WO2020121822A1

WO2020121822A1 - Liquid crystal display device

Info

Publication number: WO2020121822A1
Application number: PCT/JP2019/046532
Authority: WO
Inventors: 平田　真一; 小川　真治; 宗矩櫻井; 僚神田; 省二船倉; 竜史山崎
Original assignee: Dic株式会社
Priority date: 2018-12-11
Filing date: 2019-11-28
Publication date: 2020-06-18
Also published as: JPWO2020121822A1; CN112823309A; TW202035659A

Abstract

The present invention provides a liquid crystal display device that prevents a decrease in the voltage holding ratio (VHR) of a liquid crystal layer caused by decomposition of dyes and pigments in a liquid crystal display device manufacturing process and leakage of impurities contained in the dyes and pigments into a liquid crystal composition, and solves problems of display defects such as voids, uneven alignment, and screen burn.　The present invention solves the above problem by providing a liquid crystal display device having a first substrate (2) and a second substrate (3) disposed opposite to each other, a liquid crystal layer (4) filled between the first substrate and the second substrate, and a color filter (9) composed of a black matrix and at least an RGB three-color pixel portion, wherein the liquid crystal layer includes a specific compound, the RGB three-color pixel portion includes a specific compound as a color material, an alignment film is not provided on at least one substrate surface, and there is provided an alignment control layer formed from spontaneous alignment compounds contained in the liquid crystal layer or a polymer obtained by polymerization thereof.

Description

Liquid crystal display

The present invention relates to a liquid crystal display device.

Liquid crystal display devices are being used for various electrical appliances for home use, measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, etc., including clocks and calculators. Typical liquid crystal display methods are TN (twisted nematic) type, STN (super twisted nematic) type, DS (dynamic light scattering) type, GH (guest host) type, IPS (in-plane switching) type. Type, OCB (optical compensation birefringence) type, ECB (voltage controlled birefringence) type, VA (vertical alignment) type, CSH (color super homeotropic) type, FLC (ferroelectric liquid crystal) and the like. .. Also, as the drive system, the conventional static drive is becoming more common, and the multiplex drive is becoming common, and the simple matrix system, and recently, the active matrix (AM) system driven by a TFT (thin film transistor), TFD (thin film diode), etc. has become the mainstream. ing.

In a general color liquid crystal display device, as shown in FIG. 1, a transparent electrode layer (a common electrode) between two substrates (1) each having an alignment film (4) is used as a common electrode. 3a) and a color filter layer (2), and a pixel electrode layer (3b) between the other alignment film and the substrate. These substrates are arranged so that the alignment films face each other, and the liquid crystal layer ( 5) is sandwiched.

The color filter layer is composed of a black matrix, a red color layer (R), a green color layer (G), a blue color layer (B), and, if necessary, a yellow color layer (Y). As the coloring material, a pigment dispersion resist in which a pigment is finely dispersed is used.

On the other hand, in recent years, problems such as an increase in power consumption accompanying the increase in size of color liquid crystal display devices and a decrease in the aperture ratio of color filters due to the increase in definition have arisen, and the solution is to improve the brightness and contrast of color filters. However, it has been pointed out that the conventional pigment-dispersed resists have reached a ceiling of brightness and it is difficult to achieve higher brightness, and that the contrast is insufficient due to light scattering by pigment particles.

As a method of solving the above problems, a method of using a dye instead of a pigment is being studied. Various molecular structures of dyes have been put into practical use, and among them, those having high brightness are also known. Further, since it is not in the state of particles like pigments, light scattering is suppressed and high contrast is expected.

However, dyes are inferior in heat resistance to pigments, and there is a concern that they may decompose during the baking process of the polyimide alignment film in conventional liquid crystal display devices. When a dye is used for the color filter layer, it is expected that impurities will affect the liquid crystal layer.

Phenoxyether-substituted phthalocyanine dyes (Patent Document 1), triarylmethane dyes (Patent Document 2), xanthene dyes (Patent Document 3) and the like are disclosed as dyes, and these are used for color filters. The direct relationship between the structure of the color material and the structure of the liquid crystal material has not been examined, and the problem of display failure in the liquid crystal display device has not been solved.

In addition, in recent years, in order to save the cost for forming the alignment film layer and to simplify the manufacturing process of the liquid crystal display device, development of a liquid crystal display device without the alignment film layer has been advanced. Specifically, studies have been made to encapsulate a liquid crystal composition containing an alignment aid that imparts alignment to liquid crystal molecules and use this as a replacement for the alignment film layer. The alignment film layer was located between the color filter layer and the liquid crystal layer and prevented the impurities from seeping out from these members to some extent.However, since the liquid crystal display device does not have an alignment film, the alignment imparting component and Impurities contained in the color filter layer via the transparent electrode may cause display defects such as white spots, uneven alignment, and burn-in due to a decrease in the voltage holding ratio (VHR) of the liquid crystal layer.

As a development of a liquid crystal display device having no alignment film layer, a method of using a liquid crystal composition containing a self-aligning polymerizable compound that achieves homeotropic alignment of the liquid crystal composition on the surface or cell wall of a liquid crystal display (Patent Documents 4 and 5) are disclosed. However, in these methods, a solution to the display defect of the liquid crystal display device due to impurities contained in materials such as dyes and pigments that form the color filter is not specified.

As a method of solving a display defect caused by impurities contained in the pigment or the like constituting the color filter, attention is paid to the relationship between the organic impurities contained in the color filter and the liquid crystal composition, and the dissolution of the organic impurities in the liquid crystal layer. The difficulty is expressed by the hydrophobic parameter of the liquid crystal molecules contained in the liquid crystal layer, and the method of setting the value of the hydrophobic parameter to a certain value or more, and the correlation between the hydrophobic parameter and the -OCF ₃ group at the end of the liquid crystal molecule. Discloses a method of preparing a liquid crystal composition containing a liquid crystal compound having a —OCF ₃ group at the terminal of a liquid crystal molecule in a certain proportion or more (Patent Document 6).

However, even in the disclosure of the cited document, it is an essence of the invention to suppress the influence of impurities in the pigment on the liquid crystal layer, and the structure of the coloring material such as dye and pigment used for the color filter and the structure of the liquid crystal material are used. The direct relationship with the above has not been studied, and the problem of defective display of the liquid crystal display device due to impurities contained in materials such as dyes and pigments forming the color filter has not been solved.

US Patent No. 9581729 JP, 2005-28121, A JP, 2010-254964, A JP, 2005-168826, A International Publication No. 2016/114093 Japanese Patent Laid-Open No. 2000-192040

INDUSTRIAL APPLICABILITY The present invention uses a color filter using a specific liquid crystal composition and a specific dye/pigment in a liquid crystal display device having no alignment film, and is thus included in the dye/pigment decomposition and dye/pigment in the liquid crystal display device manufacturing process To provide a liquid crystal display device which prevents a decrease in voltage holding ratio (VHR) of a liquid crystal layer due to seepage of impurities into a liquid crystal composition and solves problems of display defects such as white spots, uneven alignment, and burning. It is in.

In order to solve the above problems, the present inventors have proposed a combination of a coloring material such as a dye or pigment for forming a color filter and an alignment aid for imparting alignment to liquid crystal molecules in a liquid crystal display device having no alignment film. As a result of diligent studies, a liquid crystal display device using a color filter using a dye/pigment having a specific structure prevents a decrease in the voltage holding ratio (VHR) of the liquid crystal layer and causes display defects such as white spots, uneven alignment, and burn-in. The inventors have found that the problem of (1) is solved and completed the present invention.

That is, the present invention is
It is composed of a first substrate and a second substrate arranged to face each other, a liquid crystal layer filled between the first substrate and the second substrate, a black matrix and at least an RGB three-color pixel portion. And a color filter,
The liquid crystal layer has the general formula (I)

(In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 8 carbon atoms. The compound represented by the general formula (II) is contained in an amount of 10 to 50% by weight.

(In the formula, R ³ and R ⁴ are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. And Z ³ and Z ⁴ are each independently a single bond, —CH═CH—, —C≡C—, —CH ₂ CH ₂ —, —(CH ₂ ) ₄ —, —COO—. , —OCO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, and B and C may each independently be substituted with a fluorine atom, 1,4 A phenylene group or a trans-1,4-cyclohexylene group, m and n each independently represent an integer of 0 to 4, and m+n=1 to 4). % By weight,
Contains an orientation aid,
The RGB three-color pixel portion contains one or more selected from diketopyrrolopyrrole pigments and oil-soluble red organic dyes in the R pixel portion as a coloring material, and the G pixel portion contains halogenated compounds. At least one selected from the group consisting of a phthalocyanine pigment, a phthalocyanine-based green dye, a mixture of a phthalocyanine-based blue dye and an azo-yellow organic dye, and selected in the B pixel portion from an ε-type copper phthalocyanine pigment and a cationic blue organic dye Which does not include an alignment film on the surface of at least one of the first substrate and the second substrate, and which contains one or more of There is provided a liquid crystal display device having an alignment control layer formed from the polymer.

FIG. 1 is an exploded perspective view schematically showing an embodiment of a liquid crystal display element. It is the top view which expanded the area|region enclosed by the I line in FIG.

1 Liquid Crystal Display Element AM Active Matrix Substrate CF Color Filter Substrate 2 First Substrate 3 Second Substrate 4 Liquid Crystal Layer 5 Pixel Electrode Layer 6 Common Electrode Layer 7 First Polarizing Plate 8 Second Polarizing Plate 9 Color Filter 11 Gate Bus line 12 Data bus line 13 Pixel electrode 14 Cs electrode 15 Source electrode 16 Drain electrode 17 Contact hole

An example of the liquid crystal display device of the present invention is shown in FIG. A color filter containing a transparent electrode layer (3a) serving as a common electrode and a specific pigment and a specific compound on one of two substrates (1) having no alignment film, a first substrate and a second substrate. A liquid crystal layer (5a) comprising a layer (2a), a pixel electrode layer (3b) on the other substrate, and a specific liquid crystal composition and an alignment aid for imparting alignment to liquid crystal molecules between these substrates. It is constituted by sandwiching.

The two substrates in the display device are bonded together by a sealing material and a sealing material arranged in a peripheral region, and in many cases, they are formed by a granular spacer or a photolithography method in order to maintain a distance between the substrates. Spacer columns made of resin are arranged.
<Liquid crystal layer>
The liquid crystal layer has the general formula (I)

(In the formula, R ³ and R ⁴ are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. And Z ³ and Z ⁴ are each independently a single bond, —CH═CH—, —C≡C—, —CH ₂ CH ₂ —, —(CH ₂ ) ₄ —, —COO—. , —OCO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, and B and C may each independently be fluorine-substituted 1,4-phenylene. Group or a trans-1,4-cyclohexylene group, m and n each independently represent an integer of 0 to 4, and m+n=1 to 4). It is composed of the contained liquid crystal composition.

The liquid crystal layer in the liquid crystal display device of the present invention contains 10 to 50% by weight of the compound represented by the general formula (I), preferably 12 to 48% by weight, and 14 to 45% by weight. Is more preferable.

In formula (I), R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a carbon atom. Represents an alkenyloxy group having 2 to 8 carbon atoms, which is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkenyl having 2 to 5 carbon atoms It preferably represents an oxy group,
More preferably, it represents an alkyl group having 2 to 5 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkenyloxy group having 2 to 4 carbon atoms,
It is preferred that R ¹ represents an alkyl group, in which case an alkyl group having 2, 3 or 4 carbon atoms is particularly preferred. When R ¹ represents an alkyl group having 3 carbon atoms, R ² is preferably an alkyl group having 2, 4 or 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, and R ² is More preferably, it is an alkyl group having 2 carbon atoms.

The content of the compound represented by the general formula (I) in which at least one of R ¹ and R ² is an alkyl group having 3 to 5 carbon atoms is 50 in the compound represented by the general formula (I). It is preferably at least wt%, more preferably at least 70 wt%, and even more preferably at least 80 wt%. The content of the compound represented by the general formula (I) in which at least one of R ¹ and R ² is an alkyl group having 3 carbon atoms is 50% in the compound represented by the general formula (I). It is preferably not less than 70% by weight, more preferably not less than 70% by weight, further preferably not less than 80% by weight, most preferably not more than 100% by weight.

Specifically, the compound represented by the general formula (I) is preferably a compound represented by the general formula (Ia) to the general formula (Ig) described below.

(Wherein, ^{R 1} and ^{R 2} each independently represent an alkyl group or an alkoxy group having 1 to 5 carbon atoms having 1 to 5 carbon atoms, and ^{R 1} and ^{R 2} in the general formula (I) Similar embodiments are preferred.)
In general formulas (Ia) to (If), general formula (Ia), general formula (Ib), and general formula (Ic) are preferable, and general formula (Ia) and general formula (Ib) are more preferable. When importance is attached to the response speed, the general formula (Ib) and the general formula (Ic) are preferable, and it is more preferable to use the general formula (Ib) and the general formula (Ic) in combination. When importance is placed on reliability, the general formula (Ia) is preferable.

From these points, the content of the compounds represented by the general formula (Ia), the general formula (Ib) and the general formula (Ic) is 80% by weight or more in the compound represented by the general formula (I). It is preferably 90% by weight or more, more preferably 95% by weight or more, and most preferably 100% by weight. Further, the content of the compound represented by the general formula (Ia) is 65% by weight to 100% by weight in the compound represented by the general formula (I), and the content of the general formula (Ib) and the general formula (Ic) is The content of the compound represented by general formula (I) is 0 wt% to 35 wt% in the compound represented by general formula (I), or the content of the compound represented by general formula (Ia) is The content of the compound represented by the general formula (Ib) and the general formula (Ic) is 0 to 10% by weight in the compound represented by the general formula (I). It is preferably 90% by weight to 100% by weight in the compound.

The liquid crystal layer in the liquid crystal display device of the present invention may contain the compound represented by the general formula (I-1) in an amount of 0 to 35% by weight, more preferably 0 to 32% by weight, and Preferably, the content may be 1 to 30% by weight.

In formula (I-1), R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or Represents an alkenyloxy group having 2 to 8 carbon atoms,
R ¹ preferably represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms,
It is more preferable to represent an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ² is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or carbon. It is preferably an alkoxy group having 1 to 5 atoms or an alkenyloxy group having 3 to 5 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. , R ¹ preferably represents an alkyl group, in which case an alkyl group having 1, 3 or 5 carbon atoms is particularly preferred. Further, R ² preferably represents an alkoxy group having 1, 2 or 4 carbon atoms.

Specifically, the compound represented by the general formula (I-1) is preferably a compound represented by the general formula (I-1h) to the general formula (I-1k) described below.

