TWI476270B - Liquid crystal display device - Google Patents

Description

Liquid crystal display device

The present invention relates to a liquid crystal display device.

The liquid crystal display device has been used in various household electric power equipment, measuring equipment, automobile panels, word processors, electronic notebooks, printers, computers, televisions, etc., starting with clocks and computers. Typical examples of the liquid crystal display method include TN (twisted nematic) type, STN (super twisted nematic) type, DS (dynamic light scattering) type, GH (guest host) type, and IPS. (in-plane switching) type, OCB (Optics Compensated), ECB (Voltage Controlled Refraction) type, VA (Vertical Alignment) type, CSH (Colored Overhang (Color) Super Homeotropic), or FLC (ferroelectric liquid crystal). Moreover, as the driving method, the conventional static driving to multiplex driving has become a general mode, a simple matrix method, and an active matrix recently driven by a TFT (Thin Film Transistor) or a TFD (Thin Film Diode). AM) is the mainstream.

As shown in Fig. 1, a general color liquid crystal display device includes a transparent electrode layer (3a) serving as a common electrode between an alignment film and a substrate of one of two substrates (1) each having an alignment film (4). And a color filter layer (2) having a pixel electrode layer (3b) disposed between the other alignment film and the substrate, wherein the substrates are disposed such that the alignment films face each other with the liquid crystal layer (5) interposed therebetween Composition.

The color filter layer comprises a black matrix and a red colored layer (R), a green colored layer (G), a blue colored layer (B), and a yellow color as needed. The color filter layer (Y) is formed by a color filter.

When the liquid crystal material constituting the liquid crystal layer has an extremely large influence on the electrical characteristics of the display device when impurities remain in the material, the impurities are highly managed. Further, the material for forming the alignment film is directly contacted with the liquid crystal layer by the alignment film, and the impurities remaining in the alignment film are moved to the liquid crystal layer, thereby affecting the electrical characteristics of the liquid crystal layer, which is caused by The study of the characteristics of liquid crystal display devices for impurities in the alignment film material is continuing.

On the other hand, the material of the organic pigment or the like used in the color filter layer is also assumed to have an influence on the liquid crystal layer due to impurities contained in the same manner as the alignment film material. However, considering that the alignment film and the transparent electrode are interposed between the color filter layer and the liquid crystal layer, the direct influence on the liquid crystal layer is greatly reduced as compared with the alignment film material. However, the alignment film is usually only a film thickness of 0.1 μm or less, and the transparent electrode is also used for a common electrode on the side of the color filter layer. In order to increase the conductivity, the film thickness is usually 0.5 μm or less. Therefore, it cannot be said that the color filter layer and the liquid crystal layer are placed in a completely isolated environment, and the color filter layer passes through the alignment film and the transparent electrode to form impurities of the color filter layer. The voltage holding ratio (VHR) is lowered, and the increase in ion density (ID) causes a possibility of display failure such as whiteness, uneven alignment, and burn marks. In the solution to the display defect caused by the impurities contained in the pigment constituting the color filter, it has been studied to use a pigment having a ratio of the extract of the pigment to ethyl acetate to a specific value or less, and to control the separation of the liquid crystal by the impurity. (Patent Document 1); or a method of controlling the elution of impurities into liquid crystals by specifying a pigment in a blue colored layer (Patent Document 2). But in these In the method, if the impurities in the pigment are simply reduced, the difference is not large. In recent years, the progress of the purification technology of the pigment has not been sufficient to improve the display defect.

On the one hand, focusing on the relationship between the organic impurities contained in the color filter and the liquid crystal composition, it is revealed that the solubility of the organic impurity to the liquid crystal layer is represented by the hydrophobicity parameter of the liquid crystal molecules contained in the liquid crystal layer. A method of forming a liquid crystal composition by a method in which the value of the hydrophobic parameter is set to a certain value or more, or a relationship between the hydrophobic parameter and the -OCF ₃ group at the end of the liquid crystal molecule, which is in the liquid crystal molecule The terminal contains a liquid crystal compound having a -OCF ₃ group in a predetermined ratio or more (Patent Document 3).

However, even if the disclosure of the cited document inhibits the influence of the liquid crystal layer caused by impurities in the pigment, it is the essence of the invention, and the structure of the coloring material such as dyes and pigments used in the color filter and the liquid crystal material are The direct relationship of the structure has not been discussed, and the problem of poor display of the liquid crystal display device has not yet been reached.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-19321

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-109542

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2000-192040

The present invention provides a liquid crystal display device which is prevented by using a color filter of a specific liquid crystal composition and a specific dye and/or pigment. The liquid crystal layer has a lower voltage holding ratio (VHR) and an increased ion density (ID), and solves problems such as whiteness, uneven alignment, and burn marks.

In order to solve the above problems, the inventors of the present invention have studied the combination of a coloring material such as a dye pigment for a color filter and a liquid crystal material structure constituting a liquid crystal layer, and have found a liquid crystal display device. A color filter that uses a specific liquid crystal material structure and a specific structure of dyes and or pigments to prevent a decrease in voltage holding ratio (VHR) of the liquid crystal layer, an increase in ion density (ID), and to solve whitening and alignment. Unevenness, burn marks, etc. showed poor problems, and thus the invention of the present invention was completed.

That is, the present invention provides a liquid crystal display device including: a first substrate; a second substrate; a liquid crystal composition layer sandwiched between the first substrate and the second substrate; and a color filter including black a matrix and at least RGB three-color pixel portion; a pixel electrode and a common electrode, wherein the liquid crystal composition layer comprises a liquid crystal composition containing 30 to 50% of a compound represented by the general formula (I) Wherein R ¹ and R ² are each independently, and 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; A represents 1,4-phenylene or trans-1,4-cyclohexenyl); contains 5 to 20% of the compound of the formula (II-1) (wherein R ³ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms; ⁴ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms; and 25 to 45 % of the compound of the formula (II-2) (wherein R ⁵ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms; ⁶ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms; and B is substituted by fluorine. 1,4-phenylene or trans-1,4-cyclohexenyl), the RGB three-color pixel portion, as a coloring material, contains a diketopyrrolopyrrole pigment and/or an anion in the R pixel portion a red organic dye; comprising at least one of the group consisting of a mixture selected from the group consisting of a copper halide phthalocyanine pigment, an indocyanine green dye, an indigo blue dye, and an azo yellow organic dye in the G pixel portion; The pixel portion contains an ε-type copper phthalocyanine pigment and/or a cationic blue organic dye.

In the liquid crystal display device of the present invention, by using a color filter which uses a specific liquid crystal composition and a specific dye and/or pigment, it is possible to prevent a decrease in the voltage holding ratio (VHR) of the liquid crystal layer and an ion density ( The ID) is increased, and it is possible to prevent display defects such as whiteness, uneven alignment, and burn marks.

[Formation of the Invention]

An example of the liquid crystal display device of the present invention is shown in Fig. 2. Between the alignment film and the substrate of one of the two substrates (1) having the first substrate and the second substrate of the alignment film (4), a transparent electrode layer (3a) serving as a common electrode, and a specific dye and a color filter layer (2) of a pigment, a pixel electrode layer (3b) disposed between the other alignment film and the substrate, and the substrates are disposed such that the alignment films face each other with a specific liquid crystal interposed therebetween It is composed of a liquid crystal layer (5) of a composition.

In the display device, two substrates are bonded by a sealing material and an encapsulant disposed in a peripheral region. In many cases, a spacer column is disposed to maintain a distance between the substrates therebetween. A spacer or a resin formed by photolithography.

(liquid crystal layer)

The liquid crystal layer of the liquid crystal display device of the present invention comprises a liquid crystal composition containing 30 to 50% of a compound represented by the general formula (I) (wherein R ¹ and R ² are each independently, and 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 2 carbon atoms; 8 alkenyloxy; A represents 1,4-phenylene or trans-1,4-cyclohexenyl); contains 5 to 20% of the compound of the formula (II-1) (wherein R ³ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms; ⁴ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms; and 25 to 45 % of the compound of the formula (II-2) (wherein R ⁵ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms; ⁶ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms; and B is substituted by fluorine. 1,4-phenylene or trans-1,4-cyclohexenyl).

In the liquid crystal display device of the present invention, the liquid crystal layer contains 30 to 50% of the compound represented by the formula (I), preferably 35 to 45%, more preferably 38 to 42%.

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 a carbon atom. The alkenyloxy group of 2 to 8 preferably represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or 2 to 5 carbon atoms. More preferably, it is an alkyl group having 2 to 5 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkenyloxy group having 2 to 4 carbon atoms. R ¹ preferably represents an alkyl group, and in this case, particularly preferably an alkyl group having 1, 3 or 5 carbon atoms.

R ¹ and R ² may be the same or different, preferably different, and R ¹ and R ² are each an alkyl group, particularly preferably an alkyl group having 1, 3 or 5 carbon atoms of different atomic numbers. .

