WO2016021583A1 - Liquid crystal display device - Google Patents

Abstract

The present invention relates to a liquid crystal display device employing a colour filter in which a specific liquid crystal composition, a specific pigment, and a specific compound are used. The present invention provides a liquid crystal display device which inhibits a reduction in the voltage holding ratio (VHR) of a liquid crystal layer, inhibits an increase in ion density (ID), and resolves problems related to display defects such as white spots, alignment unevenness, and burn-in. This liquid crystal display device is characterized in that a reduction in the voltage holding ratio (VHR) of the liquid crystal layer is inhibited, an increase in ion density (ID) is inhibited, and the occurrence of display defects such as burn-in is suppressed. Accordingly, the liquid crystal display device is particularly useful as an active-matrix-drive TN-mode, IPS-mode, polymer-stabilized IPS-mode, FFS-mode, OCB-mode, VA-mode, or ECB-mode liquid crystal display device. Furthermore, the liquid crystal display device is applicable as a liquid crystal display device such as a liquid-crystal TV, monitor, portable telephone, or smartphone.

Description

Liquid crystal display

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, automotive 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. Because of the correlation between the parameter value and the hydrophobic parameter and the —OCF ₃ group at the end of the liquid crystal molecule, a liquid crystal compound having —OCF ₃ group at the end of the liquid crystal molecule is contained in a certain proportion 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 Japanese Patent Laid-Open No. 2000-192040

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 at least an RGB three-color pixel portion; a pixel electrode and a common electrode And the liquid crystal layer has the general formula (I)

(Wherein R ³¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group, and M ³¹ to M ³³ are each independently trans-1, Represents a 4-cyclohexylene group or a 1,4-phenylene group, and one or two —CH ₂ — in the trans-1,4-cyclohexylene group is —O 2 such that an oxygen atom is not directly adjacent to the group. -One or two hydrogen atoms in the phenylene group may be substituted with a fluorine atom, X ³¹ and X ³² each independently represent a hydrogen atom or a fluorine atom, Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group, n ³¹ and n ³² each independently represent 0, 1 or 2, n ³¹ + n ³² represents 0, 1 or 2, M ¹ and M ³³ may be in the case of plurality of different be the same. The compounds represented by) contain one or two or more, the general formulas formulas (II-a) (II- f)

(Wherein R ¹⁹ to R ³⁰ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and X ²¹ represents hydrogen A liquid crystal composition containing one or more compounds selected from the group consisting of compounds represented by:
In at least one pixel portion of the RGB three-color pixel portion, as a color material, the following general formula (1)

(In the 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 represents 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)

(Wherein R ³¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms, M ³¹ to M ³³ each independently represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group, and one or two —CH in the trans-1,4-cyclohexylene group ₂ — may be substituted with —O— so that the oxygen atom is not directly adjacent, and one or two hydrogen atoms in the phenylene group may be substituted with a fluorine atom, and X ³¹ and X ³² independently represents a hydrogen atom or a fluorine atom, Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group, n ³¹ and n ³² represent 0, 1 or 2 independently of each other. , ^{31 +} n ³² is 0, 1 or 2, M ³¹ and M ³³ are contained a compound represented by may be the same or different.) One or two or more if there are a plurality, From general formula (II-a) to general formula (II-f)

(Wherein R ¹⁹ to R ³⁰ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and X ²¹ represents hydrogen A liquid crystal composition containing one or more compounds selected from the group consisting of compounds represented by the formula:

In the general formula (I), when the ring structure to which R ³¹ is bonded is a phenyl group (aromatic), R ³¹ is a linear alkyl group having 1 to 5 carbon atoms or a linear number of carbon atoms. 1 to 4 (or more) alkoxy groups and alkenyl groups having 4 to 5 carbon atoms are preferred, and when the ring structure to which they are bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, linear Are preferably an alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms (or more) and a linear alkenyl group having 2 to 5 carbon atoms.
In view of good chemical stability against heat and light, R ³¹ is preferably an alkyl group. Further, if it is important to make a liquid crystal display device having a low viscosity and a high response speed, R ³¹ is preferably an alkenyl group. Further, for the purpose of further shortening the response speed with a low viscosity and a high nematic-isotropic phase transition temperature (Tni), it is preferable to use an alkenyl group whose terminal is not an unsaturated bond. It is particularly preferred that the methyl group is adjacent to the end. Further, if importance is attached to good solubility at low temperatures, as one solution, R ³¹ is preferably an alkoxy group. As another solution, it is preferable to use many types of R ³¹ in combination. For example, as R ³¹ , a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms is preferably used in combination, and a compound having 3 or 5 carbon atoms is preferably used in combination. It is preferable to use compounds 4 and 5 in combination.
M ³¹ to M ³³ are

It is preferable that
M ³¹ is,

It is preferable that

More preferably.
M ³² is,

It is preferable that

More preferably,

More preferably.
M ³³ is

It is preferable that

More preferably,

More preferably.

