WO2018216483A1

WO2018216483A1 - Liquid crystal display device

Info

Publication number: WO2018216483A1
Application number: PCT/JP2018/018076
Authority: WO
Inventors: 栗山　毅; 士朗谷口; 省二船倉; 健太郎大石
Original assignee: Dic株式会社
Priority date: 2017-05-26
Filing date: 2018-05-10
Publication date: 2018-11-29
Also published as: JPWO2018216483A1; TW201908470A; CN110300919B; JP6680402B2; CN110300919A; TWI755533B

Abstract

The present invention pertains to a liquid crystal display device using a color filter which employs a specific liquid crystal composition, a specific pigment, and a specific compound. The present invention provides a liquid crystal display device that prevents a reduction in voltage holding rate (VHR) and an increase in ion density (ID) of a liquid crystal layer, and that solves the problem of display defects, such as voids, variations in orientation, and image persistence. Since the liquid crystal display device according to the present invention is characterized by being able to prevent a reduction in voltage holding rate (VHR) and an increase in ion density (ID) of a liquid crystal layer and to solve the problem of display defects, such as voids, variations in orientation, and image persistence; the liquid crystal display device is particularly useful for liquid crystal display devices of an ECB mode, VA mode, OCB mode, FFS mode, polymer-stabilizing IPS mode, IPS mode, and TN mode for driving an active-matrix, and is applicable to liquid crystal display devices for liquid crystal TVs, monitors, mobile phones, smart phones, etc.

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 that constitutes the liquid crystal layer has been subjected to advanced management of impurities because impurities remaining in the material greatly affect the electrical characteristics of the display device. 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, and the structure of the coloring material such as dyes and pigments used in the color filter and the structure of the liquid crystal material 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-1)

(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 ³² 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. And one hydrogen atom in the phenylene group may be substituted with a fluorine atom, and M ³³ represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group. And one or two —CH ₂ — in the trans-1,4-cyclohexylene group may be substituted with —O— so that the oxygen atom is not directly adjacent, 1 or 2 water Atom may be substituted by a fluorine atom, X ³¹ and X ³² represents a hydrogen atom or a fluorine atom independently of one another, Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group, n ³¹ And n ³² independently represent 0, 1 or 2, n ³¹ + n ³² represents 0, 1 or 2, and when there are a plurality of M ³¹ and M ^33, they may be the same or different. 1 or 2 or more of compounds represented by 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 RGB three-color pixel portion has a first group represented by the following general formula (PIG-1) having an average primary particle diameter of 5 to 50 nm in the G pixel portion as a colorant and 5 to 50 nm in the G pixel portion, and / or The second group represented by the following general formula (PIG-2)

(In the general formula (PIG-1), X ¹ⁱ to X ¹⁶ⁱ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, an optionally substituted sulfamoyl group, An alkyl group that may have a substituent, an aryl group that may have a substituent, a cycloalkyl group that may have a substituent, a heterocyclic group that may have a substituent, and a substituent. Y ¹ⁱ represents a hydroxyl group, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent. Represents a chlorine atom, —OP (═O) R1R2, or —O—SiR3R4R5, wherein R1 to R5 each independently have a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, or a substituent. Aryl group, substituted Represents an alkoxyl group which may have a group, or an aryloxy group which may have a substituent, and R1 and R2, and R3 to R5 may be bonded to each other to form a ring. , Represents a trivalent metal selected from the group consisting of Al, Sc, Y and In).

(In the general formula (PIG-2), X ¹⁷ⁱ to X ³²ⁱ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, an optionally substituted sulfamoyl group, An alkyl group that may have a substituent, an aryl group that may have a substituent, a cycloalkyl group that may have a substituent, a heterocyclic group that may have a substituent, and a substituent. Represents an alkoxyl group that may be substituted, an aryloxy group that may have a substituent, an alkylthio group that may have a substituent, or an arylthio group that may have a substituent, M represents Ga, Al Represents a trivalent metal selected from the group consisting of Sc, Y and In, Y ²ⁱ represents —O—, —O—SiR 6 R 7 —O—, —O—SiR 6 R 7 —O—SiR 8 R 9 —O—, or —O—. P (═O) R10—O— represents R6— R10 each independently has a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxyl group that may have a substituent, or a substituent. A liquid crystal display device comprising at least one kind of metal phthalocyanine pigment selected from:

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-1)

(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 ³² each independently represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group, and one —CH ₂ — in the trans-1,4-cyclohexylene group is The oxygen atom may be substituted with —O— so that the oxygen atom is not directly adjacent, one or two hydrogen atoms in the phenylene group may be substituted with a fluorine atom, and M ³³ is 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. Even if it is replaced with- Ku, one or two hydrogen atoms may be substituted by a fluorine atom, X ³¹ and X ³² represents a hydrogen atom or a fluorine atom independently of one another, Z ³¹ is a fluorine atom in the phenylene group, tri Represents a fluoromethoxy 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, and a plurality of M ³¹ and M ³³ When present, they may be the same or different.) And are composed of a liquid crystal composition containing one or more compounds represented by

In the general formula (I-1), R ³¹ is a linear alkyl group having 1 to 5 carbon atoms or a linear carbon when the ring structure to which R ³¹ is bonded is a phenyl group (aromatic). An alkoxy group having 1 to 4 (or more) atoms and an alkenyl group 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 or pyran, a straight chain 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. Furthermore, 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 ³² are

It is preferable that
M ³¹ is,

And M ³¹ is preferably

More preferably. M ³² is,

Preferably, M ³² is

More preferably, M ³² is

More preferably. M ³³ is

And M ³³ is preferably

More preferably, M ³³ is

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 = OCF ₃ . In yet another embodiment, X ³¹ = F, X ³² = F and Z ³¹ = OCF ₃ . In yet another embodiment, X ³¹ = H, X ³² = H and Z ³¹ = OCF ₃ .
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-1) 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 of 1 to 5 carbon atoms when the ring structure to which it is bonded is a phenyl group (aromatic). Alkyl groups, linear alkoxy groups having 1 to 4 (or more) carbon atoms and alkenyl groups having 4 to 5 carbon atoms are preferred, and the ring structure to which they are bonded is saturated such as cyclohexane, pyran and dioxane. In the case of a ring 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 linear carbon number of 2 to 5 Are preferred.

