TWI439538B - 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 starts with a clock and a calculator, and is gradually applied to various household electrical appliances, measuring machines, automobile panels, word processors, electronic notebooks, printers, computers, televisions, and the like. Typical examples of the liquid crystal display method include TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, DLS (Dynamic Light Scattering) type, and GH ( Guest-Host, IPS (In Plane Switching), OCB (Optical Compensated Birefringence), ECB (Electrically Controlled Birefringence), VA (Vertical Alignment) , Vertical alignment type, CSH (Color Super Homeotropic) type, or FLC (Ferroelectric Liquid Crystal). Further, as a driving method, it is usually a static driving to multiplex driving, and in the simple matrix method, an active matrix recently driven by a TFT (Thin-film transistor) or a TFD (Thin-film diode). The (AM) approach has gradually become mainstream.

As shown in FIG. 1, a typical 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 the color filter layer (2), the pixel electrode layer (3b) is provided between the other alignment film and the substrate, and the substrates are arranged such that the alignment films face each other. The liquid crystal layer (5) is sandwiched.

The color filter layer is composed of a color filter composed of a black matrix and a red colored layer (R), a green colored layer (G), a blue colored layer (B), and optionally yellow colored. Layer (Y) is constructed.

Regarding the liquid crystal material constituting the liquid crystal layer, if impurities remain in the material, the electrical characteristics of the display device are greatly affected, and thus the height management of impurities is gradually performed. Further, as for the material for forming the alignment film, it is known that the alignment film directly contacts the liquid crystal layer, and the impurities remaining in the alignment film are transferred to the liquid crystal layer, thereby affecting the electrical characteristics of the liquid crystal layer, and the industry is facing impurities in the alignment film material. The characteristics of the resulting liquid crystal display device were investigated.

On the other hand, as for the material such as the organic pigment used in the color filter layer, it is estimated that the influence on the liquid crystal layer caused by the contained impurities is similar to that of the alignment film material. However, since the alignment film and the transparent electrode are present 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 as compared with the alignment film material. However, the film thickness of the alignment film is usually not more than 0.1 μm, and the transparent electrode is usually 0.5 μm or less even if the thickness of the common electrode used for the color filter layer side is increased by increasing the conductivity. Therefore, it cannot be said that the color filter layer and the liquid crystal layer are placed in a completely isolated environment, and the color filter layer can pass through the alignment film and the transparent electrode through the impurities contained in the color filter layer, so that the liquid crystal layer The decrease in voltage holding ratio (VHR) and the increase in ion density (ID, Ion Density) are manifested by poor display such as whitening, misalignment, and image afterglow.

As a method for solving the display defect caused by the impurities contained in the pigment constituting the color filter, the industry has studied to control the elution of impurities into the liquid crystal by using a pigment having a ratio of the extract of the ethyl formate of the pigment to a specific value or less. (Patent Document 1), or a method of controlling elution of impurities into liquid crystal by specifying a pigment in a blue colored layer (Patent Document 2). However, these methods are not significantly different from the case of simply reducing the impurities in the pigment. In recent years, in the current state of progress in the refining technology of the pigment, it is not sufficient as an improvement for solving the display failure.

On the other hand, focusing on the relationship between the organic impurities contained in the color filter and the liquid crystal composition, it is revealed that the hydrophobic parameter of the liquid crystal molecules contained in the liquid crystal layer indicates the difficulty of dissolving the organic impurity on the liquid crystal layer, and The method of setting the value of the hydrophobic parameter to a value equal to or higher than a certain value, or because the hydrophobic parameter is related to the -OCF ₃ group at the end of the liquid crystal molecule, so that a certain ratio or more is contained at the end of the liquid crystal molecule to have -OCF ₃ A method of a liquid crystal composition of a liquid crystal compound (Patent Document 3).

However, in the contents disclosed in the cited documents, the essence of the invention is to suppress the influence of impurities in the pigment on the liquid crystal layer, and is not directed to the structure of the coloring matter such as the dyeing pigment used in the color filter and the structure of the liquid crystal material. The direct relationship has been studied, and it has not solved the problem of poor display of the liquid crystal display device.

[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 using a specific liquid crystal composition and a color filter using a specific dye and/or pigment, thereby preventing a decrease in voltage holding ratio (VHR) of the liquid crystal layer, and ion density (ID). The increase is solved, and the problem of poor display such as anti-white, uneven alignment, and image afterglow is solved.

In order to solve the above problems, the inventors of the present invention have been directed to constituting color filters. Efforts have been made to study a combination of a coloring material such as a dye and a liquid crystal material constituting a liquid crystal layer, and as a result, it has been found that a liquid crystal display device using a liquid crystal material having a specific structure and a color filter using a dye and/or pigment having a specific structure can be used. The invention improves the voltage holding ratio (VHR) of the liquid crystal layer, increases the ion density (ID), and solves the problem of poor display such as whitening, misalignment, and image afterglow.

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, a black matrix, and at least RGB three colors a color filter comprising a pixel portion, a pixel electrode, and a common electrode, wherein the liquid crystal composition layer is composed of a liquid crystal composition containing one or two or more compounds represented by the formula (I) and containing One or two or more compounds selected from the group consisting of compounds represented by the general formula (II-a) to the general formula (II-e),

(wherein R ³¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group, and M ³¹ to M ³³ each independently represent a trans-1,4- Cyclohexyl or 1,4-phenylene, one or two -CH ₂ - of the trans-1,4-cyclohexylene group may be substituted by -O- in a manner in which the oxygen atoms are not directly adjacent to each other, and the benzene is extended. One or two hydrogen atoms in the group may be substituted by a fluorine atom, X ³¹ and X ³² independently represent a hydrogen atom or a fluorine atom, and Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group, n ³¹ And n ³² represent 0, 1 or 2 independently of each other, and n ³¹ + n ³² represents 0, 1 or 2, and M ³¹ and M ³³ may be the same or different when there are a plurality of cases,

(wherein R ²¹ to R ³⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and X ²¹ represents a hydrogen atom or a fluorine atom), and the above-mentioned RGB three-color pixel portion In the R pixel portion, a diketopyrrolopyrrole pigment and/or an anionic red organic dye is contained as a coloring material, and the G pixel portion contains a copper phthalocyanine pigment and a phthalocyanine green dye. At least one of the group consisting of a mixture of a phthalocyanine blue dye and an azo yellow organic dye contains an ε-type copper phthalocyanine pigment and/or a cationic blue organic dye in the B pixel portion.

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 increase in the ion density (ID) by using a specific liquid crystal composition and a color filter using a specific dye and/or pigment. And to prevent whitening, uneven alignment, image afterglow and other display defects.

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 liquid crystal layer containing specific liquid crystal composition

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

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

One 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 And a color filter layer (2a) of the pigment, and a pixel electrode layer (3b) is provided between the other alignment film and the substrate, and the substrates are arranged such that the alignment films face each other, and are sandwiched therebetween It is composed of a liquid crystal layer (5a) containing a specific liquid crystal composition.

The two substrates in the display device are bonded together by a sealing material disposed in a peripheral region, and in many cases, a granular spacer for holding a distance between the substrates or a resin formed by photolithography is disposed therebetween. Spacer column.

(liquid crystal composition layer)

The liquid crystal composition layer in the liquid crystal display device of the present invention is composed of a liquid crystal composition containing one or two or more compounds represented by the general formula (I), and one or two or more selected from the group consisting of a compound of the group consisting of the compounds represented by the formula (II-a) to the formula (II-e),

(wherein R ³¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group, and M ³¹ to M ³³ each independently represent a trans-1,4- Cyclohexyl or 1,4-phenylene, one or two -CH ₂ - of the trans-1,4-cyclohexylene group may be substituted by -O- in a manner in which the oxygen atoms are not directly adjacent to each other, and the benzene is extended. One or two hydrogen atoms in the group may be substituted by a fluorine atom, X ³¹ and X ³² independently represent a hydrogen atom or a fluorine atom, and Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group, n ³¹ And n ³² represent 0, 1 or 2 independently of each other, and n ³¹ + n ³² represents 0, 1 or 2, and M ³¹ and M ³³ may be the same or different when there are a plurality of cases,

(wherein R ²¹ to R ³⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and X ²¹ represents a hydrogen atom or a fluorine atom).

