JP6589657B2 - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element using the same - Google Patents

Description

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element using the same. Specifically, a liquid crystal alignment agent for forming a photo-alignment type liquid crystal alignment film (hereinafter sometimes abbreviated as a light distribution film), and a photo-alignment type liquid crystal alignment formed using the liquid crystal alignment agent. The present invention relates to a film and a liquid crystal display element having the liquid crystal alignment film. Furthermore, it relates to a polymer such as polyamic acid or polyimide used for the liquid crystal aligning agent, and tetracarboxylic dianhydride as a raw material thereof.

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 liquid crystal alignment film is improved as the quality of the liquid crystal display element increases. 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, soluble polyimide or polyamic acid ester is dissolved in an organic solvent. After this solution is applied to the substrate, it is formed by means such as heating to form a polyimide-based liquid crystal alignment film. After film formation, an orientation treatment suitable for the above-described display mode is performed as necessary.

The rubbing method is widely used as an alignment treatment method, but problems such as dust generation and generation of static electricity have been pointed out. In recent years, photo alignment methods that perform alignment treatment by irradiating light have been actively developed. It has been broken. As the photo-alignment method, many alignment mechanisms such as a photolysis method, a photoisomerization method, a photodimerization method, and a photocrosslinking method have been proposed (see, for example, Non-Patent Document 1 and Patent Documents 1 to 7). Since the photo-alignment method is a non-contact alignment method, there is an advantage that the film is not damaged and the cause of the display failure of the liquid crystal display element such as dust generation or static electricity can be reduced.

In the case of using either the rubbing method or the photo-alignment method, liquid crystal alignment is a characteristic required for the liquid crystal alignment film. By using a liquid crystal alignment film having high liquid crystal alignment properties, a liquid crystal display element having high contrast and afterimage characteristics can be provided (for example, Patent Documents 8 and 9). The photo-alignment method has higher alignment uniformity than the rubbing method. Among them, by applying the photoisomerization technique described in Patent Documents 3 to 7, a photo-alignment film having a large anchoring energy and good liquid crystal alignment can be provided. However, as the liquid crystal display element is made higher in definition, there is a demand for a liquid crystal alignment film that exhibits higher liquid crystal alignment and excellent reliability that can withstand long-time driving.

JP 2011-175121 A JP2014-219656 JP-A-9-297313 JP-A-10-251646 JP-A-2005-275364 JP2007-248637 JP2009-069493 JP 2010-197999 A International Publication 2013/157463

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

If a liquid crystal alignment film having a low voltage holding ratio is used in the liquid crystal display element, the voltage applied to the liquid crystal during the frame period decreases, resulting in a decrease in luminance and a hindrance to normal gradation display, resulting in poor display quality. I know that. The subject of this invention is providing the liquid crystal aligning agent which shows the higher liquid crystal aligning property and can provide the liquid crystal aligning film excellent in the reliability which can maintain a high voltage holding ratio. An object of the present invention is to provide a liquid crystal alignment film that can be used for photo-alignment and can withstand long-time driving, and a liquid crystal alignment agent that provides the liquid crystal alignment film. The subject of this invention is providing further the novel tetracarboxylic dianhydride which can be used for the said liquid crystal aligning agent.

As a result of intensive studies, the present inventors have found that the level of the voltage holding ratio is related to the volume resistance of the liquid crystal alignment film, and by increasing the volume resistance of the liquid crystal alignment film, a liquid crystal alignment film exhibiting a high voltage holding ratio is obtained. I found out. The present inventors use a tetracarboxylic dianhydride having an alicyclic structure represented by the formula (1) of the present invention as a raw material for a liquid crystal aligning agent to increase the volume resistance of the liquid crystal aligning film. The headline, the present invention has been reached. The present invention comprises the following.

式（１）中、Ｒ^１は炭素数４〜９の直鎖アルキレンであり、その中の任意の−ＣＨ_２−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい。 [1] A liquid crystal aligning agent containing a polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic dianhydride containing at least one tetracarboxylic dianhydride represented by the following formula (1) with a diamine.

In the formula (1), R ¹ is a linear alkylene having 4 to 9 carbon atoms, in which any —CH ₂ — is replaced by —O—, —CH═CH— or —C≡C—. May be.

[2] A liquid crystal aligning agent containing the polyamic acid or derivative thereof according to item [1] and another polyamic acid or derivative thereof.

[3] A polyamic acid obtained by reacting a raw material monomer containing a compound having a photoreactive structure with at least one of a tetracarboxylic dianhydride and a diamine subjected to the reaction, or a derivative thereof, [1 ] Or the liquid crystal aligning agent as described in the item [2].

式（ＩＩ）〜（Ｖ）において、Ｒ^２およびＲ^３は−ＮＨ_２を有する１価の有機基または−ＣＯ−Ｏ−ＣＯ−を有する１価の有機基であり；
式（ＩＶ）において、Ｒ^４は２価の有機基であり；そして、
式（ＶＩ）において、Ｒ^５は独立して−ＮＨ_２または−ＣＯ−Ｏ−ＣＯ−を有する芳香環である。 [4] The liquid crystal aligning agent according to the item [3], wherein the compound having a photoreactive structure is at least one of compounds having a photoisomerization structure represented by formulas (II) to (VI).

In formulas (II) to (V), R ² and R ³ are a monovalent organic group having —NH ₂ or a monovalent organic group having —CO—O—CO—;
In formula (IV), R ⁴ is a divalent organic group; and
In formula (VI), R ⁵ is independently an aromatic ring having —NH ₂ or —CO—O—CO—.

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は独立して０〜２の整数であり；
式（Ｖ−３）において、環Ａおよび環Ｂはそれぞれ独立して、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−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、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−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、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１つの−ＣＨ_２−または連続しない２つの−ＣＨ_２−は−Ｏ−で置換されてもよく、
Ｒ^７〜Ｒ^１０は、それぞれ独立して、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＯＨであり、そして、
ｂ〜ｅは、それぞれ独立して０〜４の整数である。 [5] A tetracarboxylic dianhydride or diamine having a photoisomerization structure is represented by the formula (II-1), (II-2), (III-1), (III-2), (IV-1), Item [4], which is at least one selected from the group of compounds represented by (IV-2), (V-1) to (V-3), (VI-1), and (VI-2) Liquid crystal aligning agent as described in.

In 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;
In formula (V-2), R ⁶ is independently —CH ₃ , —OCH ₃ , —CF ₃ , or —COOCH ₃ , and a is independently an integer of 0 to 2;
In formula (V-3), ring A and ring B are each independently at least one selected from monocyclic hydrocarbons, condensed polycyclic hydrocarbons and heterocyclic rings,
R ¹¹ is a linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —CONH—, —NHCO—, —CON (CH ₃ ) —, or —N (CH ₃ ) CO—,
R ¹² is a linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —CONH—, —NHCO—, —CON (CH ₃ ) —, or —N (CH ₃ ) CO—,
In R ¹¹ and ^{R 12,} 1 single -CH ₂ linear alkylene - or non-contiguous two -CH ₂ - may be is replaced by -O-,
R ^{7 to} R ¹⁰ are each independently —F, —CH ₃ , —OCH ₃ , —CF ₃ , or —OH; and
b to e are each independently an integer of 0 to 4.

[6] It further contains at least one selected from the group consisting of an alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound, [1] to [1] [5] The liquid crystal aligning agent according to any one of [5].

[7] The liquid crystal aligning agent for a horizontal electric field mode liquid crystal display element according to any one of [1] to [6].

[8] A liquid crystal alignment film formed from the liquid crystal aligning agent according to any one of [1] to [7].

[9] A liquid crystal display device having the liquid crystal alignment film according to the item [8].

式（１）中、Ｒ^１は炭素数４〜９の直鎖アルキレンであり、その中の任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい。 [10] A tetracarboxylic dianhydride represented by the following formula (1).

In the formula (1), R ¹ is a linear alkylene having 4 to 9 carbon atoms, in which any —CH ₂ — is replaced by —O—, —CH═CH— or —C≡C—. Also good.

式（１−１）において、ｎは４〜９の整数であり；そして、
式（１−２）〜（１−４）において、ｎは２〜７の整数である。 [11] The tetracarboxylic dianhydride according to item [10], which is represented by any of the following formulas (1-1) to (1-4).

In formula (1-1), n is an integer of 4 to 9;
In formulas (1-2) to (1-4), n is an integer of 2 to 7.

[12] The following formulas (1-1-1) to (1-1-6), (1-2-1) to (1-2-6), (1-3-1) to (1-3- 6) and the tetracarboxylic dianhydride according to item [11], which is represented by any one of (1-4-1) to (1-4-6).

[13] A polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic acid anhydride containing at least one of the tetracarboxylic dianhydrides according to any one of [10] to [12] with a diamine.

The liquid crystal aligning agent containing the polyamic acid or its derivative synthesize | combined using the tetracarboxylic dianhydride which has an alicyclic structure represented by Formula (1) of this invention as a raw material uses the liquid crystal aligning agent. The volume resistance of the liquid crystal alignment film to be formed can be increased, and as a result, a liquid crystal alignment film having a high voltage holding ratio can be obtained. Moreover, since the liquid crystal aligning film of this invention has the long-chain alkylene structure derived from the tetracarboxylic dianhydride represented by Formula (1), it has the characteristic that anchoring energy is high. The technique of the present invention exhibits particularly excellent effects in the field of photo-alignment type liquid crystal alignment films.