In view of good chemical stability against heat and light, R ³² 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 ³² is preferably an alkenyl group. Furthermore, 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 temperature, as one solution, R ³² is preferably an alkoxy group. Moreover, as another solution, it is preferable to use many types of R ³² in combination. For example, as R ³² , it is preferable to use a compound having an alkyl group or alkenyl group having 2, 3 and 4 carbon atoms, preferably a compound having 3 and 5 carbon atoms is 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 = OCF ₃ . In yet another embodiment, X ³¹ = F, X ³² = F and Z ³¹ = OCF ₃ . In yet another embodiment, X ³¹ = H, X ³² = H and Z ³¹ = OCF ₃ .
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-1) preferably contains 1 to 8 types, particularly preferably 1 to 5 types, and its content is 3 to 60% by mass. Preferably, it is 5 to 50% by mass.

The liquid crystal layer in the liquid crystal display device of the present invention has the general formula (I-2)

(Wherein R ³³ 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 ³⁴ to M ³⁵ 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, but present At least one of M ³⁴ and M ³⁵ represents a trans-1,4-cyclohexylene group, and the two —CH ₂ — in the trans-1,4-cyclohexylene group are not directly adjacent to each other. Is substituted with -O-
M ³⁶ represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group, and one or two of —CH ₂ — in the trans-1,4-cyclohexylene group is directly represented by an oxygen atom. May be substituted with —O— so that they are not adjacent, one or two hydrogen atoms in the phenylene group may be substituted with fluorine atoms,
X ⁵¹ and X ⁵² each independently represent a hydrogen atom or a fluorine atom,
Z ³² represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group,
Z ³³ represents —CF ₂ O— or a single bond,
n ³⁴ and n ³⁶ each independently represent 0, 1 or 2, n ³⁴ + n ³⁶ represents 0, 1 or 2, and when a plurality of M ³⁴ and M ³⁶ are present, they may be the same or different. May be. And a liquid crystal composition containing one or more compounds selected from the group consisting of the compounds represented by formula (1) as optional components.

In the general formula (I-2), when the ring structure to which R ³³ is bonded is a phenyl group (aromatic), R ³³ is a linear alkyl group having 1 to 5 carbon atoms, linear carbon An alkoxy group having 1 to 4 (or more) atoms and an alkenyl group 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, A linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 (or more) carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms are preferable.

In view of good chemical stability against heat and light, R ³³ 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 ³³ is preferably an alkenyl group. Furthermore, 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 ³³ is preferably an alkoxy group. As another solution, it is preferable to use many types of R ³³ in combination. For example, as R ³³ , 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.
M ³⁴ to M ³⁵ are

It is preferable that
^M34 is

Preferably, M ³⁴ is

More preferably. M ³⁵ is

Preferably, M ³⁵ is

It is more preferable that ^M36 is

And M ³⁶ is preferably

More preferably, M ³⁶ is

More preferably.
At least one of X ⁵¹ and X ⁵² is preferably a fluorine atom, and more preferably both are fluorine atoms.
Z ³² is preferably a fluorine atom or a trifluoromethoxy group.
As a combination of X ⁵¹ , X ⁵² and Z ³² , in one embodiment, X ⁵¹ = F, X ⁵² = F and Z ³² = F. In yet another embodiment, X ⁵¹ = F, X ⁵² = H and Z ³² = F. In yet another embodiment, X ⁵¹ = F, X ⁵² = H and Z ³² = OCF ₃ . In yet another embodiment, X ⁵¹ = F, X ⁵² = F and Z ³¹ = OCF ₃ . In yet another embodiment, X ⁵¹ = H, X ⁵² = H and Z ³¹ = OCF ₃ .
n ³⁴ is preferably 1 or 2, n ³⁶ is preferably 0 or 1, more preferably 0, and n ³⁴ + n ³⁶ is preferably 1 or 2, and more preferably 2.

More specifically, the compound represented by the general formula (I-2) is preferably a compound represented by the following general formula (Ig) to general formula (Ij).

(Wherein R ³³ 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 ⁵¹ to X ⁵⁸ each independently represent a hydrogen atom or a fluorine atom, and Z ³² represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group.)
In the general formulas (Ig) to (Ij), R ³³ represents a linear carbon atom when the ring structure to which R ³³ is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane. An alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 (or more) carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms are preferable.

In view of good chemical stability against heat and light, R ³³ 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 ³² is preferably an alkenyl group. Furthermore, 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 ³³ is preferably an alkoxy group. As another solution, it is preferable to use many types of R ³³ in combination. For example, as R ³³ , 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 ⁵¹ and X ⁵² is preferably a fluorine atom, and more preferably both are fluorine atoms.
Z ³² is preferably a fluorine atom or a trifluoromethoxy group.
As a combination of X ⁵¹ , X ⁵² and Z ³² , in one embodiment, X ⁵¹ = F, X ⁵² = F and Z ³² = F. In yet another embodiment, X ⁵¹ = F, X ⁵² = H and Z ³² = F. In yet another embodiment, X ⁵¹ = F, X ⁵² = H and Z ³² = OCF ₃ . In yet another embodiment, X ⁵¹ = F, X ⁵² = F and Z ³² = OCF ₃ . In yet another embodiment, X ⁵¹ = H, X ⁵² = H and Z ³² = OCF ₃ .
At least one of X ⁵³ and X ⁵⁴ is preferably a fluorine atom.

At least one of X ⁵³ and X ⁵⁴ is preferably a fluorine atom, and both of them are fluorine atoms. This is effective for increasing Δε, but it is effective for Tni, low-temperature solubility and liquid crystal display elements. From the viewpoint of chemical stability.
At least one of X ⁵⁵ and X ⁵⁶ is preferably a hydrogen atom. If one at least one of X ⁵⁵ and X ⁵⁶ is a fluorine atom, Tni, not preferable in terms of chemical stability upon the solubility and liquid crystal display elements at low temperatures.
At least one of X ⁵⁷ and X ⁵⁸ is preferably a hydrogen atom. When at least one of X ⁵⁷ and X ⁵⁸ 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-2), more specifically, the compounds represented by the general formulas (Ig) to (Ij) are preferably contained in 1 to 5 types, It is particularly preferable to contain 1 to 3 types, and the content is preferably 2 to 30% by mass, more preferably 4 to 25% by mass, and particularly preferably 5 to 20% by mass. .

Furthermore, the liquid crystal layer in the liquid crystal display device of the present invention has a general formula (II-a) to a 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 two or more compounds selected from the group consisting of compounds represented by the formula:

In the general formulas (II-a) to (II-f), R ¹⁹ to R ³⁰ are each a straight-chain carbon atom of 1 when the ring structure to which they are bonded is a phenyl group (aromatic). Preferably an alkyl group of ˜5, a linear alkoxy group of 1 to 4 (or more) carbon atoms and an alkenyl group of 4 to 5 carbon atoms, and the ring structure to which they are bonded is cyclohexane, pyran, dioxane, etc. In the case of a saturated ring structure, 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 carbon atom number 2-5 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. Furthermore, 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. When speeding up the response, at least one of them is preferably an alkenyl group, and when emphasizing chemical reliability, both are preferably alkyl groups, in order to balance response speed and reliability. No. It is preferable to use both a compound in which only one is an alkenyl group and a compound in which both are alkyl groups.