In the general formula (I), when R ³¹ is a phenyl (aromatic) ring structure, it is preferably a linear alkyl group having 1 to 5 carbon atoms and a linear carbon. An alkoxy group having 1 to 4 (or more) atoms and an alkenyl group having 4 to 5 carbon atoms, wherein the ring structure of the bond is a saturated ring such as cyclohexane, pyran or dioxane. In the case of a structure, a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 (or more) carbon atoms, and a linear carbon atom number 2 are preferred. ~5 alkenyl.

If it is considered that the chemical stability to heat or light is good, R ^{31 is} preferably an alkyl group. Further, when it is important to produce a liquid crystal display element having a small viscosity and a fast response speed, R ^{31 is} preferably an alkenyl group. Further, in order to lower the viscosity, increase the nematic isotropic phase transition temperature (Tni), and further shorten the response speed, it is preferred to use an alkenyl group whose terminal is not an unsaturated bond, and more preferably an ortho position in the alkenyl group. Base as the end. Further, when it is considered that the solubility at a low temperature is good, R ^{31 is} preferably an alkoxy group as a countermeasure. Further, as another countermeasure, it is preferable to use a plurality of types of R ^{31 in combination} . For example, it is preferred to use a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms as R ³¹ in combination, more preferably a compound having 3 to 5 carbon atoms in combination, and further preferably a combination of 3 and 3 carbon atoms. Compounds 4 and 5.

M ³¹ ~ M ^{33 is} preferably

M ^{31 is} preferably Further preferably

M ^{32 is} preferably Better Further preferably

M ^{33 is} preferably Better Further preferably X ³¹ and X ^{32 are} preferably at least one of fluorine atoms, and more preferably both of them are fluorine atoms. Z ^{31 is} preferably a fluorine atom or a trifluoromethoxy group.

As a combination of X ³¹ , X ³² and Z ³¹ , in one embodiment, X ³¹ = F, X ³² = F and Z ³¹ = F. In still another embodiment, X ³¹ = F, X ³² = H, and Z ³¹ = F. Further, in still another embodiment, X ³¹ = F, X ³² = H, and Z ³¹ = OCF ₃ . Further, in still another embodiment, X ³¹ = F, X ³² = F, and Z ³¹ = OCF ₃ . Further, in still another embodiment, X ³¹ = H, X ³² = H, and Z ³¹ = OCF ₃ .

n ^{31 is} preferably 1 or 2, and n ^{32 is} preferably 0 or 1, more preferably 0, and n ³¹ + n ^{32 is} preferably 1 or 2, and further preferably 2.

More specifically, the compound represented by the formula (I) is preferably a compound represented by the following formula (I-a) to formula (I-f).

(wherein R ³² represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group, and X ³¹ to X ³⁸ each independently represent a hydrogen atom or a fluorine atom; Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group)

In the general formula (Ia) to the formula (If), when R ³² is bonded to a phenyl group (aromatic), it is preferably a linear alkyl group having 1 to 5 carbon atoms. a linear alkoxy group having 1 to 4 (or more) carbon atoms and an alkenyl group having 4 to 5 carbon atoms, wherein the ring structure of the bond is cyclohexane, pyran and dioxane. In the case of a saturated ring structure, a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 (or more) carbon atoms, and a linear carbon are preferable. An alkenyl group having 2 to 5 atoms.

If it is considered that the chemical stability to heat or light is good, R ^{32 is} preferably an alkyl group. Further, in order to produce a liquid crystal display element having a small viscosity and a fast response speed, R ^{32 is} preferably an alkenyl group. Further, in order to lower the viscosity, increase the nematic isotropic phase transition temperature (Tni), and further shorten the response speed, it is preferred to use an alkenyl group whose terminal is not an unsaturated bond, and more preferably an ortho position in the alkenyl group. Base as the end. Further, when it is considered that the solubility at a low temperature is good, R ^{32 is} preferably an alkoxy group as a countermeasure. Further, as another countermeasure, it is preferable to use a plurality of R ^{32 in combination} . For example, it is preferred to use a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms as R ³² , more preferably a compound having 3 to 5 carbon atoms in combination, and further preferably a combination of 3 and 3 carbon atoms. Compounds 4 and 5.

X ³¹ and X ^{32 are} preferably at least one of fluorine atoms, and more preferably both of them are fluorine atoms.

Z ^{31 is} preferably a fluorine atom or a trifluoromethoxy group.

As a combination of X ³¹ , X ³² and Z ³¹ , in one embodiment, X ³¹ = F, X ³² = F, and Z ³¹ = F. In still another embodiment, X ³¹ = F, X ³² = H, and Z ³¹ = F. Further, in still another embodiment, X ³¹ = F, X ³³ = H, and Z ³¹ = OCF ₃ . Further, in still another embodiment, X ³¹ = F, X ³² = F, and Z ³¹ = OCF ₃ . Further, in still another embodiment, X ³¹ = H, X ³² = H, and Z ³¹ = OCF ₃ .

n ^{31 is} preferably 1 or 2, and n ^{32 is} preferably 0 or 1, more preferably 0, and n ³¹ + n ^{32 is} preferably 1 or 2, and further preferably 2.

X ³³ and X ^{34 are} preferably at least one of fluorine atoms, and more preferably both of them are fluorine atoms.

X ³⁵ and X ^{36 are} preferably at least one of which is a fluorine atom, and both of them are fluorine atoms, which is effective in increasing Δ ε, but is soluble in Tni, low temperature or made into a liquid crystal display element. From the standpoint of chemical stability, it is not good.

X ³⁷ and X ^{38 are} preferably at least one of hydrogen atoms, and more preferably both are hydrogen atoms. In the case where at least one of X ³⁷ and X ³⁸ is a fluorine atom, it is not preferable from the viewpoint of Tni, solubility at low temperature, or chemical stability when a liquid crystal display element is formed.

The compound group represented by the general formula (I) preferably contains one to eight kinds, more preferably one to five kinds, and the content thereof is preferably from 3 to 50% by mass, more preferably from 5 to 40% by mass. .

In the general formula (II-a) to the general formula (II-e), when R ²¹ to R ^{30 are} bonded to a phenyl group (aromatic), a linear carbon atom is preferred. An alkyl group having 1 to 5 alkyl groups, a linear alkoxy group having 1 to 4 (or more) carbon atoms, and an alkenyl group having 4 to 5 carbon atoms, wherein the ring structure of the bond is cyclohexane. In the case of a saturated ring structure such as pyran or dioxane, a linear alkyl group having 1 to 5 carbon atoms and a linear alkoxy group having 1 to 4 (or more) carbon atoms are preferred. A base and a linear chain of 2 to 5 carbon atoms.

If it is considered that the chemical stability to heat or light is good, R ²¹ to R ^{30 are} preferably an alkyl group. Further, when it is important to produce a liquid crystal display element having a small viscosity and a fast response speed, R ²¹ to R ^{30 are} preferably alkenyl groups. Further, in order to lower the viscosity, increase the nematic isotropic phase transition temperature (Tni), and further shorten the response speed, it is preferred to use an alkenyl group whose terminal is not an unsaturated bond, and more preferably an ortho position in the alkenyl group. Base as the end. Further, when it is considered that the solubility at a low temperature is good, R ²¹ to R ^{30 are} preferably alkoxy groups as a countermeasure. Further, as another countermeasure, it is preferable to use a plurality of types of R ²¹ to R ^{30 in combination} . For example, a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms as R ²¹ to R ³⁰ is preferably used in combination, and a compound having 3 to 5 carbon atoms is preferably used in combination, and further preferably a carbon atom is used in combination. Compounds of numbers 3, 4 and 5.

R ²¹ to R ^{22 are} preferably an alkyl group or an alkenyl group, and more preferably at least one is an alkenyl group. In the case where both of them are alkenyl groups, they can be preferably used for accelerating the response speed, but are not preferable in the case where the chemical stability of the liquid crystal display element is desired.