In the present specification, the liquid crystal aligning agent may be simply abbreviated as “aligning agent”. The liquid crystal alignment film may be simply abbreviated as “alignment film”.

式（１）中、Ｒ^１は炭素数４〜１２の直鎖アルキレン構造であり、その中の任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい。 <Tetracarboxylic dianhydride represented by Formula (1)>
The tetracarboxylic dianhydride represented by the formula (1) of the present invention will be described.

In the formula (1), R ¹ is a linear alkylene structure having 4 to 12 carbon atoms, in which any —CH ₂ — is replaced by —O—, —CH═CH— or —C≡C—. May be.

式（１−１）において、ｎは４〜９の整数であり、式（１−２）〜式（１−４）において、ｎは２〜７の整数である。 Specific examples of the tetracarboxylic dianhydride of the formula (1) of the present invention are shown below.

In Formula (1-1), n is an integer of 4 to 9, and in Formula (1-2) to Formula (1-4), n is an integer of 2 to 7.

The compound represented by the formula (1-1) of the present invention is first obtained as an aromatic tetracarboxylic dianhydride by the method described in JP-A-2000-344759. Then, it can be obtained by reducing the aromatic ring in a hydrogen atmosphere in the presence of a palladium or platinum catalyst.

The compound represented by the formula (1-2) of the present invention is an aromatic tetracarboxylic dianhydride by an etherification reaction between commercially available 4-hydroxyphthalic anhydride and an appropriately selected n-alkylene dihalide. Is obtained by reducing the aromatic ring by the method described above. The compound represented by the formula (1-2) can also be synthesized from a tetracarboxylic dianhydride as a dialkyl ester in the etherification reaction.

The compound represented by the formula (1-3) and the formula (1-4) of the present invention is obtained by the method described in WO2015 / 125734A1, and after obtaining a 4-bromonitrophthalic anhydride reduced product, Obtained by ring reaction or Heck reaction. These synthesis methods will be described in detail in the Examples section below.

These compounds can also be used after being purified by recrystallization or column chromatography.

Specific examples of the tetracarboxylic dianhydride represented by the formula (1) of the present invention include the following formulas (1-1-1) to (1-1-6) and formulas (1-2-1) to formulas. Compounds represented by (1-2-6), formula (1-3-1) to formula (1-3-6), and formula (1-4-1) to formula (1-4-6) Show.

In order to provide a liquid crystal aligning agent that can be a liquid crystal aligning film having higher alignment, one of these compounds is represented by formulas (1-1-1) to (1-1-5), A tetracarboxylic dianhydride represented by (1-2-4), Formula (1-2-5), Formula (1-3-3), or Formula (1-4-3) is preferred, and Formula (1) -1-5), the formula (1-2-5), the formula (1-3-3) and the tetracarboxylic dianhydride represented by the formula (1-4-3) are more preferable. The tetracarboxylic dianhydride represented by 1-5) is more preferable.

<Polyamic acid and its derivatives>
The polyamic acid and derivatives thereof of the present invention will be described. The polyamic acid and its derivative of the present invention are a reaction product of at least one selected from tetracarboxylic dianhydride and its derivative and diamine, polyamic acid, polyamic acid ester, and polyimide obtained by imidizing them And at least one polymer selected from the group consisting of at least one of the compounds represented by formula (1). The polyamic acid, polyamic acid ester, and polyimide obtained by imidizing them are components that dissolve in a solvent when the liquid crystal aligning agent containing a solvent is described later, and the liquid crystal aligning film that describes the liquid crystal aligning agent described later Is a component capable of forming a liquid crystal alignment film containing polyimide as a main component. 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 the 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 liquid crystal aligning agent for photo-alignment of the present invention may contain one or more of these polyamic acids, polyamic acid esters, and polyimides obtained by imidizing them.

式（１）中、Ｒ^１は炭素数４〜１２の直鎖アルキレン構造であり、その中の任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい。

In the formula (1), R ¹ is a linear alkylene structure having 4 to 12 carbon atoms, in which any —CH ₂ — is replaced by —O—, —CH═CH— or —C≡C—. May be.

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).

Further, when the polyamic acid of the present invention is a polyamic acid derivative polyimide, the resulting polyamic acid solution is a dehydrating agent such as acetic anhydride, propionic anhydride, anhydrous trifluoroacetic anhydride, and the like, It can be obtained by imidization reaction at a temperature of 20 to 150 ° C. with a tertiary amine such as triethylamine, pyridine, collidine and the like as a dehydration ring closure catalyst. Alternatively, polyamic acid is precipitated from the obtained polyamic acid solution using a large amount of poor solvent (alcohol solvent or glycol solvent such as methanol, ethanol, isopropanol), and the precipitated polyamic acid is converted into toluene, xylene, or the like. The imidization reaction can also be carried out at a temperature of 20 to 150 ° C. in a solvent together with the same dehydrating agent and dehydration ring closure catalyst as described above.

In the imidization reaction, the ratio of the dehydrating agent to the dehydrating ring-closing catalyst is preferably 0.1 to 10 (molar ratio). The total amount of both used is preferably 1.5 to 10 times the total molar amount of tetracarboxylic dianhydride used for the synthesis of the polyamic acid. By adjusting the dehydrating agent, catalyst amount, reaction temperature and reaction time of this chemical imidization, the degree of imidization can be controlled and a partial polyimide can be obtained. The obtained polyimide can be separated from the solvent and redissolved in the above-mentioned solvent and used as a liquid crystal aligning agent, or can be used as a liquid crystal aligning agent without being separated from the solvent.

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.

<A tetracarboxylic dianhydride other than the tetracarboxylic dianhydride represented by the formula (1)>
The tetracarboxylic dianhydride used for producing the polyamic acid and derivatives thereof of the present invention will be described. Tetracarboxylic dianhydrides other than the tetracarboxylic dianhydrides represented by the formula (1) 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).

式（ＡＮ−Ｉ）、式（ＡＮ−ＩＶ）および式（ＡＮ−Ｖ）において、Ｘは独立して単結合または−ＣＨ_２−である。式（ＡＮ−ＩＩ）において、Ｇは単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−である。式（ＡＮ−ＩＩ）〜式（ＡＮ−ＩＶ）において、Ｙは独立して下記の３価の基の群から選ばれる１つであり、結合手は任意の炭素に連結しており、この基の少なくとも１つの水素はメチル、エチルまたはフェニルで置き換えられてもよい。

式（ＡＮ−ＩＩＩ）〜式（ＡＮ−Ｖ）において、環Ａ^１０は炭素数３〜１０の単環式炭化水素の基または炭素数６〜３０の縮合多環式炭化水素の基であり、この基の少なくとも１つの水素はメチル、エチルまたはフェニルで置き換えられていてもよく、環に掛かっている結合手は環を構成する任意の炭素に連結しており、２本の結合手が同一の炭素に連結してもよい。 Preferable examples of such tetracarboxylic dianhydrides include formulas (AN-I) to (AN-V) from the viewpoint of easy availability of raw materials, ease of polymer production, and electrical characteristics of the film. The tetracarboxylic dianhydride represented by these is mentioned.

In formula (AN-I), formula (AN-IV), and formula (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 group of trivalent groups below, and the bond is connected to any carbon. At least one hydrogen of may be replaced with methyl, ethyl or phenyl.

In Formula (AN-III) to Formula (AN-V), 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 this 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. It may be linked to carbon.

More specifically, tetracarboxylic dianhydrides represented by the following formulas (AN-1) to (AN-16-15) are exemplified.

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 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はそれぞれ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はそれぞれ独立して、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. Each 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 formula (G13-1), G ^13a and G ^13b each independently represent 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 the 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−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 _{-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はそれぞれ独立して０または１である。 [Tetracarboxylic dianhydride represented by the formula (AN-9)]

In the formula (AN-9), each 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はそれぞれ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 formula (AN-12), each of 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−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, a suitable material for improving each characteristic of the liquid crystal alignment film described later will be described. When importance is attached to improving the orientation of the liquid crystal, compounds represented by the formula (AN-1), the formula (AN-3), and the formula (AN-4) are preferred, and the formula (AN-1- 2), compounds represented by formula (AN-1-13), formula (AN-3-2), formula (AN-4-17), and formula (AN-4-29) are more preferred, In AN-1-2), m = 4 or 8 is preferable, and in formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is more preferable.

When importance is attached to improving the transmittance of the liquid crystal display element, the formula (AN-1-1), the formula (AN-1-2), the formula (AN-3-1), the formula (AN-4-) 17), Formula (AN-4-30), Formula (AN-5-1), Formula (AN-7-2), Formula (AN-10-1), Formula (AN-16-3), Formula ( AN-16-4) and a compound represented by the formula (PA-1) are preferable, and in the formula (AN-1-2), m = 4 or 8 is preferable, and the formula (AN-4-17) In this case, m = 4 or 8 is preferable, and m = 8 is more preferable.

When importance is attached to improving the VHR of the liquid crystal display element, the formula (AN-1-1), the formula (AN-1-2), the formula (AN-3-1), and the formula (AN-4-17). ), Formula (AN-4-30), Formula (AN-7-2), Formula (AN-10-1), Formula (AN-16-3), Formula (AN-16-4), and Formula ( The compound represented by PA-1) is preferable, 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 preferable. M = 8 is more 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 effective as one method for preventing image sticking. When emphasizing this purpose, the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-21), the formula (AN-4-29), and the formula (AN- The compound represented by 11-3) is preferred.