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. When importance is attached to the response speed, at least one of R ²⁵ to R ²⁶ is preferably an alkenyl group. When the balance between the response speed and the solubility at low temperature is to be obtained, a compound in which R ²⁵ to R ²⁶ are all alkyl groups, or R ²⁵ is an alkyl group and R ²⁶ is an alkoxy group is used. You can also When an alkenyl group is used, R ²⁵ is preferably an alkenyl group, and in this case, R ²⁶ is more preferably an alkyl group. In particular, when emphasizing the balance between response speed and solubility at low temperatures, it is preferable to use a compound having an alkenyl group and a compound having no alkenyl group in combination.

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 the 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. Also, R ²⁹ is preferably an alkyl group and R ³⁰ is preferably an alkenyl group, and R ²⁹ is preferably an alkenyl group and R ³⁰ is preferably an alkyl 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% by mass, more preferably 10 to 75% by mass, and particularly preferably 20 to 70% by mass.

In particular, when realizing a high-speed response by reducing γ1 of the liquid crystal composition, it is preferable to use one or more compounds from the group of compounds represented by the general formula (II-b) or (II-d), It is more preferable to use two or more compounds from the compound group represented by the general formula (II-b), two or more compounds from the compound group represented by the general formula (II-b), and a compound represented by (II-d). It is particularly preferable to use one or more compounds from the compound group. The content of the compound group represented by the general formula (II-b) or (II-d) is preferably 5 to 75% by mass, more preferably 10 to 70% by mass, and 20 to 65% by mass. % Is particularly preferred.

Further, when realizing a high-speed response by narrowing the cell gap, it is preferable to use one or more compounds from the compound group represented by the general formula (II-f), and the content thereof is 2 to 35% by mass. It is preferably 4 to 30% by mass, more preferably 6 to 25% by mass, and most preferably 6 to 20% by 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. Furthermore, 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-mentioned compounds.

The liquid crystal composition of the present invention may contain one or more polymerizable compounds in order to produce a liquid crystal display element such as PS mode, lateral electric field type PSA mode, or lateral 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. As for the polymerization rate of these compounds, diacrylate derivatives are the fastest, dimethacrylate derivatives are slow, asymmetric compounds are in the middle, and a preferred embodiment can be used depending on the application. In the PSA display element, a dimethacrylate derivative is particularly preferable.

Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or —O— (CH ₂ ) _s —, but at least one of them is a single bond in a PSA display element. A compound in which both represent a single bond or one 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 the alignment regulating power after polymerization, and a good alignment state can be obtained, so that display unevenness is suppressed or does not occur at all.

From the above, as the polymerizable compound, general formula (V-1) to general formula (V-4) are particularly preferable, and 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 in the absence of a polymerization initiator, 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 in the present invention is composed of a black matrix and at least an RGB three-color pixel unit. The RGB three-color pixel unit is used as a color material, as a G color material, and as an average in the G pixel unit by a small-angle X-ray scattering method. Contains a gallium, aluminum, scandium, yttrium or indium phthalocyanine pigment having a primary particle size of 5 to 50 nm. In addition, the RGB three-color pixel portion has a diketopyrrolopyrrole pigment and / or an anionic red organic dye in the R pixel portion and an ε-type copper phthalocyanine pigment and / or a cationic blue organic in the B pixel portion as the color material. It preferably contains a dye.

The average primary particle size can be measured by the small angle X-ray scattering method by the method described in JP-A-2006-114302.

Further, the normalized dispersion showing the particle size distribution by the small angle X-ray scattering method can be calculated by the method described in JP2013-96944A, and is preferably 20 to 50%. Note that the smaller the normalized dispersion value, the better the particle size distribution. When it exceeds 50%, coarse particles increase, and they appear on the surface of the color filter, leading to a decrease in the voltage holding ratio (VHR) of the liquid crystal layer and an increase in ion density (ID), white spots, alignment unevenness, baking, etc. It becomes a problem of display failure.
(G pixel part)
Examples of the gallium, aluminum, scandium, yttrium or indium phthalocyanine pigment in the G pixel portion include a pigment represented by the following general formula (PIG-1) and a pigment represented by the following general formula (PIG-2). . A phthalocyanine pigment corresponding to the general formula (PIG-1) or the general formula (PIG-2) may be used alone, or a plurality of pigments corresponding to the general formula (PIG-1) may be used. A plurality of pigments corresponding to the general formula (PIG-2) may be used, or both a pigment corresponding to the general formula (PIG-1) and a pigment corresponding to the general formula (PIG-2) may be used. .

(In the general formula (PIG-1), X ¹ⁱ to X ¹⁶ⁱ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, an optionally substituted sulfamoyl group, An alkyl group that may have a substituent, an aryl group that may have a substituent, a cycloalkyl group that may have a substituent, a heterocyclic group that may have a substituent, and a substituent. Y ¹ⁱ represents a hydroxyl group, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent. Represents a chlorine atom, —OP (═O) R1R2, or —O—SiR3R4R5, wherein R1 to R5 each independently have a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, or a substituent. Aryl group, substituted Represents an alkoxyl group which may have a group, or an aryloxy group which may have a substituent, and R1 and R2, and R3 to R5 may be bonded to each other to form a ring. And represents a trivalent metal selected from the group consisting of Al, Sc, Y and In.)

(In the general formula (PIG-2), X ¹⁷ⁱ to X ³²ⁱ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, an optionally substituted sulfamoyl group, An alkyl group that may have a substituent, an aryl group that may have a substituent, a cycloalkyl group that may have a substituent, a heterocyclic group that may have a substituent, and a substituent. Represents an alkoxyl group that may be substituted, an aryloxy group that may have a substituent, an alkylthio group that may have a substituent, or an arylthio group that may have a substituent, M represents Ga, Al Represents a trivalent metal selected from the group consisting of Sc, Y and In, Y ²ⁱ represents —O—, —O—SiR 6 R 7 —O—, —O—SiR 6 R 7 —O—SiR 8 R 9 —O—, or —O—. P (═O) R10—O— represents R6— R10 each independently has a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxyl group that may have a substituent, or a substituent. Represents an optionally substituted aryloxy group.)
In the above general formulas (PIG-1) and (PIG-2), examples of the phthalimidomethyl group which may have a substituent include phthalimidomethyl group, 3-chlorophthalimidomethyl group, 4- Examples include chlorophthalimidomethyl group, 3-nitrophthalimidomethyl group, 4-nitrophthalimidomethyl group, 3-sulfophthalimidomethyl group, 4-sulfophthalimidomethyl group and the like.