At least one of R ²³ to R ²⁴ is preferably an alkyl group, an alkoxy group or an alkenyl group having 4 to 5 carbon atoms. If the balance between the response speed and the Tni is required to be good, at least one of R ²³ to R ²⁴ is preferably an alkenyl group, and if the balance between the response speed and the solubility at a low temperature is required to be good, at least R ²³ to R ^{24 are} at least One is preferably an alkoxy group.

At least one of R ²⁵ to R ²⁶ is preferably an alkyl group, an alkoxy group or an alkenyl group having 2 to 5 carbon atoms. If the balance between the response speed and the Tni is required to be good, at least one of R ²⁵ to R ²⁶ is preferably an alkenyl group, and if the balance between the response speed and the solubility at a low temperature is required to be good, at least R ²⁵ to R ^{26 are} at least One is preferably an alkoxy group. More preferably, R ²⁵ is an alkenyl group and R ²⁶ is an alkyl group. Further, it is also preferred that R ²⁵ is an alkyl group and R ²⁶ is an alkoxy group.

At least one of R ²⁷ to R ²⁸ is preferably an alkyl group, an alkoxy group or an alkenyl group having 2 to 5 carbon atoms. If the balance between the response speed and the Tni is required to be good, at least one of R ²⁷ to R ²⁸ is preferably an alkenyl group, and if the balance between the response speed and the solubility at a low temperature is required to be good, at least R ²⁷ to R ^{28 are} at least One is preferably an alkoxy group. More preferably, R ²⁷ is an alkyl group or an alkenyl group and R ²⁸ is an alkyl group. Further, it is also preferred that R ²⁷ is an alkyl group and R ²⁸ is an alkoxy group. Further, it is particularly preferred that R ²⁷ is an alkyl group and R ²⁸ is an alkyl group.

X ^{21 is} preferably a fluorine atom.

The compound group represented by the formula (II-a) to the formula (II-e) preferably contains one to ten kinds, more preferably one to eight kinds, and the content thereof is preferably from 5 to 80% by mass. More preferably, it is 10 to 70% by mass, and particularly preferably 20 to 60% by mass.

The liquid crystal composition layer in the liquid crystal display device of the present invention may further contain one or two or more compounds selected from the group consisting of compounds represented by the general formula (III-a) to the general formula (III-f).

(wherein R ⁴¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group, and X ⁴¹ to X ⁴⁸ each independently represent a hydrogen atom or a fluorine atom; Z ⁴¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group).

In the general formula (III-a) to the general formula (III-f), when R ⁴¹ is bonded to a phenyl group (aromatic), the linear carbon number is preferably 1~. An alkyl group having 5 or more alkyl groups having 1 to 4 (or more) carbon atoms and an alkenyl group having 4 to 5 carbon atoms, wherein the ring structure of the bond is cyclohexane, pyran and In the case of a saturated ring structure such as dioxane, a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 (or more) carbon atoms, and a straight A chain of 2 to 5 alkenyl groups having carbon atoms.

If it is considered that the chemical stability to heat or light is good, R ^{41 is} preferably an alkyl group. Further, if it is important to produce a liquid crystal display element having a small viscosity and a fast response speed, R ^{41 is} preferably an alkenyl group. Further, in order to lower the viscosity, increase the nematic isotropic phase transition temperature (Tni), and further shorten the response speed, it is preferred to use an alkenyl group whose terminal is not an unsaturated bond, and more preferably an ortho position in the alkenyl group. Base as the end. Further, when it is considered that the solubility at a low temperature is good, R ^{41 is} preferably an alkoxy group as a countermeasure. Further, as another countermeasure, it is preferable to use a plurality of types of R ^{41 in combination} . For example, it is preferred to use a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms as R ⁴¹ in combination, more preferably a compound having 3 to 5 carbon atoms in combination, and further preferably a combination of 3 and 3 carbon atoms. Compounds 4 and 5.

X ⁴¹ and X ^{42 are} preferably at least one of fluorine atoms, and more preferably both of them are fluorine atoms.

Z ^{41 is} preferably a fluorine atom or a trifluoromethoxy group.

As a combination of X ⁴¹ , X ⁴² and Z ⁴¹ , in one embodiment, X ⁴¹ = F, X ⁴² = F, and Z ⁴¹ = F. In still another embodiment, X ⁴¹ = F, X ⁴² = H, and Z ⁴¹ = F. Further, in still another embodiment, X ⁴¹ = F, X ⁴² = H, and Z ⁴¹ = OCF ₃ . Further, in still another embodiment, X ⁴¹ = F, X ⁴² = F, and z ⁴¹ = OCF ₃ . Further, in still another embodiment, X ⁴¹ = H, X ⁴² = H, and Z ⁴¹ = OCF ₃ .

It is preferred that at least one of X ⁴³ and X ⁴⁴ is a fluorine atom, and both of them are fluorine atoms, so that a larger Δ ε is obtained, which is preferable, but conversely, when the solubility at a low temperature is good, good.

Preferably, at least one of X ⁴⁵ and X ⁴⁶ is a hydrogen atom, and more preferably both are hydrogen atoms. When a fluorine atom is used in a large amount, it is not preferable from the viewpoint of Tni, solubility at a low temperature, or chemical stability when a liquid crystal display element is formed.

Preferably, at least one of X ⁴⁷ and X ⁴⁸ is a hydrogen atom, and more preferably both are hydrogen atoms. When at least one of X ⁴⁷ and X ⁴⁸ is a fluorine atom, it is not preferable from the viewpoint of Tni, solubility at low temperature, or chemical stability when formed into a liquid crystal display element.

The compound of the compound represented by the formula (III-a) to the formula (III-f) is preferably one to ten, more preferably one to eight, and the content thereof is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.

The liquid crystal composition of the liquid crystal composition layer in the liquid crystal display device of the present invention preferably has a Δ ε at 25 ° C of +3.5 or more, more preferably +3.5 to +15.0. Further, Δn at 25 ° C is preferably from 0.08 to 0.14, more preferably from 0.09 to 0.13. If it is described in detail, it is preferably 0.10 to 0.13 in the case of a relatively thin cell gap, and preferably 0.08 to 0.10 in the case of a thick cell gap. The η at 20 ° C is preferably 10 to 45 mPa. s, more preferably 10~25mPa. s, especially good for 10~20mPa. s. Further, the Tni is preferably 60 ° C to 120 ° C, more preferably 70 ° C to 100 ° C, and particularly preferably 70 ° C to 85 ° C.

The liquid crystal composition of the present invention may contain, in addition to the above compounds, a usual nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal or the like.

In the liquid crystal composition of the present invention, a PS (Polymer Stabilised) mode, a transverse electric field type PSA (Polymer Sustained Alignment) mode or a transverse electric field type PSVA (Polymer Stabilized Vertical Alignment) is produced. The liquid crystal display element of the stable vertical alignment mode or the like may contain one or two or more kinds of polymerizable compounds. Examples of the polymerizable compound that can be used include a photopolymerizable monomer which is polymerized by an energy ray such as light, and examples of the structure include, for example, a biphenyl derivative or a terphenyl derivative, and a plurality of six-membered rings. A polymerizable compound of a liquid crystal skeleton or the like. More specifically, a difunctional monomer represented by the formula (V) is preferred,

(wherein, X ⁵¹ and X ⁵² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -O-(CH ₂ ) _s - (wherein s represents an integer from 2 to 7, the oxygen atom is bonded to the aromatic ring), and Z ⁵¹ represents -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH- , -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ - , -CH ₂ -COO-, -CH ₂ -OCO-, -CY ¹ =CY ² - (wherein Y ¹ and Y ² each independently represent a fluorine atom or a hydrogen atom), -C≡C- or a single bond M ⁵¹ represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, and any hydrogen atom of any of the 1,4-phenylene groups in the formula may be substituted by a fluorine atom).

X ⁵¹ and X ⁵² are each preferably a diacrylate derivative each having a hydrogen atom, and each of them represents a dimethacrylate derivative having a methyl group, and preferably one of them represents a hydrogen atom and the other A compound representing a methyl group. Regarding the polymerization rate of the compounds, the diacrylate derivative is the fastest, the dimethacrylate derivative is slow, and the asymmetric compound is in the middle thereof, and a preferred aspect can be used depending on the use thereof. In the PSA display element, a dimethacrylate derivative is particularly preferred.