The content of the compound of the formula (I) wherein at least one of the substituents of R ¹ and R ² is an alkyl group having 3 to 5 carbon atoms, preferably 50% or more of the compound represented by the formula (I) More preferably, it is 70% or more, and even more preferably 80% or more.

Further, the content of the compound of the formula (I) wherein at least one of the substituents of R ¹ and R ² is an alkyl group having 3 carbon atoms is preferably 50% or more of the compound represented by the formula (I). More preferably, it is 70% or more, and even more preferably 80% or more, and the best is 100%.

A represents a 1,4-phenylene group or a trans-1,4-cyclohexenyl group, and preferably represents a trans-1,4-cyclohexenyl group. Further, A represents a content of the compound represented by the formula (I) of trans-1,4-cyclohexenyl group, preferably 50% or more, more preferably 70% or more of the compound represented by the formula (I). , and then better than 80%.

The compound represented by the formula (I), specifically, a compound represented by the formula (Ia) to the formula (Ik) described below is preferred.

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, preferably in the formula (I) and R ¹ and R ² The same implementation).

In the formula (Ia) to the formula (Ik), preferred are the formula (Ia), the formula (Ib) and the formula (Ig), more preferably the formula (Ia) and the formula (Ig), Good for general formula (Ia) In the case where the response speed is emphasized, the general formula (Ib) is also preferred, and in the case where the response speed is more important, the general formula (Ib), the general formula (Ie), the general formula (If), and the general formula ( Ih), the dienyl compound of the formula (Ie) and the formula (If) is preferred in that the response speed is particularly emphasized.

From these viewpoints, the content of the compound represented by the formula (Ia) and the formula (Ig) is preferably 50% or more, more preferably 70% or more, more preferably in the compound represented by the formula (I). It is 80% or more, and the best is 100%. Further, the content of the compound represented by the formula (Ia) is preferably 50% or more, more preferably 70% or more, still more preferably 80% or more, of the compound of the formula (I).

The liquid crystal layer in the liquid crystal display device of the present invention contains 5 to 20% of the compound of the formula (II-1), preferably 10 to 15%, more preferably 12 to 14%.

In the formula (II-1), R ³ 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 a carbon number of 2 to 8 The alkenyloxy group preferably represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, more preferably an alkyl group having 2 to 5 carbon atoms or an alkyl group having 2 to 4 carbon atoms. Further, it is preferably an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 carbon atoms, particularly preferably an alkyl group having 3 carbon atoms.

R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms, preferably carbon. An alkyl group having 1 to 5 atoms or an alkoxy group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, more preferably carbon The alkyl group having 3 atomic atoms or the alkoxy group having 2 carbon atoms is particularly preferably an alkoxy group having 2 carbon atoms.

The compound of the formula (II-1) is specifically described later. A compound of the formula (II-1a) and the formula (II-1b).

(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).

In the formula (II-1a), R ^{3 is} preferably the same embodiment as in the 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, particularly preferably an alkyl group having 2 carbon atoms.

In the formula (II-1b), R ^{3 is} preferably the same embodiment as in the 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, particularly preferably an alkyl group having 3 carbon atoms.

Among the general formulae (II-1a) and (II-1b), in order to increase the absolute value of the dielectric anisotropy, the formula (II-1a) is preferred.

In the liquid crystal display device of the present invention, the liquid crystal layer contains 25 to 45% of the compound of the formula (II-2), and preferably contains 30 to 40%, more preferably 31 to 36%.

In the formula (II-2), R ⁵ 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 a carbon number of 2 to 8 The alkenyloxy group preferably represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, more preferably an alkyl group having 2 to 5 carbon atoms or 2 to 4 carbon atoms. The alkenyl group is preferably an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 carbon atoms, particularly preferably an alkyl group having 3 carbon atoms.

R ⁶ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms, preferably carbon. An alkyl group having 1 to 5 atoms or an alkoxy group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, more preferably carbon The alkyl group having 3 atomic atoms or the alkoxy group having 2 carbon atoms is particularly preferably an alkoxy group having 2 carbon atoms.

B represents a 1,4-phenylene group or a trans-1,4-cyclohexenyl group which may be substituted by fluorine, preferably an unsubstituted 1,4-phenylene group or a trans-1,4-cyclohexyl group. The alkenyl group is more preferably trans-1,4-cyclohexenyl.

The compound represented by the formula (II-2), specifically, the compound of the formula (II-2a) to the formula (II-2d) described later is preferred.

(wherein R ⁵ represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms; and R ^6a represents an alkyl group having 1 to 5 carbon atoms, and preferably a formula (II-2) In the same way as R ⁵ and R ⁶ ).

In the formula (II-2a) and the formula (II-2b), R ^{5 is} preferably the same embodiment as in the formula (II-2). R ^{6a is} preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, particularly preferably an alkyl group having 2 carbon atoms.

In the formula (II-2c) and the formula [II-2d), R ^{5 is} preferably the same embodiment as in the formula (II-2). R ^{6a is} preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 3 carbon atoms, particularly preferably an alkyl group having 3 carbon atoms.

In the general formula (II-1a) and the general formula (II-1b), in order to increase the absolute value of the dielectric anisotropy, the general formula (II-1a) is preferred.

Further, in the formula (II-2), it is preferred that B represents a compound of 1,4-phenylene group and B represents a compound of trans-1,4-cyclohexenyl group each containing at least one or more.

In the liquid crystal display device of the present invention, the liquid crystal layer further preferably contains a compound represented by the formula (III).

(wherein R ⁷ and R ⁸ are each independently, and 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 2 carbon atoms; 8 alkenyloxy; D, E, F and G are each independently, meaning 1,4-phenyl or trans-1,4-cyclohexene which can be substituted by fluorine; Z ² represents a single bond, -OCH ₂ -, -OCO-, -CH ₂ O- or -COO-; n represents 0 or 1, but n represents 0, and Z ² represents -OCH ₂ -, -OCO-, -CH ₂ O- or - COO-, or D, E, and G systems are 1,4-phenyl groups which can be substituted by fluorine. It is preferably contained in an amount of from 5 to 20% by weight of the compound of the formula (III), more preferably from 8 to 15%, still more preferably from 10 to 13%.

In the 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 oxyalkylene having 2 to 8 carbon atoms. The base preferably represents a case where D represents trans-1,4-cyclohexene, and preferably represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, more preferably An alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, more preferably an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 carbon atoms, particularly preferably a carbon atom number of 3 Alkyl group.

D represents a 1,4-phenylene group which may be substituted by fluorine, and preferably represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 or 5 carbon atoms, more preferably 2 to 5 An alkyl group of 5 or an alkenyl group having 4 carbon atoms, and more preferably an alkyl group having 2 to 4 carbon atoms.

R ⁸ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms, and G represents trans- In the case of 1,4-cyclohexene, it is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, more preferably an alkyl group having 2 to 5 carbon atoms or a carbon atom. The alkenyl group having 2 to 4 is preferably an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 carbon atoms, and particularly preferably an alkyl group having 3 carbon atoms.

G represents a 1,4-phenylene group which may be substituted by fluorine, and preferably represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 or 5 carbon atoms, more preferably 2 to 2 An alkyl group of 5 or an alkenyl group having 4 carbon atoms, and more preferably an alkyl group having 2 to 4 carbon atoms.

R ⁷ and R ⁸ represent an alkenyl group, and D or G of a bond represents a 1,4-phenylene group which may be substituted by fluorine, and in the case of an alkenyl group having 4 or 5 carbon atoms, the following structure is preferred. .

(wherein, the right end is bonded to the ring structure) In this case, it is preferably an alkenyl group having 4 carbon atoms.

D, E, F and G are each independently, and represent 1,4-phenylene or trans-1,4-cyclohexene which may be substituted by fluorine, preferably 2-fluoro-1,4-benzobenzene base, 2,3-difluoro-1,4-phenylene, 1,4-phenylene or trans-1,4-cyclohexene, more preferably 2-fluoro-1,4-phenylene or 2 , 3-difluoro-1,4-phenylene, 1,4-phenylene, particularly preferably 2,3-difluoro-1,4-phenylene or 1,4-phenylene.

Z ² represents a single bond, -OCH ₂ -, -OCO-, -CH ₂ O- or -COO-, preferably represents a single bond, -CH ₂ O- or -COO-, more preferably a single bond.

n represents 0 or 1, and Z ² represents a substituent other than a single bond, and preferably represents 0.

When the compound represented by the formula (III) represents 0, specifically, it is preferably a compound represented by the formula (III-1a) to the formula (III-1h) which will be described later.

(wherein R ⁷ and R ⁸ are each independently, and 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, in the formula (III) The same implementation as R ⁷ and R ⁸ is preferred).

In the case of the compound of the formula (III), when n is 1, in particular, the compound of the formula (III-2a) to the formula (III-2l) described later is preferred.

Wherein 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, preferably a formula ( III) The same implementation as R ⁷ and R ⁸ ).

The compound of the formula (II-1) and the formula (II-2) has a negative dielectric anisotropy and a compound having a large absolute value, and the total content of the compounds is preferably 30. It is 65%, more preferably 40 to 55%, and particularly preferably 43 to 50%.