In the above general formula (PIG-1) and general formula (PIG-2), the sulfamoyl group which may have a substituent is a dimethylaminomethylsulfamide group, a diethylaminomethylsulfamide group, a dimethylaminoethylsulfamide group. , Diethylaminoethylsulfamide group, dimethylaminopropylsulfamide group, diethylaminopropylsulfamide group and the like.

In the general formulas (PIG-1) and (PIG-2), the alkyl group is more preferably an alkyl group having 1 to 8 carbon atoms, and more specifically, a methyl group, an ethyl group, or a propyl group. , An isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, an unsubstituted alkyl group; a 2-methoxyethyl group, a 2-ethoxyethyl group, and the like; 2 Acyloxy groups such as -acetyloxyethyl group; cyanoalkyl groups such as 2-cyanoethyl group; fluoroalkyl groups such as 2,2,2-trifluoroethyl group, 4,4,4-trifluorobutyl group, etc. It is done. Further, when the alkyl group has a substituent, the trichloromethyl group, 2,2-dibromoethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4 -Methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and the like.

In the above general formulas (PIG-1) and (PIG-2), examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group. In addition, when the aryl group has a substituent, chlorophenyl group, bromophenyl group, methylphenyl group, nitrophenyl group, methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-methyl-4 -Chlorophenyl group, 2-aminophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl Group and the like.

In the general formula (PIG-1) and general formula (PIG-2), the cycloalkyl group which may have a substituent is a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group. Examples of the “cycloalkyl group having a substituent” include a cyclohexylmethyl group, a cyclohexylethyl group, a 2,5-dimethylcyclopentyl group, a 4-tert-butylcyclohexyl group, and the like.

In the general formula (PIG-1) and the general formula (PIG-2), the heterocyclic group which may have a substituent is an aromatic or aliphatic group containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. Specific examples thereof include, for example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group. Group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group Naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl Group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidinyl group, inperidinyl group , Isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

In the general formulas (PIG-1) and (PIG-2), the alkoxyl group which may have a substituent is more preferably an alkoxyl group having 1 to 8 carbon atoms, more specifically, Methoxy group, ethoxy group, propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, t-butoxy group, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2 2,3,3-tetrafluoropropoxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

In the above general formula (PIG-1) and general formula (PIG-2), the aryloxy group which may have a substituent includes a phenoxy group, a naphthoxy group, an anthryloxy group, a 3-t-butylphenoxy group. 2,4-di-t-butylphenoxy group, p-methylphenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chloro Examples include phenoxy group.

In the above general formula (PIG-1) and general formula (PIG-2), the alkylthio group which may have a substituent is a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group. Group, decylthio group, dodecylthio group, octadecylthio group, methoxyethylthio group, aminoethylthio group, benzylaminoethylthio group, methylcarbonylaminoethylthio group, phenylcarbonylaminoethylthio group and the like.

In the above general formula (PIG-1) and general formula (PIG-2), the arylthio group which may have a substituent is phenylthio group, 1-naphthylthio group, 2-naphthylthio group, 9-anthrylthio group, chlorophenyl Examples thereof include a thio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, and a 2-hydroxyphenylthio group.

Specific examples of the metal phthalocyanine pigment represented by the general formula (PIG-1) include, for example, the compounds described below, but the present invention is not limited to these unless it exceeds the gist. Absent.

(N ^1k and n ^{1l in} 1k, 1l are integers from 1 to 16)
Specific examples of the metal phthalocyanine pigment represented by the general formula (PIG-2) include, for example, the compounds described below, but the present invention is not limited to these as long as the gist thereof is not exceeded. Absent.

(N ^2g1 and n ^{2g2 in the} general formula (2g) are each independently an integer of 1 to 16)
Further, it is preferable that a pigment derivative is contained as a dispersion aid in the G pixel portion. The pigment derivative preferably contains at least one of a phthalocyanine pigment derivative and a quinophthalone pigment derivative. Examples of the derivative portion include a phthalimidomethyl group, a sulfonic acid group, the same N- (dialkylamino) methyl group, and the same N- (dialkylaminoalkyl) sulfonic acid amide group. Two or more of these derivatives can be used in combination.

The amount of the pigment derivative used is preferably 4 parts or more and 20 parts or less, more preferably 6 parts or more, based on 100 parts of the total amount of the phthalocyanine pigment represented by the general formula (PIG-1) and / or the general formula (PIG-2). 16 parts or less are more preferable.

Furthermore, it is preferable that the G pixel portion contains one or more pigments selected from the quinophthalone compounds represented by the general formula (3), the general formula (4), and the general formula (5) as a hue adjustment. .

(In General Formula (3) to General Formula (5), R ₁₀ to R ₂₄ , R ₂₅ to R ₃₉ , and R ₄₀ to R ₅₅ each independently have a hydrogen atom, a halogen atom, or a substituent. A monovalent alkyl group, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, a —SO ₃ H group, a —COOH group, a —SO ₃ H group or a —COOH group Trivalent metal salt; an alkylammonium salt, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
In the general formulas (3) to (5), R ₁₀ to R ₂₄ , R ₂₅ to R ₃₉ , and R ₄₀ to R ₅₅ may each independently have a hydrogen atom, a halogen atom, or a substituent. An alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms which may have a substituent, an aryl group having 1 to 4 carbon atoms which may have a substituent, —SO ₃ H group, —COOH group, —SO ₃ H group or monovalent to trivalent metal salt of —COOH group; alkyl ammonium salt, phthalimidomethyl group which may have a substituent, or substituent A good sulfamoyl group is preferable, and examples of the substituent include a dimethylaminopropylsulfamoyl group and a diethylaminopropylsulfamoyl group.

Specific examples of the quinophthalone pigment represented by the general formula (3), the general formula (4), and the general formula (5) are represented by the following formulas (3a) to (5a). However, the present invention is not limited to these compounds as long as the gist of the present invention is not exceeded.

(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, 73, and brominated diketopyrrolopyrrole are preferable. From Red 254, 255, 264, and 272 One or more selected are 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.

