TW201410850A - Liquid crystal display device - Google Patents

Abstract

The present invention relates to a liquid crystal display device of a color filter using a specific liquid crystal composition and using a specific pigment. The present invention provides a liquid crystal display device which prevents the liquid crystal layer from reduction of the voltage holding ratio (VHR) and enlargement of the ion density (ID) and solves the problems of display defects such as whitening, uneven orientation, and image residue. Because of the characteristics of the present invention bestowed in prevention of the reduction of the voltage holding ratio (VHR) of the liquid crystal layer and the enlargement of the ion density (ID) and inhibition of the generation of display defects such as the image residue, it can be particularly used in the IPS mode/FFS mode liquid crystal display devices with active matrix driving which can be applied to the liquid crystal display devices in a liquid crystal TV, a monitor, a mobile phone, a smart phone, etc.

Description

Liquid crystal display device

The present invention relates to a liquid crystal display device.

The liquid crystal display device is started with a clock and a calculator, and is gradually applied to various electric appliances, measuring machines, automobile panels, word processors, electronic notebooks, printers, computers, televisions, and the like for household use. 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 (Optically Compensated Birefringence), ECB (Electrically Controlled Birefringence), VA (Vertical Alignment) Vertical alignment type, CSH (Color Super Homeotropic) type, or FLC (Ferroelectric Liquid Crystal). Moreover, as a driving method, it has generally become a multiplex drive since the previous static driving, and in the simple matrix method, a TFT (Thin Film Transistor) or a TFD (Thin Film Diode) has recently been used. The active matrix (AM) mode of the drive is gradually becoming the mainstream.

As shown in FIG. 1, a typical color liquid crystal display device is configured such that a transparent electrode layer serving as a common electrode is provided between an alignment film of one of the two substrates (1) having the alignment film (4) and the substrate. (3a) and color filter layer (2) on another alignment film and substrate The pixel electrode layer (3b) is disposed such that the alignment films face each other, and the liquid crystal layer (5) is sandwiched therebetween.

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 a yellow color. The colored layer (Y) is composed of.

When the liquid crystal material constituting the liquid crystal layer has impurities remaining in the material, the electrical characteristics of the display device are greatly affected, and therefore, the height management of the impurities is continuously performed. Further, regarding the material for forming the alignment film, it is also 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 the alignment. The characteristics of the liquid crystal display device caused by impurities in the film material were investigated.

On the other hand, as for the material such as the organic pigment used for the color filter layer, the influence on the liquid crystal layer due to the impurities contained in the same manner as the alignment film material can be expected. 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 greatly reduced as compared with the alignment film material. However, the film thickness of the alignment film is usually only 0.1 μm or less, and the transparent electrode, that is, the common electrode for the color filter layer side, is generally 0.5 μm or less in order to increase the film thickness in order to increase the conductivity. Therefore, it cannot be said that the color filter layer and the liquid crystal layer are completely isolated, and the color filter layer may exhibit the liquid crystal layer through the alignment film and the transparent electrode through the impurities contained in the color filter layer. The voltage holding ratio (VHR) is lowered, and the whitening, uneven alignment, and residual image caused by an increase in ion density (ID, Ion Density) are poor.

As a method for solving the display failure caused by the impurities contained in the pigment constituting the color filter, the industry has studied a method of controlling the elution of impurities into the liquid crystal by using a pigment obtained by extracting the pigment using ethyl formate. The ratio is set to a specific value or less (Patent Document 1); or a method of controlling the elution of impurities into the liquid crystal by specifying the pigment in the blue colored layer (Patent Document 2). However, these methods are not much different from simply reducing the impurities in the pigment. In recent years, even in the current state of progress in the purification of pigments, there are still deficiencies in the improvement of display defects.