The compound represented by the formula (III) has a dielectric compound anisotropy, a positive compound and a negative compound, and a dielectric anisotropy is negative, wherein a compound having an absolute value of 0.3 or more is used. The total content of the compounds of the formula (II-1), the formula (II-2) and the formula (III) is preferably from 35 to 70%, more preferably from 45 to 65%, particularly preferably from 50 to 60%. .

Containing 30 to 50% of the compound of the formula (I), and containing 35 to 70% of the compound of the formula (II-1), the formula (II-2) and the formula (III), more preferably There are 35 to 45% of the compound of the formula (I), and 45 to 65% of the compound of the formula (II-1), the formula (II-2) and the formula (III), particularly preferably 38 To 42% of the compound of the formula (I), and 50 to 60% of the compound of the formula (II-1), the formula (II-2) and the formula (III).

The total content of the compound represented by the general formula (I), the general formula (II-1), the general formula (II-2) and the general formula (III) is preferably from 80 to 100%, more preferably 90, based on the entire composition. Up to 100%, especially preferably 95 to 100%.

In the liquid crystal display device of the present invention, the liquid crystal layer can be used in a wide range of nematic phases. The isotropic liquid phase transfer temperature (Tn i) is preferably from 60 to 120 ° C, more preferably from 70 to 100 ° C, particularly preferably from 70 to 85 ° C.

The dielectric anisotropy is preferably -2.0 to -6.0, more preferably -2.5 to -5.0, particularly preferably -2.5 to -3.5 at 25 °C.

The refractive index anisotropy is at 25 ° C, preferably 0.08 to 0.13, more preferably 0.09 to 0.12. More specifically, in the case of a thin cell gap, it is preferably 0.10 to 0.12, and in the case of 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, Z which is a function of rotational viscosity and refractive index anisotropy indicates a specific value.

(wherein γ1 represents rotational viscosity; 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.

In the case where the liquid crystal layer in the liquid crystal display device of the present invention is used for an active matrix display element, it must have a specific resistance of 10 ¹² (Ω·m) or more, preferably 10 ¹³ (Ω·m), 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 above-mentioned compounds, a normal nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, an antioxidant, an ultraviolet absorber, a polymerizable monomer, or the like. .

In terms of a polymerizable monomer, a difunctional monomer represented by the formula (V) is preferred, Wherein X ¹ and X ² are each independently represented by a hydrogen atom or a methyl group; and Sp ¹ and Sp ² are each independently represented by a single bond, a C 1 to 8 alkyl group or a -O-(CH ₂ ) group. _s - (wherein s represents an integer from 2 to 7; the oxygen atom is bonded to the 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 are each independently represent a fluorine atom or a hydrogen atom), -C≡C- Or a single bond; C represents 1,4-phenylene, trans-1,4-cyclohexenyl or a single bond, all of which are 1,4-phenylene, and any hydrogen atom may be Replace).

X ¹ and X ^{2 each} represent a diacrylate derivative which is a hydrogen atom, and each of them has a methyl dimethacrylate derivative, and one of them may represent a hydrogen atom, and the other may represent a methyl group. The polymerization rate of these compounds is the fastest in diacrylate derivatives, the slower in dimethacrylic acid derivatives, and the asymmetric compounds are in the middle, and the preferred embodiment can be used according to the use thereof. Among the PSA display elements, a dimethacrylic acid derivative is particularly preferred.

Sp ¹ and Sp ² each independently line represents a single bond, an alkylene group or a carbon atom -O- 1 to 8 ter (CH _{2) s} -, in a PSA display element is preferably at least one of a single bond, then Preferably, the compound represented by a single bond or one of them represents a single bond, and the other represents a state of an alkylene group having 1 to 8 carbon atoms or -O-(CH ₂ ) _s -. In this case, it is preferably an alkyl group of 1 to 4, more preferably s is 1 to 4.

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 The key is more preferably -COO-, -OCO- or a single bond, and particularly preferably a single bond.

C represents a 1,4-phenylene group, a trans-1,4-cyclohexenyl group or a single bond in which any hydrogen atom may be substituted by a fluorine atom, and preferably a 1,4-phenylene group or a single bond. . In the case where C represents a single bond outer ring structure, Z ^{1 is} also preferably a linking group other than a single bond, and C is a single bond, and Z ^{1 is} preferably a single bond.

From the above, the ring structure between the general formula (V), Sp ¹ and Sp ² is, in particular, preferably the structure described later.

In the general formula (V), C represents a single bond; in the case where the ring structure is formed by two rings, it is preferably a subtype (Va-1) to a formula (Va-5), more preferably a formula (Va). -1) to the formula (Va-3), particularly preferably the formula (Va-1).

(wherein, both ends are bonded to Sp ¹ or Sp ² ).

Such a polymerizable compound containing a skeleton, an alignment restraining force after polymerization is optimum in a PSA type liquid crystal display device, and a good alignment state can be obtained, so that display unevenness can be suppressed or not occurred at all. .

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

(wherein, Sp ² represents an alkylene group having 2 to 5 carbon atoms).

In the case where a polymerizable monomer is added, the polymerization may be carried out even in the absence of a polymerization initiator, but a polymerization initiator may be contained in order to promote the polymerization. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and mercaptophosphine oxides. Further, in order to improve storage stability, a stabilizer may be added. Examples of the stabilizer which can be used include hydroquinones, hydroquinone monoalkyl ethers, tertiary butyl brown phenols, gallic phenols, thiophenols, nitro compounds, and β-naphthylamines. Classes, β-naphthols, nitroso compounds, and the like.

A liquid crystal layer containing a polymerizable monomer is useful for a liquid crystal display element, and is particularly useful for a liquid crystal display element for active matrix driving, and can be used for a liquid crystal display element for PSA mode, PSVA mode, VA mode, IPS mode, or ECB mode. .

The liquid crystal layer containing a polymerizable monomer is polymerized by ultraviolet irradiation to provide a liquid crystal alignment energy, and a liquid crystal for controlling the amount of light transmitted by the birefringence of the liquid crystal composition. Display component. As a liquid crystal display element, for AM-LCD (active matrix liquid crystal display element), TN (nematic liquid crystal display element), STN-LCD (super twisted nematic liquid crystal display element), OCB-LCD, and IPS-LCD (in-plane) It is useful for turning to a liquid crystal display element, and is particularly useful for an AM-LCD, and can be used for a transmissive or reflective liquid crystal display element.

(color filter)

In the present invention, the color filter is composed of a black matrix and at least a RGB three-color pixel portion, and the RGB three-color pixel portion contains a diketopyrrolopyrrole pigment and/or a R-pixel portion as a coloring material. An anionic red organic dye; containing in the G pixel portion selected from the group consisting of containing copper halide At least one of a group consisting of a mixture of a green pigment, an indigo green dye, an indigo blue dye, and an azo yellow organic dye; and an ε-type copper indigo pigment and/or a cationic blue in the B pixel portion Color organic dyes.

The RGB three-color pixel portion preferably contains C.I. Solvent Red 124 or C.I. Pigment Red 254 in the R pixel portion as a coloring material.

The RGB three-color pixel portion preferably contains, as a coloring material, a mixture of C.I. Solvent Blue 67 and C.I. Solvent Yellow 162 in the G pixel portion, or C.I. Pigment Green 7 and/or 36.

The RGB three-color pixel portion preferably contains C.I. Solvent Blue 7 or C.I. Pigment Blue 15:6 in the B pixel portion as a coloring material.

The RGB three-color pixel portion preferably contains a CI solvent red 124 in the R pixel portion, a mixture of CI solvent blue 67 and CI solvent yellow 162 in the G pixel portion, and CI in the B pixel portion. Solvent Blue 7.

Further, the RGB three-color pixel portion preferably contains CI Pigment Red 254 in the R pixel portion as the coloring material, CI Pigment Green 7 and/or 36 in the G pixel portion, and CI in the B pixel portion. Pigment Blue 15:6.

The RGB three-color pixel portion preferably contains, in the R pixel portion, a color selected from the group consisting of CI Pigment Red 177, 242, 166, 167, 179, CI Pigment Orange 38, 71, CI. At least one of the group of pigment yellow 150, the same 215, the same 185, the same 138, the same 139, the CI solvent red 89, the CI solvent orange 56, the CI solvent yellow 21, the same 82, the same 83:1, the same 33, the same 162 Organic dye pigments.

The RGB three-color pixel portion is preferably a coloring material, and further preferably contains, in the G pixel portion, a color selected from the group consisting of C.I. Pigment Yellow 150, the same 215, and the same 185. An organic dye pigment of at least one of the group of 138, C.I. Solvent Yellow 21, the same 82, the same 83:1, and the same 33.

The RGB three-color pixel portion preferably contains, in the B pixel portion, a color selected from the group consisting of CI Pigment Blue 1, CI Pigment Violet 23, CI Basic Blue 7, CI Basic Violet 10, and CI Acid Blue 1 as a coloring material. An organic dye pigment of at least one of the group of 90, 83, and CI Direct Blue 86.

