agent of the present invention. Can be selected without limitation from known tetracarboxylic dianhydrides, and the same as those exemplified above can be mentioned.

Among them, in the tetracarboxylic dianhydride, when importance is attached to improving the layer separation property, the formula (AN-3-2), the formula (AN-1-13), and the formula (AN-4-) 30) is preferred.

When importance is attached to improving the transmittance of the liquid crystal display element, among the above tetracarboxylic dianhydrides, the formula (AN-1-1), the formula (AN-1-2), the formula (PA- 1), Formula (AN-3-1), Formula (AN-4-17), Formula (AN-4-30), Formula (AN-5-1), Formula (AN-7-2), Formula ( The compounds represented by AN-10-1), formula (AN-10-2), formula (AN-16-3), and formula (AN-16-4) are preferred. In the formula (AN-1-2), m = 4 or 8 is preferable. In formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is more preferable.

In the case where importance is attached to improving the VHR of the liquid crystal display element, among the above tetracarboxylic dianhydrides, the formula (PA-1), the formula (AN-4-17), the formula (AN-7-2) ), Formula (AN-10-1), formula (AN-10-2), formula (AN-16-1), formula (AN-16-3) and formula (AN-16-4). Compounds are preferred. In Formula (AN-1-2) and Formula (AN-4-17), m = 4 or 8 is preferable.

Increasing the relaxation rate of residual charges (residual DC) in the alignment film by reducing the volume resistance value of the liquid crystal alignment film is an effective method for preventing burn-in. When importance is attached to this purpose, among the above tetracarboxylic dianhydrides, the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-21), the formula (AN -4-29) and a compound represented by the formula (AN-11-3) are preferable.

  The tetracarboxylic dianhydride used for synthesizing the polymer (b) preferably contains 10 mol% or more of the aromatic tetracarboxylic dianhydride with respect to the total tetracarboxylic dianhydride, More preferably, it contains 30 mol% or more.

  The diamine and dihydrazide used for synthesizing the polymer (b) are exemplified above as other diamines which can be used for synthesizing the polyamic acid or a derivative thereof which is an essential component of the liquid crystal aligning agent of the present invention. The same thing can be mentioned.

Among them, when emphasizing further improving the layer separation, that is, the orientation of the liquid crystal, among the above diamine and dihydrazide, the formula (DI-4-1), the formula (DI-4-2), the formula Compounds represented by (DI-4-10), formula (DI-5-1), formula (DI-5-9), formula (DI-5-28), and formula (DIH-2-1) It is preferable to use it. In the formula (DI-5-1), m = 1, 2, or 4 is preferable, and m = 1 or 2 is more preferable.

When importance is attached to improving the transmittance, among the above diamines and dihydrazides, the formula (DI-1-2), the formula (DI-2-1), the formula (DI-5-1), and the formula It is preferable to use a diamine represented by (DI-7-3), and a diamine represented by the formula (DI-2-1) is more preferable. In the formula (DI-5-1), m = 1, 2, or 4 is preferable, and m = 1 or 2 is more preferable. In formula (DI-7-3), m = 2 or 3, n = 1 or 2 are preferable, and m = 1 is more preferable.

When importance is attached to improving the VHR of the liquid crystal display element, among the above diamines and dihydrazides, the formula (DI-2-1), formula (DI-4-1), formula (DI-4-2) , Formula (DI-4-15), formula (DI-5-1), formula (DI-5-28), formula (DI-5-30), formula (DI-13-1) and formula (DI- It is preferable to use a diamine represented by 31-56). Diamines represented by formula (DI-2-1), formula (DI-5-1), formula (DI-13-1) and formula (DI-36-14) are more preferred. In the formula (DI-5-1), m = 1 or 2 is preferable. In the formula (DI-5-30), k = 2 is preferable.

Increasing the relaxation rate of residual charges (residual DC) in the alignment film by reducing the volume resistance value of the liquid crystal alignment film is an effective method for preventing burn-in. When emphasizing this purpose, among the above diamines and dihydrazides, formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4- 15), formula (DI-5-1), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula ( It is preferable to use a compound represented by formula (DI-5-30) and formula (DI-16-1), and formula (DI-4-1), formula (DI-5-1), and formula (DI- The diamine represented by 5-12) is more preferable. In the formula (DI-5-1), m = 1 or 2 is preferable. In formula (DI-5-12), m = 2 to 6 is preferable, and m = 5 is more preferable. In formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is more preferable. In the formula (DI-5-30), k = 2 is preferable.

The diamine used for synthesizing the polymer (b) preferably contains an aromatic diamine in an amount of 30 mol% or more, more preferably 50 mol% or more based on the total diamine.

In the liquid crystal aligning agent of the present invention, the ratio of the polymer (a) to the total amount of the polymer (a) and the polymer (b) is preferably 10% by weight to 100% by weight, more preferably 20% by weight to 100% by weight. preferable.

The liquid crystal aligning agent of this invention may further contain other components other than the polyamic acid of this invention, or its derivative (s). The other component may be one type or two or more types. Examples of other components include other polymers and compounds described below.

Examples of the other polymer include polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, and the like. 1 type or 2 types or more may be sufficient. Of these, polysiloxane is preferred.

Examples of the polysiloxane include JP2009-036966, JP2010-185001, JP2011-109633, JP2011-253175, JP2012-159825, International Publication 2008/044644, International Publication 2009/148099, International Publication. 2010/074261, International Publication 2010/074264, International Publication 2010/126108, International Publication 2011/068123, International Publication 2011/068127, International Publication 2011/068128, International Publication 2012/115157, International Publication 2012/165354, etc. The polysiloxane may be further contained.

Moreover, the liquid crystal aligning agent of this invention may contain the additive. Examples include alkenyl-substituted nadiimide compounds, oxazine compounds, oxazoline compounds, epoxy compounds, high molecular compounds other than polyamic acid and its derivatives, and other low molecular compounds, which can be selected and used according to each purpose. .

<Alkenyl-substituted nadiimide compound>
The liquid crystal aligning agent of the present invention may further contain an alkenyl-substituted nadiimide compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. An alkenyl substituted nadiimide compound may be used by 1 type, and may use 2 or more types together. For the above purpose, the content of the alkenyl-substituted nadiimide compound is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, and more preferably 1 to 50% by weight with respect to the polyamic acid or derivative thereof. More preferably.

式（ＮＡ）において、Ｌ^１およびＬ^２は独立して水素、炭素数１〜１２のアルキル、炭素数３〜６のアルケニル、炭素数５〜８のシクロアルキル、炭素数６〜１２のアリールまたはベンジルであり、ｎは１または２である。 The nadiimide compound will be specifically described below.
The alkenyl-substituted nadiimide compound is preferably a compound that can be dissolved in a solvent that dissolves the polyamic acid or derivative thereof used in the present invention. Examples of such alkenyl-substituted nadiimide compounds include compounds represented by the following formula (NA).

In the formula (NA), L ¹ and L ² are independently hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons, or Benzyl and n is 1 or 2.

In the formula (NA), when n = 1, W is alkyl having 1 to 12 carbons, alkenyl having 2 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons, benzyl,- Z ^1- (O) _r- (Z ² O) _k -Z ³ -H (wherein Z ¹ , Z ² and Z ³ are independently alkylene having 2 to 6 carbon atoms, and r is 0 or 1 And k is an integer of 1 to 30.), a group represented by — (Z ⁴ ) _r —BZ ⁵ —H (wherein Z ⁴ and Z ⁵ are independently a carbon number) A group represented by the formula: -B-T-B-H (which is an alkylene having 1 to 4 carbon atoms or a cycloalkylene having 5 to 8 carbon atoms, B is phenylene, and r is 0 or 1) B is phenylene, and T is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —CO—, — S— or —SO ₂ —), or a group in which 1 to 3 hydrogens of these groups are substituted with —OH.

At this time, preferable W is alkyl having 1 to 8 carbons, alkenyl having 3 to 4 carbons, cyclohexyl, phenyl, benzyl, poly (ethyleneoxy) ethyl having 4 to 10 carbons, phenyloxyphenyl, phenylmethylphenyl, Phenylisopropylidenephenyl and groups in which one or two hydrogens of these groups are replaced by —OH.

Wherein in (NA), when n = 2, W is alkylene of 2 to 20 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, arylene having 6 to 12 carbon ^{atoms, -Z 1 -O- (Z 2 O} ) a group represented by _k— Z ³ — (wherein Z ^{1 to} Z ³ and k are as defined above), —Z ⁴ —BZ ⁵ — (where Z ⁴ , Z defining ⁵ and B are as defined above. groups represented _{by), -B- (O-B)} r -T- (B-O) r -B- ( wherein, B is phenylene, T is alkylene having 1 to 3 carbon atoms, —O— or —SO ₂ —, and the definition of r is as described above), or 1 to 3 hydrogens of these groups are It is a group replaced by —OH.

In this case, preferable W is alkylene having 2 to 12 carbon atoms, cyclohexylene, phenylene, tolylene, xylylene, —C ₃ H ₆ —O— (Z ² —O) _n —O—C ₃ H ₆ — (where, Z ² is alkylene having 2 to 6 carbon atoms, and n is 1 or 2.) —B—T—B— (where B is phenylene, and T is — A group represented by CH ₂ —, —O— or —SO ₂ —), —B—O—B—C ₃ H ₆ —B—O—B—, wherein B is phenylene. And a group in which one or two hydrogens of these groups are replaced by —OH.

Such an alkenyl-substituted nadiimide compound is synthesized, for example, by maintaining an alkenyl-substituted nadic acid anhydride derivative and a diamine at a temperature of 80 to 220 ° C. for 0.5 to 20 hours as described in Japanese Patent No. 2729565. Or a commercially available compound can be used. Specific examples of the alkenyl-substituted nadiimide compound include the following compounds.