<Diamine and dihydrazide>
The diamine and dihydrazide used for producing the polyamic acid and derivatives thereof of the present invention will be described. In producing the polyamic acid or derivative thereof of the present invention, it can be selected without limitation from known diamines and dihydrazides.

上記の式（ＤＩ−１）において、Ｇ^２０は、−ＣＨ_２−であり、少なくとも１つの−ＣＨ_２−は−ＮＨ−、−Ｏ−に置き換えられてもよく、ｍは１〜１２の整数であり、アルキレンの少なくとも１つの水素は−ＯＨに置き換えられてもよい。式（ＤＩ−３）および式（ＤＩ−５）〜式（ＤＩ−７）において、Ｇ^２１は独立して単結合、−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_２Ｈ_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_３Ｈ_６−（ＮＨ−Ｃ_３Ｈ_６）_ｎ−ＣＯ−、または−Ｓ−（ＣＨ_２）_ｍ−Ｓ−であり、ｍは独立して１〜１２の整数であり、ｋは１〜５の整数であり、ｎは１または２である。式（ＤＩ−４）において、ｓは独立して０〜２の整数である。式（ＤＩ−６）および式（ＤＩ−７）において、Ｇ^２２は独立して単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−ＮＨ−、または炭素数１〜１０のアルキレンである。式（ＤＩ−２）〜式（ＤＩ−７）中のシクロヘキサン環およびベンゼン環の少なくとも１つの水素は、−Ｆ、−Ｃｌ、炭素数１〜３のアルキル、−ＯＣＨ_３、−ＯＨ、−ＣＦ_３、−ＣＯ_２Ｈ、−ＣＯＮＨ_２、−ＮＨＣ_６Ｈ_５、フェニル、またはベンジルで置き換えられてもよく、加えて式（ＤＩ−４）においては、ベンゼン環の少なくとも１つの水素は下記式（ＤＩ−４−ａ）〜式（ＤＩ−４−ｅ）で表される基の群から選ばれる１つで置き換えられていてもよい。環を構成する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す。そして、シクロヘキサン環またはベンゼン環への−ＮＨ_２の結合位置は、Ｇ^２１またはＧ^２２の結合位置を除く任意の位置である。

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。 Examples of known diamines 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 an integer from 1 to 5 , 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 benzene ring is represented by the following formula ( DI-4-a) to one selected from the group of groups represented by formula (DI-4-e) may be substituted. 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 .

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.

式（ＤＩ−１２）において、Ｒ^２１およびＲ^２２は独立して炭素数１〜３のアルキルまたはフェニルであり、Ｇ^２３は独立して炭素数１〜６のアルキレン、フェニレンまたはアルキル置換されたフェニレンであり、ｗは１〜１０の整数である。式（ＤＩ−１３）において、Ｒ^２３は独立して炭素数１〜５のアルキル、炭素数１〜５のアルコキシまたは−Ｃｌであり、ｐは独立して０〜３の整数であり、ｑは０〜４の整数である。式（ＤＩ−１４）において、環Ｂは単環の複素環式芳香族基であり、Ｒ^２４は水素、−Ｆ、−Ｃｌ、炭素数１〜６のアルキル、アルコキシ、ビニル、アルキニルであり、ｑは独立して０〜４の整数である。式（ＤＩ−１５）において、環Ｃは複素環式芳香族基または複素環式脂肪族基である。式（ＤＩ−１６）において、Ｇ^２４は単結合、炭素数２〜６のアルキレンまたは１，４−フェニレンであり、ｒは０または１である。そして、環を構成する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す。式（ＤＩ−１３）〜式（ＤＩ−１６）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 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 the formula (DI-14), ring B is a monocyclic heteroaromatic group, R ²⁴ is hydrogen, —F, —Cl, C 1-6 alkyl, alkoxy, vinyl, alkynyl, q is an integer of 0 to 4 independently. In formula (DI-15), ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group. 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はそれぞれ独立して、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 each independently an integer of 1 to 3.

Examples of diamines represented by formula (DI-2) to 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−５−１２）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-5-12) 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 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.

式（ＤＩ−３６−９）〜式（ＤＩ−３６−１１）において、ｅは２〜１０の整数であり、式（ＤＩ−３６−１２）中、Ｒ^４３はそれぞれ独立して水素、−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、そして、ｍは１〜１２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。 Diamines other than the diamines of the above formulas (DI-1) to (DI-16) can also be used for the polyamic acid and derivatives thereof of the present invention. An example is shown below.

In the formula (DI-36-9) to the formula (DI-36-11), e is an integer of 2 to 10, and in the formula (DI-36-12), each 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 and m is an integer from 1 to 12. Here, Boc is a t-butoxycarbonyl group.

Diamines having side chains other than those of formula (DI-1) to formula (DI-16) can also be used. An example is 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−３４−１）〜式（ＤＩ−３４−１２）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。

In Formula (DI-34-1) to Formula (DI-34-12), 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.

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

式（ＤＩＨ−１）において、Ｇ^２５は単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−である。
式（ＤＩＨ−２）において、環Ｄはシクロヘキサン環、ベンゼン環またはナフタレン環であり、この基の少なくとも１つの水素はメチル、エチル、またはフェニルで置き換えられてもよい。式（ＤＩＨ−３）において、環Ｅはそれぞれ独立してシクロヘキサン環、またはベンゼン環であり、この基の少なくとも１つの水素はメチル、エチル、またはフェニルで置き換えられてもよく、Ｙは単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−である。式（ＤＩＨ−２）および式（ＤＩＨ−３）において、環に結合する−ＣＯＮＨＮＨ_２の結合位置は、任意の位置である。

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 group may be replaced with methyl, ethyl or phenyl. In the formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of this group may be replaced with methyl, ethyl, or phenyl, Y is a single bond, alkylene having 1 to 20 carbon atoms, -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 formula (DIH-1) to formula (DIH-3) are shown below.

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

In the diamine and dihydrazide, suitable materials for improving each characteristic of the liquid crystal alignment film described later will be described. When importance is attached to further improving the orientation of the liquid crystal, the formula (DI-1-3), 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), Formula (DI-7-3), and Formula (DI-7-3) It is preferable to use a compound represented by DI-11-2). 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.

When emphasizing improving the transmittance, formula (DI-1-3), formula (DI-2-1), formula (DI-5-1), formula (DI-5-5), formula It is preferable to use a diamine represented by (DI-5-24) and formula (DI-7-3), and a compound represented by formula (DI-2-1) is more preferable. In the formula (DI-5-1), m = 2, 4 or 6 is preferable, and m = 4 is more preferable. In formula (DI-7-3), m = 2 or 3, n = 1 or 2 are preferable, and m = 3 and n = 1 are more preferable.

When importance is attached to improving the VHR of the liquid crystal display element, the formula (DI-2-1), the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10) ), Formula (DI-4-15), formula (DI-5-28), formula (DI-5-30), formula (DI-13-1), and formula (DI-31-56). The diamines represented by the formula (DI-2-1), the formula (DI-5-1), the formula (DI-13-1) and the like are more preferable. In the formula (DI-5-1), m = 1 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 effective as one method for preventing image sticking. When emphasizing this purpose, 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), formula (DI-7-12), and formula (DI-16-1) It is preferable to use a compound represented by the formula (DI-4-1), a formula (DI-5-1), and a compound represented by the formula (DI-5-13). In 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 formula (DI-7-12), m = 3 or 4 is preferable, and m = 4 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 or a derivative thereof) can be easily controlled by such replacement, and for example, the coating characteristics of the liquid crystal aligning agent are improved without impairing the effects of the present invention. be able to. 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 or 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.

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。 <Monomer having photoreactive structure>
When the polyamic acid or derivative thereof of the present invention is used as a photo-alignment film imparted with liquid crystal alignment ability by light irradiation, for example, ultraviolet irradiation, a monomer having a photoreactive structure is used as a raw material for the polyamic acid and derivative thereof. It can be used suitably. By using a monomer having a photoreactive structure, a polyamic acid and a derivative thereof having a photoreactive structure can be synthesized. The photoreactive structure is represented by, for example, a photolytic structure represented by the following formula (P-1) that causes decomposition by ultraviolet irradiation, or a formula (P-2) to a formula (P-4) that causes isomerization. And photodimerization structures represented by formulas (P-5) to (P-7) that cause dimerization.

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

Examples of the compound having a photolytic structure represented by the formula (P-1) include compounds represented by the following formulas (PA-1) to (PA-3).

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

In addition, the compound represented by Formula (PA-1)-Formula (PA-3) is a liquid crystal aligning agent using the liquid crystal aligning ability based on photoisomerization reaction, and the liquid crystal aligning using the liquid crystal aligning ability based on photodimerization. When used as a raw material monomer for a polymer used in an agent or a liquid crystal aligning agent for rubbing, it is treated as a tetracarboxylic dianhydride having no photoreactive structure.

式（ＩＩ）〜式（Ｖ）において、Ｒ^２およびＲ^３は−ＮＨ_２を有する１価の有機基または−ＣＯ−Ｏ−ＣＯ−を有する１価の有機基であり、式（ＩＶ）においてＲ^４は２価の有機基であり、式（ＶＩ）においてＲ^５は独立して−ＮＨ_２もしくは−ＣＯ−Ｏ−ＣＯ−を有する芳香環である。 Examples of the compound having a photoisomerized structure represented by formula (P-2) to formula (P-4) include compounds having a good photosensitivity from the group of compounds represented by formula (II) to formula (VI) below. It is preferably at least one selected, and a compound represented by the formula (V) is more preferable.