Further, the color filter is composed of a black matrix, an RGB three-color pixel portion, and a Y pixel portion, and the Y pixel portion preferably contains a color selected from the group consisting of CI Pigment Yellow 150, 215, and 185. 138. Yellow organic dye pigment of at least one of the group of 139, CI solvent yellow 21, 82, the same 83:1, the same 33, and the same 162.

In the color filter of the color filter of the present invention, the chromaticity x and the chromaticity y of the XYZ color system are reduced by the voltage holding ratio (VHR) of the liquid crystal layer and the ion density (ID). The viewpoint of suppressing the occurrence of problems such as whiteness, uneven alignment, and burn marks, and the like, is preferably the following.

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

The chromaticity x of the XYZ color system is preferably 0.19 to 0.35, more preferably 0.20 to 0.26, and the chromaticity y is preferably 0.54 to 0.74, more preferably 0.64 to 0.73, under the C light source of the G pixel portion. Preferably, the chromaticity x is from 0.19 to 0.35, and the chromaticity y is from 0.54 to 0.74, more preferably the chromaticity x is from 0.20 to 0.26, and the chromaticity y is from 0.64 to 0.73.

The chromaticity x of the XYZ color system is preferably 0.11 to 0.16, more preferably 0.12 to 0.15, and the chromaticity y is preferably 0.04 to 0.15, more preferably 0.05 to 0.10, under the C light source of the B pixel portion. Preferably, the chromaticity x is from 0.11 to 0.16, and the chromaticity y is from 0.04 to 0.15, more preferably the chromaticity x is from 0.12 to 0.15, and the chromaticity y is from 0.05 to 0.10.

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

Here, the XYZ colorimetric system means the color system recognized as the standard color system by the CIE (International Commission on Illumination) in 1931.

The chromaticity in each of the above-mentioned pixel portions can be adjusted by changing the type of the dye pigment to be used or the mixing ratio of the above. For example, in the case of R pixels, a yellow dye pigment and/or an orange pigment is added to the red dye pigment in an appropriate amount, and in the case of a G pixel, a yellow dye pigment is added to the green dye pigment in an appropriate amount, and in the case of the B pixel, in the blue color. The purple dye pigment is added to the color dye pigment in an appropriate amount and can be adjusted. Further, it can be adjusted by appropriately adjusting the particle diameter of the pigment.

The color filter can be formed into a color filter pixel portion by a conventionally known method.

A representative method of forming a pixel portion is a photolithography method in which a photo-curable composition to be described later is provided with a color filter. After coating and heat-drying (pre-baking) the surface of the transparent substrate on the black matrix side, the pattern is exposed by irradiating ultraviolet rays through the mask, and the photocurable compound corresponding to the pixel portion is cured. The unexposed portion is developed with a developing solution, the non-pixel portion is removed, and the pixel portion is fixed to the transparent substrate. In this method, a pixel portion of a hard colored film containing a photocurable composition is formed on a transparent substrate.

R pixels, G pixels, and B pixels may be prepared by modulating a photocurable composition described later with pixels of other colors such as Y pixels as needed, by repeating the above operation, and having R pixels and G at predetermined positions. A color filter of a color pixel portion of a pixel, a B pixel, or a Y pixel.

The method of applying the photocurable composition described later to a transparent substrate such as glass may, for example, be a spin coating method, a roll coating method, an inkjet method, or the like.

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

Examples of the development method include a liquid-filling method, a dipping method, a spraying method, and the like.

After exposure and development of the photocurable composition, a transparent substrate having a pixel portion of a necessary color is formed, washed with water, and dried. The color filter thus obtained is removed by heat treatment (post-baking) at a temperature of 90 to 280 ° C for a predetermined time by a heating means such as a hot plate or an oven. While the volatile component is colored in the coating film, the unreacted photocurable compound remaining in the hardened colored film of the photocurable composition is thermally cured, and the color filter is completed.

The coloring material for a color filter of the present invention can provide a liquid crystal display device which can be used to prevent a decrease in the voltage holding ratio (VHR) of the liquid crystal layer and an ion density (ID) by using the liquid crystal composition of the present invention. Increase, and solve the problem of poor display, such as whiteness, uneven alignment, and burn marks.

In the method for producing the photocurable composition, 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 the mixture is stirred and dispersed so that the mixing becomes Uniformly, after the pigment dispersion liquid for forming the pixel portion of the color filter is prepared, the photocurable compound, the thermoplastic resin or the photopolymerization initiator which can be optionally used, and the like are added to prepare the photocurability. The method of composition is a general method.

The organic solvent used herein is preferably an aromatic solvent such as toluene or xylene or methoxybenzene; ethyl acetate or propyl acetate or butyl acetate, propylene glycol monomethyl ether acetate. Acetic acid such as propylene glycol monoethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol diethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol butyl ether acetate Ester solvent; propionate solvent such as ethoxyethyl propionate; alcohol solvent such as methanol or ethanol; butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether Ether solvent; ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; aliphatic hydrocarbon solvent such as hexane; N,N-dimethylformamide, γ a nitrogen compound solvent such as butyrolactam, N-methyl-2-pyrrolidone, aniline or pyridine; γ-butyrolactone And the lactone solvent; a urethane such as a mixture of methyl carbamate and ethyl urethane at 48:52.

For the dispersing agent used herein, for example, DisperByk 130, DisperByk 161, DisperByk 162, DisperByk 163, DisperByk 170, DisperByk 171, DisperByk 174, DisperByk 180, DisperByk 182, DisperByk 183, DisperByk 184, DisperByk of BYK Corporation of Japan, Japan. 185, DisperByk 2000, DisperByk 2001, DisperByk 2020, DisperByk 2050, DisperByk 2.070, DisperByk 2096, DisperByk 2150, DisperByk LPN21116, DisperByk LPN6919; Efka 46, Efka 47, Efka 452, Efka LP4008, Efka 4009, Efka LP4010, Efka Efka LP4050, LP4055, Efka 400, Efka 401, Efka 402, Efka 403, Efka 450, Efka 451, Efka 453, Efka 4540, Efka 4550, Efka LP4560, Efka 120, Efka 150, Efka 1501, Efka 1502, Efka 1503; Lubrizol's Solsperse 3000, Solsperse 9000, Solsperse 13240, Solsperse 13650, Solsperse 13940, Solsperse 17000, 18000, Solsperse 20000, Solsperse 21000, Solsperse 20000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, Solsperse 32000, Solsperse 36000, Solsperse 3 7000, Solsperse 38000, Solsperse 41000, Solsperse 42000, Solsperse 43000, Solsperse 46000, Solsperse 54000, Solsperse 71000; Ajisper PB711, Ajisper PB821, Ajisper PB822, Ajisper PB814, Ajisper PN411 , a dispersing agent such as Ajisper PA111, or an acrylic resin, urethane resin, alkyd resin, woodrosin, gumrosin, tall oil rosin, etc. Rosin; denatured rosin such as polymerized rosin, dismutation rosin, hydrogenated rosin, oxidized rosin, maleic rosin, rosin amine, lime rosin, rosin alkylene oxide adduct, A synthetic resin containing a liquid and water-insoluble at room temperature, such as a rosin alkyd adduct or a rosin derivative such as rosin modified phenol. The addition of such dispersing agents or resins also contributes to a reduction in flocculation, an improvement in pigment dispersion stability, and an increase in viscosity characteristics of the dispersion.

Further, as the dispersing aid, an organic pigment derivative such as a phthalimide methylamine derivative, a homosulfonic acid derivative, a N-(dialkylamino)methyl derivative, or the like may be contained. A N-(dialkylaminoalkyl)sulfonate decylamine derivative or the like. Of course, these derivatives may be used in combination of two or more kinds of different kinds.

The thermoplastic resin to be used for the preparation of the photocurable composition may, for example, be a urethane resin, an acrylic resin, a polyamine resin, a polyimide resin, or a styrene maleic acid resin. A styrene maleic anhydride resin or the like.

Examples of the photocurable compound include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, and bis(propylene oxide). 2-functional monomer such as ethoxylated bisphenol A or 3-methylpentanediol diacrylate; trimethylolpropane triacrylate, neopentyl glycol triacrylate, ginseng [2] -(Methyl)acryloyloxyethyl)isocyanate, Hexapropyl a polyfunctional monomer having a relatively small molecular weight such as dipentatyl enoate or dipentaerythritol pentaacrylate; a molecular weight larger than polyester acrylate, polyurethane acrylate, polyether acrylate, etc. Polyfunctional monomer.