Further, it is preferable to contain a pigment derivative as a dispersion aid. The pigment derivative preferably contains at least one of a quinacridone pigment derivative, a diketopyrrolopyrrole pigment derivative, an anthraquinone pigment derivative, and a thiazine pigment derivative. Examples of the derivative portion include a phthalimidomethyl group, a sulfonic acid group, the same N- (dialkylamino) methyl group, and the same N- (dialkylaminoalkyl) sulfonic acid amide group. Two or more of these derivatives can be used in combination.

The amount of the pigment derivative used is preferably 4 to 20 parts, more preferably 6 to 16 parts, based on 100 parts of the diketopyrrolopyrrole red pigment and / or anionic red organic dye.
(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 dye or a triarylmethane lake pigment is preferably contained.

As triarylmethane lake pigment, the following general formula (6)

(In the general formula (6), R ^11j to R ^16j are each independently a hydrogen atom, an ^optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted carbon number. Represents an aryl group of 1 to 8. When R ^11j to R ^16j represent an alkyl group which may have a substituent, adjacent R ^11j and R ^12j , R ^13j and R ^14j , R ^15j and R ^16j are combined with good .X ^11j and X ^12j also form a ring each independently represents a hydrogen atom, a halogen atom, or an alkyl group having a substituent and 1 carbon atoms which may have 8 .Z ^- Is a heteropolyoxometalate anion represented by (P ₂ Mo _y W _18-y O ₆₂ ) ^6- / 6 and an integer of y = 0, 1, 2, or 3, or (SiMoW ₁₁ O ₄₀ ) ⁴⁻ / Heteropolyoxometalate anion which is 4 , At least one anion selected from a deficient Dawson-type phosphotungstic acid heteropolyoxometalate anion, when a plurality of formulas (1) are contained in one molecule, they may have the same structure or different structures. A triarylmethane lake pigment represented by the following formula is preferred.

In the general formula (6), R ^11j to R ^16j may be the same or different. Accordingly, the —NRR (RR represents any combination of R ^11j R ^12j , R ^13j R ^14j , and R ^15j R ^16j ) group may be symmetric or asymmetric.

In the general formula (6), when adjacent Rs (R represents any one of R ^11j to R ^16j ) are bonded to form a ring, these may be a ring bridged with a heteroatom. Specific examples of this ring include the following. These rings may have a substituent.

In the general formula (6), R ^11j to R ^16j each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent from the viewpoint of chemical stability. An aryl group which may be present is preferable.

Among them, in the general formula (6), R ^11j to R ^16j are each independently a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, It is more preferably any of alkyl groups such as tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group and 2-ethylhexyl group, and aryl groups such as phenyl group and naphthyl group. .

When R ^11j to R ^16j represent an alkyl group or an aryl group, the alkyl group or aryl group may further have an arbitrary substituent. Examples of the optional substituent that the alkyl group or aryl group may further have include the following [Substituent group Y].

[Substituent group Y]
Methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, Alkyl groups such as 2-ethylhexyl group; aryl groups such as phenyl group and naphthyl group; halogen atoms such as fluorine atom and chlorine atom; cyano group; hydroxyl group; methoxy group, ethoxy group, propoxy group, butoxy group, etc. An alkoxy group of 8 to 8; an amino group which may have a substituent such as an amino group, a diethylamino group, a dibutylamino group or an acetylamino group; an acyl group such as an acetyl group or a benzoyl group; an acetyloxy group or a benzoyloxy group; And the like.

In the general formula (6), R ^11j to R ^16j are more preferably an alkyl group having 1 to 8 carbon atoms which may have a substituent, and more specifically, a methyl group, an ethyl group, or a propyl group. Group, isopropyl group, butyl group, isobutyl group, sec-butyl group, pentyl group, hexyl group, 2-ethylhexyl group, unsubstituted alkyl group; 2-methoxyethyl group, 2-ethoxyethyl group, etc .; Acyloxy groups such as 2-acetyloxyethyl groups; cyanoalkyl groups such as 2-cyanoethyl groups; fluoroalkyl groups such as 2,2,2-trifluoroethyl groups, 4,4,4-trifluorobutyl groups, etc. Can be mentioned.

In the general formula (6), when X ^11j and X ^12j are the above alkyl groups, they may further have an arbitrary substituent. Examples of these substituents include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and propoxy group. Specific examples of X ^11j and X ^12j include haloalkyl groups such as a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, and a 2,2,2-trifluoroethyl group; an alkoxyalkyl group such as a methoxymethyl group, and the like Is mentioned.

In the general formula (6), X ^11j and X ^12j are preferably a substituent having an appropriate steric hindrance such as a hydrogen atom, a methyl group, a chlorine atom or a trifluoromethyl group that does not affect the twist. . X ^11j and X ^12j are most preferably a hydrogen atom, a methyl group or a chlorine atom from the viewpoint of color tone and heat resistance.

Z ⁻ is a heteropolyoxometalate anion represented by (P ₂ Mo _y W _18-y O ₆₂ ) ⁶⁻ / 6 and an integer of y = 0, 1, 2, or 3, or (SiMoW ₁₁ O ₄₀ ) It is a triarylmethane compound of at least one anion selected from a heteropolyoxometalate anion represented by ^4- / 4 or a deficient Dawson-type phosphotungstic acid heteropolyoxometalate anion. Specifically, the deficient Dawson-type phosphotungstic acid is preferably a 1-deficient Dawson-type phosphotungstic acid heteropolyoxometalate anion (P ₂ W ₁₇ O ₆₁ ) ¹⁰⁻ / 10 from the viewpoint of durability.

Specific examples of the triarylmethane lake pigment represented by the general formula (6) include, for example, compounds described in the following Tables 1 to 7. The present invention includes these compounds as long as the gist thereof is not exceeded. It is not limited.

The RGB three-color pixel portion is a color material that contains C.I. I. Solvent Red 124, G pixel part contains gallium or aluminum phthalocyanine, B pixel part contains Pigment Blue 15: 6, and R pixel part and / or B pixel part contains a xanthene compound. preferable.

Specific examples of the xanthene compound include, for example, compounds represented by the following general formulas (7a) to (7b), but the present invention is not limited to these unless the gist is exceeded. It is not a thing.

(In the general formulas (7a) to (7b), R ^a represents ^a dodecyl group, R ^b represents a 2-ethylhexyl group, and R ^c represents a 2-ethylhexyl group.)
The RGB three-color pixel portion is further provided with C.I. I. Pigment Red 177, 242, 166, 167, 179, 269, 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 further includes 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 has a 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.

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

In the color filter according to the present invention, the chromaticity x and chromaticity y in the XYZ color system under the C light source of each pixel portion prevent a decrease in voltage holding ratio (VHR) and an increase in ion density (ID) of the liquid crystal layer. From the viewpoint of suppressing the occurrence of display defect problems such as white spots, uneven alignment, and baking, the following are preferable.

