JPWO2016021582A1 - Liquid crystal display - Google Patents

Abstract

The present invention relates to a liquid crystal display device using a color filter using a specific liquid crystal composition, a specific pigment, and a specific compound. The present invention provides a liquid crystal display device that prevents a decrease in voltage holding ratio (VHR) and an increase in ion density (ID) of a liquid crystal layer and solves display defect problems such as white spots, uneven alignment, and burn-in. It is. The liquid crystal display device of the present invention has a feature that prevents a decrease in voltage holding ratio (VHR) and an increase in ion density (ID) of the liquid crystal layer and suppresses the occurrence of display defects such as image sticking. It is useful for liquid crystal display devices in driving VA mode, PSVA mode, and FSS mode, and can be applied to liquid crystal display devices such as liquid crystal TVs, monitors, mobile phones, and smartphones.

Description

  The present invention relates to a liquid crystal display device.

  Liquid crystal display devices are used in various electric 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 include TN (twisted nematic), STN (super twisted nematic), DS (dynamic light scattering), GH (guest / host), and IPS (in-plane switching). Type, OCB (optical compensation birefringence) type, ECB (voltage controlled birefringence) type, VA (vertical alignment) type, CSH (color super homeotropic) type, FLC (ferroelectric liquid crystal), etc. . As a driving method, multiplex driving is generally used instead of conventional static driving, and the active matrix (AM) method driven by a TFT (thin film transistor), TFD (thin film diode) or the like has become mainstream recently. ing.

As shown in FIG. 1, a general color liquid crystal display device has a transparent electrode layer (a common electrode) between one alignment film of two substrates (1) each having an alignment film (4) and the substrate. 3a) and a color filter layer (2), a pixel electrode layer (3b) is provided between the other alignment film and the substrate, these substrates are arranged so that the alignment films face each other, and a liquid crystal layer ( 5) is sandwiched.
The color filter layer is composed of a color filter composed of a black matrix, a red colored layer (R), a green colored layer (G), a blue colored layer (B), and, if necessary, a yellow colored layer (Y). The

The liquid crystal material constituting the liquid crystal layer has been subjected to a high degree of management because impurities have a great influence on the electrical characteristics of the display device if the impurities remain in the material. In addition, regarding the material for forming the alignment film, it is already known that the alignment film directly affects the liquid crystal layer and the impurities remaining in the alignment film move to the liquid crystal layer, thereby affecting the electrical characteristics of the liquid crystal layer. The characteristics of the liquid crystal display device due to the impurities in the alignment film material are being studied.
On the other hand, the material such as the organic pigment used for the color filter layer is also assumed to have an influence on the liquid crystal layer due to impurities contained in the same manner as the alignment film material. However, since an alignment film and a transparent electrode are interposed between the color filter layer and the liquid crystal layer, it has been considered that the direct influence on the liquid crystal layer is significantly less than that of the alignment film material. However, the alignment film is usually only 0.1 μm or less in thickness, and the common electrode used on the color filter layer side for the transparent electrode is usually 0.5 μm or less even if the film thickness is increased to increase the conductivity. . Therefore, it cannot be said that the color filter layer and the liquid crystal layer are placed in a completely isolated environment, and the color filter layer is formed by impurities contained in the color filter layer through the alignment film and the transparent electrode. There is a possibility that display defects such as white spots due to a decrease in voltage holding ratio (VHR), an increase in ion density (ID), uneven alignment, and burn-in may occur.

As a method of solving display defects caused by impurities contained in pigments constituting the color filter, the elution of impurities into the liquid crystal is controlled by using pigments whose ratio of the extract of ethyl formate is not more than a specific value. A method (Patent Document 1) and a method (Patent Document 2) for controlling the elution of impurities into a liquid crystal by specifying a pigment in a blue colored layer have been studied. However, these methods are not significantly different from simply reducing impurities in the pigment, and are insufficient as an improvement to solve display defects even in the current state of progress in pigment purification technology. Met.
On the other hand, paying attention to the relationship between the organic impurities contained in the color filter and the liquid crystal composition, the difficulty of dissolving the organic impurities in the liquid crystal layer is expressed by the hydrophobic parameter of the liquid crystal molecules contained in the liquid crystal layer. Since there is a correlation between the parameter value of a certain value or more and the hydrophobic parameter and the -OCF ₃ group at the liquid crystal molecule terminal, a liquid crystal compound having a -OCF ₃ group at the liquid crystal molecule terminal is contained in a certain ratio or more. A method for producing a liquid crystal composition (Patent Document 3) is disclosed.

  However, in the disclosure of the cited document as well, it is the essence of the invention to suppress the influence of impurities in the pigment on the liquid crystal layer. The direct relationship with the above has not been studied, and the problem of display defects of liquid crystal display devices that have been advanced has not been solved.

JP 2000-19321 A JP 2009-109542 A JP 2000-192040 A

  In the present invention, by using a color filter using a specific liquid crystal composition and a specific pigment, a decrease in voltage holding ratio (VHR) and an increase in ion density (ID) of the liquid crystal layer are prevented, white spots, alignment An object of the present invention is to provide a liquid crystal display device that solves the problem of display defects such as unevenness and burn-in.

In order to solve the above-mentioned problems, the inventors of the present application have made extensive studies on a combination of a coloring material and the like for constituting a color filter and a structure of a liquid crystal material constituting a liquid crystal layer, and as a result, a liquid crystal material having a specific structure. And a liquid crystal display device using a color filter using a pigment and a compound having a specific structure prevents a decrease in voltage holding ratio (VHR) and an increase in ion density (ID) of the liquid crystal layer, and causes white spots and uneven alignment. The inventors have found that the problem of display defects such as image sticking is solved, and have completed the present invention.
That is, the present invention
A first substrate; a second substrate; a liquid crystal layer sandwiched between the first substrate and the second substrate; a color filter comprising a black matrix and at least an RGB three-color pixel portion; and a pixel electrode And a common electrode,
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 2 carbon atoms. 8 represents an alkenyloxy group, and A represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group). The compound represented by the general formula (II):

Wherein 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 2 to 8 carbon atoms. 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—, wherein B and C are each independently fluorine-substituted 1,4-phenylene A group or a trans-1,4-cyclohexylene group, m and n each independently represents an integer of 0 to 4, and m + n = 1 to 4). Containing a liquid crystal composition containing,
In at least one pixel portion of the RGB three-color pixel portion, as a color material, the following general formula (1)

(In Formula (1), R ^{1 to} R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, an alkoxy group, —CO ₂ ^— (carboxylate ion group), —CO _2. R ^21, -SO ₃ ^- (sulfonic acid ion ^{_{group), - SO 3 M, .R}} 21 and ^{R 22} represents an -SO ^{2 NR} 21 ^{R 22} are each independently a hydrogen atom, a branched structure having 1 to 12 carbon atoms Represents a good alkyl group or a cyclic alkyl group having 1 to 10 carbon atoms, and R ²¹ and R ²² may form a ring structure.
R ¹¹ is -CO ₂ ^- (carboxylate ion ^{_{group), - CO 2 R 21,}} -SO 3 - ( sulfonic acid ion _group), - SO _{3 M,} represents a -SO ^{2 NR} 23 ^{R 24.} R ²³ and R ²⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, or a cyclic alkyl group having 1 to 10 carbon atoms, and R ²³ and R ²⁴ form a ring structure. Also good. M represents a hydrogen atom, a sodium atom or a potassium atom. However, one or more of R ^{1 to} R ¹⁰ are —SO ₂ NR ²¹ R ²² . The liquid crystal display device characterized by containing the xanthene compound represented by this.

  The liquid crystal display device of the present invention uses a color filter that uses a specific liquid crystal composition, a specific pigment, and a specific compound, thereby reducing the voltage holding ratio (VHR) of the liquid crystal layer and increasing the ion density (ID). Thus, it is possible to prevent display defects such as white spots, uneven alignment, and baking.

It is a figure which shows an example of the conventional common liquid crystal display device. It is a figure which shows an example of the liquid crystal display device of this invention.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Color filter layer 2a Color filter layer 3a containing specific pigment and specific compound Transparent electrode layer (common electrode)
3b Pixel electrode layer 4 Alignment film 5 Liquid crystal layer 5a Liquid crystal layer containing a specific liquid crystal composition

An example of the liquid crystal display device of the present invention is shown in FIG. A transparent electrode layer (3a) serving as a common electrode, a specific pigment, and a specific pigment between one of the two substrates (1) of the first substrate and the second substrate (1) having the alignment film (4) A color filter layer (2a) containing a specific compound is provided, a pixel electrode layer (3b) is provided between the other alignment film and the substrate, and these substrates are arranged so that the alignment films face each other. A liquid crystal layer (5a) containing a specific liquid crystal composition is sandwiched.
The two substrates in the display device are bonded together by a sealing material and a sealing material disposed in the peripheral region, and in many cases, formed by a granular spacer or a photolithography method in order to maintain a distance between the substrates. Spacer pillars made of the prepared resin are arranged.

(Liquid crystal layer)
The liquid crystal layer in the liquid crystal display device of the present invention 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 2 carbon atoms. 8 represents an alkenyloxy group, and A represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group). The compound represented by the general formula (II):

Wherein 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 2 to 8 carbon atoms. 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—, wherein B and C are each independently fluorine-substituted 1,4-phenylene A group or a trans-1,4-cyclohexylene group, m and n each independently represents an integer of 0 to 4, and m + n = 1 to 4). It is comprised from the liquid crystal composition to contain.
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 15 to 48% by weight, and preferably 20 to 46% by weight. Is more preferable.

In the general 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. In the case where A represents a trans-1,4-cyclohexylene group,
It 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,
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,
R ¹ preferably represents an alkyl group, and in this 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 preferred is an alkyl group having 2 carbon atoms.
When A represents a 1,4-phenylene group,
It preferably represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an alkenyloxy group having 3 to 5 carbon atoms,
More preferably, it represents an alkyl group having 2 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkenyloxy group having 2 to 4 carbon atoms,
R ¹ preferably represents an alkyl group, and in this case, an alkyl group having 1, 3 or 5 carbon atoms is particularly preferred. Further, R ² preferably represents an alkoxy group having 1 to ² carbon atoms.

The content of the compound represented by the general formula (I) in which at least one substituent of R ¹ and R ² is an alkyl group having 3 to 5 carbon atoms is in the compound represented by the general formula (I) It is preferably 50% by weight or more, more preferably 70% by weight or more, and further preferably 80% by weight or more. In addition, the content of the compound represented by the general formula (I) in which at least one substituent of R ¹ and R ² is an alkyl group having 3 carbon atoms is in the compound represented by the general formula (I) It is preferably 50% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, and most preferably 100% by weight.
Although the compound represented by general formula (I) can contain 1 type (s) or 2 or more types, the compound in which A represents a trans- 1,4- cyclohexylene group, and A represents a 1, 4- phenylene group. It is preferable to contain at least one compound.
In addition, the content of the compound represented by the general formula (I) in which A represents a trans-1,4-cyclohexylene group may be 50% by weight or more in the compound represented by the general formula (I). Preferably, 70% by weight or more is more preferable, and 80% by weight or more is further preferable.

  Specifically, the compound represented by the general formula (I) is preferably a compound represented by the following general formula (Ia) to general formula (Ik).

(In the formula, each of R ¹ and R ² independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and R ¹ and R ² in the general formula (I)) Similar embodiments are preferred.)
In general formula (Ia)-general formula (Ik), general formula (Ia), general formula (Ib), general formula (Ic), and general formula (Ig) are preferable, and general formula (Ia), general formula (Ib) ) And general formula (Ic) are more preferable, and general formula (Ia) and general formula (Ib) are more preferable. Yes. When emphasizing the response speed, the general formula (Ib) and the general formula (Ic) are preferable, and the general formula (Ib) and the general formula (Ic) are more preferably used in combination. When emphasizing reliability, the general formula (Ia) is preferable.

From these points, the content of the compound 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. 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 general formula (Ib) and the general formula (Ic) The content of the compound represented by general formula (I) is 0% by weight to 35% by weight 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% by weight to 10% by weight in the compound represented by the formula (I). It is preferable that it is 90 to 100 weight% in the compound.
The liquid crystal layer in the liquid crystal display device of the present invention contains 35 to 80% by weight of the compound represented by the general formula (II), preferably 40 to 75% by weight, and 45 to 70% by weight. Is more preferable.