At least one of X ³¹ and X ³² is preferably a fluorine atom, more preferably both are fluorine atoms.
Z ³¹ is preferably a fluorine atom or a trifluoromethoxy group.
As a combination of X ³¹ , X ³² and Z ³¹ , in one embodiment, X ³¹ = F, X ³² = F and Z ³¹ = F. In yet another embodiment, X ³¹ = F, X ³² = H and Z ³¹ = F. In yet another embodiment, X ³¹ = F, X ³² = H and Z ³¹ = OCF3. In yet another embodiment, X ³¹ = F, X ³² = F and Z ³¹ = OCF3. In yet another embodiment, X ³¹ = H, X ³² = H and Z ³¹ = OCF3.
n ³¹ is preferably 1 or 2, n ³² is preferably 0 or 1, more preferably 0, and n ³¹ + n ³² is preferably 1 or 2, and more preferably 2.

More specifically, the compound represented by the general formula (I) is preferably a compound represented by the following general formula (Ia) to general formula (If).

(Wherein R ³² represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms, X ³¹ to X ³⁸ each independently represent a hydrogen atom or a fluorine atom, and Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group.)
In the general formulas (Ia) to (If), R ³² is a straight-chain alkyl group having 1 to 5 carbon atoms and a straight chain when the ring structure to which R ³² is bonded is a phenyl group (aromatic). A chain-like alkoxy group having 1 to 4 (or more) carbon atoms and an alkenyl group having 4 to 5 carbon atoms are preferred, and the ring structure to which they are bonded is a saturated ring structure such as cyclohexane, pyran and dioxane Includes a straight-chain alkyl group having 1 to 5 carbon atoms, a straight-chain alkoxy group having 1 to 4 (or more) carbon atoms and a straight-chain alkenyl group having 2 to 5 carbon atoms. preferable.

In view of good chemical stability against heat and light, R ³¹ is preferably an alkyl group. Further, if it is important to make a liquid crystal display device having a low viscosity and a high response speed, R ³¹ is preferably an alkenyl group. Further, for the purpose of further shortening the response speed with a low viscosity and a high nematic-isotropic phase transition temperature (Tni), it is preferable to use an alkenyl group whose terminal is not an unsaturated bond. It is particularly preferred that the methyl group is adjacent to the end. Further, if importance is attached to good solubility at low temperatures, as one solution, R ³¹ is preferably an alkoxy group. As another solution, it is preferable to use many types of R ³¹ in combination. For example, as R ³¹ , a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms is preferably used in combination, and a compound having 3 or 5 carbon atoms is preferably used in combination. It is preferable to use compounds 4 and 5 in combination.

At least one of X ³¹ and X ³² is preferably a fluorine atom, more preferably both are fluorine atoms.
Z ³¹ is preferably a fluorine atom or a trifluoromethoxy group.
As a combination of X ³¹ , X ³² and Z ³¹ , in one embodiment, X ³¹ = F, X ³² = F and Z ³¹ = F. In yet another embodiment, X ³¹ = F, X ³² = H and Z ³¹ = F. In yet another embodiment, X ³¹ = F, X ³² = H and Z ³¹ = OCF3. In yet another embodiment, X ³¹ = F, X ³² = F and Z ³¹ = OCF3. In yet another embodiment, X ³¹ = H, X ³² = H and Z ³¹ = OCF3.
n ³¹ is preferably 1 or 2, n ³² is preferably 0 or 1, more preferably 0, and n ³¹ + n ³² is preferably 1 or 2, and more preferably 2.
At least one of X ³³ and X ³⁴ is preferably a fluorine atom, and more preferably both are fluorine atoms.

At least one of X ³⁵ and X ³⁶ is preferably a fluorine atom, and the fact that both are fluorine atoms is effective in increasing Δε, but it is effective for Tni, solubility at low temperatures and liquid crystal display elements. From the viewpoint of chemical stability.
At least one of X ³⁷ and X ³⁸ is preferably a hydrogen atom, and preferably both of them are hydrogen atoms. When at least one of X ³⁷ and X ³⁸ is a fluorine atom, it is not preferable from the viewpoint of Tni, solubility at low temperature, and chemical stability when a liquid crystal display device is formed.
The compound group represented by the general formula (I) preferably contains 1 to 8 types, particularly preferably 1 to 5 types, and the content thereof is preferably 3 to 50% by mass, More preferably, it is 5 to 40% by mass.