(Wherein, ^{R 1} and ^{R 2} each independently represent an alkyl group or an alkoxy group having 1 to 5 carbon atoms having 1 to 5 carbon atoms, ^{R 1} and R in the general formula (I-1) An embodiment similar to ² is preferred.)
The liquid crystal layer in the liquid crystal display device of the present invention contains the compound represented by the general formula (II) in an amount of 35 to 80% by weight, preferably 40 to 75% by weight, and 42 to 70% by weight. Is more preferable.

(In the formula, R ³ and R ⁴ are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. And Z ³ and Z ⁴ are each independently a single bond, —CH═CH—, —C≡C—, —CH ₂ CH ₂ —, —(CH ₂ ) ₄ —, —COO—. , —OCO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, and B and C may each independently be fluorine-substituted 1,4-phenylene. Or a trans-1,4-cyclohexylene group, m and n each independently represent an integer of 0 to 4, and m+n=1 to 4.)
In the general formula (II), R ³ is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. It is preferable to represent an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 4 carbon atoms. More preferably, it represents an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 or 3 carbon atoms, and more preferably an alkyl group having 2 or 3 carbon atoms or an alkenyl group having 2 carbon atoms. Particularly preferably, it most preferably represents an alkyl group having 2 or 3 carbon atoms.

R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms. It is preferably an alkyl group having 1 to 5 or an alkoxy group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and more preferably a carbon atom. More preferably, it represents an alkoxy group of the formula 2-4.

Z ³ and Z ⁴ are each independently a single bond, —CH═CH—, —C≡C—, —CH ₂ CH ₂ —, —(CH ₂ ) ₄ —, —COO—, —OCO—, —OCH. ₂ -, -CH ₂ O-, -OCF ₂ -or -CF ₂ O- is represented by a single bond, -CH ₂ CH ₂ -, -COO-, -OCH ₂ -, -CH ₂ O-, -OCF. ₂ - or preferably representing a _-CF 2 O-, single bond, _-CH 2 CH ₂ - or more preferably represents _-CH 2 O-.

Preferably, m and n each independently represent an integer of 0 to 3, preferably an integer of 0 to 2, and m+n is preferably 1 to 3 and preferably 1 to 2.

The liquid crystal layer in the liquid crystal display device of the present invention may contain 3 to 10 kinds of the compound represented by the general formula (II), preferably 4 to 9 kinds, and preferably 5 to 8 kinds. It is preferable to contain.

As the compound represented by the general formula (II), it is preferable to contain a compound represented by the following general formula (II-1).

In the formula, R ³ and R ⁴ are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. Represents an alkenyloxy group, Z ⁵ is a single bond, —CH═CH—, —C≡C—, —CH ₂ CH ₂ —, —(CH ₂ ) ₄ —, —COO—, —OCO—, —OCH ₂ Represents —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, and m1 represents 0 or 1.

In the general formula (II-1), R ³ preferably represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and an alkyl group having 2 to 5 carbon atoms or an alkyl group having 2 to 5 carbon atoms. More preferably, it represents an alkenyl group having 2 to 4 carbon atoms, more preferably an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 carbon atoms, particularly preferably an alkyl group having 3 carbon atoms. , R ⁴ preferably represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. More preferably, it represents an alkyl group having 3 carbon atoms or an alkoxy group having 2 carbon atoms, particularly preferably an alkoxy group having 2 carbon atoms, Z ⁵ is a single bond, —CH ₂ It is preferably CH ₂ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, more preferably a single bond or —CH ₂ O—.

The liquid crystal layer in the liquid crystal display device of the present invention preferably contains the compound represented by the general formula (II-1) in an amount of 3% by weight to 60% by weight, preferably 5% by weight to 55% by weight. The content is preferably 50% by weight to 50% by weight, particularly preferably 10% by weight to 40% by weight.

The liquid crystal layer in the liquid crystal display device of the present invention may contain one or more compounds represented by formula (II-1), but preferably contains one to six compounds. It is preferable to contain 5 to 5 kinds, preferably 3 kinds or 4 kinds.

As the compound represented by the general formula (II-1), specifically, compounds represented by the general formulas (II-1a) to (II-1d) described below are preferable.

(In the formula, R ³ represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^4a represents an alkyl group having 1 to 5 carbon atoms.)
In the general formula (II-1a) and the general formula (II-1c), R ³ is preferably the same embodiment as in the general formula (II-1). R ^4a is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably an alkyl group having 2 carbon atoms.

In the general formula (II-1b) and the general formula (II-1d), R ³ is preferably the same embodiment as in the general formula (II-1). R ^4a is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 3 carbon atoms, and particularly preferably an alkyl group having 3 carbon atoms.

Among the general formulas (II-1a) to (II-1d), the general formulas (II-1a) and (II-1c) are preferable in order to increase the absolute value of the dielectric anisotropy. And the general formula (II-1a) is preferable.

The liquid crystal layer in the liquid crystal display device of the present invention preferably contains one or more compounds represented by the general formulas (II-1a) to (II-1d), and preferably contains one or two compounds. And preferably contains one or two compounds represented by general formula (II-1a).

As the compound represented by the general formula (II-1), specifically, compounds represented by the general formulas (II-1e) to (II-1h) described below are also preferable.

(In the formula, R ³ represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^4b represents an alkyl group having 1 to 5 carbon atoms.)
In the general formula (II-1e) and the general formula (II-1g), R ³ is preferably the same embodiment as in the general formula (II-1). R ^4b is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably an alkyl group having 2 carbon atoms.

In the general formula (II-1f) and the general formula (II-1h), R ³ is preferably the same embodiment as in the general formula (II-1). R ^4b is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 3 carbon atoms, and particularly preferably an alkyl group having 3 carbon atoms.

Among the general formulas (II-1e) to (II-1f), the general formulas (II-1e) and (II-1g) are preferable in order to increase the absolute value of the dielectric anisotropy. ..

In formula (II-2), R ³ and R ⁴ are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a carbon atom. Represents an alkenyloxy group having 2 to 8 atoms, Z ⁶ and Z ⁷ are each independently a single bond, —CH═CH—, —C≡C—, —CH ₂ CH ₂ —, —(CH ₂ ) ₄ Represents a —, —COO—, —OCO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, and D may be a fluorine-substituted 1,4-phenylene group Alternatively, it represents a trans-1,4-cyclohexylene group, and m2 and n2 each independently represent 0 or 1.

In the general formula (II-2), R ³ is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and an alkyl group having 2 to 5 carbon atoms or an alkyl group having 2 to 5 carbon atoms. More preferably, it represents an alkenyl group having 2 to 4 carbon atoms, more preferably an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 carbon atoms, and more preferably an alkyl group having 2 or 3 carbon atoms. Particularly preferably, R ⁴ represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. Is more preferable, and an alkyl group having 3 carbon atoms or an alkoxy group having 2 carbon atoms is more preferable.

In the general formula (II-2), Z ⁶ represents a single bond, —CH ₂ CH ₂ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—. Is preferred, and a single bond or —CH ₂ O— is more preferred.

In the general formula (II-2), Z ⁷ represents a single bond, —CH ₂ CH ₂ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—. Is preferred, and more preferably a single bond or —CH ₂ CH ₂ —.

The liquid crystal layer in the liquid crystal display device of the present invention preferably contains one or more compounds represented by general formula (II-2), more preferably one to six compounds. It is more preferable to contain 3 to 4 kinds, and it is particularly preferable to contain 3 or 4 kinds.

As the compound represented by the general formula (II-2), specifically, compounds represented by the general formulas (II-2a) to (II-2d) described below are preferable.

(In the formula, R ³ represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^4c represents an alkyl group having 1 to 5 carbon atoms. An embodiment similar to R ³ and R ⁴ in 2) is preferable.)
In the general formula (II-2a) and the general formula (II-2c), R ³ is preferably the same embodiment as in the general formula (II-2). R ^4c is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably an alkyl group having 2 carbon atoms.

In the general formula (II-2b) and the general formula (II-2d), R ³ is preferably the same embodiment as in the general formula (II-2). R ^4c is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 3 carbon atoms, and particularly preferably an alkyl group having 3 carbon atoms.

Among the general formulas (II-2a) to (II-2d), the general formula (II-2a) and the general formula (II-2c) are preferable for increasing the absolute value of the dielectric anisotropy. In particular, the general formula (II-2a) is preferable.

As the compound represented by the general formula (II-2), specifically, compounds represented by the general formulas (II-2e) to (II-21) described below are also preferable.

(In the general formulas (II-2e) to (II-21), R ³ represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^4d represents the number of carbon atoms. (Although the alkyl groups 1 to 5 are represented, preferred embodiments are the same as R ³ and R ⁴ in the general formula (II-2), respectively.)
In the general formula (II-2e), the general formula (II-2g) and the general formula (II-2i), R ³ is preferably the same embodiment as in the general formula (II-2). R ^4d is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably an alkyl group having 2 carbon atoms.

In the general formula (II-2f), the general formula (II-2h) and the general formula (II-2j), R ³ is preferably the same embodiment as in the general formula (II-2). R ^4d is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 3 carbon atoms, and particularly preferably an alkyl group having 2 carbon atoms.

In the general formula (II-2k) and the general formula (II-21), R ³ is preferably the same embodiment as in the general formula (II-2). R ^4d is preferably an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 or 3 carbon atoms, or an alkoxy group having 1 to 2 carbon atoms, and more preferably a carbon atom. An alkyl group having 2 or an alkoxy group having 2 carbon atoms is particularly preferable.

Among general formulas (II-2e) to general formula (II-21), general formula (II-2e), general formula (II-2h) and general formula (II-2k) are preferable.

In the liquid crystal layer of the liquid crystal display device of the present invention, the total content of the compounds represented by the general formulas (I) and (II) is preferably 75% by weight to 100% by weight, and 80% by weight to 100% by weight. It is preferably in the range of 80% by weight, preferably in the range of 80% by weight to 95% by weight, more preferably in the range of 80% by weight to 100% by weight, and preferably in the range of 95% by weight to 100% by weight.

The liquid crystal layer in the liquid crystal display device of the present invention may further contain a compound represented by the general formula (III).

(In the formula, R ⁷ and R ⁸ are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. 8 is an alkenyloxy group, D, E and F are each independently a fluorine-substituted 1,4-phenylene group or trans-1,4-cyclohexylene, and Z ² is a single bond. , —OCH ₂ —, —OCO—, —CH ₂ O— or —COO—, —OCO—, and n represents 0, 1 or 2. provided that the formula (I) or the formula (II-1) ) And compounds represented by the general formula (II-2) are excluded.)
The compound represented by the general formula (III) is preferably contained in an amount of 1 to 20%, preferably 2 to 15%, and more preferably 4 to 10%.

In the general formula (III), D, E and F each independently represent a fluorine-substituted 1,4-phenylene group or trans-1,4-cyclohexylene, but 2-fluoro-1 , 4-phenylene group, 2,3-difluoro-1,4-phenylene group, 1,4-phenylene group or trans-1,4-cyclohexylene is preferred, and 2-fluoro-1,4-phenylene group Alternatively, a 2,3-difluoro-1,4-phenylene group or a 1,4-phenylene group is more preferable, and a 2,3-difluoro-1,4-phenylene group or a 1,4-phenylene group is preferable.

In the general formula (III), R ⁷ is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. Represents,
When D represents trans-1,4-cyclohexylene, it preferably represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and an alkyl group or carbon having 2 to 5 carbon atoms. It is more preferably an alkenyl group having 2 to 4 atoms, more preferably an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 or 3 carbon atoms, and still more preferably an alkyl group having 3 carbon atoms. Particularly preferred,
When D represents a 1,4-phenylene group which may be substituted with fluorine, it preferably represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 or 5 carbon atoms, and 2 to 4 carbon atoms. It is more preferable to represent an alkyl group having 5 carbon atoms or an alkenyl group having 4 carbon atoms, and it is more preferable to represent an alkyl group having 2 to 4 carbon atoms.

In the general formula (III), R ⁸ is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms. Represents,
When F represents trans-1,4-cyclohexylene, it is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and an alkyl group or carbon having 2 to 5 carbon atoms. It is more preferably an alkenyl group having 2 to 4 atoms, more preferably an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 or 3 carbon atoms, and still more preferably an alkyl group having 3 carbon atoms. Particularly preferred,
When F represents a 1,4-phenylene group which may be fluorine-substituted, it preferably represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 or 5 carbon atoms, and 2 to 4 carbon atoms. It is more preferable to represent an alkyl group having 5 carbon atoms or an alkenyl group having 4 carbon atoms, and it is more preferable to represent an alkyl group having 2 to 4 carbon atoms.

In the general formula (III), when R ⁷ and R ⁸ represent an alkenyl group, and D or F to be bonded represents a 1,4-phenylene group which may be fluorine-substituted, it has 4 or 5 carbon atoms. The following structure is preferable as the alkenyl group.

(In the above formula, the ring structure is bound at the right end.)
Also in this case, an alkenyl group having 4 carbon atoms is more preferable.

In the general formula (III), ^{Z 2} is a single _{bond, -OCH 2 -, - OCO -} , - CH 2 O- or represents a -COO-, single bond, represent a _-CH 2 O-or -COO- Is preferred, and a single bond is more preferred.

In the general formula (III), n represents 0, 1 or 2, but preferably 0 or 1. Moreover, when Z ² represents a substituent other than a single bond, it is preferably 1;

When n is 1, the compound represented by the general formula (III) has the following general formulas (III-1c) to (III-1e) from the viewpoint of increasing the negative dielectric anisotropy. The compound represented by the formula (1) is preferable, and from the viewpoint of increasing the response speed, the compounds represented by the general formulas (III-1f) to (III-1j) are preferable.

(In the general formulas (III-1f) to (III-1j), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom. (Although it represents an alkoxy group having 1 to 5 atoms, an embodiment similar to R ⁷ and R ⁸ in the general formula (III) is preferable.)
When n is 2, the compound represented by the general formula (III) is represented by the general formula (III-2a) to the general formula (III-2h) from the viewpoint of increasing the negative dielectric anisotropy. The compound represented by formula (II-2j) to formula (III-21) is preferable from the viewpoint of increasing the response speed.

(In the general formulas (III-2j) to (III-21), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom. (Although it represents an alkoxy group having 1 to 5 atoms, an embodiment similar to R ⁷ and R ⁸ in the general formula (III) is preferable.)
When n is 0, the compound represented by the general formula (III) is preferably the compound represented by the general formula (III-3b) from the viewpoint of increasing the response speed.

(In the general formula (III-3b), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. However, an embodiment similar to R ⁷ and R ⁸ in the general formula (III) is preferable.
R ⁷ is preferably an alkyl group having 2 to 5 carbon atoms, and more preferably an alkyl group having 3 carbon atoms. R ⁸ is preferably an alkoxy group having 1 to 3 carbon atoms, and more preferably an alkoxy group having 2 carbon atoms.