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 -, and a PSA display element, preferably at least one of which is a single bond, more preferably A compound which represents a single bond or one represents a single bond, and the other represents an alkylene group having 1 to 8 carbon atoms or -O-(CH ₂ ) _s -. In this case, it is preferably an alkyl group of 1 to 4, and s is preferably 1 to 4.

Z ^{51 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.

M ⁵¹ represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond in which any hydrogen atom may be substituted by a fluorine atom, but is preferably a 1,4-phenylene group or a single bond. In the case where C represents a ring structure other than a single bond, Z ^{51 is} also preferably a linking group other than a single bond. When M ⁵¹ is a single bond, Z ^{51 is} preferably a single bond.

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

In the general formula (V), when M ⁵¹ represents a single bond and the ring structure is formed of two rings, it is preferably represented by the following formula (Va-1) to formula (Va-5), and more preferably Preferably, the formula is (Va-1)~form (Va-3), and more preferably expressed as formula (Va-1).

(where the two ends are bonded to Sp ¹ or Sp ² )

The alignment restricting power after polymerization of the polymerizable compound containing these skeletons is most suitable for a PSA type liquid crystal display element, and a good alignment state can be obtained, so that display unevenness is suppressed or not generated at all.

As described above, the polymerizable compound is preferably a compound of the formula (V-1) to the formula (V-4), and most preferably, it is a formula (V-2).

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

In the case where a polymerizable compound is added to the liquid crystal composition of the present invention, the polymerization proceeds even in the absence of a polymerization initiator, but may also contain a polymerization initiator in order to promote polymerization. Examples of the polymerization initiator include benzoin ethers, diphenylketones, acetophenones, benzoin ketals, and fluorenylphosphine oxides.

The liquid crystal composition containing a polymerizable compound of the present invention is provided with a liquid crystal alignment ability by polymerizing a polymerizable compound contained therein by ultraviolet irradiation, and is used for liquid crystal display for controlling the amount of light transmitted by the birefringence of the liquid crystal composition. In the component. As a liquid crystal display element, an AM-LCD (Active Matrix-Liquid Crystal Display), a TN-LCD (Twisted Nematic Liquid Crystal Display Element), and an STN-LCD (Super Torsional Nematic Liquid Crystal Display Element) OCB-LCD and IPS-LCD (coplanar switching liquid crystal display elements) are useful, especially for AM-LCDs, and can be used in transmissive or reflective liquid crystal display elements.

(color filter)

The color filter of the present invention comprises a black matrix and at least RGB three-color pixel portions, and the RGB three-color pixel portion contains, as a color material, a diketopyrrolopyrrole pigment and/or an anionic red organic in the R pixel portion. The dye contains a copper phthalocyanine pigment selected from the group consisting of copper phthalocyanine pigment and phthalocyanine green in the G pixel portion. At least one of a group consisting of a mixture of a color dye, a phthalocyanine blue dye, and an azo yellow organic dye contains an ε-type copper phthalocyanine pigment and/or a cationic blue organic dye in the B pixel portion.

In the RGB three-color pixel portion, it is preferable that the R pixel portion contains C.I. Solvent Red 124 or C.I. Pigment Red 254 as a color material.

In the RGB three-color pixel portion, it is preferable that the G pixel portion contains a mixture of C.I. Solvent Blue 67 and C.I. Solvent Yellow 162, or C.I. Pigment Green 7 and/or C.I. Pigment Green 36 as a colorant.

In the RGB three-color pixel portion, it is preferable that the B pixel portion contains C.I. Solvent Blue 7 or C.I. Pigment Blue 15:6 as a color material.

In the RGB three-color pixel portion, the color material is preferably in the R pixel portion. C.I. Solvent Red 124 is contained, and a mixture of C.I. Solvent Blue 67 and C.I. Solvent Yellow 162 is contained in the G pixel portion, and C.I. Solvent Blue 7 is contained in the B pixel portion.

Further, in the RGB three-color pixel portion, it is preferable that the coloring material contains CI Pigment Red 254 in the R pixel portion and CI Pigment Green 7 and/or CI Pigment Green 36 in the G pixel portion, and the B pixel. The department contains CI Pigment Blue 15:6.

Preferably, the RGB three-color pixel portion further includes, in the R pixel portion, a color 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, 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 Solvent Red 89, CI Solvent Orange 56, CI Solvent Yellow 21, CI Solvent Yellow 82, At least one organic dye of the group consisting of CI Solvent Yellow 83:1, CI Solvent Yellow 33, and CI Solvent Yellow 162 is used as a colorant.

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

Preferably, in the RGB three-color pixel portion, the B pixel portion further includes an option At least 1 of the group consisting of free CI Pigment Blue 1, CI Pigment Violet 23, CI Basic Blue 7, CI Basic Violet 10, CI Acid Blue 1, CI Acid Blue 90, CI Acid Blue 83, CI Direct Blue 86 An organic dye is used as a colorant.

Further, the color filter is composed of a black matrix, an RGB three-color pixel portion, and a Y pixel portion, and preferably contains a color selected from the group consisting of CI Pigment Yellow 150, CI Pigment Yellow 215, CI Pigment Yellow 185, and CI Pigment Yellow 138 in the Y pixel portion. At least one yellow organic dye pigment of the group consisting of 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 is used as the colorant.

The color filter of the present invention is used to prevent a decrease in the voltage holding ratio (VHR) of the liquid crystal layer, an increase in the ion density (ID), and a problem of suppressing display defects such as whitening, misalignment, and image afterglow. The chromaticity x and the chromaticity y of each pixel portion in the light sheet in the XYZ color system under the C light source are preferably as follows.

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

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

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

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

Here, the XYZ color system refers to the color system approved by the CIE (The International Commission on Illumination) in 1931 as a standard color system.

The chromaticity in each of the above-described pixel portions can be adjusted by changing the type of the dye to be used or the mixing ratio of the above. For example, in the case of R pixels, it can be adjusted by adding an appropriate amount of yellow dye and/or orange dye to the red dye. In the case of G pixels, an appropriate amount of yellow can be added by the green dye. It is adjusted by dyeing the pigment, and in the case of B pixel, it can be adjusted by adding an appropriate amount of purple dye to the blue dye. Further, it is also possible to adjust 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 method of forming a pixel portion is a photolithography method in which a photocurable composition described below is applied to a surface on a black matrix side of a transparent substrate for a color filter. After heat drying (pre-baking), pattern exposure is performed by irradiating ultraviolet rays through a mask to cure the photocurable compound corresponding to the portion of the pixel portion, and thereafter, the unexposed portion is developed by the developer to remove the non-pixel portion. The part is fixed to the transparent substrate. In this method, a pixel portion composed of a hard colored film of a photocurable composition is formed on a transparent substrate.

The photocurable composition described below is prepared for each of pixels of other colors such as R pixels, G pixels, B pixels, and Y pixels as needed, and the above operation is repeated, whereby R pixels and G can be manufactured at specific 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 below to a transparent substrate such as glass may, for example, be a spin coating method, a roll coating method, or an inkjet method.

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

Examples of the development method include a liquid discharge method, a dipping method, and a spray method. After exposure and development of the photocurable composition, the transparent substrate on which the pixel portion having the necessary color is formed is washed with water and dried. The color filter thus obtained is subjected to a specific time heat treatment (post-baking) at a temperature of 90 to 280 ° C by a heating means such as a hot plate or an oven, thereby removing volatile components in the colored coating film while remaining in photocurability. The unreacted photocurable compound in the hardened pigmented film of the composition is thermally hardened to complete a color filter. Further, it may be a structure in which a color filter on Array having a color filter is formed on the pixel substrate.

The color filter coloring material of the present invention can be used together with the liquid crystal composition of the present invention to provide a reduction in voltage holding ratio (VHR) of the liquid crystal layer, an increase in ion density (ID), and resolution of whitening. A liquid crystal display device having a problem of poor display such as misalignment and image afterglow.

The method for producing the photocurable composition is generally as follows: a dye and/or a 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 and stirred. Dispersing to make it uniform, first preparing a pigment dispersion for forming a pixel portion of a color filter, and thereafter adding a photocurable compound, an optional thermoplastic resin or a photopolymerization initiator, etc., to form the above photohardening Sexual composition.