N-methyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-methyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N-methyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-methyl-methallylmethylbicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,

N- (2-ethylhexyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-allylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide, N-allyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-methallylbicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, N-isopropenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-isopropenyl- Allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboxyl N-cyclohexyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-cyclohexyl-allyl (methyl) bicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N-cyclohexyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-phenyl-allylbicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide,

N-phenyl-allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-benzyl-allylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N-benzyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-benzyl-methallylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (2-hydroxyethyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2- Hydroxyethyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-hydroxyethyl) -methallylbicyclo [2.2.1] hept -5-ene- , 3-dicarboximide,

N- (2,2-dimethyl-3-hydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2,2-dimethyl-3-hydroxy Propyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2,3-dihydroxypropyl) -allylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (2,3-dihydroxypropyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-hydroxy-1-propenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-hydroxycyclohexyl) -allyl (methyl) bicycle [2.2.1] hept-5-ene-2,3-dicarboximide,

N- (4-hydroxyphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-hydroxyphenyl) -allyl (methyl) bicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide, N- (4-hydroxyphenyl) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-hydroxyphenyl) -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-hydroxyphenyl) -allylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide, N- (3-hydroxyphenyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide , -(P-hydroxybenzyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2- (2-hydroxyethoxy) ethyl} -allylbicyclo [2. 2.1] hept-5-ene-2,3-dicarboximide,

N- {2- (2-hydroxyethoxy) ethyl} -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2- (2-hydroxyethoxy) ) Ethyl} -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2- (2-hydroxyethoxy) ethyl} -methallylmethylbicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide, N- 2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {4- (4-hydroxyphenyl) Isopropylidene) phenyl} -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {4- (4-hydroxyphenylisopropylidene) phenyl} -allyl (methyl) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- {4- (4-hydroxyphenylisopropylidene) phenyl} -methallylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide, and oligomers thereof,

N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene Bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5- Ene-2,3-dicarboximide), N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′— Cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),

1,2-bis {3 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethane, 1,2-bis {3 ′-(allylmethylbicyclo) [2.2.1] Hept-5-ene-2,3-dicarboximido) propoxy} ethane, 1,2-bis {3 ′-(methallylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximido) propoxy} ethane, bis [2 '-{3'-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethyl] Ether, bis [2 ′-{3 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethyl] ether, 1,4-bis {3 ′ -(Allylbicyclo [2.2.1] he To-5-ene-2,3-dicarboximido) propoxy} butane, 1,4-bis {3 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido) propoxy} butane,

N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p-phenylene-bis (allylmethylbicyclo [ 2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide), N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N ′-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p-xylylene-bis (allylbicyclo) [2.2.1] Hept-5-ene-2,3-dica Boxoxyimide), N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis ( Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide),

2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4- { 4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4- {4- (methallylbicyclo [2] 2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-di Carboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,

Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (methallylmethylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (methallylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, bis {4 -(Ant Methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl} sulfone,

Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, 1,6-bis (allylbicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide) -3-hydroxy-hexane, 1,12-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide)- 3,6-dihydroxy-dodecane, 1,3-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -5-hydroxy-cyclohexane, 1,5-bis { 3 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} -3-hydroxy-pentane, 1,4-bis (allylbicyclo [2.2.1 ] Hept-5-ene 2,3-dicarboximide) -2-hydroxy - benzene,

1,4-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2,5-dihydroxy-benzene, N, N′-p- (2-hydroxy ) Xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p- (2-hydroxy) xylylene-bis (allylmethylcyclo [2] 2.1] hept-5-ene-2,3-dicarboximide), N, N′-m- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide), N, N'-m- (2-hydroxy) xylylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) , N, N′-p- (2,3-dihi Proxy) xylylene - bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),

2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) -2-hydroxy-phenoxy} phenyl] propane, bis {4- (Allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2-hydroxy-phenyl} methane, bis {3- (allylbicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide) -4-hydroxy-phenyl} ether, bis {3- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -5-hydroxy-phenyl} sulfone, 1,1,1-tri {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide)} phenoxymethylpropane, N , N , N "- tri (ethylene methallyl ruby [2.2.1] hept-5-ene-2,3-dicarboximide) isocyanurate, and the like of these oligomers.

Furthermore, the alkenyl-substituted nadiimide compound used in the present invention may be a compound represented by the following formula containing an asymmetric alkylene / phenylene group.

Of the alkenyl-substituted nadiimide compounds, preferred compounds are shown below.
N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene-bis (a) Rilbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide), N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-cyclohexylene- Bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),

N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p-phenylene-bis (allylmethylbicyclo [ 2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide), N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N ′-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p-xylylene-bis (allylbicyclo) [2.2.1] Hept-5-ene-2,3-dica Boxoxyimide), N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis ( Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide), 2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane 2,2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4 -{4- (methallylbicyclo 2.2.1] Hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3- Dicarboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane.

Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (methallylmethylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (methallylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, bis {4 -(Ant Methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-Dicarboximido) phenyl} sulfone.

Further preferred alkenyl-substituted nadiimide compounds are shown below.
N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene-bis (a) Rilbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide), N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-cyclohexylene- Bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide).

N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p-phenylene-bis (allylmethylbicyclo [ 2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide), N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N ′-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p-xylylene-bis (allylbicyclo) [2.2.1] Hept-5-ene-2,3-dica Boxoxyimide), N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis ( Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide).

2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4- { 4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4- {4- (methallylbicyclo [2] 2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-di Carboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (methallylbicyclo [2] 2.1] Hept 5-ene-2,3-dicarboximide) phenyl} methane, bis {4- (methallyl methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl} methane.

And as a particularly preferable alkenyl substituted nadiimide compound, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the following formula (NA-1): Phenyl} methane, N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the formula (NA-2), and N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the formula (NA-3) may be mentioned.

<Compound having radically polymerizable unsaturated double bond>
The liquid crystal aligning agent of this invention may further contain the compound which has a radically polymerizable unsaturated double bond from the objective of stabilizing the electrical property of a liquid crystal display element for a long term. The compound having a radically polymerizable unsaturated double bond may be one type of compound or two or more types of compounds. The compound having a radical polymerizable unsaturated double bond does not include an alkenyl-substituted nadiimide compound. The content of the compound having a radically polymerizable unsaturated double bond is preferably 1 to 100% by weight, more preferably 1 to 70% by weight with respect to the polyamic acid or derivative thereof for the above purpose. Preferably, it is 1 to 50% by weight.

The ratio of the compound having a radical polymerizable unsaturated double bond to the alkenyl-substituted nadiimide compound reduces the ion density of the liquid crystal display element, suppresses the increase in ion density over time, and further suppresses the occurrence of afterimages. Therefore, the compound / alkenyl-substituted nadiimide compound having a radically polymerizable unsaturated double bond is preferably 0.1 to 10 and more preferably 0.5 to 5 in weight ratio.

The compound having a radical polymerizable unsaturated double bond will be specifically described below.
Examples of the compound having a radical polymerizable unsaturated double bond include (meth) acrylic acid esters, (meth) acrylic acid derivatives such as (meth) acrylic acid amide, and bismaleimide. The compound having a radically polymerizable unsaturated double bond is more preferably a (meth) acrylic acid derivative having two or more radically polymerizable unsaturated double bonds.

Specific examples of the (meth) acrylic acid ester include, for example, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. Examples include oxyethyl, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.

Specific examples of the bifunctional (meth) acrylic acid ester include, for example, ethylene bisacrylate, Aronix M-210, Aronix M-240 and Aronix M-6200, which are products of Toa Gosei Chemical Co., Ltd., Nippon Kayaku Co., Ltd. ) Products KAYARADHDDA, KAYAARADHX-220, KAYARADR-604 and KAYARADR-684, Osaka Organic Chemicals Co., Ltd. products V260, V312 and V335HP, and Kyoeisha Yushi Chemicals Co., Ltd., Light Acrylate BA-4EA, light acrylate BP-4PA and light acrylate BP-2PA.

Specific examples of the trifunctional or higher polyfunctional (meth) acrylic acid ester include, for example, 4,4'-methylenebis (N, N-dihydroxyethylene acrylate aniline), Aronix M-, a product of Toa Gosei Chemical Co., Ltd. 400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, Nippon Kayaku Co., Ltd. products KAYARADTMPTA, KAYARADDPCA-20, KAYARADDPCA-30, KAYARADDPCA-60 , KAYARADDPCA-120, and VGPT which is a product of Osaka Organic Chemical Industry Co., Ltd.

Specific examples of the (meth) acrylic acid amide derivative include, for example, N-isopropylacrylamide, N-isopropylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-cyclopropylacrylamide, N-cyclopropyl. Methacrylamide, N-ethoxyethylacrylamide, N-ethoxyethylmethacrylamide, N-tetrahydrofurfurylacrylamide, N-tetrahydrofurfurylmethacrylamide, N-ethylacrylamide, N-ethyl-N-methylacrylamide, N, N-diethyl Acrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N-acryloylpyrrolidine, N, N′-methyl Nbisacrylamide, N, N′-ethylenebisacrylamide, N, N′-dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacrylamide, N-phenylmethacrylamide, N-butylmethacrylamide, N- (iso -Butoxymethyl) methacrylamide, N- [2- (N, N-dimethylamino) ethyl] methacrylamide, N, N-dimethylmethacrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- ( Methoxymethyl) methacrylamide, N- (hydroxymethyl) -2-methacrylamide, N-benzyl-2-methacrylamide, and N, N′-methylenebismethacrylamide.

Among the above (meth) acrylic acid derivatives, N, N′-methylenebisacrylamide, N, N′-dihydroxyethylene-bisacrylamide, ethylenebisacrylate, and 4,4′-methylenebis (N, N-dihydroxyethyleneacrylate) Aniline) is particularly preferred.

Examples of the bismaleimide include BMI-70 and BMI-80 manufactured by Kay Kasei Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, BMI-5000 and BMI- manufactured by Daiwa Kasei Kogyo Co., Ltd. 7000.

<Oxazine compound>
The liquid crystal aligning agent of the present invention may further contain an oxazine compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The oxazine compound may be one type of compound or two or more types of compounds. The content of the oxazine compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the polyamic acid or derivative thereof for the above purpose. More preferably.

The oxazine compound will be specifically described below.
The oxazine compound is soluble in a solvent that dissolves the polyamic acid or a derivative thereof, and in addition, an oxazine compound having ring-opening polymerizability is preferable.

Further, the number of oxazine structures in the oxazine compound is not particularly limited.

Various structures are known for the structure of oxazine. In the present invention, the structure of oxazine is not particularly limited, but examples of the oxazine structure in the oxazine compound include an oxazine structure having an aromatic group containing a condensed polycyclic aromatic group such as benzoxazine and naphthoxazine.

式（ＯＸ−１）〜式（ＯＸ−３）において、Ｌ^３およびＬ^４は炭素数１〜３０の有機基であり、式（ＯＸ−１）〜式（ＯＸ−６）において、Ｌ^５〜Ｌ^８は水素または炭素数１〜６の炭化水素基であり、式（ＯＸ−３）、式（ＯＸ−４）および式（ＯＸ−６）において、Ｑ^１は単結合、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−（ＣＨ_２）_ｖ−、−Ｏ−（ＣＨ_２）_ｖ−Ｏ−、−Ｓ−（ＣＨ_２）_ｖ−Ｓ−であり、ここでｖは１〜６の整数であり、式（ＯＸ−５）および式（ＯＸ−６）において、Ｑ^２は独立して単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−または炭素数１〜３のアルキレンであり、Ｑ^２におけるベンゼン環、ナフタレン環に結合している水素は独立して−Ｆ、−ＣＨ_３、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、−ＰＯ_３Ｈ_２と置き換えられていてもよい。 Examples of the oxazine compound include compounds represented by the following formulas (OX-1) to (OX-6). In the following formula, the bond displayed toward the center of the ring indicates that it is bonded to any carbon that forms the ring and can be bonded to a substituent.

In Formula (OX-1) to Formula (OX-3), L ³ and L ⁴ are organic groups having 1 to 30 carbon atoms, and in Formula (OX-1) to Formula (OX-6), L ⁵ to L ⁸ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. In the formula (OX-3), the formula (OX-4), and the formula (OX-6), Q ¹ is a single bond, —O—, — _{S -, - S-S -} , - SO 2 -, - CO -, - CONH -, - NHCO -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) v _{-, - O- (CH 2)} v -O -, - S- (CH 2) v is -S-, where v is an integer from 1 to 6, formula (OX-5) and formula (OX −6), Q ² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or C 1-3. Is alkylene And hydrogen bonded to the benzene ring and naphthalene ring in Q ² may be independently replaced with —F, —CH ₃ , —OH, —COOH, —SO ₃ H, —PO ₃ H _2. .

The oxazine compound includes an oligomer or polymer having an oxazine structure in the side chain, and an oligomer or polymer having an oxazine structure in the main chain.