The liquid crystal layer in the liquid crystal display device of the present invention can use a nematic phase-isotropic liquid phase transition temperature (T _ni ) in a wide range, but is preferably 60 to 120° C., and 70 To 100°C is more preferable, and 70 to 85°C is particularly preferable.

The dielectric anisotropy at 25° C. is preferably −2.0 to −6.0, more preferably −2.5 to −5.0, and −2.5 to −4. Particularly preferably 0.

The refractive index anisotropy at 25° C. is preferably 0.08 to 0.13, more preferably 0.09 to 0.12. More specifically, it is preferably 0.10 to 0.12 when it corresponds to a thin cell gap, and 0.08 to 0.10 when it corresponds to a thick cell gap.

The rotational viscosity (γ1) is preferably 150 or less, more preferably 130 or less, and particularly preferably 120 or less.

In the liquid crystal layer in the liquid crystal display device of the present invention, it is preferable that Z, which is a function of rotational viscosity and refractive index anisotropy, has a specific value.

(In the formula, γ1 represents rotational viscosity, and Δn represents refractive index anisotropy.)
Z is preferably 13000 or less, more preferably 12000 or less, and particularly preferably 11000 or less.

The liquid crystal layer in the liquid crystal display device of the present invention is required to have a specific resistance of 10 ¹² (Ω·cm) or more when used for an active matrix display element, and 10 ¹³ (Ω·cm) is preferable. It is more preferably 10 ¹⁴ (Ω·cm) or more.

The liquid crystal layer in the liquid crystal display device of the present invention may contain a usual nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, an antioxidant, an ultraviolet absorber, a polymerizable monomer, etc., in addition to the above-mentioned compounds. good.

The polymerizable monomer preferably contains a polymerizable compound represented by the following general formula (P). The polymerizable compound has a function of imparting a predetermined pretilt angle to liquid crystal molecules. The liquid crystal composition may contain two or more kinds of this polymerizable compound.

In the formula (P), R ^p1 represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms, or —Sp ^p2 —P ^p2 . However, one or two or more non-adjacent —CH ₂ — present in the alkyl group are each independently —CH═CH—, —C≡C—, —O—, —CO—, —COO. It may be substituted with -or -OCO-. In addition, one or more hydrogen atoms present in the alkyl group may be independently substituted with a cyano group, a fluorine atom or a chlorine atom.

P ^p1 and P ^p2 each independently represent one of the following general formulas (P ^p1 -1) to formula (P ^p1 -9).

(In the formula, R ^p11 and R ^p12 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and W ^p11 is a single bond, Represents —O—, —COO—, —OCO—, or —CH ₂ —, and t ^p11 represents 0, 1 or 2, but R ^p11 , R ^p12 , W ^p11 and/or t ^p11 are in the molecule. When there are a plurality of them, they may be the same or different.)
Sp ^p1 and Sp ^p2 each independently represent a single bond or a spacer group.

Z ^p1 and Z ^p2 are each independently a single bond, —O—, —S—, —CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, —COO—, —OCO—, —OCOOCH ₂ —, —CH ₂ OCOO—, —OCH ₂ CH ₂ O—, —CO—NR ^ZP1 —, —NR ^ZP1 —CO—, ^—SCH ₂ —, —CH ₂ S ^{^{^{-, - CH = CR ZP1 -COO}}} -, - CH = CR ZP1 -OCO -, - COO-CR ZP1 = CH -, - OCO-CR ZP1 = CH -, - COO-CR ZP1 = CH-COO -, - ^{^{COO-CR ZP1 = CH-OCO}} -, - OCO-CR ZP1 = CH-COO -, - OCO-CR ZP1 = CH-OCO -, - (CH 2) 2 -COO -, - (CH 2) 2 -OCO _{_{-, - OCO- (CH 2)}} 2 -, - (C = O) -O- (CH 2) 2 -, - CH = CH -, - CF = CF -, - CF = CH -, - CH = CF —, —CF ₂ —, —CF ₂ O—, —OCF ₂ —, —CF ₂ CH ₂ —, —CH ₂ CF ₂ —, —CF ₂ CF ₂ — or —C≡C— (wherein R ^ZP1 Each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but when a plurality of R ^ZP1's are present in the molecule, they may be the same or different.

A ^p1 , A ^p2 and A ^p3 are each independently
(A ^p )1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more —CH ₂ — not adjacent to each other may be substituted with —O—. )
(B ^p ) 1,4-phenylene group (one —CH═ present in this group or two or more —CH═ which are not adjacent to each other may be substituted with —N═) and ( c ^p) naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydro Naphthalene-2,6-diyl group, phenanthrene-2,7-diyl group or anthracene-2,6-diyl group (one --CH= present in these groups or two or more non-adjacent --) CH= may be substituted with -N=.)
Group selected from the group consisting of (said group (a ^p), group (b ^p) and group (c ^p) are each independently hydrogen atoms present in this group, a halogen atom, carbon atom 1 Represents an alkyl group having 8 to 8 or an alkenyl group having 1 to 8 carbon atoms, a cyano group, or -Sp ^p2- P ^p2 ).

m ^p1 represents 0, 1, 2 or 3.

When multiple Z ^p1 , A ^p2 , Sp ^p2 and/or P ^p2 are present in the molecule, they may be the same or different. ^{However, A p3} ^is the ^{m p1} is ^0, is a ^{group A p1} is represented by group ^{(c p),} may be a single bond.

Note that the alignment aid is excluded from the polymerizable compound.

R ^p1 is preferably —Sp ^p2 —P ^p2 .

It is preferable that P ^p1 and P ^p2 are each independently one of the formulas (P ^p1 -1) to (P ^p1 -3), and more preferably (P ^p1 -1).

R ^p11 and R ^p12 are preferably each independently a hydrogen atom or a methyl group.

^tp11 is preferably 0 or 1.

W ^p11 is preferably a single bond, —CH ₂ — or —C ₂ H ₄ —.

m ^p1 is preferably 0, 1 or 2, and is preferably 0 or 1.

Z ^p1 and Z ^p2 are each independently a single bond, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, —COO—, —OCO—, —COOC ₂ H ₄ -, -OCOC ₂ H ₄ -, -C ₂ H ₄ OCO-, -C ₂ H ₄ COO-, -CH=CH-, -CF ₂ -, -CF ₂ O-, -(CH ₂ ) ₂ -COO -, -(CH ₂ ) ₂ -OCO-, -OCO-(CH ₂ ) ₂ -, -CH=CH-COO-, -COO-CH=CH-, -OCOCH=CH-, -COO-(CH ₂ ) ₂ —, —OCF ₂ — or —C≡C— is preferred, and a single bond, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —COO—, —OCO—, — COOC ₂ H ₄ -, -OCOC ₂ H ₄ -, -C ₂ H ₄ OCO-, -C ₂ H ₄ COO-, -CH=CH-, -(CH ₂ ) ₂ -COO-, -(CH ₂ ) ₂ —OCO—, —OCO—(CH ₂ ) ₂ —, —CH═CH—COO—, —COO—CH═CH—, —OCOCH═CH—, —COO—(CH ₂ ) ₂ — or —C≡ It is more preferably C-.

Note that only one of Z ^p1 and Z ^p2 existing in the molecule is —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —COO—, —OCO—, —COOC ₂ H ₄ —, _{_{_{_{-OCOC 2 H 4 -, - C}}}} 2 H 4 OCO -, - C 2 H 4 COO -, - CH = CH -, - (CH 2) 2 -COO -, - (CH 2) 2 -OCO -, - OCO-(CH ₂ ) ₂ -, -CH=CH-COO-, -COO-CH=CH-, -OCOCH=CH-, -COO-(CH ₂ ) ₂ -or -C≡C-, and others Are all single bonds, and only one of Z ^p1 and Z ^p2 present in the molecule is —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —COO— or —OCO. It is more preferable that all of them are a single bond, and that all of Z ^p1 and Z ^p2 existing in the molecule are single bonds.

Further, only one of Z ^p1 and Z ^p2 existing in the molecule is —CH═CH—COO—, —COO—CH═CH—, —(CH ₂ ) ₂ —COO—, —(CH ₂ ) ₂ It is preferably a linking group selected from the group consisting of —OCO—, —O—CO—(CH ₂ ) ₂ —, and —COO—(CH ₂ ) ₂ —, and all others are single bonds.

Sp ^p1 and Sp ^p2 each independently represent a single bond or a spacer group, and the spacer group is preferably an alkylene group having 1 to 30 carbon atoms. However, —CH ₂ — in the alkylene group is substituted with —O—, —CO—, —COO—, —OCO—, —CH═CH— or —C≡C— unless oxygen atoms are directly linked. The hydrogen atom in the alkylene group may be replaced with a halogen atom.

Among them, Sp ^p1 and Sp ^p2 are preferably each independently a linear alkylene group having 1 to 10 carbon atoms or a single bond.

A ^p1 , A ^p2, and A ^p3 are each independently preferably a 1,4-phenylene group or a 1,4-cyclohexylene group, and more preferably a 1,4-phenylene group.

The 1,4-phenylene group is preferably substituted with one fluorine atom, one methyl group or one methoxy group in order to improve the compatibility with liquid crystal molecules (liquid crystal compounds).

The amount of the polymerizable compound contained in the liquid crystal composition is preferably 0.05 to 10% by mass, more preferably 0.1 to 8% by mass, and 0.1 to 5% by mass. It is more preferably 0.1 to 3% by mass, further preferably 0.2 to 2% by mass, further preferably 0.2 to 1.3% by mass, and 0. It is particularly preferably 0.2 to 1% by mass, and most preferably 0.2 to 0.56% by mass.

The preferable lower limit values thereof are 0.01% by mass, 0.03% by mass, 0.05% by mass, 0.08% by mass, 0.1% by mass and 0.15% by mass. %, 0.2% by mass, 0.25% by mass, and 0.3% by mass. On the other hand, the preferable upper limit values are 10% by mass, 8% by mass, 5% by mass, 3% by mass, 1.5% by mass, 1.2% by mass, and 1% by mass. %, 0.8% by mass, and 0.5% by mass.

When the amount of the polymerizable compound is small, the effect of adding the polymerizable compound to the liquid crystal composition is difficult to appear, and for example, depending on the type of the liquid crystal molecule or the alignment aid, the alignment regulating force of the liquid crystal molecule is weak or weak with time. Problems such as being lost may occur. On the other hand, if the amount of the polymerizable compound is too large, for example, depending on the illuminance of ultraviolet rays, the amount of the polymerizable compound remaining after curing increases, the curing takes time, and the reliability of the liquid crystal composition decreases. There may be problems. Therefore, it is preferable to set the amount of the polymerizable compound in consideration of these balances.

Preferred examples of the polymerizable compound represented by the general formula (P) include polymerizable compounds represented by the following formulas (P-1-1) to (P-1-46).

In the formula, P ^p11 , P ^p12 , Sp ^p11, and Sp ^p12 have the same meanings as P ^p1 , P ^p2 , Sp ^p1, and Sp ^p2 in the general formula (P).

Further, preferred examples of the polymerizable compound represented by the general formula (P) also include the polymerizable compounds represented by the following formulas (P-2-1) to (P-2-12).

In the formula, P ^p21 , P ^p22 , Sp ^p21, and Sp ^p22 have the same meanings as P ^p1 , P ^p2 , Sp ^p1, and Sp ^p2 in the general formula (P).

Further, preferable examples of the polymerizable compound represented by the general formula (P) also include the polymerizable compounds represented by the following formulas (P-3-1) to (P-3-15).

In the formula, P ^p31 , P ^p32 , Sp ^p31, and Sp ^p32 have the same meanings as P ^p1 , P ^p2 , Sp ^p1, and Sp ^p2 in the general formula (P).

Further, preferred examples of the polymerizable compound represented by the general formula (P) also include the polymerizable compounds represented by the following formulas (P-4-1) to (P-4-19).

In the formula, P ^p41 , P ^p42 , Sp ^p41 and Sp ^p42 have the same meanings as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).

When a polymerizable monomer is added, the polymerization will proceed even if no polymerization initiator is present, but a polymerization initiator may be contained in order to accelerate the polymerization. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides and the like. In addition, a stabilizer may be added to improve storage stability. Examples of stabilizers that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, and nitroso compounds. Be done.

The liquid crystal layer in the present invention is useful for a liquid crystal display device, and includes AM-LCD (active matrix liquid crystal display device), TN (nematic liquid crystal display device), STN-LCD (super twisted nematic liquid crystal display device), OCB-LCD and It is useful for an IPS-LCD (in-plane switching liquid crystal display element), but is particularly useful for an AM-LCD, and can be used for a PSA mode, PSVA mode, VA mode, IPS mode or ECB mode liquid crystal display element.
<Alignment aid>
The alignment aid is a member (electrode (for example, ITO), substrate (for example, glass substrate, acrylic substrate, transparent substrate, flexible substrate, or the like)) that directly contacts the liquid crystal layer containing the liquid crystal composition, resin layer (for example, color filter). , An alignment film, an overcoat layer, etc.) and an insulating film (for example, an inorganic material film, SiNx, etc.) and induce a homeotropic alignment of liquid crystal molecules contained in the liquid crystal layer.

The alignment aid induces alignment of the liquid crystal molecules, a polymerizable group for polymerization, a mesogenic group similar to the liquid crystal molecules, an adsorption group (polar group) capable of interacting with a member that directly contacts the liquid crystal layer. It is preferable to have an orientation-inducing group.

It is preferable that the adsorption group and the orientation-inducing group are bonded to the mesogen group, and the polymerizable group is substituted on the mesogen group, the adsorption group and the orientation-inducing group directly or via a spacer group as necessary. In particular, the polymerizable group is preferably substituted with a mesogenic group in a state of being incorporated in the adsorptive group.

In the following, * at the left end and * at the right end in the chemical formulas represent bonds.

"Orientation-inducing group"
The orientation-inducing group has a function of inducing the orientation of liquid crystal molecules, and is preferably a group represented by the following general formula (AK).

In the formula, R ^AK1 represents a linear or branched alkyl group having 1 to 20 carbon atoms. However, one or two or more non-adjacent —CH ₂ — groups in the alkyl group are independently —CH═CH—, —C≡C—, —O—, —CO—, —COO— or It may be substituted with —OCO—, and one or more hydrogen atoms in the alkyl group may be independently substituted with a halogeno group.

R ^AK1 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 20 carbon atoms, and more preferably a linear alkyl group. It is more preferable to represent an alkyl group having 1 to 8 carbon atoms.

Further, one or two or more non-adjacent —CH ₂ — groups in the alkyl group are independently —CH═CH—, —C≡C—, —O—, —CO—, —COO— or It may be replaced with —OCO—.

Further, the hydrogen atom in the alkyl group may be substituted with a fluorine atom or a chlorine atom, or may be substituted with a fluorine atom.

From the viewpoint of imparting so-called amphiphilicity to the orientation aid, it is preferable that the orientation-inducing group is bonded to the side opposite to the adsorption group of the mesogenic group.