Examples of the organic solvent to be used herein include aromatic solvents such as toluene or xylene and methoxybenzene, ethyl acetate or propyl acetate or butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether. Acetate solvent such as acetate, diethylene glycol methyl ether acetate, diethylene glycol diethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol butyl ether acetate, etc. a propionate solvent such as acid ethoxyethyl ester, an alcohol solvent such as methanol or ethanol, or an ether solvent such as butyl racelusu, propylene glycol monomethyl ether, diethylene glycol diethyl ether or diethylene glycol dimethyl ether. Methyl ethyl ketone, A A ketone solvent such as isobutyl ketone or cyclohexanone, an aliphatic hydrocarbon solvent such as hexane, N,N-dimethylformamide, γ-butylimamine or N-methyl-2-pyrrolidine A solvent such as a nitrogen compound such as a ketone, aniline or pyridine, a lactone solvent such as γ-butyrolactone, or a urethane such as a mixture of methyl carbamate and ethyl urethane at 48:52.

As 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, BYK-Chemie, DISPERBYK 185, DISPERBYK 2000, DISPERBYK 2001, DISPERBYK 2020, DISPERBYK 2050, DISPERBYK 2070, DISPERBYK 2096, DISPERBYK 2150, DISPERBYK LPN21116, DISPERBYK LPN6919, Efka 46 of Efka, Efka 47, Efka 452, Efka LP4008, Efka 4009, Efka LP4010 , Efka LP4050, Efka 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, Solsperse 18000, Solsperse 20000, Solsperse 21000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, Solsperse 32000, Solsperse 36000, Solsp Erse 37000, Solsperse 38000, Solsperse 41000, Solsperse 42000, Solsperse 43000, Solsperse 46000, Solsperse 54000, Solsperse 71000, Ajisper PB711, Ajisper PB821, Ajisper PB822, Ajisper PB814, Ajisper PN411, Ajisper PA111, etc. Agent, or acrylic resin, amine ester resin, alkyd resin, wood rosin, rosin gum, tall oil rosin and other natural rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, oxidized rosin, maleic rosin, etc. Modified rosin, rosin amine, lime rosin, rosin alkylene oxide adduct, rosin alkyd adduct, rosin modified phenol and other rosin derivatives are equal to room temperature liquid and water insoluble synthetic resin. Such The addition of the dispersant or resin also contributes to a reduction in flocculation, an increase in the dispersion stability of the pigment, and an increase in the viscosity characteristics of the dispersion.

Further, as the dispersing aid, an organic pigment derivative such as phthalimide methylamine derivative, phthalimide sulfonic acid derivative, orthophthalimide N-( Dialkylamino)methyl derivative, phthalimide N-(dialkylaminoalkyl)sulfonate derivative, and the like. Of course, these derivatives may also be used in combination of two or more different types.

Examples of the thermoplastic resin used in the preparation of the photocurable composition include an amine ester resin, an acrylic resin, a polyamide resin, a polyimide resin, and 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 decyloxy). 2-functional monomer such as ethoxy)bisphenol A or 3-methylpentanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tris[2-(methyl)acryloxyloxy group Methyl]isocyanurate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and other relatively small molecular weight polyfunctional monomers, polyester acrylate, polyacrylic acid amide, polyether acrylate, etc. a polyfunctional monomer.

Examples of the photopolymerization initiator include acetophenone, diphenyl ketone, benzyl dimethyl ketal, benzammonium peroxide, and 2-chloro 9-oxosulfuric acid. , 1,3-bis(4'-azidobenzylidene)-2-propane, 1,3-bis(4'-azidobenzylidene)-2-propane-2'-sulfonic acid, 4 , 4'-diazide 茋-2,2'-disulfonic acid and the like. As a commercially available photopolymerization initiator, for example, "Irgacure (trade name)-184", "Irgacure (trade name)-369", "Darocur (trade name)-1173" manufactured by BASF Corporation, manufactured by BASF Corporation "Lucirin-TPO", "Kayacure (trade name) DETX" manufactured by Nippon Kayaku Co., Ltd., "Kayacure (trade name) OA", "Vicure 10" manufactured by Stauffer, "Vicure 55", and "made by Akzo" Trigonal PI", "Sundray 1000" manufactured by Sando, "Deep" manufactured by UPJOHN, and "Biimidazole" manufactured by Heijin Chemical Co., Ltd.

Further, a photo-polymerization initiator may be used in combination with a conventionally known photosensitizer. 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 singly 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 compound having a photopolymerizable or photocurable functional group. When it is less than 0.1%, the sensitivity at the time of photocuring tends to be lowered, and when it exceeds 30%, the crystal of the photopolymerization initiator is precipitated when the coating film of the pigment-dispersed resist is dried, and the physical properties of the coating film are deteriorated. The situation.

Each of the above materials may be used, and 300 to 1000 parts of the organic solvent and 1 to 100 parts of the dispersant are stirred per 100 parts of the dye and/or pigment composition for the color filter of the present invention on a mass basis. The above pigmented liquid was obtained by dispersing to make it uniform. Then, a total of 3 to 20 parts by weight of the thermoplastic resin and the photocurable compound per one part of the pigment composition for a color filter of the present invention, and one part per part of the photocurable compound may be added to the pigment dispersion liquid. The photopolymerization initiator is used in an amount of 0.05 to 3 parts, and an organic solvent is further added as needed, and stirred and dispersed to make it uniform, thereby obtaining a photocurable composition for forming a pixel portion of the color filter.

As the developer, a known organic solvent or an alkaline aqueous solution can be used. In particular, when the photocurable composition contains a thermoplastic resin or a photocurable compound, and at least one of them has an acid value and is alkali-soluble, it is washed with an alkaline aqueous solution to the pixel portion of the color filter. Formed with effect.

The method of manufacturing the color filter pixel portion by the photolithography method has been described in detail. However, the color filter pixel portion prepared by using the pigment composition for a color filter of the present invention can also be rotated by other plating methods. Printing, micellar electrolysis, PVED (photovoltaic electrodeposition), inkjet, reverse printing, thermosetting, etc. A color filter is produced.

(alignment film)

In the liquid crystal display device of the present invention, the liquid crystal composition is aligned on the surface of the first substrate and the liquid crystal composition on the second substrate. Therefore, in the liquid crystal display device requiring the alignment film, the alignment film is disposed on the color filter and Between the liquid crystal layers, the film thickness of the alignment film is also as thin as 100 nm or less, and the interaction between the dye 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 in which the alignment film is not used, 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) or polyvinyl alcohol can be used, in particular, p-phenylenediamine, 4, An aliphatic or alicyclic four such as an aliphatic or alicyclic diamine such as 4'-diaminodiphenylmethane; and a butane tetracarboxylic anhydride or 2,3,5-tricarboxycyclopentyl acetic anhydride; A polyimine alignment film obtained by imidating a polyamidite synthesized by aromatic tetracarboxylic anhydride such as formic anhydride or pyromellitic dianhydride is preferred. In this case, the alignment imparting method is usually rubbing, but when it is used in a vertical alignment film or the like, it may be used without imparting alignment.

As the alignment film material, a material containing a chalcone, a cinnamate group, a cinnamyl group or an azo group in the compound may be used, and may be used in combination with a material such as polyimine or polyamine. The alignment film can be rubbed or optical alignment technology.

The alignment film is usually formed by applying the alignment film material onto a substrate by a spin coating method or the like to form a resin film. However, a uniaxial stretching method, a Langmuir-Blodgett method, or the like can be used.

(transparent electrode)

In the liquid crystal display device of the present invention, as the material of the transparent electrode, a conductive metal oxide can be used, 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), added titanium dioxide (Ti _1-x Nb _x O ₂ ), fluorine-doped tin oxide, The graphene nanobelt or the metal nanowire or the like is preferably zinc oxide (ZnO), indium tin oxide (In ₂ O ₃ -SnO ₂ ) or indium zinc oxide (In ₂ O ₃ -ZnO). The patterning of the transparent conductive films may be performed by photolithography or a method using a mask.