In the formulas (II) to (V), R ² and R ³ are a monovalent organic group having —NH ₂ or a monovalent organic group having —CO—O—CO—, and in the formula (IV) R ⁴ is a divalent organic group, and in formula (VI), R ⁵ is independently an aromatic ring having —NH ₂ or —CO—O—CO—.

The photoisomerization structure may be incorporated in either the main chain or the side chain of the polyamic acid or derivative thereof in the present invention, but can be suitably used for a horizontal electric field type liquid crystal display element by incorporating it in the main chain.

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は独立して０〜２の整数であり、式（Ｖ−３）において、環Ａおよび環Ｂはそれぞれ独立して、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、それぞれ独立して、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＯＨであり、そして、ｂ〜ｅは、それぞれ独立して、０〜４の整数である。 Examples of the material having the photoisomerization structure include the following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), and formula (IV). -2), at least one selected from the group of compounds represented by formula (V-1) to formula (V-3), formula (VI-1), and formula (VI-2) is preferably used. Can do.

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 _and, -OCH 3, a -CF ₃ or -COOCH _3,, a is an integer of 0 to 2 independently, in formula (V-3), respectively rings a and B are independently And at least one selected from a monocyclic 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—, and R ¹² is a linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —NHCO— or —N (CH ₃ ) CO—. , R ¹¹ and R ¹² One or two of —CH ₂ — may be substituted with —O—, and R ^{7 to} R ¹⁰ are each independently —F, —CH ₃ , —OCH ₃ , —CF ₃ , Or -OH, and b to e are each independently an integer of 0 to 4.

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

Tetracarboxylic dianhydrides or diamines having a structure capable of causing isomerization 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). -3).

Among these, for formulas (VI-1-1) to (V-3-8) containing a structure capable of causing isomerization by ultraviolet irradiation, for photo-alignment with higher sensitivity to ultraviolet irradiation. A liquid crystal aligning agent 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.

In an embodiment 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 alignment film is sensitive to light. In order to prevent the decrease, the photosensitive tetracarboxylic dianhydride is preferably 0 to 70 mol% based on the total amount of the tetracarboxylic dianhydride used as a raw material for producing the polyamic acid or derivative thereof of the present invention. 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 or derivative thereof. 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.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention may be composed of one kind of the polyamic acid of the present invention, two or more kinds of the polyamic acid of the present invention may be mixed, and other polymers may be mixed. Also good. The other polymer is not only polyamic acid not using tetracarboxylic dianhydride represented by the formula (1) as a raw material, but also polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene- (Phenylmaleimide) derivatives, poly (meth) acrylates and the like. However, in consideration of the storage stability of the liquid crystal aligning agent, the printability of the liquid crystal aligning agent on the display element substrate and the characteristics of the liquid crystal aligning film to be formed, the polyamic acid of the present invention or a mixture of its derivatives or the polyamic acid of the present invention Or the liquid crystal aligning agent obtained by mixing with the derivative and the polyamic acid which does not use the tetracarboxylic dianhydride represented by Formula (1) as a raw material or its derivative (s) is preferable.

The tetracarboxylic dianhydride diamine and dihydrazide described above are preferably used for the production of polyamic acid and its derivatives that do not use the tetracarboxylic dianhydride represented by the formula (1) as a raw material.

When such a two-component polymer is used, for example, a polymer having performance superior in liquid crystal alignment ability is selected on the one hand, and the performance superior in improving the electrical characteristics of the liquid crystal display element on the other hand. There is an embodiment in which a polymer having is selected. In this case, by controlling the structure and molecular weight of each polymer, a liquid crystal aligning agent obtained by dissolving these polymers in a solvent is applied to a substrate and preliminarily dried to form a thin film as described later. In the process, a polymer having excellent performance in liquid crystal alignment ability can be segregated in the upper layer of the thin film, and a polymer having excellent performance in improving the electrical characteristics of the liquid crystal display element can be segregated in the lower layer of the thin film. For this, in the mixed polymer, 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 can be applied. The confirmation of such layer separation is that the surface energy of the formed alignment film is the same as or close to the surface energy of the film formed by the liquid crystal aligning agent containing only the polymer intended to be segregated in the upper layer. It can be confirmed by the value.

As a method for expressing the layer separation, it is also possible to reduce the molecular weight of the polymer to be segregated in the upper layer.

In a liquid crystal aligning agent composed of a mixture of polyamic acids, layer separation can be expressed by using a polyimide as a polymer to be segregated in the upper layer.

The tetracarboxylic dianhydride represented by the formula (1) of the present invention may be used as a raw material monomer for a polymer that segregates in the upper layer of the thin film, or as a raw material monomer for a polymer that segregates in the lower layer of the thin film. May be. Moreover, you may use as a raw material monomer of both polymers.

The tetracarboxylic dianhydride used for synthesizing the polyamic acid or derivative thereof segregated on the upper layer of the thin film can be selected without limitation from the known tetracarboxylic dianhydrides exemplified above. it can.

Tetracarboxylic acid dianhydrides used for synthesizing polyamic acid or a derivative thereof segregated in the upper layer of the thin film are represented by the formulas (1-1-3) to (1-1-6) and (1-2). 3) to Formula (1-2-6), Formula (1-3-3) to Formula (1-3-6), Formula (1-4-3) to Formula (1-4-6), Formula ( The compounds represented by AN-1-1), formula (AN-4-17), and formula (PA-1) are preferred, and the formula (1-1-5), formula (1-2-5), and formula (1-3-5), Formula (1-2-5), and Formula (AN-4-17) are more preferable. In formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is more preferable.

The diamine and hydrazide used for synthesizing the polyamic acid or derivative thereof segregated on the upper layer of the thin film can be selected from the known diamines exemplified above.

Examples of the diamine and hydrazide used for synthesizing the polyamic acid or its derivative segregated on the upper layer of the thin film include the formula (DI-4-1), the formula (DI-5-1), and the formula (DI-7-3). It is preferable to use a compound represented by Among these, in formula (DI-5-1), m = 1, 2 or 4 is preferable, and m = 4 is more preferable. In the formula (DI-7-3), m = 3 and n = 1 are preferable.

The non-photosensitive diamine used for synthesizing the polyamic acid or its derivative segregated in the upper layer of the thin film preferably contains 30 mol% or more of aromatic diamine in the total amount of diamine, and more preferably contains 50% or more.

The acid dianhydride and diamine having the above-mentioned photoisomerization structure are preferably used for synthesizing polyamic acid or its derivative segregating in the upper layer of the thin film.

The tetracarboxylic dianhydride used for synthesizing the polyamic acid or its derivative segregated in the lower layer of the thin film can be selected without limitation from the known tetracarboxylic dianhydrides exemplified above. .

The tetracarboxylic dianhydride used for synthesizing the polyamic acid or derivative thereof segregated in the lower layer of the thin film includes the formula (1-1-1), formula (1-1-2), formula (1-1). -5), Formula (1-2-1), Formula (1-2-2), Formula (1-2-4), Formula (1-3-1), Formula (1-3-2), Formula (1-4-1), Formula (1-4-2), Formula (AN-3-2), Formula (AN-1-13), Formula (AN-1-1), and Formula (AN-4) Compound represented by formula (1-1-1), formula (1-1-5), formula (1-2-4), formula (AN-1-1), and formula ( AN-3-2) is more preferred.

The tetracarboxylic dianhydride used for synthesizing the polyamic acid or its derivative segregating in the lower layer of the thin film contains 10 mol% or more of aromatic tetracarboxylic dianhydride in the total amount of tetracarboxylic dianhydride. Is preferable, and it is more preferable to contain 30% or more.

The diamine and hydrazide used for synthesizing the polyamic acid or derivative thereof segregated in the lower layer of the thin film can be selected from the known diamines exemplified above.

Examples of the diamine and hydrazide used for synthesizing the polyamic acid or its derivative segregated in the lower layer of the thin film include formula (DI-4-1), formula (DI-4-2), and formula (DI-4-10). The compounds represented by formula (DI-5-9), formula (DI-5-28), formula (DI-5-30), and formula (DIH-2-1) are preferred. Among these, in formula (DI-5-30), a diamine in which k = 2 is preferable.

The diamine used for synthesizing the polyamic acid or its derivative segregated in the lower layer of the thin film is preferably an aromatic diamine containing 30 mol% or more, more preferably 50% or more of the total diamine. preferable.

The polyamic acid or derivative thereof segregated on the upper layer of the thin film and the polyamic acid or derivative thereof segregated on the lower layer of the thin film are both described below as methods for synthesizing the polyamic acid or derivative thereof as an essential component of the liquid crystal aligning agent of the present invention. Can be synthesized in accordance with the method described in.

The ratio of the polyamic acid or derivative thereof segregated in the upper layer of the thin film and the polyamic acid or derivative thereof segregated in the upper layer of the thin film with respect to the total amount of polyamic acid or derivative thereof segregated in the lower layer of the thin film is 5 wt% to 50 wt%. % Is preferable, and 10 wt% to 40 wt% is more preferable.

<Solvent>
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 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.