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. Represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably represents 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 represents an alkyl group having 2 or 3 carbon atoms or an alkenyl group having 2 carbon atoms. It is particularly preferred to represent 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 preferably represents an alkyl group having 1 to 5 carbon atoms 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, more preferably carbon atoms. It is more preferable to represent an alkoxy group having 2 to 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 represents a _-CF 2 O-, a single _{bond, -CH 2 CH 2 -, -} COO -, - OCH 2 -, - CH 2 O -, - OCF ₂ - or preferably representing a _-CF 2 O-, and more preferably represents a single bond or _-CH 2 O-.
m and n each independently preferably represents an integer of 0 to 3, preferably an integer of 0 to 2, 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 can contain 3 to 10 compounds represented by the general formula (II), preferably 4 to 9 compounds, and preferably 5 to 8 compounds. It is preferable to contain.

The compound represented by the general formula (II) is preferably a compound represented by the following general formula (II-1) or (II-2).

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 2 to 8 carbon atoms. Represents an alkenyloxy group, Z ⁵ and Z ⁶ each independently represent 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-a represents, m1, m @ 2 and n2 each independently represent 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 the number of 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 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, more preferably represents an alkoxy group having 2 carbon atoms, Z ⁵ represents a single bond,- It is preferably CH ₂ CH ₂ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, and more preferably represents a single bond or —CH ₂ O—. preferable.

The liquid crystal layer in the liquid crystal display device of the present invention preferably contains 15% to 60% by weight, more preferably 17% to 50% by weight of the compound represented by the general formula (II-1). The content is preferably 40% by weight to 40% by weight, and more preferably 19% to 30% by weight.
The liquid crystal layer in the liquid crystal display device of the present invention can contain one or more compounds represented by the general formula (II-1), but preferably contains 1 to 6 types. It is preferable to contain-5 types, and it is preferable to contain 3 types or 4 types.

In the general formula (II-2), 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 the number of carbon atoms. More preferably, it represents an alkenyl group having 2 to 4 carbon atoms, more preferably represents an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 carbon atoms, and represents 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. More preferably, an alkyl group having 3 carbon atoms or an alkoxy group having 2 carbon atoms is more preferable, and Z ⁶ is a single bond, —CH ₂ CH ₂ —, —COO—, —OCH ₂ —. , _{-CH 2 O -, - OCF 2} - or preferably representing a _-CF 2 O-, and more preferably represents a single bond or _-CH 2 O-.

The liquid crystal layer in the liquid crystal display device of the present invention preferably contains 10% by weight to 50% by weight of the compound represented by the general formula (II-2), preferably 15% by weight to 45% by weight, It is preferable to contain 20 to 40 weight%, and it is preferable to contain 25 to 35 weight%.
The liquid crystal layer in the liquid crystal display device of the present invention can contain one or more compounds represented by the general formula (II-2), but preferably contains 1 to 6 types. It is preferable to contain-5 types, and it is preferable to contain 3 types or 4 types.

  As the compound represented by the general formula (II-1), specifically, compounds represented by the following general formulas (II-1a) to (II-1d) 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 general formula (II-1a) and general formula (II-1c), R ³ is preferably the same embodiment as in 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 general formula (II-1b) and general formula (II-1d), R ³ is preferably the same embodiment as in 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 general formulas (II-1a) to (II-1d), in order to increase the absolute value of dielectric anisotropy, general formula (II-1a) and general formula (II-1c) are preferable. And general formula (II-1a) is preferred.
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-1a) to general formula (II-1d). It is preferable to contain 1 type or 2 types of compounds represented by general formula (II-1a).

  As the compound represented by the general formula (II-1), specifically, compounds represented by the following general formula (II-1e) to general formula (II-1h) 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 general formula (II-1e) and general formula (II-1g), R ³ is preferably the same embodiment as in 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 general formula (II-1f) and general formula (II-1h), R ³ is preferably the same embodiment as in 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 general formulas (II-1e) to (II-1h), general formula (II-1e) and general formula (II-1g) are preferred in order to increase the absolute value of dielectric anisotropy. .

  As the compound represented by the general formula (II-2), specifically, compounds represented by the following general formula (II-2a) to general formula (II-2d) 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 preferred.)
In general formula (II-2a) and general formula (II-2c), R ³ is preferably the same embodiment as in 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 general formula (II-2b) and general formula (II-2d), R ³ is preferably the same embodiment as in 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 general formulas (II-2a) to (II-2d), in order to increase the absolute value of dielectric anisotropy, general formula (II-2a) and general formula (II-2c) are preferable. In particular, the general formula (II-2a) is preferable.

  As the compound represented by the general formula (II-2), specifically, compounds represented by the following general formula (II-2e) to (II-2j) 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 ^4d represents an alkyl group having 1 to 5 carbon atoms. An embodiment similar to R ³ and R ⁴ in 2) is preferred.)
In general formula (II-2e), general formula (II-2g) and general formula (II-2i), R ³ is preferably the same embodiment as in 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 general formula (II-2f), general formula (II-2h) and general formula (II-2j), R ³ is preferably the same embodiment as in 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.
Among general formulas (II-2e) to (II-2i), general formula (II-2e) and general formula (II-2h) 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 formula (I) and the general formula (II) is preferably 75% by weight to 100% by weight, and 80% by weight to 100%. % By weight is preferable, 85% by weight to 100% by weight is preferable, 90% by weight to 100% by weight is preferable, and 95% by weight to 100% by weight is preferable.

  The liquid crystal layer in the liquid crystal display device of the present invention further comprises a 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 2 to 2 carbon atoms. 8 represents an alkenyloxy group, D, E and F each independently represent a fluorine-substituted 1,4-phenylene group or trans-1,4-cyclohexylene, and Z ² represents a single bond. _{, -OCH 2 -, - OCO -} , - CH 2 O- or -COO -, -. OCO- represents, n represents 0, 1 or 2 provided that formula (I), formula (II-1 And the compound 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%, more preferably 2 to 15%, and preferably 4 to 10%.

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. More preferably, it represents 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 represents an alkyl group having 3 carbon atoms. Is particularly preferred,
When D represents a 1,4-phenylene group optionally 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 2 carbon atoms. More preferably, it represents a 5 alkyl group or an alkenyl group having 4 carbon atoms, and more preferably represents an alkyl group having 2 to 4 carbon atoms.

R ⁸ represents 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,
When F 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. More preferably, it represents 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 represents an alkyl group having 3 carbon atoms. Is particularly preferred,
When F represents a 1,4-phenylene group optionally 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, More preferably, it represents a 5 alkyl group or an alkenyl group having 4 carbon atoms, and more preferably represents an alkyl group having 2 to 4 carbon atoms.

In the case where R ⁷ and R ⁸ represent an alkenyl group and the bonded D or F represents a 1,4-phenylene group which may be fluorine-substituted, the alkenyl group having 4 or 5 carbon atoms is as follows: A structure is preferred.

（式中、環構造へは右端で結合するものとする。）
この場合においても、炭素原子数４のアルケニル基がさらに好ましい。

(In the formula, it shall be bonded to the ring structure at the right end.)
Also in this case, an alkenyl group having 4 carbon atoms is more preferable.

D, E and F each independently represents a 1,4-phenylene group or trans-1,4-cyclohexylene which may be substituted with fluorine, but represents a 2-fluoro-1,4-phenylene group, 2 , 3-difluoro-1,4-phenylene group, 1,4-phenylene group or trans-1,4-cyclohexylene, preferably 2-fluoro-1,4-phenylene group or 2,3-difluoro- A 1,4-phenylene group and a 1,4-phenylene group are more preferable, and a 2,3-difluoro-1,4-phenylene group or a 1,4-phenylene group is preferable. Z ² is a single _{bond, -OCH 2 -, - OCO -} , - CH 2 O- or represents a -COO-, single bond, it is preferable to represent a _-CH 2 O-or -COO-, a single bond is more preferable.
n represents 0, 1 or 2, but preferably represents 0 or 1. Also, if Z ² represents a substituent other than a single bond, preferably it represents 1.

  In the case where n represents 1, the compound represented by the general formula (III) is represented by the general formula (III-1c) to the general formula (III-1e) from the viewpoint of increasing the negative dielectric anisotropy. From the viewpoint of increasing the response speed, compounds represented by general formula (III-1f) to general formula (III-1j) are preferable.

(Wherein R ⁷ and R ⁸ each independently represents 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, An embodiment similar to R ⁷ and R ⁸ in (III) is preferred.)
The compound represented by general formula (III) is represented by general formula (III-2a) to general formula (III-2h) from the viewpoint of increasing negative dielectric anisotropy when n is 2. From the viewpoint of increasing the response speed, compounds represented by general formula (III-2j) to general formula (III-2l) are preferable.

(Wherein R ⁷ and R ⁸ each independently represents 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, An embodiment similar to R ⁷ and R ⁸ in (III) is preferred.)
The compound represented by the general formula (III) is preferably a compound represented by the general formula (III-3b) from the viewpoint of increasing the response speed when n is 0.

(Wherein R ⁷ and R ⁸ each independently represents 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, An embodiment similar to R ⁷ and R ⁸ in (III) is preferred.)
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., 70 To 100 ° C is more preferable, and 70 to 85 ° C is particularly preferable.

The dielectric anisotropy is preferably −2.0 to −6.0, more preferably −2.5 to −5.0, and −2.5 to −4. Particularly preferred is 0.
The refractive index anisotropy is preferably 0.08 to 0.13 at 25 ° C., more preferably 0.09 to 0.12. More specifically, it is preferably 0.10 to 0.12 when corresponding to a thin cell gap, and preferably 0.08 to 0.10 when corresponding 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 as a function of rotational viscosity and refractive index anisotropy shows 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 · m) or more, preferably 10 ¹³ (Ω · m), when used for an active matrix display element. 10 ¹⁴ (Ω · m) or more is more preferable.

The liquid crystal layer in the liquid crystal display device of the present invention may contain a normal 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-described compound, depending on the application. good.
As a polymerizable monomer, general formula (V)

(Wherein, X ¹ and X ² each independently represent a hydrogen atom or a methyl group,
Sp ¹ and Sp ² are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH ₂ ) _s — (wherein _s represents an integer of 2 to 7, Represents an aromatic ring).
Z ¹ represents —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═ CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CY ¹ ═CY ² — (Wherein Y ¹ and Y ² each independently represents a fluorine atom or a hydrogen atom), —C≡C— or a single bond;
C represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, and all of the 1,4-phenylene groups in the formula may be substituted with any hydrogen atom by a fluorine atom. good. ) Is preferred.

X ¹ and X ² are each preferably a diacrylate derivative that represents a hydrogen atom, or a dimethacrylate derivative that has a methyl group, and a compound in which one represents a hydrogen atom and the other represents a methyl group. As for the polymerization rate of these compounds, diacrylate derivatives are the fastest, dimethacrylate derivatives are slow, asymmetric compounds are in the middle, and a preferred embodiment can be used depending on the application. In the PSA display element, a dimethacrylate derivative is particularly preferable.
Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH ₂ ) _s —, but at least one of them is a single bond in a PSA display element. A compound in which both represent a single bond or one represents a single bond and the other represents an alkylene group having 1 to 8 carbon atoms or —O— (CH ₂ ) _s — is preferable. In this case, the alkyl group of 1-4 is preferable, and 1-4 is preferable for s.

Z ¹ is —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ — or a single bond Are preferred, —COO—, —OCO— or a single bond is more preferred, and a single bond is particularly preferred.
C represents a 1,4-phenylene group, trans-1,4-cyclohexylene group or a single bond in which any hydrogen atom may be substituted by a fluorine atom, but a 1,4-phenylene group or a single bond is preferred. . When C represents a ring structure other than a single bond, Z ¹ is preferably a linking group other than a single bond. When C is a single bond, Z ¹ is preferably a single bond.

From these points, in the general formula (V), the ring structure between Sp ¹ and Sp ² is specifically preferably the structure described below.
In the general formula (V), when C represents a single bond and the ring structure is formed of two rings, it is preferable to represent the following formulas (Va-1) to (Va-5): It is more preferable to represent the formula (Va-3) from Va-1), and it is particularly preferable to represent the formula (Va-1).