The photopolymerization initiator may, for example, be acetophenone, benzophenone, benzyldimethylketanol, benzyl peroxide or 2-chloro 9-oxosulfuric acid. , 1,3-bis(4'-azidobenzyl)-2-propane, 1,3-bis(4'-azidobenzylidene)-2-propane-2'-sulfonate Acid, 4,4'-diazide stilbene-2,2'-disulfonic acid and the like. For example, "Irgacure (trade name) - 184", "Irgacure (trade name) - 369", "Darocure (trade name) - 1173", "made by BASF", manufactured by BASF Corporation, are commercially available. "Lucirin-TPO", "Kayacure (trade name) DETX", "Kayacure (trade name) OA" manufactured by Nippon Kasei Co., Ltd., "Vicure 10" manufactured by STAUFFER, "Vicure-55", "Trigonal PI" manufactured by Akzo Co., Ltd. "SANDORY1000" manufactured by Sandoz Co., "Deap" manufactured by UPJOHN, and "biimidazole" manufactured by Heijin Chemical Co., Ltd.

Further, a photo-sensitizer known in the art can be used in combination with the above-mentioned photopolymerization initiator. The photosensitizer may, for example, be an amine, a urea, a compound having a sulfur atom, a compound having a phosphorus atom, a compound having a chlorine atom or a nitrile or another compound 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 is preferably in the range of 0.1 to 30% based on the mass of the photopolymerizable or photocurable functional group. When it is less than 0.1%, the sensitivity of photohardening tends to decrease, and when it exceeds 30%, the pigment is dispersed. When the coating film of the photoresist is dried, crystals of the photopolymerization initiator are precipitated, which may cause deterioration of the physical properties of the coating film.

Using the above-mentioned various materials, 300 to 1000 parts of the organic solvent and 1 to 100 parts of the dispersing agent per 100 parts of the dye and/or pigment composition for color filters of the present invention are used. The dye pigment liquid can be obtained by stirring and dispersing to be uniform. Then, in the pigment dispersion liquid, 3 to 20 parts of the total of the thermoplastic resin and the photocurable compound are added per part of the pigment composition for a color filter of the present invention, and the photocurable compound is added per part. 0.05 to 3 parts of the photopolymerization initiator, and if necessary, an organic solvent is further added, and the mixture is stirred and dispersed to obtain a photocurable composition for forming a pixel portion of the color filter.

As the developer, a well-known organic solvent or an aqueous alkali solution can be used. In particular, the photocurable composition contains a thermoplastic resin or a photocurable compound, and at least one of them has an acid value, and in the case of exhibiting alkali solubility, it is washed with an alkali aqueous solution to the pixel portion of the color filter. The formation is more effective.

The method of manufacturing the color filter pixel portion caused by the photolithography method will be described in detail, but the color filter pixel portion modulated by the pigment composition for a color filter of the present invention may be other electrodeposition method. , a transfer method, a micelle electrolysis method, a PVED (photovoltaic electrodeposition) method, an inkjet method, a reverse printing method, a thermosetting method, or the like, forming a pixel portion of each color to produce color Filter.

(alignment film)

In the liquid crystal display device of the present invention, in order to be on the first substrate, Since the liquid crystal composition is aligned on the surface on which the liquid crystal composition on the substrate is in contact with each other, the liquid crystal display device which is considered to be necessary for the alignment film is disposed between the color filter and the liquid crystal layer, and even if the film thickness of the alignment film is thick, When the thickness is as small as 100 nm or less, the interaction between the pigment such as the pigment constituting the color filter and the liquid crystal compound constituting the liquid crystal layer cannot be completely blocked.

Further, in the liquid crystal display device which does not use the alignment film, the pigment such as the pigment constituting the color filter has a larger interaction with the liquid crystal compound constituting the liquid crystal layer.

As the alignment film material, a transparent organic material such as polyimine, polyamine, BCB (benzocyclobutene polymer), polyvinyl alcohol or the like can be used, in particular, p-phenylenediamine, 4 An aliphatic or alicyclic diamine such as 4'-diaminodiphenylmethane or a diamine such as butane tetracarboxylic anhydride or 2,3,5-tricarboxycyclopentyl acetic anhydride or the like A polyimine acid synthesized from an aromatic tetracarboxylic anhydride such as an alicyclic tetracarboxylic anhydride or a pyromellitic dianhydride is preferably a ruthenium imidized polyimide film. In this case, the alignment method is used, and polishing is used in a general method, and in the case of a vertical alignment film or the like, the alignment may not be used.

As the alignment film material, a material containing a chalcone, a cinamate, a cinnamyl group or an azo group in a compound may be used, or may be combined with a material such as polyimine or polyamine. In this case, the alignment film may also be polished, or a photo-alignment technique may be used.

The alignment film is applied to the substrate by a spin coating method or the like to form a resin film. The one-axis stretching method, the Iangmuir-Blodgett method, or the like can 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 indium oxide (In ₂ O ₃ ) or tin oxide (SnO ₂ ) can be used as the metal oxide. , zinc oxide (ZnO), indium tin oxide (In ₂ O ₃ -SnO ₂ ), indium zinc oxide (In ₂ O ₃ -ZnO), lanthanum added titanium dioxide (Ti _1-x Nb _x O ₂ }, fluorine doped oxidation Tin, graphene nanobelt or metal nanowire, etc., and preferably zinc oxide (ZnO), indium tin oxide (In ₂ O ₃ -SnO ₂ ) or indium zinc oxide (In ₂ O ₃ -ZnO). For the patterning of the transparent conductive films, a photolithography method or a method using a photomask can be used.

The combination of the liquid crystal display device and the backlight can be used for a liquid crystal television, a personal computer monitor, a portable telephone, a smart phone display or a notebook personal computer, a portable information terminal device, a digital signage (digital signage) ) and a variety of uses. The backlight includes a cold cathode tube type backlight, a light-emitting diode using an inorganic material, a virtual white backlight using a two-wavelength peak of an organic EL element, and a backlight of a three-wavelength peak.

[Examples]

The embodiments are described in detail, and a part of the best mode of the present invention is as follows, but the present invention is not limited to the embodiments. Further, in the compositions of the following examples and comparative examples, "%" means "% by mass".

In the examples, the properties measured were as follows.

T _n i: nematic phase-isotropic liquid phase transfer temperature (°C)

△n: refractive index anisotropy at 25 ° C

△ ε: 25 ° C dielectric anisotropy

η: viscosity at 20 ° C (mPa.s)

Γ1: rotational viscosity (mPa.s) in 25°C

d _gap : the gap between the first substrate and the second substrate of the unit cell (μm)

VHR: Voltage holding ratio at 70 ° C (%)

(Injecting a liquid crystal composition into a cell having a cell thickness of 3.5 μm, plus 5 V, when measured at a frame time of 200 ms and a pulse width of 64 μs, the ratio of the measured voltage to the initial applied voltage is expressed in %. value)

ID: ion density (pC/cm ² ) at 70 ° C

(Injecting a liquid crystal composition into a unit cell having a cell thickness of 3.5 μm, and adding 20 V to MTR-1 (manufactured by Toyo Technica Co., Ltd.), and measuring the ion density value at a frequency of 0.05 Hz) burn marks:

In the evaluation of the burn marks of the liquid crystal display device, after the predetermined fixed pattern was displayed for 1000 hours in the display region, the image sticking level of the fixed pattern when the full screen was uniformly displayed was visually observed, and the following four-stage evaluation was performed.

◎ no residual image

○ There are very few residual images, which are also acceptable levels.

△ There is residual image, the level that cannot be tolerated

×There is a bad shadow

Further, in the examples, the following abbreviations are used for the description of the compounds.

(side chain)

-n -C _n H _2n+1 linear alkyl group having n carbon atoms

-On -OC _n H _2n+1 linear alkoxy group with n number of carbon atoms

(ring structure)

[Make color filter] [Modulation of coloring composition] [Red dye coloring composition 1]

Put 10 parts of red dye 1 (CI Solvent Red 124) into plastic bottles, add 55 parts of propylene glycol monomethyl ether acetate, 0.3-0.4 mm The SEPR beads were dispersed by a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, and then filtered through a 5 μm filter to obtain a dye coloring liquid. 75.00 parts of dye coloring liquid, 5.50 parts of polyester acrylate resin (Aronics (trade name) M7100, manufactured by Toagosei Chemical Co., Ltd.), and 5.00 parts of dipentaerythritol hexaacrylate (KAYARAD (trade name) DPHA) , Japan Pharmaceutical Co., Ltd.), 1.00 parts of benzophenone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.), 13.5 parts of Ucar Ester EEP, stirred with a dispersing mixer, and with a pore size of 1.0 μm The filter was filtered to obtain a red dye coloring composition 1.

[Red dye coloring composition 2]

8 parts of red dye 1 (CI solvent red 124) and 2 parts of yellow dye 2 (CI solvent yellow 21) were used instead of the above red dye coloring composition 1 of 10 parts of red dye 1, in the same manner as above, to obtain a red dye coloring composition. Object 2.

[Red dye coloring composition 3]

The red dye coloring composition 3 was obtained by using 10 parts of red dye 2 (C.I. Solvent Red 1) in place of the above-mentioned red dye coloring composition 1 of 10 parts of red dye 1.

[Green dye coloring composition 1]

3 parts of blue dye 1 (CI solvent blue 67) and 7 parts of yellow dye 1 (CI solvent yellow 162) were used instead of the above red dye coloring composition 1 of 10 parts of red dye 1, in the same manner as above, to obtain green dye coloring Composition 1.