Examples of the solvent include a parent solvent for the polyamic acid or a derivative thereof, and other solvents for the purpose of improving coatability.

Examples of the aprotic polar organic solvent that is a parent solvent for polyamic acid or its derivatives include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N, N-dimethylacetamide. , Dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide, γ-butyrolactone, and other lactones.

Examples of other solvents for the purpose of improving coating properties include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, etc. Diethylene glycol monoalkyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether such as propylene glycol monomethyl ether, propylene glycol monobutyl ether, dialkyl malonate such as diethyl malonate, dipropylene glycol monomethyl Dipropylene glycol monoalkyl ethers such as ethers and esters such as these acetates Compounds, and the like.

Among these, the solvent is N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether, and dipropylene glycol. Monomethyl ether is particularly preferred.

The concentration of the polyamic acid 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 measurement method, and is measured (measurement temperature: 25 ° C.) using, for example, a rotational viscometer (TVE-20L type manufactured by Toki Sangyo).

<Alkenyl-substituted nadiimide compound>
For example, 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 over 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 (allylmethylbicyclo [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-di Dorokishi) 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>
For example, the liquid crystal aligning agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. 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 Chemical Co., Ltd. products 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>
For example, the liquid crystal aligning agent of this invention may further contain the oxazine compound from the objective of stabilizing the electrical property in a 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は独立して炭素数１〜３０の有機基であり、式（ＯＸ−１）〜式（ＯＸ−６）において、Ｌ^５〜Ｌ^８は独立して水素または炭素数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 independently an organic group having 1 to 30 carbon atoms, and in Formula (OX-1) to Formula (OX-6), L ^{5 to} L ⁸ are each independently hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and in Formula (OX-3), Formula (OX-4), and 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 —S—, wherein v is an integer of 1 to 6, and the 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 1 to 3 carbon atoms The hydrogen bonded to the benzene ring and naphthalene ring in Q ² is independently replaced with —F, —CH ₃ , —OH, —COOH, —SO ₃ H, —PO ₃ H _2. May be.

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.

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.

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は独立して炭素数１〜３０の有機基であり、Ｌ^５からＬ^８は独立して水素または炭素数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 the formula (OX-3-I), L ³ and L ⁴ are each independently an organic group having 1 to 30 carbon atoms, and L ⁵ to L ⁸ are independently hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. 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 adding a primary amine to formaldehyde gradually, 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>
For example, 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 period of time. 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. It is preferable that 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 may be 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 a copolymer of a monomer having an oxazoline structure in the side chain and a monomer having no oxazoline structure It may be. 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 an oxazoline structure. It may also be a copolymer with a monomer that does not have.

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>
For example, 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 methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer and styrene-glycidyl methacrylate copolymer Is mentioned.

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 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 name, 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 names, 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 (formula EP-16 below), 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).

式（ＥＰ−４８）において、Ｐｈは「フェニル」を表す。 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.

In the formula (EP-48), Ph represents “phenyl”.

Examples of the homopolymer of the monomer having oxiranyl include polyglycidyl methacrylate. Examples of the copolymer of monomers having oxiranyl include N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer. Examples thereof include 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (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, and 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, Examples include 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-diepoxylimonene (Celoxide 3000 (trade name, ( Manufactured by Daicel Corporation), the following formula EP-55), a compound represented by the following formula EP-56 CY-175, CY-177, CY-179 (all trade names, manufactured by The Ciba-Geigy Chemical Corp. (available from Huntsman Japan Co.)), 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 novolak type Epoxy compounds, It is preferable and at least one cresol novolac type epoxy compound.

<Additives>
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.

For example, the polymer compound includes a polymer compound that is 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. In the case where it is desired to improve the properties, a silane coupling agent or a titanium-based coupling agent, and 4) an imidization catalyst in the case where imidization proceeds at a low temperature can be mentioned.

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.

<Liquid crystal alignment film>
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 rub.

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 on 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 140 ° C., and the second time is preferably 180 ° C. or more.

In the method for forming a liquid crystal alignment film of the present invention, as a 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, a rubbing method, a photo alignment method, or the like is known. 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.

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, and 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.

<Liquid crystal display element>
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 Laid-Open No. 5-501735, Japanese Patent Laid-Open No. 8-157826, Japanese Patent Laid-Open No. 8-231960, Japanese Patent Laid-Open No. 9-241644 (EP8827272A1), 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. As the liquid crystal composition having negative dielectric anisotropy, for example, a liquid crystal 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: Can be mentioned.

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 represented by the above formula (NL-1) include compounds represented by the following formula (NL-1-1) to formula (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, 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 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 represented by the formula (NL-1) in which the liquid crystal composition having the negative dielectric anisotropy is preferably used as the first component is represented by the formula (NL-1-1) or the formula (NL-1-4). , A compound represented by formula (NL-1-7) and formula (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 liquid crystal display element 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, ultraviolet 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 represented by 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 develop the effect of determining the tilt direction of the liquid crystal after polymerization. Further, in order to make the orientation effect of the polymer suitable after the polymerization, or in order to avoid the unreacted monomer or oligomer from eluting into the liquid crystal after the ultraviolet irradiation, it may be 30% by weight or less. desirable.

An optically active compound is mixed with the liquid crystal composition for the purpose of inducing a helical structure of the liquid crystal to give a twist angle. Examples of such a compound are compounds represented by formula (PAC-1-1) to formula (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 liquid crystal display element for a long time, an antioxidant is a liquid crystal composition. To be mixed.

Preferred examples of the antioxidant include compounds represented by formula (AO-1) wherein w is an integer of 1 to 10. In the formula (AO-1), preferred w is 1, 3, 5, 7, or 9. Further preferred w is 1 or 7. Since the compound represented by the formula (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. The compound represented by the formula (AO-1) in which w is 7 has low volatility, and therefore, after using the liquid crystal display element for a long time, to maintain a large voltage holding ratio not only at room temperature but also at a high temperature. It is valid. 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 include 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 liquid crystal composition in order to adapt to a GH (Guest host) mode liquid crystal display 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 liquid crystal 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 liquid crystal composition in order to be adapted to a liquid crystal display element in a PSA (polymer sustained alignment) 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 compounds are compounds represented by formula (PM-2-1) to formula (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はそれぞれ独立して、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 each 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% by weight 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 include nitro, nitriso, amino, and polyhydroxy compounds. 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.

By using a liquid crystal composition having negative dielectric anisotropy for the liquid crystal display element of the present invention, a liquid crystal display element having excellent afterimage characteristics and good alignment stability can be provided.

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

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. The voltage holding ratio was measured by the method described in “Mizushima et al., 14th Liquid Crystal Discussion Group Proceedings p78 (1988)”. The measurement was performed by applying a rectangular wave having a wave height of ± 5 V to the cell. The measurement was performed at 60 ° C. This value is an index indicating how much the applied voltage is retained after the frame period. If this value is 100%, it indicates that all charges are retained. A liquid crystal display element having a good display quality is obtained when the cell having the positive type liquid crystal is 99.0% or more and the cell having the negative type liquid crystal is 97.5% or more.
3. Measurement of ion content in liquid crystal (ion density)
According to the method described in Applied Physics, Vol. 65, No. 10, 1065 (1996), measurement was performed using a liquid crystal property measuring system 6254 type manufactured by Toyo Technica. Using a triangular wave with a frequency of 0.01 Hz, measurement was performed at a voltage range of ± 10 V and a temperature of 60 ° C. (electrode area is 1 cm ² ). If the ion density is high, defects such as seizure due to ionic impurities are likely to occur. That is, the ion density is a physical property value that serves as an index for predicting the occurrence of image sticking. If this value is 20 pC or less in a cell equipped with a positive type liquid crystal and 50 pC or less in a cell equipped with a negative type liquid crystal, a liquid crystal display element with good display quality is obtained.
4). Confirmation of orientation When a liquid crystal cell is visually observed between two polarizing plates arranged in crossed Nicols, the phenomenon in which liquid crystals are aligned along the direction in which the liquid crystal flows from the inlet is called fluid orientation. The fluid orientation is an index of the orientation of the orientation film, and the orientation film in which no fluid orientation occurs has a good orientation.
5. Confirmation of printability In the liquid crystal aligning agent, the viscosity and the solvent contained therein are appropriately adjusted by a coating method on a glass substrate. In particular, application of a liquid crystal aligning agent to a glass substrate by an ink jet method has recently become mainstream. The applicability can be confirmed by confirming the rattling of the edge portion of the coating film to be applied and formed by the ink jet coating apparatus. If this shakiness is within a range of 0.2 mm, a liquid crystal aligning agent having good printability is obtained. In addition, it is effective to use a poor solvent in combination with the solvent of the liquid crystal aligning agent in order to make the ink jet aligning agent with better printability. However, there is no polymer precipitation even in such a solvent system. It is essential to have excellent stability.

<Solvent>
NMP: N-methyl-2-pyrrolidone BC: Butyl cellosolve (ethylene glycol monobutyl ether)
GBL: γ-butyrolactone EDM: ethylene glycol ethyl methyl ether DIBK: diisobutyl ketone (2,6-dimethyl-4-heptanone)

<Additives>
Ad1: N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane Ad2: 1,3-bis (4,5-dihydro-2-oxazolyl) benzene Ad3: 2- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane

Example 1 Synthesis of Compound (1-1-5) <First Step: Synthesis of Diethyl Ester>
To a 3 L three-necked flask equipped with a reflux tube, a thermometer and a stirring blade, 500 g (2.2 mol) of commercially available 4-bromophthalic anhydride, 10 mL of sulfuric acid and 2 L of ethanol were added and heated to reflux. After completion of the reaction, ethanol was distilled off under reduced pressure to obtain a crude product. The obtained crude product was distilled under reduced pressure at 160 ° C. and 500 Pa to obtain 4-bromophthalic acid diethyl ester (yield: 623 g, yield: 94%).