式（ＯＸ−１−２）において、Ｌ^３は炭素数１〜３０のアルキルが好ましく、炭素数１〜２０のアルキルがさらに好ましい。 Examples of the oxazine compound represented by the formula (OX-1) include the following oxazine compounds.

In Formula (OX-1-2), L ³ is preferably alkyl having 1 to 30 carbons, and more preferably alkyl having 1 to 20 carbons.

式中、Ｌ^３は炭素数１〜３０のアルキルが好ましく、炭素数１〜２０のアルキルがさらに好ましい。 Examples of the oxazine compound represented by the formula (OX-2) include the following oxazine compounds.

In the formula, L ³ is preferably alkyl having 1 to 30 carbons, and more preferably alkyl having 1 to 20 carbons.

式（ＯＸ−３−Ｉ）において、Ｌ^３およびＬ^４は炭素数１〜３０の有機基であり、Ｌ^５からＬ^８は水素または炭素数１〜６の炭化水素基であり、Ｑ^１は単結合、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−ＣＯ−、−Ｏ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−である。式（ＯＸ−３−Ｉ）で表されるオキサジン化合物としては、例えば以下のオキサジン化合物が挙げられる。 As the oxazine compound represented by the formula (OX-3), an oxazine compound represented by the following formula (OX-3-I) can be given.

In Formula (OX-3-I), L ³ and L ⁴ are each an organic group having 1 to 30 carbon atoms, L ⁵ to L ⁸ are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and Q ¹ is A single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —CO—, —O—, —SO ₂ —, —C (CH ₃ ) ₂ —, or —C (CF ₃ ) ₂ —. . Examples of the oxazine compound represented by the formula (OX-3-I) include the following oxazine compounds.

式中、Ｌ^３およびＬ^４は炭素数１〜３０のアルキルが好ましく、炭素数１〜２０のアルキルがさらに好ましい。

In the formula, L ³ and L ⁴ are preferably alkyl having 1 to 30 carbon atoms, more preferably alkyl having 1 to 20 carbon atoms.

Examples of the oxazine compound represented by the formula (OX-4) include the following oxazine compounds.

Examples of the oxazine compound represented by the formula (OX-5) include the following oxazine compounds.

Examples of the oxazine compound represented by the formula (OX-6) include the following oxazine compounds.

Of these, more preferably, the formula (OX-2-1), the formula (OX-3-1), the formula (OX-3-3), the formula (OX-3-5), and the formula (OX-3- 7), formula (OX-3-9), formula (OX-4-1) to formula (OX-4-6), formula (OX-5-3), formula (OX-5-4), and formula Oxazine compounds represented by (OX-6-6-2) to formula (OX-6-4) can be given.

The oxazine compound can be produced by the same method as described in International Publication No. 2004/009708, JP-A-11-12258, and JP-A-2004-352670.

The oxazine compound represented by the formula (OX-1) is obtained by reacting a phenol compound, a primary amine, and an aldehyde (see International Publication 2004/009708).

The oxazine compound represented by the formula (OX-2) is obtained by reacting by a method of gradually adding a primary amine to formaldehyde, and then adding and reacting a compound having a naphthol-based hydroxyl group (International Publication 2004 / (See 009708.)

The oxazine compound represented by the formula (OX-3) is a secondary aliphatic compound in which 1 mol of a phenol compound, at least 2 mol or more of an aldehyde, and 1 mol of a primary amine are added to one phenolic hydroxyl group in an organic solvent. It can be obtained by reacting in the presence of an amine, a tertiary aliphatic amine or a basic nitrogen-containing heterocyclic compound (see International Publication No. 2004/009708 and JP-A-11-12258).

The oxazine compound represented by the formula (OX-4) to the formula (OX-6) is a diamine having a plurality of benzene rings and an organic group that binds them, such as 4,4′-diaminodiphenylmethane, and formalin. It can be obtained by subjecting an aldehyde and phenol to a dehydration condensation reaction in n-butyl alcohol at a temperature of 90 ° C. or higher (see JP 2004-352670 A).

<Oxazoline compound>
The liquid crystal aligning agent of this invention may further contain the oxazoline compound from the objective of stabilizing the electrical property in a liquid crystal display element for a long term. An oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one type of compound or two or more types of compounds. The content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the polyamic acid or a derivative thereof for the above purpose. More preferably. Alternatively, the content of the oxazoline compound is preferably 0.1 to 40% by weight with respect to the polyamic acid or a derivative thereof when the oxazoline structure in the oxazoline compound is converted to oxazoline.

The oxazoline compound will be specifically described below.
The oxazoline compound may have only one type of oxazoline structure in one compound, or may have two or more types. Further, the oxazoline compound may have one oxazoline structure in one compound, but preferably has two or more. The oxazoline compound may be a polymer having an oxazoline structure in the side chain or a copolymer. The polymer having an oxazoline structure in the side chain may be a homopolymer of a monomer having an oxazoline structure in the side chain, or may be a copolymer of a monomer having an oxazoline structure in the side chain and a monomer having no oxazoline structure. Good. The copolymer having an oxazoline structure in the side chain may be a copolymer of two or more monomers having an oxazoline structure in the side chain, or two or more monomers having an oxazoline structure in the side chain and a monomer having no oxazoline structure And a copolymer thereof.

The oxazoline structure is preferably a structure present in the oxazoline compound so that one or both of oxygen and nitrogen in the oxazoline structure can react with the carbonyl group of the polyamic acid.

Examples of the oxazoline compound include 2,2′-bis (2-oxazoline), 1,2,4-tris- (2-oxazolinyl-2) -benzene, 4-furan-2-ylmethylene-2-phenyl-4H—. Oxazol-5-one, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, 1,3-bis (4,5-dihydro-2-oxazolyl) benzene, 2,3-bis (4- Isopropenyl-2-oxazolin-2-yl) butane, 2,2′-bis-4-benzyl-2-oxazoline, 2,6-bis (isopropyl-2-oxazolin-2-yl) pyridine, 2,2 ′ -Isopropylidenebis (4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis (4-phenyl-2-oxazoline), 2,2'-methylenebi (4-tert-butyl-2-oxazoline), and 2,2'-methylenebis (4-phenyl-2-oxazoline) and the like. In addition to these, polymers and oligomers having oxazolyl such as Epocross (trade name, manufactured by Nippon Shokubai Co., Ltd.) are also included. Of these, 1,3-bis (4,5-dihydro-2-oxazolyl) benzene is more preferable.

<Epoxy compound>
The liquid crystal aligning agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The epoxy compound may be one type of compound or two or more types of compounds. The content of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the polyamic acid or derivative thereof for the above purpose. More preferably.

The epoxy compound will be specifically described below.
Examples of the epoxy compound include various compounds having one or more epoxy rings in the molecule. Examples of the compound having one epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, 3-glycidoxy Propyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-glycidylphthalimide, (nonafluoro-N-butyl) epoxide, perfluoroethylglycidyl ether, epichlorohydrin, epibromohydrin, N, N-diglycidylaniline, and 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane.

Examples of the compound having two epoxy rings in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl. Ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate and 3 -(N, N-diglycidyl) aminopropyltrimethoxysilane.

Examples of the compound having three epoxy rings in the molecule include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3- Epoxypropoxy] phenyl)] ethyl] phenyl] propane (trade name “Techmore VG3101L” (manufactured by Mitsui Chemicals, Inc.)).

Examples of the compound having four epoxy rings in the molecule include 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, and 3- (N-allyl-N-glycidyl) Aminopropyltrimethoxysilane is mentioned.

In addition to the above, examples of the compound having an epoxy ring in the molecule include oligomers and polymers having an epoxy ring. Examples of the monomer having an epoxy ring include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

Examples of other monomers copolymerized with a monomer having an epoxy ring include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and iso-butyl. (Meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, chloromethyl Styrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide and N-phenylmaleimide.

Preferable specific examples of the monomer polymer having an epoxy ring include polyglycidyl methacrylate. Preferred examples of the copolymer of the monomer having an epoxy ring and another monomer include N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl. Mention may be made of methacrylate copolymers, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymers, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymers and styrene-glycidyl methacrylate copolymers.

Among these examples, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′ Tetraglycidyl-4,4′-diaminodiphenylmethane, trade name “Techmore VG3101L”, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, and 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane is particularly preferred.

More systematically, examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic epoxy compound. Is mentioned. In addition, an epoxy compound means the compound which has an epoxy group, and an epoxy resin means resin which has an epoxy group.

Examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic epoxy compound.

Examples of the glycidyl ether include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, bisphenol type epoxy compound, hydrogenated bisphenol-A type epoxy compound, hydrogenated bisphenol-F type epoxy compound, hydrogenated bisphenol. -S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, brominated phenol novolak type epoxy compound Brominated cresol novolac type epoxy compound, bisphenol A novolac type epoxy compound, naphthalene skeleton-containing epoxy compound, aromatic polymer Glycidyl ether compounds, dicyclopentadiene phenol type epoxy compound, alicyclic diglycidyl ether compounds, aliphatic polyglycidyl ether compound, a polysulfide-type diglycidyl ether compound, and biphenol type epoxy compound.

Examples of the glycidyl ester include a diglycidyl ester compound and a glycidyl ester epoxy compound.

Examples of the glycidylamine include polyglycidylamine compounds and glycidylamine type epoxy resins.

Examples of the epoxy group-containing acrylic compound include homopolymers and copolymers of monomers having oxiranyl.

Examples of glycidyl amide include glycidyl amide type epoxy compounds.

Examples of the chain aliphatic epoxy compound include compounds containing an epoxy group obtained by oxidizing a carbon-carbon double bond of an alkene compound.

Examples of the cycloaliphatic epoxy compound include a compound containing an epoxy group obtained by oxidizing a carbon-carbon double bond of a cycloalkene compound.

Examples of the bisphenol A type epoxy compound include jER828, jER1001, jER1002, jER1003, jER1004, jER1007, jER1010 (all trade names, manufactured by Mitsubishi Chemical Corporation), Epototo YD-128 (manufactured by Tohto Kasei Co., Ltd.), DER -331, DER-332, DER-324 (all manufactured by The Dow Chemical Company), Epicron 840, Epicron 850, Epicron 1050 (all trade names, manufactured by DIC Corporation), Epomic R-140, Epomic R-301 , And Epomic R-304 (both trade names, manufactured by Mitsui Chemicals, Inc.).

Examples of the bisphenol F type epoxy compound include jER806, jER807, jER4004P (all trade names, manufactured by Mitsubishi Chemical Corporation), Epototo YDF-170, Epototo YDF-175S, Epototo YDF-2001 (all trade names, Toto Kasei) DER-354 (trade name, manufactured by The Dow Chemical Company), Epicron 830, and Epicron 835 (all trade names, manufactured by DIC Corporation).

Examples of the bisphenol type epoxy compound include epoxidized products of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

Examples of the hydrogenated bisphenol-A type epoxy compound include Santo Tote ST-3000 (trade name, manufactured by Toto Kasei Co., Ltd.), Rica Resin HBE-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), and Denacol EX-252. (Trade name, manufactured by Nagase ChemteX Corporation).