[Green dye coloring composition 2]

The above green dye was colored to 7 parts of the yellow dye 1 of the composition 1, instead of 4 parts of the yellow dye 1 (CI solvent yellow 162) and 3 parts of the yellow dye 3 (CI solvent yellow 82), and the green dye coloring composition was obtained in the same manner as above. 2.

[Green dye coloring composition 3]

The green dye coloring composition 3 was obtained in the same manner as above except that 10 parts of the green dye 1 (C.I. Solvent Green 7) was used instead of the above-mentioned green dye coloring composition 1 of 3 parts of the blue dye 1 and 7 parts of the yellow dye 1.

[Blue dye coloring composition 1]

The blue dye coloring composition 1 was obtained by using 10 parts of blue dye 1 (C.I. Solvent Blue 7) in place of 10 parts of the red dye 1 of the above red dye coloring composition 1.

[Blue dye coloring composition 2]

7 parts of blue dye 1 (CI solvent blue 7) and 3 parts of purple dye 1 (CI basic violet 10) were used instead of the blue dye 1 of the above blue dye coloring composition 1 in the same manner as above. Blue dye coloring composition 2.

[Blue dye coloring composition 3]

10 parts of blue dye 2 (CI solvent blue 12) was used instead of the above-mentioned blue dye coloring composition 2, 7 parts of blue dye 1 and 3 parts of purple dye 1, and the blue dye coloring composition 3 was obtained in the same manner as above. .

[Yellow dye coloring composition 1]

10 parts of yellow dye 2 (C.I. Solvent Yellow 21) was used instead of the above red dye coloring composition 1 of 10 parts of red dye 1, and the yellow dye coloring composition 1 was obtained in the same manner as above.

[Yellow dye coloring composition 2]

10 parts of yellow dye 4 (C.I. Solvent Yellow 2) was used in place of 10 parts of the yellow dye 2 of the above yellow dye coloring composition 1, and the yellow dye coloring composition 2 was obtained in the same manner as above.

[Red Pigment Coloring Composition 1]

10 parts of red pigment 1 (CI Pigment Red 254, "IRGAPHOR RED BT-CF" manufactured by BASF Corporation) was placed in a plastic bottle, and 55 parts of propylene glycol monomethyl ether acetate and 7.0 parts of DisperByk LPN21116 (made by BYK CHEMI Co., Ltd.) were added. ), 0.3-0.4mm The SEPR beads were dispersed by a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, and then filtered through a 5 μm filter to obtain a pigment dispersion liquid.

75.00 parts of the pigment dispersion liquid and 5.50 parts of polyester acrylate resin (Aronics (trade name) M7100, manufactured by Toagosei Chemical Co., Ltd.), 5.00 parts of dipentaerythritol hexaacrylate (KAYARAD (trade name) DPHA) , Japan Chemical Pharmaceutical Co., Ltd.), 1.00 parts of benzophenone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.), 13.5 parts of Ucar ester EEP stirred with a dispersing mixer, and the pore diameter A 1.0 μm filter was filtered to obtain a red pigment coloring composition 1.

[Red Pigment Coloring Composition 2]

In place of the above red pigment coloring composition, 6 parts of red pigment 1 and 2 parts of red pigment 2 (FASTOGEN SUPER RED ATY-TR manufactured by CI Pigment Red 177 DIC Co., Ltd.) and 2 parts of yellow pigment 2 (CI Pigment Yellow 139) were used. 10 parts of red pigment 1 was obtained in the same manner as above to obtain a red pigment coloring composition 2.

[Green Pigment Coloring Composition 1]

6 parts of green pigment 1 (CI Pigment Green 36, "FASTOGEN GREEN 2YK-CF" by DIC Corporation) and 4 parts of yellow pigment 1 (CI Pigment Yellow 150, FANCHON FAST YELLOW E4GN by BAYER) were used instead of the above red 10 parts of the red pigment 1 of the pigment coloring composition 1 was the same as above, and the green pigment coloring composition 1 was obtained.

[Green Pigment Coloring Composition 2]

4 parts of green pigment 2 (CI Pigment Green 7, FASTOGEN GREEN S by DIC Corporation) and 6 parts of yellow pigment 3 (CI Pigment Yellow 138) were used in place of the above-mentioned green pigment coloring composition 1 of 6 parts of green pigment 1 and Four parts of the yellow pigment 1 were obtained in the same manner as above to obtain a green pigment coloring composition 2.

[Blue pigment coloring composition 1]

9 parts of blue pigment 1 (CI Pigment Blue 15:6, "FASTOGEN BLUE EP-210" by DIC Corporation) and 1 part of violet pigment 1 (CI Pigment Violet 23) were used instead of the above red pigment coloring composition 1 Ten parts of red pigment 1 were obtained in the same manner as above to obtain a blue pigment coloring composition 1.

[Blue pigment dye coloring composition 2]

One part of the purple pigment 1 was replaced with 1 part of the purple dye 1 (C.I. Basic Violet 10) in place of the above-mentioned blue pigment coloring composition 1, and the blue pigment dye coloring composition 2 was obtained in the same manner as above.

[Yellow Pigment Coloring Composition 1]

In place of 10 parts of the red pigment 1 of the above red pigment coloring composition 1, 10 parts of yellow pigment 1 (C.I. Pigment Yellow 150, FANCHON FAST YELLOW E4GN manufactured by BAYER Co., Ltd.) was used, and a yellow pigment coloring composition 1 was obtained in the same manner as above.

[Production of color filter]

On the glass substrate in which the black matrix was formed in advance, the red colored composition was applied by spin coating to a film thickness of 2 μm. After drying at 70 ° C for 20 minutes, the ultraviolet rays were exposed in a stripe pattern by an exposure machine equipped with an ultrahigh pressure mercury lamp through a photomask. It was spray-developed with an alkali developer for 90 seconds, washed with ion-exchanged water, and air-dried. Further, in a clean oven, post-baking was performed at 230 ° C for 30 minutes to form a red pixel of a strip-shaped colored layer on the transparent substrate.

Next, similarly to the green colored composition, the coating was applied by spin coating to have a film thickness of 2 μm. After drying, it is developed by exposing the strip-shaped colored layer to the place where the red pixel is offset by an exposure machine, thereby forming a green pixel adjacent to the red pixel.

Next, in the same manner as the blue coloring composition, a blue pixel adjacent to the red pixel and the green pixel was formed by spin coating at a film thickness of 2 μm. Thereby, a color filter having strip-shaped pixels of three colors of red, green, and blue on a transparent substrate is obtained.

The yellow coloring composition can be colored as needed, and the same can be applied by spin coating to form a blue pixel adjacent to the red pixel and the green pixel with a film thickness of 2 μm. Thereby, a color filter having strip-shaped pixels of four colors of red, green, blue, and yellow is obtained on the transparent substrate.

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

For each pixel portion of the color filter, an Olympus microscope MX-50 and an Otsuka electronic spectrophotometer MCPD-3000 microspectrophotometer were used to measure the x value and the y value of the C light source of the CIE1931 XYZ color system. The results are shown in the table below.

(Examples 1 to 4)

An electrode structure is formed on the first and second substrates, and a vertical alignment alignment film is formed on each of the opposite sides, and then subjected to a weak grinding treatment to form a VA unit cell, and the following is sandwiched between the first substrate and the second substrate. The liquid crystal composition 1 is shown. The physical properties of the liquid crystal composition 1 are shown in Table 3. Next, the color filters 1 to 4 shown in Table 1 were used to prepare liquid crystal display devices of Examples 1 to 4 (d _gap = 3.5 μm, alignment film SE-). 5300). The VHR and ID of the obtained liquid crystal display device were measured. Moreover, the burn-in evaluation of the obtained liquid crystal display device was performed. The results are shown in Table 4.

It is understood that the liquid crystal composition 1 has a practical liquid crystal layer temperature range of 81 ° C which is a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, and has low viscosity and optimum Δn.

The liquid crystal display devices of Embodiments 1 to 4 can realize high VHR and small ID values. In addition, there is no residual image in the evaluation of burn marks, or even if there are residual images, it is an acceptable level.

(Examples 5 to 12)

In the same manner as in Example 1, the liquid crystal compositions shown in Table 5 were sandwiched, and the color filters shown in Table 1 were used to prepare liquid crystal display devices of Examples 5 to 12, and their VHR and ID were measured. Moreover, the burn-in evaluation of this liquid crystal display device was performed. The results are shown in Tables 6 and 7.

The liquid crystal display devices of Examples 5 to 12 can realize high VHR and small ID values. In addition, there is no residual image in the evaluation of burn marks, and even if there are residual images, it is an acceptable level.

(Examples 13 to 24)

In the same manner as in Example 1, the liquid crystal compositions shown in Table 8 were sandwiched, and the color filters shown in Table 1 were used to prepare liquid crystal display devices of Examples 13 to 24, and their VHR and ID were measured. Moreover, the burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 9 to 11.