(In the formula, both ends shall be bonded to Sp ¹ or Sp ^2. )
The polymerizable compounds containing these skeletons are optimal for PSA-type liquid crystal display elements because of the alignment regulating power after polymerization, and a good alignment state can be obtained, so that display unevenness is suppressed or does not occur at all.

  From the above, as the polymerizable monomer, the general formula (V-1) to the general formula (V-4) are particularly preferable, and the general formula (V-2) is most preferable.

(In the formula, Sp ² represents an alkylene group having 2 to 5 carbon atoms.)
In the case of adding a polymerizable monomer, the polymerization proceeds even in the absence of a polymerization initiator, 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. Further, a stabilizer may be added in order to improve storage stability. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. It is done.

  The liquid crystal layer in the present invention is useful for a liquid crystal display element, such as AM-LCD (active matrix liquid crystal display element), TN (nematic liquid crystal display element), STN-LCD (super twisted nematic liquid crystal display element), OCB-LCD and Although it is useful for IPS-LCD (in-plane switching liquid crystal display element), it is particularly useful for AM-LCD, and can be used for liquid crystal display elements for PSA mode, PSVA mode, VA mode, IPS mode, or ECB mode.

(Color filter)
The color filter according to the present invention includes a black matrix and at least an RGB three-color pixel portion. In at least one pixel portion of the RGB three-color pixel portion, a color material represented by the following general formula (1)

(In Formula (1), R ^{1 to} R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, an alkoxy group, —CO ₂ ^— (carboxylate ion group), —CO _2. R ^21, -SO ₃ ^- (sulfonic acid ion ^{_{group), - SO 3 M, .R}} 21 and ^{R 22} represents an -SO ^{2 NR} 21 ^{R 22} are each independently a hydrogen atom, a branched structure having 1 to 12 carbon atoms Represents a good alkyl group or a cyclic alkyl group having 1 to 10 carbon atoms, and R ²¹ and R ²² may form a ring structure.
R ¹¹ is -CO ₂ ^- (carboxylate ion ^{_{group), - CO 2 R 21,}} -SO 3 - ( sulfonic acid ion _group), - SO _{3 M,} represents a -SO ^{2 NR} 23 ^{R 24.} R ²³ and R ²⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, or a cyclic alkyl group having 1 to 10 carbon atoms, and R ²³ and R ²⁴ form a ring structure. Also good. M represents a hydrogen atom, a sodium atom or a potassium atom. However, one or more of R ^{1 to} R ¹⁰ are —SO ₂ NR ²¹ R ²² . The xanthene compound represented by this is contained.
Especially, it is preferable to contain the xanthene compound represented by the said General formula (1) in at least 1 pixel part of R pixel part and B pixel part.

  In addition, the RGB three-color pixel portion includes, as coloring materials, a diketopyrrolopyrrole pigment and / or an anionic red organic dye in the R pixel portion, a metal halide phthalocyanine pigment, a phthalocyanine green dye, and a phthalocyanine in the G pixel portion. It is preferable that at least one selected from the group consisting of a mixture of a blue-based dye and an azo-based yellow organic dye contains an ε-type phthalocyanine pigment or a cationic blue organic dye in the B pixel portion.

In the general formula (1), the alkyl group represented by R ^{1 to} R ¹⁰ is a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group. , Undecyl group, dodecyl group, hydroxyl group, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group group, -CO ₂ ^- (carboxylate ion ^{_{group), - CO 2 R 21,}} -SO 3 - ( sulfonic acid ion _{group), - SO 3 Na, -SO} 3 K or _-SO 3 _{H, -SO} 2 ^{NR 23} R24 etc. are mentioned.

Examples of the alkyl group represented by R ²¹ and R ²² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and heptyl. Groups, octyl groups, 2-ethylhexyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, and the like, such as hexyl groups, heptyl groups, octyl groups, 2-ethylhexyl groups, nonyl groups, decyl groups, undecyl groups. The dodecyl group is preferred. Examples of the cyclic alkyl group having 1 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 2-cyclohexylethyl group, and the like. A cyclopentyl group, a cyclohexyl group , Cycloheptyl group, cyclooctyl group, and 2-cyclohexylethyl group are preferable.
When R ²¹ and R ²² form a ring structure, specific examples include the following structures.

Either one of R ²¹ and R ²² is preferably other than hydrogen.
R ¹¹ is -CO ₂ ^- (carboxylate ion ^{_{group), - CO 2 R 21,}} -SO 3 - ( sulfonic acid ion _group), - SO _{3 M,} represents a -SO ^{2 NR} 23 ^{R 24.} R ²³ and R ²⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, or a cyclic alkyl group having 1 to 10 carbon atoms, and R ²³ and R ²⁴ form a ring structure. Also good. Examples of the alkyl group represented by R ²³ and R ²⁴ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and heptyl. Groups, octyl groups, 2-ethylhexyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, and the like, such as hexyl groups, heptyl groups, octyl groups, 2-ethylhexyl groups, nonyl groups, decyl groups, undecyl groups. The dodecyl group is preferred. Examples of the C1-C10 cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclohexylmethyl group, and the like. A cyclopentyl group, a cyclohexyl group, a cyclo It is preferably a heptyl group, a cyclooctyl group, or a 2-cyclohexylethyl group.

When R ²³ and R ²⁴ form a ring structure, specific examples include the following structures.

Ｒ^２３およびＲ^２４のうちどちらか１つは水素以外であることが好ましい。

Either one of R ²³ and R ²⁴ is preferably other than hydrogen.

  Specific examples of the xanthene compound represented by the general formula (1) include, for example, the compounds described below, but the present invention is not limited to these unless it exceeds the gist.

No.1: R^a=ドデシル
No.2: R^a=2-エチルヘキシル
No.3: R^a=2-シクロヘキシルエチル

No.1: ^Ra = dodecyl
No.2: R ^a = 2-ethylhexyl
No.3: R ^a = 2-cyclohexylethyl

No.4: R^a=2-エチルヘキシル, R^b=2-エチルヘキシルNo.5: R^a=デシル, R^b=デシル

No.4: R ^a = 2-ethylhexyl, R ^b = 2-ethylhexyl No.5: R ^a = decyl, R ^b = decyl

No.6: R^a=ドデシル
No.7: R^a=2-エチルヘキシルNo.8: R^a=2-シクロヘキシルエチル

No.6: ^Ra = dodecyl
No. 7: R ^a = 2-ethylhexyl No. 8: R ^a = 2-cyclohexylethyl

No.9: R^a=2-エチルヘキシル, R^b=2-エチルヘキシルNo.10: R^a=デシル, R^b=デシル

No. 9: R ^a = 2-ethylhexyl, R ^b = 2-ethylhexyl No. 10: R ^a = decyl, R ^b = decyl

No.11:R^a=ドデシル
No.12:R^a=2-エチルヘキシルNo.13: R^a=2-シクロヘキシルエチル

No. 11: R ^a = dodecyl
No. 12: R ^a = 2-ethylhexyl No. 13: R ^a = 2-cyclohexylethyl

No.14: R^a=2-エチルヘキシル, R^b=2-エチルヘキシル
No.15: R^a=デシル, R^b=デシル

No. 14: R ^a = 2-ethylhexyl, R ^b = 2-ethylhexyl
No.15: R ^a = decyl, R ^b = decyl

No.16：Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ２８９

No. 16: C.I. I. Acid Red 289

(G pixel part)
The G pixel portion preferably contains at least one selected from the group consisting of metal halide phthalocyanine pigments, phthalocyanine green dyes, and mixtures of phthalocyanine blue dyes and azo yellow organic dyes. The metal halide phthalocyanine pigment is selected from the group consisting of Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Cu, Ga, Ge, Y, Zr, Nb, In, Sn and Pb. Is a halogenated metal phthalocyanine pigment having a central metal as a central metal, and when the central metal is trivalent, either one halogen atom, a hydroxyl group or a sulfonic acid group is bonded to the central metal, Or when the central metal is a tetravalent metal, the central metal is either one oxygen atom or two halogen atoms, hydroxyl groups or sulfonic acid groups which may be the same or different. Metal halide phthalocyanine pigments that are bonded together are preferred. Examples of the metal halide phthalocyanine pigment include the following two groups of metal halide phthalocyanine pigments.

(First group)
It has a metal selected from the group consisting of Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Cu, Ga, Ge, Y, Zr, Nb, In, Sn, and Pb as a central metal. A halogenated metal phthalocyanine pigment in which 8 to 16 halogen atoms per phthalocyanine molecule are bonded to the benzene ring of the phthalocyanine molecule, and when the central metal is trivalent, the central metal has one halogen atom In the case where either a hydroxyl group or a sulfonic acid group (—SO 3 H) is bonded and the central metal is a tetravalent metal, the central metal has one oxygen atom or two halogens which may be the same or different. A halogenated metal phthalocyanine pigment to which any one of an atom, a hydroxyl group and a sulfonic acid group is bonded.

(Second group)
2 of halogenated metal phthalocyanine having a trivalent metal selected from the group consisting of Al, Sc, Ga, Y and In as a central metal and having 8 to 16 halogen atoms bonded to the benzene ring of the phthalocyanine molecule per phthalocyanine molecule. Halogenation in which a molecule is a structural unit and each central metal of these structural units is bonded through a divalent atomic group selected from the group consisting of oxygen atom, sulfur atom, sulfinyl (—SO—) and sulfonyl (—SO 2 —) A pigment composed of a metal phthalocyanine dimer.
In the metal halide phthalocyanine pigment, all the halogen atoms bonded to the benzene ring may be the same or different. Different halogen atoms may be bonded to one benzene ring.

  Here, the halogenated metal phthalocyanine pigment in which 9 to 15 bromine atoms out of 8 to 16 halogen atoms per phthalocyanine molecule are bonded to the benzene ring of the phthalocyanine molecule exhibits a yellowish bright green color, It is most suitable for use in the green pixel portion of the color filter. The metal halide phthalocyanine pigment is insoluble or hardly soluble in water or an organic solvent. The halogenated metal phthalocyanine pigment includes both a pigment that has not been subjected to a finishing treatment described later (also referred to as a crude pigment) and a pigment that has been subjected to a finishing treatment.

  The halogenated metal phthalocyanine pigments belonging to the first group and the second group can be represented by the following general formula (PIG-1).

第一群に属するハロゲン化金属フタロシアニン顔料は、前記一般式（ＰＩＧ−１）において、次の通りである。

In the general formula (PIG-1), the metal halide phthalocyanine pigment belonging to the first group is as follows.

In General Formula (PIG-1), X _{1 to} X ₁₆ represent a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom. The four X atoms bonded to one benzene ring may be the same or different. Of X _{1 to} X ₁₆ bonded to four benzene rings, 8 to 16 are chlorine atoms, bromine atoms or iodine atoms. M represents a central metal. In the range of the halogenated metal phthalocyanine pigments in which Y and the number m thereof described later are the same, a pigment having a total of less than 8 chlorine atoms, bromine atoms and iodine atoms out of ₁₆ X _{1 to} X ₁₆ is blue. Similarly, among the ₁₆ X _{1 to} X ₁₆ , the yellow color becomes stronger as the total value of the pigments having a total of 8 or more chlorine atoms, bromine atoms and iodine atoms increases. Y bonded to the central metal M is a monovalent atomic group selected from the group consisting of a halogen atom of any one of fluorine, chlorine, bromine or iodine, an oxygen atom, a hydroxyl group and a sulfonic acid group, and m is bonded to the central metal M. Represents the number of Y to be represented and is an integer of 0-2.

  The value of m is determined by the valence of the central metal M. When the central metal M is trivalent like Al, Sc, Ga, Y, and In, m = 1, and is selected from the group consisting of fluorine, chlorine, bromine, iodine, hydroxyl group, and sulfonic acid group. One of the groups is attached to the central metal. When the central metal M is tetravalent like Si, Ti, V, Ge, Zr, Sn, m = 2 and one of oxygen is bonded to the central metal or fluorine, chlorine, Two of the groups selected from the group consisting of bromine, iodine, hydroxyl group and sulfonic acid group are bonded to the central metal. When the central metal M is divalent like Mg, Fe, Co, Ni, Zn, Cu, Zr, Sn, Pb, Y does not exist.