"Polymerizable group"
The polymerizable group is represented by P ^AP1 − and is preferably bonded to the mesogen group via —Sp ^AP1 — (single bond or spacer group).

P ^AP1 is preferably a group selected from the group represented by the following general formulas (AP-1) to (AP-9).

In the formula, R ^AP1 and R ^AP2 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 10 carbon atoms. However, one or more —CH ₂ — in the alkyl group may be substituted with —O— or —CO— so that oxygen atoms are not directly adjacent to each other, and one or two —CH ₂ — in the alkyl group may be substituted. The above hydrogen atoms may be independently substituted with a halogen atom or a hydroxyl group.

W ^AP1 represents a single bond, —O—, —COO—, —OCO— or —CH ₂ —.

t ^AP1 represents 0, 1 or 2.

P ^AP1 is preferably a group represented by the following general formula (AP-1) to general formula (AP-7), and is represented by the following general formula (AP-1) or general formula (AP-2). Group is more preferred, and general formula (AP-1) is even more preferred.

Sp ^AP1 is preferably a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and more preferably a single bond or a linear alkylene group having 1 to 20 carbon atoms. It is more preferable to represent a single bond or a linear alkylene group having 2 to 10 carbon atoms.

In Sp ^AP1 , one or more —CH ₂ — in the alkylene group are independently —CH═CH—, —C≡C—, —O so that oxygen atoms are not directly adjacent to each other. It may be substituted with -, -CO-, -COO- or -OCO-.

In the alignment aid, the number of P ^AP1 −Sp ^AP1 − is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, and 2 or more and 4 or less. More preferably, 2 or 3 is particularly preferable, and 2 is most preferable.

The hydrogen atom in P ^AP1- Sp ^AP1- may be substituted with a polymerizable group, an adsorption group and/or an orientation-inducing group.

P ^AP1- Sp ^AP1- may be bonded to a polymerizable group, a mesogenic group, an adsorption group and/or an orientation-inducing group.

Further, P ^AP1 -Sp ^AP1- is preferably bound to a mesogenic group, an adsorptive group or an orientation-inducing group, and more preferably bound to a mesogenic group or an adsorptive group.

When there are a plurality of P ^AP1 and/or Sp ^AP1 − molecules in the molecule, they may be the same or different from each other.

"Mesogenic group"
The mesogen group means a group having a rigid portion, for example, a group having at least one cyclic group, preferably a group having 2 to 4 cyclic groups, and 3 to 4 cyclic groups. Groups are more preferred. The cyclic group may be linked by a linking group, if necessary. The mesogen group preferably has a skeleton similar to that of liquid crystal molecules (liquid crystal compound) used in the liquid crystal layer.

In addition, in the present specification, the “cyclic group” refers to an atomic group in which constituent atoms are cyclically bonded, and includes a carbocycle, a heterocycle, a saturated or unsaturated cyclic structure, a monocyclic and bicyclic structure, Includes polycyclic structures, aromatics, non-aromatics, and the like.

The cyclic group may contain at least one hetero atom, and may be further substituted with at least one substituent (halogeno group, polymerizable group, organic group (alkyl group, alkoxy group, aryl group, etc.). When the cyclic group is monocyclic, the mesogen group preferably contains two or more monocyclic rings.

The mesogen group is preferably represented by, for example, general formula (AL).

In the formula, Z ^AL1 is a single bond, —CH═CH—, —CF═CF—, —C≡C—, —COO—, —OCO—, —OCOO—, —CF ₂ O—, —OCF ₂ —. _{_{, -CH = CHCOO -, - OCOCH}} = CH -, - CH 2 -CH 2 COO -, - OCOCH 2 -CH 2 -, - CH = C (CH 3) COO -, - OCOC (CH 3) = CH- , —CH ₂ —CH(CH ₃ )COO—, —OCOCH(CH ₃ )—CH ₂ —, —OCH ₂ CH ₂ O— or an alkylene group having 1 to 20 carbon atoms. However, one or more —CH ₂ — in the alkylene group may be substituted with —O—, —COO— or —OCO— so that oxygen atoms are not directly adjacent.

A ^AL1 and A ^AL2 each independently represent a divalent cyclic group.

One or more hydrogen atoms in Z ^AL1 , A ^AL1 and A ^AL2 may be each independently substituted with a halogeno group, an adsorptive group, P ^AP1- Sp ^AP1 -or a monovalent organic group. ,
When a plurality of Z ^AL1 and A ^AL1 are present in the molecule, they may be the same or different from each other.

m ^AL1 represents an integer of 1 to 5.

In formula (AL), Z ^AL1 is preferably a single bond or an alkylene group having 2 to 20 carbon atoms, more preferably a single bond or an alkylene group having 2 to 10 carbon atoms, and a single bond. , -(CH ₂ ) ₂ -or -(CH ₂ ) _4- is more preferable. One or more —CH ₂ — in the alkylene group may be substituted with —O—, —COO— or —OCO— so that oxygen atoms are not directly adjacent.

Furthermore, when it is intended to increase the linearity of a rod-shaped molecule, Z ^AL1 has a single bond in which rings are directly connected to each other or an even number of atoms directly connecting the rings is even. The form is preferred. For example, in the case of —CH ₂ —CH ₂ COO—, the number of atoms directly connecting the rings is four.

In formula (AL), A ^AL1 and A ^AL2 each independently represent a divalent cyclic group. Examples of the divalent cyclic group include 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2, 5-diyl group, tetrahydrothiopyran-2,5-diyl group, thiophene-2,5-diyl group, 1,4-bicyclo(2.2.2)octylene group, decahydronaphthalene-2,6-diyl group , Pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2 ,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a,9,10a- Octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo[1,2-b:4,5-b']dithiophene-2,6-diyl group, benzo[1,2-b: 4,5-b']diselenophen-2,6-diyl group, [1]benzothieno[3,2-b]thiophene-2,7-diyl group, [1]benzoselenopheno[3,2-b]selenophene It is preferably one selected from the group consisting of -2,7-diyl group and fluorene-2,7-diyl group, and is 1,4-phenylene group, 1,4-cyclohexylene group, 2,6- A naphthylene group or a phenanthrene-2,7-diyl group is more preferable, and a 1,4-phenylene group or a 1,4-cyclohexylene group is further preferable.

Incidentally, these groups may be unsubstituted or substituted with a substituent. The substituent is preferably a fluorine atom or an alkyl group having 1 to 8 carbon atoms. Further, the alkyl group may be substituted with a fluorine atom or a hydroxyl group.

Further, one or more hydrogen atoms in the cyclic group may be substituted with a halogeno group, an adsorptive group, P ^AP1- Sp ^AP1 -or a monovalent organic group.

In the general formula (AL), the monovalent organic group is a group having a chemical structure formed by the organic compound being in the form of a monovalent group, and is formed by removing one hydrogen atom from the organic compound. An atomic group.

Examples of the monovalent organic group include an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, and an alkenyloxy group having 2 to 15 carbon atoms. Groups, etc., preferably an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms, and an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Is more preferable, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 2 carbon atoms is more preferable. An alkoxy group is particularly preferable, and an alkyl group having 1 or 2 carbon atoms or an alkoxy group having 1 carbon atom is most preferable.

Further, one or more —CH ₂ — in the above alkyl group, alkenyl group, alkoxy group, alkenyloxy group is —O—, —COO— or —OCO— so that oxygen atoms are not directly adjacent to each other. It may be replaced. Further, the monovalent organic group may have a role as the above-mentioned orientation-inducing group.

In the general formula (AL), m ^AL1 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 2 or 3.

The following formulas (me-1) to (me-44) are mentioned as preferable forms of the mesogen group.

General formula (AL) is a structure in which two hydrogen atoms are eliminated from these compounds.

In these formulas (me-1) to (me-44), one or more hydrogen atoms in the cyclohexane ring, benzene ring or naphthalene ring are each independently a halogeno group, P ^AP1 -Sp ^AP1. -It may be substituted with a monovalent organic group (for example, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms), an adsorption group or an orientation inducing group.

Of the above mesogen groups, preferred forms are formulas (me-8) to (me-44), and more preferred forms are formulas (me-8) to (me-10) and formulas (me-12) to (Me-18), formulas (me-22) to (me-24), formulas (me-26) to (me-27) and formulas (me-29) to (me-44), and more preferred forms Is a formula (me-12), (me-14), (me-16), (me-22) to (me-24), (me-29), (me-34), (me-36) To (me-37) and (me-42) to (me-44).

Among the above mesogen groups, a particularly preferable form is the following general formula (AL-1) or (AL-2), and a most preferable form is the following general formula (AL-1).

In the formula, X ^AL101 to X ^AL118 and X ^AL201 to X ^AL214 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogeno group, P ^APl- Sp ^APl- represents an adsorption group described later or the above-mentioned orientation-inducing group.

Ring ^{A AL11,} Ring ^{A AL12} and ring ^{A AL21} each independently represent a cyclohexane ring or a benzene ring.

Any one or more of X ^AL101 to X ^AL118 and X ^AL201 to X ^AL214 are substituted with an adsorption group described later.

Any one or more of X ^AL101 to X ^AL118 and X ^AL201 to X ^AL214 are substituted with the orientation-inducing group.

Adsorptive group and the orientation induced group will be described ^later, P ^{AP1 -Sp} AP1 - may be substituted with.

The general formula (AL-1) or the general formula (AL-2) has one or two or more P ^AP1 -Sp ^APl- in its molecule.

In formula (AL-1), X ^AL101 is preferably the above-mentioned orientation-inducing group.

In the general formula (AL-1), at least one of X ^AL109 , X ^AL110 and X ^AL111 is preferably an adsorption group described below, and both X ^AL109 and X ^AL110 are adsorption groups described below or X ^AL110 is described later. Is more preferable, and X ^AL110 is further preferable to be an adsorption group described later.

Is preferably an adsorptive group having or structure in the polymerizable site - in the general formula ^(AL-1), at least one of ^{X AL109,} X ^AL110 and ^{X AL111} ^P ^{AP1 -Sp} AP1 of the adsorptive group described below , both or one of ^{X AL109} and ^{X AL111} is ^P AP1 ^{-Sp AP1} - is more preferable.

In formula (AL-1), one or two of X ^AL104 to X ^AL108 and X ^AL112 to X ^AL116 are independently an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. Alternatively, it is preferably a halogeno group, and more preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom. Particularly, it is preferable that each of X ^AL105 , X ^{AL106, and} X ^AL107 is independently an alkyl group having 1 to 3 carbon atoms or a fluorine atom.

In formula (AL-2), X ^AL201 is preferably the above-mentioned orientation-inducing group.

In the general formula (AL-2), at least one of X ^AL207 , X ^AL208 and X ^AL209 is preferably an adsorption group described below, and both X ^AL207 and X ^AL208 are adsorption groups described below or X ^AL208 is described later. Is more preferable, and X ^AL208 is further preferable to be an adsorption group described later.

In the general formula (AL-2), it is preferable that at least one of X ^AL207 , X ^AL208, and X ^AL209 is P ^AP1- Sp ^AP1- of the adsorbing groups described below or an adsorbing group having a polymerizable site in the structure. , X ^{AL2 07} and X ^{AL 209} , or both, are more preferably P ^AP1 —Sp ^AP1 −.

In formula (AL-2), one or two of X ^AL202 to X ^AL206 and X ^AL210 to X ^AL214 each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. Alternatively, it is preferably a halogeno group, and more preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom. In ^particular, ^{X AL204,} X ^AL205 or ^{X AL206} are each independently preferably an alkyl group or a fluorine atom of 1 to 3 carbon atoms.

"Adsorption group"
The adsorptive group is a group having a role of adsorbing an adsorbent which is a layer that comes into contact with the liquid crystal composition such as a substrate, a film and an electrode.

Adsorption is generally classified into chemisorption in which a chemical bond (covalent bond, ionic bond or metal bond) is formed and adsorbed between the adsorbent and the adsorbate, and physical adsorption other than chemisorption. In the present specification, the adsorption may be either chemical adsorption or physical adsorption, but physical adsorption is preferable. Therefore, the adsorption group is preferably a group capable of physically adsorbing to the adsorption medium, and more preferably a group capable of binding to the adsorption medium by intermolecular force.

As the form of binding to the adsorbent by intermolecular force, there are forms such as permanent dipole, permanent quadrupole, dispersive force, charge transfer force, or hydrogen bond.

A preferred form of the adsorbing group is a form capable of binding to the adsorbent by a hydrogen bond. In this case, the adsorptive group may serve as either a donor or an acceptor of protons that mediate hydrogen bonding, or both.

The adsorption group is preferably a group containing a polar element having an atomic group in which a carbon atom and a hetero atom are linked (hereinafter, the “adsorption group” is also referred to as a “polar group”). In the present specification, the polar element refers to an atomic group in which a carbon atom and a hetero atom are directly linked.

The hetero atom is preferably at least one selected from the group consisting of N, O, S, P, B and Si, and at least one selected from the group consisting of N, O and S. Is more preferable, at least one selected from the group consisting of N and O is more preferable, and O is particularly preferable.

In addition, in the orientation aid, the valence of the polar element is not particularly limited, such as monovalent, divalent, and trivalent, and the number of polar elements in the adsorbing group is not particularly limited.

The orientation aid preferably has 1 to 8 adsorption groups in one molecule, more preferably 1 to 4 adsorption groups, and further preferably 1 to 3 adsorption groups.

Incidentally, the adsorption group, excluding a polymerizable group and orientation induced group, a hydrogen atom is ^P AP1 ^{-Sp AP1} in adsorptive group - substituted with structural and ^P AP1 ^{-Sp AP1} - hydrogen atoms in the -OH The structure substituted with is included in the adsorptive group.

Adsorption group contains one or more polar elements, and is roughly classified into a cyclic group type and a chain group type.

The cyclic group type is a form including a cyclic group having a cyclic structure containing a polar element in its structure, and the chain group type is a cyclic group having a cyclic structure containing a polar element in its structure. It is a form that does not include.

The chain type is a form having a polar element in a linear or branched chain group, and may have a cyclic structure that does not include a polar element in a part thereof.

A cyclic group-type adsorptive group means a form having a structure containing at least one polar element in a cyclic atomic arrangement.

In the present specification, the cyclic group is as described above. Therefore, the cyclic group-type adsorptive group need only include a cyclic group containing a polar element, and the entire adsorptive group may be branched or linear.

On the other hand, a chain-type adsorptive group is a structure that does not include a cyclic atomic array containing polar elements in the molecule and contains at least one polar element in a linear atomic array (which may be branched). Means a form having.

In addition, in the present specification, the chain group refers to an atomic group in which the constituent atoms do not include a cyclic atomic array in the structural formula and the constituent atoms are linearly (may be branched), and are acyclic. Refers to the group. In other words, the chain group means a linear or branched aliphatic group, and may contain either a saturated bond or an unsaturated bond.