On the other hand, focusing on the relationship between the organic impurities contained in the color filter and the liquid crystal composition, a method of dissolving the organic impurity on the liquid crystal layer by the hydrophobic parameter of the liquid crystal molecules contained in the liquid crystal layer is disclosed. Difficulty, and setting the value of the hydrophobic parameter to a specific value or more; or because the hydrophobic parameter is related to the -OCF ₃ group at the end of the liquid crystal molecule, so that the liquid crystal molecule having a specific ratio or more has a terminal end - A method of a liquid crystal composition of an OCF ₃ based liquid crystal compound (Patent Document 3).

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

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

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

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

The present invention provides a liquid crystal display device which prevents a voltage holding ratio (VHR) of a liquid crystal layer from being lowered and an ion density (ID) by using a specific liquid crystal composition and a color filter using a specific dye and/or pigment. Increase, and solve the problem of poor display, such as anti-white, misalignment, and afterimage.

In order to solve the above problems, the inventors of the present invention have made an effort to study the structural combination of a coloring material such as a dye for constituting a color filter and a liquid crystal material constituting a liquid crystal layer, and as a result, it has been found that a liquid crystal material having a specific structure and a specific use are used. The liquid crystal display device of the color filter of the dye and/or pigment of the structure can prevent the voltage holding ratio (VHR) of the liquid crystal layer from being lowered, the ion density (ID) is increased, and the display of anti-white, misalignment, afterimage, etc. is solved. The problem of the bad, thus completing the invention of the case.

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-color pixels a color filter, a pixel electrode, and a common electrode formed of a portion, wherein the liquid crystal composition layer is composed of a liquid crystal composition containing one or two or more compounds represented by the general formula (I), and containing one Or a compound of two or more selected from the group consisting of 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 trans-1, 4 - a cyclohexyl group or a 1,4-phenylene group, wherein one or two -CH ₂ - groups of the trans-1,4-cyclohexylene group can be substituted by -O- in such a manner that the oxygen atoms are not directly adjacent to each other, One or two hydrogen atoms in the phenyl 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, n ³¹ + n ³² represents 0, 1 or 2, and may be the same or different when a plurality of M ³¹ and M ³³ are present);

(wherein R ²¹ to R ³⁰ independently of each other represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms; X ²¹ represents a hydrogen atom or a fluorine atom); and the above-mentioned RGB three-color pixel portion The G pixel portion contains a halogenated metal indigo pigment as a coloring material selected from the group consisting of Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr. a metal in a group consisting of Nb, In, Sn, and Pb as a central metal, and when the central metal is trivalent, a halogen atom, a hydroxyl group, or a sulfonic acid group is bonded to the central metal. Alternatively, or oxo or thiocrosslinking, when the central metal is a tetravalent metal, one oxygen atom may be bonded to the central metal or two halogen atoms or hydroxyl groups which may be the same or different Any of the sulfonic acid groups.

The liquid crystal display device of the present invention can prevent the voltage holding ratio (VHR) of the liquid crystal layer from being lowered and the ion density (ID) from increasing by using a specific liquid crystal composition and a color filter using a specific pigment, thereby preventing whitening. , uneven alignment, residual image, etc. display defects.

1‧‧‧Substrate

2‧‧‧Color filter layer

2a‧‧‧Color filter layer with specific 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 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 . It is configured to include a transparent electrode layer (3a) serving as a common electrode between an alignment film and a substrate of one of the first substrate and the second substrate (1) having the alignment film (4) and a color filter layer (2a) containing a specific pigment, and a pixel electrode layer (3b) is 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 A liquid crystal layer (5a) of a liquid crystal composition.

The two substrates in the display device are bonded together by a sealing material and a sealing material disposed in the peripheral region, and in order to maintain the distance between the substrates, a granular spacer is often disposed therebetween or formed by photolithography. a spacer made of resin.