The halogenated metal phthalocyanine pigment belonging to the second group is as follows in the general formula (PIG-1).
In the general formula (PIG-1), X _{1 to} X ₁₆ are as defined above, and the central metal M represents a trivalent metal selected from the group consisting of Al, Sc, Ga, Y and In, m represents 1. Y represents the following atomic group.

In addition, in the chemical structure of the atomic group Y, the central metal M has the same definition as described above, and X _{17 to} X ₃₂ have the same definition as the definition of X _{1 to} X ₁₆ described above in the general formula (PIG-1). is there. A represents a divalent atomic group selected from the group consisting of an oxygen atom, a sulfur atom, sulfinyl (—SO—) and sulfonyl (—SO 2 —). M in the general formula (PIG-1) and M of the atomic group Y represent that they are bonded via the divalent atomic group A.
That is, the metal halide phthalocyanine pigment belonging to the second group is a metal halide phthalocyanine dimer in which two molecules of metal halide phthalocyanine are constituent units and these are bonded via the divalent atomic group.

Specific examples of the halogenated metal phthalocyanine pigment represented by the general formula (PIG-1) include the following (1) to (4).
(1) A group consisting of Mg, Fe, Co, Ni, Zn, Cu, Zr, Sn, and Pb, such as a halogenated copper phthalocyanine pigment, a halogenated tin phthalocyanine pigment, a halogenated nickel phthalocyanine pigment, and a halogenated zinc phthalocyanine pigment. A halogenated metal phthalocyanine pigment having a divalent metal selected from 1 as a central metal and 8 to 16 halogen atoms bonded to 4 benzene rings per phthalocyanine molecule. Of these, chlorinated brominated zinc phthalocyanine pigments include C.I. I. Pigment Green 58, particularly preferred.
(2) A trivalent metal selected from the group consisting of Al, Sc, Ga, Y and In, such as a halogenated chloroaluminum phthalocyanine, is used as a central metal, and the central metal contains one halogen atom, hydroxyl group or sulfonic acid. A halogenated metal phthalocyanine pigment having any of the groups and having 8 to 16 halogen atoms bonded to 4 benzene rings per phthalocyanine molecule.
(3) The center metal has a tetravalent metal selected from the group consisting of Si, Ti, V, Ge, Zr and Sn, such as halogenated oxytitanium phthalocyanine and halogenated oxyvanadium phthalocyanine. 8 to 16 halogen atoms bonded to four benzene rings per one phthalocyanine molecule, having one oxygen atom or two halogen atoms which may be the same or different, a hydroxyl group or a sulfonic acid group Halogenated metal phthalocyanine pigment.
(4) Three selected from the group consisting of Al, Sc, Ga, Y and In, such as a halogenated μ-oxo-aluminum phthalocyanine dimer and a halogenated μ-thio-aluminum phthalocyanine dimer The valence metal is the central metal, and two molecules of halogenated metal phthalocyanine in which 8 to 16 halogen atoms are bonded to four benzene rings per phthalocyanine molecule are the structural units, and each central metal of these structural units is an oxygen atom. And a pigment comprising a metal halide phthalocyanine dimer bonded through a divalent atomic group selected from the group consisting of sulfur atom, sulfinyl and sulfonyl.

  Specific examples of the halogenated metal phthalocyanine pigment include C.I. I. One or more selected from Pigment Green 7, 36 and 58 are preferred, and one or two selected from Green 36 and 58 are more preferred. Specific examples of the phthalocyanine green dye include C.I. I. One or more selected from Solvent Green 4, 5, 7, and 28 are preferred. Specific examples of phthalocyanine blue dyes include C.I. I. Solvent Blue 4, 5, 25, 35, 36, 38, 58, 59, 67 and 70 are preferred, and Blue 25, 38, 67 are preferred. And one or more selected from 70 are more preferred. Specific examples of the azo yellow organic dye include C.I. I. Solvent Yellow 2, 4, 14, 16, 18, 21, 56, 72, 82, 124, 162, and 163 are preferable, or Yellow 82 And one or two selected from 162 are more preferred.

(R pixel part)
The R pixel portion preferably contains a diketopyrrolopyrrole pigment and / or an anionic red organic dye. Specific examples of the diketopyrrolopyrrole pigment include C.I. I. One or two or more selected from Pigment Red 254, 255, 264, 272, Orange 71 and 73 are preferred, and one or more selected from Red 254, 255, 264 and 272 Is more preferred, and C.I. I. Pigment Red 254 is particularly preferred. Specific examples of the anionic red organic dye include C.I. I. One or more selected from Solvent Red 124, Acid Red 52 and 289 are preferred. I. Solvent Red 124 is particularly preferred.

(B pixel part)
The B pixel portion preferably contains an ε-type phthalocyanine pigment or a cationic blue organic dye. As the ε-type phthalocyanine pigment, Pigment Blue 15: 6 is preferable, and as the cationic blue organic dye, a triarylmethane-based dye is preferably contained.

The RGB three-color pixel portion is a color material that contains C.I. I. Solvent Red 124 in the G pixel portion I. Solvent Blue 67 and C.I. I. Solvent Yellow 82 or a mixture thereof with 162 contains Pigment Blue 15: 6 in the B pixel portion, and the xanthene compound represented by the general formula (1) in the R pixel portion and / or the B pixel portion. It is preferable to contain.
In addition, the RGB three-color pixel portion includes C.I. I. Pigment Red 254 in the G pixel portion. I. 1 or 2 or more selected from Pigment Green 7, 36 and 58, Pigment Blue 15: 6 and / or a triarylmethane dye in the B pixel portion, and in the R pixel portion and / or B It is also preferable to contain the xanthene compound represented by the general formula (1) in the pixel portion.

The RGB three-color pixel portion is further provided with C.I. I. Pigment Red 177, 242, 166, 167, 179, C.I. I. Pigment Orange 38, 71, C.I. I. Pigment Yellow 150, 215, 185, 138, 139, C.I. I. Acid Red 52, C.I. I. Basic Red 1, C.I. I. Solvent Red 89, C.I. I. Solvent Orange 56, C.I. I. It is preferable to contain at least one organic dye / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1, 33 and 162.
The RGB three-color pixel portion is further provided with C.I. I. Pigment Yellow 150, 215, 185, 138, C.I. I. It is preferable to contain at least one organic dye / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1 and 33.
The RGB three-color pixel portion further includes C.I. I. Pigment Violet 23, C.I. I. Basic Violet 10, C.I. I. Acid Blue 1, 90, 83, C.I. I. Direct Blue 86, C.I. I. It is preferable to contain at least one organic dye / pigment selected from the group consisting of Pigment Blue 15, 15: 1, 15: 2, 15: 3 and 15: 4.

  The color filter is composed of a black matrix, an RGB three-color pixel portion, 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 / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1, 33 and 162.

In the color filter according to the present invention, the chromaticity x and chromaticity y in the XYZ color system under the C light source of each pixel portion prevent a decrease in voltage holding ratio (VHR) and an increase in ion density (ID) of the liquid crystal layer. From the viewpoint of suppressing the occurrence of display defect problems such as white spots, uneven alignment, and baking, 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. .30 to 0.36 is preferable, 0.31 to 0.35 is more preferable, chromaticity x is 0.58 to 0.69, and 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 0.26, and the chromaticity y is 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 0.26, 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. 0.04 to 0.12 is preferable, 0.05 to 0.09 is more preferable, chromaticity x is 0.12 to 0.18, and 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. .48 to 0.53 is preferable, 0.50 to 0.52 is more preferable, chromaticity x is 0.46 to 0.50, and 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 means a color system approved as a standard color system by the CIE (International Lighting Commission) in 1931.

  The chromaticity in each of the pixel portions can be adjusted by changing the type of dye / pigment used and the mixing ratio thereof. For example, in the case of the R pixel, a yellow dye and / or orange pigment is used as the red dye / pigment, in the case of the G pixel, the yellow dye / pigment is used as the green dye / pigment, and in the case of the B pixel, a purple dye or yellowish dye is used as the blue dye It is possible to adjust 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 for forming the pixel portion is a photolithography method, which applies and heats a photocurable composition to be described later on the surface of the transparent substrate for the color filter provided with the black matrix. After drying (pre-baking), pattern exposure is performed by irradiating ultraviolet rays through a photomask to cure the photo-curable compound at the location corresponding to the pixel portion, and then developing the unexposed portion with a developer. In this method, the non-pixel portion is removed and the pixel portion is fixed to the transparent substrate. In this method, a pixel portion made of a cured colored film of a photocurable composition is formed on a transparent substrate.
A photocurable composition to be described later is prepared for each pixel of other colors such as an R pixel, a G pixel, a B pixel, and a Y pixel as necessary. A color filter having colored pixel portions of pixels, G pixels, B pixels, and Y pixels can be manufactured.
Examples of a method for applying a photocurable composition described later on a transparent substrate such as glass include a spin coating method, a slit coating method, a roll coating method, and an ink jet method.

Although the drying conditions of the coating film of the photocurable composition apply | coated to the transparent substrate differ also with the kind of each component, a compounding ratio, etc., they are 50-150 degreeC and are about 1 to 15 minutes normally. Moreover, as light used for photocuring of a photocurable composition, it is preferable to use the ultraviolet-ray of a wavelength range of 200-500 nm, or visible light. Various light sources that emit light in this wavelength range can be used.
Examples of the developing method include a liquid piling method, a dipping method, and a spray method. After exposure and development of the photocurable composition, the transparent substrate on which the necessary color pixel portion 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 by 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, light The unreacted photocurable compound remaining in the cured colored film of the curable composition is thermally cured to complete the color filter.
By using the color material for a color filter of the present invention with the liquid crystal composition of the present invention, the voltage holding ratio (VHR) of the liquid crystal layer is reduced and the ion density (ID) is prevented from being increased. It is possible to provide a liquid crystal display device that solves the problem of display defects such as baking.

As the method for producing the photocurable composition, the color filter dye and / or pigment composition of the present invention, an organic solvent and a dispersant are used as essential components, and these are mixed and stirred so as to be uniform. First, a pigment dispersion for forming the pixel portion of the color filter is prepared by dispersion, and then a photocurable compound and, if necessary, a thermoplastic resin or a photopolymerization initiator are added. The method of making the said photocurable composition is common.
Examples of the organic solvent used here include aromatic solvents such as toluene, xylene, methoxybenzene, ethyl acetate, propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol methyl ether acetate. , Acetate 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 Ether, diethylene glycol dimethyl ether Ether solvents such as methyl, 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-pyrrolidone, aniline And nitrogen compound solvents such as pyridine, lactone solvents such as γ-butyrolactone, and carbamic acid esters such as a 48:52 mixture of methyl carbamate and ethyl carbamate.

  Dispersants used here include, for example, Big Chemie's Dispersic 130, Dispersic 161, Dispersic 162, Dispersic 163, Dispersic 170, Dispersic 171, Dispersic 174, Dispersic 180, Dispersic 182, Dispersic 183, Dispersic 184, Dispersic 185, Dispersic 2000, Dispersic 2001, Dispersic 2020, Dispersic 2050, Dispersic 2070, Dispersic 2096, Dispersic 2150, Dispersic LPN21116, Dispersic LPN6919 Efka EFKA46, EFKA47, EFKA452, EFKALP4008, EFKA4 09, EFKA LP4010, EFKA LP4050, LP4055, EFKA400, EFKA401, EFKA402, EFKA403, EFKA450, EFKA451, EFKA453, EFKA4540, EFKA4550, EFKALP4560, EFKA120, EFKA150, EFKA1501, EFKA1501 1502, Efka 1503, Lubrizol's Sol Sparse 3000, Sol Sparse 9000, Sol Sparse 13240, Sol Sparse 13650, Sol Sparse 13940, Sol Sparse 17000, 18000, Sol Sparse 20000, Sol Sparse 21000, Sol Sparse 20000, Sol Sparse 24000, Sol Sparse 26000, Sol Sparse 28000, Sol Sparse 28000, Solsparse 32000, Solsparse 36 00, Solsperse 37000, Solsperse 38000, Solsperse 41000, Solsperse 42000, Solsperse 43000, Solsperse 44000, Solsperse 71000, Ajinomoto Co., Inc. Agents, natural rosin such as acrylic resin, urethane resin, alkyd resin, wood rosin, gum rosin, tall oil rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, oxidized rosin, modified rosin such as maleated rosin, Rosin derivatives such as rosinamine, lime rosin, rosin alkylene oxide adduct, rosin alkyd adduct, rosin modified phenol, etc. A synthetic resin that is liquid and water-insoluble at room temperature 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 derivatives, sulfonic acid derivatives, N- (dialkylamino) methyl derivatives, N- (dialkylaminoalkyl) sulfonic acid amide derivatives, etc. You can also. Of course, two or more of these derivatives can be used in combination.

