TW201918761A - Liquid crystal display capable of reducing voltage holding ratio, increasing ion density caused by white spots, uneven alignment, and burn-in - Google Patents

Abstract

The present invention relates to a liquid crystal display that incorporates a particular liquid crystal composition and a color filter that uses specific pigments and specific compounds. The present invention provides a liquid crystal display that prevents reduced voltage holding ratio (VHR) and increased ion density (ID) in the liquid crystal layer and solves the problems of display defects such as white spots, uneven alignment, and burn-in. The liquid crystal display device of the present invention is characterized in that it has display defects such as the voltage holding ratio (VHR) of the liquid crystal layer being prevented from decreasing, the ion density (ID) being increased, and is burning being suppressed, so that in particular it is useful for liquid crystal display of VA modes, PSVA mode, and FFS mode for active matrix driving, and is applicable to liquid crystal display devices such as liquid crystal TVs, monitors, mobile phones, and smartphones.

Description

Liquid crystal display device

The invention relates to a liquid crystal display device.

The liquid crystal display device is typified by clocks and desk calculators and is used in various household electrical appliances, measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, and the like. As the liquid crystal display mode, representative examples include: twisted nematic (TN) type, super twisted nematic (STN) type, dynamic light scattering (DS) type, guest-host ( guest host (GH) type, in-plane switching (IPS) type, optically compensated birefringence (OCB) type, electrically controlled birefringence (ECB) type, vertical alignment alignment (VA) type, color super homeotropic (CSH) type, or ferroelectric liquid crystal (FLC). In addition, as a driving method, a conventional static driving is changed to a multiplex driving, a simple matrix method, a thin film transistor (TFT) or a thin film diode (TFD), etc. Driven active matrix (AM) methods have become mainstream.

As shown in FIG. 1, a general color liquid crystal display device includes a transparent electrode layer (3 a) and a color electrode serving as a common electrode between one of the two substrates (1) each having an alignment film (4) and the substrate. The filter layer (2) includes a pixel electrode layer (3b) between the other alignment film and the substrate, and the substrates are arranged so that the alignment films face each other, and a liquid crystal layer (5) is sandwiched therebetween. Make up.

The color filter layer includes a color filter including a black matrix and a red coloring layer (R), a green coloring layer (G), a blue coloring layer (B), and a yellow coloring layer (Y) as needed.

If impurities are left in the liquid crystal material constituting the liquid crystal layer, the electrical characteristics of the display device will be greatly affected. Therefore, impurities are being highly managed. In addition, as for the material for forming the alignment film, it is also known that the alignment film is in direct contact with the liquid crystal layer, and impurities remaining in the alignment film move toward the liquid crystal layer, thereby affecting the electrical characteristics of the liquid crystal layer. Study on the characteristics of liquid crystal display devices caused by impurities in film materials.

On the other hand, regarding materials such as organic pigments used for the color filter layer, the effect on the liquid crystal layer due to impurities contained in the alignment film material can be expected similarly to 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 is considered that the direct influence on the liquid crystal layer is significantly reduced compared to the alignment film material. However, the film thickness of the alignment film is usually only 0.1 μm or less, and the common electrode used for the color filter layer side of the transparent electrode is usually 0.5 μm or less even if the film thickness is increased in order to increase the conductivity. Furthermore, the development of a liquid crystal display device without an alignment film has been continuously advanced. Therefore, it cannot be said that the color filter layer and the liquid crystal layer are placed in a completely isolated environment. It is possible that impurities in the color filter layer may be contained in the color filter layer through the alignment film and the transparent electrode in the color filter layer. The display of the liquid crystal layer has a poor voltage holding ratio (VHR), white spots, uneven alignment, and poor adhesion caused by an increase in ion density (ID).

As a method for solving display defects caused by impurities contained in pigments constituting a color filter, research is being conducted on a method in which impurities are controlled by using a pigment in which the ratio of an ethyl formate extract of the pigment is equal to or less than a specific value. A method for elution of liquid crystals (Patent Document 1) or a method for controlling the elution of impurities into liquid crystals by identifying a pigment in a blue colored layer (Patent Document 2). However, in these methods, there is no big difference when simply reducing the impurities in the pigment. In recent years, with the continuous progress of the purification technology of the pigment, the improvement to solve the display defects is still insufficient.

On the other hand, focusing on the relationship between the organic impurities contained in the color filter and the liquid crystal composition, it is disclosed that the hydrophobicity parameters of the liquid crystal molecules contained in the liquid crystal layer indicate the organic impurities in the liquid crystal layer. A method of dissolving difficulty and setting the value of the hydrophobicity parameter to a certain value or more, or the hydrophobicity parameter has a correlation with the -OCF ₃ group at the end of the liquid crystal molecule, so it is made to contain A method of a liquid crystal composition of a liquid crystal compound having an -OCF ₃ group at a molecular terminal (Patent Document 3).

However, in the publication of the cited document, the suppression of the effect on the liquid crystal layer caused by impurities in the pigment has become the essence of the invention. The direct relationship between the two is studied, and the problem of poor display of the advanced liquid crystal display device is not solved. [Prior Art Literature] [Patent Literature]

[Patent Literature 1] Japanese Patent Laid-Open No. 2000-19321 [Patent Literature 2] Japanese Patent Laid-Open No. 2009-109542 [Patent Literature 3] Japanese Patent Laid-Open No. 2000-192040

[Problems to be Solved by the Invention] The present invention provides a method of preventing a decrease in voltage retention (VHR) and an increase in ion density (ID) of a liquid crystal layer by using a specific liquid crystal composition and a color filter using a specific pigment. A liquid crystal display device that solves the problems of poor display such as white spots, uneven alignment, and burning. [Technical means to solve the problem]

In order to solve the above problems, the inventors of the present application have made intensive research on the combination of color materials such as dyes and pigments used to form a color filter and the liquid crystal material used to form a liquid crystal layer. As a result, it has been found that a liquid crystal having a specific structure is used. Materials and liquid crystal display devices using pigments and compounds with specific structures prevent color voltage drop (VHR) and increase in ion density (ID) of the liquid crystal layer, and solve problems such as white spots, uneven alignment, and burn-in. The problem was solved and the invention of the present application was completed.

That is, the present invention provides a liquid crystal display device including a first substrate, a second substrate, a liquid crystal layer sandwiched between the first substrate and the second substrate, a color including a black matrix and at least three RGB pixel portions. A filter, a pixel electrode and a common electrode, the liquid crystal layer contains a liquid crystal composition, and the liquid crystal composition has a general formula (I) of 10% to 50% by weight;

[Chemical 1]

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or 2 to 8 carbon atoms. Compound represented by alkenyloxy) and having a general formula (II) of 35% to 80% by weight

[Chemical 2]

(In the formula, R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or 2 to 8 carbon atoms. Alkenyloxy, Z ³ and Z ⁴ each independently represent a single bond, -CH = CH-, -C≡C-, -CH ₂ CH ₂ -,-(CH ₂ ) _4- , -COO-, -OCO -, -OCH _2- , -CH ₂ O-, -OCF ₂ -or -CF ₂ O-, B and C each independently represent a fluorine-substituted 1,4-phenylene group or trans-1,4 -Cyclohexylene, m and n each independently represent an integer of 0 to 4, and m + n = 1 to 4), the RGB tri-color pixel portion contains at least one selected from the G pixel portion The first group represented by the following general formula (PIG-1) and / or the second group represented by the following general formula (PIG-2) with an average primary particle diameter of 5 to 50 nm by a small-angle X-ray scattering method. group

[Chemical 3]

(In the general formula (PIG-1), X ¹ⁱ to X ¹⁶ⁱ each independently represent a halogen atom, a nitro group, a phthalimideimide methyl group which may have a substituent, an sulfamoyl group which may have a substituent, An alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, and an aryloxy group which may have a substituent Group, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent. Y ¹ⁱ represents a hydroxyl group, a chlorine atom, -OP (= O) R1R2, or -O-SiR3R4R5. Here, R1 to R5 are respectively Independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent, R1 and R2, R3 to R5 They can be bonded to each other to form a ring. M represents a trivalent metal selected from the group consisting of Ga, Al, Sc, Y, and In)

[Chemical 4]

(Formula (PIG-2) in, X ¹⁷ⁱ ~ X ³²ⁱ each independently represent a halogen atom, a nitro group, a phthaloyl may have substituent (PEI) methyl group, a sulfo acyl amine may have a substituent, An alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, and an aryloxy group which may have a substituent Group, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent. M represents a trivalent metal selected from the group consisting of Ga, Al, Sc, Y, and In. Y ²ⁱ represents -O -, -O-SiR6R7-O-, -O-SiR6R7-O-SiR8R9-O-, or -OP (= O) R10-O-, R6 to R10 each independently represent a hydrogen atom, a hydroxyl group, and may have a substituent The metal phthalocyanine pigment in an alkyl group, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent) is used as a color material.

[Effects of the Invention] The liquid crystal display device of the present invention can prevent a decrease in the voltage holding ratio (VHR) of the liquid crystal layer and an ion density (by using a specific liquid crystal composition and a color filter using a specific pigment and a specific compound). ID) increase, and can prevent the appearance of white spots, uneven alignment, and poor display.

An example of the liquid crystal display device of the present invention is shown in FIG. 2. A transparent electrode layer (3a) serving as a common electrode is included between one of the two substrates (1) of the first substrate and the second substrate having the alignment film (4) and the substrate, and contains a specific pigment and a specific The compound's color filter layer (2a) includes a pixel electrode layer (3b) between the other alignment film and the substrate, and these substrates are arranged so that the alignment films face each other, and a specific The liquid crystal layer (5a) of the liquid crystal composition.

The two substrates in the display device are bonded by using a sealing material and a sealing material arranged in a peripheral area. In most cases, a granular spacer is arranged to maintain a distance between the substrates or is formed by a photolithography method. Spacer containing resin. (Liquid Crystal Layer) The liquid crystal layer in the liquid crystal display device of the present invention contains a liquid crystal composition containing 10 to 50% by weight of the general formula (I)

[Chemical 5]

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or 2 to 8 carbon atoms. Compound represented by alkenyloxy), and contains 35% to 80% by weight of general formula (II)

[Chemical 6]

(In the formula, R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or 2 to 8 carbon atoms. Alkenyloxy, Z ³ and Z ⁴ each independently represent a single bond, -CH = CH-, -C≡C-, -CH ₂ CH ₂ -,-(CH ₂ ) _4- , -COO-, -OCO -, -OCH _2- , -CH ₂ O-, -OCF ₂ -or -CF ₂ O-, B and C each independently represent a fluorine-substituted 1,4-phenylene group or trans-1,4 -A cyclohexylene group, m and n each independently represent an integer of 0 to 4, and a compound represented by m + n = 1 to 4).

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

In the general formula (I), R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or carbon number. The alkenyloxy group of 2 to 8 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or 2 to 5 carbon atoms. Alkenyloxy is more preferably an alkyl group having 2 to 5 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, R ¹ preferably represents an alkyl group, in which case an alkyl group having 2, 3 or 4 carbon atoms is particularly preferred. When R ¹ represents an alkyl group having 3 carbon atoms, it is preferred that R ² is an alkyl group having 2, 4 or 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, and R ^{2 is} more preferred. In the case of an alkyl group having 2 carbon atoms.

The content of the compound represented by the general formula (I) in which at least one group of R ¹ and R ² is an alkyl group having 3 to 5 carbon atoms is preferably 50% by weight or more of the compound represented by the general formula (I), and more preferably It is preferably 70% by weight or more, and more preferably 80% by weight or more. The content of the compound represented by the general formula (I) in which at least one group of R ¹ and R ² is an alkyl group having 3 carbon atoms is preferably 50% by weight or more of the compound represented by the general formula (I), and more preferably It is preferably 70% by weight or more, more preferably 80% by weight or more, and most preferably 100% by weight.

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

[Chemical 7]

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, but are preferably the same as R ¹ and R ² in the general formula (I). The same embodiment) Among general formulas (Ia) to (If), general formula (Ia), general formula (Ib), and general formula (Ic) are preferred, and general formula (Ia) and general formula (Ia) are more preferred. Ib). When the response speed is important, the general formula (Ib) and the general formula (Ic) are preferred, and the general formula (Ib) and the general formula (Ic) are used in combination. When reliability is important, general formula (Ia) is preferable.