The liquid crystal display device of the present invention is particularly useful for a liquid crystal display device for active matrix driving, and can be applied to a liquid crystal display device for a TN mode, an IPS mode, a polymer stabilized IPS mode, an FFS mode, an OCB mode, a VA mode, or an ECB mode.

[Examples]

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the examples. Further, "%" in the compositions of the following examples and comparative examples means "% by mass".

In the examples, the characteristics of the measurement were as follows.

Tni: nematic phase-isotropic liquid phase transfer temperature (°C)

Δn: refractive index anisotropy at 25 ° C

Δε: dielectric anisotropy at 25 ° C

η: viscosity at 20 ° C (mPa.s)

Γ1: Rotational viscosity at 25 ° C (mPa.s)

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

(A value obtained by injecting a liquid crystal composition into a cell having a cell thickness of 3.5 μm and measuring a ratio of a measured voltage to an initial applied voltage when measured under conditions of a voltage of 5 V, a frame time of 200 ms, and a pulse width of 64 μs)

ID: ion density at 70 ° C (pC/cm ² )

(Injecting a liquid crystal composition into a cell having a cell thickness of 3.5 μm, and measuring the ion at a voltage of 20 V and a frequency of 0.05 Hz by using MTR-1 (manufactured by Toyo Technology Co., Ltd.) Density value)

Image afterglow:

The image afterglow evaluation of the liquid crystal display element was performed by displaying the specific fixed pattern for 1000 hours in the display area, and then visually evaluating the level of the afterimage of the fixed pattern when the entire screen was uniformly displayed in accordance with the following four levels.

◎ no afterimage

○ There are very few afterimages, which are also allowable levels

△ There is an afterimage, which is an unacceptable level

×There is an afterimage, which is quite bad

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

(ring structure)

(side chain structure and joint structure)

[Production of color filter] [Preparation of coloring composition]

[Red dye coloring composition 1]

Add 10 parts of red dye 1 (CI Solvent Red 124) to a plastic bottle, add 55 parts of propylene glycol monomethyl ether acetate, 0.3-0.4mm Sepabeads was dispersed by a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, and then filtered using a 5 μm filter to obtain a dye coloring liquid. 75.00 parts of the dye coloring liquid and 5.50 parts of polyester acrylate resin (ARONIX (trade name) M7100, manufactured by Toagosei Chemical Co., Ltd.), dipentaerythritol hexaacrylate (KAYARAD (trade name) DPHA, Nippon Chemical Co., Ltd.) Manufactured by 5.00 parts, 1.00 parts of diphenyl ketone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.), 13.5 parts of UCAR Ester EEP, stirred by a dispersing mixer, using a filter with a pore size of 1.0 μm Filtration was carried out to obtain a red dye coloring composition 1.

[Red dye coloring composition 2]

Red dye coloring composition was obtained in the same manner as above except that 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 red dye 1 of the above red dye coloring composition 1. Object 2.

[Red dye coloring composition 3]

Red dye coloring composition 3 was obtained in the same manner as above except that 10 parts of red dye 2 (C.I. Solvent Red 1) was used instead of 10 parts of red dye 1 of the above red dye coloring composition 1.

[Green dye coloring composition 1]

Green dye dyeing was obtained in the same manner as above except that 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 7 parts of red dye 1 of the above red dye coloring composition 1. Composition 1.

[Green dye coloring composition 2]

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

[Green dye coloring composition 3]

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

[Blue dye coloring composition 1]

The blue dye coloring composition 1 was obtained in the same manner as above except that 10 parts of the red dye 1 (C.I. Solvent Blue 7) was used instead 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 (C.I. Solvent Blue 7), 3 parts of purple dye 1 (C.I. Basic Violet 10) In place of the above-mentioned 10 parts of the blue dye 1 of the blue dye coloring composition 1, the blue dye coloring composition 2 was obtained in the same manner as above.

[Blue dye coloring composition 3]

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

[Yellow dye coloring composition 1]

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

[Yellow dye coloring composition 2]

Yellow pigment dyeing composition 2 was obtained in the same manner as above except that 10 parts of yellow dye 4 (C.I. Solvent Yellow 2) was used instead of 10 parts of yellow dye 2 of the above yellow dye coloring composition 1.

[Red Pigment Coloring Composition 1]

Add 10 parts of red pigment 1 (CI Pigment Red 254, "IRGAPHOR RED BT-CF" manufactured by BASF Corporation) to a plastic bottle, add 55 parts of propylene glycol monomethyl ether acetate, DISPERBYK LPN21116 (manufactured by BYK-Chemie Co., Ltd.) ) 7.0 parts, 0.3-0.4mm Sepabeads was dispersed by a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, and then filtered using a filter of 5 μm to obtain a pigment dispersion liquid.

75.00 parts of the pigment dispersion and 5.50 parts of polyester acrylate resin (ARONIX (trade name) M7100, manufactured by Toagosei Chemical Co., Ltd.), dipentaerythritol hexaacrylate (KAYARAD (trade name) DPHA, Nippon Chemical Co., Ltd.) Manufactured by 5.00 parts, 1.00 parts of diphenyl ketone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.), 13.5 parts of UCAR Ester EEP, stirred by a dispersing mixer, using a filter with a pore size of 1.0 μm Filtration was carried out to obtain a red pigment coloring composition 1.

[Red Pigment Coloring Composition 2]

2 parts of red pigment 1, red pigment 2 (CI Pigment Red 177, FASTOGEN SUPER RED ATY-TR manufactured by DIC Corporation), and 2 parts of yellow pigment 2 (CI Pigment Yellow 139) were used instead of the above red pigment coloring composition. The red pigment coloring composition 2 was obtained in the same manner as above for 10 parts of red pigment 1 of the material 1.

[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 In the same manner as above, the green pigment coloring composition 1 was obtained in 10 parts of the red pigment 1 of the pigment coloring composition 1.

[Green Pigment Coloring Composition 2]

4 parts of green pigment 2 (CI Pigment Green 7, FASTOGEN GREEN S manufactured by DIC Co., Ltd.) and 6 parts of yellow pigment 3 (CI Pigment Yellow 138) were used instead of 6 parts of green pigment 1 and 4 of the above green pigment coloring composition 1. The yellow pigment 1 was 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 purple pigment 1 (CI Pigment Violet 23) were used instead of the above red pigment coloring composition 1 Ten parts of red pigment 1, a blue pigment coloring composition 1 was obtained in the same manner as above.

[Blue pigment dye coloring composition 2]

A blue pigment dye coloring composition 2 was obtained in the same manner as above except that one part of the above-mentioned blue pigment coloring composition 1 was replaced with 1 part of the purple dye 1 (C.I. Basic Violet 10).

[Yellow Pigment Coloring Composition 1]

10 parts of red pigment 1 of the above red pigment coloring composition 1 was replaced with 10 parts of yellow pigment 1 (C.I. Pigment Yellow 150, FANCHON FAST YELLOW E4GN manufactured by BAYER). Yellow pigment coloring composition 1 was obtained in the same manner as above.

[Production of color filter]

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

Then, the green coloring composition was applied in the same manner by spin coating so that the film thickness became 2 μm. After drying, the stripe-shaped color layer is exposed and developed by an exposure machine to a portion shifted from the red pixel, thereby forming a green pixel adjacent to the red pixel.

Then, the blue coloring composition was similarly formed into a blue pixel adjacent to the red pixel and the green pixel so that the film thickness became 2 μm by spin coating. Thereby, a color filter having stripes of three colors of red, green, and blue on a transparent substrate is obtained.

Similarly to the yellow colored composition, a yellow pixel adjacent to the red pixel and the green pixel is formed by spin coating so that the film thickness becomes 2 μm. Thereby, a color filter having pixels of stripes of four colors of red, green, blue, and yellow on a transparent substrate is obtained.

The color filter composition or the pigment coloring composition shown in Table 2 was used to prepare color filters 1 to 4 and comparative color filter 1.

For each pixel portion of the color filter, the x value and the y of the CIE 1931 XYZ color system under the C light source were measured using a microscope MX-50 manufactured by Olympus and a spectrophotometer MCPD-3000 microspectrophotometer manufactured by Otsuka Electronics. value. The results are shown in Table 3 below.