Examples of the thermoplastic resin used for the preparation of the photocurable composition include urethane resins, acrylic resins, polyamide resins, polyimide resins, styrene maleic acid resins, styrene maleic anhydride resins, and the like. .
Examples of the photocurable compound include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol di Bifunctional monomers such as acrylate, trimethylol propaton triacrylate, pentaerythritol triacrylate, tris [2- (meth) acryloyloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. Relatively high molecular weight such as low molecular weight polyfunctional monomer, polyester acrylate, polyurethane acrylate, polyether acrylate, etc. Functional monomer.

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 (trade name) -184”, “Irgacure (trade name) -369”, “Darocur (trade name) -1173” manufactured by BASF, and “Lucirin-” manufactured by BASF. "TPO", Nippon Kayaku Co., Ltd. "Kayacure (trade name) DETX", "Kayacure (trade name) OA", Stofer "Bicure 10", "Bicure 55", Akzo "Trigonal PI", Sand "Sandray 1000" manufactured by Upjohn, "Deep" manufactured by Upjohn, and "Biimidazole" manufactured by Kurokin Kasei.
Moreover, a well-known and usual photosensitizer can also be used together with the said photoinitiator. Examples of the photosensitizer include amines, ureas, compounds having a sulfur atom, compounds having a phosphorus atom, compounds having a chlorine atom, nitriles or other compounds having a nitrogen atom. These can be used alone or in combination of two or more.
The blending ratio of the photopolymerization initiator is not particularly limited, but is preferably in the range of 0.1 to 30% with respect to the compound having a photopolymerizable or photocurable functional group on a mass basis. If it is less than 0.1%, the photosensitivity at the time of photocuring tends to decrease, and if it exceeds 30%, crystals of the photopolymerization initiator are precipitated when the pigment-dispersed resist coating film is dried. May cause deterioration of film properties.

  Using each material as described above, on a mass basis, 300 to 1000 parts of an organic solvent and 1 to 100 parts of a dispersant per 100 parts of the dye and / or pigment composition for a color filter of the present invention. The dye / pigment solution can be obtained by stirring and dispersing so as to be uniform. Next, in this pigment dispersion, the total amount of the thermoplastic resin and the photocurable compound is 3 to 20 parts per part of the pigment composition for a color filter of the present invention, and 0.05 to 3 parts per part of the photocurable compound. A photopolymerization initiator and, if necessary, an organic solvent may be further added, and a photocurable composition for forming a color filter pixel portion can be obtained by stirring and dispersing so as to be uniform.

As the developer, a known and commonly used organic solvent or alkaline aqueous solution can be used. In particular, when the photocurable composition contains a thermoplastic resin or a photocurable compound, and at least one of them has an acid value and exhibits alkali solubility, the color filter can be washed with an alkaline aqueous solution. This is effective for forming the pixel portion.
Although the manufacturing method of the color filter pixel part by the photolithographic method was described in detail, the color filter pixel part prepared by using the pigment composition for the color filter of the present invention can be used in other electrodeposition methods, transfer methods, and micelle electrolysis methods. A color filter may be manufactured by forming each color pixel portion by a PVED (Photovoltaic Electrodeposition) method, an inkjet method, a reverse printing method, a thermosetting method, or the like.
A color filter may be used in a state where an organic pigment is applied to a substrate and dried, and when a curable resin is contained in the pigment dispersion, a color filter may be obtained by curing with heat or active energy rays. Moreover, you may perform the process of removing the volatile component in a coating film by heat-processing (post-baking) for a predetermined time at 100-280 degreeC with heating apparatuses, such as a hotplate and oven.

[Pigment particle state in color filter]
In the color filter of the present invention, the volume fraction of particles of ε-type phthalocyanine pigment, which is an organic pigment, is preferably 1% or less for particles larger than 1000 nm, and preferably 25% or less for 40 nm or more and 1000 nm or less. In the color filter, the state of the organic pigment in the state of the color filter contributes to the suppression of display defects such as white spots, alignment unevenness, and burn-in. By defining the organic pigment particles in the state of being a color filter, it is possible to effectively prevent the above display defects.
The particles having a particle size of 40 nm or more and 1000 nm or less are high-order particles in which primary particles are aggregated, such as secondary particles or tertiary and quaternary particles, and more preferably have a volume fraction of 15% or less.
Moreover, when there are many particles of 100 nm or more and 1000 nm or less, the display state is affected. The volume fraction of particles of 100 nm or more and 1000 nm or less is preferably 7% or less, more preferably 3% or less.
In the ε-type phthalocyanine pigment, coarse particles larger than 1000 nm are not preferable because they may adversely affect the display state. This can be done by observing the color filter surface with an appropriate optical microscope or the like.

(Ultra-small angle X-ray scattering profile)
In order to measure the volume fraction of particles of 1000 nm or less, it can be obtained by analyzing an ultra small angle X-ray scattering profile based on the ultra small angle X-ray scattering method.
Specifically, based on the ultra-small-angle X-ray scattering method, a step (A) of measuring an ultra-small-angle X-ray scattering profile (measured scattering profile) of an organic pigment, and the organic pigment is a spherical particle having a radius R and having a particle size Assuming that there is a variation in distribution, the step (B) of obtaining a theoretical scattering profile from the value of the temporary radius R ₁ and the temporary normalized dispersion value by simulation, and the theoretical scattering profile and the measured scattering profile are: Step (C) for obtaining a residual square sum Z value between the theoretical scattering profile and the measured scattering profile by curve fitting, and the residual square sum Z value obtained in step (C) is 2% or less. to the (n is an _{integer, R n <R n + 1} ) a new radius R _{n + 1} of the value added to the respective normalized variance of provisionally setting a plurality of particle size distribution model Steps (B) to (C) are repeated n times, and from the results of curve fitting the theoretical scattering profile and the measured scattering profile, the primary particle diameter of organic pigment and the average particle diameter of higher order particles, normalized dispersion value, A step (D) of determining at least one of the volume fractions.

  Ultra-Small Angle X-ray Scattering (USAXS) is not only a small-angle region where the scattering angle is 0.1 ° <(2θ) <10 °, but also 0 ° <(2θ) ≦ 0. It is a method that simultaneously measures diffuse scattering and diffraction occurring in the ultra-small angle region of 1 °. In the small-angle X-ray scattering method, if there are regions with different electron densities of about 1 to 100 nm in the substance, the diffuse scattering of X-rays can be measured by the difference in electron density. In this ultra-small angle X-ray scattering method, If there are regions with different electron densities of about 1 to 1000 nm in the substance, X-ray diffuse scattering is measured due to the difference in electron density. The particle diameter of the measurement object is obtained based on the scattering angle and the scattering intensity.

The main technology for realizing the ultra-small angle X-ray scattering method is to reduce the background scattering intensity in the ultra-small angle region by reducing the wavelength width and beam diameter of incident X-rays, and from the sample to the detector as much as possible. This is achieved by two techniques for measuring a portion having a small scattering angle with high accuracy by increasing a distance, that is, a so-called camera length. In the small laboratory apparatus, this is mainly achieved by the former technique.
Moreover, as a program for obtaining the particle size distribution from the X-ray small angle scattering curve, it is preferable to use a program such as NANO-solver (manufactured by Rigaku Corporation) or GIFT (manufactured by PANalytical).

When measuring the particle size physical property value of the ε-type phthalocyanine pigment, it is sufficient if the luminance of the incident X-ray of the X-ray scattering apparatus is 10 ⁶ Brilliance (photons / sec / mm ² / mrad ² /0.1% bandwidth) or more. The scattering intensity can be measured, and is preferably 10 ⁷ Brilliance or higher. When the substrate of the coating film is glass or the like, it is easy to absorb X-rays, so the brightness of incident X-rays is extremely insufficient, so the average particle size, normalized dispersion value, volume fraction of primary and high-order particles of ε-type phthalocyanine pigment In order to accurately measure the rate, the luminance of the incident X-ray is preferably 10 ¹⁶ Brilliance or higher, more preferably 10 ¹⁸ Brilliance or higher.
In order to obtain a high-intensity X-ray source of 10 ¹⁶ Brilliance or higher, a large-scale synchrotron radiation facility such as a light source such as SPring-8 in Hyogo Prefecture or Photon Factory in Ibaraki Prefecture can be used. In such a facility, a desired scattering region can be set by selecting an arbitrary camera length. Further, in order to obtain sufficient scattering intensity, to prevent sample damage, and to protect the detector, several kinds of metal absorbing plates called attenuators are used on the incident side, and the exposure time is set to 0. 0. By arbitrarily adjusting in about 5 to 60 seconds, the optimum measurement conditions can be selected from a wide range of purposes. Examples of the attenuator include a thin film made of Au, Ag, or molybdenum.

As a specific procedure of the measurement, first, in step (A), after setting the color filter on the sample holder, sample stage, etc. of a commercially available X-ray diffractometer, each of the scattering angles (2θ) in the range of less than 10 °. The scattering intensity I at the scattering angle (2θ) is measured to measure a small-angle X-ray scattering profile (measured scattering profile).
The ultra-small-angle scattering device using synchrotron radiation used when the substrate is a glass coating uses a double crystal spectrometer to monochromatic white light extracted from a circular accelerator called a storage ring, and changes the wavelength in the X-ray region (for example, 1Å). As a radiation source, it is made incident on a coating film placed on a sample stage, and the scattered light is exposed for a certain time with a two-dimensional detector, and the scattering profile obtained concentrically is averaged in one dimension, and the scattering angle (2θ) is 10 The step (A) is an operation for converting to a scattering intensity I at each scattering angle (2θ) in a range of less than 0 ° to obtain a small-angle X-ray scattering profile (measured scattering profile).
Next, in step (B), from the measured scattering profile obtained, it is assumed that the organic pigment is a spherical particle with a radius R and there is a variation in the particle size distribution, and the value of the temporary radius R ₁ and the temporary standard A theoretical scattering profile is obtained from the normalized dispersion value using a commercially available analysis software.

  In general, when an electron density difference region of Δρ (r) exists in a substance, the scattering intensity I can be approximated as in the following formula (1).

  In the above formula (1), q represents a scattering vector, V represents a volume integration region, and means that integration is performed for the entire substance. Further, F (q) is a shape factor, and S (q) is a structure factor, and S (q) = 1 when the particles are randomly present in the substance. The scattering vector q is expressed by the following formula (2).

  In the above formula (2), λ is the X-ray wavelength, and 2θ is the scattering angle. In the above formula (1), if the particle is spherical with a radius R, the shape factor F (q) is represented by the following formula (3).

  Therefore, from the above formulas (1), (2), and (3), the scattering intensity I can be described if the shape factor F (q) is calculated assuming a temporary radius R value. However, the scattering intensity I is assumed only when the particles in the substance have a certain size (the radius R is constant). However, in an actual substance, the particles are rarely present in a certain size, and there is generally some variation (particle size distribution variation) in the particle size. In addition, since the object of the present invention is to accurately and accurately measure the particle size distribution of organic pigments having such a particle size distribution variation, it is necessarily assumed that the particle size distribution varies. Will be needed.

  When there is a variation in the particle size distribution, the scattering intensity I is given by a superposition of scattering generated from particles having various sizes. As the distribution function used to assume the dispersion of the particle size distribution, a known distribution function used in statistics can be used. However, in consideration of the dispersion of the particle size distribution in an actual substance, the Γ distribution function is used. Is preferred. This Γ distribution function is expressed by the following formula (4).