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

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

[Chemical 8]

In the general formula (I-1), R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or carbon The alkenyloxy group having 2 to 8 atoms, and R ¹ is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or 2 carbon atoms. Alkenyl to 5 is more preferably an alkyl group having 1 to 5 carbon atoms, alkenyl having 2 to 5 carbon atoms, and R ² is preferably an alkyl group having 1 to 5 carbon atoms and 4 carbon atoms. Alkenyl to 5, alkoxy having 1 to 5 carbon atoms or alkenyl to 3 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or an alkane having 1 to 5 carbon atoms The oxy group and R ¹ preferably represent an alkyl group, and in this case, an alkyl group having 1, 3 or 5 carbon atoms is particularly preferred. Furthermore, R ² is preferably an alkoxy group having 1, 2, or 4 carbon atoms.

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

[Chemical 9]

(Wherein R ¹ and R ² each independently represent an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, but are preferably the same as R ¹ and R ¹ in the general formula (I-1) The same embodiment of R ² ) The liquid crystal layer in the liquid crystal display device of the present invention contains 35% to 80% by weight of a compound represented by the general formula (II), but preferably contains 40% to 75% by weight, and more preferably It contains 42 to 70 weight%.

[Chemical 10]

(In the formula, R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or 2 to 8 carbon atoms. Alkenyloxy, Z ³ and Z ⁴ each independently represent a single bond, -CH = CH-, -C≡C-, -CH ₂ CH ₂ -,-(CH ₂ ) _4- , -COO-, -OCO -, -OCH _2- , -CH ₂ O-, -OCF ₂ -or -CF ₂ O-, B and C each independently represent a fluorine-substituted 1,4-phenylene group or trans-1,4 -Cyclohexylene, m and n each independently represent an integer of 0 to 4, m + n = 1 to 4) In the general formula (II), R ³ represents an alkyl group having 1 to 8 carbon atoms, and 2 carbon atoms Alkenyl to 8, alkoxy having 1 to 8 carbon atoms or alkenyl to 2 to 8 carbon atoms, but preferably an alkyl group having 1 to 5 carbon atoms or an olefin having 2 to 5 carbon atoms Group is more preferably an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, and still more preferably an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 or 3 carbon atoms, It is particularly preferably an alkyl group having 2 or 3 carbon atoms or an alkenyl group having 2 carbon atoms, and most preferably an alkyl group having 2 or 3 carbon atoms.

R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyl group having 3 to 8 carbon atoms, but preferably represents carbon The alkyl group having 1 to 5 carbon atoms or the alkoxy group having 1 to 5 carbon atoms is more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and more preferably carbon Alkoxy having 2 to 4 atoms.

Z ³ and Z ⁴ each independently represent a single bond, -CH = CH-, -C≡C-, -CH ₂ CH ₂ -,-(CH ₂ ) _4- , -COO-, -OCO-, -OCH ₂ -, -CH ₂ O-, -OCF ₂ -or -CF ₂ O-, but preferably represents a single bond, -CH ₂ CH _2- , -COO-, -OCH _2- , -CH ₂ O-, -OCF ₂ -or -CF ₂ O-, more preferably a single bond, -CH ₂ CH ₂ -or -CH ₂ O-.

m and n are each preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and m + n is preferably 1 to 3, and more preferably 1 to 2.

The liquid crystal layer in the liquid crystal display device of the present invention may contain three to ten compounds represented by the general formula (II), but preferably contains four to nine compounds, and more preferably contains five to eight compounds.

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

[Chemical 11]

In the formula, R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or 2 to 8 carbon atoms. Alkenyloxy, Z ⁵ represents a single bond, -CH = CH-, -C≡C-, -CH ₂ CH ₂ -,-(CH ₂ ) _4- , -COO-, -OCO-, -OCH _2- , -CH ₂ O-, -OCF _2- , or -CF ₂ O-, and m1 represents 0 or 1.

In the general formula (II-1), R ³ is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an alkyl group or carbon atom having 2 to 5 carbon atoms. The alkenyl group having 2 to 4 is more preferably an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 carbon atoms, particularly preferably an alkyl group having 3 carbon atoms, and R ⁴ is preferably a carbon atom The 1 to 5 alkyl group or the alkoxy group having 1 to 5 carbon atoms is more preferably an alkyl group having 1 to 3 carbon atoms or the alkoxy group having 1 to 3 carbon atoms, and still more preferably a carbon number An alkyl group of 3 or an alkoxy group having 2 carbon atoms is particularly preferably an alkoxy group having 2 carbon atoms, and Z ⁵ is preferably a single bond, -CH ₂ CH _2- , -COO-, -OCH _2- , -CH ₂ O-, -OCF ₂ -or -CF ₂ O-, more preferably a single bond or -CH ₂ O-.

The liquid crystal layer in the liquid crystal display device of the present invention preferably contains 3 to 60% by weight of a compound represented by the general formula (II-1), more preferably contains 5 to 55% by weight, and further preferably contains 8%. It is particularly preferably contained in an amount of 10% to 40% by weight.

The liquid crystal layer in the liquid crystal display device of the present invention may contain one or two or more compounds represented by the general formula (II-1), but preferably contains one to six, more preferably two to five, and further It preferably contains three or four.

The compound represented by general formula (II-1) is specifically preferably a compound represented by general formula (II-1a) to general formula (II-1d) described below.

[Chemical 12]

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

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

In the general formulae (II-1a) to (II-1d), in order to increase the absolute value of the dielectric constant anisotropy, the general formulae (II-1a) and (II-1c) are more preferable, and more preferable It is the general formula (II-1a).

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

In addition, the compound represented by the general formula (II-1) is also preferably a compound represented by the general formula (II-1e) to the general formula (II-1h) described below.

[Chemical 13]

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

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

In the general formulae (II-1e) to (II-1h), in order to increase the absolute value of the dielectric anisotropy, the general formulae (II-1e) and (II-1g) are preferred.

[Chemical 14]

In the general formula (II-2), R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a carbon Alkenyloxy groups 2 to 8 and Z ⁶ and Z ⁷ each independently represent a single bond, -CH = CH-, -C≡C-, -CH ₂ CH ₂ -,-(CH ₂ ) ₄ -,- COO-, -OCO-, -OCH _2- , -CH ₂ O-, -OCF ₂ -or -CF ₂ O-, D represents 1,4-phenylene or trans-1,4 which may be substituted by fluorine -Cyclohexylene, m2 and n2 each independently represent 0 or 1.

In the general formula (II-2), R ³ is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an alkyl group or carbon atom having 2 to 5 carbon atoms. The alkenyl group having 2 to 4 is more preferably an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 carbon atoms, particularly preferably an alkyl group having 2 or 3 carbon atoms, and R ⁴ is preferably carbon An alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and further preferably carbon An alkyl group having 3 atoms or an alkoxy group having 2 carbon atoms.

In the general formula (II-2), Z ⁶ preferably represents a single bond, -CH ₂ CH _2- , -COO-, -OCH _2- , -CH ₂ O-, -OCF _2- , or -CF ₂ O-, More preferably, it represents a single bond or -CH ₂ O-.

In the general formula (II-2), Z ⁷ preferably represents a single bond, -CH ₂ CH _2- , -COO-, -OCH _2- , -CH ₂ O-, -OCF _2- , or -CF ₂ O-, More preferably, it represents a single bond or -CH ₂ CH _2- .

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

Specifically, the compound represented by general formula (II-2) is preferably a compound represented by general formula (II-2a) to general formula (II-2d) described below.

[Chemical 15]

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

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

In the general formulae (II-2a) to (II-2d), in order to increase the absolute value of the dielectric constant anisotropy, the general formulae (II-2a) and (II-2c) are preferred, and particularly preferred It is the general formula (II-2a).

In addition, the compound represented by the general formula (II-2) is also preferably a compound represented by the general formula (II-2e) to the general formula (II-2k) described below.

[Chemical 16]

[Chemical 17]

(In the general formulae (II-2e) to (II-2k), R ³ represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^4d represents 1 carbon atom. ~ 5 alkyl group, but preferably the same embodiment as R ³ and R ⁴ in the general formula (II-2), respectively) General formula (II-2e), general formula (II-2g), and general formula (II R ^{3 in} -2i) is preferably the same embodiment as in the general formula (II-2). R ^4d is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably an alkyl group having 2 carbon atoms.

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

R ^{3 in the} general formula (II-2k) is preferably the same embodiment in the general formula (II-2). R ^4d is preferably an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 or 3 carbon atoms and an alkoxy group having 1 to 2 carbon atoms, and particularly It is preferably an alkyl group having 2 carbon atoms or an alkoxy group having 2 carbon atoms.

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

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

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

[Chemical 18]

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

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

In the general formula (III), R ⁷ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms. When D represents trans-1,4-cyclohexylene, it is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably 2 carbon atoms. Alkyl group having 5 to 5 carbon atoms or alkenyl group having 2 to 4 carbon atoms, more preferably alkyl group having 3 to 5 carbon atoms or alkenyl group having 2 or 3 carbon atoms, and particularly preferably alkyl group having 3 carbon atoms When D represents a 1,4-phenylene group which may be substituted by fluorine, it is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 or 5 carbon atoms, and more preferably a carbon atom. The alkyl group having 2 to 5 or the alkenyl group having 4 carbon atoms is more preferably an alkyl group having 2 to 4 carbon atoms.

In the general formula (III), R ⁸ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyl group having 3 to 8 carbon atoms. When F represents trans-1,4-cyclohexylene, it is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably 2 carbon atoms. Alkyl group having 5 to 5 carbon atoms or alkenyl group having 2 to 4 carbon atoms, more preferably alkyl group having 3 to 5 carbon atoms or alkenyl group having 2 or 3 carbon atoms, and particularly preferably alkyl group having 3 carbon atoms When F represents a 1,4-phenylene group which may be substituted with fluorine, it is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 or 5 carbon atoms, and more preferably a carbon atom. The alkyl group having 2 to 5 or the alkenyl group having 4 carbon atoms is more preferably an alkyl group having 2 to 4 carbon atoms.

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

[Chemical 19]

(In the above formula, a ring structure is bonded to the right end.) In this case, an alkenyl group having 4 carbon atoms is more preferable.

In the general formula (III), Z ² represents a single bond, -OCH _2- , -OCO-, -CH ₂ O-, or -COO-, but preferably represents a single bond, -CH ₂ O- or -COO-, more It is preferably a single bond.

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

When n represents 1, from the viewpoint of increasing the negative dielectric constant anisotropy, the compound represented by the general formula (III) is preferably the following general formula (III-1c) to the general formula (III- The compound represented by 1e) is preferably a compound represented by the general formula (III-1f) to the general formula (III-1j) from the viewpoint of improving the response speed.

[Chemical 20]

[Chemical 21]

(In the general formulae (III-1f) to (III-1j), R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom. 1 to 5 alkoxy groups, but preferably the same embodiment as R ⁷ and R ⁸ in the general formula (III)) When n represents 2, the viewpoint of increasing the negative dielectric constant anisotropy The compound represented by the general formula (III) is preferably a compound represented by the general formula (III-2a) to the general formula (III-2h). From the viewpoint of making the response speed faster, the general formula (III) The compound represented is preferably a compound represented by general formula (III-2j) to general formula (III-2l).

[Chemical 22]

[Chemical 23]

(In the general formulae (III-2j) to (III-2l), R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon number An alkoxy group of 1 to 5 is preferably the same embodiment as R ⁷ and R ⁸ in the general formula (III)) When n represents 0, the general formula is from the viewpoint of increasing the response speed. The compound represented by (III) is preferably a compound represented by general formula (III-3b).

[Chemical 24]

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

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

The dielectric constant anisotropy is preferably -2.0 to -6.0, more preferably -2.5 to -5.0, and particularly preferably -2.5 to -4.0 at 25 ° C.

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

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

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

[Number 1]

(In the formula, γ1 represents rotational viscosity, and Δn represents refractive index anisotropy.) Z is preferably 13,000 or less, more preferably 12,000 or less, and particularly preferably 11,000 or less.

When the liquid crystal layer in the liquid crystal display device of the present invention is used for an active matrix display element, it is necessary to have a specific resistance of 10 ¹² (Ω · m) or more, preferably 10 ¹³ (Ω · m) or more, and more preferably 10 ¹⁴ (Ω · m) or more.

The liquid crystal layer in the liquid crystal display device of the present invention may contain, in addition to the compound, a normal nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, an antioxidant, an ultraviolet absorber, a polymerizable monomer, and the like depending on the application.

The polymerizable monomer is preferably a difunctional monomer represented by the general formula (V).