Examples of the hydrogenated bisphenol type epoxy compound include an epoxidized product of hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

Examples of brominated bisphenol-A type epoxy compounds include jER5050, jER5051 (both trade names, manufactured by Mitsubishi Chemical Corporation), Epototo YDB-360, Epototo YDB-400 (both trade names, manufactured by Toto Kasei Co., Ltd.). ), DER-530, DER-538 (all are trade names, manufactured by The Dow Chemical Company), Epicron 152, and Epicron 153 (all are trade names, manufactured by DIC Corporation).

Examples of the phenol novolac type epoxy compound include jER152, jER154 (both trade names, manufactured by Mitsubishi Chemical Corporation), YDPN-638 (trade names, manufactured by Tohto Kasei Co., Ltd.), DEN431, DEN438 (both trade names, The Dow Chemical Company), Epicron N-770 (trade name, manufactured by DIC Corporation), EPPN-201, and EPPN-202 (all trade names, manufactured by Nippon Kayaku Co., Ltd.).

Examples of the cresol novolac type epoxy compound include jER180S75 (trade name, manufactured by Mitsubishi Chemical Corporation), YDCN-701, YDCN-702 (all trade names, manufactured by Tohto Kasei Co., Ltd.), Epicron N-665, Epicron N-695. (All trade names, manufactured by DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all trade names, manufactured by Nippon Kayaku Co., Ltd.) ).

Examples of the bisphenol A novolac type epoxy compound include jER157S70 (trade name, manufactured by Mitsubishi Chemical Corporation), and Epicron N-880 (trade name, manufactured by DIC Corporation).

As the naphthalene skeleton-containing epoxy compound, for example, Epicron HP-4032, Epicron HP-4700, Epicron HP-4770 (all trade names, manufactured by DIC Corporation), and NC-7000 (trade names, manufactured by Nippon Kayaku Co., Ltd.) Is mentioned.

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (following formula EP-1), catechol diglycidyl ether (following formula EP-2), resorcinol diglycidyl ether (following formula EP-3), 2- [4 -(2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane (formula EP-4 below) , Tris (4-glycidyloxyphenyl) methane (following formula EP-5), jER1031S, jER1032H60 (all trade names, manufactured by Mitsubishi Chemical Corporation), TACTIX-742 (trade name, manufactured by The Dow Chemical Company), Denacol EX-201 (trade name, manufactured by Nagase ChemteX Corporation), DPPN-503, DPPN-50 H, DPPN-501H, NC6000 (all trade names, manufactured by Nippon Kayaku Co., Ltd.), Techmore VG3101L (trade names, manufactured by Mitsui Chemicals, Inc.), a compound represented by the following formula EP-6, and the following formula The compound represented by EP-7 is mentioned.

Examples of the dicyclopentadiene phenol type epoxy compound include TACTIX-556 (trade name, manufactured by The Dow Chemical Company), and Epicron HP-7200 (trade name, manufactured by DIC Corporation).

Examples of the alicyclic diglycidyl ether compound include cyclohexane dimethanol diglycidyl ether compound and licarresin DME-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.).

Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (following formula EP-8), diethylene glycol diglycidyl ether (following formula EP-9), polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (following formula EP). -10), tripropylene glycol diglycidyl ether (following formula EP-11), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (following formula EP-12), 1,4-butanediol diglycidyl ether (following formula EP-13), 1,6-hexanediol diglycidyl ether (following formula EP-14), dibromoneopentyl glycol diglycidyl ether (following formula EP-15), Denacol EX 810, Denacol EX-851, Denacol EX-8301, Denacol EX-911, Denacol EX-920, Denacol EX-931, Denacol EX-211, Denacol EX-212, Denacol EX-313 (all trade names, Nagase Chemtex) Co., Ltd.), DD-503 (trade name, manufactured by ADEKA Co., Ltd.), Rica Resin W-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), 1,3,5,6-tetraglycidyl-2, 4-hexanediol (following formula EP-16), glycerin polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, Denacol EX-313, Denacol EX-611, Denacol EX-321, And de Call EX-411 (trade names, manufactured by Nagase Chemtex Co., Ltd.) and the like.

Examples of the polysulfide-type diglycidyl ether compound include FLDP-50 and FLDP-60 (both are trade names, manufactured by Toraythiol Co., Ltd.).

Examples of the biphenol type epoxy compound include YX-4000, YL-6121H (all trade names, manufactured by Mitsubishi Chemical Corporation), NC-3000P, and NC-3000S (all trade names, manufactured by Nippon Kayaku Co., Ltd.). ).

Examples of the diglycidyl ester compound include diglycidyl terephthalate (following formula EP-17), diglycidyl phthalate (following formula EP-18), bis (2-methyloxiranylmethyl) phthalate (following formula EP-19), di Examples include glycidyl hexahydrophthalate (following formula EP-20), a compound represented by the following formula EP-21, a compound represented by the following formula EP-22, and a compound represented by the following formula EP-23.

Examples of the glycidyl ester epoxy compound include jER871, jER872 (both trade names, manufactured by Mitsubishi Chemical Corporation), Epicron 200, Epicron 400 (all trade names, manufactured by DIC Corporation), Denacol EX-711, and Denacol. EX-721 (all are trade names, manufactured by Nagase ChemteX Corporation).

Examples of the polyglycidylamine compound include N, N-diglycidylaniline (following formula EP-24), N, N-diglycidyl-o-toluidine (following formula EP-25), N, N-diglycidyl-m-toluidine ( The following formula EP-26), N, N-diglycidyl-2,4,6-tribromoaniline (the following formula EP-27), 3- (N, N-diglycidyl) aminopropyltrimethoxysilane (the following formula EP-28 ), N, N, O-triglycidyl-p-aminophenol (following formula EP-29), N, N, O-triglycidyl-m-aminophenol (following formula EP-30), N, N, N ′ , N′-tetraglycidyl-4,4′-diaminodiphenylmethane (following formula EP-31), N, N, N ′, N′-tetraglycidyl-m-xylylenediamine (TETRAD) X (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.), the following formula EP-32), 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (TETRAD-C (trade name, Mitsubishi Gas Chemical Co., Ltd.) )), Following formula EP-33), 1,4-bis (N, N-diglycidylaminomethyl) cyclohexane (following formula EP-34), 1,3-bis (N, N-diglycidylamino) cyclohexane (Formula EP-35), 1,4-bis (N, N-diglycidylamino) cyclohexane (Formula EP-36), 1,3-bis (N, N-diglycidylamino) benzene (Formula EP -37), 1,4-bis (N, N-diglycidylamino) benzene (the following formula EP-38), 2,6-bis (N, N-diglycidylaminomethyl) bicyclo [2.2.1] Heptane (Formula EP- 39), N, N, N ′, N′-tetraglycidyl-4,4′-diaminodicyclohexylmethane (the following formula EP-40), 2,2′-dimethyl- (N, N, N ′, N′- Tetraglycidyl) -4,4′-diaminobiphenyl (following formula EP-41), N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenyl ether (following formula EP-42), 1,3 , 5-Tris (4- (N, N-diglycidyl) aminophenoxy) benzene (following formula EP-43), 2,4,4′-tris (N, N-diglycidylamino) diphenyl ether (following formula EP-44) ), Tris (4- (N, N-diglycidyl) aminophenyl) methane (following formula EP-45), 3,4,3 ′, 4′-tetrakis (N, N-diglycidylamino) biphenyl (following formula EP) -46), 3, 4, 3 Examples include ', 4'-tetrakis (N, N-diglycidylamino) diphenyl ether (the following formula EP-47), a compound represented by the following formula EP-48, and a compound represented by the following formula EP-49.

Examples of homopolymers of monomers having oxiranyl include polyglycidyl methacrylate. Examples of the copolymer of monomers having oxiranyl include, for example, N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate. Copolymers, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.

Examples of the monomer having oxiranyl include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

Examples of the monomer other than the monomer having oxiranyl in the copolymer of the monomer having oxiranyl include, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene , Chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

Examples of glycidyl isocyanurate include 1,3,5-triglycidyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (the following formula EP-50), 1,3. -Diglycidyl-5-allyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (following formula EP-51) and glycidyl isocyanurate type epoxy resin.

Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and epolide PB3600 (trade name, manufactured by Daicel Corporation).

Examples of the cycloaliphatic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (Celoxide 2021 (manufactured by Daicel Corporation), the following formula EP-52), 2-methyl -3,4-epoxycyclohexylmethyl-2'-methyl-3 ', 4'-epoxycyclohexylcarboxylate (following formula EP-53), 2,3-epoxycyclopentane-2', 3'-epoxycyclopentane ether (Formula EP-54), ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2: 8,9-diepoxy limonene (Celoxide 3000 (trade name, ( Manufactured by Daicel Corporation), the following formula EP-55), a compound represented by the following formula EP-56, Y-175, CY-177, CY-179 (all are trade names, manufactured by The Ciba-Geigy Chemical Corp. (available from Huntsman Japan)), EHPD-3150 (trade names, Daicel Corporation) And cycloaliphatic epoxy resins.

The epoxy compound is preferably one or more of a polyglycidylamine compound, a bisphenol A novolac type epoxy compound, a cresol novolac type epoxy compound, and a cyclic aliphatic type epoxy compound, and N, N, N ′, N′-tetraglycidyl -M-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, trade name “Techmore VG3101L” 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, N, N, O-triglycidyl-p-aminophenol, bisphenol A novolac type epoxy compound And more preferably one or more cresol novolac type epoxy compound.

For example, the liquid crystal aligning agent of this invention may further contain various additives. Examples of the various additives include high molecular compounds other than polyamic acid and its derivatives, and low molecular compounds, which can be selected and used according to their respective purposes.

Examples of the polymer compound include polymer compounds that are soluble in an organic solvent. It is preferable to add such a polymer compound to the liquid crystal aligning agent of the present invention from the viewpoint of controlling the electrical characteristics and orientation of the liquid crystal alignment film to be formed. Examples of the polymer compound include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, and silicone-modified polyester.

Examples of the low molecular weight compound include 1) a surfactant in accordance with the purpose when improvement in coatability is desired, 2) an antistatic agent when improvement in antistatic is required, and 3) adhesion to the substrate. A silane coupling agent or a titanium-based coupling agent is desired when improvement is desired, and 4) an imidization catalyst when imidization proceeds at a low temperature.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyltri Methoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane , 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, and N, N′-bis [3- (trimethoxysilyl) Propyl] ethylenediamine. A preferred silane coupling agent is 3-aminopropyltriethoxysilane.

Examples of imidation catalysts include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline, methyl-substituted aniline, and hydroxy-substituted aniline. And cyclic amines such as pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxy-substituted isoquinoline, imidazole, methyl-substituted imidazole, and hydroxy-substituted imidazole. . The imidation catalyst may be one or more selected from N, N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline. preferable.

The addition amount of the silane coupling agent is usually 0 to 20% by weight, preferably 0.1 to 10% by weight, based on the total weight of the polyamic acid or its derivative.

The amount of the imidation catalyst added is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents, relative to the carbonyl group of the polyamic acid or derivative thereof.

The addition amount of other additives varies depending on the application, but is usually 0 to 100% by weight, preferably 0.1 to 50% by weight, based on the total weight of the polyamic acid or derivative thereof.

The polyamic acid or derivative thereof of the present invention can be produced in the same manner as a known polyamic acid or derivative thereof used for forming a polyimide film. The total amount of tetracarboxylic dianhydride is preferably approximately equimolar to the total number of moles of diamine (molar ratio of about 0.9 to 1.1).