(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 formula (I), and one or two or more selected from the group consisting of a compound of the group consisting of the compounds of 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 trans-1, 4 - a cyclohexyl group or a 1,4-phenylene group, wherein one or two -CH ₂ - groups of the trans-1,4-cyclohexylene group can be substituted by -O- in such a manner that the oxygen atoms are not directly adjacent to each other, One or two hydrogen atoms in the phenyl 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, n ³¹ + n ³² represents 0, 1 or 2, and may be the same or different when a plurality of M ³¹ and M ³³ are present);

(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 formula (I), when R ³¹ is a phenyl group (aromatic) in which the ring structure to which it is bonded, a linear alkyl group having 1 to 5 carbon atoms and a linear carbon number are preferable. The alkoxy group of 1 to 4 (or more) and the alkenyl group having 4 to 5 carbon atoms, when the ring structure to which the bond is bonded is a saturated ring structure such as cyclohexane, pyran or dioxane Preferably, it is a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms or more, and a linear alkyl group having 2 to 5 carbon atoms. base.

If it is considered that the chemical stability to heat or light is good, R ^{31 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 ^{31 is} preferably an alkenyl group. Further, if the viscosity is small and the nematic-isotropic phase transition temperature (Tni) is high and the response speed is further shortened, it is preferred to use an alkenyl group whose terminal is not an unsaturated bond, and particularly preferably The ortho position of the alkenyl group has a methyl group as a terminal. Further, when attention is paid to the solubility at a low temperature, 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, a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms as R ³¹ is preferably used in combination, and a compound having 3 to 5 carbon atoms is preferably used in combination, and preferably a combined carbon atom is used. Compounds 4 and 5.

M ³¹ ~ M ^{33 is} preferably

M ^{31 is} preferably Better

M ^{32 is} preferably Better Further preferably

M ^{33 is} preferably Better Further preferably

It is preferred that at least one of X ³¹ and X ³² is a fluorine atom, and it is more preferred that 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. Further, in 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 formula (Ia) to the formula (If), when R ³² is a phenyl (aromatic) ring structure, it is preferably a linear alkyl group having 1 to 5 carbon atoms and a straight line. a chain-like alkoxy group having 1 to 4 (or more) carbon atoms and an alkenyl group having 4 to 5 carbon atoms, wherein the ring structure to which the bond is bonded is saturated with cyclohexane, pyran and di-alkane. In the 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 atom number 2 are preferable. 5 alkenyl.

If it is considered that the chemical stability to heat or light is good, R ^{31 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 ^{31 is} preferably an alkenyl group. Further, if the viscosity is small and the nematic-average phase transition temperature (Tni) is high and the response speed is further shortened, it is preferred to use an alkenyl group having no terminal unsaturated bond, and more preferably an ortho position of the alkenyl group. It has a methyl group as a terminal. Further, when attention is paid to the solubility at a low temperature, 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, a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms as R ³¹ is preferably used in combination, and a compound having 3 to 5 carbon atoms is preferably used in combination, and preferably 3 to 4 carbon atoms are used in combination. And 5 compounds.

It is preferred that at least one of X ³¹ and X ³² is a fluorine atom, and it is more preferred that 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. Further, in 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.

It is preferred that at least one of X ³³ and X ³⁴ is a fluorine atom, and it is more preferred that both of them are fluorine atoms.

It is preferred that at least one of X ³⁵ and X ³⁶ is a fluorine atom, and both of them are effective for increasing Δ ε by a fluorine atom, but in the case of Tni, solubility at a low temperature or when a liquid crystal display element is formed Poor chemical stability.

It is preferred that at least one of X ³⁷ and X ³⁸ is a hydrogen atom, and it is preferred that both are hydrogen atoms. When at least one of X ³⁷ and X ³⁸ is a fluorine atom, it is not preferable from the viewpoint of Tni, solubility at a low temperature, or chemical stability when a liquid crystal display element is formed.