[Chemical 25]

(Wherein X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or -O- (CH ₂ ) _s -(Where s represents an integer from 2 to 7, and an oxygen atom is bonded to an aromatic ring), Z ¹ represents -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O -, -OCF _2- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = _{CH -, - COO-CH 2} CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO-, -CY ¹ = CY ^2- (wherein Y ¹ and Y ² each independently represent a fluorine atom or a hydrogen atom), -C≡C- or Single bond, C represents 1,4-phenylene, trans-1,4-cyclohexylene or single bond, and any hydrogen atom in all 1,4-phenylene groups in the formula may be substituted by a fluorine atom) In the general formula (V), it is also preferably a diacrylate derivative in which any of X ¹ and X ² represents a hydrogen atom, or a dimethacrylate derivative in which any one has a methyl group, and is also preferably A compound in which one represents a hydrogen atom and the other represents a methyl group. Regarding the polymerization rate of these compounds, a diacrylate derivative is the fastest, a dimethacrylate derivative is slow, an asymmetric compound is in between, and a preferred embodiment can be used depending on the application. Among PSA display elements, a dimethacrylate derivative is particularly preferred.

In the general formula (V), 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 it is preferably at least one in a PSA display element. One is a single bond, and is preferably an embodiment of a compound each representing a single bond, or one of which is a single bond and the other representing an alkylene group having 1 to 8 carbon atoms or -O- (CH ₂ ) _s- . In this case, it is preferably an alkylene group having 1 to 4 carbon atoms, and s is preferably 1 to 4 carbon atoms.

In the general formula (V), Z ¹ is preferably -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CF ₂ CF ₂ -or a single bond, more preferably -COO-, -OCO- or a single bond, and particularly preferably a single bond.

In the general formula (V), C represents 1,4-phenylene, trans-1,4-cyclohexylene or a single bond in which any hydrogen atom may be substituted with a fluorine atom, but 1,4-phenylene is preferred Base or single bond. When C represents a ring structure other than a single bond, Z ¹ is also preferably a linking group other than a single bond, and when C is a single bond, Z ¹ is preferably a single bond.

In these points, the ring structure between Sp ¹ and Sp ² in the general formula (V) is preferably a structure described below.

In the general formula (V), when C represents a single bond and the ring structure is formed by two rings, the ring structure between Sp ¹ and Sp ² is preferably represented by the following formula (Va-1) to (Va- 5), more preferably the formula (Va-1) to the formula (Va-3), and particularly preferably the formula (Va-1).

[Chemical 26]

(In formulas (Va-1) to (Va-5), both ends are bonded to Sp ¹ or Sp ^2. ) In the general formula (V), C represents 1,4-phenylene and the ring structure is When three rings are formed, the ring structure between Sp ¹ and Sp ² is preferably represented by the following formula (Va-6) to (Va-9), and more preferably represented by the formula (Va-6) to ( Va-8) is particularly preferably an expression (Va-6) or (Va-7).

[Chemical 27]

(In formulas (Va-6) to (Va-9), both ends are bonded to Sp ¹ or Sp ² ) Polymerization of a polymerizable compound containing the (Va-1) skeleton to (Va-9) skeleton The latter alignment limiting force is most suitable for PSA type liquid crystal display elements, and a good alignment state can be obtained, so display unevenness is suppressed or does not occur at all.

As described above, the compound represented by the general formula (V) in the polymerizable monomer is particularly preferably the general formula (V-1) to the general formula (V-8), and among these, the general formula (V-2) and the general formula are most preferable. (V-4), general formula (V-6), general formula (V-8).

[Chemical 28]

[Chemical 29]

(In the general formula (V-1) to the general formula (V-8), any hydrogen atom in the 1,4-phenylene group may be substituted with a fluorine atom, and Sp ² represents an alkylene group having 2 to 5 carbon atoms. It is also preferable to use a difunctional monomer represented by the general formula (V2) as the polymerizable monomer.

[Chemical 30]

(Wherein X ¹⁰ and X ¹¹ each independently represent a hydrogen atom or a methyl group, and Sp ³ and Sp ⁴ each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or -X- (CH ₂ ) _t -(In the formula, t represents an integer of 2 to 7, X represents -O-, -OCOO-, -OCO-, or -COO-, and X is bonded to the phenanthrene ring), any of the phenanthrene rings in the formula A hydrogen atom may be substituted by a fluorine atom) In the general formula (V2), X ¹⁰ and X ¹¹ each independently represent a hydrogen atom or a methyl group. When the reaction speed is important, a hydrogen atom is preferred, and when reducing the reaction residue is important In the case of the amount, it is preferably a methyl group.

In the general formula (V2), Sp ³ and Sp ⁴ each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or -X- (CH ₂ ) _t- (wherein, t represents 2 to 7 Integer, X represents -O-, -OCOO-, -OCO-, or -COO-, and X is bonded to the phenanthrene ring), but preferably the carbon chain is not too long, and is preferably a single bond or the number of carbon atoms The alkylene group having 1 to 5 is more preferably a single bond or an alkylene group having 1 to 3 carbon atoms. When Sp ³ and Sp ⁴ represent -X- (CH ₂ ) _t- , t is also preferably 1 to 5, more preferably 1 to 3, and even more preferably at least one of Sp ³ and Sp ⁴ It is a single bond, and it is especially preferable that both are single bonds.

Specifically, the compound represented by the general formula (V2) is preferably a compound represented by the following general formula (V2-1) to general formula (V2-52).

[Chemical 31]

[Chemical 32]

[Chemical 33]

When at least one or two or more polymerizable compounds represented by the general formula (V) and / or the general formula (V2) are used in a liquid crystal composition forming a liquid crystal layer, the liquid crystal composition is more suitable for use in a liquid crystal composition. In the total amount of the liquid crystal compound and the polymerizable compound in the formula, the content of the polymerizable compound is preferably 0.05% to 6% by mass, more preferably 0.1% to 5% by mass, and still more preferably 0.15% to 4% by mass. It is particularly preferably 0.2% to 3% by mass.

When a polymerizable monomer is added, the polymerization proceeds even when a polymerization initiator is not present, but it may contain a polymerization initiator in order to promote the polymerization. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and fluorenyl phosphine oxides. In order to improve storage stability, a stabilizer may be added. Examples of usable stabilizers include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, and nitro compounds. , Β-naphthylamines, β-naphthols, nitroso compounds, etc.

The liquid crystal layer in the present invention is useful for liquid crystal display elements, such as active matrix-liquid crystal display (AM-LCD) and twisted nematic-liquid crystal display (TN-LCD). ), Super twisted nematic-liquid crystal display (STN-LCD), OCB-LCD and in-plane switching-liquid crystal display (IPS-LCD) , But it is particularly useful for AM-LCD and can be used for liquid crystal display elements for PSA mode, PSVA mode, VA mode, IPS mode or ECB mode. (Color filter) The color filter in the present invention includes a black matrix and at least RGB three-color pixel sections. Among the RGB three-color pixel sections, the G pixel section includes an average using a small-angle X-ray scattering method. Gallium phthalocyanine, aluminum phthalocyanine, europium phthalocyanine, yttrium phthalocyanine, or indium phthalocyanine pigment having a primary particle diameter of 5 nm to 50 nm is used as the G color material. In addition, it is preferable that the RGB tri-color pixel portion includes 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 in the B pixel portion. Organic dyes are used as color materials.

The measurement of the average primary particle size by the small-angle X-ray scattering method can be performed by a method described in Japanese Patent Laid-Open No. 2006-113042.

The standardized dispersion indicating the particle size distribution by the small-angle X-ray scattering method can be calculated by a method described in Japanese Patent Laid-Open No. 2013-96944, and is preferably 20% to 50%. In addition, the smaller the value of the normalized dispersion, the sharper and better the particle size distribution. If it exceeds 50%, coarse particles will increase, which will ooze out of the surface of the color filter, resulting in a decrease in the voltage holding ratio (VHR) of the liquid crystal layer and an increase in the ion density (ID), which will cause white spots, uneven alignment, and burning Showing bad problems. (G pixel portion) Examples of the gallium phthalocyanine, aluminum phthalocyanine, europium phthalocyanine, yttrium phthalocyanine, or indium phthalocyanine pigment in the G pixel portion include pigments represented by the following general formula (PIG-1) or A pigment represented by the following general formula (PIG-2). The phthalocyanine pigments 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. Pigments of PIG-2) or both pigments corresponding to the general formula (PIG-1) and pigments corresponding to the general formula (PIG-2) can be used.

[Chem 34]

(In the general formula (PIG-1), X ¹ⁱ to X ¹⁶ⁱ each independently represent a halogen atom, a nitro group, a phthalimideimide methyl group which may have a substituent, an sulfamoyl group which may have a substituent, An alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, and an aryloxy group which may have a substituent Group, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent. Y ¹ⁱ represents a hydroxyl group, a chlorine atom, -OP (= O) R1R2, or -O-SiR3R4R5. Here, R1 to R5 are respectively Independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent, R1 and R2, R3 to R5 They can be bonded to each other to form a ring. M represents a trivalent metal selected from the group consisting of Ga, Al, Sc, Y, and In)

[Chemical 35]

(Formula (PIG-2) in, X ¹⁷ⁱ ~ X ³²ⁱ each independently represent a halogen atom, a nitro group, a phthaloyl may have substituent (PEI) methyl group, a sulfo acyl amine may have a substituent, An alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, and an aryloxy group which may have a substituent Group, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent. M represents a trivalent metal selected from the group consisting of Ga, Al, Sc, Y, and In. Y ²ⁱ represents -O -, -O-SiR6R7-O-, -O-SiR6R7-O-SiR8R9-O-, or -OP (= O) R10-O-, R6 to R10 each independently represent a hydrogen atom, a hydroxyl group, and may have a substituent An alkyl group, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent) In the general formula (PIG-1) and the general formula (PIG-2), Specific examples of the phthalimide methyl group which may have a substituent include phthalimide methyl group, 3-chlorophthalimide methyl group, and 4-chlorophthalimide methyl group. Hydrazone Dimethyimidine methyl, 4-nitrophthalimide methyl, 3-sulfophthalimide methyl, 4-sulfophthalimide methyl, etc. .

In the general formula (PIG-1) and the general formula (PIG-2), examples of the aminesulfonyl group which may have a substituent include dimethylaminomethylsulfonylamino group and diethylcarbamyl group. Sulfosulfonylamino, dimethylaminoethylsulfonamido, diethylaminoethylsulfonamido, dimethylaminopropylsulfonamido, diethylaminopropylsulfonyl Hydrazone and the like.

In the general formula (PIG-1) and the general formula (PIG-2), the alkyl group is more preferably an alkyl group having 1 to 8 carbon atoms. More specifically, methyl, ethyl, and propyl are listed. , Unsubstituted alkyl such as isopropyl, butyl, isobutyl, sec-butyl, pentyl, hexyl, 2-ethylhexyl; 2-methoxyethyl, 2-ethoxyethyl, etc. Alkoxyalkyl groups; ethoxy groups such as 2-ethoxyethyl; cyanoalkyl groups such as 2-cyanoethyl; 2,2,2-trifluoroethyl, 4,4,4-trifluoro Butyl and other fluoroalkyl groups. When the alkyl group has a substituent, trichloromethyl, 2,2-dibromoethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, 2,4-dichlorobenzyl, and the like. In the general formula (PIG-1) and the general formula (PIG-2), examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group. In the case where the aryl group has a substituent, examples thereof include chlorophenyl, bromophenyl, methylphenyl, nitrophenyl, methoxyphenyl, and 2,4-dichlorobenzene. Methyl, pentafluorophenyl, 2-methyl-4-chlorophenyl, 2-aminophenyl, 4-hydroxy-1-naphthyl, 6-methyl-2-naphthyl, 4,5,8-tris Chloro-2-naphthyl, anthraquinone, 2-aminoanthraquinone, and the like.

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

In the general formula (PIG-1) and the general formula (PIG-2), the heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples thereof include thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, thiathranyl, furyl, pyranyl, and isobenzofuran. Furanyl, benzopyranyl, xanthenyl, phenoxathienyl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, ind Idolazinyl, isoindolyl, 3H-indolyl, indolyl, 1H-indazolyl, purinyl, 4H-quinazinyl, isoquinolinyl, quinolinyl, phthalazinyl, naphthyridinyl , Quinoxalinyl, quinazolinyl, fluorinyl, pyridinyl, 4aH-oxazolyl, oxazolyl, β-fluorinyl, phenanthridyl, acridinyl, pyridinyl, phenanthroline Group, phenazinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furfuryl, phenoxazinyl, isobenzodihydropyranyl, benzodihydropyranyl , Pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, Thiazolidinyl, pyrazolinyl, piperidyl, piperazinyl, indolinyl, iso indolinyl, quinuclidinyl, morpholinyl, thioxanthene group.