The molecular weight of the polyamic acid or derivative thereof according to the present invention is preferably 7,000 to 500,000, more preferably 10,000 to 200,000 in terms of polystyrene-equivalent weight average molecular weight (Mw). The molecular weight of the polyamic acid or derivative thereof can be determined from measurement by gel permeation chromatography (GPC).

The presence of the polyamic acid or derivative thereof of the present invention can be confirmed by analyzing the solid content obtained by precipitation with a large amount of poor solvent by IR or NMR. It is also possible to confirm the monomer used by analyzing the extract of the decomposition product of the polyamic acid or its derivative with an aqueous solution of strong alkali such as KOH or NaOH by an organic solvent by GC, HPLC or GC-MS. it can.

For example, the liquid crystal aligning agent of this invention may further contain the solvent from a viewpoint of the applicability | paintability of a liquid crystal aligning agent, and the adjustment of the density | concentration of the said polyamic acid or its derivative (s). The solvent can be applied without any particular limitation as long as it has a capability of dissolving the polymer component. The said solvent contains the solvent normally used in the manufacturing process and use surface of polymer components, such as a polyamic acid and a soluble polyimide, and can be suitably selected according to the intended purpose. The solvent may be one type or a mixed solvent of two or more types.

The concentration of the polyamic acid or derivative thereof in the alignment agent of the present invention is preferably 0.1 to 40% by weight. When this aligning agent is applied to the substrate, an operation of diluting the contained polyamic acid with a solvent in advance may be required to adjust the film thickness.

The solid content concentration in the alignment agent of the present invention is not particularly limited, and an optimum value may be selected according to the following various coating methods. Usually, in order to suppress unevenness and pinholes at the time of application, the content is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight, based on the varnish weight.

The preferred range of the viscosity of the liquid crystal aligning agent of the present invention varies depending on the coating method, the concentration of the polyamic acid or derivative thereof, the type of polyamic acid or derivative used, and the type and ratio of the solvent. For example, in the case of application by a printing press, it is 5 to 100 mPa · s (more preferably 10 to 80 mPa · s). If it is less than 5 mPa · s, it is difficult to obtain a sufficient film thickness, and if it exceeds 100 mPa · s, printing unevenness may increase. In the case of application by spin coating, 5 to 200 mPa · s (more preferably 10 to 100 mPa · s) is suitable. In the case of coating using an inkjet coating apparatus, 5 to 50 mPa · s (more preferably 5 to 20 mPa · s) is suitable. The viscosity of the liquid crystal aligning agent is measured by a rotational viscosity measuring method, and is measured using a rotational viscometer (TVE-20L type manufactured by Toki Sangyo Co., Ltd.) (measurement temperature: 25 ° C.).

The liquid crystal alignment film of the present invention will be described in detail. The liquid crystal alignment film of this invention is a film | membrane formed by heating the coating film of the liquid crystal aligning agent of this invention mentioned above. The liquid crystal alignment film of the present invention can be obtained by an ordinary method for producing a liquid crystal alignment film from a liquid crystal aligning agent. For example, the liquid crystal alignment film of the present invention can be obtained through a step of forming a coating film of the liquid crystal alignment agent of the present invention, a step of drying by heating, and a step of baking by heating. About the liquid crystal aligning film of this invention, you may give anisotropy by rubbing the film | membrane obtained through a heat-drying process and a heat-firing process as needed later as needed. Or as needed, you may provide anisotropy by irradiating light after a coating-film process and a heat drying process, or irradiating light after a heat-firing process. Moreover, you may use as a liquid crystal aligning film for VA which does not perform a rubbing process.

A coating film can be formed by apply | coating the liquid crystal aligning agent of this invention to the board | substrate in a liquid crystal display element similarly to preparation of a normal liquid crystal aligning film. Examples of the substrate include a glass substrate in which electrodes such as ITO (Indium Tin Oxide), IZO (In ₂ O ₃ —ZnO), and IGZO (In—Ga—ZnO ₄ ) electrodes and a color filter may be provided. .

As a method for applying a liquid crystal aligning agent to a substrate, a spinner method, a printing method, a dipping method, a dropping method, an ink jet method and the like are generally known. These methods are similarly applicable in the present invention.

As the heat drying step, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. The heat drying step is preferably performed at a temperature within a range where the solvent can be evaporated, and more preferably at a temperature relatively lower than the temperature in the heat baking step. Specifically, the heat drying temperature is preferably in the range of 30 ° C to 150 ° C, and more preferably in the range of 50 ° C to 120 ° C.

The heating and baking step can be performed under conditions necessary for the polyamic acid or its derivative to exhibit a dehydration / ring-closure reaction. As for the baking of the coating film, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. These methods are equally applicable in the present invention. In general, it is preferably performed at a temperature of about 100 to 300 ° C for 1 minute to 3 hours, more preferably 120 to 280 ° C, and further preferably 150 to 250 ° C. Further, it can be heated and fired a plurality of times at different temperatures. A plurality of heating devices set to different temperatures may be used, or a single heating device may be used while sequentially changing to different temperatures. When performing baking twice at different temperatures, the first time is preferably 90 to 180 ° C., and the second time is preferably 185 ° C. or more.

In the method for forming a liquid crystal alignment film of the present invention, a rubbing method, a photo alignment method, etc. are known as means for imparting anisotropy to the alignment film in order to align the liquid crystal in one direction with respect to the horizontal and / or vertical direction. The forming method can be suitably used.

The liquid crystal alignment film of the present invention using the rubbing method includes a step of applying the liquid crystal alignment agent of the present invention to a substrate, a step of heating and drying the substrate coated with the alignment agent, a step of heating and baking the film, Can be formed through a rubbing process.

The rubbing treatment can be performed in the same manner as the rubbing treatment for the alignment treatment of a normal liquid crystal alignment film, and may be any conditions as long as sufficient retardation is obtained in the liquid crystal alignment film of the present invention. The preferable conditions are a push-in amount of 0.2 to 0.8 mm, a stage moving speed of 5 to 250 mm / sec, and a roller rotation speed of 500 to 2,000 rpm.

The method for forming the liquid crystal alignment film of the present invention by the photo-alignment method will be described in detail. The liquid crystal alignment film of the present invention using the photo-alignment method gives the film anisotropy by irradiating with linearly polarized light or non-polarized light after the coating film is heated and dried, and the film is heated and fired. Can be formed. Or it can form by irradiating the linearly polarized light or non-polarized light of a radiation, after heating-drying and heating-baking a coating film. From the viewpoint of orientation, the radiation irradiation step is preferably performed before the heating and baking step.

Furthermore, in order to raise the liquid crystal aligning ability of a liquid crystal aligning film, a linearly polarized light or non-polarized light can be irradiated while heating a coating film. Irradiation may be performed in a step of heating and drying the coating film or a step of heating and baking, or may be performed between the heating and drying step and the heating and baking step. The heating and drying temperature in this step is preferably in the range of 30 ° C to 150 ° C, and more preferably in the range of 50 ° C to 120 ° C. Moreover, it is preferable that the heat-firing temperature in this process is the range of 30 degreeC-300 degreeC, Furthermore, it is preferable that it is the range of 50 degreeC-250 degreeC.

As the radiation, for example, ultraviolet light or visible light including light having a wavelength of 150 to 800 nm can be used, but ultraviolet light including light of 300 to 400 nm is preferable. Further, linearly polarized light or non-polarized light can be used. These lights are not particularly limited as long as they can impart a liquid crystal alignment ability to the coating film, but linearly polarized light is preferable when it is desired to develop a strong alignment regulating force for liquid crystals.

The liquid crystal alignment film of the present invention can exhibit high liquid crystal alignment ability even with low energy light irradiation. Dose of linearly polarized light in the irradiation step is preferably from 0.05~20J / cm ^2, more preferably 0.5~10J / cm ^2. The wavelength of linearly polarized light is preferably 200 to 400 nm, and more preferably 300 to 400 nm. Although the irradiation angle with respect to the film surface of linearly polarized light is not particularly limited, it is preferable from the viewpoint of shortening the alignment processing time that it is as perpendicular as possible to the film surface in order to develop a strong alignment regulating force for the liquid crystal. The liquid crystal alignment film of the present invention can align liquid crystal in a direction perpendicular to the polarization direction of linearly polarized light by irradiating linearly polarized light.

When the pretilt angle is to be expressed, the light applied to the film may be linearly polarized light or non-polarized light as described above. Dose of light applied to the film when it is desired to express a pre-tilt angle is preferably from 0.05~20J / cm ^2, particularly preferably 0.5~10J / cm ^2, its wavelength is 250 400 nm is preferable, and 300 to 380 nm is particularly preferable. When it is desired to develop a pretilt angle, the irradiation angle of the light applied to the film with respect to the film surface is not particularly limited, but is preferably 30 to 60 degrees from the viewpoint of shortening the alignment processing time.

The light source used in the process of irradiating linearly polarized light or non-polarized light includes ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, deep UV lamp, halogen lamp, metal halide lamp, high power metal halide lamp, xenon lamp, mercury A xenon lamp, an excimer lamp, a KrF excimer laser, a fluorescent lamp, an LED lamp, a sodium lamp, a microwave excitation electrodeless lamp, or the like can be used without limitation.

The liquid crystal alignment film of the present invention can be suitably obtained by a method that further includes steps other than the steps described above. For example, the liquid crystal alignment film of the present invention does not require a process of cleaning the film after baking or radiation irradiation with a cleaning liquid, but a cleaning process can be provided for convenience of other processes.

Examples of the cleaning method using the cleaning liquid include brushing, jet spray, steam cleaning, and ultrasonic cleaning. These methods may be performed alone or in combination. The cleaning liquid is pure water, various alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, xylene, halogen solvents such as methylene chloride, and ketones such as acetone and methyl ethyl ketone. Although it can be used, it is not limited to these. Of course, these cleaning liquids are sufficiently purified and have few impurities. Such a cleaning method can also be applied to the cleaning step in the formation of the liquid crystal alignment film of the present invention.

In order to enhance the liquid crystal alignment ability of the liquid crystal alignment film of the present invention, annealing treatment with heat or light can be used before or after the heating and baking step, before or after the rubbing step, or before or after irradiation with polarized or non-polarized radiation. . In the annealing treatment, the annealing temperature is 30 to 180 ° C., preferably 50 to 150 ° C., and the time is preferably 1 minute to 2 hours. Examples of the annealing light used for the annealing treatment include a UV lamp, a fluorescent lamp, and an LED lamp. The light irradiation amount is preferably 0.3 to 10 J / cm ² .

Although the film thickness of the liquid crystal aligning film of this invention is not specifically limited, It is preferable that it is 10-300 nm, and it is more preferable that it is 30-150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as a step meter or an ellipsometer.

The liquid crystal alignment film of the present invention is particularly characterized by having a large alignment anisotropy. The magnitude of such anisotropy can be evaluated by a method using polarized IR described in JP-A-2005-275364. Further, as shown in the following examples, evaluation can also be made by a method using ellipsometry. Specifically, the retardation value of the liquid crystal alignment film can be measured by a spectroscopic ellipsometer. The retardation value of the film increases in proportion to the degree of orientation of the polymer main chain. That is, those having a large retardation value have a large degree of alignment, and when used as a liquid crystal alignment film, an alignment film having a greater anisotropy is considered to have a large alignment regulating force on the liquid crystal composition.