The chromaticity x in the XYZ color system under the C light source of the R pixel portion is preferably 0.58 to 0.69, more preferably 0.62 to 0.68, and the chromaticity y is 0. .30 to 0.36 is preferable, 0.31 to 0.35 is more preferable, chromaticity x is 0.58 to 0.69, and chromaticity y is 0.30 to 0. More preferably, the chromaticity x is 0.62 to 0.68, and the chromaticity y is 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 0.29, 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 0.29, and the chromaticity y is 0.64 to 0.74.

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

The chromaticity x in the XYZ color system under the C light source of the Y pixel portion is preferably 0.46 to 0.50, more preferably 0.47 to 0.48, and the chromaticity y is 0. .48 to 0.53 is preferable, 0.50 to 0.52 is more preferable, chromaticity x is 0.46 to 0.50, and chromaticity y is 0.48 to 0. More preferably, the chromaticity x is 0.47 to 0.48, and the chromaticity y is 0.50 to 0.52.

Here, the XYZ color system means a color system approved as a standard color system by the CIE (International Lighting Commission) in 1931.

The chromaticity in each of the pixel portions can be adjusted by changing the type of dyes and pigments used and their mixing ratio. 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 a 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 of 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 vary depending on the type of each component, the blending ratio, and the like, but are usually about 50 to 150 ° C. for about 1 to 15 minutes. 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 filling 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, Lubrizol Solsperse 3000, Solsperse 9000, Solsper 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 32000, Sol Sparse 36000, Sol Sparse 37000, Sol Sparse 1000, Sparse Sparse 4 42000, Solsperse 43000, Solsperse 46000, Solsperse 54000, Solsperse 71000, Ajinomoto Co., Inc. Ajisper PB711, Ajisper PB821, Ajisper PB822, Ajisper PB814, Ajisper PN411, Ajisper PA111, Natural rosin such as krill 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, rosinamine, lime rosin , A rosin alkylene oxide adduct, a rosin alkyd adduct, a rosin derivative such as rosin-modified phenol, and the like, and a synthetic resin that is liquid and insoluble at room temperature. 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. High molecular weight such as low molecular weight polyfunctional monomer, polyester acrylate, polyurethane acrylate, polyether acrylate, etc. Polyfunctional monomers.

Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethyl ketal, 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.

Also, a known and commonly used photosensitizer can be used in combination with the photopolymerization initiator. Examples of the photosensitizer include amines, ureas, compounds having a sulfur atom, compounds having a phosphorus atom, compounds having a chlorine atom, nitriles 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 photolithography method has been 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 micellar electrolysis. A color filter may be manufactured by forming each color pixel portion by a method such as a method, a PVED (Photovoltaic Electrodeposition) method, an ink jet method, a reverse printing method, or a thermosetting method.

A color filter may be used in a state where an organic pigment is applied to a substrate and dried, and when a curable resin is contained in the pigment dispersion, a color filter may be obtained by curing with heat or active energy rays. 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.
(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 greater.

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.

This liquid crystal display device and backlight are used in various applications such as LCD TVs, 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.

Hereinafter, the present invention will be described in more detail with reference to examples, 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]
[Green pigment coloring composition 1]
4.8 parts of the gallium phthalocyanine pigment 1 of the above general formula (1a) having a mean primary particle diameter of 25 nm and a normalized dispersion of 40% by a small angle X-ray scattering method, a yellow having a mean primary particle diameter of 30 nm and a normalized dispersion of 40% 47 parts of Pigment 1 (CI Pigment Yellow 138), 5 parts of a sulfonic acid derivative of Yellow 138, 7.0 parts of Dispersic LPN6919 (manufactured by Big Chemie Co., Ltd.) are placed in a polybin, 55 parts of propylene glycol monomethyl ether acetate, Add 0.3-0.4 mmφ 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 5 μm filter to obtain a pigment coloring liquid. .

75.00 parts of this pigment 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, benzophenone (KAYACURE (trade name) BP-100, Nippon Kayaku Co., Ltd.) 1.00 parts, and 13.5 parts Euker ester EEP are stirred with a dispersion stirrer, and the pore size is 1.0 μm. And a green pigment coloring composition 1 was obtained.

In the examples of the present invention, the average primary particle size and particle size distribution of the organic pigment are based on the small angle X-ray scattering profile (measured scattering profile) of the organic pigment dispersion based on the small angle X-ray scattering method disclosed in JP-A-2006-113042. It is obtained. The normalized dispersion indicating the particle size distribution by the small angle X-ray scattering method is calculated by the method described in JP2013-96944A.
[Green pigment coloring composition 2]
Instead of 4.8 parts of the gallium phthalocyanine pigment of the green pigment coloring composition 1, 4.5 parts of the aluminum phthalocyanine pigment 2 of the above general formula (1b) having an average primary particle diameter of 40 nm and a normalized dispersion of 50%, copper phthalocyanine Using 0.3 part of a sulfonic acid derivative, instead of yellow pigment 1 (CI Pigment Yellow 138), using a quinophthalone pigment of the above general formula (3a) having an average primary particle size of 30 nm and a normalized dispersion of 40% In the same manner as above, a green pigment coloring composition 2 was obtained.
[Green pigment coloring composition 3]
In place of 4.8 parts of the gallium phthalocyanine pigment 1 of the green pigment coloring composition 1, an aluminum phthalocyanine pigment 3 having an average primary particle diameter of 20 nm and a normalized dispersion of 35% and having the average number of bromine substituents of 8 in the general formula (1l) And 4.5 parts of copper phthalocyanine sulfonic acid derivative, and 47 parts of yellow pigment 1 (CI Pigment Yellow 138), the average primary particle diameter is 30 nm and the normalized dispersion is 40%. Using 20 parts of the quinophthalone pigment of the formula (3a), a green pigment coloring composition 3 was obtained in the same manner as described above.

[Green pigment coloring composition 4]
In place of 4.8 parts of the gallium phthalocyanine pigment 1 of the green pigment coloring composition 1, the mixture is a mixture of the above general formula (1b) / (2a) = 95/5 having an average primary particle diameter of 25 nm and a normalized dispersion of 45%. Using 4.5 parts of aluminum phthalocyanine pigment 4 and 0.3 parts of copper phthalocyanine sulfonic acid derivative, instead of yellow pigment 1 (CI Pigment Yellow 138), the average primary particle diameter is 20 nm, and the normalized dispersion is 35%. Using the quinophthalone pigment which is the compound of (4a), a green pigment coloring composition 5 was obtained in the same manner as described above.