In the general formula (PIG-1) and the general formula (PIG-2), the alkoxy group which may have a substituent is more preferably an alkoxy group having 1 to 8 carbon atoms, and more specifically, it may be: Oxy, ethoxy, propoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, trichloromethoxy, trifluoromethoxy, 2,2,2-tri Fluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 2,2-di-trifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy , 2-nitropropoxy, benzyloxy, etc. Examples of the aryloxy group which may have a substituent in the general formula (PIG-1) and (PIG-2) include a phenoxy group, a naphthyloxy group, an anthryloxy group, and 3-tert-butylbenzene. Oxygen, 2,4-di-tert-butylphenoxy, p-methylphenoxy, p-nitrophenoxy, p-methoxyphenoxy, 2,4-dichlorophenoxy, pentafluoro Phenoxy, 2-methyl-4-chlorophenoxy and the like.

Examples of the alkylthio group which may have a substituent in the general formula (PIG-1) and (PIG-2) include methylthio, ethylthio, propylthio, butylthio, and pentylthio. Methyl, hexylthio, octylthio, decylthio, dodecylthio, octadecylthio, methoxyethylthio, aminoethylthio, benzylaminoethylthio, methylcarbonylaminoethyl Thio, phenylcarbonylaminoethylthio, and the like.

In the general formula (PIG-1) and general formula (PIG-2), examples of the arylthio group which may have a substituent include phenylthio, 1-naphthylthio, 2-naphthylthio, 9- Anthracenyl, chlorophenylthio, trifluoromethylphenylthio, cyanophenylthio, nitrophenylthio, 2-aminophenylthio, 2-hydroxyphenylthio, and the like.

Specific examples of the metal phthalocyanine pigment represented by the general formula (PIG-1) include the compounds described below, but the present invention is not limited to these as long as it does not exceed the gist thereof.

[Chemical 36]

[Chemical 37]

(N ^1k and n ^{1l in 1k} and ^1l are 1 to 16) Specific examples of the metal phthalocyanine pigment represented by the general formula (PIG-2) include the compounds described below. Beyond its gist, it is not limited to these.

[Chemical 38]

[Chemical 39]

(N ^2g1 and n ^2g2 in the general formula (2g) are each independently 1 to 16) In addition, it is preferable to include a pigment derivative as a dispersing aid in the G pixel portion. The pigment derivative preferably contains at least one of a phthalocyanine-based pigment derivative and a quinophthalone-based pigment derivative. Examples of the derivative include phthalimidomethyl, sulfonic acid group, iso-N- (dialkylamino) methyl group, and iso-N- (dialkylaminoalkyl) sulfonylamino group. These derivatives may be used in combination of two or more different kinds of derivatives.

The use amount of the pigment derivative is preferably 4 parts or more and 20 parts or less with respect to 100 parts of the total amount of the phthalocyanine pigment represented by the general formula (PIG-1) and / or the general formula (PIG-2). It is preferably 6 parts or more and 16 parts or less.

Furthermore, it is also preferable that the G pixel portion contains one or more pigments selected from the quinophthalone compound represented by the general formula (3), the general formula (4), and the general formula (5) so as to adjust the hue.

[Chemical 40]

(In the general formulae (3) to (5), R ₁₀ to R ₂₄ , R ₂₅ to R ₃₉ , and R ₄₀ to R ₅₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and Monovalent to trivalent metal salts of alkoxy groups having substituents, aryl groups which may have substituents, -SO ₃ H group, -COOH group, -SO ₃ H group, or -COOH group; alkylammonium salts, An phthalimidomethyl group which may have a substituent, or an aminesulfonyl group which may have a substituent) In the general formulae (3) to (5), R ₁₀ to R ₂₄ , R ₂₅ to R ₃₉ And R ₄₀ to R ₅₆ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, an alkoxy group having 1 to 4 carbon atoms which may have a substituent, or Monovalent to trivalent metal salts of aryl groups having 1 to 4 carbon atoms having a substituent, -SO ₃ H group, -COOH group, -SO ₃ H group, or -COOH group; alkylammonium salts, and may have The phthalimide methyl group as a substituent or the sulfamoyl group which may have a substituent. Examples of the substituent include dimethylaminopropylaminosulfonyl, diethylaminopropyl Aminosulfenyl.

Specific examples of the quinophthalone pigment represented by the general formula (3), the general formula (4), and the general formula (5) include the following formulae (3a) to (5a) The compounds shown are not limited to these as long as they do not exceed the gist of the present invention.

[Chemical 41]

[Chemical 42]

(R pixel portion) The R pixel portion preferably contains a diketopyrrolopyrrole pigment and / or an anionic red organic dye. As the diketopyrrolopyrrole pigment, specifically, it is preferably selected from CI Pigment Red 254, Red 255, Red 264, Red 272, Orange 71, Orange One or two or more of (Orange) 73 and bromodione pyrrolopyrrole, more preferably selected from Red (Red) 254, Red (255), Red (264), and Red (272) One or two or more of them are preferable, and CI Pigment Red (Pigment Red) 254 is particularly preferable. As the anionic red organic dye, specifically, one or two or more selected from CI Solvent Red 124, Acid Red 52, and Acid Red 289 are preferable, and particularly preferably CI Solvent Red 124.

Moreover, it is preferable to contain a pigment derivative as a dispersion aid. The pigment derivative preferably contains at least one of a quinacridone-based pigment derivative, a diketopyrrolopyrrole-based pigment derivative, an anthraquinone-based pigment derivative, and a thiazine-based pigment derivative. Examples of the derivative include phthalimidomethyl, sulfonic acid group, iso-N- (dialkylamino) methyl group, and iso-N- (dialkylaminoalkyl) sulfonylamino group. These derivatives may be used in combination of two or more different kinds of derivatives.

The use amount of the pigment derivative is preferably 4 or more and 20 or less, and more preferably 6 or more and 16 or less based on 100 parts of the diketopyrrolopyrrole-based red pigment and / or the anionic red organic dye. (B pixel part) It is preferable to contain an ε-type phthalocyanine pigment or a cationic blue organic dye in the B pixel part. The ε-type phthalocyanine pigment is preferably Pigment Blue 15: 6, and the cationic blue organic dye is preferably a triarylmethane-based dye or a triarylmethane lake pigment.

The triarylmethane lake pigment is preferably the following general formula (6)

[Chemical 43]

(In the general formula (6), R ^11j to R ^16j each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbons which may have a substituent, or an aryl group having 1 to 8 carbons which may have a substituent. 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 may be bonded to form a ring structure. X ^11j and X ^12j are respectively Independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms which may have a substituent. Z ^- is selected from the group consisting of (P ₂ Mo _y W _18-y O ₆₂ ) ^6- / 6 and y = Integer heteropolyoxometalate anion of 0, 1, 2 or 3, heteropolyoxometalate anion as (SiMoW ₁₁ O ₄₀ ) ^4- / 4, defect Dawson-type phosphotungstate heteropolymetal At least one of the oxo acid anions. When a plurality of formulas (1) are contained in one molecule, these may be the same structure or different structures represented by triarylmethane lake pigments.

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

When adjacent R (R represents any of R ^11j to R ^16j ) is bonded to form a ring, these may be a ring crosslinked by a hetero atom. Specific examples of the ring include the followings. These rings may also have a substituent.

[Chemical 44]

In general formula (6), in terms of chemical stability, R ^11j to R ^16j are each preferably a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.

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

When R ^11j to R ^16j represent an alkyl group or an aryl group, the alkyl group or the aryl group may further have an arbitrary substituent. As an arbitrary substituent which the said alkyl group or aryl group may have further, the following [substituent group Y] is mentioned, for example.

[Substituent Group Y] Methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, cyclopentyl, hexyl , Cyclohexyl, heptyl, octyl, 2-ethylhexyl and other alkyl groups; aryl groups such as phenyl and naphthyl; halogen atoms such as fluorine and chlorine atoms; cyano; hydroxyl; methoxy, ethoxy, Alkyl groups having 1 to 8 carbon atoms, such as propoxy and butoxy; amino groups which may have a substituent, such as amino, diethylamino, dibutylamino, and ethylamino; ethylamino, benzamidine And other fluorenyl groups;

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. More specific examples include methyl, ethyl, propyl, and isopropyl. Unsubstituted alkyl such as butyl, isobutyl, sec-butyl, pentyl, hexyl, 2-ethylhexyl; alkoxyalkanes such as 2-methoxyethyl, 2-ethoxyethyl Groups; fluorenyl groups such as 2-ethenyloxyethyl; cyanoalkyl groups such as 2-cyanoethyl; fluorine such as 2,2,2-trifluoroethyl, 4,4,4-trifluorobutyl Alkyl, etc.

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

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

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

Specific examples of the triarylmethane lake pigment represented by the general formula (6) include, for example, the compounds described in Tables 1 to 7 below, and the present invention is not limited to these as long as it does not exceed the gist thereof. .

[Table 1]

[Table 2]

[table 3]

[Table 4]

[table 5]

[TABLE 6]

[TABLE 7]

It is preferable that the RGB three-color pixel portion includes CI Solvent Red 124 in the R pixel portion, gallium phthalocyanine or aluminum phthalocyanine in the G pixel portion, and Pigment Blue (Pigment Blue) in the B pixel portion. ) 15: 6 as a color material, and a xanthene compound is contained in the R pixel portion and / or the B pixel portion.

Specific examples of the xanthene compound include, for example, compounds represented by the following general formula (7a) to general formula (7b), and the present invention is not limited to these as long as it does not exceed the gist thereof.

[Chemical 45]

(In the general formulae (7a) to (7b), R ^a represents dodecyl, R ^b represents 2-ethylhexyl, and R ^c represents 2-ethylhexyl.) The RGB three-color pixel portion is preferably The R pixel portion further contains a member selected from the group consisting of CI Pigment Red 177, CI Pigment Red 242, CI Pigment Red 166, CI Pigment Red 167, CI Pigment Red 179, CI Pigment Red 269, and CI Pigment Orange 38. , CI Pigment Orange 71, CI Pigment Yellow 150, CI Pigment Yellow 215, CI Pigment Yellow 185, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Acid Red 52, CI Basic Red Red) 1. CI Solvent Red 89, CI Solvent Orange 56, CI Solvent Yellow 21, CI Solvent Yellow 82, CI Solvent Yellow 83: 1, CI Solvent Yellow 33, and CI Solvent At least one organic dye pigment in the group consisting of yellow 162 serves as a color material.

The RGB three-color pixel portion preferably further includes a G pixel portion selected from the group consisting of CI Pigment Yellow 150, CI Pigment Yellow 215, CI Pigment Yellow 185, CI Pigment Yellow 138, and CI Solvent Yellow 21. At least one organic dye pigment in the group consisting of CI solvent yellow 82, CI solvent yellow 83: 1, and CI solvent yellow 33 is used as a color material.

The RGB three-color pixel portion preferably further includes a B pixel portion selected from the group consisting of CI Pigment Violet 23, CI Basic Violet 10, CI Acid Blue 1, and CI Acid Blue 90. , CI Acid Blue 83, CI Direct Blue 86, CI Pigment Blue 15, CI Pigment Blue 15: 1, CI Pigment Blue 15: 2, CI Pigment Blue 15: 3, and CI Pigment Blue 15: At least one organic dye pigment in the group consisting of 4 is used as a color material.

In addition, the color filter includes a black matrix, RGB three-color pixel portions, and a Y pixel portion. It is also preferable that the Y pixel portion contains a member selected from CI Pigment Yellow 150, CI Pigment Yellow 215, CI Pigment Yellow 185, At least one yellow in the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 139, CI Solvent Yellow 21, CI Solvent Yellow 82, CI Solvent Yellow 83: 1, CI Solvent Yellow 33, and CI Solvent Yellow 162 Organic dye pigments are used as color materials.

From the viewpoint of preventing a decrease in the voltage holding ratio (VHR) and an increase in the ion density (ID) of the liquid crystal layer, and suppressing problems such as white spots, uneven alignment, and poor display, the color filter in the present invention The chromaticity x and chromaticity y in the XYZ color system under the C light source of each pixel portion in the sheet are preferably as follows.

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 preferably 0.30 to 0.36, more preferably 0.31 to 0.35, and more preferably color. The degree x is 0.58 to 0.69 and the chromaticity y is 0.30 to 0.36, and more preferably the chromaticity x is 0.62 to 0.68 and the chromaticity y is 0.31 to 0.35.