In the general formulas (IIa) to (IIf), R ¹⁹ to R ³⁰ are linear alkyl groups having 1 to 5 carbon atoms when the ring structure to which they are bonded is a phenyl group (aromatic). A straight-chain alkoxy group having 1 to 4 (or more) carbon atoms and an alkenyl group having 4 to 5 carbon atoms, and the ring structure to which they are bonded is a saturated ring such as cyclohexane, pyran and dioxane. In the case of the structure, a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 (or more) carbon atoms, and a straight chain having 2 to 5 carbon atoms. Alkenyl groups are preferred.

In view of good chemical stability against heat and light, R ¹⁹ to R ³⁰ are preferably alkyl groups. In addition, if it is important to make a liquid crystal display device having a low viscosity and a high response speed, R ¹⁹ to R ³⁰ are preferably alkenyl groups. Further, for the purpose of further shortening the response speed with a low viscosity and a high nematic-isotropic phase transition temperature (Tni), it is preferable to use an alkenyl group whose terminal is not an unsaturated bond. It is particularly preferred that the methyl group is adjacent to the end. If importance is placed on good solubility at low temperatures, as one solution, R ¹⁹ to R ³⁰ are preferably alkoxy groups. As another solution, it is preferable to use many types of R ¹⁹ to R ³⁰ in combination. For example, as R ¹⁹ to R ³⁰ , a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms is preferably used in combination, and a compound having 3 or 5 carbon atoms is preferably used in combination. It is preferable to use the compounds of formulas 3, 4 and 5 in combination.

R ¹⁹ to R ²⁰ are preferably an alkyl group or an alkoxy group, and at least one of them is preferably an alkoxy group. More preferably, R ¹⁹ is an alkyl group and R ²⁰ is an alkoxy group. More preferably, R ¹⁹ is an alkyl group having 3 to 5 carbon atoms, and R ²⁰ is an alkoxy group having 1 to 2 carbon atoms.
R ²¹ to R ²² are preferably an alkyl group or an alkenyl group, and at least one of them is preferably an alkenyl group. In the case where both are alkenyl groups, they are preferably used to increase the response speed, but are not preferable when it is desired to improve the chemical stability of the liquid crystal display element.
At least one of R ²³ to R ²⁴ is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 4 to 5 carbon atoms. If a good balance between the response speed and Tni is required, at least one of R ²³ to R ²⁴ is preferably an alkenyl group. If a good balance between the response speed and solubility at low temperature is required, R ²³ to At least one of R ²⁴ is preferably an alkoxy group.

At least one of R ²⁵ to R ²⁶ is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms. By obtaining the balance of response speed and Tni are good, it is preferable that at least one of R ^{25 ~} R ²⁶ is an alkenyl group, by obtaining a good balance of solubility in response speed and low temperature, R ²⁵ ~ At least one of R ²⁶ is preferably an alkoxy group. More preferably, R ²⁵ is an alkenyl group and R ²⁶ is an alkyl group. It is also preferred that R ²⁵ is an alkyl group and R ²⁶ is an alkoxy group.
At least one of R ²⁷ to R ²⁸ is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms. By obtaining the balance of response speed and Tni are good, it is preferable that at least one of R ^{27 ~} R ²⁸ is an alkenyl group, by obtaining a good balance of solubility in response speed and low temperature, R ²⁷ ~ At least one of R ²⁸ is preferably an alkoxy group. More preferably, R ²⁷ is an alkyl group or an alkenyl group, and R ²⁸ is an alkyl group. It is also preferred that R ²⁷ is an alkyl group and R ²⁸ is an alkoxy group. Furthermore, it is particularly preferred that R ²⁷ is an alkyl group and R ²⁸ is an alkyl group.
X ²¹ is preferably a fluorine atom.

At least one of R ²⁹ to R ³⁰ is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 to 5 carbon atoms. If a good balance between response speed and Tni is required, at least one of R ²⁹ to R ³⁰ is preferably an alkenyl group, and if high reliability is required, at least one of R ²⁹ to R ³⁰ is an alkyl group. It is preferable that More preferably, R ²⁹ is an alkyl group or an alkenyl group, and R ³⁰ is an alkyl group or an alkenyl group. It is also preferred that R ²⁹ is an alkyl group and R ³⁰ is an alkenyl group. Furthermore, it is also preferred that R ²⁹ is an alkyl group and R ³⁰ is an alkyl group.
The compound group represented by the general formula (II-a) to the general formula (II-f) preferably contains 1 to 10 types, particularly preferably 1 to 8 types, and its content is 5 It is preferably ˜80 mass%, more preferably 10 to 70 mass%, and particularly preferably 20 to 60 mass%.