[Green pigment coloring composition 5]
In place of 4.8 parts of the gallium phthalocyanine pigment 1 of the green pigment coloring composition 1, an aluminum phthalocyanine pigment having an average primary particle size of 30 nm and a normalized dispersion of 50% and having an average bromine group of 8 substituents of the general formula (1l) / (2g) 4.5 parts of aluminum phthalocyanine pigment 5 which is a mixture of dialuminum phthalocyanine pigment = 97/3 having an average number of bromine substituents of 8 = 0.3 parts of copper phthalocyanine sulfonic acid derivative, and yellow pigment 1 ( CI Pigment Yellow 138) Instead of 47 parts, using 20 parts of quinophthalone pigment, which is a compound of (4a) having an average primary particle size of 20 nm and a normalized dispersion of 35%, a green pigment is colored in the same manner as described above. Composition 5 was obtained.

[Green pigment coloring composition 6]
Instead of 4.8 parts of the gallium phthalocyanine pigment 1 of the green pigment coloring composition 1, 4.8 parts of the aluminum phthalocyanine pigment 6 of the general formula (1b) having an average primary particle diameter of 55 nm and a normalized dispersion of 65% are used. In the same manner as above, a green pigment coloring composition 6 was obtained.
[Red pigment coloring composition 1]
10 parts of red pigment 1 (CI Pigment Red 254) having an average primary particle diameter of 25 nm and a normalized dispersion of 40% in a small angle X-ray scattering method is placed in a polybin, 55 parts of propylene glycol monomethyl ether acetate, Dispersic LPN21116 ( After adding 7.0 parts of Saint-Gobain's 0.3-0.4mmφ zirconia beads “ER-120S” and dispersing with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, 1 μm Filtration through a filter gave a pigment dispersion. 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, benzophenone (KAYACURE (trade name) BP-100, Nippon Kayaku Co., Ltd.) 1.00 parts, and 13.5 parts Euker ester EEP are stirred with a dispersion stirrer, and the pore size is 1.0 μm. And a red pigment coloring composition 1 was obtained.
[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.
[Blue pigment coloring composition 1]
1.80 parts of triarylmethane lake pigment represented by the general formula (6) (Table 1 Compound No. 2), 2.10 parts of BYK-2164 (Bic Chemie), 11.10 parts of propylene glycol monomethyl ether acetate, 0.3-0.4 mmφ Sepul beads were placed in a polybin and dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours to obtain a pigment dispersion. 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 Co., Ltd.) 5.00 parts of a company), 1.00 parts of benzophenone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.), and 13.5 parts of Euker ester EEP (manufactured by Union Carbide) with a dispersion stirrer. And it filtered with the filter of 1.0 micrometer of hole diameters, and obtained the blue pigment coloring composition 1.
[Blue pigment coloring composition 2]
The average primary particle diameter in a small angle X-ray scattering method is 20 nm, normalized dispersion 50% blue pigment (CI Pigment Blue 15: 6) 1.80 parts, 0.18 parts of the xanthene compound of the general formula (7a), BYK-LPN21116 (Bic Chemie) 2.84 parts, propylene glycol monomethyl ether acetate 10.19 parts, Saint-Gobain 0.3-0.4mmφ zirconia beads “ER-120S” are put in a polybin, and paint conditioner (Toyo For 4 hours to obtain a pigment dispersion. 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 Co., Ltd.) 5.00 parts of a company), 1.00 parts of benzophenone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.), and 13.5 parts of Euker ester EEP (manufactured by Union Carbide) with a dispersion stirrer. And filtered through a filter having a pore diameter of 1.0 μm to obtain a blue pigment coloring composition 2.
[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, with respect to the blue coloring composition, red pixels and blue pixels adjacent to the green pixels were similarly 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 5 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 G pixel portion of the obtained color filters 1 to 5, when any five points were observed with a Nikon optical microscope Optiphot 2 at a magnification of 2000, coarse particles of 1000 nm or more were not observed in any of them. It was.
(Measurement of color filters 1 to 6 with USAXS)
The G pixel portions of the color filters 1 to 5 were affixed 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 by the method described in JP 2013-96944 A and analyzing the results, 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 obtained. A primary particle, similarly, a distribution of 40 nm or more and less than 100 nm is represented as a secondary particle, and a distribution of 100 nm or more and 1000 nm or less is represented as a tertiary particle.

As a result of the above measurement and analysis, the volume fraction of primary particles represented by the distribution of the average particle diameter of 1 nm or more and less than 40 nm in the G pixel portion of the color filters 1 to 5 is 81 to 91%, and the distribution is 40 nm or more and less than 100 nm. The volume fraction of secondary particles represented is 9 to 19%, 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 9-19%.

In comparison, the volume fraction of primary particles represented by a distribution having an average particle diameter of 1 nm or more and less than 40 nm in the G pixel portion of the color filter 6 is 74%, and the volume of secondary particles represented by a distribution of 40 nm or more and less than 100 nm. The volume fraction of tertiary particles represented by a distribution of 21%, a distribution of 100 nm to 1000 nm was 5%, and the volume fraction of particles of 40 nm to 1000 nm was 25%.

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 in a C light source of the CIE1931 XYZ color system were measured using a color filter microspectrophotometer LCF-100 manufactured by Otsuka Electronics. 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 of the obtained liquid crystal display device was measured. The obtained liquid crystal display device was evaluated for burn-in. The results are shown in the table below.

It can be seen that the liquid crystal composition 1 has a liquid crystal phase temperature range of 79 ° C. that is practical as a liquid crystal composition for TV, and has a low viscosity and an optimal Δn.

The liquid crystal display devices of Examples 1 to 5 were able to realize a high VHR. 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 table below 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, and the VHR is measured. did. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

The liquid crystal display devices of Examples 6 to 15 were able to realize a high VHR. 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 were sandwiched, and the liquid crystal display devices of Examples 16 to 30 were prepared using the color filters 1 to 5 shown in the above table, and the VHR was measured. did. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