The liquid crystal alignment film of the present invention can be suitably used for a horizontal electric field type liquid crystal display element. When used in a horizontal electric field type liquid crystal display element, the smaller the Pt angle and the higher the liquid crystal alignment ability, the higher the black display level in the dark state and the better the contrast. The Pt angle is preferably 0.1 ° or less.

The liquid crystal alignment film of the present invention can be used for alignment control of an optical compensation material and all other liquid crystal materials in addition to the alignment use of a liquid crystal composition for a liquid crystal display. Further, since the alignment film of the present invention has large anisotropy, it can be used alone for an optical compensator application.

The liquid crystal display element of the present invention will be described in detail.
The present invention is formed on a pair of substrates disposed opposite to each other, an electrode formed on one or both of the surfaces opposed to each of the pair of substrates, and a surface opposed to each of the pair of substrates. A liquid crystal display element having a liquid crystal alignment film formed and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the alignment film of the present invention.

The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such electrodes include ITO and metal vapor deposition films. Further, the electrode may be formed on the entire surface of one surface of the substrate, or may be formed in a desired shape that is patterned, for example. Examples of the desired shape of the electrode include a comb shape or a zigzag structure. The electrode may be formed on one of the pair of substrates, or may be formed on both substrates. The form of electrode formation varies depending on the type of liquid crystal display element. For example, in the case of an IPS liquid crystal display element, an electrode is disposed on one of the pair of substrates, and in the case of other liquid crystal display elements, the electrodes of the pair of substrates are arranged. Electrodes are arranged on both sides. The liquid crystal alignment film is formed on the substrate or electrode.

The liquid crystal layer is formed in such a manner that the liquid crystal composition is sandwiched between the pair of substrates facing each other on which the liquid crystal alignment film is formed. In the formation of the liquid crystal layer, a spacer such as fine particles or a resin sheet that is interposed between the pair of substrates to form an appropriate interval can be used as necessary.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having a positive or negative dielectric anisotropy can be used. Preferred liquid crystal compositions having a positive dielectric anisotropy include Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Application Laid-Open No. 5-501735, Japanese Patent Application Laid-Open No. 8-157826, Japanese Patent Application Laid-Open No. 8-231960, Japanese Patent Application Laid-Open No. 9-241644 (EP 8852272A1), Kaihei 9-302346 (EP806466A1), JP-A-8-199168 (EP722998A1), JP-A-9-235552, JP-A-9-255556, JP-A-9-241643 (EP885271A1), JP-A-10-204016 (EP844229A1), JP-A-10 -204436, JP-A-10-231482, JP-A-2000-087040, JP-A-2001-48822, and the like.

One or more optically active compounds may be added to a liquid crystal composition having a positive or negative dielectric anisotropy.

ここで、Ｒ^１ａおよびＲ^２ａは独立して、炭素数１〜１２のアルキル、炭素数１〜１２のアルコキシ、炭素数２〜１２のアルケニル、または少なくとも１つの水素がフッ素で置き換えられた炭素数２〜１２のアルケニルであり、環Ａ^２および環Ｂ^２は独立して、１，４−シクロへキシレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，５−ジフルオロ−１，４−フェニレン、２，３−ジフルオロ−１，４−フェニレン、２−フルオロ−３−クロロ−１，４−フェニレン、２，３−ジフルオロ−６−メチル−１，４−フェニレン、２，６−ナフタレンジイル、または７，８−ジフルオロクロマン−２，６−ジイルであり、ここで、環Ａ^２および環Ｂ^２の少なくとも１つは２，３−ジフルオロ−１，４−フェニレン、２−フルオロ−３−クロロ−１，４−フェニレン、２，３−ジフルオロ−６−メチル−１，４−フェニレン、または７，８−ジフルオロクロマン−２，６−ジイルであり、Ｚ^１は独立して単結合、−（ＣＨ_２）_２−、−ＣＨ_２Ｏ−、−ＣＯＯ−、または−ＣＦ_２Ｏ−であり、ｊは１、２、または３であり、ｊが２または３である時、任意の２つの環Ａ^２は同じであっても異なってもよく、任意の２つのＺ^１は同じであっても異なってもよい。 The liquid crystal composition having a negative dielectric anisotropy will be described. Examples of the negative dielectric anisotropy liquid crystal composition include a composition containing at least one liquid crystal compound selected from the group of liquid crystal compounds represented by the following formula (NL-1) as the first component. .

Here, R ^1a and R ^2a are independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or a carbon number in which at least one hydrogen is replaced by fluorine. 2-12 alkenyl, ring A ² and ring B ² are independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1 , 4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-fluoro-3-chloro-1,4 - phenylene, a 2,3-difluoro-6-methyl-1,4-phenylene, 2,6-naphthalene-diyl or 7,8-difluoro-chroman-2,6-diyl, wherein the ring ^{a 2} Contact At least one 2,3-difluoro-1,4-phenylene fine ring ^{B 2,} 2-fluoro-3-chloro-1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phenylene , Or 7,8-difluorochroman-2,6-diyl, and Z ¹ is independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —COO—, or —CF ₂ O—. And j is 1, 2 or 3, and when j is 2 or 3, any two rings A ² may be the same or different and any two Z ¹ are the same It may or may not be.

Preferred ring A ² and ring B ² are each 2,3-difluoro-1,4-phenylene or tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and 1, for decreasing the viscosity, 4-cyclohexylene.

Preferred Z ¹ is —CH ₂ O— for increasing the dielectric anisotropy, and a single bond for decreasing the viscosity.

Preferred j is 1 for decreasing the minimum temperature, and 2 for increasing the maximum temperature.

ここで、Ｒ^１aおよびＲ^２ａは独立して、炭素数１〜１２のアルキル、炭素数１〜１２のアルコキシ、炭素数２〜１２のアルケニル、または少なくとも１つの水素がフッ素で置き換えられた炭素数２〜１２のアルケニルであり、環Ａ^２１、環Ａ^２２、環Ａ^２３、環Ｂ^２１、および環Ｂ^２２は独立して、１，４−シクロへキシレンまたは１，４−フェニレンであり、Ｚ^１１およびＺ^１２は、独立して単結合、−（ＣＨ_２）_２−、−ＣＨ_２Ｏ−、または−ＣＯＯ−である。 Specific examples of the liquid crystal compound of the above formula (NL-1) include compounds represented by the following formulas (NL-1-1) to (NL-1-32).

Here, R ^1a and R ^2a are independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or a carbon number in which at least one hydrogen is replaced by fluorine. 2-12 alkenyl, ring A ²¹ , ring A ²² , ring A ²³ , ring B ²¹ , and ring B ²² are independently 1,4-cyclohexylene or 1,4-phenylene; ¹¹ and Z ¹² are each independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, or —COO—.

Desirable R ^1a and R ^2a are alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat, etc., or alkoxy having 1 to 12 carbons for increasing the absolute value of dielectric anisotropy.

Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More desirable alkyl is ethyl, propyl, butyl, pentyl, or heptyl for decreasing the viscosity.

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More desirable alkoxy is methoxy or ethoxy for decreasing the viscosity.

Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More desirable alkenyl is vinyl, 1-propenyl, 3-butenyl or 3-pentenyl for decreasing the viscosity. The preferred configuration of —CH═CH— in these alkenyls depends on the position of the double bond. Trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for the purpose of decreasing the viscosity. Cis is preferable in alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl. In these alkenyl, linear alkenyl is preferable to branching.

Preferred examples of alkenyl in which at least one hydrogen is replaced by fluorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro-4 -Pentenyl, and 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl and 4,4-difluoro-3-butenyl for decreasing the viscosity.

Desirable ring A ²¹ , ring A ²² , ring A ²³ , ring B ²¹ , and ring B ²² are each 1,4-cyclohexylene for decreasing the viscosity.

Desirable Z ¹¹ and Z ¹² are —CH ₂ O— for increasing the dielectric anisotropy, and a single bond for decreasing the viscosity.

The compound (NL-1) in which the liquid crystal composition having negative dielectric anisotropy is preferably used as the first component is the compounds (NL-1-1), (NL-1-4), (NL-1- 7) or (NL-1-32).

Preferred examples of the liquid crystal composition having negative dielectric anisotropy are disclosed in JP-A-57-114532, JP-A-2-4725, JP-A-4-224855, JP-A-8-40953, JP-A-8-104869, Kaihei 10-168076, JP-A-10-168453, JP-A-10-236989, JP-A-10-236990, JP-A-10-236992, JP-A-10-236993, JP-A-10-236994, JP-A-10-237000, JP-A-10-237000 -237004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075, JP-A-10-237076, JP-A-10-237448 (EP967261A1), JP-A-10-287874, JP-A-10-287875, JP-A-10-287875. 10-291945, JP-A-11-029581, Kaihei 11-080049, JP 2000-256307, JP 2001-019965, JP 2001-072626, JP 2001-192657, JP 2010-037428, International Publication 2011/024666, International Publication 2010/072370, Special Table 2010. Examples thereof include liquid crystal compositions disclosed in Japanese Patent No. 5370010, Japanese Patent Application Laid-Open No. 2012-0702201, Japanese Patent Application Laid-Open No. 2009-084362, and the like.

Further, for example, the liquid crystal composition used in the device of the present invention may further contain an additive from the viewpoint of improving the orientation. Such additives are photopolymerizable monomers, optically active compounds, antioxidants, UV absorbers, dyes, antifoaming agents, polymerization initiators, polymerization inhibitors, and the like.

As the most preferable structure of the photopolymerizable monomer or oligomer for the purpose of improving the orientation of the liquid crystal, structures of the formulas (PM-1-1) to (PM-1-6) are exemplified.

The photopolymerizable monomer or oligomer is desirably 0.01% by weight or more in order to exhibit the effect of determining the tilt direction of the liquid crystal after polymerization. Further, in order to make the orientation effect of the polymer after polymerization appropriate, or in order to avoid the unreacted monomer or oligomer from eluting into the liquid crystal after ultraviolet irradiation, the content is preferably 30% by weight or less.

An optically active compound is mixed with the composition for the purpose of inducing a helical structure of liquid crystal to give a twist angle. Examples of such compounds are compound (PAC-1-1) to compound (PAC-1-4). A desirable ratio of the optically active compound is 5% by weight or less. A more desirable ratio is in the range of 0.01% to 2% by weight.

In order to prevent a decrease in specific resistance due to heating in the atmosphere or to maintain a large voltage holding ratio not only at room temperature but also at a high temperature after using the device for a long time, an antioxidant is added to the liquid crystal composition. Mixed.

A preferable example of the antioxidant is a compound (AO-1) or the like in which w is an integer of 1 to 10. In the compound (AO-1), preferred w is 1, 3, 5, 7, or 9. Further preferred w is 1 or 7. Since the compound (AO-1) in which w is 1 has high volatility, it is effective in preventing a decrease in specific resistance due to heating in the atmosphere. Since the compound (AO-1) in which w is 7 has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a high temperature after the device has been used for a long time. A desirable ratio of the antioxidant is 50 ppm or more for achieving its effect, and is 600 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of 100 ppm to 300 ppm.

Preferred examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines. A desirable ratio in these absorbents and stabilizers is 50 ppm or more for obtaining the effect thereof, and 10,000 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of 100 ppm to 10,000 ppm.