The liquid crystal layer in the liquid crystal display device of the present invention may further have the general formula (III-a) to the general formula (III-f)

(Wherein R ⁴¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms, X ⁴¹ to X ⁴⁸ each independently represent a hydrogen atom or a fluorine atom, and Z ⁴¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group.) Two or more kinds can be contained.
In the general formulas (IIIa) to (IIIf), R ⁴¹ is a straight-chain alkyl group having 1 to 5 carbon atoms and a straight chain when the ring structure to which R ⁴¹ is bonded is a phenyl group (aromatic). A chain-like alkoxy group having 1 to 4 (or more) carbon atoms and an alkenyl group having 4 to 5 carbon atoms are preferred, and the ring structure to which they are bonded is a saturated ring structure such as cyclohexane, pyran and dioxane Includes a straight-chain alkyl group having 1 to 5 carbon atoms, a straight-chain alkoxy group having 1 to 4 (or more) carbon atoms and a straight-chain alkenyl group having 2 to 5 carbon atoms. preferable.

In view of good chemical stability against heat and light, R ⁴¹ is preferably an alkyl group. Further, if it is important to make a liquid crystal display device having a low viscosity and a high response speed, R ⁴¹ is preferably an alkenyl group. Further, for the purpose of further shortening the response speed with a low viscosity and a high nematic-isotropic phase transition temperature (Tni), it is preferable to use an alkenyl group whose terminal is not an unsaturated bond. It is particularly preferred that the methyl group is adjacent to the end. Moreover, if importance is attached to good solubility at low temperature, as one solution, R ⁴¹ is preferably an alkoxy group. Moreover, as another solution, it is preferable to use many types of R ⁴¹ in combination. For example, as R ⁴¹ , it is preferable to use a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms, preferably a compound having 3 and 5 carbon atoms is preferably used in combination, It is preferable to use compounds 4 and 5 in combination.

At least one of X ⁴¹ and X ⁴² is preferably a fluorine atom, more preferably both are fluorine atoms.
Z ⁴¹ is preferably a fluorine atom or a trifluoromethoxy group.
As a combination of X ⁴¹ , X ⁴² and Z ⁴¹ , in one embodiment, X ⁴¹ = F, X ⁴² = F and Z ⁴¹ = F. In yet another embodiment, X ⁴¹ = F, X ⁴² = H and Z ⁴¹ = F. In yet another embodiment, X ⁴¹ = F, X ⁴² = H and Z ⁴¹ = OCF3. In yet another embodiment, X ⁴¹ = F, X ⁴² = F and Z ⁴¹ = OCF 3. In yet another embodiment, X ⁴¹ = H, X ⁴² = H and Z ⁴¹ = OCF 3.
For X ⁴³ and X ⁴⁴ , at least one of them is preferably a fluorine atom, and both of them are preferably a fluorine atom in order to obtain a large Δε. On the other hand, when improving solubility at low temperatures, It is not preferable.

At least one of X ⁴⁵ and X ⁴⁶ is preferably a hydrogen atom, and preferably both of them are hydrogen atoms. The heavy use of fluorine atoms is not preferable from the viewpoints of Tni, solubility at low temperatures, and chemical stability when a liquid crystal display device is formed.
At least one of X ⁴⁷ and X ⁴⁸ is preferably a hydrogen atom, and preferably both are hydrogen atoms. When at least one of X ⁴⁷ and X ⁴⁸ is a fluorine atom, it is not preferable from the viewpoint of Tni, solubility at low temperature, and chemical stability when a liquid crystal display device is formed.
The compound selected from the group of compounds represented by general formula (III-a) to general formula (III-f) preferably contains 1 to 10 types, more preferably 1 to 8 types, The content is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass.

In the liquid crystal composition of the liquid crystal display device of the present invention, Δε at 25 ° C. is preferably +3.5 or more, more preferably +3.5 to +15.0. Further, Δn at 25 ° C. is preferably 0.08 to 0.14, and more preferably 0.09 to 0.13. More specifically, when it corresponds to a thin cell gap, it is preferably 0.10 to 0.13, and when it corresponds to a thick cell gap, it is preferably 0.08 to 0.10. The η at 20 ° C. is preferably 10 to 45 mPa · s, more preferably 10 to 25 mPa · s, and particularly preferably 10 to 20 mPa · s. Further, T _ni is preferably 60 ° C. to 120 ° C., more preferably 70 ° C. to 100 ° C., and particularly preferably 70 ° C. to 85 ° C.