The chromaticity x in the XYZ color system under the C light source of the G pixel portion is preferably 0.19 to 0.35, more preferably 0.20 to 0.29, and the chromaticity y is preferably 0.54 to 0.76, more preferably 0.64 to 0.74, and more preferably color The degree x is 0.19 to 0.35 and the chromaticity y is 0.54 to 0.76, and 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 preferably 0.04 to 0.12, more preferably 0.05 to 0.09, and more preferably color The degree x is 0.12 to 0.18 and the chromaticity y is 0.04 to 0.12, and 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 preferably 0.48 to 0.53, more preferably 0.50 to 0.52, and more preferably color. The degree x is 0.46 to 0.50 and the chromaticity y is 0.48 to 0.53, and more preferably the chromaticity x is 0.47 to 0.48 and the chromaticity y is 0.50 to 0.52.

Here, the so-called XYZ color system refers to a color system recognized as a standard color system by the International Commission on Illumination (CIE) in 1931.

The chromaticity in each pixel portion can be adjusted by changing the type of the dye pigment used or the mixing ratio of these. For example, in the case of R pixels, it can be adjusted by adding an appropriate amount of yellow dye pigment and / or orange pigment to the red dye pigment, and in the case of G pixels, it can be adjusted by adding an appropriate amount of yellow dye pigment to the green dye pigment. In the case of B pixels, it can be adjusted by adding an appropriate amount of a purple dye pigment or a yellowish blue dye pigment to the blue dye pigment. It is also possible to adjust by appropriately adjusting the particle diameter of the pigment.

The color filter can be formed using a conventionally known method to form the color filter pixel portion. A typical method for forming a pixel portion is a photolithography method, which is a method in which a photocurable composition described later is applied to a surface of a transparent substrate for a color filter provided on the side of the black matrix and heated and dried. (Pre-baking), and then irradiate ultraviolet rays through a light mask to perform pattern exposure to harden the photocurable compound corresponding to the pixel portion, and then develop the unexposed portion with a developing solution, and The pixel portion is removed to fix the pixel portion to the transparent substrate. In the method, a pixel portion of a cured colored film containing a photocurable composition is formed on a transparent substrate.

For each pixel of other colors, such as R pixels, G pixels, B pixels, and optionally Y pixels, a photocurable composition described below is prepared and the above-mentioned operations are repeated, thereby producing an R pixel having a predetermined position , G pixels, B pixels, and Y pixels are color filters in the colored pixel portion.

Examples of a method for applying a photocurable composition described later on a transparent substrate such as glass include a spin coating method, a slit coating method, a roll coating method, and an inkjet 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, and are usually about 50 ° C to 150 ° C, and about 1 minute to 15 minutes. In addition, it is preferable that the light used for the photo-curing of the photo-curable composition is ultraviolet light or visible light in a wavelength range of 200 nm to 500 nm. Various light sources that emit light in the wavelength range can be used.

Examples of the development method include a liquid coating method, a dipping method, and a spray method. After the photocurable composition is exposed and developed, the transparent substrate on which the pixel portion of a desired color is formed is washed with water and dried. The color filter obtained in the above-mentioned manner is subjected to a heating treatment (post-baking) at a temperature of 90 ° C. to 280 ° C. for a predetermined time using a heating device such as a hot plate or an oven, thereby removing volatility in the colored coating film. The component and the unreacted photocurable compound remaining in the cured colored film of the photocurable composition are thermally cured to complete a color filter.

The color material for a color filter of the present invention, by using it with the liquid crystal composition of the present invention, can prevent a decrease in the voltage holding ratio (VHR) of the liquid crystal layer and an increase in the ion density (ID), solve white spots, uneven alignment, A liquid crystal display device having a problem of poor display, such as being burnt.

The method for producing the photocurable composition is generally a method in which the dye and / or pigment composition for a color filter of the present invention, an organic solvent, and a dispersant are used as essential components, and these are mixed uniformly. Stirring and dispersing, firstly preparing a pigment dispersion for forming a pixel portion of a color filter, and adding a photocurable compound and a thermoplastic resin or a photopolymerization initiator as needed to prepare the photocurable composition. Thing.

Examples of the organic solvent used herein include aromatic solvents such as toluene, xylene, and methoxybenzene, ethyl acetate, propyl acetate or butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether. Acetate-based solvents such as acetate, diethylene glycol methyl ether acetate, diethylene glycol ether acetate, diethylene glycol propyl ether acetate, diethylene glycol butyl ether acetate, etc. Propionate solvents such as ethoxyethyl ester, alcohol solvents such as methanol and ethanol, butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ether, diethylene glycol dimethyl ether, and other ether solvents, methyl Ketone solvents such as ethyl ketone, methyl isobutyl ketone, cyclohexanone, aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, γ-butyrolactam, N-methyl Nitrogen compound solvents such as 2-pyrrolidone, aniline, and pyridine; lactone solvents such as γ-butyrolactone; and urethanes such as 48:52 mixtures of urethane and urethane.

The dispersant used herein may include, for example, Disperbyk 130, Disperbyk 161, and Disperbyk of BYK-Chemie. 162, Disperbyk (163), Disperbyk (170), Disperbyk (171), Disperbyk (174), Disperbyk (Disperbyk) 180, Disperbyk 182, Disperbyk 183, Disperbyk 184, Disperbyk 185, Disperbyk 2000, Disperbyk 2001, Disperbyk 2020, Disperbyk 2050, Disperbyk 2070, Disperbyk 2096, Disperbyk 2150, Disperbyk LPN21116, Disperbyk LPN6919, Lubrizol Corporation's Solsperse 3000, Solvay Solsperse 9000, Solsperse 13240, Solpasse 13650, Solupsse 13940, Solupsse 17000, Solupsse 18000, Solupsse 20000, Solupsse ) 21000, Solsperse 24000, Solsperse 26000, Solupsse 27000, Solsperse 28000, Solupsse 32000, Solups Solsperse 36000, Solsperse 37000, Solsperse 38000, Solupsse 41000, Solupsse 42000, Solupsse 43000, Solsperse 46000, Solsperse 54000, Solsperse 71000, Ajinomoto Ajisper PB711, Ajispar ( Ajisper PB821, Ajisper PB822, Ajisper PB814, Ajisper PN411, Ajisper PA111 and other dispersants, or acrylic resin, carbamate Ester-based resin, alkyd Natural rosin such as resin, wood rosin, gum rosin, tarot oil rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, oxidized rosin, modified rosin such as rosin, rosinamine, lime rosin, rosin alkylene oxide , Rosin alkyd adducts, rosin derivatives such as rosin-modified phenol, etc. are synthetic resins that are liquid at room temperature and insoluble in water. The addition of these dispersants or resins also contributes to a reduction in floculation, an improvement in the dispersion stability of the pigment, and an improvement in the viscosity characteristics of the dispersion.

In addition, as a dispersing aid, an organic pigment derivative such as a phthalimide methyl derivative, a homosulfonic acid derivative, a N- (dialkylamino) methyl derivative, or a N -(Dialkylaminoalkyl) sulfonamide derivatives and the like. Of course, these derivatives may be used in combination of two or more different kinds of derivatives.

Examples of the thermoplastic resin used for the preparation of the photocurable composition include a urethane resin, an acrylic resin, a polyamide resin, a polyimide resin, a styrene maleic resin, Styrene maleic anhydride resin and the like.

Examples of the photocurable compound include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, and bis (propylene fluorenyloxy) (Ethoxy) Bifunctional monomers such as bisphenol A, 3-methylpentanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tri (2- (meth) propylene) (Methoxyethyl) isocyanurate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and other polyfunctional monomers with smaller molecular weight, polyester acrylate, polyurethane acrylate, polyether acrylate And other polyfunctional monomers with a relatively large molecular weight.

Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethylketal, benzophenone peroxide, 2-chlorothiaxanthone, 1,3-bis (4 ' -Azidobenzylidene) -2-propane, 1,3-bis (4'-azidobenzylidene) -2-propane-2'-sulfonic acid, 4,4'-diazidediphenyl Ethylene-2,2'-disulfonic acid and the like. Examples of commercially available photopolymerization initiators include "Irgacure (trade name) -184", "Irgacure (trade name) -369", "369" manufactured by BASF, " "Darocur (trade name) -1173", "Lucirin-TPO" manufactured by BASF, "Kayacure (trade name) DETX" manufactured by Nippon Kayaku Co., Ltd., "Kayacure (trade name) OA", "vicure 10" manufactured by Stauffer, "vicure 55", manufactured by Akzo "Trigonal PI", "Sandray 1000" manufactured by Sandoz, "deap" manufactured by Upjohn, Black Gold Chemical Company Manufactured "biimidazole" and the like.

In addition, a known and commonly used photosensitizer may 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 may be used alone or in combination of two or more.

The blending ratio of the photopolymerization initiator is not particularly limited, but it is preferably in the range of 0.1% to 30% by mass based on the compound having a photopolymerizable or photocurable functional group. When the content is less than 0.1%, the sensitivity at the time of photocuring tends to decrease. When the content exceeds 30%, when the coating film of the pigment-dispersed resist is dried, crystals of the photopolymerization initiator may precipitate to cause physical properties of the coating film. Degradation.

Using each of the above-mentioned materials, 300 to 1,000 parts of an organic solvent and 1 to 100 parts are dispersed with respect to 100 parts of the dye and / or pigment composition for a color filter of the present invention on a mass basis. The agent is uniformly stirred and dispersed to obtain the dye pigment solution. Next, a thermoplastic resin, a photocurable compound, and a photocurable compound in an amount of 3 to 20 parts based on 1 part of the pigment composition for a color filter of the present invention, and 1 part to the photocurable compound are added to the pigment dispersion liquid. The photopolymerization initiator is 0.05 to 3 parts, and if necessary, an organic solvent is further added, and the mixture is uniformly stirred and dispersed to obtain a photocurable composition for forming a pixel portion of a color filter.

As the developing solution, a known and commonly used organic solvent or an alkaline aqueous solution can be used. In particular, the photocurable composition contains a thermoplastic resin or a photocurable compound, and at least one of these compounds has an acid value and exhibits alkali solubility. In this case, the color filter is washed with an alkaline aqueous solution. The formation of the sheet pixel portion is effective. The manufacturing method of the color filter pixel portion by the photolithography method is described in detail, but the color filter pixel portion prepared by using the pigment composition for a color filter of the present invention can be converted by other electrodeposition methods, Printing methods, micellar electrolytic method, photovoltaic voltaic electrodeposition (PVED) method, inkjet method, reverse printing method, thermal curing method and the like are used to form the pixel portions of each color, so that a color filter can be manufactured.

The color filter can be prepared by applying an organic pigment to a substrate and drying it, or when the pigment dispersion contains a curable resin, and can be cured by heat or active energy rays. Color filters. In addition, using a heating device such as a hot plate or an oven, a step of removing volatile components from the coating film can be performed by performing a heat treatment (post-baking) at 100 ° C to 280 ° C for a predetermined time. (Alignment film) In the liquid crystal display device of the present invention, in order to align the liquid crystal composition on the surfaces of the first substrate and the second substrate that are in contact with the liquid crystal composition, the liquid crystal display device that requires an alignment film is disposed in a color filter. Between the light sheet and the liquid crystal layer, the thickness of the alignment film is as thin as 100 nm or less, which does not completely block the interaction between the pigments such as pigments constituting the color filter and the liquid crystal compound constituting the liquid crystal layer.

In a liquid crystal display device that does not use an alignment film, the interaction between a pigment such as a pigment constituting a color filter and a liquid crystal compound constituting a liquid crystal layer becomes larger.

As the alignment film material, transparent organic materials such as polyimide, polyimide, benzocyclobutene polymer (BCB), and polyvinyl alcohol can be used. Particularly preferred are p-phenylenediamine, 4,4 '. -Diamines such as diaminodiphenylmethane or diamines such as alicyclic diamines; butane tetracarboxylic anhydrides such as butane tetracarboxylic anhydride; 2,3,5-tricarboxycyclopentylacetic anhydride; Polyimide alignment film formed by polyimidization of a polyfluorinated acid synthesized from an aromatic tetracarboxylic anhydride such as pyromellitic dianhydride and the like. The rubbing method is generally used as the alignment providing method in this case, but when it is used for a vertical alignment film or the like, it may be used without providing alignment.

As the alignment film material, chalcone, cinnamate, a compound containing a cinnamyl group or an azo group, or the like may be used in combination with materials such as polyimide and polyimide, as described above. The alignment film can be rubbed or photo-aligned.