<Second stage: Sonogashira coupling reaction>
To a 3 L four-necked flask equipped with a reflux tube, a thermometer, a stirring blade and a dropping funnel, 582 g (1.9 mol) of 4-bromophthalic acid diethyl ester obtained in the first stage, commercially available dichlorobis (triphenylphosphine) palladium ( II) 26 g (38 mmol) and 14 g (76 mmol) of CuI were added, and 2000 mL of triethylamine was added. A solution prepared by dissolving 100 g (0.9 mol) of commercially available 1,7-octadiyne in 400 mL of tetrahydrofuran was gradually added thereto from the dropping funnel, and the mixture was heated to reflux for 5 hours after completion of the dropping. After completion of the reaction, triethylamine was distilled off under reduced pressure, 2 L of ethyl acetate was added, and the separated ethyl acetate solution was washed 3 times with 2 L of pure water. The organic layer was dried over magnesium sulfate, and the solvent was distilled off from the filtered solution under reduced pressure to obtain crude crystals. Recrystallization from ethanol twice the weight of the obtained crude crystals gave the following compound (yield: 454 g, yield: 86%).

<Stage 3: Reduction of aromatic ring and acetylene>
Into a 3LSUS autoclave reactor equipped with a thermometer and pressure gauge, 200 g (366 mmol) of the compound obtained in the second stage and 20 g of a commercially available ruthenium catalyst supported on 5% activated carbon (dried product) were added, and 1.5 L of ethanol was added. It was. The system was placed in a hydrogen atmosphere and reacted at a hydrogen pressure of 4900 kPa and 100 ° C. for 12 hours. After the reaction solution was filtered to remove the catalyst, ethanol was distilled off under reduced pressure to obtain the following compound (yield: 183 g, yield: 88%).

<Fourth stage: hydrolysis (deethyl esterification)>
150 g (265 mmol) of the compound obtained in the third stage and 51 g (1.3 mol) of sodium hydroxide were placed in a 2 L three-necked flask equipped with a thermometer and a stirring blade, and 204 g of pure water and 1.5 L of ethanol were added. After stirring at room temperature for 12 hours, ethanol was distilled off under reduced pressure. 6N hydrochloric acid was added thereto until the pH of the solution was 1 or less, and the precipitated crystals were collected by filtration. The obtained crystal was washed with pure water to obtain the following compound (yield: 111 g, yield: 94%).

<5th stage: Dehydration ring closure>
100 g (220 mmol) of the compound obtained in the fourth stage was placed in a 1 L eggplant flask, and 200 g of acetic anhydride was added. The mixture was heated to reflux for 8 hours, and the crystal precipitated after cooling was collected by filtration. The obtained crude product was separated and purified by column chromatography (filler: silica gel, added solvent: toluene / ethyl acetate = 2/1 (v / v)). The solvent was distilled off under reduced pressure, and the resulting crude crystals were recrystallized from twice the weight of acetic anhydride to obtain a compound represented by the formula (1-1-5) (yield: 72 g, yield: 78 %).

Example 2 Synthesis of Compound (1-2-5) <First Step: Esterification>
To a 3 L three-necked flask equipped with a reflux tube, a thermometer and a stirring blade, 300 g (1.8 mol) of commercially available 4-hydroxyphthalic anhydride, 10 mL of sulfuric acid and 2 L of ethanol were added and heated to reflux. After completion of the reaction, ethanol was distilled off under reduced pressure to obtain a crude product. The crude product was separated and purified by column chromatography (filler: silica gel, added solvent: toluene / ethyl acetate = 4/1 (v / v)). The solvent was distilled off under reduced pressure to obtain 4-hydroxyphthalic acid diethyl ester (yield: 405 g, yield: 93%).

<Second stage: etherification>
In a 2 L three-necked flask equipped with a thermometer and a stirring blade, 50 g (423 mmol) of commercially available 1,6-hexanediol, 211 g (889 mmol) of 4-hydroxyphthalic acid diethyl ester obtained in the first stage, and commercially available potassium carbonate 140 g (1.0 mol) was added, and 1 L of N, N-dimethylformamide was added. The mixture was heated and stirred at 80 ° C. for 12 hours under a nitrogen atmosphere and allowed to cool, and then the reaction solution was poured into 2 L of pure water, and the precipitated crystals were collected by filtration. The obtained crude product was separated and purified by column chromatography (filler: silica gel, added solvent: toluene / ethyl acetate = 6/1 (v / v)). The solvent was distilled off under reduced pressure to obtain the following compound (yield: 194 g, yield: 82%).

<Third stage: Reduction of aromatic ring>
100 g (179 mmol) of the compound obtained in the second stage and 10 g of a commercially available 5% activated carbon-supported ruthenium catalyst (dried product) were placed in a 3LSUS autoclave reactor equipped with a thermometer and a pressure gauge, and 800 mL of ethanol was added. The inside of the system was placed in a hydrogen atmosphere and reacted at a hydrogen pressure of 4900 kPa and 100 ° C. for 12 hours. After completion of the reaction, the catalyst was removed by filtration, and then ethanol was distilled off under reduced pressure to obtain the following compound (yield: 85 g, yield: 83%).

<Fourth stage: hydrolysis (deethyl esterification)>
70 g (123 mmol) of the compound obtained in the third step and 24 g (589 mmol) of sodium hydroxide were placed in a 1 L three-necked flask equipped with a thermometer and a stirring blade, and 120 g of pure water and 750 mL of ethanol were added. After stirring at room temperature for 12 hours, ethanol was distilled off under reduced pressure. 6N hydrochloric acid was added thereto until the pH of the solution was 1 or less, and the precipitated crystals were collected by filtration. The obtained crystal was washed with pure water to obtain the following compound (yield: 51 g, yield: 91%).

<5th stage: Dehydration ring closure>
In a 300 mL eggplant flask, 50 g (109 mmol) of the compound obtained in the fourth stage was added, and 100 g of acetic anhydride was added. The mixture was heated to reflux for 8 hours, and the crystal precipitated after standing to cool was obtained by filtration. The obtained crude product was separated and purified by column chromatography (filler: silica gel, added solvent: toluene: ethyl acetate = 2: 1 (v / v)), the solvent was distilled off under reduced pressure, and the resulting crude crystals were obtained. Was recrystallized from 2-fold weight of acetic anhydride to obtain a compound represented by the formula (1-2-5) (yield: 36 g, yield: 79%).

Example 3 Synthesis of Compound (1-4-3) <First Step: Sonogashira Coupling Reaction>
To a 3 L four-necked flask equipped with a reflux tube, thermometer, stirring blade and dropping funnel, 231 g (989 mmol) of 4-bromohexahydrophthalic anhydride synthesized by the method described in WO2015 / 125734A1, commercially available dichlorobis (triphenyl) Phosphine) 13 g (19 mmol) of palladium (II) and 7 g (38 mmol) of CuI were added, and 1 L of triethylamine was added. A solution obtained by dissolving 50 g (471 mmol) of commercially available 1,7-octadiyne in 200 mL of tetrahydrofuran was gradually added thereto from the dropping funnel, and the mixture was heated to reflux for 5 hours after the completion of the dropping. After completion of the reaction, the solvent was distilled off under reduced pressure, 1 L of ethyl acetate was added thereto, and the separated ethyl acetate solution was washed 3 times with 1 L of pure water. After the organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain crude crystals. The obtained crude crystals were separated and purified by column chromatography (filler: silica gel, added solvent: toluene / ethyl acetate = 3/1 (v / v)). The solvent was distilled off under reduced pressure, and the resulting crude crystals were recrystallized from twice the weight of acetic anhydride to obtain a compound represented by the formula (1-4-3) (yield: 141 g, yield: 73). %).

Example 4 Synthesis of Compound (1-3-3) <First Step: Reduction of Triple Bond>
50 g (122 mmol) of the compound (1-9-3) obtained in Example 8 in a 3LSUS autoclave reactor equipped with a thermometer and a pressure gauge, commercially available lead poisoned 5% palladium / calcium carbonate (Lindler catalyst) 5 g was added and 1 L of ethanol was added. The inside of the system was in a hydrogen atmosphere, and the reaction was performed at a hydrogen pressure of 196 kPa and room temperature for 12 hours. After completion of the reaction, the catalyst was removed by filtration, and then ethanol was distilled off under reduced pressure to obtain crude crystals. The obtained crude crystals were separated and purified by column chromatography (filler: silica gel, added solvent: toluene / ethyl acetate = 3/1 (v / v)). The solvent was distilled off under reduced pressure, and the obtained crystal was recrystallized from double weight acetic anhydride to obtain a compound represented by the formula (1-3-3) (yield; 32 g, yield 64%). .