The liquid crystal display devices of Examples 13 to 24 can realize high VHR and small ID values. In addition, there is no residual image in the evaluation of burn marks, and even if there are residual images, it is an acceptable level.

(Examples 25 to 36)

In the same manner as in Example 1, the liquid crystal compositions shown in Table 12 were sandwiched, and the color filters shown in Table 1 were used to prepare liquid crystal display devices of Examples 29 to 36, and their VHR and ID were measured. Moreover, the burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 13 to 15.

The liquid crystal display devices of Examples 25 to 36 can realize high VHR and small ID values. In addition, there is no residual image in the evaluation of burn marks, and even if there are residual images, it is an acceptable level.

(Examples 37 to 48)

In the same manner as in Example 1, the liquid crystal compositions shown in Table 16 were sandwiched, and the color filters shown in Table 1 were used to prepare liquid crystal display devices of Examples 37 to 48, and their VHR and ID were measured. Moreover, the burn-in evaluation of this liquid crystal display device was performed. The results are shown in Tables 17 to 19.

The liquid crystal display devices of Examples 37 to 48 can realize high VHR and small ID values. In addition, there is no residual image in the evaluation of burn marks, and even if there are residual images, it is an acceptable level.

(Examples 49 to 60)

In the same manner as in Example 1, the liquid crystal compositions shown in Table 20 were sandwiched, and the color filters shown in Table 1 were used to prepare liquid crystal display devices of Examples 49 to 60, and their VHR and ID were measured. Moreover, the burn-in evaluation of this liquid crystal display device was performed. The results are shown in Tables 21 to 23.

The liquid crystal display devices of Examples 49 to 60 can realize high VHR and small ID values. In addition, there is no residual image in the evaluation of burn marks, and even if there are residual images, it is an acceptable level.

(Examples 61 to 72)

In the same manner as in Example 1, the liquid crystal compositions shown in Table 24 were sandwiched, and the color filters shown in Table 1 were used to prepare liquid crystal display devices of Examples 61 to 72, and their VHR and ID were measured. Moreover, the burn-in evaluation of this liquid crystal display device was performed. The results are shown in Tables 25 to 27.

The liquid crystal display devices of Examples 61 to 72 can realize high VHR and small ID values. In addition, there is no residual image in the evaluation of burn marks, and even if there are residual images, it is an acceptable level.

(Examples 73 to 84)

In the same manner as in Example 1, the liquid crystal compositions shown in Table 28 were sandwiched, and the color filters shown in Table 1 were used to prepare liquid crystal display devices of Examples 73 to 84, and their VHR and ID were measured. Moreover, the burn-in evaluation of this liquid crystal display device was performed. The results are shown in Tables 29 to 31.

The liquid crystal display devices of Examples 73 to 84 can realize high VHR and small ID values. In addition, there is no residual image in the evaluation of burn marks, and even if there are residual images, it is an acceptable level.

(Examples 85 to 96)

In the same manner as in Example 1, the liquid crystal compositions shown in Table 32 were sandwiched, and the color filters shown in Table 1 were used to prepare liquid crystal display devices of Examples 85 to 96, and their VHR and ID were measured. Moreover, the burn-in evaluation of this liquid crystal display device was performed. The results are shown in Tables 33 to 35.

The liquid crystal display devices of Examples 85 to 96 can realize high VHR and small ID values. In addition, there is no residual image in the evaluation of burn marks, and even if there are residual images, it is an acceptable level.

(Examples 97 to 108)

In the same manner as in Example 1, the liquid crystal compositions shown in Table 36 were sandwiched, and the color filters shown in Table 1 were used to prepare liquid crystal display devices of Examples 97 to 108, and their VHR and ID were measured. Moreover, the burn-in evaluation of this liquid crystal display device was performed. The results are shown in Tables 37 to 39.

The liquid crystal display devices of Examples 97 to 108 can realize high VHR and small ID values. In addition, there is no residual image in the evaluation of burn marks, and even if there are residual images, it is an acceptable level.

(Examples 109 to 112)

In the liquid crystal composition 1, 0.3% by mass of 2-methyl-acrylic acid 4'-{2-[4-(2-propenyloxy-ethyl)-phenoxycarbonyl]-ethyl}-linked was mixed. Phen-4-yl ester was prepared into a liquid crystal composition 28. The liquid crystal composition 28 was sandwiched between the VA unit cells used in Example 1, and a driving voltage was applied between the electrodes, and ultraviolet rays were irradiated for 600 seconds (3.0 J/cm ² ) to carry out polymerization treatment. Next, Table 1 was used. The color filters 1 to 4 were prepared into liquid crystal display devices of Examples 109 to 112, and their VHR and ID were measured, and the burn marks of the liquid crystal display device were evaluated. The results are shown in Table 40.

The liquid crystal display devices of Examples 109 to 112 can realize high VHR and small ID values. In addition, there is no residual image in the evaluation of burn marks, and even if there are residual images, it is an acceptable level.

(Examples 113 to 116)

In the liquid crystal composition 13, 0.3% by mass of biphenyl-4,4'-diester dimethacrylate was mixed to prepare a liquid crystal composition 29. The liquid crystal composition 29 was sandwiched between the VA unit cells used in Example 1, and a driving voltage was applied between the electrodes, and ultraviolet rays were irradiated for 600 seconds (3.0 J/cm ² ) to carry out polymerization treatment. Next, Table 1 was used. The color filters 1 to 4 were fabricated to form liquid crystal display devices of Examples 113 to 116, and their VHR and ID were measured. Moreover, the burn-in evaluation of this liquid crystal display device was performed. The results are shown in Table 41.

The liquid crystal display devices of Examples 113 to 116 can realize high VHR and small ID values. In addition, there is no residual image in the evaluation of burn marks, and even if there are residual images, it is an acceptable level.

(Examples 117 to 120)

In the liquid crystal composition 19, 0.3% by mass of 3-fluorobiphenyl-4,4'-diester dimethacrylate was mixed to prepare a liquid crystal composition 30. In the VA unit cell used in Example 1, the liquid crystal composition 30 was sandwiched, and a driving voltage was applied between the electrodes, and ultraviolet rays were irradiated for 600 seconds (3.0 J/cm ² ) to carry out polymerization treatment, and then, as shown in Table 1, The color filters 1 to 4 were prepared, and the liquid crystal display devices of Examples 117 to 120 were fabricated, and their VHR and ID were measured. Moreover, the burn-in evaluation of this liquid crystal display device was performed. The results are shown in Table 42.

The liquid crystal display devices of Examples 117 to 120 can realize high VHR and small ID values. In addition, there is no residual image in the evaluation of burn marks, and even if there are residual images, it is an acceptable level.

(Comparative Examples 25 to 36)

In the same manner as in the first embodiment, the liquid crystal compositions of Comparative Examples 25 to 36 were produced by comparing the liquid crystal compositions shown in Table 52 with the color filters 1 to 4 shown in Table 1, and the VHR and ID were measured.

Moreover, the burn-in evaluation of this liquid crystal display device was performed. The results are shown in Tables 53 to 55.

In the liquid crystal display devices of Comparative Examples 25 to 36, the VHR was lower and the ID was larger as compared with the liquid crystal display device of the present invention. Further, the burn marks evaluation can also confirm the occurrence of the afterimage, and is not an acceptable level.

(Comparative Examples 37 to 48)

In the same manner as in the first embodiment, the comparative liquid crystal compositions shown in the table 56 were sandwiched, and the color filters 1 to 4 shown in Table 1 were used to fabricate the liquid crystal display devices of Comparative Examples 37 to 48, and the VHR and ID thereof were measured.

Moreover, the burn-in evaluation of this liquid crystal display device was performed. The results are shown in Tables 57 to 59.

In the liquid crystal display devices of Comparative Examples 37 to 48, the VHR was lower and the ID was larger as compared with the liquid crystal display device of the present invention. Further, the burn marks evaluation can also confirm the occurrence of the afterimage, and is not an acceptable level.

(Comparative Examples 49 to 60)

In the same manner as in the first embodiment, the comparative liquid crystal compositions shown in the table 60 were sandwiched, and the color filters 1 to 4 shown in Table 1 were used to fabricate the liquid crystal display devices of Comparative Examples 49 to 60, and the VHR and ID thereof were measured.

Moreover, the burn-in evaluation of this liquid crystal display device was performed. The results are shown in Tables 61-63.

In the liquid crystal display devices of Comparative Examples 49 to 60, the VHR was lower and the ID was larger as compared with the liquid crystal display device of the present invention. Further, the burn marks evaluation can also confirm the occurrence of the afterimage, and is not an acceptable level.

(Comparative Examples 61 to 72)

In the same manner as in the first embodiment, the comparative liquid crystal compositions shown in Table 64 were sandwiched, and the color filters 1 to 4 shown in Table 1 were used to prepare liquid crystal display devices of Comparative Examples 61 to 72, and their VHR and ID were measured.

Moreover, the burn-in evaluation of this liquid crystal display device was performed. The results are shown in Tables 65 to 67.