A dichroic dye such as an azo dye or an anthraquinone dye is mixed with the composition in order to adapt to a GH (Guest host) mode element. A preferred ratio of the dye is in the range of 0.01% by weight to 10% by weight.

In order to prevent foaming, an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is mixed with the composition. A desirable ratio of the antifoaming agent is 1 ppm or more for obtaining the effect thereof, and 1000 ppm or less for preventing a poor display. A more desirable ratio is in the range of 1 ppm to 500 ppm.

A polymerizable compound can be mixed with the composition in order to adapt to a device having a polymer sustained alignment (PSA) mode. Preferred examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. Particularly preferred examples are acrylate or methacrylate derivatives. Examples of such a compound are from the compound (PM-2-1) to the compound (PM-2-9). A desirable ratio of the polymerizable compound is approximately 0.05% by weight or more for obtaining the effect thereof, and approximately 10% by weight or less for preventing a display defect. A more desirable ratio is in the range of approximately 0.1% by weight to approximately 2% by weight.

ここで、Ｒ^３ａ、Ｒ^４ａ、Ｒ^５ａ、およびＲ^６ａは独立して、アクリロイルまたはメタクリロイルであり、Ｒ^７ａおよびＲ^８ａは独立して、水素、ハロゲン、または炭素数１から１０のアルキルであり、Ｚ^１３、Ｚ^１４、Ｚ^１５、およびＺ^１６は独立して、単結合または炭素数１から１２のアルキレンであり、少なくとも１つの−ＣＨ_２−は−Ｏ−または−ＣＨ＝ＣＨ−により置き換えられていてもよく、ｓ、ｔ、およびｕは独立して、０、１、または２である。

Wherein R ^3a , R ^4a , R ^5a , and R ^6a are independently acryloyl or methacryloyl, and R ^7a and R ^8a are independently hydrogen, halogen, or alkyl having 1 to 10 carbons. , Z ¹³ , Z ¹⁴ , Z ¹⁵ , and Z ¹⁶ are each independently a single bond or alkylene having 1 to 12 carbons, and at least one —CH ₂ — is replaced by —O— or —CH═CH—. S, t, and u are independently 0, 1, or 2.

A polymerization initiator can be mixed as a substance necessary for easily generating radicals or ions and initiating a chain polymerization reaction. For example, Irgacure 651 (registered trademark), Irgacure 184 (registered trademark), or Darocure 1173 (registered trademark) (Ciba Japan KK), which is a photopolymerization initiator, is suitable for radical polymerization. The polymerizable compound preferably contains a photopolymerization initiator in the range of 0.1% to 5% by weight. Particularly preferably, the photopolymerization initiator is contained in the range of 1 to 3% by weight.

In a radical polymerization system, a polymerization inhibitor is mixed for the purpose of rapidly reacting with a radical generated from a polymerization initiator or monomer to change to a stable radical or neutral compound, and as a result, stop the polymerization reaction. Can do. Polymerization inhibitors are classified into several structures. One is a radical that is itself stable, such as tri-p-nitrophenylmethyl, di-p-fluorophenylamine, and the other is a stable radical that reacts readily with radicals present in the polymerization system. Typical examples are nitro, nitriso, amino, polyhydroxy compounds and the like. Representative examples of the latter include hydroquinone and dimethoxybenzene. A desirable ratio of the polymerization inhibitor is 5 ppm or more for obtaining the effect thereof, and 1000 ppm or less for preventing a poor display. A more desirable ratio is in the range of 5 ppm to 500 ppm.

Hereinafter, the present invention will be described with reference to examples. The evaluation methods and compounds used in the examples are as follows.

<Evaluation method>
1. Weight average molecular weight (Mw)
The weight average molecular weight of the polyamic acid was measured by GPC method using a 2695 separation module / 2414 differential refractometer (manufactured by Waters) and calculated by polystyrene conversion. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid / DMF = 0.6 / 100: weight ratio) so that the polyamic acid concentration was about 2% by weight. The column was HSPgel RT MB-M (manufactured by Waters), and measurement was performed under the conditions of a column temperature of 50 ° C. and a flow rate of 0.40 mL / min using the mixed solution as a developing agent. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh Corporation was used.

2. Wetting and spreading by drop test Nichipet EX Plus II (volume range: 0.5 to 10 μl) manufactured by NICHIYO is equipped with Pipette Tips (Volume: 20 μl) manufactured by BioPoint Scientific and filled with 10 μl of alignment film. This was dropped on a substrate with ITO, allowed to stand for 240 seconds, and then dried on a hot plate at 60 ° C. for 600 seconds. Thereafter, the wetting spread of the alignment film was measured with a ruler, and a judgment criterion was set as follows.
Criteria for wet spreading by drop test-Less than 40mm ×
・ 40mm or more and less than 43mm △
・ 43mm or more and less than 45mm ○ ・ 45mm or more ◎

3. It applied to the board | substrate with ITO using the inkjet apparatus EB100XY100 by the in-plane smooth laconica Minolta company in inkjet printing. After coating, the solution was allowed to stand for 180 seconds and dried on a 60 ° C. hot plate for 80 seconds. Then, the presence or absence of in-plane uneven stripes on the coated substrate was visually confirmed.
Head: KM512MH (No. of nozzles: 512 droplets 14pL)
Head temperature: 25 ° C
Applied voltage: 19V
Frequency 709Hz
Resolution 360 dpi
Conveyance speed 50mm / sec
Head / glass substrate spacing 28mm

4). Contrast The contrast of the liquid crystal display element described later was evaluated using a luminance meter (YOKOGAWA 3298F). A liquid crystal display element was placed under a polarizing microscope in a crossed Nicol state, and the minimum luminance was measured as black luminance. Next, an arbitrary rectangular wave voltage was applied to the device, and the maximum luminance was measured as white luminance. This white luminance / black luminance value was defined as contrast. The contrast is less than 2500, poor, 2500 or more and less than 3000, good, and 3000 or more is judged to be the best.

5. AC Afterimage Measurement Luminance-voltage characteristics (BV characteristics) of a liquid crystal display element described later were measured. This is the luminance-voltage characteristic before stress application: B (before). Next, a 4.5 V, 60 Hz alternating current was applied to the device for 20 minutes, then shorted for 1 second, and the luminance-voltage characteristics (BV characteristics) were measured again. This is the luminance-voltage characteristic after stress application: B (after). Based on these values, the luminance change rate ΔB (%)

ΔB (%) = [B (after) −B (before)] / B (before) (formula AC1)

Estimated using the following formula. These measurements were performed with reference to International Publication No. 2000/43833 pamphlet. It can be said that the smaller the value of ΔB (%) at a voltage of 0.75 V, the more the generation of AC afterimages can be suppressed, which is defective at 6.0% or more, good at 3.0% or more and less than 6.0%, 3.0% Less than the best.

<Tetracarboxylic dianhydride>

<Diamine>

<Solvent>
NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone BC: butyl cellosolve BP: 1-butoxy-2-propanol EDM: diethylene glycol ethyl methyl ether EDE: diethylene glycol diethyl ether BDM: diethylene glycol butyl methyl ether DIBC: diisobutyl carbinol 2P: 2-pentanone 3P: 3-pentanone 4M2P: 4-methyl-2-pentanone DIBK: diisobutyl ketone MIBC: 4-methyl-2-pentanol

<Additives>
Add. 1: 1,3-bis (4,5-dihydro-2-oxazolyl) benzene Add. 2: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Add. 3: 3,3 ′, 4,4′-diepoxybicyclohexyl

<Synthesis of polyamic acid>
[Synthesis Example A-1]
In a 200 mL brown four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet and a nitrogen gas inlet, 1.4209 g of the compound represented by formula (V-2-1), formula (DI-5-1) 0.6666 g of the compound represented by (m = 4), 0.0257 g of the compound represented by the formula (DI-13-1) and 44.0 g of dehydrated NMP were added and dissolved by stirring under a dry nitrogen stream. Next, 3.8869 g of a compound represented by the formula (AN-4-17) (m = 8) and 20.0 g of dehydrated NMP were added, and stirring was continued at room temperature for 24 hours. BC20.0g was added to this reaction solution, and the polyamic acid solution whose polymer solid content concentration is 6 weight% was obtained. Let this polyamic acid solution be (PA-1). The weight average molecular weight of the polyamic acid contained in (PA-1) was 10,300.

[Synthesis Examples A-2 to A-4]
Except for changing the tetracarboxylic dianhydride, diamine, and solvent composition, polyamic acid solutions (PA-2) to (PA-4) having a polymer solid concentration of 6% by weight in accordance with Synthesis Example A-1 Was prepared. The composition of the raw material and the solvent is shown in Table 1 together with (PA-1).

[Synthesis Example B-1]
In a 200 mL brown four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet and a nitrogen gas inlet, 1.9123 g of a compound represented by formula (DI-13-1), formula (DI-5-9) 1.3670 g of the compound represented by formula (DI-4-1) and 44.0 g of dehydrated NMP were added and dissolved under stirring in a dry nitrogen stream. 1.8354 g of a compound represented by the formula (AN-1-1), 1.0880 g of a compound represented by the formula (AN-3-2), and 20.0 g of dehydrated NMP were added, and stirring was continued at room temperature for 24 hours. . BC30.0g was added to this reaction solution, and the polyamic acid solution whose polymer solid content concentration is 6 weight% was obtained. This polyamic acid solution is defined as (PB-1). The weight average molecular weight of the polyamic acid contained in (PB-1) was 50,000.

[Synthesis Examples B-2 to B-7]
Except for changing the solvent composition, polyamic acid solutions (PB-2) to (PB-7) having a polymer solid concentration of 6% by weight were prepared according to Synthesis Example B-1. The composition of the raw material and the solvent is shown in Table 2 together with (PB-1).

<Polymer blend>
[Synthesis Example C-1]
[A] A polyamic acid solution (PA-1) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example A-1 and a polyamic acid having a polymer solid content concentration of 6% by weight prepared in [B] Synthesis Example B-1 The solution (PB-1) was mixed at [A] / [B] = 3.0 / 7.0 (weight ratio). This mixed solution was further diluted with an NMP / BC solution, and a polyamic acid solution having a polymer solid content concentration of 4.0% by weight was defined as (PC-1). At this time, the composition ratio (weight ratio) of the solvent used for dilution is NMP 25.667 g and BC 11.000 g.

[Synthesis Examples C-2 to C-35]
[A] One polyamic acid solution selected from polyamic acid solutions (PA-1) to (PA-4), and [B] a polyamic acid solution consisting of polyamic acid solutions (PB-1) to (PB-5) The mixture is mixed at a weight ratio [A] / [B] = 3.0 / 7.0, and further diluted with various solvents so that the polymer solid content concentration becomes 4.0% by weight. Solutions (PC-1) to (PC-31) were prepared. For polyamic acids (PC-32) to (PC-35), one polyamic acid solution selected from polyamic acids (PB-6) and (PB-7) is used with a polymer solid content concentration of 4.0 weight. % Was prepared by diluting with various solvents. Table 3 shows the composition ratio of the polyamic acid solution and the solvent together with (PC-1).

[Synthesis Example D-1]
In a polyamic acid solution (PC-3) having a polymer solid content concentration of 4.0 parts by weight, 15 parts by weight of additive (Add.1) and 100 parts by weight of additive (Add.2) are added to 100 parts by weight of polymer. It added in the ratio of 10 weight part with respect to part. Let the obtained polyamic acid solution be (PD-1).