Here, R ₀ is an average radius of the spherical particles, and M is a spread parameter of the particle size distribution. Now, assuming that the particle size distribution in the material is given by the above Γ distribution function and that the scattering intensity I is given by the superposition of scattering resulting from particles of various radii R ₁ (average radius is R ₀ ), The scattering intensity I when there is a variation in the particle size distribution is expressed by the following formula (5) using the above formulas (3) and (4).

  M, which is a spread parameter of the particle size distribution in Expression (5), is output as a normalized dispersion value σ (%) as a result of analysis by conversion of Expression (6).

From the above equation (5), in step (B), the scattering intensity I at the scattering angle (2θ) is calculated by simulation from the value of the temporary radius R ₁ and the temporary normalized dispersion value to obtain the theoretical scattering profile.
Next, in step (C), curve fitting between the theoretical scattering profile calculated from the scattering intensity I and the measured scattering profile is performed by the method of least squares.

  Variables to be refined in profile fitting are an average particle diameter (nm) and a normalized dispersion value (%). Profile fitting is performed so that the residual square sum Z value between the measurement profile and the theoretical scattering profile is minimized by the method of least squares. The smaller the residual square sum Z value, the higher the accuracy of particle size analysis. The In general, when the Z value decreases to less than 2%, it may be determined that the two profiles almost overlap and converge at the visual level. The Z value is preferably less than 1%, more preferably less than 0.5%. An average primary particle diameter and a normalized dispersion value, which are variables at the time of convergence, are obtained as analysis results.

When X-ray scattering is measured in the step (A) including the ultra-small angle scattering region, a relatively large particle size is included in the analysis range, so one kind of particle size distribution assumed in the step (B), that is, one kind of average. In the fitting analysis of step C assuming the primary particle size and the normalized dispersion value, the residual sum of squares Z value does not sufficiently decrease, and the measurement profile and the theoretical scattering profile may not show good agreement.
The reason for this is that the particle size distribution is not a single type, and pigment particles having a larger particle size and particles aggregated in a higher order are included. Introduce a diameter distribution model.

In step (D), until the residual sum of squares Z value obtained in step (C) becomes 2% or less, a new value of radius R _{n + 1} (n is an integer, R _n <R _{n + 1} ) and temporary The normalized dispersion value is added to set a plurality of particle size distribution models, and the steps (B) to (C) are repeated n times.
Specifically, a new particle size distribution model having a larger average particle size is assumed, the radius is R ₂ (in this case, R ₂ > R ₁ ), and the scattering intensity I of each component is I (1 ) And I (2), the left term of the pre-scattering intensity equation (5) is corrected as in equations (7) and (8).

Ｍ_１は１種類目の粒径分布広がりパラメータである。

M ₁ is a first type particle size distribution spread parameter.

Ｍ_２は２種類目の粒径分布広がりパラメータである。
同様に３つ目の半径Ｒ３やそれ以上の分布を仮定した場合もＩ（３）、Ｉ（４）・・Ｉ（ｎ）と記述することができる。

M ₂ is a second type of particle size distribution spread parameter.
Similarly, when assuming a distribution of the third radius R3 or higher, it can be described as I (3), I (4)... I (n).

The total scattering intensity I _Total of the particle size distribution model system having two average particle sizes is expressed by Equation (9).
I _Total = k (1) I (1) + k (2) I (2) (9)
k (1) and k (2) are scale factors representing the composition ratio of each component.
Similarly, assuming a particle size distribution model having three or more average particle sizes, the total scattering intensity can be described as in equation (10) with a total of n particle size distribution models.
I _Total = k (1) I (1) + k (2) I (2) +... + K (n) I (n) (10)
In the plurality of particle size distributions in the previous period, for example, the volume fractions w (1), w (2)... W (n) of each of the n particle size distribution components are represented by the ratio shown in Equation (11). .
w (1): w (2): ...: w (n) = k (1): k (2): ...: k (n) (11)

The variables to be refined in profile fitting are the average particle size (nm) of each particle size distribution component, the normalized dispersion value (%) representing the width of each particle size distribution, and the volume fraction (%) of each component. . Further, profile fitting is performed so that the Z value, which is the residual sum of squares of the measurement profile and the total theoretical scattering profile, is minimized, and each of the variables is determined.
When the profile fitting in this step (D) does not converge well, that is, when the minimum value of the residual square sum Z value cannot be obtained, it may be caused by too many variables to be determined. At this time, the normalized dispersion value of each particle size distribution component may be fixed with reference to the normalized dispersion value obtained in the step (C). By this operation, the profile fitting by the least square method with fewer variables becomes easier to converge. In this way, the average particle diameter, normalized dispersion value (%), and volume fraction (%) of each component are obtained as analysis results.

(Alignment film)
In the liquid crystal display device of the present invention, the liquid crystal composition is aligned on the first substrate and the surface in contact with the liquid crystal composition on the second substrate. Although arranged between the liquid crystal layers, even if the alignment film is thick, it is as thin as 100 nm or less, and completely blocks the interaction between the pigment such as a pigment constituting the color filter and the liquid crystal compound constituting the liquid crystal layer. It is not a thing.
Further, in a liquid crystal display device that does not use an alignment film, the interaction between a pigment such as a pigment constituting a color filter and a liquid crystal compound constituting a liquid crystal layer becomes larger.

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, etc. Aliphatic or alicyclic tetracarboxylic anhydrides such as aliphatic or alicyclic diamines, and butanetetracarboxylic anhydrides, 2,3,5-tricarboxycyclopentylacetic anhydride, pyromellitic dianhydride A polyimide alignment film obtained by imidizing a polyamic acid synthesized from an aromatic tetracarboxylic anhydride such as a product is preferable. In this case, rubbing is generally used as a method for imparting orientation, but when used for a vertical orientation film or the like, it can be used without imparting orientation.
As the alignment film material, a material containing chalcone, cinnamate, cinnamoyl or azo group in the compound can be used, and it may be used in combination with materials such as polyimide and 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 a substrate by a method such as spin coating to form a resin film, but a uniaxial stretching method, 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 a material for the transparent electrode. Examples of the metal oxide include indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), and zinc oxide. (ZnO), indium tin oxide (In ₂ O ₃ —SnO ₂ ), indium zinc oxide (In ₂ O ₃ —ZnO), niobium-doped titanium dioxide (Ti _1-x Nb _x O ₂ ), fluorine-doped tin oxide, graphene Although nanoribbons or metal nanowires can be used, zinc oxide (ZnO), indium tin oxide (In ₂ O ₃ —SnO ₂ ), or indium zinc oxide (In ₂ O ₃ —ZnO) is preferable. For patterning these transparent conductive films, a photo-etching method or a method using a mask can be used.
The liquid crystal display device of the present invention has a feature that prevents a decrease in voltage holding ratio (VHR) and an increase in ion density (ID) of the liquid crystal layer and suppresses the occurrence of display defects such as image sticking. It is useful for liquid crystal display devices for driving VA mode, PSVA mode, and FSS mode, and can be applied to liquid crystal display devices such as liquid crystal TVs, monitors, mobile phones, and smartphones.

EXAMPLES The present invention will be described in further detail with reference to examples below, but the present invention is not limited to these examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”. In the examples, the measured characteristics are as follows.
T _ni : Nematic phase-isotropic liquid phase transition temperature (° C.)
Δn: refractive index anisotropy at 25 ° C. Δε: dielectric anisotropy at 25 ° C. η: viscosity at 20 ° C. (mPa · s)
γ1: rotational viscosity at 25 ° C. (mPa · s)
VHR: Voltage holding ratio at 70 ° C. (%)
(The ratio of the measured voltage to the initial applied voltage in% when the liquid crystal composition was injected into a cell having a cell thickness of 3.5 μm and measured under the conditions of 5 V applied, frame time 200 ms, and pulse width 64 μs)
ID: Ion density at 70 ° C. (pC / cm ² )
(Ion density value measured by injecting a liquid crystal composition into a cell having a cell thickness of 3.5 μm and applying 20 V with MTR-1 (manufactured by Toyo Corporation) at a frequency of 0.05 Hz)
Burn-in:
The burn-in evaluation of the liquid crystal display element is based on the following four-level evaluation of the afterimage level of the fixed pattern when the predetermined fixed pattern is displayed in the display area for 1000 hours and then the entire screen is uniformly displayed. went.
◎ No afterimage ○ Although there is a slight afterimage Acceptable level △ Without afterimage Unacceptable level × Afterimage fairly bad In addition, the following abbreviations are used for the description of compounds in the examples.
(Ring structure)

(Side chain structure and linking structure)

[Create color filter]
[Preparation of colored composition]
[Red dye coloring composition 1]
Put 10 parts of Red Dye 1 (CI Solvent Red 124) in a plastic bottle, add 55 parts of propylene glycol monomethyl ether acetate and 0.3-0.4 mmφ Sepul beads, and use paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours. After dispersion, the mixture was filtered through a 5 μm filter to obtain a dye coloring liquid. 75.00 parts of this dye coloring liquid, 5.50 parts of polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Gosei Chemical Co., Ltd.), dipentaerystol hexaacrylate (KAYARAD (trade name) DPHA, Nippon Kayaku) 5.00 parts of Yakuhin Co., Ltd., 1.00 parts of benzophenone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.) and 13.5 parts of Euker Ester EEP are stirred with a dispersion stirrer. Filtration through a 0 μm filter gave a red dye coloring composition 1.

[Red dye coloring composition 2]
Instead of 10 parts of red dye 1 of the red dye coloring composition 1, 8 parts of red dye 1 (CI Solvent Red 124) and 2 parts of yellow dye 1 (CI Solvent Yellow 21) are used. In the same manner as above, a red dye coloring composition 2 was obtained.

[Red dye coloring composition 3]
Instead of 10 parts of the red dye 1 of the red dye coloring composition 1, 10 parts of red dye 2 (CI Solvent Red 1) was used to obtain a red dye coloring composition 3 in the same manner as described above.

[Green Dye Coloring Composition 1]
Instead of 10 parts of red dye 1 of the red dye coloring composition 1, 3 parts of blue dye 1 (CI Solvent Blue 67) and 7 parts of yellow dye 1 (CI Solvent Yellow 162) are used. The green dye coloring composition 1 was obtained in the same manner as above.

[Green Dye Coloring Composition 2]
Instead of 7 parts of the yellow dye 1 of the green dye coloring composition 1, 4 parts of yellow dye 1 (CI Solvent Yellow 162) and 3 parts of yellow dye 3 (CI Solvent Yellow 82) are used. In the same manner as above, a green dye coloring composition 2 was obtained.

[Green dye coloring composition 3]
Instead of 3 parts of blue dye 1 and 7 parts of yellow dye 1 in the green dye coloring composition 1, 10 parts of green dye 1 (CI Solvent Green 7) is used in the same manner as described above to give a green dye coloring composition. Product 3 was obtained.

[Blue dye coloring composition 1]
Instead of 10 parts of the red dye 1 of the red dye coloring composition 1, 10 parts of blue dye 2 (CI Solvent Blue 12) was used in the same manner as above to obtain a blue dye coloring composition 1. .

[Yellow dye coloring composition 1]
Instead of 10 parts of the red dye 1 of the red dye coloring composition 1, 10 parts of a yellow dye 1 (CI Solvent Yellow 21) was used to obtain a yellow dye coloring composition 1 in the same manner as described above.

[Yellow dye coloring composition 2]
A yellow dye coloring composition 2 was obtained in the same manner as described above using 10 parts of yellow dye 4 (CI Solvent Yellow 2) instead of 10 parts of yellow dye 1 of the yellow dye coloring composition 1.

[Red pigment coloring composition 1]
10 parts of red pigment 1 (CI Pigment Red 254, “IRGAPHOR RED BT-CF” manufactured by BASF) is put in a polybin, 55 parts of propylene glycol monomethyl ether acetate, Dispersic LPN21116 (manufactured by BYK Chemie) 7.0 Part, 0.3-0.4 mmφ zirconia beads “ER-120S” manufactured by Saint-Gobain, and dispersed for 4 hours with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.), then filtered through a 1 μm filter to obtain a pigment dispersion. Obtained. 75.00 parts of this pigment dispersion, 5.50 parts of polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Gosei Chemical Co., Ltd.), dipentaerystol hexaacrylate (KAYARAD (trade name) DPHA, Nippon Kayaku) 5.00 parts of Yakuhin Co., Ltd., 1.00 parts of benzophenone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.) and 13.5 parts of Euker Ester EEP are stirred with a dispersion stirrer. Filtration through a 0 μm filter gave a red pigment coloring composition 1.