The alignment film is generally formed by coating the alignment film material on a substrate by a spin coating method or the like to form a resin film. A uniaxial stretching method, a Langmuir-Blodgett method, or the like can also be used. (Transparent electrode) In the liquid crystal display device of the present invention, a conductive metal oxide can be used as the material of the transparent electrode, and as the metal oxide, indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), or zinc oxide can be used. (ZnO), indium tin oxide (In ₂ O ₃ -SnO ₂ ), indium zinc oxide (In ₂ O ₃ -ZnO), titanium dioxide with added niobium (Ti _1-x Nb _x O ₂ ), fluorine-doped tin oxide, The graphene nanobelt, metal nanowire, and the like are preferably zinc oxide (ZnO), indium tin oxide (In ₂ O ₃ -SnO ₂ ), or indium zinc oxide (In ₂ O ₃ -ZnO). In the patterning of these transparent conductive films, a photo-etching method or a method using a mask can be used.

The liquid crystal display device of the present invention has the following characteristics: prevents a decrease in the voltage holding ratio (VHR) of the liquid crystal layer, an increase in the ion density (ID), and suppresses the occurrence of display defects such as burn-in. The liquid crystal display devices for mode, PSVA mode, and FFS mode are useful, and can be applied to liquid crystal display devices such as televisions (TVs), monitors, mobile phones, and smartphones. [Example]

The following examples further illustrate the present invention in detail, but the present invention is not limited to these examples. In addition, "%" in the composition of the following Example and a comparative example means "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 (mPa · s) at 25 ° C VHR: Voltage retention (%) at 70 ° C (indicated by%) The liquid crystal composition is injected into a cell having a cell thickness of 3.5 μm, and is applied by 5 V, frame time 200 ms, pulse width 64 μs, and the ratio of the measured voltage to the initial applied voltage. ID: Ion density at 70 ° C (pC / cm ² ) (Injecting the liquid crystal composition into the cell Ion density value when measuring with a cell of 3.5 μm thickness using MTR-1 (manufactured by Toyo Technology Co., Ltd. under conditions of applying 20 V and a frequency of 0.05 Hz) After a predetermined fixed pattern is displayed in the display area for 1200 hours or 1000 hours, the level of the afterimage of the fixed pattern when uniform display is performed on the entire screen is evaluated visually in the following four stages.

◎: No residual image after 1200 hours display ○: No residual image after 1000 hours display ○: Very few residual images after 1000 hours display are acceptable level △: Unacceptable after image after 1000 hours display Level x: The afterimage is displayed after 1000 hours and is extremely bad. Furthermore, the following abbreviations are used to describe the compounds in the examples. (Ring structure)

[Chemical 46]

(Side chain structure)

[TABLE 8]

(Where n in the table is a natural number) (connection structure)

[TABLE 9]

(Where n in the table is a natural number) [Production of color filter] [Preparation of coloring composition] [Green pigment coloring composition 1] The average primary particle diameter by the small-angle X-ray scattering method is 25 nm 14.8 parts of gallium phthalocyanine pigment of the general formula (1a) with a standardized dispersion of 40%, 47 parts of yellow pigment 1 (CI Pigment Yellow 138) with an average primary particle size of 30 nm and a standardized dispersion of 40% 5 parts of yellow 138 sulfonic acid derivative, 7.0 parts of Disperbyk LPN6919 (manufactured by BYK Chemical Co., Ltd.) were put into polyethylene bottles, and propylene glycol monomethyl ether acetate was added 55 parts of 0.3 mmf-0.4 mmf zirconia beads "ER-120S" manufactured by Saint-Gobain, dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, and then 5 μm Filter to obtain a pigment coloring solution. Furthermore, 75.00 parts of the pigment coloring solution, 5.50 parts of polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Synthetic Chemical Industry Co., Ltd.), and dipentaerythritol hexaacrylate were dispersed with a dispersing mixer. (KAYARAD (brand name) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 5.00 parts, benzophenone (KAYACURE (brand name) BP-100, Nippon Kayaku Co., Ltd. (Production) 1.00 parts, UCAR Ester EEP 13.5 parts were stirred, and filtered with a filter having a pore size of 1.0 μm to obtain a green pigment colored composition 1.

Furthermore, in the embodiment of the present invention, the average primary particle diameter and particle size distribution of the organic pigment can be determined according to the small-angle X-ray scattering distribution of the organic pigment dispersion based on the small-angle X-ray scattering method disclosed in Japanese Patent Laid-Open No. 2006-113042 ( Measure the scattering distribution). The standardized dispersion indicating the particle size distribution by the small-angle X-ray scattering method is calculated using the method described in Japanese Patent Laid-Open No. 2013-96944. [Green pigment coloring composition 2] Instead of the 4.8 parts of gallium phthalocyanine pigment 1 of the green pigment coloring composition 1, a phthalate of the general formula (1b) having an average primary particle diameter of 40 nm and a standardized dispersion of 50% is used Aluminium cyanocyanine pigment 2 4.5 parts and copper phthalocyanine sulfonic acid derivative 0.3 part, instead of yellow pigment 1 (CI Pigment Yellow 138), the average primary particle size was 30 nm and standardized dispersion was 40%. The quinophthalone pigment of the general formula (3a) is performed in the same manner as described above to obtain a green pigment coloring composition 2. [Green Pigment Coloring Composition 3] Instead of 4.8 parts of the gallium phthalocyanine pigment 1 of the green pigment coloring composition 1, bromine in the general formula (1l) having an average primary particle diameter of 20 nm and standardized dispersion of 35% was used. 4.5 parts of aluminum phthalocyanine pigments with an average substituent number of 8 and 0.3 parts of copper phthalocyanine sulfonic acid derivatives, and replaced 47 parts of yellow pigment 1 (CI Pigment Yellow 138) with an average primary particle size of 30 20 parts of the quinophthalone pigment of the general formula (3a) with a standardized dispersion of 40 nm and 40% were performed in the same manner as described above to obtain a green pigment coloring composition 3.

[Green pigment coloring composition 4] Instead of the 4.8 parts of gallium phthalocyanine pigment of the green pigment coloring composition 1, the general formula (1b) / (with an average primary particle diameter of 25 nm and a standardized dispersion of 45% is used. 2a) = 95/5 is a mixture of 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), and the average primary particle size is A quinophthalone pigment, which is a compound of (4a) at 20 nm and standardized dispersion of 35%, was carried out in the same manner as described above to obtain a green pigment coloring composition 4.

[Green pigment coloring composition 5] Instead of the 4.8 parts of gallium phthalocyanine pigment 1 of the green pigment coloring composition 1, bromine in the general formula (1l) having an average primary particle diameter of 30 nm and a standardized dispersion of 50% is used. Aluminum phthalocyanine pigment with an average number of substituents of 8 / (2g) Bromine with an average number of bromine substituents of 8 phthalocyanine dialuminum pigment = 97/3 is a mixture of 5 4.5 parts of aluminum phthalocyanine pigment, copper phthalocyanine sulfonic acid derivative 0.3 parts, instead of 47 parts of Yellow Pigment 1 (CI Pigment Yellow 138), and 20 parts of a compound (4a), which is an average primary particle size of 20 nm and a standardized dispersion of 35%, is used, and This is performed in the same manner to obtain a green pigment coloring composition 5.

[Green Pigment Coloring Composition 6] Instead of the 4.8 parts of gallium phthalocyanine pigment of the green pigment coloring composition 1, a phthalate of the general formula (1b) having an average primary particle size of 55 nm and a standardized dispersion of 65% was used. 4.8 parts of aluminum cyanine pigment was carried out in the same manner as described above to obtain green pigment coloring composition 6. [Red pigment coloring composition 1] 10 parts of a red pigment 1 (CI Pigment Red 254) having an average primary particle diameter of 25 nm and a standardized dispersion of 40% by a small-angle X-ray scattering method was put into a polyethylene bottle 55 parts of propylene glycol monomethyl ether acetate, 7.0 parts of Disperbyk LPN21116 (manufactured by BYK Chemical Co., Ltd.), and 0.3 mmf-0.4 mmf zirconia manufactured by Saint-Gobain The beads "ER-120S" were dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, and then filtered through a 1 μm filter to obtain a pigment dispersion liquid. 75.00 parts of the pigment dispersion liquid, 5.50 parts of polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Synthetic Chemical Industry Co., Ltd.), dipentaerythritol hexaacrylate (Kaya KAYARAD (brand name) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 5.00 parts, benzophenone (KAYACURE (brand name) BP-100, manufactured by Nippon Kayaku Co., Ltd.) 1.00 13.5 parts of UCAR Ester EEP were stirred, and filtered with a filter having a pore size of 1.0 μm to obtain a red pigment coloring composition 1. [Red Pigment Coloring Composition 2] 10 parts of Red Pigment 1 instead of Red Pigment Coloring Composition 1 was used, and 16 parts of Red Pigment and Red Pigment 2 (Pigment Red 177, DIC) were used. Two parts of FASTOGEN SUPER RED (ATY-TR) and two parts of yellow pigment 2 (CI Pigment Yellow 139) manufactured by the Corporation are obtained in the same manner as described above to obtain a red pigment coloring composition.物 2。 Object 2. [Blue Pigment Coloring Composition 1] 1.80 parts of triarylmethane lake pigment (Compound No. 2 in Table 1) represented by the general formula (6), BYK-2164 (BYK Chemical Co., Ltd.) 2.10 parts, 11.10 parts of propylene glycol monomethyl ether acetate, 0.3 mmf-0.4 mmf zirconia-silica beads were placed in a polyethylene bottle, and dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours to obtain Pigment dispersion. 75.00 parts of the pigment dispersion liquid, 5.50 parts of polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Synthetic Chemical Industry Co., Ltd.), dipentaerythritol hexaacrylate (Kaya KAYARAD (brand name) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 5.00 parts, benzophenone (KAYACURE (brand name) BP-100, manufactured by Nippon Kayaku Co., Ltd.) 1.00 13.5 parts of UCAR Ester EEP (manufactured by Union Carbide) were stirred and filtered with a filter having a pore size of 1.0 μm to obtain a blue pigment coloring composition 1. [Blue Pigment Coloring Composition 2] 1.80 parts of a blue pigment (CI Pigment Blue 15: 6) with an average primary particle diameter of 20 nm and a standardized dispersion of 50% by the small-angle X-ray scattering method, described above 0.18 parts of xanthene compound of general formula (7a), 2.84 parts of BYK-LPN21116 (Bike Chemical Company), 10.19 parts of propylene glycol monomethyl ether acetate, 0.3 mmf-0.4 mmf zirconia manufactured by Saint-Gobain The beads "ER-120S" were put into a polyethylene bottle and dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours to obtain a pigment dispersion liquid. 75.00 parts of the pigment dispersion liquid, 5.50 parts of polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Synthetic Chemical Industry Co., Ltd.), dipentaerythritol hexaacrylate (Kaya KAYARAD (brand name) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 5.00 parts, benzophenone (KAYACURE (brand name) BP-100, manufactured by Nippon Kayaku Co., Ltd.) 1.00 13.5 parts of UCAR Ester EEP (manufactured by Union Carbide) were stirred, and filtered with a filter having a pore size of 1.0 μm to obtain a blue pigment coloring composition 2. [Yellow pigment coloring composition 1] Instead of 10 parts of the red pigment 1 of the red pigment coloring composition 1, yellow pigment 1 (CI Pigment Yellow 150) was used, and Fansen Express made by LANXESS 10 parts of FANCHON FAST YELLOW (E4GN) were carried out in the same manner as described above to obtain a yellow pigment coloring composition 1. [Production of color filter] A red coloring composition was applied to a glass substrate having a black matrix formed in advance by spin coating with a film thickness of 2 μm. After drying at 70 ° C. for 20 minutes, a stripe pattern exposure was performed with an ultraviolet ray through an exposure machine equipped with an ultra-high pressure mercury lamp through a light mask. It was spray-developed with an alkaline developer for 90 seconds, washed with ion-exchanged water, and air-dried. Further, post-baking was performed at 230 ° C. for 30 minutes in a clean oven to form a red pixel as a striped colored layer on a transparent substrate.

Next, similarly, the green coloring composition was applied so that the film thickness became 2 μm by spin coating. After drying, the stripe-shaped coloring layer is exposed and developed using an exposure machine at a place staggered from the red pixel, thereby forming a green pixel adjacent to the red pixel.

Next, the blue coloring composition was similarly formed by spin coating with a film thickness of 2 μm to form a blue pixel adjacent to the red pixel and the green pixel. As a result, a color filter having striped pixels of three colors of red, green, and blue on a transparent substrate can be obtained.