Therefore, the chain group includes, for example, an alkyl group, an alkenyl group, an alkoxy group, an ester group, an ether group or a ketone group. The hydrogen atom in these groups is substituted with at least one substituent (reactive functional group (vinyl group, acryl group, methacryl group, etc.), chain organic group (alkyl group, cyano group, etc.)) Good. Further, the chain group may be linear or branched.

The cyclic group-type adsorbing group may be a heteroaromatic group having 3 to 20 carbon atoms (including a condensed ring) or a heteroalicyclic group having 3 to 20 carbon atoms (including a condensed ring). A heteroaromatic group having 3 to 12 carbon atoms (including a condensed ring) or a heteroalicyclic group having 3 to 12 carbon atoms (including a condensed ring) is more preferable, and a 5-membered hetero group. It is more preferably an aromatic group, a 5-membered heteroalicyclic group, a 6-membered heteroaromatic group, or a 6-membered heteroalicyclic group. The hydrogen atom in these ring structures may be substituted with a halogeno group, a linear or branched alkyl group having 1 to 5 carbon atoms or an alkyloxy group.

The chain-type adsorptive group is preferably a hydrogen atom in the structure or a linear or branched alkyl group having 1 to 20 carbon atoms in which —CH ₂ — is substituted with a polar element. It should be noted that one or two or more non-adjacent —CH ₂ — groups in the alkyl group are replaced with —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—. May be done. In addition, the chain-type adsorptive group preferably contains one or more polar elements at the ends thereof.

The hydrogen atom in the adsorption group may be replaced with a polymerizable group.

Specific examples of the polar element include a polar element containing an oxygen atom (hereinafter, oxygen-containing polar element), a polar element containing a nitrogen atom (hereinafter, nitrogen-containing polar element), a polar element containing a phosphorus atom (hereinafter, phosphorus-containing polar element). Element), a polar element containing a boron atom (hereinafter, boron-containing polar element), a polar element containing a silicon atom (hereinafter, silicon-containing polar element), or a polar element containing a sulfur atom (hereinafter, sulfur-containing polar element). .. From the viewpoint of adsorption ability, the polar element is preferably a nitrogen-containing polar element or an oxygen-containing polar element, and more preferably an oxygen-containing polar element.

As the oxygen-containing polar element, at least one group selected from the group consisting of a hydroxyl group, an alkylol group, an alkoxy group, a formyl group, a carboxyl group, an ether group, a carbonyl group, a carbonate group, and an ester group or the group is carbon. It is preferably a group linked to an atom.

As the nitrogen-containing polar element, at least one group selected from the group consisting of a cyano group, a primary amino group, a secondary amino group, a tertiary amino group, a pyridyl group, a carbamoyl group, and a ureido group, or the group is a carbon atom. It is preferably a group linked to an atom.

Therefore, as the adsorbing group, a cyclic group having an oxygen-containing polar element (hereinafter, oxygen-containing cyclic group), a cyclic group having a nitrogen-containing polar element (hereinafter, nitrogen-containing cyclic group), an oxygen-containing polar group One or more selected from the group consisting of a chain group having an element (hereinafter, oxygen-containing chain group) and a chain group having a nitrogen-containing polar element (hereinafter, nitrogen-containing chain group) It is preferable to include the group itself or the group.

The oxygen-containing cyclic group preferably contains any of the following groups having an oxygen atom as an ether group in the ring structure.

The oxygen-containing cyclic group preferably contains any of the following groups having an oxygen atom as a carbonyl group, a carbonate group and an ester group in the ring structure.

The nitrogen-containing cyclic group preferably contains any of the following groups.

The oxygen-containing chain group preferably contains any of the following groups.

In the formula, R ^at1 represents an alkyl group having 1 to 5 carbon atoms.

Z ^at1 represents a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms. However, —CH ₂ — in the alkylene group or alkenylene group may be substituted with —O—, —COO—, —C(═O)—, or —OCO— so that oxygen atoms are not directly adjacent to each other.

X ^at1 represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms. However, —CH ₂ — in the alkyl group may be substituted with —O—, —COO—, —C(═O)—, or —OCO— so that oxygen atoms are not directly adjacent to each other.

The nitrogen-containing chain group preferably contains any of the following groups.

In the formula, R ^at , R ^bt , R ^ct and R ^dt each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

The adsorbing group is preferably a group represented by the following general formula (AT).

In the formula, Sp ^AT1 represents a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms. However, the hydrogen atom in the alkylene group may be substituted with —OH, —CN, —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkylene group is directly bonded to the oxygen atom. It may be substituted with a cyclic group, —O—, —COO—, —C(═O)—, —OCO—, or —CH═CH— so as not to bond.

W ^AT1 represents a single bond or the following general formula (WAT1) or (WAT2).

Z ^AT1 represents a monovalent group containing a polar element. However, the hydrogen atom in Z ^AT1 may be replaced with —OH, —CN or P ^AP1 —Sp ^AP1 —.

(In the formula, Sp ^WAT1 and Sp ^WAT2 each independently represent a single bond, a linear or branched alkylene group having 1 to 25 carbon atoms, and a hydrogen atom in the alkylene group is —OH, — CN or P ^AP1 —Sp ^AP1 — may be substituted, and —CH ₂ — in the alkylene group is a cyclic group, —O—, —COO—, —C(═O) so that oxygen atoms are not directly adjacent to each other. )-, -OCO- or -CH=CH- may be substituted.)
It is preferable that Sp ^AT1 , Sp ^WAT1 and Sp ^WAT2 each independently represent a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and a single bond or a linear carbon atom number. It is more preferable to represent an alkylene group having 1 to 20 and even more preferable to represent a single bond or a linear alkylene group having 2 to 10 carbon atoms.

Further, in Sp ^AT1 , Sp ^WAT1 and Sp ^WAT2 , one or more —CH ₂ — in the alkylene group are independently —CH═CH—, — so that oxygen atoms are not directly adjacent to each other. It may be substituted with C≡C-, -O-, -CO-, -COO- or -OCO-.

The ^hydrogen atoms in ^{Sp AT1} and ^{Sp WAT1} are each ^{independently,} -W AT1 ^{-Z AT1} or ^P AP1 ^{-Sp AP1} - it may be substituted with.

Z ^AT1 represents a monovalent group containing a polar element and is preferably a group represented by the following general formula (ZAT1-1) or (ZAT1-2).

In the formula, Sp ^ZAT11 and Sp ^ZAT12 each independently represent a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms. However, the hydrogen atom in the alkylene group may be substituted with —OH, —CN, —Z ^ZAT11 —R ^ZAT11 or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkylene group is directly bonded to the oxygen atom. It may be substituted with a cyclic group, —O—, —COO—, —C(═O)—, —OCO— or —CH═CH— so as not to be adjacent to each other.

Z ^ZAT11 represents a group containing a polar element.

The structure represented by the ring containing Z ^ZAT12 in the general formula (ZAT1-2) represents a 5- to 7-membered ring.

The hydrogen atom in Z ^ZAT11 and Z ^ZAT12 may be substituted with —OH, —CN or P ^AP1 —Sp ^AP1 —.

R ^ZAT11 and R ^ZAT12 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. However, a hydrogen atom in the alkyl group may be replaced by —OH, —CN or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkyl group is a cyclic group so that oxygen atoms are not directly adjacent to each other. , -O-, ^-COO- , -C(=O)-, ^-OCO-, -CH=CH- or -Z ^ZAT11- .

The group represented by the general formula (ZAT1-1) is preferably a group represented by the following general formulas (ZAT1-1-1) to (ZAT1-1-30).

In the formula, the hydrogen atom bonded to the carbon atom may be substituted with —OH, —CN or P ^AP1 —Sp ^AP1 —.

Sp ^ZAT11 represents a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms. However, the hydrogen atom in the alkylene group may be substituted with —OH, —CN, —Z ^ZAT11 —R ^ZAT11 or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkylene group is directly bonded to the oxygen atom. It may be substituted with a cyclic group, —O—, —COO—, —C(═O)—, —OCO— or —CH═CH— so as not to be adjacent to each other.

R ^ZAT11 represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. However, the hydrogen atom in the alkyl group may be substituted with —OH, —CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkyl group is oxygen. It may be substituted with a cyclic group, —O—, ^—COO— , —C(═O)—, ^—OCO—, —CH═CH— or —Z ^ZAT11 — such that the atoms are not directly adjacent.

The group represented by the general formula (ZAT1-2) is preferably a group represented by the following general formulas (ZAT1-2-1) to (ZAT1-2-9).

In the formula, the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, —OH, —CN or P ^AP1 —Sp ^AP1 —.

Sp ^ZAT11 represents a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms. However, the hydrogen atom in the alkylene group may be substituted with —OH, —CN or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkylene group is a cyclic group so that oxygen atoms are not directly adjacent to each other. , -O-, ^-COO- , -C(=O)-, ^-OCO-, -CH=CH- or -Z ^ZAT11- .

Examples of the group represented by the general formula (ZAT1-1) include the following groups.

In the formula, R ^tc represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or P ^AP1 —Sp ^AP1 —. However, a hydrogen atom in the alkyl group may be replaced by —OH, —CN or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkyl group is a cyclic group so that oxygen atoms are not directly adjacent to each other. , -O-, ^-COO- , -C(=O)-, ^-OCO-, -CH=CH- or -Z ^ZAT11- .

Hydrogen atoms in the ^molecule, P ^{AP1 -Sp} AP1 - may be substituted with.

* Represents a bond.

Among the groups preferable as Z ^AT1 described above, since the storage stability can be ensured by stable incorporation into the liquid crystal composition, and a good alignment control force derived from an appropriately high adsorption force to the adsorbent is exhibited. , OH containing groups are particularly preferred. Further, the combination with (AL-1) is particularly preferable as the mesogen group.

The orientation aid is preferably in a form in which the polar element contained in the adsorption group or the polar element contained in the polymerizable group is localized. The adsorptive group is an important structure for vertically aligning liquid crystal molecules, and when the adsorptive group and the polymerizable group are adjacent to each other, a better alignment property can be obtained, and a good liquid crystal composition can be obtained. Shows solubility.

Specifically, the orientation aid is preferably in a form having a polymerizable group and an adsorptive group on the same ring of the mesogen group. Such a form includes a form in which one or more polymerizable groups and one or more adsorption groups are bonded on the same ring, and at least one or one or more adsorption groups of the one or more polymerizable groups. Of at least one of the above, one having a polymerizable group and an adsorptive group on the same ring, one of which is bonded to the other.

Further, in this case, a hydrogen atom in the spacer group bonded to the polymerizable group may be replaced with an adsorptive group, and further, a hydrogen atom in the adsorptive group may be replaced with a polymerizable group through the spacer group. Good.

The orientation aid (spontaneous orientation compound) is preferably a compound represented by the following general formula (SAL).

In the formula, the hydrogen atom bonded to the carbon atom is a linear or branched alkyl group having 1 to 25 carbon atoms, —OH, —CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1. It may be replaced with-. However, the hydrogen atom in the alkyl group may be substituted with —OH, —CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkyl group is oxygen. It may be substituted with a cyclic group, —O—, —COO—, —C(═O)—, —OCO— or —CH═CH— so that the atoms are not directly bonded.

R ^AK1 has the same meaning as R ^AK1 in formula (AK).

A ^AL1 and A ^AL2 each independently have the same meaning as A ^AL1 and A ^AL2 in formula (AL).

Z ^AL1 has the same meaning as Z ^AL1 in formula (AL).

m ^AL1 has the same meaning as m ^AL1 in formula (AL).

Sp ^AT1 has the same meaning as Sp ^AT1 in formula (AT).

W ^AT1 has the same meaning as W ^AT1 in formula (AT).

Z ^AT1 has the same meaning as Z ^AT1 in formula (AT).

The compound represented by the general formula (SAL) is preferably a compound represented by the following formulas (SAL-1.1) to (SAL-2.9).

The amount of the alignment aid contained in the liquid crystal composition is preferably about 0.01 to 10% by mass. The more preferable lower limit values thereof are 0.05% by mass and 0.1% by mass from the viewpoint of aligning liquid crystal molecules more preferably. On the other hand, the more preferable upper limit value thereof is 7% by mass, 5% by mass, 4% by mass, 3% by mass, and 1% by mass from the viewpoint of improving response characteristics. By adopting the constitution of the present invention, a sufficient amount of the alignment aid can be dissolved in the liquid crystal composition.

The total content of the above-mentioned alignment aid is preferably 0.05 to 10%, and more preferably 0.1 to 8% with respect to the composition containing the alignment aid of the present application. , 0.1 to 5% is preferable, 0.1 to 3% is preferable, 0.2 to 2% is preferable, and 0.2 to 1.3% is included. It is preferable that the content is 0.2 to 1%, and the content is 0.2 to 0.56%.

A preferred lower limit value of the total content of the alignment aids is 0.01% and 0.03% with respect to the composition containing the compound represented by the general formula (P) of the present application, and 0 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%.

A preferable upper limit value of the total content of the alignment aids is 10%, 8% and 5% with respect to the composition containing the compound represented by the general formula (P) of the present application, 3%, 1.5%, 1.2%, 1%, 0.8%, 0.5%.

If the content is too small, the effect of adding the above-mentioned alignment aid is less likely to appear, and problems such as the spontaneous alignment of the liquid crystal composition becoming weaker occur, and if it is too large, problems such as lowering the reliability of the liquid crystal occur. .. Therefore, the content is set in consideration of these balances.
<Color filter>
The color filter in the present invention is composed of a black matrix and at least an RGB three-color pixel portion. The RGB three-color pixel portion serves as a coloring material, as a coloring material, and in the R pixel portion, a diketopyrrolopyrrole pigment and/or Or one or more selected from oil-soluble anionic red organic dyes, and a mixture of a halogenated phthalocyanine pigment, a phthalocyanine green dye, a phthalocyanine blue dye and an azo yellow organic dye in the G pixel portion. The B pixel portion contains at least one selected from the group consisting of, and one or more selected from ε-type copper phthalocyanine pigments and/or cationic blue organic dyes.
(R pixel part)
The diketopyrrolopyrrole pigment in the R pixel portion is C.I. I. Pigment Red 254, 255, 264, brominated diketopyrrolopyrrole pigments, and solvent-based red organic dyes are C.I. I. Solvent Red 52, the same 111, the same 124, the same 135, the same 141, the same 145, the same 151, and the same 179 are preferable.