[Red pigment coloring composition 2]
Instead of 10 parts of the red pigment 1 of the red pigment coloring composition 1, 6 parts of red pigment 1 and 2 parts of red pigment 2 (FASTOGEN SUPER RED ATY-TR manufactured by CI Pigment Red 177 DIC Corporation), yellow pigment 2 Using 2 parts of (C.I. Pigment Yellow 139), a red pigment coloring composition 2 was obtained in the same manner as described above.

[Red pigment coloring composition 3]
Instead of 10 parts of the red pigment 1 of the red pigment coloring composition 1, 8 parts of the red pigment 1 and 2 parts of the xanthene compound represented by the general formula (1) (compound No. 16: CI Acid Red 289) In the same manner as above, a red pigment composition 3 was obtained.

[Green pigment coloring composition 1]
Instead of 10 parts of the red pigment 1 of the red pigment coloring composition 1, 6 parts of green pigment 1 (CI Pigment Green 36, “FASTOGEN GREEN 2YK-CF” manufactured by DIC Corporation) and yellow pigment 1 (C.I. Pigment Yellow 150, 4 parts of FANCHON FAST YELLOW E4GN manufactured by BAYER) was used in the same manner as above to obtain a green pigment coloring composition 1.

[Green pigment coloring composition 2]
Instead of 6 parts of green pigment 1 and 4 parts of yellow pigment 1 in the green pigment coloring composition 1, 4 parts of green pigment 2 (CI Pigment Green 58, FASTOGEN GREEN A110 manufactured by DIC Corporation) and yellow pigment 3 (C Green pigment coloring composition 2 was obtained in the same manner as described above using 6 parts of I. Pigment YELLOW 138).

[Blue pigment coloring composition 1]
Blue pigment 1 (CI Pigment Blue 15: 6, FASTOGEN Blue A510 manufactured by DIC Corporation) 1.80 parts, xanthene compound (Compound No. 2) represented by the general formula (1) 0.18 parts, BYK-LPN21116 (Bic Chemie) 2.84 parts, cyclohexanone 10.19 parts, 0.3-0.4 mmφ Sepul beads are placed in a polybin and dispersed in a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours. Obtained. 75.00 parts of this pigment dispersion, 5.50 parts of polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Gosei Chemical Co., Ltd.), dipentaerythritol hexaacrylate (KAYARAD (trade name) DPHA, Nippon Kayaku) 5.00 parts manufactured by Co., Ltd., 1.00 parts benzophenone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.), and 13.5 parts Euker ester EEP (manufactured by Union Carbide) with a dispersion stirrer. The mixture was stirred and filtered through a filter having a pore size of 1.0 μm to obtain a blue pigment coloring composition 1.

[Blue pigment coloring composition 2]
In place of the xanthene compound of the blue pigment coloring composition 1, the xanthene compound (compound No. 4) represented by the general formula (1) was used to obtain a blue pigment coloring composition 2 in the same manner as described above.

[Blue pigment coloring composition 3]
In place of the xanthene compound of the blue pigment coloring composition 1, the xanthene compound (compound No. 1) represented by the general formula (1) was used to obtain a blue pigment coloring composition 3 in the same manner as described above.

[Blue pigment coloring composition 4]
Instead of the xanthene compound of the blue pigment coloring composition 1, a blue pigment coloring composition 4 was obtained in the same manner as described above using the xanthene compound (Compound No. 12) represented by the general formula (1).

[Yellow pigment coloring composition 1]
In place of 10 parts of the red pigment 1 of the red pigment coloring composition 1, 10 parts of yellow pigment 1 (CI Pigment Yellow 150, FANCHON FAST YELLOW E4GN manufactured by LANXESS) was used in the same manner as described above, and yellow pigment 1 A colored composition 1 was obtained.

[Production of color filter]
The red coloring composition was applied to a glass substrate on which a black matrix had been formed in advance so as to have a film thickness of 2 μm by spin coating. After drying at 70 ° C. for 20 minutes, a striped pattern was exposed to ultraviolet rays through a photomask in an exposure machine equipped with an ultrahigh pressure mercury lamp. Spray development with an alkali developer for 90 seconds, washing with ion exchange water, and air drying. Further, post-baking was performed at 230 ° C. for 30 minutes in a clean oven to form red pixels, which are striped colored layers, on a transparent substrate.
Next, the green coloring composition is similarly applied by spin coating so that the film thickness becomes 2 μm. After drying, the striped colored layer was exposed and developed at a place different from the above-mentioned red pixel by an exposure machine, thereby forming a green pixel adjacent to the above-mentioned red pixel.
Next, similarly for the blue coloring composition, red pixels and blue pixels adjacent to the green pixels were formed by spin coating with a film thickness of 2 μm. Thus, a color filter having striped pixels of three colors of red, green, and blue on the transparent substrate was obtained.
If necessary, the yellow coloring composition was similarly formed by spin coating to form a yellow pixel adjacent to the red pixel and the green pixel with a film thickness of 2 μm. As a result, a color filter having striped pixels of four colors of red, green, blue and yellow on the transparent substrate was obtained.

  Color filters 1 to 4 and comparative color filter 1 were prepared using a dye coloring composition or a pigment coloring composition shown in the following table.

[Measurement of organic pigment volume fraction in color filter]
(Measurement of coarse particles with a microscope)
Regarding the B pixel portion of the obtained color filters 1 to 5, when arbitrary 5 points were observed at 2000 times with an optical microscope Optipho 2 manufactured by Nikon, coarse particles of 1000 nm or more were not observed in any of them. It was.

(Measurement of color filters 1 to 4 with USAXS)
The B pixel portions of the color filters 1 to 5 were attached to an Al sample holder with tape and set on a transmission sample stage. As a result of performing ultra-small-angle X-ray scattering measurement and analyzing under the following conditions, three particle size distributions are obtained. Of these, particles represented by a distribution having an average particle size of 1 nm or more and less than 40 nm are primary particles, similarly 40 nm or more. The distribution of less than 100 nm was expressed as secondary particles, and the distribution of 100 nm or more and 1000 nm or less was expressed as tertiary particles, and the total of the secondary particles and the tertiary particles was defined as high-order particles.
As a result of the above measurement / analysis, the volume fraction of primary particles represented by the distribution of the average particle diameter of 1 nm or more and less than 40 nm in the B pixel portion of the color filters 1 to 5 is 88.4%, and the distribution is 40 nm or more and less than 100 nm. The volume fraction of secondary particles represented is 11.6%, the volume fraction of tertiary particles represented by a distribution of 100 nm to 1000 nm is 0.0%, and the volume fraction occupied by particles of 40 nm to 1000 nm is The rate was 11.6%.
Measuring instruments and measuring methods are as follows.
Measuring device: Large synchrotron radiation facility: SPring-8, Frontier Soft Matter Development Industry-Academia Union beamline: BL03XU Second hatch measurement mode: Ultra-small angle X-ray scattering (USAXS)
Measurement conditions: wavelength 0.1 nm, camera length 6 m, beam spot size 140 μm × 80 μm, no attenuator, exposure time 30 seconds, 2θ = 0.01-1.5 °
Analysis software: Fit2D for two-dimensional data imaging and one-dimensionalization (obtained from the homepage of the European Synchron Radiation Facility [http://www.esrf.eu/computing/scientific/FIT2D/])
Analysis of the particle size distribution was performed with software NANO-Solver (Ver 3.6) manufactured by Rigaku Corporation.

  About each pixel part of the said color filter, x value and y value in C light source of CIE1931 XYZ color system were measured using Olympus microscope MX-50 and Otsuka Electronics spectrophotometer MCPD-3000 microspectrophotometer. . The results are shown in the table below.

(Examples 1-5)
An electrode structure is formed on the first and second substrates, a vertical alignment film is formed on each facing side, and then a weak rubbing process is performed to create a VA cell. The first substrate and the second substrate The liquid crystal composition 1 shown in the following table was sandwiched between them. Next, the liquid crystal display device of Examples 1-5 was created using the color filters 1-5 shown in the said table _{| surface} ( _dgap = 3.5micrometer, alignment film SE-5300). VHR and ID of the obtained liquid crystal display device were measured. The obtained liquid crystal display device was evaluated for burn-in. The results are shown in the table below.

The liquid crystal composition 1 has a practical liquid crystal phase temperature range of 81 ° C. as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, has a low viscosity, and an optimal Δn. I understand that.
The liquid crystal display devices of Examples 1 to 5 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 6 to 15)
In the same manner as in Example 1, the liquid crystal compositions shown in the following table were held, and the liquid crystal display devices of Examples 6 to 15 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Examples 6 to 15 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 16 to 30)
The liquid crystal compositions shown in the following table were sandwiched in the same manner as in Example 1, and liquid crystal display devices of Examples 16 to 30 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Examples 16 to 30 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 31-45)
The liquid crystal compositions shown in the following table were sandwiched in the same manner as in Example 1, and liquid crystal display devices of Examples 31 to 45 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Examples 31 to 45 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 46 to 60)
The liquid crystal compositions shown in the following table were sandwiched in the same manner as in Example 1, and liquid crystal display devices of Examples 46 to 60 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Examples 46 to 60 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 61 to 75)
The liquid crystal compositions shown in the following table were sandwiched in the same manner as in Example 1, and the liquid crystal display devices of Examples 61 to 75 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Examples 61 to 75 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 76 to 90)
The liquid crystal compositions shown in the following table were sandwiched in the same manner as in Example 1, and liquid crystal display devices of Examples 76 to 90 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Examples 76 to 90 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 91-105)
In the same manner as in Example 1, the liquid crystal compositions shown in the following table were sandwiched, and the liquid crystal display devices of Examples 91 to 105 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Examples 91 to 105 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 106 to 120)
The liquid crystal compositions shown in the following table were sandwiched in the same manner as in Example 1, and the liquid crystal display devices of Examples 106 to 120 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Examples 116 to 120 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 121-135)
In the same manner as in Example 1, the liquid crystal compositions shown in the following table were sandwiched, and the liquid crystal display devices of Examples 121 to 135 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Examples 121 to 135 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 136 to 140)
The liquid crystal composition 1 was mixed with 0.3% by mass of 2-methyl-acrylic acid 4- {2- [4- (2-acryloyloxy-ethyl) -phenoxycarbonyl] -ethyl} -biphenyl-4′-yl ester. A liquid crystal composition 28 was obtained. The liquid crystal composition 28 was sandwiched between the VA cells used in Example 1, and irradiated with ultraviolet rays (3.0 J / cm ² ) for 600 seconds while applying a driving voltage between the electrodes, followed by polymerization treatment, The liquid crystal display devices of Examples 136 to 140 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Examples 136 to 140 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 141-145)
The liquid crystal composition 13 was mixed with 0.3% by mass of bismethacrylic acid biphenyl-4,4′-diyl to obtain a liquid crystal composition 29. The liquid crystal composition 29 was sandwiched between the VA cells used in Example 1, and irradiated with ultraviolet rays (3.0 J / cm ² ) for 600 seconds while a driving voltage was applied between the electrodes, followed by polymerization treatment, The liquid crystal display devices of Examples 141 to 145 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Examples 141 to 145 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 146 to 150)
Liquid crystal composition 30 was prepared by mixing 0.3% by mass of bismethacrylic acid 3-fluorobiphenyl-4,4′-diyl with liquid crystal composition 19. The liquid crystal composition 30 was sandwiched between the VA cells used in Example 1 and irradiated with ultraviolet rays (3.0 J / cm ² ) for 600 seconds with a drive voltage applied between the electrodes, followed by a polymerization treatment. The liquid crystal display devices of Examples 146 to 150 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Examples 146 to 150 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 151-165)
The liquid crystal compositions shown in the following table were sandwiched in the same manner as in Example 1, and liquid crystal display devices of Examples 151 to 165 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Examples 151 to 165 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 166 to 175)
The liquid crystal compositions shown in the following table were sandwiched in the same manner as in Example 1, and liquid crystal display devices of Examples 166 to 175 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Examples 166 to 175 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Comparative Examples 1-15)
The liquid crystal display devices of Comparative Examples 1 to 15 were prepared using the color filters 1 to 5 shown in the above table by sandwiching the comparative liquid crystal composition shown in the following table in the same manner as in Example 1, and the VHR and ID were measured. did. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Comparative Examples 1 to 15 had lower VHR and larger ID than the liquid crystal display devices of the present invention. Also, in the burn-in evaluation, afterimages were observed and the level was not acceptable.