(Examples 1 to 4)

Forming an electrode structure on at least one of the first and second substrates, forming a horizontally-aligned alignment film on opposite sides of each of the electrodes, and performing a weak rubbing treatment to form an IPS unit on the first substrate and the second substrate The liquid crystal composition 1 shown below was sandwiched between them. The physical property values of the liquid crystal composition 1 are shown in Table 4. Then, liquid crystal display devices (d _gap = 4.0 μm, alignment film AL-1051) of Examples 1 to 4 were produced using the color filters 1 to 4 shown in Table 2. The VHR and ID of the obtained liquid crystal display device were measured. Further, image afterglow evaluation of the obtained liquid crystal display device was performed. The results are shown in Table 5.

Liquid crystal composition 1

[table 5]

It is understood that the liquid crystal composition 1 has a liquid crystal layer temperature range of 75.8 ° C which is practical as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, and has a low viscosity and an optimum Δn. .

The liquid crystal display devices of Embodiments 1 to 4 can realize a higher VHR and a smaller ID. Moreover, there is no residual image in the evaluation of image afterglow, or even if it exists, it is a level which is extremely small and tolerable.

(Examples 5 to 12)

The liquid crystal compositions 2 to 3 shown in Table 6 were sandwiched in the same manner as in Example 1, and the liquid crystal display devices of Examples 5 to 12 were formed using the color filters shown in Table 2, and their VHR and ID were measured. Further, image afterglow evaluation of the liquid crystal display device was performed. The results are shown in Tables 7-8.

The liquid crystal display devices of Examples 5 to 12 can achieve a higher VHR and a smaller ID. Moreover, there is no residual image in the evaluation of image afterglow, or even if it exists, it is a level which is extremely small and tolerable.

(Examples 13 to 24)

The liquid crystal compositions 4 to 6 shown in Table 9 were sandwiched in the same manner as in Example 1, and the liquid crystal display devices of Examples 13 to 24 were formed using the color filters shown in Table 2, and their VHR and ID were measured. Further, image afterglow evaluation of the liquid crystal display device was performed. The results are shown in Tables 10 to 12.

The liquid crystal display devices of Examples 13 to 24 can realize a higher VHR and a smaller ID. Moreover, there is no residual image in the evaluation of image afterglow, or even if it exists, it is a level which is extremely small and tolerable.

(Examples 25 to 36)

Forming an electrode structure on the first and second substrates, forming a horizontally-aligned alignment film on opposite sides of each of the layers, and performing a weak rubbing treatment to form a TN unit, sandwiching between the first substrate and the second substrate The liquid crystal compositions 7 to 9 shown in Table 13. Then, liquid crystal display devices (d _gap = 3.5 μm, alignment film SE-7492) of Examples 25 to 36 were fabricated using the color filters 1 to 4 shown in Table 2. The VHR and ID of the obtained liquid crystal display device were measured. Further, image afterglow evaluation of the obtained liquid crystal display device was performed. The results are shown in Tables 14 to 16.

The liquid crystal display devices of Examples 25 to 36 can realize a higher VHR and a smaller ID. Moreover, there is no residual image in the evaluation of image afterglow, or even if it exists, it is a level which is extremely small and tolerable.

(Examples 37 to 44)

Forming an electrode structure on at least one of the first and second substrates, forming a horizontally-aligned alignment film on opposite sides of each of the electrodes, and performing a weak rubbing treatment to form an FFS unit on the first substrate and the second substrate The liquid crystal compositions 10 to 11 shown in Table 17 were sandwiched between the substrates. Then, liquid crystal display devices (d _gap = 4.0 μm, alignment film AL-1051) of Examples 37 to 44 were produced using the color filters 1 to 4 shown in Table 2. The VHR and ID of the obtained liquid crystal display device were measured. Further, image afterglow evaluation of the obtained liquid crystal display device was performed. The results are shown in Tables 18 to 19.

The liquid crystal display devices of Examples 37 to 44 can realize a higher VHR and a smaller ID. also, There is no residual image in the evaluation of image afterglow, or even if it exists, it is a level that is extremely small and tolerable.

(Examples 45 to 56)

The liquid crystal compositions 12 to 14 shown in Table 20 were sandwiched in the same manner as in Example 37, and the liquid crystal display devices of Examples 45 to 56 were formed using the color filters shown in Table 2, and their VHR and ID were measured. Further, image afterglow evaluation of the liquid crystal display device was performed. The results are shown in Tables 21 to 23.

The liquid crystal display devices of Examples 45 to 56 can realize a higher VHR and a smaller ID. Moreover, there is no residual image in the evaluation of image afterglow, or even if it exists, it is a level which is extremely small and tolerable.

(Examples 57 to 60)

The liquid crystal composition 10 used in Example 37 was mixed with 0.3% by mass of diphenyl-4,4'-diester methacrylate to prepare a liquid crystal composition 15. The liquid crystal composition 15 was sandwiched between the counter electrodes, and ultraviolet rays were irradiated for 600 seconds (3.0 J/cm ² ) in a state where a driving voltage was applied between the electrodes, and polymerization treatment was performed. Then, the color filter 1 shown in Table 2 was used. ~4 was prepared into liquid crystal display devices of Examples 57 to 60, and their VHR and ID were measured. Further, image afterglow evaluation of the liquid crystal display device was performed. The results are shown in Table 24.

The liquid crystal display devices of Examples 57 to 60 can realize a higher VHR and a smaller ID. Moreover, there is no residual image in the evaluation of image afterglow, or even if it exists, it is a level which is extremely small and tolerable.

(Examples 61 to 64)

The liquid crystal composition 8 used in Example 29 was mixed with 0.3% by mass of diphenyl-4,4'-diester methacrylate to prepare a liquid crystal composition 16. The liquid crystal composition 16 was sandwiched between the IPS units, and ultraviolet rays were irradiated for 600 seconds (3.0 J/cm ² ) in a state where a driving voltage was applied between the electrodes, and polymerization treatment was performed. Then, the color filter 1 shown in Table 2 was used. ~4 The liquid crystal display devices of Examples 61 to 64 were fabricated, and their VHR and ID were measured. Further, image afterglow evaluation of the liquid crystal display device was performed. The results are shown in Table 25.

The liquid crystal display devices of Examples 61 to 64 can realize a higher VHR and a smaller ID. Moreover, there is no residual image in the evaluation of image afterglow, or even if it exists, it is a level which is extremely small and tolerable.

(Examples 65 to 68)

The liquid crystal composition 6 used in Example 21 was mixed with 0.3% by mass of 3-fluorobiphenyl-4,4'-diester methacrylate to prepare a liquid crystal composition 17. The liquid crystal composition 17 was sandwiched between the electrodes and irradiated with ultraviolet rays for 600 seconds (3.0 J/cm ² ) in a state where a driving voltage was applied between the electrodes, and polymerization treatment was performed. Then, the color filter 1 shown in Table 2 was used. ~4 The liquid crystal display devices of Examples 65 to 68 were fabricated, and their VHR and ID were measured. Further, image afterglow evaluation of the liquid crystal display device was performed. The results are shown in Table 26.

The liquid crystal display devices of Examples 65 to 68 can realize a higher VHR and a smaller ID. Moreover, there is no residual image in the evaluation of image afterglow, or even if it exists, it is a level which is extremely small and tolerable.

(Comparative examples 1 to 4)

The comparative liquid crystal composition 1 shown below was sandwiched in the IPS unit used in Example 1. The physical property values of the comparative liquid crystal compositions are shown in Table 27. The liquid crystal display devices of Comparative Examples 1 to 4 were produced using the color filters 1 to 4 shown in Table 2, and their VHR and ID were measured. Further, image afterglow evaluation of the liquid crystal display device was performed. The results are shown in Table 28.

Comparison of liquid crystal composition 1

In the liquid crystal display devices of Comparative Examples 1 to 4, the VHR was lowered and the ID was increased as compared with the liquid crystal display device of the present invention. Moreover, the generation of afterimages was also confirmed in the evaluation of image afterglow, which is not acceptable. The level.

(Comparative examples 5 to 12)

In the same manner as in the first embodiment, the comparative liquid crystal compositions 2 and 3 shown in Table 29 were sandwiched, and the liquid crystal display devices of Comparative Examples 5 to 12 were produced using the color filters 1 to 4 shown in Table 2, and the VHR and ID thereof were measured. . Further, image afterglow evaluation of the liquid crystal display device was performed. The results are shown in Tables 30 to 31.