The liquid crystal composition in the present invention may contain a normal nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal and the like in addition to the above-described compounds.
The liquid crystal composition in the present invention may contain one or more polymerizable compounds in order to produce a liquid crystal display element such as a PS mode, a transverse electric field type PSA mode, or a transverse electric field type PSVA mode. Examples of the polymerizable compound that can be used include a photopolymerizable monomer that undergoes polymerization by energy rays such as light. The structure has, for example, a liquid crystal skeleton in which a plurality of six-membered rings such as biphenyl derivatives and terphenyl derivatives are connected. Examples thereof include a polymerizable compound. More specifically, the general formula (V)

(Wherein, X ⁵¹ and X ⁵² 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, Z ⁵¹ 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} it Independently represents a fluorine atom or a hydrogen atom), -. C≡C- or a single bond,
M ⁵¹ 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 have an arbitrary hydrogen atom substituted by a fluorine atom. Also good. ) Is preferred.

X ⁵¹ and X ⁵² 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. The polymerization rate of these compounds is the fastest for diacrylate derivatives, slow for dimethacrylate derivatives, and intermediate for asymmetric compounds, 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 in which 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, 1 to 4 alkyl groups are preferable, and s is preferably 1 to 4.

Z ⁵¹ 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.
M ⁵¹ represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond in which any hydrogen atom may be substituted by a fluorine atom. preferable. When C represents a ring structure other than a single bond, Z ⁵¹ is preferably a linking group other than a single bond. When M ⁵¹ is a single bond, Z ⁵¹ 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 M ⁵¹ represents a single bond and the ring structure is formed of two rings, the following formulas (Va-1) to (Va-5) are preferable. It is more preferable to represent (Va-1) to formula (Va-3), and it is particularly preferable to represent 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 their alignment restriction power after polymerization, and a good alignment state is obtained, so that display unevenness is suppressed or does not occur at all.
From the above, as the polymerizable compound, 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 compound to the liquid crystal composition in the present invention, the polymerization proceeds even when no polymerization initiator is present, but may contain a polymerization initiator in order to accelerate the polymerization. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides, and the like.

The liquid crystal composition containing the polymerizable compound in the present invention is provided with liquid crystal alignment ability by polymerization of the polymerizable compound contained therein by ultraviolet irradiation, and transmits light through the birefringence of the liquid crystal composition. It is used in a liquid crystal display element that controls As liquid crystal display elements, 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 IPS-LCD (in-plane switching liquid crystal display element) However, it is particularly useful for AM-LCDs and can be used for transmissive or reflective liquid crystal display elements.

(Color filter)
The color filter according to the present invention includes at least an RGB three-color pixel portion. In at least one pixel portion of the RGB three-color pixel portion, the following general formula (1) is used as a color material.

(In the 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 represents 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 above general formula (1), the alkyl groups represented by R ¹ to R ¹⁰ are 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a heptyl group. Group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc., and hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group 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 2-cyclohexylethyl group, and the like. A cyclopentyl group, a cyclohexyl group And a cycloheptyl group, a cyclooctyl group, and a 2-cyclohexylethyl group.
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 represents 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a heptyl group. Group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc., and hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group 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 cyclohexyl group, and the like can be given. A heptyl group, a cyclooctyl group, and a 2-cyclohexylethyl group are preferable.
When R ²³ and R ²⁴ form a ring structure, specific examples include the following structures.

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

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

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

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

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

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

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 When 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 via 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).

In the general formula (PIG-1), the metal halide phthalocyanine pigments belonging to the first group are as follows.
In the general formula (PIG-1), X ₁ to X _{16 each} represents 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, bromine or iodine atoms. M represents a central metal. In the range of Y and the number of halogenated metal phthalocyanine pigments having the same number m, 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 pigments, the total of chlorine atom, bromine atom and iodine atom is 8 or more, and the yellow color becomes stronger as the total value is larger. 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 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 X ₁ to X _{16 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 in the atomic group Y 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 the halogenated metal phthalocyanine is composed of two molecules of 8-16 halogen atoms bonded to 4 benzene rings per phthalocyanine molecule. 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 metal halide 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 preferred, preferably 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 further includes 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.
Further, the color filter is composed of at least 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. The color filter may have a black matrix.