(Comparative Examples 16-30)
The liquid crystal display devices of Comparative Examples 16 to 30 were prepared using the color filters 1 to 5 shown in the above table by sandwiching the comparative liquid crystal composition shown in the following table in the same manner as in Example 1, and the VHR and ID were measured. did. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Comparative Examples 16 to 30 had lower VHR and larger ID than the liquid crystal display devices of the present invention. Also, in the burn-in evaluation, afterimages were observed and the level was not acceptable.

(Comparative Examples 31-45)
The liquid crystal display devices of Comparative Examples 31 to 45 were prepared using the color filters 1 to 5 shown in the above table by sandwiching the comparative liquid crystal composition shown in the following table in the same manner as in Example 1, and the VHR and ID were measured. did. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  In the liquid crystal display devices of Comparative Examples 31 to 45, VHR was low and ID was large as compared with the liquid crystal display device of the present invention. Also, in the burn-in evaluation, afterimages were observed and the level was not acceptable.

(Comparative Examples 46-55)
As in Example 1, the liquid crystal display devices of Comparative Examples 46 to 55 were produced by sandwiching the comparative liquid crystal compositions shown in the following table and using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. did. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Comparative Examples 46 to 55 had lower VHR and larger ID than the liquid crystal display devices of the present invention. Also, in the burn-in evaluation, afterimages were observed and the level was not acceptable.

(Comparative Examples 56-70)
The liquid crystal display devices of Comparative Examples 56 to 70 were prepared using the color filters 1 to 5 shown in the above table by sandwiching the comparative liquid crystal compositions shown in the following table in the same manner as in Example 1, and the VHR and ID were measured. did. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Comparative Examples 56 to 70 had lower VHR and larger ID than the liquid crystal display devices of the present invention. Also, in the burn-in evaluation, afterimages were observed and the level was not acceptable.

(Comparative Examples 71-75)
The liquid crystal display devices of Comparative Examples 71 to 75 were prepared using the color filters 1 to 5 shown in the above table by sandwiching the comparative liquid crystal composition shown in the following table in the same manner as Example 1, and the VHR and ID were measured. did. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Comparative Examples 71 to 75 had lower VHR and larger ID than the liquid crystal display devices of the present invention. Also, in the burn-in evaluation, afterimages were observed and the level was not acceptable.

(Comparative Examples 76-83)
Liquid crystal compositions 1, 3, 7, 10, 15, 21, 30, and 34 are sandwiched between the VA cells used in Example 1, and the liquid crystals of Comparative Examples 76 to 83 are used by using the comparative color filter 1 shown in the above table. A display device was manufactured and its VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

  The liquid crystal display devices of Comparative Examples 76 to 83 had lower VHR and larger ID than the liquid crystal display devices of the present invention. Also, in the burn-in evaluation, afterimages were observed and the level was not acceptable.

[Red pigment coloring composition 3]
Instead of 10 parts of red pigment 1 in the red pigment coloring composition 1, 8 parts of red pigment 1 , Compound No. 16: C.I. I. Acid Red 289 Using 2 parts, a red pigment composition 3 was obtained in the same manner as described above.

Claims (17)

A first substrate; a second substrate; a liquid crystal layer sandwiched between the first substrate and the second substrate; a color filter comprising a black matrix and at least an RGB three-color pixel portion; and a pixel electrode And a common electrode,
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 2 carbon atoms. 8 represents an alkenyloxy group, and A represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group). The compound represented by the general formula (II):

Wherein 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 2 to 8 carbon atoms. 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—, wherein B and C are each independently fluorine-substituted 1,4-phenylene A group or a trans-1,4-cyclohexylene group, m and n each independently represents an integer of 0 to 4, and m + n = 1 to 4). Containing a liquid crystal composition containing,
In at least one pixel portion of the RGB three-color pixel portion, as a color material, the following general formula (1)

(In Formula (1), R ^{1 to} R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, an alkoxy group, —CO ₂ ^— (carboxylate ion group), —CO _2. R ^21, -SO ₃ ^- (sulfonic acid ion ^{_{group), - SO 3 M, .R}} 21 and ^{R 22} represents an -SO ^{2 NR} 21 ^{R 22} are each independently a hydrogen atom, a branched structure having 1 to 12 carbon atoms Represents a good alkyl group or a cyclic alkyl group having 1 to 10 carbon atoms, and R ²¹ and R ²² may form a ring structure.
R ¹¹ is -CO ₂ ^- (carboxylate ion ^{_{group), - CO 2 R 21,}} -SO 3 - ( sulfonic acid ion _group), - SO _{3 M,} represents a -SO ^{2 NR} 23 ^{R 24.} R ²³ and R ²⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, or a cyclic alkyl group having 1 to 10 carbon atoms, and R ²³ and R ²⁴ form a ring structure. Also good. M represents a hydrogen atom, a sodium atom or a potassium atom. However, one or more of R ^{1 to} R ¹⁰ are —SO ₂ NR ²¹ R ²² . The liquid crystal display device containing the xanthene compound represented by this. In the at least one pixel portion of the R pixel portion and the B pixel portion of the RGB three-color pixel portion, as a color material, the following general formula (1)

(In Formula (1), R ^{1 to} R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, an alkoxy group, —CO ₂ ^— (carboxylate ion group), —CO _2. R ^21, -SO ₃ ^- (sulfonic acid ion ^{_{group), - SO 3 M, .R}} 21 and ^{R 22} represents an -SO ^{2 NR} 21 ^{R 22} are each independently a hydrogen atom, a branched structure having 1 to 12 carbon atoms Represents a good alkyl group or a cyclic alkyl group having 1 to 10 carbon atoms, and R ²¹ and R ²² may form a ring structure.
R ¹¹ is -CO ₂ ^- (carboxylate ion ^{_{group), - CO 2 R 21,}} -SO 3 - ( sulfonic acid ion _group), - SO _{3 M,} represents a -SO ^{2 NR} 23 ^{R 24.} R ²³ and R ²⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, or a cyclic alkyl group having 1 to 10 carbon atoms, and R ²³ and R ²⁴ form a ring structure. Also good. M represents a hydrogen atom, a sodium atom or a potassium atom. However, one or more of R ^{1 to} R ¹⁰ are —SO ₂ NR ²¹ R ²² . The liquid crystal display device of Claim 1 containing the xanthene compound represented by this.   3. The liquid crystal display device according to claim 1, wherein an ε-type phthalocyanine pigment is contained as a color material in the B pixel portion of the RGB three-color pixel portion. As an ε-type phthalocyanine pigment in the B pixel, C.I. I. The liquid crystal display device according to claim 3, which contains Pigment Blue 15: 6. In the ε-type phthalocyanine pigment in the B pixel portion, the volume fraction occupied by particles having a particle size larger than 1000 nm out of all particles is 1% or less, and the volume fraction occupied by particles of 40 nm or more and 1000 nm or less is 25%. The liquid crystal display device according to claim 3 or 4, which is an ε-type phthalocyanine pigment as described below. The RGB three-color pixel portion includes, as a color material, a diketopyrrolopyrrole pigment and / or an anionic red organic dye in the R pixel portion, a metal halide phthalocyanine pigment, a phthalocyanine green dye, and a phthalocyanine type in the G pixel portion. The liquid crystal display device according to claim 1, comprising at least one selected from the group consisting of a mixture of a blue dye and an azo yellow organic dye. In the G pixel portion, a metal selected from the group consisting of Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Cu, Ga, Ge, Y, Zr, Nb, In, Sn, and Pb is used. A halogenated metal phthalocyanine pigment having a central metal, and when the central metal is trivalent, either one halogen atom, hydroxyl group or sulfonic acid group is bonded to the central metal, or oxo or When thio-bridged and the central metal is a tetravalent metal, one oxygen atom or two halogen atoms, which may be the same or different, a hydroxyl group, or a sulfonic acid group is bonded to the central metal. The liquid crystal display device according to claim 1, comprising a halogenated metal phthalocyanine pigment. In the R pixel portion, C.I. I. Solvent Red 124 with C.I. I. Solvent Blue 67 and C.I. I. The liquid crystal display device according to any one of claims 1 to 7, which contains a mixture with Solvent Yellow 82 or 162. In the R pixel portion, C.I. I. Pigment Red 254 in the G pixel portion. I. The liquid crystal display device according to any one of claims 1 to 7, comprising one or more selected from Pigment Green 7, 36 and 58. The color filter is composed of a black matrix, an RGB three-color pixel portion, and a Y pixel portion. I. Pigment Yellow 150, 215, 185, 138, 139, C.I. I. The liquid crystal display device according to any one of claims 1 to 9, comprising at least one yellow organic dye / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1, 33, and 162. The liquid crystal composition constituting the liquid crystal layer is further 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 2 to 2 carbon atoms. 8 represents an alkenyloxy group, D, E and F each independently represents a fluorine-substituted 1,4-phenylene group or trans-1,4-cyclohexylene, Z ² represents a single bond, Represents —OCH ₂ —, —OCO—, —CH ₂ O— or —COO—, and n represents 0, 1 or 2. However, General Formula (I), General Formula (II-1) and General Formula ( The liquid crystal display device according to any one of claims 1 to 10, which contains the compound represented by II-2). The compound according to any one of claims 1 to 11, which contains at least one compound in which A in general formula (I) represents a trans-1,4-cyclohexylene group and a compound in which A represents a 1,4-phenylene group. The liquid crystal display device according to item. The liquid crystal display as described in any one of Claims 1-12 in which the liquid-crystal composition which comprises the said liquid-crystal layer contains the compound represented by general formula (II-1) and / or general formula (II-2). apparatus.

Wherein 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 2 to 8 carbon atoms. Z ⁵ and Z ⁶ 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-a represents, m1, m @ 2 and n2 each independently represent 0 or 1). Z represented by the following formula of the liquid crystal composition constituting the liquid crystal layer:

(Wherein γ1 represents rotational viscosity and Δn represents refractive index anisotropy) is 13000 or less, γ1 is 150 or less, and Δn is 0.08 to 0.13. 14. The liquid crystal display device according to any one of items 13. The liquid crystal composition constituting the liquid crystal layer has a nematic liquid crystal phase upper limit temperature of 60 to 120 ° C., a nematic liquid crystal phase lower limit temperature of −20 ° C. or less, and a difference between the nematic liquid crystal phase upper limit temperature and the lower limit temperature of 100 to 100 ° C. It is 150, The liquid crystal display device as described in any one of Claims 1-14. The liquid crystal display device according to claim 1, wherein a specific resistance of a liquid crystal composition constituting the liquid crystal layer is 10 ¹² (Ω · m) or more. The liquid crystal layer has the general formula (V)

(In the formula, X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or —O—. (CH ₂ ) _s — (wherein _s represents an integer of 2 to 7 and an oxygen atom is bonded to an aromatic ring), Z ¹ represents —OCH ₂ —, —CH ₂ O—, _{-COO -, - OCO -, -} CF 2 O -, - OCF 2 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - _{COO-CH = CH -, -} OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO- _{, -COO-CH 2 -, -} OCO-CH 2 -, - CH 2 -COO -, - C ^{_{2 -OCO -, - CY 1 =}} CY 2 - ( wherein, ^{Y 1} and ^{Y 2} each independently represents a fluorine atom or a hydrogen atom.), - C≡C- or a single bond, C is It represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, and all 1,4-phenylene groups in the formula may have an arbitrary hydrogen atom substituted with a fluorine atom. The liquid crystal display device as described in any one of Claims 1-16 comprised by the polymer formed by superposing | polymerizing the liquid crystal composition containing the polymeric compound represented by this.

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