In the liquid crystal display devices of Comparative Examples 5 to 12, the VHR was lowered and the ID was increased as compared with the liquid crystal display device of the present invention. Moreover, the generation of afterimages was also confirmed in the image afterglow evaluation, which is not an allowable level.

(Comparative examples 13 to 20)

In the same manner as in the first embodiment, the comparative liquid crystal compositions 4 to 5 shown in Table 32 were sandwiched, and the liquid crystal display devices of Comparative Examples 13 to 20 were produced using the color filters 1 to 4 shown in Table 2, and the VHR and ID thereof were measured. . Further, image afterglow evaluation of the liquid crystal display device was performed. The results are shown in Tables 33 to 34.

In the liquid crystal display devices of Comparative Examples 13 to 20, the VHR was lowered and the ID was increased as compared with the liquid crystal display device of the present invention. Moreover, the generation of afterimages was also confirmed in the image afterglow evaluation, which is not an allowable level.

(Comparative examples 21 to 32)

In the same manner as in the first embodiment, the comparative liquid crystal compositions 6 to 8 shown in Table 35 were sandwiched, and the liquid crystal display devices of Comparative Examples 21 to 32 were produced using the color filters 1 to 4 shown in Table 2, and the VHR and ID thereof were measured. . Further, image afterglow evaluation of the liquid crystal display device was performed. The results are shown in Tables 36 to 38.

In the liquid crystal display devices of Comparative Examples 21 to 32, the VHR was lowered and the ID was increased as compared with the liquid crystal display device of the present invention. Moreover, the generation of afterimages was also confirmed in the image afterglow evaluation, which is not an allowable level.

(Comparative Examples 33 to 44)

In the same manner as in the first embodiment, the comparative liquid crystal compositions 9 to 11 shown in Table 39 were sandwiched, and the liquid crystal display devices of Comparative Examples 33 to 44 were produced using the color filters 1 to 4 shown in Table 2, and the VHR and ID thereof were measured. . Further, image afterglow evaluation of the liquid crystal display device was performed. The results are shown in Tables 40 to 42.

In the liquid crystal display devices of Comparative Examples 33 to 44, the VHR was lowered and the ID was increased as compared with the liquid crystal display device of the present invention. Moreover, the generation of afterimages was also confirmed in the image afterglow evaluation, which is not an allowable level.

(Comparative examples 45 to 52)

In Comparative Examples 5, 13, 17, 25, 37, 45, 61 and 65, a comparative color filter 1 shown in Table 2 was used instead of the color filter 1, except that a comparative example was produced in the same manner. 45~52 liquid crystal display device, measuring its VHR and ID. Further, image afterglow evaluation of the liquid crystal display device was performed. The results are shown in Tables 43 and 44.

The liquid crystal display device of Comparative Examples 45 to 52 is compared with the liquid crystal display device of the present invention, VHR Lower, the ID also increases. Moreover, the generation of afterimages was also confirmed in the image afterglow evaluation, which is not an allowable level.

1‧‧‧Substrate

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

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

3b‧‧‧pixel electrode layer

4‧‧‧Alignment film

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

Claims (11)

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 composed of a black matrix and at least RGB three-color pixel portions The liquid crystal composition layer is composed of a liquid crystal composition containing one or two or more compounds represented by the formula (I), and one or two or more selected from the group consisting of a liquid crystal composition. a compound of the group consisting of the compounds represented by the formula (II-a) to the formula (II-e), (wherein R ³¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group, and M ³¹ to M ³³ each independently represent a trans-1,4- Cyclohexyl or 1,4-phenylene, one or two -CH ₂ - of the trans-1,4-cyclohexylene group may be substituted by -O- in a manner in which the oxygen atoms are not directly adjacent to each other, and the benzene is extended. One or two hydrogen atoms in the group may be substituted by a fluorine atom, X ³¹ and X ³² independently represent a hydrogen atom or a fluorine atom, and Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group, n ³¹ and n ³² represent 0, 1 or 2 independently of each other, and n ³¹ + n ³² represents 0, 1 or 2, and M ³¹ and M ³³ may be the same or different when there are a plurality of cases, (wherein R ²¹ to R ³⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and X ²¹ represents a hydrogen atom or a fluorine atom), and the above-mentioned RGB three-color pixel portion The coloring material contains a diketopyrrolopyrrole pigment and/or an anionic red organic dye in the R pixel portion, and contains a copper phthalocyanine pigment, a phthalocyanine green dye, and a phthalocyanine system in the G pixel portion. At least one of the group consisting of a mixture of a blue dye and an azo yellow organic dye contains an ε-type copper phthalocyanine pigment and/or a cationic blue organic dye in the B pixel portion. The liquid crystal display device of claim 1, wherein the RGB three-color pixel portion contains CI solvent red 124 in the R pixel portion and CI solvent blue 67 and CI solvent yellow in the G pixel portion. A mixture of 162 contains CI Solvent Blue 7 in the B pixel portion. The liquid crystal display device of claim 1, wherein the RGB three-color pixel portion contains, as a color material, CI Pigment Red 254 in the R pixel portion and CI Pigment Green 7 and/or CI in the G pixel portion. Pigment green 36 contains CI Pigment Blue 15:6 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 contains a pigment selected from C.I. Pigment Red 177, C.I. Pigment Red 242, C.I. Pigment Red 166, CI Pigment Red 167, CI Pigment Red 179, 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 Solvent Red 89, At least one organic dye pigment of the group consisting of CI Solvent Orange 56, CI Solvent Yellow 21, CI Solvent Yellow 82, CI Solvent Yellow 83:1, CI Solvent Yellow 33, and CI Solvent Yellow 162. The liquid crystal display device according to any one of claims 1 to 3, wherein the G pixel portion further contains a color selected from the group consisting of CI Pigment Yellow 150, CI Pigment Yellow 215, CI Pigment Yellow 185, CI Pigment Yellow 138, CI At least one organic dye pigment of the group consisting of Solvent Yellow 21, CI Solvent Yellow 82, CI Solvent Yellow 83:1, and CI Solvent Yellow 33. The liquid crystal display device according to any one of claims 1 to 3, wherein the B pixel portion further contains a color selected from the group consisting of CI Pigment Blue 1, CI Pigment Violet 23, CI Basic Blue 7, CI Basic Violet 10 At least one organic dye of the group consisting of CI Acid Blue 1, CI Acid Blue 90, CI Acid Blue 83, and CI Direct Blue 86. The liquid crystal display device according to any one of claims 1 to 3, wherein 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 is selected from the group consisting of CI Pigment Yellow 150, CI Pigment Yellow 215, CI Pigment Yellow 185, 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, CI Solvent Yellow 162 At least one of the yellow organic dyes in the group is used as a colorant. The liquid crystal display device according to any one of claims 1 to 3, wherein the compound represented by the formula (I) is a compound represented by the formula (Ia) to the formula (If), (wherein R ³² represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group, and X ³¹ to X ³⁸ each independently represent a hydrogen atom or a fluorine atom; Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group). The liquid crystal display device according to any one of the items 1 to 3, wherein the liquid crystal composition layer further contains one or two or more selected from the group consisting of the formula (III-a) to the formula (III-f). a compound in the group of compounds indicated, (wherein R ⁴¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group, and X ⁴¹ to X ⁴⁸ each independently represent a hydrogen atom or a fluorine atom; Z ⁴¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group). The liquid crystal display device according to any one of claims 1 to 3, wherein the liquid crystal composition layer is made of a liquid crystal composition containing one or two or more polymerizable compounds. The resulting polymer is composed. The liquid crystal display device according to any one of claims 1 to 3, wherein the liquid crystal composition layer contains a difunctional monomer represented by the formula (V), (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 - (wherein s represents an integer from 2 to 7, the oxygen atom is 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 - (wherein Y ¹ and Y ² each independently represent a fluorine atom or a hydrogen atom), -C≡C- or a single bond C represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, and any of the hydrogen atoms of all of the 1,4-phenylene groups in the formula may be substituted by a fluorine atom).