If necessary, the yellow coloring composition is similarly formed by spin coating with a film thickness of 2 μm to form a yellow pixel adjacent to the red pixel and the green pixel. Thus, a color filter having striped pixels of four colors of red, green, blue, and yellow on a transparent substrate can be obtained.

The color filter 1 to the color filter 5 and the comparative color filter 1 were prepared using the dye coloring composition or pigment coloring composition shown in the following table.

[TABLE 10]

[Measurement of Volume Fraction of Organic Pigment in Color Filter] (Measurement of Coarse Particles Using a Microscope) For the G pixel portion of the obtained color filter 1 to color filter 5, Nikon Corporation was used. The optical microscope Optiphot 2 was manufactured and observed at arbitrary five places at a magnification of 2,000 times. As a result, no coarse particles of 1000 nm or more were observed at any place. (Measurement using USAXS color filter 1 to color filter 5 and comparative color filter 1) The G pixel portion of color filter 1 to color filter 5 was attached to a sample made of Al with tape. The holder is set on a sample stand for transmission. Using the method described in Japanese Patent Laid-Open No. 2013-96944 to perform ultra-small angle X-ray scattering measurement and analysis, the results can obtain three particle size distributions, where the average particle size is greater than 1 nm and less than 40 nm The particles are represented as primary particles. Similarly, the distribution of 40 nm or more and less than 100 nm is expressed as secondary particles, and the distribution of 100 nm or more and 1000 nm or less is expressed as tertiary particles. The total of secondary particles is set to higher-order particles.

As a result of the measurement / analysis, the volume fraction of the 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 1 to the color filter 5 is shown. 81% to 91%, the volume fraction of secondary particles represented by a distribution from 40 nm to 100 nm is 9% to 19%, and the volume of tertiary particles represented by a distribution from 100 nm to 1000 nm The fraction is 0.0%, and the volume fraction occupied by particles above 40 nm and below 1000 nm is 9% to 19%.

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

The measurement equipment and measurement method are as follows. Measuring device: Large-scale radiation facility: Frontier Soft Matter developed by SPring-8 Beamline: BL03XU Second hatch measurement mode: Ultra-small angle X-ray scattering (USAXS) Measurement conditions : Wavelength of 0.1 nm, camera length of 6 m, beam spot size of 140 μm × 80 μm, no attenuator, exposure time of 30 seconds, 2θ = 0.01 ° ～ 1.5 ° Analysis software: visualization and analysis of two-dimensional data One-dimensional and two-dimensional fitting (obtained from the homepage of the European Synchrotron Radiation Facility [http://www.esrf.eu/computing/scientific/FIT2D/]) Using Rigaku (share ) The software NANO-Solver (Ver 3.6) is manufactured to analyze the particle size distribution.

For each pixel portion of the color filter, a color filter microspectrometer LCF-100 manufactured by Otsuka Electronics was used to measure the x value and y value under the C light source of the CIE1931 XYZ color system. The results are shown in the following table.

[TABLE 11]

(Example 1 to Example 5) An electrode structure was formed on the first substrate and the second substrate, and a vertical alignment alignment film was formed on each of the opposite sides, and then subjected to a weak friction treatment to prepare a VA unit. The liquid crystal composition 1 shown in the table is sandwiched between a first substrate and a second substrate. Next, the color filters 1 to 5 shown in the table were used to prepare the liquid crystal display devices of Examples 1 to 5 (d _gap = 3.5 μm, alignment film SE-5300). The VHR and ID of the obtained liquid crystal display device were measured. In addition, the obtained liquid crystal display device was evaluated for baking. The results are shown in the following table.

[TABLE 12]

[TABLE 13]

It can be seen that the liquid crystal composition 1 has a practical liquid crystal phase temperature range of 74.3 ° C. as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, and has low viscosity and optimal Δn.

The liquid crystal display devices of the first to fifth embodiments can realize a high VHR and a small ID. In addition, there were no afterimages in the burn-in evaluation, or there were very few and allowable levels. (Examples 6 to 20) In the same manner as in Example 1, a liquid crystal composition shown in the following table was held, and a color filter 1 to a color filter 5 shown in the table were used to form an example. The liquid crystal display device of 6 to Example 20 was measured for VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 14]

[Table 15]

[TABLE 16]

[TABLE 17]

The liquid crystal display devices of Examples 6 to 20 can realize a high VHR and a small ID. In addition, there were no afterimages in the burn-in evaluation, or there were very few and allowable levels. (Examples 21 to 25) In the same manner as in Example 1, the liquid crystal composition shown in the following table was sandwiched, and the color filters 1 to 5 shown in the table were used to prepare examples. The liquid crystal display devices of 21 to Example 25 were measured for VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 18]

[TABLE 19]

The liquid crystal display devices of Examples 21 to 25 can realize a high VHR and a small ID. In addition, the burn-in evaluation was also performed at a level without afterimages. (Example 26 to Example 27) The liquid crystal composition shown in the following table was held in the same manner as in Example 1, and the color filters 3 shown in the table were used to prepare Examples 26 and 27. A liquid crystal display device, and measured its VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 20]

[TABLE 21]

The liquid crystal display devices of Examples 26 to 27 can realize a high VHR and a small ID. In addition, the burn-in evaluation was also performed at a level without afterimages. (Examples 28 to 32) In the same manner as in Example 1, the liquid crystal composition shown in the following table was held, and the color filters 1 to 5 shown in the table were used to prepare examples. The liquid crystal display devices of 28 to Example 32 were measured for their VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 22]

[TABLE 23]

The liquid crystal display devices of Examples 28 to 32 can realize a high VHR and a small ID. In addition, even if there is an afterimage in the burn-in evaluation, it is extremely small and is acceptable. (Example 33 to Example 35) The liquid crystal composition shown in the following table was held in the same manner as in Example 1, and the color filters 3 shown in the table were used to prepare Examples 33 to 35. A liquid crystal display device, and measured its VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 24]

[TABLE 25]

The liquid crystal display devices of Examples 33 to 35 can realize a high VHR and a small ID. In addition, there were no afterimages in the burn-in evaluation, or there were very few and allowable levels. (Examples 36 to 40) In the same manner as in Example 1, the liquid crystal composition shown in the following table was sandwiched, and the color filters 1 to 5 shown in the table were used to prepare examples. The liquid crystal display devices of 36 to Example 40 were measured for VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 26]

[TABLE 27]

The liquid crystal display devices of Examples 36 to 40 can realize a high VHR and a small ID. In addition, even if there is an afterimage in the burn-in evaluation, it is extremely small and is acceptable. (Example 41 to Example 42) As in Example 1, the liquid crystal composition shown in the following table was held, and the color filters 3 shown in the table were used to prepare Examples 41 and 42. A liquid crystal display device, and measured its VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 28]

[TABLE 29]

The liquid crystal display devices of Examples 41 to 42 can realize a high VHR and a small ID. In addition, the afterimage in the burn-in evaluation was also very small and was tolerable. (Examples 43 to 47) In the same manner as in Example 1, the liquid crystal composition shown in the following table was held, and the color filters 1 to 5 shown in the table were used to prepare examples. 43 to Example 47. The liquid crystal display devices were measured for VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 30]

[TABLE 31]

The liquid crystal display devices of Examples 43 to 47 can realize a high VHR and a small ID. In addition, even if there is an afterimage in the burn-in evaluation, it is extremely small and is acceptable. (Example 48 to Example 49) The liquid crystal composition shown in the following table was held in the same manner as in Example 1, and the color filters 3 shown in the table were used to prepare Examples 48 and 49. A liquid crystal display device, and measured its VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 32]

[TABLE 33]

The liquid crystal display devices of Examples 48 to 49 can realize a high VHR and a small ID. In addition, the afterimage in the burn-in evaluation was also very small and was tolerable. (Examples 50 to 54) In the same manner as in Example 1, the liquid crystal composition shown in the following table was held, and the color filters 1 to 5 shown in the table were used to prepare examples. The liquid crystal display devices of 50 to Example 54 were measured for VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 34]

[TABLE 35]

The liquid crystal display devices of Examples 50 to 54 can realize a high VHR and a small ID. In addition, the burn-in evaluation was also performed at a level without afterimages. (Example 55 to Example 57) In the same manner as in Example 1, the liquid crystal composition shown in the following table was sandwiched, and the color filter 3 shown in the table was used to prepare Examples 55 to 57. A liquid crystal display device, and measured its VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 36]

[TABLE 37]

The liquid crystal display devices of Examples 55 to 57 can realize a high VHR and a small ID. In addition, the burn-in evaluation was also performed at a level without afterimages. (Examples 58 to 62) In the same manner as in Example 1, a liquid crystal composition shown in the following table was held, and a color filter 1 to a color filter 5 shown in the table were used to form an example. The liquid crystal display devices of 58 to Example 62 were measured for VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 38]

[TABLE 39]

The liquid crystal display devices of Examples 58 to 62 can realize a high VHR and a small ID. In addition, the burn-in evaluation was also performed at a level without afterimages. (Examples 63 to 65) In the same manner as in Example 1, the liquid crystal compositions shown in the following table were held, and the color filters 3 shown in the table were used to prepare examples 63 to 65. A liquid crystal display device, and measured its VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 40]

[TABLE 41]

The liquid crystal display devices of Examples 63 to 65 can realize a high VHR and a small ID. In addition, the burn-in evaluation was also performed at a level without afterimages. (Examples 66 to 70) In the same manner as in Example 1, the liquid crystal composition shown in the following table was sandwiched, and the color filters 1 to 5 shown in the table were used to prepare examples. The liquid crystal display devices of 66 to Example 70 were measured for their VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 42]

[TABLE 43]

The liquid crystal display devices of Examples 66 to 70 can realize a high VHR and a small ID. In addition, there were no afterimages in the burn-in evaluation, or there were very few and allowable levels. (Examples 71 to 72) In the same manner as in Example 1, the liquid crystal composition shown in the following table was held, and the color filters 3 shown in the table were used to prepare examples 71 to 72. A liquid crystal display device, and measured its VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 44]

[Table 45]

The liquid crystal display devices of Examples 71 to 72 can realize a high VHR and a small ID. In addition, the burn-in evaluation was also performed at a level without afterimages. (Examples 73 to 77) In the same manner as in Example 1, the liquid crystal composition shown in the following table was held, and the color filters 1 to 5 shown in the table were used to prepare examples. 73 to Example 77. The liquid crystal display device was measured for VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[Table 46]

[TABLE 47]

The liquid crystal display devices of Examples 73 to 77 can realize a high VHR and a small ID. In addition, there were no afterimages in the burn-in evaluation, or there were very few and allowable levels. (Example 78 to Example 79) As in Example 1, the liquid crystal composition shown in the following table was held, and the color filter 3 shown in the table was used to prepare Examples 78 to 79. A liquid crystal display device, and measured its VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 48]

[TABLE 49]

The liquid crystal display devices of Examples 78 to 79 can realize a high VHR and a small ID. In addition, the burn-in evaluation was tolerable even if there was an afterimage. (Examples 80 to 84) In the same manner as in Example 1, the liquid crystal composition shown in the following table was sandwiched, and the color filters 1 to 5 shown in the table were used to prepare examples. The liquid crystal display devices of 80 to Example 84 were measured for VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 50]

[TABLE 51]

The liquid crystal display devices of Examples 80 to 84 can realize a high VHR and a small ID. In addition, the burn-in evaluation was also performed at a level without afterimages. (Examples 85 to 86) In the same manner as in Example 1, the liquid crystal compositions shown in the following table were held, and the color filters 3 shown in the table were used to prepare examples 85 to 86. A liquid crystal display device, and measured its VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 52]

[TABLE 53]

The liquid crystal display devices of Examples 85 to 86 can realize a high VHR and a small ID. In addition, in the burn-in evaluation, there is no afterimage or even if there is an afterimage, it is extremely small and acceptable. (Examples 87 to 91) In the same manner as in Example 1, the liquid crystal composition shown in the following table was sandwiched, and the color filters 1 to 5 shown in the table were used to prepare examples. 87 to Example 91. The liquid crystal display device was measured for VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 54]

[TABLE 55]

The liquid crystal display devices of Examples 87 to 91 can realize a high VHR and a small ID. In addition, even if there is an afterimage in the burn-in evaluation, it is extremely small and is acceptable. (Examples 92 to 94) In the same manner as in Example 1, the liquid crystal composition shown in the following table was held, and the color filters 3 shown in the table were used to prepare examples 92 to 94. A liquid crystal display device, and measured its VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 56]

[TABLE 57]