[Synthesis Examples D-2 to D-13]
Except having changed the polyamic acid solution and the additive, the polyamic acid solutions (PD-2) to (PD-13) were prepared according to Synthesis Example D-1. Table 4 shows the additive and solvent composition together with (PD-1).

[Example 1]
<Wet spread by drop test>
A drop test was conducted by the method described above using a blended polymer solid concentration of 4.0% by weight of polyamic acid solution (PC-22) as a liquid crystal aligning agent.
As a result, the wetting spread was 45 mm or more.

<In-plane smoothing in inkjet printing>
Furthermore, the polyamic acid solution (PC-22) was subjected to ink jet printing by the method described above.
As a result, no in-plane unevenness was observed.

[Examples 1 to 20, Comparative Examples 1 to 28]
Except for changing the polyamic acid solution used as the liquid crystal aligning agent, wetting spread and in-plane unevenness were evaluated by the method according to Example 1. The results are shown in Table 5 and Table 6 together with Example 1.

As shown in Tables 5 and 6, when a drop test and inkjet printing were performed on a polyamic acid solution containing MIBC or DIBK as the third solvent, wetting spread and in-plane unevenness were improved. Further, even when an additive was added to the polyamic acid solution, no change was observed in the good wetting spread. On the other hand, the polyamic acid solution containing DIBC, 2P, 3P and 4M2P, which is similar in structure to MIBC, showed no improvement in wetting and spreading.

Although DIBK exhibits the same wetting and spreading as MIBC, it can only be added up to 5% by weight with respect to the polyamic acid solution due to its low solubility, and when it is added more than that, white turbidity and solids are precipitated. On the other hand, MIBC can be added in an amount of 15% by weight or more with respect to the polyamic acid solution, and exhibits higher wetting spread.

<Evaluation of presence / absence of flow orientation during cell injection, contrast and AC afterimage>
[Example 21]
A polyamic acid solution (PC-22) having a polymer solid content concentration of 4% by weight prepared as a blend was used as a liquid crystal aligning agent. ) With an inkjet coating apparatus (inkjet apparatus EB100XY100 manufactured by Konica Minolta). The liquid crystal alignment film was adjusted to the following film thickness by adjusting the droplet interval and the cartridge applied voltage. After the application, it was heated and dried at 70 ° C. for 80 seconds on a hot plate (manufactured by AS ONE, EC hot plate (EC-1200N)). Next, using a multi-light ML-501C / B manufactured by Ushio Electric Co., Ltd., the substrate was irradiated with linearly polarized ultraviolet light from the vertical direction through the polarizing plate. The exposure energy at this time is 1.0 ± 0.1 J / cm ² at a wavelength of 365 nm by measuring the amount of light using a UV integrated light meter UIT-150 (receiver UVD-S365) manufactured by USHIO INC. The exposure time was adjusted. Subsequently, a heat treatment was performed at 230 ° C. for 15 minutes in a clean oven (Espec Corp., PVHC-231) to form a liquid crystal alignment film having a thickness of 100 ± 10 nm.

<FFS cell preparation, flow orientation confirmation, contrast and AC afterimage measurement>
Two substrates on which a liquid crystal alignment film is formed on the substrate are opposed to each other, and the opposite alignment is performed so that the polarization directions of ultraviolet rays irradiated to the respective liquid crystal alignment films are parallel to each other. A gap for injecting the liquid crystal composition was formed between the films and bonded together to assemble an empty FFS cell having a cell thickness of 4 μm. The positive liquid crystal composition 1 was vacuum-injected into the produced empty FFS cell, and the injection port was sealed with a photo-curing agent to produce an FFS liquid crystal display element. When the alignment of the liquid crystal in the obtained liquid crystal display element was confirmed, no fluid alignment was observed. When the contrast value was measured, it was 3010, and when the AC afterimage was measured, ΔB was 1.9%.

Positive liquid crystal composition 1

[Example 22]
Using a polyamic acid solution (PC-22) having a polymer solid content concentration of 4% by weight as a liquid crystal aligning agent, a spinner (Mikasa) on a substrate with SiNx / ITO comb electrodes and a glass substrate with spacers (spacer height: 4 μm). It apply | coated with the spin coater (1H-DX2) made by Corporation. Including the following examples, the rotation speed of the spinner was adjusted according to the viscosity of the liquid crystal aligning agent so that the alignment film had the following film thickness. After the application, it was heated and dried at 70 ° C. for 80 seconds on a hot plate (manufactured by AS ONE, EC hot plate (EC-1200N)). Next, using a multi-light ML-501C / B manufactured by Ushio Electric Co., Ltd., the substrate was irradiated with linearly polarized ultraviolet light from the vertical direction through the polarizing plate. The exposure energy at this time is 1.0 ± 0.1 J / cm ² at a wavelength of 365 nm by measuring the amount of light using a UV integrated light meter UIT-150 (receiver UVD-S365) manufactured by USHIO INC. The exposure time was adjusted. Subsequently, heat treatment was performed at 230 ° C. for 15 minutes in a clean oven (ESPEC Co., Ltd., PVHC-231) to form an alignment film having a thickness of 100 ± 10 nm.

<Preparation of FFS cell, confirmation of flow alignment, contrast and AC afterimage measurement> Two substrates with alignment films formed on the substrate face each other and the alignment films are irradiated to each other. An empty FFS cell having a cell thickness of 4 μm was assembled by forming a gap for injecting the liquid crystal composition between the facing alignment films so that the polarization directions of the ultraviolet rays were parallel. The positive liquid crystal composition 1 was vacuum-injected into the produced empty FFS cell, and the injection port was sealed with a photocuring agent to produce an FFS liquid crystal display element. When the alignment of the liquid crystal in the obtained liquid crystal display element was confirmed, no fluid alignment was observed. When the contrast value was measured, it was 3020, and when the AC afterimage was measured, ΔB was 1.9%.

[Example 23]
An FFS liquid crystal display element was prepared in accordance with the method described in Example 21 except that a polyamic acid solution (PD-10) was used as the liquid crystal aligning agent, and the heat treatment after ultraviolet irradiation was performed at 210 ° C. for 30 minutes. Produced. When the alignment of the liquid crystal in the obtained liquid crystal display element was confirmed, no fluid alignment was observed. When the contrast value was measured, it was 3030, and when the AC afterimage was measured, ΔB was 2.1%.

[Example 24]
An FFS liquid crystal display element was prepared in accordance with the method described in Example 22 except that a polyamic acid solution (PD-10) was used as the liquid crystal aligning agent and the heat treatment after ultraviolet irradiation was performed at 210 ° C. for 30 minutes. Produced. When the alignment of the liquid crystal in the obtained liquid crystal display element was confirmed, no fluid alignment was observed. When the contrast value was measured, it was 3000, and when the AC afterimage was measured, ΔB was 2.3%.

[Example 25]
As described in Example 21, except that a polyamic acid solution (PD-11) was used as the liquid crystal aligning agent, and the heat treatment after irradiation with ultraviolet rays was performed at 160 ° C. for 20 minutes and then at 230 ° C. for 15 minutes. An FFS liquid crystal display element was produced according to the method. When the alignment of the liquid crystal in the obtained liquid crystal display element was confirmed, no fluid alignment was observed. When the contrast value was measured, it was 3010, and when the AC afterimage was measured, ΔB was 2.2%.

[Example 26]
As described in Example 22, except that a polyamic acid solution (PD-11) was used as the liquid crystal aligning agent, and the heat treatment after irradiation with ultraviolet rays was performed at 160 ° C. for 20 minutes and then at 230 ° C. for 15 minutes. An FFS liquid crystal display element was produced according to the method. When the alignment of the liquid crystal in the obtained liquid crystal display element was confirmed, no fluid alignment was observed. When the contrast value was measured, it was 3000, and when the AC afterimage was measured, ΔB was 2.3%.

[Example 27]
As described in Example 21, except that a polyamic acid solution (PC-30) was used as the liquid crystal aligning agent, and the heat treatment after UV irradiation was performed at 180 ° C. for 20 minutes and then at 220 ° C. for 15 minutes. An FFS liquid crystal display element was produced according to the method. When the alignment of the liquid crystal in the obtained liquid crystal display element was confirmed, no fluid alignment was observed. When the contrast value was measured, it was 3100, and when the AC afterimage was measured, ΔB was 2.1%.

[Example 28]
As described in Example 22, except that a polyamic acid solution (PC-30) was used as the liquid crystal aligning agent, and the heat treatment after irradiation with ultraviolet rays was performed at 180 ° C. for 20 minutes and then at 220 ° C. for 15 minutes. An FFS liquid crystal display element was produced according to the method. When the alignment of the liquid crystal in the obtained liquid crystal display element was confirmed, no fluid alignment was observed. When the contrast value was measured, it was 3120, and when the AC afterimage was measured, ΔB was 2.2%.

As described above, the same liquid crystal aligning agent as the FFS liquid crystal display element having the liquid crystal aligning film formed by drying, irradiating with ultraviolet rays, and heat-treating the coating film obtained by printing the liquid crystal aligning agent of the present invention on the substrate by the inkjet method is spin. When an FFS liquid crystal display element having a liquid crystal alignment film formed by coating, coating, drying, ultraviolet irradiation, and heat treatment was compared in terms of the presence / absence of flow alignment, contrast, and AC afterimage, it was determined by the inkjet method. The performance of the photo-alignment film obtained from the coating film was not different from that of the photo-alignment film obtained from the coating film by the spin coating method, and showed good cell characteristics.

It was confirmed that the liquid crystal aligning agent of this invention can form the liquid crystal aligning film with favorable discharge property, in-plane unevenness, and edge linearity. The liquid crystal aligning agent of this invention can be applied suitably in the model which requires a narrow frame.

Claims (8)

  A liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyamic acid and derivatives thereof and a solvent, wherein the solvent contains 4-methyl-2-pentanol.   The liquid crystal aligning agent of Claim 1 whose ratio of 4-methyl-2- pentanol in the said solvent is 0.1 to 20 weight%.   The solvent contains at least one selected from the group consisting of N-methyl-2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, and N-ethyl-2-pyrrolidone as a good solvent. The liquid crystal aligning agent of Claim 1 or 2.   The solvent contains at least one selected from the group consisting of butyl cellosolve, 1-butoxy-2-propanol, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol butyl methyl ether as a poor solvent. The liquid crystal aligning agent of any one of these.   The ratio of the good solvent in the said solvent is 20 to 89 weight%, The liquid crystal of any one of Claims 1-4 whose ratio of a poor solvent is 10 to 60 weight% with respect to the total solvent weight. Alignment agent.   A method for forming a liquid crystal alignment film, comprising a step of applying the liquid crystal aligning agent according to claim 1 to a substrate by an inkjet method.   The manufacturing method of the liquid crystal aligning film containing the process of apply | coating the liquid crystal aligning agent in any one of Claims 1-5, and the process of irradiating this coating film with an ultraviolet-ray. A pair of opposed substrates, an electrode group formed on one or both of the opposed surfaces of each of the pair of substrates, a plurality of active elements connected to the electrode group, and the pair of substrates In a method of manufacturing a liquid crystal display element having a liquid crystal alignment film formed on the opposing surfaces of each substrate and a liquid crystal layer formed between the pair of substrates,
The said liquid crystal aligning film is a manufacturing method of the liquid crystal display element formed by the method of Claim 6 or 7.