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 more preferably 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 preferred, 0.64 to 0.74 is more preferred, 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 0.19, and the chromaticity y is 0. 0.01 to 0.16 is preferable, 0.03 to 0.09 is more preferable, chromaticity x is 0.12 to 0.20, and chromaticity y is 0.01 to 0. More preferably, the chromaticity x is 0.13 to 0.19, and the chromaticity y is 0.03 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 / pigment. 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.
The drying conditions of the coating film of the photocurable composition applied to the transparent substrate are usually about 50 to 150 ° C. for about 1 to 15 minutes, although it varies depending on the type of each component, the blending ratio and the like. Further, as the light used for photocuring the photocurable composition, it is preferable to use ultraviolet rays or visible light in the wavelength range of 200 to 500 nm. 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 a 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, thereby removing volatile components in the colored coating film and simultaneously applying 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 a method for producing the photocurable composition, the color filter pigment composition of the present invention, an organic solvent and a dispersant are used as essential components, and these are mixed and stirred and dispersed so as to be uniform. First, after preparing a pigment dispersion for forming the pixel portion of the color filter, a photocurable compound and, if necessary, a thermoplastic resin or a photopolymerization initiator are added to the photocurable composition. A method of forming a 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 tellurium, 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 carbamate 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 EFKA 46, EFKA 47, EFKA 452, EFKA LP4008, EFKA 009, Efka LP4010, Efka LP4050, LP4055, Efka400, Efka401, Evka402, Efka403, Efka450, Efka451, Efka453, Evka4540, Efka4550, EfkaLP4560, Efka120, Efka150, Evka1501, Evka1501, 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, Sol Sparse 32000, Sol Sparse 3 000, Solsperce 37000, Solsperse 38000, Solsperse 41000, Solsperse 42000, Solsperse 43000, Solsperse 46000, Solsperse 54000, Solsperse 71000, Ajinomoto Co., Ltd. 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 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, and 3-methylpentanediol diacrylate. 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. Commercially available photopolymerization initiators include, for example, “Irgacure (trade name) -184”, “Irgacure (trade name) -369”, “Darocur (trade name) -1173” manufactured by BASF, “Lucirin- "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 of the materials as described above, 300 to 1000 parts of the organic solvent and 1 to 100 parts of the dispersant are made uniform per 100 parts of the color filter pigment composition of the present invention on a mass basis. The dye / pigment solution can be obtained by stirring and dispersing in the same manner. Next, the pigment dispersion is combined with 3 to 20 parts in total of the thermoplastic resin and the photocurable compound per 1 part of the pigment composition for a color filter of the present invention and 0.05 to 3 parts per 1 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. It 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, or when a curable resin is contained in the pigment dispersion, a color filter may be obtained by curing with heat or active energy rays. In addition, a volatile component in the coating film may be removed by heat treatment (post-baking) at 100 to 280 ° C. for a predetermined time using a heating device such as a hot plate or an oven.

[Pigment particle state in color filter]
In the color filter of the present invention, it is preferable that particles having an ε-type phthalocyanine pigment, which is an organic pigment, have a volume fraction of 1% or less of particles greater than 1000 nm and 25% or less of 40 nm to 1000 nm. 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 preferred because they may adversely affect the display state, and are preferably 1% or less. 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.

The ultra-small angle X-ray scattering method (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 material, 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, diffuse scattering of X-rays 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.
Further, 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 GIF (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 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.

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

In the above formula (1), q represents a scattering vector, V represents a volume integration region, and means that the entire material is integrated. 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.

If 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 the conversion of Expression (6) as an analysis result.

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.

The variables to be refined in profile fitting are the average particle diameter (nm) and the 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 is a first type particle size distribution spread parameter.

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 sum of squares 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), polyvinyl alcohol and the like can be used. Particularly, p-phenylenediamine, 4,4′-diaminodiphenylmethane, etc. Aliphatic or alicyclic tetracarboxylic anhydrides such as aliphatic or alicyclic diamines, butanetetracarboxylic anhydride, 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 is particularly useful for a liquid crystal display device for active matrix driving, and is used for a liquid crystal display device for TN mode, IPS mode, polymer-stabilized IPS mode, FFS mode, OCB mode, VA mode or ECB mode. Applicable.
The liquid crystal display device is combined with a backlight and used in various applications such as liquid crystal televisions, personal computer monitors, mobile phones, smartphone displays, notebook personal computers, personal digital assistants, and digital signage. Examples of the backlight include a cold cathode tube type backlight, a two-wavelength peak pseudo-white backlight and a three-wavelength peak backlight using a light emitting diode or an organic EL element using an inorganic material.

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) and 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]
Place 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 (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, 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 the 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. In the same manner as above, a green dye coloring composition 1 was obtained.

[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]
Blue dye coloring composition 1 was obtained in the same manner as described above using 10 parts of blue dye 2 (CI Solvent Blue 12) instead of 10 parts of red dye 1 of red dye coloring composition 1 above. .

[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 placed in a polybin, 55 parts of propylene glycol monomethyl ether acetate, Dispersic LPN21116 (manufactured by BYK Chemie) 7.0 Add 0.3-0.4mmφ zirconia beads “ER-120S” manufactured by Saint-Gobain, and disperse with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, and then filter 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, 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 red pigment 1 of the above-mentioned 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 of 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 with 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 KK, 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 the dye coloring composition or 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 any five points were observed at 2000 times with Nikon optical microscope Optiphot 2, coarse particles of 1000 nm or more were not observed in any of them. It was.