Further, C.I. I. Pigment Red 177, 242, 166, 167, 179, C.I. I. Pigment Orange 38, the same 71, C.I. I. Pigment Yellow 150, 215, 185, 138, 139, C.I. I. Solvent Red 89, C.I. I. Solvent Orange 56, C.I. I. It is preferable that at least one organic dye or pigment selected from the group consisting of Solvent Yellow 21, 82, 83:1, 33, and 162 is contained and hybridized.
(G pixel part)
The halogenated phthalocyanine pigment in the G pixel portion is C.I. I. Pigment Green 7, the same 36, the same 58, the same 59, the same 62, the same 63, a phthalocyanine green dye is a dye represented by the following general formula (PIG-1), and a phthalocyanine blue dye is C.I. I. Solvent Blue 67, an azo yellow organic dye is C.I. I. It is preferably Solvent Yellow 162.

(In the formula, in the general formula (PIG-1), X1i to X16i represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a general formula (PIG-2), (PIG-3), (PIG-4), (PIG-5) The four X atoms bonded to one benzene ring may be the same or different, M is a central metal, and Zn, Cu, Mg, Ca, Sr, Ba, Mn, Co, Ni, Pd, Pt, Sn, Fe, InCl, VCl X17i represents oxygen, sulfur, sulfone (—SO ₂ —) X18i represents a hydrogen atom or a carbon atom which may have a substituent. An alkyl group having 1 to 29 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 3 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenyl group having 3 to 30 carbon atoms, and a cyclo having 6 to 30 carbon atoms It represents an alkynyl group or an aryl group having 6 to 30 carbon atoms, and k represents an integer of 1 to 5.

In the previous G pixel part, C.I. I. Pigment Yellow 150, 215, 185, 138, C.I. I. It is preferable that at least one organic dye or pigment selected from the group consisting of Solvent Yellow 21, 82, 83:1, and 33 is contained and hybridized.
(B pixel part)
The ε-type copper phthalocyanine pigment in the B pixel portion is C.I. I. Pigment 15:6 and the cationic blue organic dye are preferably dyes represented by the following general formulas (PIG-6) and (PIG-7).

(In the formula, R ^1j to R ^6j each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, or an aryl group which may have a substituent. ^{When 1j} to R ^6j represent an alkyl group which may have a substituent, R ^1j and R ^2j , R ^3j and R ^4j , and R ^5j and R ^{6j which} are adjacent to each other may combine to form a ring structure. R ^7j and X ^8j each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms which may have a substituent, Z ^1j represents an alkyl group having 4 to 12 carbon atoms, Or, represents —R ^7j —B ^1j —R ^8j —, wherein R ^7j and R ^8j each independently represent an alkyl group having 2 to 8 carbon atoms which may have a substituent, and [A] ^b— is Represents an arbitrary b-valent anion, a represents an integer of 2 or more, and b represents an integer of 2 or more)
Further, xanthene dye, C.I. I. Pigment Blue 1, C.I. I. Pigment Violet 23, C.I. I. Basic Blue 7, C.I. I. Basic Violet 10, C.I. I. Acid Blue 1, 90, 83, C.I. I. It is preferable that at least one organic dye or pigment selected from the group consisting of Direct Blue 86 is contained and hybridized.

Further, the color filter is composed of a black matrix, RGB three-color pixel portions and a Y pixel portion. I. Pigment Yellow 150, 215, 185, 138, 139, C.I. I. It is also preferable to contain at least one yellow organic dye or pigment selected from the group consisting of Solvent Yellow 21, 82, ibid 83:1, ibid 33 and ibid 162.

The chromaticity x and the chromaticity y in the XYZ color system under the C light source of each pixel portion in the color filter of the present invention prevent the voltage holding ratio (VHR) of the liquid crystal layer from decreasing and the ion density (ID) from increasing. However, from the viewpoint of suppressing the occurrence of display defects such as white spots, uneven alignment, and burning, the following are preferable.

The chromaticity x in the XYZ color system under the C light source of the R pixel portion is preferably 0.58 to 0.69, more preferably 0.62 to 0.68, and the chromaticity y is 0. It is preferably 0.30 to 0.36, more preferably 0.31 to 0.35, the chromaticity x is 0.58 to 0.69, and the chromaticity y is 0.30 to 0. More preferably, the chromaticity x is 0.62 to 0.68, and the chromaticity y is 0.31 to 0.35.

The chromaticity x in the XYZ color system under the C light source of the G pixel portion is preferably 0.19 to 0.35, more preferably 0.20 to 0.29, and the chromaticity y is 0. 0.54 to 0.76 is preferable, 0.64 to 0.74 is more preferable, chromaticity x is 0.19 to 0.35, and chromaticity y is 0.54 to 0. More preferably, the chromaticity x is 0.20 to 0.29, and the chromaticity y is 0.64 to 0.74.

The chromaticity x in the XYZ color system under the C light source of the B pixel portion is preferably 0.12 to 0.20, more preferably 0.13 to 0.18, and the chromaticity y is 0. It is preferably 0.04 to 0.12, more preferably 0.05 to 0.09, the chromaticity x is 0.12 to 0.18, and the chromaticity y is 0.04 to 0. More preferably, the chromaticity x is 0.13 to 0.17, and the chromaticity y is 0.04 to 0.09.

The chromaticity x in the XYZ color system under the C light source of the Y pixel portion is preferably 0.46 to 0.50, more preferably 0.47 to 0.48, and the chromaticity y is 0. It is preferably 0.48 to 0.53, more preferably 0.50 to 0.52, the chromaticity x is 0.46 to 0.50, and the chromaticity y is 0.48 to 0. More preferably, the chromaticity x is 0.47 to 0.48, and the chromaticity y is 0.50 to 0.52.

Here, the XYZ color system refers to the color system that was approved as a standard color system by the CIE (International Commission on Illumination) in 1931.

The chromaticity in each of the above-mentioned pixel parts can be adjusted by changing the types of dyes and pigments used and their mixing ratio. For example, in the case of an R pixel, a yellow dye and/or an orange pigment is used as a red dye/pigment, in the case of a G pixel, a yellow dye/pigment is used as a green dye/pigment, and in the case of a B pixel, a blue dye/pigment is used as a purple dye/yellow tint. It can be adjusted by adding an appropriate amount of the blue dye/pigment. It can also be adjusted by appropriately adjusting the particle size of the pigment.

The color filter can form the color filter pixel portion by a conventionally known method. A typical method of forming the pixel portion is a photolithography method, which is a method in which a photocurable composition described below is applied to a surface of a transparent substrate for a color filter on a side provided with a black matrix and heated. After drying (prebaking), pattern exposure is performed by irradiating ultraviolet rays through a photomask to cure the photocurable compound in the area corresponding to the pixel area, and then develop the unexposed area with a developer. The method is to remove the non-pixel portion and fix the pixel portion to the transparent substrate. In this method, the pixel portion composed of the cured colored film of the photocurable composition is formed on the transparent substrate.

A photo-curable composition described below is prepared for each pixel of other colors such as R pixel, G pixel, B pixel, and Y pixel as necessary, and the above-described operation is repeated, so that R A color filter having colored pixel portions of pixels, G pixels, B pixels, and Y pixels can be manufactured.

Examples of the method for applying the photocurable composition described below onto a transparent substrate such as glass include spin coating, slit coating, roll coating, and inkjet coating.

The drying conditions for the coating film of the photocurable composition applied on the transparent substrate are usually 50 to 150° C. and about 1 to 15 minutes, although they vary depending on the type and mixing ratio of each component. As the light used for photocuring the photocurable composition, it is preferable to use ultraviolet rays in the wavelength range of 200 to 500 nm or visible light. Various light sources that emit light in this wavelength range can be used.

Examples of the developing method include a puddle method, a dipping method, and a spray method. After exposure and development of the photocurable composition, the transparent substrate on which the pixel portion of the required color is formed is washed with water and dried. The color filter thus obtained is subjected to heat treatment (post-baking) at 90 to 280° C. for a predetermined time with a heating device such as a hot plate or an oven to remove volatile components in the colored coating film and at the same time to remove light. The unreacted photocurable compound remaining in the cured colored film of the curable composition is thermally cured, and the color filter is completed.

The color material for a color filter of the present invention, when used together with the liquid crystal composition of the present invention, prevents the voltage holding ratio (VHR) of the liquid crystal layer from decreasing and the ion density (ID) from increasing, resulting in white spots, uneven alignment, It is possible to provide a liquid crystal display device that solves the problem of display failure such as burning.

As the method for producing the photocurable composition, the color filter pigment composition of the present invention, an organic solvent and a dispersant are used as essential components, and these are mixed by stirring and dispersing so as to be uniform. First, a pigment dispersion liquid for forming the pixel portion of the color filter is prepared, and then a photocurable compound and, if necessary, a thermoplastic resin, a photopolymerization initiator, or the like are added to the photocurable liquid. A method of forming a composition is common.

Examples of the organic solvent used here include aromatic solvents such as toluene, xylene, and methoxybenzene, ethyl acetate, propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and diethylene glycol methyl ether acetate. , Acetic acid ester solvents such as diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol butyl ether acetate, propionate solvents such as ethoxyethyl propionate, alcohol solvents such as methanol and ethanol, butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl Ethers, ether solvents such as diethylene glycol dimethyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aliphatic hydrocarbon solvents such as hexane, N,N-dimethylformamide, γ-butyrolactam, N-methyl-2- Examples thereof include nitrogen compound-based solvents such as pyrrolidone, aniline and pyridine, lactone-based solvents such as γ-butyrolactone, and carbamate esters such as a 48:52 mixture of methyl carbamate and ethyl carbamate.

Examples of the dispersant used here include Disperbic 130, Disperbic 161, Disperbic 162, Disperbic 163, Disperbic 170, Disperbic 171, Disperbic 174, Disperbic 180, Disperbic 182, manufactured by Big Chemie. Dispervik 183, Dispervik 184, Dispervik 185, Dispervik 2000, Dispervik 2001, Dispervik 2020, Dispervik 2050, Dispervik 2070, Dispervik 2096, Dispervik 2150, Dispervik LPN21116, Dispervik LPN6919, Lubrizol Solsparse 3000, Solsperse 9000, Solsperse 13240, Solsperse 13650, Solsperse 13940, Solsperse 17000, 18000, Solsperse 20000, Solsperse 21000, Solsperse 20000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 38000, Solsperse 36000, Solsperse 36000, 37,000, Solsperse 38000, Solsperse 41000, Solsperse 42000, Solsperse 43000, Solsperse 46000, Solsperse 54000, Solsperse 71000, Ajinomoto Co.'s Azisper PB711, Ajisper PB821, Ajisper PB822, Ajisper PB814, Ajisper PN411, Ajisper PA111, etc. Acrylic resin, urethane resin, alkyd resin, natural rosin such as wood rosin, gum rosin and tall oil rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, oxidized rosin, modified rosin such as maleated rosin, rosin amine, lime rosin , A rosin alkylene oxide adduct, a rosin alkyd adduct, a rosin derivative such as a rosin-modified phenol, and the like, and a synthetic resin which is liquid at room temperature and insoluble in water can be contained. Addition of these dispersants and resins also contributes to reduction of flocculation, improvement of pigment dispersion stability, and improvement of viscosity characteristics of the dispersion.

Further, as a dispersion aid, organic pigment derivatives such as phthalimidomethyl derivative, sulfonic acid derivative, N-(dialkylamino)methyl derivative, N-(dialkylaminoalkyl)sulfonic acid amide derivative, etc. should be contained. You can also Of course, these derivatives may be used in combination of two or more different types.

Examples of the thermoplastic resin used to prepare the photocurable composition include urethane resins, acrylic resins, polyamide resins, polyimide resins, styrene maleic acid resins, and styrene maleic anhydride resins. ..

Examples of the photocurable compound include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis(acryloxyethoxy)bisphenol A, and 3-methylpentanediol diacrylate. Difunctional monomers such as acrylates, trimethylolpropaton triacrylate, pentaerythritol triacrylate, tris[2-(meth)acryloyloxyethyl)isocyanurate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. Examples thereof include polyfunctional monomers having a small molecular weight and polyfunctional monomers having a relatively large molecular weight such as polyester acrylate, polyurethane acrylate, and polyether acrylate.

Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethylketanol, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis(4'-azidobenzal)-2-propane, 1,3-bis(4' -Azidobenzal)-2-propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid and the like. Examples of commercially available photopolymerization initiators include “IRGACURE (trademark)-184”, “IRGACURE (trademark)-369”, “DAROCURE (trademark)-1173” manufactured by BASF, and “Lucillin-trademark” manufactured by BASF. "TPO", "Kayakyu (trade name) DETX" manufactured by Nippon Kayaku Co., "Kaya cure (trade name) OA", "Vicure 10", "Vicure 55" manufactured by Stouffer, "Trigonal PI" manufactured by Akzo, Sand Corp. "Sandray 1000" manufactured by Upjohn, "Deep" manufactured by Upjohn, and "Biimidazole" manufactured by Kurogane Kasei.

Also, a known and commonly used photosensitizer may be used in combination with the above photopolymerization initiator. Examples of the photosensitizer include amines, ureas, compounds having a sulfur atom, compounds having a phosphorus atom, compounds having a chlorine atom, nitriles, and other compounds having a nitrogen atom. These may be used alone or in combination of two or more.

The compounding ratio of the photopolymerization initiator is not particularly limited, but is preferably in the range of 0.1 to 30% based on the mass of the compound having a photopolymerizable or photocurable functional group. If it is less than 0.1%, the photosensitivity during photocuring tends to decrease, and if it exceeds 30%, the photopolymerization initiator crystals precipitate when the coating film of the pigment-dispersed resist is dried. This may cause deterioration of the physical properties of the film.

Using each of the above-mentioned materials, 300 to 1000 parts of the organic solvent and 1 to 100 parts of the dispersant are made uniform per 100 parts by weight of the pigment composition for a color filter of the present invention. Thus, the dye/pigment liquid can be obtained by stirring and dispersing. Next, in this pigment dispersion, the total amount of the thermoplastic resin and the photocurable compound was 3 to 20 parts per 1 part of the color filter pigment composition of the present invention, and 0.05 to 3 parts per 1 part of the photocurable compound. It is possible to obtain a photocurable composition for forming a color filter pixel portion by adding a photopolymerization initiator and, if necessary, an organic solvent further and stirring and dispersing so as to be uniform.

As the developing solution, a known and commonly used organic solvent or alkaline aqueous solution can be used. In particular, in the case where the photocurable composition contains a thermoplastic resin or a photocurable compound, and at least one of these has an acid value and exhibits alkali solubility, washing with an aqueous alkali solution is a color filter. It is effective for forming the pixel portion.

Although the method for producing the color filter pixel portion by the photolithography method has been described in detail, the color filter pixel portion prepared by using the pigment composition for a color filter of the present invention can be used for other electrodeposition method, transfer method, micelle electrolysis method. , A PVED (Photovoltaic Electrodeposition) method, an inkjet method, a reverse printing method, a thermosetting method, or the like may be used to form each color pixel portion to manufacture a color filter.