<Preparation of polyamic acid solution (varnish)>
[Example 5]
In a 100 mL three-necked flask equipped with a stirring blade and a nitrogen introduction tube, 2.1203 g of the compound represented by the formula (DI-7-3) (m = 3, n = 1), and the formula (DI-5-9) 0.6266 g of the represented compound and 0.2256 g of the compound represented by the formula (DI-4-1) were added, and 74 g of N-methyl-2-pyrrolidone was added. The solution was ice-cooled and the liquid temperature was adjusted to 5 ° C., and then the compound represented by formula (1-1-1) 1.8901 g and the compound represented by formula (AN-3-2) 1.1375 g And stirred at room temperature for 12 hours. 20.0 g of butyl cellosolve was added thereto, and the solution was heated and stirred at 60 ° C. until the weight average molecular weight of the solute polymer reached the desired weight average molecular weight. A varnish 1 having a solute weight average molecular weight of approximately 60,000 and a resin concentration of 6% by weight was obtained.

[Examples 6 to 40, Comparative Examples 1 to 12]
Varnish 2 to Varnish 48 having a polymer solid content concentration of 6% by weight were prepared according to Example 5 except that tetracarboxylic dianhydride and diamine were changed. The weight average molecular weight was adjusted to approximately 11,000 to 12,000 for a polymer using a raw material having a photoisomerization structure, and to about 60,000 for a polymer not using a raw material having a photoisomerization structure. Table 1-1, Table 1-2, Table 1-3, and Table 2 show the weight average molecular weights of the tetracarboxylic dianhydride and diamine used and the polyamic acid in the obtained varnish. Example 5 is also shown in Table 1-1.

<Preparation of liquid crystal aligning agent, production of cell for measuring electrical characteristics, and measurement of voltage holding ratio / ion density>
[Example 41]
In a 50 mL eggplant flask, 10 g of varnish 1 was weighed, 5.0 g of N-methyl-2-pyrrolidone and 5.0 g of butyl cellosolve were added, and the mixture was shaken for 2 hours to give liquid crystal aligning agent 1 having a solid content of 3 wt%. Obtained. This aligning agent 1 was applied to a glass substrate with an FFS electrode and a glass substrate with a column spacer by a spinner method (2,000 rpm, 15 seconds). After the coating, it was pre-baked at 80 ° C. for about 5 minutes, and then baked at 200 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of about 100 nm. Using a rubbing treatment apparatus manufactured by Iinuma Gauge Co., Ltd., the resulting polyimide film was pushed into a rubbing cloth (hair leg length 1.9 mm: rayon) by 0.40 mm, and the stage moving speed was 60 mm / sec. The rubbing process was performed at a rotation speed of 1000 rpm. The obtained substrate was subjected to ultrasonic cleaning in ethanol for 5 minutes, the surface was cleaned with ultrapure water, and then dried in an oven at 120 ° C. for 30 minutes. A liquid crystal composition between two alignment films facing each other so that the surfaces on which two alignment films are formed are opposed to each other and the rubbing direction is parallel to each alignment film. A void for injecting was formed and bonded together to assemble an empty FFS cell having a cell thickness of 4 μm. The following positive liquid crystal composition A was vacuum injected into the produced empty FFS cell, and the injection port was sealed with a photocuring agent. Next, a heat treatment was performed at 110 ° C. for 30 minutes to produce a measurement liquid crystal cell.

物性値：ＮＩ １００．１℃； Δε ５．１； Δｎ ０．０９３； η ２５．６ｍＰａ・ｓ． <Positive liquid crystal composition A>

Physical property values: NI 100.1 ° C .; Δε 5.1; Δn 0.093; η 25.6 mPa · s.

The voltage holding ratio of the obtained measurement cell was 99.8% at 5 V-30 Hz, and the ion density was 20 pC. A reliability test was performed by placing the cell on a backlight tester (Fuji Film Co., Ltd., FujiCOLOR LED Viewer Pro HR-2; luminance 2,700 cd / m ² ) for 1,000 hours. The voltage holding ratio of the measurement cell after the reliability test was 99.7%, and the ion density was 20 pC. Further, the orientation of the liquid crystal in this cell was good.

[Examples 42 to 51, Comparative Examples 13 to 16]
For the varnishes 2 to 11 prepared in Examples 6 to 15 and the varnishes 37 to 40 prepared in Comparative Examples 1 to 4, according to the method described in Example 41, preparation of the liquid crystal aligning agent, preparation of the electrical property measurement cell, In addition, voltage holding ratio and ion density were measured. The results are shown in Table 3. The results of Example 41 are also shown in Table 3.

In Examples 41 to 51 and Comparative Examples 13 to 16, the orientation was good. In Examples 41 to 51, the voltage holding ratio, the initial value of the ion density, and the results after 1,000 hours were good, but in Comparative Examples 13 to 16, the voltage holding ratio, the initial value of the ion density, and Both values after 1,000 hours were bad.

[Example 52]
According to the method described in Example 41 except that the liquid crystal composition to be injected was changed to the following negative liquid crystal composition B, a cell for measuring electrical characteristics was prepared using the liquid crystal aligning agent 1, and the voltage holding ratio and ion density were measured. Went.

物性値：ＮＩ ７５．７℃； Δε −４．１； Δｎ ０．１０１； η １４．５ｍＰａ・ｓ． <Negative liquid crystal composition B>

Physical property values: NI 75.7 ° C .; Δε-4.1; Δn 0.101; η 14.5 mPa · s.

The voltage holding ratio of the obtained measurement cell was 98.2% at 5 V-30 Hz, and the ion density was 50 pC. A reliability test was performed by placing the cell on a backlight tester (Fuji Film Co., Ltd., FujiCOLOR LED Viewer Pro HR-2; luminance 2,700 cd / m ² ) for 1,000 hours. The voltage holding ratio of the measurement cell after the reliability test was 98.1%, and the ion density was 50 pC. Further, the orientation of the liquid crystal in this cell was good.

[Examples 53 to 62, Comparative Examples 17 to 20]
For the varnishes 2 to 11 prepared in Examples 6 to 15 and the varnishes 37 to 40 prepared in Comparative Examples 1 to 4, according to the method described in Example 52, preparation of a liquid crystal aligning agent, production of an electrical property measurement cell, In addition, voltage holding ratio and ion density were measured. The results are shown in Table 4. The results of Example 52 are also shown in Table 4.

In Examples 52 to 62 and Comparative Examples 17 to 20, the orientation was good. In Examples 52 to 62, the voltage holding ratio, the initial value of the ion density, and the results after 1,000 hours were good, but in Comparative Examples 17 to 20, the voltage holding ratio, the initial value of the ion density, and The results after 1,000 hours were both bad.

<Preparation of liquid crystal aligning agent for photo-alignment, production of cell for measuring electrical characteristics, and measurement of voltage holding ratio / ion density>
[Example 63]
7.0 g of varnish 4 synthesized in Example 8 and 3.0 g of varnish 12 synthesized in Example 16 were weighed into a 50 mL eggplant flask equipped with a stirring blade and a nitrogen introduction tube, and N-methyl-2 was added thereto. -5.0 g of pyrrolidone and 5.0 g of butyl cellosolve were added and stirred at room temperature for 1 hour to obtain an aligning agent 16 having a resin concentration of 3% by weight. This aligning agent was applied to a glass substrate with an FFS electrode and a glass substrate with a column spacer by a spinner method (2,000 rpm, 15 seconds). After coating, the substrate was heated at 80 ° C. for 3 minutes to evaporate the solvent, and then UV light was passed through the polarizing plate from the vertical direction with respect to the substrate using Multilight ML-501C / B manufactured by USHIO INC. The linearly polarized light was irradiated. The exposure energy at this time is 1.3 ± 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 so that 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. Two substrates on which these alignment films were formed were bonded to each other with the surfaces on which the alignment films were formed facing each other and with a gap for injecting the liquid crystal composition between the facing alignment films. At this time, the polarization directions of the linearly polarized light irradiated to the respective alignment films were made parallel. The positive liquid crystal composition A was injected into these cells to produce a liquid crystal cell (liquid crystal display element) having a cell thickness of 7 μm.

The voltage holding ratio of the obtained measurement cell was 99.8% at 5 V-30 Hz, and the ion density was 20 pC. The voltage holding ratio of the measurement cell after the reliability test was 99.8%, and the ion density was 20 pC. Further, the orientation of the liquid crystal in this cell was good.

[Examples 64 to 209, Comparative Examples 21 to 76]
Except that the varnish used was changed, according to the method described in Example 63, a liquid crystal aligning agent was prepared, an electrical property measurement cell was prepared, and a voltage holding ratio and ion density were measured. The results are shown in Table 5-1, Table 5-2, Table 5-3, Table 5-4, Table 6-1 and Table 6-2. The results of Example 63 are also shown in Table 5-1.

In Examples 63 to 209, the initial values of orientation, voltage holding ratio and ion density, and the results after 1,000 hours were good. On the other hand, in Comparative Examples 21, 22, 24-30, 32-38, 40-46, 48-54, 56-62, 64-70, 72-76, the initial values of voltage holding ratio and ion density are 20 The results after 1,000 hours were good, but the orientation was poor. In Comparative Examples 23, 31, 39, 47, 55, 63 and 71, the orientation was good, but the initial values of voltage holding ratio and ion density and the results after 1,000 hours were poor. It was.

[Example 210]
According to the method described in Example 63 except that the liquid crystal composition to be injected was a negative liquid crystal composition B, a cell for measuring electrical characteristics was prepared using the liquid crystal aligning agent 16, and the voltage holding ratio and ion density were measured. Went.