(Measurement of color filters 1-5 at 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 is expressed as secondary particles, and the distribution of 100 nm or more and 1000 nm or less is expressed as tertiary particles.
As a result of the above measurement and analysis, the primary particle volume fraction 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 of 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/])
The analysis of the particle size distribution was performed with software NANO-Solver (Ver 3.6) manufactured by Rigaku Corporation.

For each pixel portion of the color filter, an x value and a y value were measured for a CIE 1931ＩXYZ color system C light source using an Olympus microscope MX-50 and an Otsuka Electronics spectrophotometer MCPD-3000 microspectrophotometer. . The results are shown in the table below.

(Examples 1 to 5)
An electrode structure is formed on at least one of the first and second substrates, a horizontal alignment film is formed on each facing side, and then a weak rubbing process is performed to create an IPS cell. A liquid crystal composition 1 shown below was sandwiched between two substrates. The physical property values of the liquid crystal composition 1 are shown in the following table. Next, liquid crystal display devices of Examples 1 to 5 were produced using the color filters 1 to 5 shown in the above table (d _gap = 4.0 μm, alignment film AL-1051). 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 liquid crystal phase temperature range of 75.5 ° C. that is practical as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, has a low viscosity, and an optimal Δn. You can see 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)
As in Example 1, the liquid crystal compositions 2 to 3 shown in the following table are sandwiched, and the liquid crystal display devices of Examples 6 to 15 are prepared using the color filters 1 to 5 shown in the above table. Was 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)
As in Example 1, the liquid crystal compositions 4 to 6 shown in the following table are sandwiched, and the liquid crystal display devices of Examples 16 to 30 are prepared using the color filters 1 to 5 shown in the above table. Was 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 to 45)
An electrode structure is formed on the first and second substrates, a horizontal alignment film is formed on each opposing side, and then a weak rubbing treatment is performed to create a TN cell. The first substrate and the second substrate Between these, liquid crystal compositions 7 to 9 shown in the following table were sandwiched. Next, liquid crystal display devices of Examples 31 to 45 were prepared using the color filters 1 to 5 shown in the above table (d _gap = 3.5 μm, alignment film SE-7492). 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 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 55)
An electrode structure is formed on at least one of the first and second substrates, a horizontal alignment film is formed on each facing side, and then a weak rubbing process is performed to create an FFS cell. Liquid crystal compositions 10 to 11 shown in the following table were sandwiched between two substrates. Next, liquid crystal display devices of Examples 46 to 55 were prepared using the color filters 1 to 5 shown in the above table (d _gap = 4.0 μm, alignment film AL-1051). 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 display devices of Examples 46 to 55 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 56 to 70)
As in Example 37, the liquid crystal compositions 12 to 14 shown in the following table are sandwiched, and the liquid crystal display devices of Examples 56 to 70 are prepared using the color filters 1 to 5 shown in the above table, and the VHR and ID are set. It was 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 56 to 70 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 71 to 75)
A liquid crystal composition 15 was prepared by mixing 0.3% by mass of bismethacrylic acid biphenyl-4,4′-diyl with the liquid crystal composition 10 used in Example 37. The liquid crystal composition 15 is sandwiched between TN cells, and a polymerization treatment is performed by irradiating with ultraviolet rays (3.0 J / cm ² ) for 600 seconds while a driving voltage is applied between the electrodes. Liquid crystal display devices of Examples 71 to 75 were prepared using the filters 1 to 5, 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 71 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 80)
A liquid crystal composition 16 was prepared by mixing 0.3% by mass of bismethacrylic acid biphenyl-4,4′-diyl with the liquid crystal composition 8 used in Example 29. The liquid crystal composition 16 was sandwiched between IPS cells, and ultraviolet light was irradiated (3.0 J / cm ² ) for 600 seconds while a driving voltage was applied between the electrodes, followed by polymerization treatment. Liquid crystal display devices of Examples 76 to 80 were prepared using filters 1 to 5, 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 80 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 81 to 85)
A liquid crystal composition 17 was prepared by mixing 0.3% by mass of bismethacrylic acid 3-fluorobiphenyl-4,4′-diyl with the liquid crystal composition 6 used in Example 21. The liquid crystal composition 17 is sandwiched between FFS cells, and a polymerization treatment is performed by irradiating with ultraviolet rays (3.0 J / cm ² ) for 600 seconds while a driving voltage is applied between the electrodes. Liquid crystal display devices of Examples 81 to 85 were prepared using filters 1 to 5, 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 81 to 85 were able to realize high VHR and small ID. Also, no afterimage was found in the burn-in evaluation.