The organic pigment may be applied to a substrate and dried to form a color filter, or when the pigment dispersion contains a curable resin, the pigment may be cured by heat or an active energy ray to form a color filter. Further, the step of removing the volatile components in the coating film may be performed by heating (post-baking) at 100 to 280° C. for a predetermined time with a heating device such as a hot plate or an oven.
(Alignment film)
In the liquid crystal display device of the present invention, an alignment film may be provided on the surface of one of the first substrate and the second substrate which is in contact with the liquid crystal composition in order to align the liquid crystal composition. In a liquid crystal display device that requires an alignment film, it is arranged between a color filter and a liquid crystal layer. However, even if the alignment film has a large film thickness, it is as thin as 100 nm or less. It does not completely block the interaction with the liquid crystal compound constituting the.

In addition, in a liquid crystal display device that does not use an alignment film, the interaction between a dye such as a pigment that forms a color filter and a liquid crystal compound that forms a liquid crystal layer becomes greater.

As the alignment film material, transparent organic materials such as polyimide, polyamide, BCB (penzocyclobutene polymer) and polyvinyl alcohol can be used. In particular, p-phenylenediamine, 4,4′-diaminodiphenylmethane and the like can be used. Diamines such as aliphatic or alicyclic diamines and butanetetracarboxylic acid anhydrides, and aliphatic or alicyclic tetracarboxylic acid anhydrides such as 2,3,5-tricarboxycyclopentyl acetic acid anhydride, pyromellitic dianhydride A polyimide alignment film obtained by imidizing a polyamic acid synthesized from an aromatic tetracarboxylic acid anhydride such as a compound is preferable. In this case, rubbing is generally used as a method for providing orientation, but when used for a vertical orientation film or the like, it may be used without giving orientation.

As the alignment film material, a material containing chalcone, cinnamate, cinnamoyl or azo group in the compound can be used, and may be used in combination with a material such as polyimide or polyamide. In this case, the alignment film is rubbed. Or a photo-alignment technique may be used.

The alignment film is generally formed by applying the alignment film material on the substrate by a method such as spin coating to form a resin film, but a uniaxial stretching method, a Langmuir-Blodgett method, or the like can also be used. ..
(Transparent electrode)
In the liquid crystal display device of the present invention, a conductive metal oxide can be used as the material of the transparent electrode, and as the metal oxide, indium oxide (In2O3), tin oxide (SnO2), zinc oxide (ZnO), indium tin oxide (In2O3-SnO2), indium zinc oxide (In2O3-ZnO), niobium added titanium dioxide _{_{(Ti 1-x Nb x O2}} ), fluorine-doped tin oxide, although graphene nanoribbons or metal nanowires and the like can be used, oxide Zinc (ZnO), indium tin oxide (In2O3-SnO2) or indium zinc oxide (In2O3-ZnO) is preferred. For patterning these transparent conductive films, a photo-etching method or a method using a mask can be used.

INDUSTRIAL APPLICABILITY The liquid crystal display device of the present invention is particularly useful as an active matrix driving liquid crystal display device, and is useful as a liquid crystal display device for TN mode, IPS mode, polymer stabilized IPS mode, FFS mode, OCB mode, VA mode or ECB mode. Applicable.

Combined with the liquid crystal display device and a backlight, it is used in various applications such as LCD TVs, PC monitors, mobile phones, smartphone displays, notebook personal computers, personal digital assistants, and digital signage. As the backlight, there are a cold cathode tube type backlight, a pseudo white backlight having a two-wavelength peak and a backlight having a three-wavelength peak, which uses a light emitting diode or an organic EL element using an inorganic material.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the examples, the following abbreviations are used for describing compounds. In addition, n represents a natural number.

(Side chain)
-N -C _n H _{2n + 1} linear carbon atoms n alkyl group n- C _n H _{2n + 1} - linear straight chain alkyl group -On -OC _n H _{2n + 1} carbon atoms n carbon atoms n -Like alkoxyl group nO- C _n H _2n+1 O- Linear alkoxyl group having a carbon atom number of -V -CH=CH ₂
V-CH ₂ =CH-
-V1 -CH=CH-CH ₃
1V- CH ₃ -CH=CH-
_{_{-2V -CH 2 -CH 2 -CH = CH}} 3
V2-CH ₂ =CH-CH ₂ -CH _2-
-2V1 -CH ₂ -CH ₂ -CH=CH-CH ₃
1V2- CH ₃ -CH=CH-CH ₂ -CH ₂
(Linking group)
-N- -C _n H _2n-
-NO- -C _n H _2n -O-
-On- _-O-C _{n H 2n} -
-COO- -C(=O)-O-
-OCO- -OC(=O)-
-CF2O- -CF ₂ -O-
-OCF2- -O-CF ₂ -
(Ring structure)

The characteristics measured in the examples are as follows.

T _NI : Nematic phase-isotropic liquid phase transition temperature (°C)
Δn: Anisotropy of refractive index at 25° C. Δε: Anisotropy of dielectric constant at 25° C. γ ₁ : Rotational viscosity at 25° C. (mPa·s)
K ₁₁ : Elastic constant K ₁₁ (pN) at 25° C.
K ₃₃ : Elastic constant K ₃₃ (pN) at 25° C.
VHR: voltage holding ratio (%) under conditions of a frequency of 60 Hz at 60°C and an applied voltage of 1 V
"Creating a Color Filter"
[Preparation of coloring composition]
[Red dye coloring composition 1]
Put 10 parts of Red Dye 1 (CI Solvent Red 124) in a polybin, add 55 parts of propylene glycol monomethyl ether acetate, 0.3-0.4 mmφ sepul beads, and paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours. After dispersion, the solution was filtered through a 5 μm filter to obtain a dye coloring solution. 75.00 parts of this dye coloring liquid, 5.50 parts of polyester acrylate resin (Aronix (trademark) M7100, manufactured by Toagosei Kagaku Kogyo Co., Ltd.), dipentaerythritol hexaacrylate (KAYARAD (trademark) DPHA, made by Japan) (Yaku Co., Ltd.) 5.00 parts, benzophenone (KAYACURE (trade name) BP-100, Nippon Kayaku Co., Ltd.) 1.00 parts, and Eukerester EEP 13.5 parts were stirred with a dispersion stirrer to obtain a pore size of 1. A red dye coloring composition 1 was obtained by filtering with a 0 μm filter.
[Red dye coloring composition 2]
In place of 10 parts of the red dye 1 of the red dye coloring composition 1, 8 parts of the red dye 2 (CI Solvent Red 135) and 2 parts of the yellow dye 1 (CI Solvent Yellow 21) were used. In the same manner as described above, a red dye coloring composition 2 was obtained.
[Red dye coloring composition 3]
A red dye coloring composition 3 was obtained in the same manner as above using 10 parts of the red dye 3 (CI Solvent Red 52) instead of 10 parts of the red dye 1 of the red dye coloring composition 1.
[Red dye/pigment coloring composition 1]
14 parts of the above red dye, 2 parts of red pigment 1 (CI Pigment Red 254) having an average primary particle diameter of 25 nm in the small angle X-ray scattering method and standardized dispersion of 40%, and the average primary particle of the small angle X-ray scattering method. 2 parts of red pigment 2 (CI Pigment Red 177) having a diameter of 30 nm and a standardized dispersion of 50%, an average primary particle diameter of 35 nm by a small angle X-ray scattering method, a standardized dispersion of 60% yellow pigment 2 (C.I. Pigment Yellow 139) 2 parts in a polybin, propylene glycol monomethyl ether acetate 55 parts, Disperbic LPN21116 (manufactured by Big Chemie Co., Ltd.) 7.0 parts, Saint-Gobain 0.3-0.4 mmφ zirconia beads “ER”. -120S" was added, and the mixture was dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, and then filtered through a 1 μm filter to obtain a pigment dispersion liquid. 75.00 parts of this pigment dispersion and 5.50 parts of polyester acrylate resin (Aronix (trademark) M7100, manufactured by Toagosei Kagaku Kogyo Co., Ltd.), dipentaerythritol hexaacrylate (KAYARAD (trademark) DPHA, manufactured by Japan) (Yaku Co., Ltd.) 5.00 parts, benzophenone (KAYACURE (trade name) BP-100, Nippon Kayaku Co., Ltd.) 1.00 parts, and Eukerester EEP 13.5 parts were stirred with a dispersion stirrer to obtain a pore size of 1. A red dye-pigment coloring composition 1 was obtained by filtering with a 0 μm filter.

The average primary particle diameter and the particle diameter distribution of the organic pigment are obtained from the small-angle X-ray scattering profile (measured scattering profile) of the organic pigment dispersion based on the small-angle X-ray scattering method disclosed in JP-A 2006-113042.
[Red dye/pigment coloring composition 2]
The red pigment 1 of the above red dye/pigment coloring composition 1 was replaced with a red pigment 3 having an average primary particle diameter of 20 nm by a small angle X-ray scattering method and a standardized dispersion of 40% (a brominated diketopyrrolopyrrole pigment of PIG-8). A red dye/pigment coloring composition 2 was obtained in the same manner as described above.

[Red pigment coloring composition 1]
In place of the red dye 14 parts, the red pigment 12 parts, the red pigment 22 parts, and the yellow pigment 22 parts of the above red dye/pigment coloring composition 1, the average primary particle diameter in the small-angle X-ray scattering method is 50 nm, and standardized. Red Pigment Coloring Composition 1 was obtained in the same manner as above using Red Pigment 4 (CI Pigment Red 48:1) having a dispersion of 70%.
[Green dye coloring composition 1]
In place of 10 parts of red dye 1 of the above red dye coloring composition 1, 3 parts of blue dye 1 (CI Solvent Blue 67) and 7 parts of yellow dye 2 (CI Solvent Yellow 162) were used, A green dye coloring composition 1 was obtained in the same manner as described above.
[Green dye coloring composition 2]
In the above green dye coloring composition 1, 3 parts of blue dye 1 was replaced with 8 parts of green dye 1 (structure of PIG-9), and 7 parts of yellow dye 2 (CI Solvent Yellow 162) was replaced with 2 parts. Similarly, a green dye coloring composition 2 was obtained.

[Green dye coloring composition 3]
3 parts of the blue dye 1 of the above green dye coloring composition 1 was replaced with 9 parts of the green dye 2 (structure of PIG-10), and 7 parts of the yellow dye 2 (CI Solvent Yellow 162) was replaced with 1 part. Similarly, a green dye coloring composition 3 was obtained.

[Green dye coloring composition 4]
In the same manner as described above, 10 parts of green dye 1 (CI Solvent Green 7) was used in place of 3 parts of blue dye 1 and 7 parts of yellow dye 2 of the above-mentioned green dye coloring composition 1. Got 4.
[Green dye/pigment coloring composition 1]
Instead of the red dye 14 parts, the red pigment 1 2 parts, the red pigment 22 2 parts, and the yellow pigment 22 2 parts of the red dye/pigment coloring composition 1, the green dye 1 3 parts and the green pigment 1 (C.I. Pigment Green 58, 3 parts of "FASTOGEN GREEN A350" manufactured by DIC Co., Ltd., and 4 parts of yellow pigment 1 (CI Pigment Yellow 150, FANCHON FAST YELLOW E4GN manufactured by BAYER) in the same manner as above, and green. A dye-pigment coloring composition 1 was obtained.
[Green dye/pigment coloring composition 2]
In place of the green pigment 1 3 parts and the yellow pigment 1 4 parts of the green dye/pigment coloring composition 1, 2 parts of the green pigment 2 (CI Pigment Green 63) and the yellow pigment 2 (CI Pigment YELLOW 138) were used. A green dye/pigment coloring composition 2 was obtained in the same manner as above using 5 parts.
[Blue dye coloring composition 1]
In place of 10 parts of the red dye 1 of the red dye coloring composition 1, 10 parts of the blue dye 2 (C.I. Basic Blue 7, structure of PIG-11) was used, and the blue dye coloring composition was obtained in the same manner as above. Item 1 was obtained.

[Blue dye coloring composition 2]
A blue dye coloring composition 2 was obtained in the same manner as above using 10 parts of the blue dye 3 (structure of PIG-12) instead of 10 parts of the red dye 1 of the red dye coloring composition 1.

[Blue dye coloring composition 3]
A blue dye coloring composition 3 was obtained in the same manner as above using 10 parts of the blue dye 4 (structure of PIG-13) instead of 10 parts of the red dye 1 of the red dye coloring composition 1.

[Blue dye coloring composition 4]
A blue dye coloring composition 4 was obtained in the same manner as above using 10 parts of the blue dye 5 (CI Solvent Blue 12) in place of 10 parts of the blue dye 1 of the blue dye coloring composition 2.
[Blue dye/pigment coloring composition 1]
In place of the red dye 14 parts, the red pigment 12 parts, the red pigment 22 parts, and the yellow pigment 22 parts of the red dye/pigment coloring composition 1, the average primary particle diameter in the small-angle X-ray scattering method is 20 nm, and standardization is performed. A blue dye-pigment coloring composition 1 was obtained in the same manner as described above using 8 parts of 50% dispersed blue pigment 1 (CI Pigment Blue 15:6) and 2 parts of xanthene dye of PIG-14. ..

[Blue dye/pigment coloring composition 2]
In the same manner as described above, except that 8 parts of blue pigment 1 in blue dye/pigment coloring composition 1 was replaced with 9 parts, and 2 parts of xanthene dye was replaced with blue dye 2 (structure of CI Basic Blue 7, PIG-11). Thus, a blue dye/pigment coloring composition 2 was obtained.
[Yellow dye/pigment coloring composition 1]
In place of the red dye 1 4 parts, the red pigment 1 2 parts, the red pigment 22 2 parts, and the yellow pigment 22 2 parts of the above red dye/pigment coloring composition 1, 6 parts of yellow dye 1 and yellow pigment 1 (CI Pigment) were used. A yellow dye/pigment coloring composition 1 was obtained in the same manner as above using 4 parts of Yellow 150 and FANCHON FAST YELLOW E4GN manufactured by LANXESS.

Color filters 1 to 5 were prepared using the dye coloring composition, pigment coloring composition or dye/pigment coloring composition shown in the following table.

(Examples 1 to 20)
The liquid crystal compositions of LC-1 shown in the table below were prepared and their physical properties were measured. The physical properties are shown in the table below.

A polymerizable compound-containing liquid crystal composition was prepared in which the polymerizable compound was added in the addition amount shown in Table 3 with respect to 100 parts by mass of the above liquid crystal composition.