The initial voltage holding ratio was 98.4% at 5 V-30 Hz, and the ion density was 50 pC. The voltage holding ratio after 1,000 hours was 98.4%, and the ion density was 50 pC. Further, the orientation of the liquid crystal in this cell was good.

[Examples 211 to 356, Comparative Examples 77 to 132]
Except that the varnish used was changed, according to the method described in Example 210, a liquid crystal aligning agent was prepared, an electrical property measurement cell was prepared, and a voltage holding ratio and ion density were measured. The results are shown in Table 7-1, Table 7-2, Table 7-3, Table 7-4, Table 8-1, and Table 8-2. The results of Example 210 are also shown again in Table 7-1.

In Examples 210 to 356, the orientation, the initial value of the voltage holding ratio and the ion density, and the results after 1,000 hours were good. On the other hand, in Comparative Examples 77, 78, 80 to 86, 88 to 94, 96 to 102, 104 to 110, 112 to 118, 120 to 126, and 128 to 132, the initial values of voltage holding ratio and ion density, The result after 000 hours was good, but the orientation was poor. In Comparative Examples 79, 87, 95, 103, 111, 119 and 127, the orientation was good, but the initial values of voltage holding ratio and ion density and the results after 1,000 hours were poor. It was.

[Example 357]
10 g of the liquid crystal aligning agent 4 prepared in Example 44 was weighed, and 15 mg of N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane (additive (Ad1)) was added and dissolved therein. A liquid crystal aligning agent 219 was prepared. Using this liquid crystal aligning agent 219, according to the method described in Example 41, a cell for measuring electrical characteristics was measured, and the voltage holding ratio and ion density were measured.

The voltage holding ratio of the obtained measurement cell was 99.9% at 5 V-30 Hz, and the ion density was 20 pC. The voltage holding ratio of the measurement cell after the reliability test was 99.8%, and the ion density was 20 pC. Further, the orientation of the liquid crystal in this cell was good.

[Examples 358 to 365]
Except for changing the liquid crystal aligning agent and additives to be used, the liquid crystal aligning agent was prepared, the electrical property measuring cell was prepared, and the voltage holding ratio and ion density were measured according to the method described in Example 357. The results are shown in Table 9. The results of Example 357 are also shown in Table 9 again.

Regardless of which additive was added to any liquid crystal aligning agent, the initial values of orientation, voltage holding ratio and ion density and the results after 1,000 hours were good.

[Example 366]
According to the method described in Example 357 except that the liquid crystal composition to be injected was changed to the negative liquid crystal composition B, a liquid crystal aligning agent 219 was used to produce a cell for measuring electrical characteristics, and the voltage holding ratio and ion density were measured. Went.

[Examples 367 to 374]
Except that the liquid crystal aligning agent and additives used were changed, the liquid crystal aligning agent was prepared, the electrical property measurement cell was prepared, and the voltage holding ratio and ion density were measured according to the method described in Example 366. The results are shown in Table 10. The results of Example 366 are also shown in Table 10 again.

Regardless of which additive was added to any liquid crystal aligning agent, the initial values of orientation, voltage holding ratio and ion density and the results after 1,000 hours were good.

[Example 375]
10 g of the liquid crystal aligning agent 19 prepared in Example 66 was weighed, and 15 mg of N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane (additive (Ad1)) was added and dissolved therein. Liquid crystal aligning agent 228 was prepared. Using this liquid crystal aligning agent 228, according to the method described in Example 63, a cell for measuring electrical characteristics was measured, and the voltage holding ratio and ion density were measured.

The voltage holding ratio of the obtained measurement cell was 99.9% at 5 V-30 Hz, and the ion density was 20 pC. The voltage holding ratio of the measurement cell after the reliability test was 99.8%, and the ion density was 20 pC. Further, the orientation of the liquid crystal in this cell was good.

[Examples 376 to 392]
Except that the liquid crystal aligning agent and additives used were changed, the liquid crystal aligning agent was prepared, the electrical property measurement cell was prepared, and the voltage holding ratio and ion density were measured according to the method described in Example 375. The results are shown in Table 11. The results of Example 375 are also shown in Table 11.

Regardless of which additive was added to any liquid crystal aligning agent, the initial values of orientation, voltage holding ratio and ion density and the results after 1,000 hours were good.

[Example 393]
According to the method described in Example 210, using the liquid crystal aligning agent 228, a cell for measuring electrical characteristics was measured, and the voltage holding ratio and ion density were measured.

The voltage holding ratio of the obtained measurement cell was 98.2% at 5 V-30 Hz, and the ion density was 50 pC. The voltage holding ratio of the measurement cell after the reliability test was 98.2%, and the ion density was 50 pC. Further, the orientation of the liquid crystal in this cell was good.

[Examples 394 to 410]
Except for changing the liquid crystal aligning agent and additives to be used, according to the method described in Example 393, the liquid crystal aligning agent was prepared, the electrical property measuring cell was prepared, and the voltage holding ratio and ion density were measured. The results are shown in Table 12. The results of Example 393 are also shown in Table 12.

Regardless of which additive was added to any liquid crystal aligning agent, an alignment film with good alignment was obtained, and good results were obtained in the measurement of voltage holding ratio and ion density.

<Confirmation of ink jet coating properties>
[Example 411]
Into a 2 L three-necked flask equipped with a stirring blade and a nitrogen introducing tube, 466.67 g of varnish 7 prepared in Example 11 and 200.00 g of varnish 16 prepared in Example 20 were weighed, and 0.667 g of NMP was added thereto. , GBL 136.00 g, BC 26.667 g, EDM 160.00 g and DIBK 10.00 g were added to obtain an inkjet alignment agent 246 having a polyamic acid concentration of 4.0%. This orientation agent 246 was applied to a glass substrate with an ITO electrode using an inkjet coating apparatus (type: IJ-0011-A2FS-M0) manufactured by Shibaura Mechatronics Corporation. After coating the alignment agent, the substrate was heated at 60 ° C. for 80 seconds to evaporate the solvent, and then the roughness of the edge portion of the coated surface was measured to be 0.1 mm. Indicated.

Further, when the aligning agent 246 was stored at −25 ° C. for 1 month, no precipitation of solute was confirmed, and it was found that there was no problem in storage stability at low temperatures.

The liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention has a high liquid crystal alignment property and can maintain a high voltage holding ratio for a long time. An excellent liquid crystal display element that does not deteriorate in quality can be obtained.

Claims (9)

A liquid crystal aligning agent containing a polyamic acid or a derivative thereof obtained by reacting a diamine with a tetracarboxylic dianhydride containing at least one tetracarboxylic dianhydride represented by the following formula (1).

In the formula (1), R ¹ is a linear alkylene having 4 to 9 carbon atoms, in which any —CH ₂ — is replaced by —O—, —CH═CH— or —C≡C—. May be. A liquid crystal aligning agent containing the polyamic acid or derivative thereof according to claim 1 and other polyamic acid or derivative thereof. 3. A polyamic acid obtained by reacting a raw material monomer containing a compound having a photoreactive structure with at least one of a tetracarboxylic dianhydride and a diamine subjected to the reaction, or a derivative thereof. Liquid crystal aligning agent as described in. The liquid crystal aligning agent of Claim 3 whose compound which has a photoreactive structure is at least 1 of the compound which has a photoisomerization structure represented by Formula (II)-(VI).

In formulas (II) to (V), R ² and R ³ are a monovalent organic group having —NH ₂ or a monovalent organic group having —CO—O—CO—;
In formula (IV), R ⁴ is a divalent organic group; and
In formula (VI), R ⁵ is independently an aromatic ring having —NH ₂ or —CO—O—CO—. A tetracarboxylic dianhydride or diamine having a photoisomerization structure is represented by the formula (II-1), (II-2), (III-1), (III-2), (IV-1), (IV- The liquid crystal according to claim 4, which is at least one selected from the group of compounds represented by 2), (V-1) to (V-3), (VI-1), and (VI-2). Alignment agent.

In 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;
In formula (V-2), R ⁶ is independently —CH ₃ , —OCH ₃ , —CF ₃ , or —COOCH ₃ , and a is independently an integer of 0 to 2;
In formula (V-3), ring A and ring B are each independently at least one selected from monocyclic hydrocarbons, condensed polycyclic hydrocarbons and heterocyclic rings,
R ¹¹ is a linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —CONH—, —NHCO—, —CON (CH ₃ ) —, or —N (CH ₃ ) CO—,
R ¹² is a linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —CONH—, —NHCO—, —CON (CH ₃ ) —, or —N (CH ₃ ) CO—,
In R ¹¹ and ^{R 12,} 1 single -CH ₂ linear alkylene - or non-contiguous two -CH ₂ - may be is replaced by -O-,
R ^{7 to} R ¹⁰ are each independently —F, —CH ₃ , —OCH ₃ , —CF ₃ , or —OH; and
b to e are each independently an integer of 0 to 4. The alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and at least one selected from the group consisting of epoxy compounds, further containing any one of claims 1-5 Item 1. A liquid crystal aligning agent according to item 1. The liquid crystal aligning agent for horizontal electric field type liquid crystal display elements of any one of Claims 1-6. The liquid crystal aligning film formed from the liquid crystal aligning agent of any one of Claims 1-7. The liquid crystal display element which has a liquid crystal aligning film of Claim 8.