The liquid crystal display devices of Examples 92 to 94 can realize a high VHR and a small ID. In addition, even if there is an afterimage in the burn-in evaluation, it is extremely small and is acceptable. (Examples 95 to 99) Liquid crystal composition 15 was mixed with 2-methyl-acrylic acid 4- ｛2- [4- (2-propenyloxy-ethyl) -phenoxycarbonyl] -ethyl The fluorene-biphenyl-4'-yl ester was 0.3% by mass to prepare a liquid crystal composition 39. The liquid crystal composition 39 was sandwiched between the VA cells used in Example 1, a driving voltage was applied between the electrodes, and ultraviolet light with 365 nm as the main wavelength was irradiated for 600 seconds in the state. A driving voltage was applied and irradiation was performed for 60 minutes with ultraviolet light having 313 nm as the main wavelength to perform polymerization treatment, and then the color filters 1 to 5 shown in the table were used to prepare Examples 95 to Implementation. The liquid crystal display device of Example 99 was measured for VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 58]

The liquid crystal display devices of Examples 95 to 99 can realize a high VHR and a small ID. In addition, there were no afterimages in the burn-in evaluation, or there were very few and allowable levels. (Examples 100 to 104) The liquid crystal composition 32 was mixed with 0.3% by mass of biphenyl bismethacrylate-4,4'-diyl ester to prepare a liquid crystal composition 40. The liquid crystal composition 40 was sandwiched between the VA cells used in Example 1, a driving voltage was applied between the electrodes, and ultraviolet light with 365 nm as the main wavelength was irradiated for 600 seconds in the state. A driving voltage was applied and irradiation was performed for 60 minutes with ultraviolet light having 313 nm as the main wavelength to perform polymerization treatment. Next, the color filters 1 to 5 shown in the table were used to prepare Examples 100 to 100. The liquid crystal display device of Example 104 was measured for VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 59]

The liquid crystal display devices of the embodiments 100 to 104 can realize a high VHR and a small ID. In addition, the burn-in evaluation was also performed at a level without afterimages. (Examples 105 to 109) A liquid crystal composition 32 was prepared by mixing 0.3% by mass of the compound represented by the following formula (V-8-3) into the liquid crystal composition 32. The liquid crystal composition 41 was sandwiched between the VA cells used in Example 1, a driving voltage was applied between the electrodes, and ultraviolet light with 365 nm as the main wavelength was irradiated for 600 seconds in the state, and then The driving voltage was applied and irradiation was performed for 60 minutes with ultraviolet light having 313 nm as the main wavelength to perform polymerization treatment, and then the color filters 1 to 5 shown in the table were used to prepare Examples 105 to Implementation The liquid crystal display device of Example 109 was measured for VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[Chemical 47]

[TABLE 60]

The liquid crystal display devices of Examples 105 to 109 can realize a high VHR and a small ID. In addition, there were no afterimages in the burn-in evaluation, or there were very few and allowable levels. (Comparative Example 1 to Comparative Example 5) A comparative liquid crystal composition shown in the following table was held in the same manner as in Example 1, and a color filter 1 to a color filter 5 shown in the table were used to create a comparative example. The liquid crystal display devices of 1 to Comparative Example 5 were measured for their VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 61]

[TABLE 62]

Compared with the liquid crystal display device of the present invention, the liquid crystal display devices of Comparative Examples 1 to 5 have the same or slightly worse VHR and ID. However, the occurrence of afterimages was confirmed in the burn-in evaluation. Allowable level. (Comparative Example 6 to Comparative Example 10) A comparative liquid crystal composition shown in the following table was held in the same manner as in Example 1, and a color filter 1 to a color filter 5 shown in the table were used to create a comparative example. 6 to Comparative Example 10 liquid crystal display devices, and measured their VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[Table 63]

[TABLE 64]

Compared with the liquid crystal display device of the present invention, the liquid crystal display devices of Comparative Examples 6 to 10 have a lower VHR and a larger ID. In addition, it was confirmed that the occurrence of afterimages was not at an acceptable level in the burn-in evaluation. (Comparative Example 11 to Comparative Example 18) Liquid crystal composition 1, liquid crystal composition 5, liquid crystal composition 8, liquid crystal composition 15, liquid crystal composition 18, liquid crystal composition 29, liquid crystal composition 32, and liquid crystal composition 35 were respectively The liquid crystal display devices of Comparative Examples 11 to 18 were fabricated by sandwiching the VA unit used in Example 1 using the comparative color filter 1 shown in the table, and measuring their VHR and ID. In addition, a burn-in evaluation of the liquid crystal display device was performed. The results are shown in the following table.

[TABLE 65]

[TABLE 66]

Compared with the liquid crystal display device of the present invention, the liquid crystal display devices of Comparative Examples 11 to 18 have a lower VHR and a larger ID. In addition, it was confirmed that the occurrence of afterimages was not at an acceptable level in the burn-in evaluation.

1‧‧‧ substrate

2‧‧‧ color filter layer

2a‧‧‧ Color filter layer containing specific pigment and specific compound

3a‧‧‧Transparent electrode layer (common electrode)

3b‧‧‧pixel electrode layer

4‧‧‧alignment film

5‧‧‧LCD layer

5a‧‧‧ Liquid crystal layer containing specific liquid crystal composition

FIG. 1 is a diagram showing an example of a conventional general liquid crystal display device. FIG. 2 is a diagram showing an example of a liquid crystal display device of the present invention.

Claims (10)

A liquid crystal display device includes a first substrate, a second substrate, a liquid crystal layer sandwiched between the first substrate and the second substrate, and a color filter including a black matrix and at least three RGB pixel portions. A light sheet, and a pixel electrode and a common electrode, the liquid crystal layer contains a liquid crystal composition, the liquid crystal composition has 10 to 50% by weight of a compound represented by the general formula (I), and has 35% to 80% % By weight of a compound represented by the general formula (II), In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or 2 to 8 carbon atoms. Alkenyl, In the formula, R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or 2 to 8 carbon atoms. Alkenyloxy, Z ³ and Z ⁴ each independently represent a single bond, -CH = CH-, -C≡C-, -CH ₂ CH ₂ -,-(CH ₂ ) _4- , -COO-, -OCO- , -OCH _2- , -CH ₂ O-, -OCF _2- , or -CF ₂ O-, and B and C each independently represent fluorine-substituted 1,4-phenylene or trans-1,4- Cyclohexyl groups, m and n each independently represent an integer of 0 to 4, m + n = 1 to 4, the RGB three-color pixel portion contains at least one or more selected from the G pixel portion and is selected from a method using a small angle X-ray scattering method The metal phthalocyanine in the first group represented by the following general formula (PIG-1) and / or the second group represented by the following general formula (PIG-2) with an average primary particle diameter of 5 nm to 50 nm Pigments as color materials, In the general formula (PIG-1), X ¹ⁱ to X ¹⁶ⁱ each independently represent a halogen atom, a nitro group, a phthalimideimide methyl group which may have a substituent, an sulfamoyl group which may have a substituent, and An alkyl group having a substituent, an aryl group having a substituent, a cycloalkyl group having a substituent, a heterocyclic group having a substituent, an alkoxy group having a substituent, and an aryloxy group having a substituent , An alkylthio group which may have a substituent, or an arylthio group which may have a substituent; Y ¹ⁱ represents a hydroxyl group, a chlorine atom, -OP (= O) R1R2, or -O-SiR3R4R5; here, R1 to R5 are independent A hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent, R1 and R2, R3 to R5 each other Can be bonded to each other to form a ring; M represents a trivalent metal selected from the group consisting of Ga, Al, Sc, Y, and In, In the general formula ^{(PIG-2), X 17i} ~ X 32i each independently represent a halogen atom, a nitro group, a phthaloyl may have substituent (PEI) methyl group, a sulfo acyl amine may have a substituent, may be An alkyl group having a substituent, an aryl group having a substituent, a cycloalkyl group having a substituent, a heterocyclic group having a substituent, an alkoxy group having a substituent, and an aryloxy group having a substituent , An alkylthio group which may have a substituent, or an arylthio group which may have a substituent; M represents a trivalent metal selected from the group consisting of Ga, Al, Sc, Y, and In; Y ²ⁱ represents -O- , -O-SiR6R7-O-, -O-SiR6R7-O-SiR8R9-O-, or -OP (= O) R10-O-, R6 to R10 each independently represent a hydrogen atom, a hydroxyl group, and may have a substituent An alkyl group, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. The liquid crystal display device according to claim 1, wherein the RGB three-color pixel portion includes a diketopyrrolopyrrole pigment and / or an anionic red organic dye in the R pixel portion, and the B pixel portion It contains at least one selected from the group consisting of an ε-type copper phthalocyanine pigment, a triarylmethane dye, a triarylmethane lake pigment, and a cationic blue organic dye as a color material. The liquid crystal display device according to claim 1 or claim 2, wherein the G pixel portion contains a pigment derivative. The liquid crystal display device according to claim 1 or claim 2, wherein the G pixel portion includes one selected from the group consisting of the general formula (3), the general formula (4), and the general formula (5). One or more pigments in a quinophthalone compound, In the general formulae (3) to (5), R ₁₀ to R ₂₄ , R ₂₅ to R ₃₉ , and R ₄₀ to R ₅₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and Alkoxy groups of substituents, aryl groups which may have substituents, -SO ₃ H group, -COOH group, -SO ₃ H group, or -COOH group monovalent to trivalent metal salts; alkylammonium salts, may An phthalimidomethyl group having a substituent, or an sulfamoyl group which may have a substituent. The liquid crystal display device according to claim 1 or claim 2, wherein the liquid crystal composition constituting the liquid crystal layer contains a compound represented by general formula (II-1) as the general formula (II ), In the formula, R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or 2 to 8 carbon atoms. Alkenyloxy, Z ⁵ represents a single bond, -CH = CH-, -C≡C-, -CH ₂ CH ₂ -,-(CH ₂ ) _4- , -COO-, -OCO-, -OCH _2- , -CH ₂ O-, -OCF _2- , or -CF ₂ O-, and m1 represents 0 or 1. The liquid crystal display device according to claim 1 or claim 2, wherein the liquid crystal composition constituting the liquid crystal layer further contains a compound represented by the general formula (III), In the formula, R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or 2 to 8 carbon atoms. Alkenyloxy, D, E and F each independently represent fluorine-substituted 1,4-phenylene or trans-1,4-cyclohexylene, and Z ² represents a single bond, -OCH _2- , -OCO -, -CH ₂ O- or -COO-, n represents 0, 1 or 2; except for compounds represented by the general formula (I) and the general formula (II-1). The liquid crystal display device according to item 1 or 2 of the scope of patent application, wherein Z of the liquid crystal composition constituting the liquid crystal layer represented by the following formula is 13,000 or less, and γ1 is 150 or less. △ n is 0.08 to 0.13, In the formula, γ1 represents the rotational viscosity, and Δn represents the refractive index anisotropy. The liquid crystal display device according to claim 1 or claim 2, wherein the upper limit temperature of the nematic liquid crystal phase of the liquid crystal composition constituting the liquid crystal layer is 60 ° C to 120 ° C, and the lower limit of the nematic liquid crystal phase. The temperature is -20 ° C or lower, and the difference between the upper limit temperature of the nematic liquid crystal phase and the lower limit temperature of the nematic liquid crystal phase is 100 to 150. The liquid crystal display device according to claim 1 or claim 2, wherein the specific resistance of the liquid crystal composition constituting the liquid crystal layer is 10 ¹² Ω · m or more. The liquid crystal display device according to item 1 or item 2 of the patent application scope, wherein the liquid crystal layer includes a polymer, and the polymer is to contain at least one or two or more general formula (V) and / or The liquid crystal composition of the polymerizable compound represented by the general formula (V2) is polymerized, In the general formula (V), X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or -O- (CH ₂ ) _s- , where s represents an integer from 2 to 7, the oxygen atom is set to be bonded to the aromatic ring, and 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- , -C≡C- or a single bond, where Y ¹ and Y ² each independently represent a fluorine atom Or a hydrogen atom, C represents 1,4-phenylene, trans-1,4-cyclohexylene, or a single bond, and any hydrogen atom in all 1,4-phenylenes in the formula may be replaced by a fluorine atom , In the general formula (V2), X ¹⁰ and X ¹¹ each independently represent a hydrogen atom or a methyl group, and Sp ³ and Sp ⁴ each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or -X- (CH ₂ ) _t- , where t is an integer from 2 to 7, X is -O-, -OCOO-, -OCO-, or -COO-, and X is bonded to the phenanthrene ring, where An arbitrary hydrogen atom may be substituted with a fluorine atom.