In the liquid crystal display devices of Comparative Examples 61 to 72, the VHR was lower and the ID was larger as compared with the liquid crystal display device of the present invention. Further, the burn marks evaluation can also confirm the occurrence of the afterimage, and is not an acceptable level.

(Comparative Examples 73 to 84)

In the same manner as in Example 1, the comparative liquid crystal compositions shown in Table 68 were sandwiched, and the color filters 1 to 4 shown in Table 1 were used to prepare liquid crystal display devices of Comparative Examples 73 to 84, and their VHR and ID were measured.

Moreover, the burn-in evaluation of this liquid crystal display device was performed. The results are shown in Tables 69 to 71.

In the liquid crystal display devices of Comparative Examples 73 to 84, the VHR was lower than that of the liquid crystal display device of the present invention, and the ID was also increased. The burn-in evaluation also confirmed the occurrence of image sticking, which was not an acceptable level.

(Comparative Examples 85 to 88)

In the same manner as in the first embodiment, the comparative liquid crystal compositions shown in the table 72 were sandwiched, and the color filters 1 to 4 shown in Table 1 were used to fabricate liquid crystal display devices of Comparative Examples 85 to 88, and their VHR and ID were measured.

Moreover, the burn-in evaluation of this liquid crystal display device was performed. The results are shown in Table 73.

The liquid crystal display devices of Comparative Examples 85 to 88 have a lower VHR and a larger ID than the liquid crystal display device of the present invention. Further, the burn marks evaluation can also confirm the occurrence of the afterimage, and is not an acceptable level.

(Comparative Examples 89 to 96)

The liquid crystal compositions 1, 2, 8, 13, 14, 19, 20, and 26 were sandwiched in the VA unit cells used in Example 1, and Comparative Color Filters 1 shown in Table 1 were used to prepare Comparative Examples 89 to 96. The liquid crystal display device is measured for its VHR and ID. Moreover, the burn-in evaluation of this liquid crystal display device was performed. The results are shown in Tables 74 and 75.

In the liquid crystal display devices of Comparative Examples 89 to 96, the VHR was lower and the ID was larger as compared with the liquid crystal display device of the present invention. Further, the burn marks evaluation can also confirm the occurrence of the afterimage, and is not an acceptable level.

1‧‧‧Substrate

2‧‧‧Color filter layer

2a‧‧‧Color filter layer containing specific dyes and/or pigments

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

3b‧‧‧pixel electrode layer

4‧‧‧Alignment film

5‧‧‧Liquid layer

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

Fig. 1 is a view showing an example of a conventional general liquid crystal display device.

Fig. 2 is a view showing an example of a liquid crystal display device of the present invention.

Claims (16)

A liquid crystal display device comprising: a first substrate; a second substrate; a liquid crystal composition layer sandwiched between the first substrate and the second substrate; and a color filter comprising a black matrix and at least RGB three-color pixel portion a pixel electrode and a common electrode, the liquid crystal composition layer comprising a liquid crystal composition comprising: 30 to 50% of a compound represented by the general formula (I) (wherein R ¹ and R ² are each independently, and 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 2 carbon atoms; 8 alkenyloxy; A represents 1,4-phenylene or trans-1,4-cyclohexenyl); contains 5 to 20% of the compound of the formula (II-1) (wherein R ³ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms; ⁴ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms; and 25 to 45 % of the compound of the formula (II-2) (wherein R ⁵ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms; ⁶ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms; and B is substituted by fluorine. 1,4-phenylene or trans-1,4-cyclohexenyl), the RGB three-color pixel portion, as a coloring material, contains a diketopyrrolopyrrole pigment and/or an anion in the R pixel portion a red organic dye; comprising at least one selected from the group consisting of a mixture of a halogenated copper indigo pigment, an indigo green dye, an indigo blue dye, and an azo yellow organic dye in the G pixel portion; The B pixel portion contains an ε-type copper phthalocyanine pigment and/or a cationic blue organic dye. The liquid crystal display device of claim 1, wherein the liquid crystal composition layer further contains 5 to 20% of the compound of the formula (III) (wherein R ⁷ and R ⁸ are each independently, and 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 2 carbon atoms; 8 alkenyloxy; D, E, F and G are each independently, meaning 1,4-phenyl or trans-1,4-cyclohexene which can be substituted by fluorine; Z ² represents a single bond, -OCH ₂ -, -OCO-, -CH ₂ O- or -COO-; n represents 0 or 1, but n represents 0, and Z ² represents -OCH ₂ -, -OCO-, -CH ₂ O- or -COO - or D, E and G represent a 1,4-phenylene group which may be substituted by fluorine). The liquid crystal display device of claim 2, which contains 35 to 70% of the compound of the formula (II-1), the formula (II-2) and the formula (III). The liquid crystal display device according to any one of claims 1 to 3, wherein the RGB three-color pixel portion, as a coloring material, contains CI solvent red 124 in the R pixel portion and CI solvent blue in the G pixel portion. A mixture of 67 and CI Solvent Yellow 162 contains CI Solvent Blue 7 in the B pixel portion. The liquid crystal display device according to any one of claims 1 to 3, wherein the RGB three-color pixel portion contains, as a coloring material, CI Pigment Red 254 in the R pixel portion and CI Pigment in the G pixel portion. Green 7 and/or 36; CI Pigment Blue 15:6 is contained in the B pixel portion. The liquid crystal display device according to any one of claims 1 to 3, wherein the R pixel portion further comprises a color selected from the group consisting of CI Pigment Red 177, the same 242, the same 166, the same 167, and the same 179; CI Pigment Orange 38 , 71; CI Pigment Yellow 150, the same 215, the same 185, the same 138, the same 139; CI Solvent Red 89; CI Solvent Orange 56; CI Solvent Yellow 21, the same 82, the same 83:1, the same 33, the same 162 At least one organic dye pigment in the group. The liquid crystal display device according to any one of claims 1 to 3, wherein the G pixel portion further comprises a component selected from the group consisting of CI Pigment Yellow 150, the same 215, the same 185, and the same 138; CI Solvent Yellow 21, the same 82 An organic dye pigment of at least one of the group of 83:1 and 33. The liquid crystal display device according to any one of claims 1 to 3, wherein the B pixel portion further comprises a component selected from the group consisting of CI Pigment Blue 1; CI Pigment Violet 23; CI Basic Blue 7; CI Basic Violet 10 An organic dye pigment of at least one of the group consisting of CI Acid Blue 1, 90, and 83; CI Direct Blue 86. The liquid crystal display device according to any one of claims 1 to 3, wherein the color filter comprises a black matrix, an RGB three-color pixel portion, and a Y pixel portion, and the coloring material is selected from the Y pixel portion. A yellow organic dye pigment of at least one of CI Pigment Yellow 150, 215, 185, 138, and 139; CI Solvent Yellow 21, 82, and 83:1, 33, and 162. The liquid crystal display device according to any one of claims 1 to 3, wherein in the formula (I), A represents a compound of 1,4-phenylene group and A represents trans-1,4-cyclohexene. Each of the compounds of the group contains at least one or more. The liquid crystal display device according to any one of claims 1 to 3, wherein in the formula (II-2), B represents a compound of 1,4-phenylene group and B represents a trans-1,4-ring ring. Each of the hexenyl compounds contains at least one or more. The liquid crystal display device according to any one of claims 1 to 3, wherein the liquid crystal composition constituting the liquid crystal composition layer is represented by the following formula (wherein γ1 represents a rotational viscosity; Δn represents a refractive index anisotropy), Z is 13,000 or less, γ1 is 150 or less, and Δn is 0.08 to 0.13. The liquid crystal display device according to any one of claims 1 to 3, wherein the liquid crystal composition constituting the liquid crystal composition layer has a nematic liquid crystal phase upper limit temperature of 60 to 120 ° C, and the nematic liquid crystal phase lower limit temperature is - Below 20 ° C, the difference between the upper limit temperature and the lower limit temperature of the nematic liquid crystal phase is from 100 to 150. The liquid crystal display device according to any one of claims 1 to 3, wherein the liquid crystal composition constituting the liquid crystal composition layer has a specific resistance of 10 ¹² (Ω··m) or more. The liquid crystal display device according to any one of claims 1 to 3, wherein the liquid crystal composition layer is a polymer obtained by polymerizing a liquid crystal composition containing a polymerizable compound represented by the general formula (V). Composition (wherein, X ¹ and X ² are each independently represented by a hydrogen atom or a methyl group; and Sp ¹ and Sp ² are each independently represented by a single bond, an alkylene group having 1 to 8 carbon atoms or -O-(CH _{2 ) s} - (wherein s represents an integer from 2 to 7; the oxygen atom is bonded to the 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 are each independently represent a fluorine atom or a hydrogen atom), -C≡C- Or a single bond; C represents 1,4-phenylene, trans-1,4-cyclohexenyl or a single bond, wherein all 1,4-phenylene groups, any hydrogen atom can be replaced by a fluorine atom ). The liquid crystal display device of claim 15, wherein in the general formula (V), C represents a single bond, and Z ¹ represents a single bond.