(Comparative Examples 1 to 5)
The comparative liquid crystal composition 1 shown below was sandwiched between the IPS cells used in Example 1. Liquid crystal display devices of Comparative Examples 1 to 5 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 Comparative Examples 1 to 5 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 6 to 15)
In the same manner as in Example 1, the liquid crystal display devices of Comparative Examples 6 to 15 were prepared by sandwiching the comparative liquid crystal compositions 2 and 3 shown in the following table and using the color filters 1 to 5 shown in the above table. ID was 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 6 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 to 25)
As in Example 1, the liquid crystal display devices of Comparative Examples 16 to 25 were prepared by sandwiching the comparative liquid crystal compositions 4 to 5 shown in the following table and using the color filters 1 to 5 shown in the above table. ID was 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 16 to 25 had lower VHR and larger ID than 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 26 to 40)
As in Example 1, the liquid crystal display devices of Comparative Examples 26 to 40 were prepared by sandwiching the comparative liquid crystal compositions 6 to 8 shown in the following table and using the color filters 1 to 5 shown in the above table. ID was 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 26 to 40 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 41 to 55)
As in Example 1, the liquid crystal display devices of Comparative Examples 41 to 55 were prepared by sandwiching the comparative liquid crystal compositions 9 to 11 shown in the following table and using the color filters 1 to 5 shown in the above table. ID was 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 41 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 56-63)
In Examples 5, 13, 17, 25, 37, 45, 61 and 65, except that the comparative color filter 1 shown in the above table was used in place of the color filter 1, the liquid crystal display devices of Comparative Examples 56 to 63 were similarly used. Was prepared, 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 56 to 63 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.

Claims (14)

1. A first substrate; a second substrate; a liquid crystal composition layer sandwiched between the first substrate and the second substrate; a color filter comprising at least an RGB three-color pixel portion; and a pixel electrode; A liquid crystal composition layer having the general formula (I)
   

   

   (Wherein R ³¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms, M ³¹ to M ³³ each independently represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group, and one or two —CH in the trans-1,4-cyclohexylene group ₂ — may be substituted with —O— so that the oxygen atom is not directly adjacent, and one or two hydrogen atoms in the phenylene group may be substituted with a fluorine atom, and X ³¹ and X ³² represents a hydrogen atom or a fluorine atom independently of one another, Z ³¹ is a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group, n ³¹ is and n ³² independently from each other 0, 1 or 2 ^{Represents, n} 31 ⁺ n ³² is 0, 1 or ^{2, M 31} and ^{M 33} may be in the case of plurality of different be the same.) In the compound one or two or more represented From general formula (II-a) to general formula (II-f)
   

   

   (Wherein R ¹⁹ to R ³⁰ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and X ²¹ represents hydrogen A liquid crystal composition containing one or more compounds selected from the group consisting of compounds represented by:
   In at least one pixel portion of the RGB three-color pixel portion, as a color material, the following general formula (1)
   

   

   (In the 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 represents 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.
2. 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 the 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 represents 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. 3. A liquid crystal display device according to claim 1, wherein an epsilon phthalocyanine pigment is contained as a color material in the B pixel portion of the RGB three-color pixel portion.
4. 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.
5. 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.
6. 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. 6. 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.
7. 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 any one of claims 1 to 6, comprising a halogenated metal phthalocyanine pigment.
8. 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, comprising a mixture with Solvent Yellow 82 or 162.
9. In the R pixel portion, C.I. I. Pigment Red 254 in the G pixel portion, C.I. 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.
10. The color filter is composed of at least an RGB three-color pixel portion and a Y pixel portion. I. Pigment Yellow 150, 215, 185, 138, 139, C.I. I. 10. The liquid crystal display device according to claim 1, comprising at least one yellow organic dye / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1, 33, 162.
11. The compounds represented by the general formula (I) are converted from the general formula (Ia) to the general formula (If).
    

    

    (Wherein R ³¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms, X ³¹ to X ³⁸ each independently represents a hydrogen atom or a fluorine atom, and Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group.) The liquid crystal display device according to any one of the above.
12. In the liquid crystal composition layer, the general formula (III-a) to the general formula (III-f)
    

    

    (Wherein R ⁴¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms, X ⁴¹ to X ⁴⁸ each independently represent a hydrogen atom or a fluorine atom, and Z ⁴¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group.) The liquid crystal display device according to any one of claims 1 to 11, comprising two or more kinds.
13. The liquid crystal display device according to any one of claims 1 to 12, wherein the liquid crystal composition layer is composed of a polymer obtained by polymerizing a liquid crystal composition containing one or more polymerizable compounds.
14. The liquid crystal composition layer has the 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, 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} are each And 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, All of the 1,4-phenylene groups therein may have an arbitrary hydrogen atom substituted with a fluorine atom. The liquid crystal display device according to any one of claims 1 to 13, which contains a bifunctional monomer represented by formula (1).

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