A first substrate (common electrode substrate) having a transparent electrode layer made of a patterned transparent common electrode on an insulating layer and having no alignment film having a color filter layer shown in Table 1, and an active element And a second substrate (pixel electrode substrate) having no alignment film having a pixel electrode layer having a transparent pixel electrode driven by. The liquid crystal composition was dropped on the first substrate, sandwiched between the second substrates, and the sealing material was cured at 110° C. for 2 hours under normal pressure. Thereafter, a UV fluorescent lamp manufactured by Toshiba Lighting & Technology Co. was irradiated for 120 minutes (illuminance at 313 nm was 1.7 mW/cm ² ) to obtain a liquid crystal display device having a cell gap of 3.5 μm.

As a result of measuring VHR of the obtained liquid crystal cell, it was confirmed that the liquid crystal display device having the color filter of the present invention and the polymerizable liquid crystal composition had excellent characteristics.

(Examples 21 to 140)
Liquid crystal compositions LC-2 to LC-7 shown in the table below were prepared and their physical properties were measured. The physical properties are shown in the table below.

A polymerizable compound-containing liquid crystal composition was prepared by adding the polymerizable compound in an addition amount shown in the following table to 100 parts by mass of each of the above liquid crystal compositions. After that, a liquid crystal display element was prepared in the same manner as in Example 1 and VHR was measured. It was confirmed that the liquid crystal display device having the color filter of the present invention and the polymerizable liquid crystal composition had excellent properties.

(Comparative Examples 1 to 8)
A polymerizable compound-containing liquid crystal composition was prepared by adding the polymerizable compound in an addition amount shown in the following table to 100 parts by mass of the liquid crystal composition LC-1.

Driven by an active element and a first substrate (common electrode substrate) having a transparent electrode layer consisting of a transparent common electrode patterned on an insulating layer, a color filter layer and a vertical alignment film (JALS-2096) A pixel electrode layer having a transparent pixel electrode and a second substrate (pixel electrode substrate) having a vertical alignment film were prepared. The firing conditions for the alignment film were 200° C. and 40 minutes. The liquid crystal composition was dropped on the first substrate, sandwiched between the second substrates, and the sealing material was cured at 110° C. for 2 hours under normal pressure. Thereafter, a UV fluorescent lamp manufactured by Toshiba Lighting & Technology Co. was irradiated for 120 minutes (illuminance at 313 nm was 1.7 mW/cm ² ) to obtain a liquid crystal display device having a cell gap of 3.5 μm.

As a result of measuring VHR of the obtained liquid crystal cell, it was confirmed that the characteristics were inferior.

Claims

It is composed of a first substrate and a second substrate arranged to face each other, a liquid crystal layer filled between the first substrate and the second substrate, a black matrix and at least an RGB three-color pixel portion. And a color filter,
The liquid crystal layer has the general formula (I)

(In the formula, R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 8 carbon atoms. The compound represented by the general formula (II) is contained in an amount of 10 to 50% by weight.

(In the formula, R 3 and R 4 are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. And Z 3 and Z 4 are each independently a single bond, —CH═CH—, —C≡C—, —CH 2 CH 2 —, —(CH 2 ) 4 —, —COO—. , —OCO—, —OCH 2 —, —CH 2 O—, —OCF 2 — or —CF 2 O—, and B and C may each independently be substituted with a fluorine atom, 1,4 A phenylene group or a trans-1,4-cyclohexylene group, m and n each independently represent an integer of 0 to 4, and m+n=1 to 4). % By weight,
Contains an orientation aid,
The RGB three-color pixel portion contains one or more selected from diketopyrrolopyrrole pigments and oil-soluble red organic dyes in the R pixel portion as a coloring material, and the G pixel portion contains halogenated compounds. At least one selected from the group consisting of a phthalocyanine pigment, a phthalocyanine-based green dye, a mixture of a phthalocyanine-based blue dye and an azo-yellow organic dye, and selected in the B pixel portion from an ε-type copper phthalocyanine pigment and a cationic blue organic dye. Which does not include an alignment film on the surface of at least one of the first substrate and the second substrate, and which contains one or more of Liquid crystal display device having an alignment control layer formed from the above polymer.
The diketopyrrolopyrrole pigment in the R pixel portion is C.I. I. Pigment Red 254, 255, 264, brominated diketopyrrolopyrrole pigment, and solvent-based red organic dye are C.I. I. The liquid crystal display device according to claim 1, which is Solvent Red 52, the same 111, the same 124, the same 135, the same 141, the same 145, the same 151, and the same 179.
The halogenated phthalocyanine pigment in the G pixel portion is C.I. I. Pigment Green 7, the same 36, the same 58, the same 59, the same 62, the same 63, a phthalocyanine green dye is a dye represented by the following general formula (PIG-1), and a phthalocyanine blue dye is C.I. I. Solvent Blue 67, an azo yellow organic dye is C.I. I. The liquid crystal display device according to claim 1 or 2, wherein the liquid crystal display device is Solvent Yellow 162.

(In the formula, in the general formula (PIG-1), X1i to X16i represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a general formula (PIG-2), (PIG-3), (PIG-4), (PIG-5) The four X atoms bonded to one benzene ring may be the same or different, M is a central metal, and Zn, Cu, Mg, Ca, Sr, Ba, Mn, Co, Ni, Pd, Pt, Sn, Fe, InCl, and VCl, X17i represents oxygen, sulfur, and sulfone (-SO 2 -), X18i represents a hydrogen atom, and a carbon atom which may have a substituent. An alkyl group having 1 to 29 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 3 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenyl group having 3 to 30 carbon atoms, and a cyclo having 6 to 30 carbon atoms It represents an alkynyl group or an aryl group having 6 to 30 carbon atoms, and k represents an integer of 1 to 5.
The ε-type copper phthalocyanine pigment in the B pixel portion is C.I. I. Pigment 15:6, the cationic blue organic dye is a dye represented by the following general formulas (PIG-6) and (PIG-7), wherein: Liquid crystal display device.

(In the formula, R 1j to R 6j each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, or an aryl group which may have a substituent. When 1j to R 6j represent an alkyl group which may have a substituent, R 1j and R 2j , R 3j and R 4j , and R 5j and R 6j which are adjacent to each other may combine to form a ring structure. R 7j and X 8j each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms which may have a substituent, Z 1j represents an alkyl group having 4 to 12 carbon atoms, Or, represents —R 7j —B 1j —R 8j —, wherein R 7j and R 8j each independently represent an alkyl group having 2 to 8 carbon atoms which may have a substituent, and [A] b— is Represents an arbitrary b-valent anion, a represents an integer of 2 or more, and b represents an integer of 2 or more)
The liquid crystal display device according to any one of claims 1 to 4, wherein the alignment aid has a mesogen group, an adsorption group, and an alignment induction group.
The liquid crystal display device according to claim 5, wherein the adsorptive group is a group capable of being bonded to an adsorbent by a hydrogen bond.
6. The adsorbing group is a group containing a polar element having an atomic group in which a carbon atom is linked to at least one hetero atom selected from the group consisting of N, O, S, P, B and Si. 6. The liquid crystal display device according to any one of 6.
The adsorption group is represented by the general formula (AT)

(In the formula, Sp AT1 represents a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms, and the hydrogen atom in the alkylene group is —OH, —CN, —W AT1 —Z It may be substituted with AT1 or P AP1 —Sp AP1 —, and —CH 2 — in the alkylene group is a cyclic group, —O—, —COO—, —C(═O so that an oxygen atom is not directly bonded. )-, -OCO-, -CH=CH-,
W AT1 represents a single bond or a general formula (WAT1) or (WAT2),

(In the formula, Sp WAT1 and Sp WAT2 each independently represent a single bond, a linear or branched alkylene group having 1 to 25 carbon atoms, and the hydrogen atom in the alkylene group is —OH, — CN, —Sp AT1 —W AT1 —Z AT1 or P AP1 —S AP1 — may be substituted, and —CH 2 — in the alkylene group is a cyclic group, —O— so that an oxygen atom is not directly bonded. , -COO-, -C(=O)-, -OCO-, -CH=CH-.)
Z AT1 represents a monovalent group containing a polar component, a hydrogen atom in Z AT1 is -OH, -CN, -Sp AT1 -W AT1 -Z AT1 or P AP1 -S AP1 - may be substituted by ,
P AP1- Sp AP1- represents a polymerizable group. )
The liquid crystal display device according to any one of claims 5 to 7, represented by:
The mesogenic group has the general formula (AL)

(In the formula, Z AL1 is a single bond, —CH═CH—, —CF═CF—, —C≡C—, —COO—, —OCO—, —OCOO—, —CF 2 O—, —OCF 2 -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 -CH 2 COO -, - OCOCH 2 -CH 2 -, - CH = C (CH 3) COO -, - OCOC (CH 3) = CH —, —CH 2 —CH(CH 3 )COO—, —OCOCH(CH 3 )—CH 2 —, —OCH 2 CH 2 O— or an alkylene group having 1 to 20 carbon atoms, One or two or more non-adjacent —CH 2 — may be substituted with —O—, —COO— or —OCO—,
A AL1 and A AL2 each independently represent a divalent cyclic group,
One or more hydrogen atoms in Z AL and A AL may be independently substituted with a halogeno group, an adsorption group, P al —Sp al — or a monovalent organic group,
In addition, when a plurality of Z AL1 and A AL1 are present in the molecule, they may be the same or different from each other,
m AL1 represents an integer of 1 to 5,
P al —Sp al — represents a polymerizable group,
The * at the left end and the * at the right end in the above formula represent a bond. 9. The liquid crystal display device according to claim 5, which is represented by
The orientation-inducing group represents a linear or branched alkyl group having 1 to 20 carbon atoms, and 1 or 2 or more —CH 2 — in the alkyl group is not directly bonded to an oxygen atom, Each of them may be independently substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—, and 1 or 2 of the alkyl group. The liquid crystal display device according to claim 5, wherein each of the above hydrogen atoms may be independently substituted with a halogeno group.
11. The liquid crystal display device according to claim 5, wherein the alignment aid has a polymerizable group for polymerization.
The polymerizable group P AP1 -Sp AP1 - a group represented by, P AP1 is the following general formula (AP1) ~ formula (AP-9)

(In the formula, R AP1 and R AP2 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 10 carbon atoms, and one of the alkyl groups or Two or more —CH 2 — may be substituted by —O— or —CO—, and one or more hydrogen atoms in the alkyl group are independently substituted by a halogen atom or a hydroxyl group. W AP1 represents a single bond, —O—, —COO— or —CH 2 —, and t AP1 represents 0, 1 or 2.
The liquid crystal display device according to claim 11, represented by:
13. The liquid crystal composition forming the liquid crystal layer contains a compound represented by the general formula (II-1) as the compound represented by the general formula (II). Liquid crystal display device.

(In the formula, R 3 and R 4 are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. Represents an alkenyloxy group of, Z 5 is a single bond, —CH═CH—, —C≡C—, —CH 2 CH 2 —, —(CH 2 ) 4 —, —COO—, —OCO—, —OCH. 2 —, —CH 2 O—, —OCF 2 — or —CF 2 O—, and m1 represents 0 or 1.)
The liquid crystal composition constituting the liquid crystal layer further has the general formula (III)

(In the formula, R 7 and R 8 are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. 8 is an alkenyloxy group, D, E and F are each independently a fluorine-substituted 1,4-phenylene group or trans-1,4-cyclohexylene, Z 2 is a single bond, Represents —OCH 2 —, —OCO—, —CH 2 O— or —COO—, and n represents 0, 1 or 2. However, it is represented by formula (I) or formula (II-1). The liquid crystal display device according to claim 13, further comprising a compound represented by the formula (excluding compounds).
15. The liquid crystal display device according to claim 1, wherein the alignment control layer is an alignment control layer formed from a polymer obtained by polymerizing an alignment aid having a polymerizable group.
The liquid crystal layer has the following general formula (P)

(In the formula (P), R p1 represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms or —Sp p2 —P p2 . Two or more non-adjacent —CH 2 — may be independently substituted with —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—. Further, one or more hydrogen atoms present in the alkyl group may be independently substituted with a cyano group, a fluorine atom or a chlorine atom.
P p1 and P p2 each independently represent one of the following general formulas (P p1 -1) to formula (P p1 -9).

(In the formula, R p11 and R p12 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and W p11 is a single bond, Represents —O—, —COO—, —OCO—, or —CH 2 —, and t p11 represents 0, 1 or 2, but R p11 , R p12 , W p11 and/or t p11 are in the molecule. When there are a plurality of them, they may be the same or different.)
Sp p1 and Sp p2 each independently represent a single bond or a spacer group.
Z p1 and Z p2 are each independently a single bond, —O—, —S—, —CH 2 —, —OCH 2 —, —CH 2 O—, —CO—, —C 2 H 4 —, —COO—, —OCO—, —OCOOCH 2 —, —CH 2 OCOO—, —OCH 2 CH 2 O—, —CO—NR ZP1 —, —NR ZP1 —CO—, —SCH 2 —, —CH 2 S -, - CH = CR ZP1 -COO -, - CH = CR ZP1 -OCO -, - COO-CR ZP1 = CH -, - OCO-CR ZP1 = CH -, - COO-CR ZP1 = CH-COO -, - COO-CR ZP1 = CH-OCO -, - OCO-CR ZP1 = CH-COO -, - OCO-CR ZP1 = CH-OCO -, - (CH 2) 2 -COO -, - (CH 2) 2 -OCO -, - OCO- (CH 2) 2 -, - (C = O) -O- (CH 2) 2 -, - CH = CH -, - CF = CF -, - CF = CH -, - CH = CF —, —CF 2 —, —CF 2 O—, —OCF 2 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 — or —C≡C— (wherein R ZP1 Each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but when a plurality of R ZP1's are present in the molecule, they may be the same or different.
A p1 , A p2 and A p3 are each independently
(A p )1,4-cyclohexylene group (one —CH 2 — present in this group or two or more —CH 2 — not adjacent to each other may be substituted with —O—. )
(B p ) 1,4-phenylene group (one —CH═ present in this group or two or more —CH═ which are not adjacent to each other may be substituted with —N═) and ( c p) naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydro Naphthalene-2,6-diyl group, phenanthrene-2,7-diyl group or anthracene-2,6-diyl group (one --CH= present in these groups or two or more non-adjacent --) CH= may be substituted with -N=.)
Group selected from the group consisting of (said group (a p), group (b p) and group (c p) are each independently hydrogen atoms present in this group, a halogen atom, carbon atom 1 Represents an alkyl group having 8 to 8 or an alkenyl group having 1 to 8 carbon atoms, a cyano group, or -Sp p2- P p2 ).
m p1 represents 0, 1, 2 or 3.
When multiple Z p1 , A p2 , Sp p2 and/or P p2 are present in the molecule, they may be the same or different. However, A p3 is the m p1 is 0, is a group A p1 is represented by group (c p), may be a single bond.
Note that the alignment aid is excluded from the polymerizable compound. )
16. The liquid crystal display device according to claim 1, which is composed of a polymer obtained by polymerizing a liquid crystal composition containing one kind or two or more kinds of the polymerizable compound represented by.