The liquid crystal display devices of Examples 16 to 30 were able to realize a high VHR. 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 50)
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. A liquid crystal composition 10 shown in the following table was 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 of the obtained liquid crystal display device was 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 50 were able to realize high VHR. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.
(Examples 51 to 55)
A liquid crystal composition 11 was prepared by mixing 0.3 mass% of biphenyl-4,4′-diyl bismethacrylate with 89.7 mass% of the liquid crystal composition 8 used in Example 36. The liquid crystal composition 11 was sandwiched between TN 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 a polymerization treatment. Liquid crystal display devices of Examples 51 to 55 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 51 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 60)
A liquid crystal composition 12 was prepared by mixing 0.3 mass% of biphenyl-4,4′-diyl bismethacrylate with 99.7 mass% of the liquid crystal composition 9 used in Example 41. The liquid crystal composition 12 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, and then the color shown in the above table. Liquid crystal display devices of Examples 76 to 80 were prepared using filters 1 to 5, and their VHR 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 60 were able to realize high VHR. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.
(Examples 61 to 65)
Liquid crystal composition 13 was prepared by mixing 0.3% by mass of bismethacrylic acid 3-fluorobiphenyl-4,4′-diyl with 99.7% by mass of liquid crystal composition 10 used in Example 46. The liquid crystal composition 13 was sandwiched between FFS cells, and a polymerization treatment was performed by irradiating with ultraviolet rays (3.0 J / cm ² ) for 600 seconds while applying a driving voltage between the electrodes. Liquid crystal display devices of Examples 61 to 65 were produced using filters 1 to 5, and their VHR 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 61 to 65 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 produced using the color filters 1 to 5 shown in the above table, and their VHR was measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

In the liquid crystal display devices of Comparative Examples 1 to 5, the VHR was lower than that of 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 6 to 10)
The liquid crystal display devices of Comparative Examples 6 to 10 were prepared using the color filters 1 to 5 shown in the above table by sandwiching the comparative liquid crystal composition 2 shown in the following table in the same manner as Example 1, and the VHR was measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.

In the liquid crystal display devices of Comparative Examples 6 to 10, the VHR was lower than that of 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 111 to 15)
As in Example 1, the liquid crystal display devices of Comparative Examples 11 to 15 were prepared by sandwiching the comparative liquid crystal composition 3 shown in the following table and using the color filters 1 to 5 shown in the above table, and the VHR 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 11 to 15 were not at an acceptable level because afterimages were observed in the burn-in evaluation as compared with the liquid crystal display devices of the present invention.
(Comparative Examples 16 to 20)
In the same manner as in Example 1, the comparative liquid crystal composition 4 shown in the following table was sandwiched, and the liquid crystal display devices of Comparative Examples 16 to 20 were produced using the color filters 1 to 5 shown in the above table, and the VHR was measured. .

In the liquid crystal display devices of Comparative Examples 16 to, the VHR was lower than that of 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 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.

In the liquid crystal display devices of Comparative Examples 21 to 25, VHR was lower than that of 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 33)
In the same manner as in Examples 1, 16, 21, 26, 31, 36, 41, and 46, except that the comparative color filter 1 shown in the above table was used instead of the color filter 1, the liquid crystal display devices of Comparative Examples 56 to 63 were used. The VHR was measured and ID was also measured for the TN cell. 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 33 had a lower VHR 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.

Claims

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-1)

(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 32 each independently represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group, and one —CH 2 — in the trans-1,4-cyclohexylene group is The oxygen atom may be substituted with —O— so that the oxygen atom is not directly adjacent, one or two hydrogen atoms in the phenylene group may be substituted with a fluorine atom, and M 33 is 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. Replaced with- May have, one or two hydrogen atoms in the phenylene group may be substituted with a fluorine atom, X 31 and X 32 represents a hydrogen atom or a fluorine atom independently of one another, Z 31 is a fluorine atom Represents 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 31 and M 33 In the presence of a plurality of compounds, the compounds may be the same or different.)
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 RGB three-color pixel portion has a first group represented by the following general formula (PIG-1) having an average primary particle diameter of 5 to 50 nm in the G pixel portion as a colorant and 5 to 50 nm in the G pixel portion, and / or A liquid crystal display device comprising at least one metal phthalocyanine pigment selected from the second group represented by the following general formula (PIG-2).

(In the general formula (PIG-1), X 1i to X 16i each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, an optionally substituted sulfamoyl group, An alkyl group that may have a substituent, an aryl group that may have a substituent, a cycloalkyl group that may have a substituent, a heterocyclic group that may have a substituent, and a substituent. Y 1i represents a hydroxyl group, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent. Represents a chlorine atom, —OP (═O) R1R2, or —O—SiR3R4R5, wherein R1 to R5 each independently have a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, or a substituent. Aryl group, substituted Represents an alkoxyl group which may have a group, or an aryloxy group which may have a substituent, and R1 and R2, and R3 to R5 may be bonded to each other to form a ring. , Represents a trivalent metal selected from the group consisting of Al, Sc, Y and In).

(In the general formula (PIG-2), X 17i to X 32i each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, an optionally substituted sulfamoyl group, An alkyl group that may have a substituent, an aryl group that may have a substituent, a cycloalkyl group that may have a substituent, a heterocyclic group that may have a substituent, and a substituent. Represents an alkoxyl group that may be substituted, an aryloxy group that may have a substituent, an alkylthio group that may have a substituent, or an arylthio group that may have a substituent, M represents Ga, Al Represents a trivalent metal selected from the group consisting of Sc, Y and In, Y 2i represents —O—, —O—SiR 6 R 7 —O—, —O—SiR 6 R 7 —O—SiR 8 R 9 —O—, or —O—. P (═O) R10—O— represents R6— R10 each independently has a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxyl group that may have a substituent, or a substituent. Represents an optionally substituted aryloxy group.)
The RGB three-color pixel portion has, as a color material, a diketopyrrolopyrrole pigment and / or an anionic red organic dye in the R pixel portion, an ε-type copper phthalocyanine pigment, a triarylmethane dye, a triaryl in the B pixel portion. The liquid crystal display device according to claim 1, comprising at least one selected from the group consisting of methane lake pigments and cationic blue organic dyes.
The liquid crystal display device according to claim 1, wherein the G pixel portion contains a pigment derivative.
General formula (3), general formula (4) and general formula (5) in the G pixel portion.

(In General Formula (3) to General Formula (5), R 10 to R 24 , R 25 to R 39 , and R 40 to R 56 each independently have a hydrogen atom, a halogen atom, or a substituent. A monovalent alkyl group, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, a —SO 3 H group, a —COOH group, a —SO 3 H group or a —COOH group One or more pigments selected from quinophthalone compounds represented by trivalent metal salts; alkylammonium salts, optionally substituted phthalimidomethyl groups, or optionally substituted sulfamoyl groups. The liquid crystal display device according to any one of claims 1 to 3, comprising:
The compound represented by the general formula (I-1) is 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.
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 5, comprising two or more kinds.
The liquid crystal display device according to any one of claims 1 to 6, wherein the liquid crystal composition layer is composed of a polymer obtained by polymerizing a liquid crystal composition containing one or more polymerizable compounds.
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 7, which comprises a bifunctional monomer represented by formula (1).