It is preferably one to eight kinds of the compound group represented by the general formula (I), and 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 formula (IIa) to the formula (IIe), when R ²¹ to R ³⁰ are a phenyl group (aromatic) in which the ring structure to which the bond is bonded, a linear alkyl group having 1 to 5 carbon atoms is preferred. Alkoxy groups having a carbon number of 1 to 4 (or more) and an alkenyl group having 4 to 5 carbon atoms, wherein the ring structure to which the bond is bonded is cyclohexane, pyran and When a saturated ring structure such as an alkane is used, 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 ²¹ to R ^{30 are} preferably an alkyl group. Further, in order to produce a liquid crystal display element having a small viscosity and a fast response speed, R ²¹ to R ^{30 are} preferably an alkenyl group. Further, if the viscosity is small and the nematic-average phase transition temperature (Tni) is high and the reaction speed is further shortened, it is preferred to use an alkenyl group whose terminal is not an unsaturated bond, and more preferably an alkenyl neighbor. There is a methyl group 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 preferably, the number of carbon atoms is used in combination. Compounds 3, 4 and 5.

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

Preferably, at least one of R ²³ to R ²⁴ is an alkyl group, an alkoxy group or an alkenyl group having 4 to 5 carbon atoms. When it is required that the balance between the response speed and the Tni is good, at least one of R ²³ to R ²⁴ is preferably an alkenyl group. If the balance between the response speed and the solubility at a low temperature is required to be good, R ²³ ~ is preferable. At least one of R ²⁴ is an alkoxy group.

Preferably, at least one of R ²⁵ to R ²⁶ is an alkyl group, an alkoxy group or an alkenyl group having 2 to 5 carbon atoms. If the balance between the response speed and Tni is required to be good, at least one of R ²⁵ to R ²⁶ is preferably an alkenyl group. If the balance between the response speed and the solubility at low temperature is required to be good, R ²⁵ ~ is preferred. At least one of R ²⁶ is 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.

Preferably, at least one of R ²⁷ to R ²⁸ is 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. If the balance between the response speed and the solubility at a low temperature is required to be good, R ²⁷ ~ is preferable. At least one of R ²⁸ is 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.

It is preferably one to ten kinds of the compound group represented by the general formula (II-a) to the general formula (II-e), and more preferably one to eight kinds, and the content thereof is preferably from 5 to 80. %, more preferably 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 of the formula (III-a) to the 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 formula (IIIa) to the formula (IIIf), when the ring structure to which R ^{41 is} bonded is a phenyl group (aromatic), it is preferably a linear alkyl group having 1 to 5 carbon atoms and a straight line. Alkoxy groups having a chain number of 1 to 4 (or more) carbon atoms and alkenyl groups having 4 to 5 carbon atoms, wherein the ring structure to which the bond is bonded is cyclohexane, pyran and When a saturated ring structure such as an alkane is used, 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 ^{41 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 ^{41 is} preferably an alkenyl group. Further, if the viscosity is small and the nematic-average phase transition temperature (Tni) is high and the response speed is further shortened, it is preferred to use an alkenyl group having no terminal unsaturated bond, and more preferably an ortho position of the alkenyl group. There is a methyl group 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, a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms as R ⁴¹ is preferably used in combination, and a compound having 3 to 5 carbon atoms is preferably used in combination, and preferably a combined carbon atom is used. Compounds 4 and 5.

It is preferred that at least one of X ⁴¹ and X ⁴² is a fluorine atom, and it is more preferred that 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. Further, in 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 preferable that at least one of X ⁴³ and X ⁴⁴ is a fluorine atom, and it is preferable that both are fluorine atoms in order to obtain a large Δ ε, but on the other hand, it is owed when the solubility is good at a low temperature. good.

It is preferred that at least one of X ⁴⁵ and X ⁴⁶ is a hydrogen atom, and it is preferred that both are hydrogen atoms. From the viewpoint of Tni, solubility at a low temperature, or chemical stability when a liquid crystal display element is formed, it is not preferable to use a fluorine atom in a large amount.

It is preferred that at least one of X ⁴⁷ and X ⁴⁸ is a hydrogen atom, and it is preferred that 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 a low temperature, or chemical stability when a liquid crystal display element is formed.

It is preferably one to ten kinds of compounds containing a compound selected from the group consisting of the compounds of the formula (III-a) to the formula (III-f), more preferably one to eight, and the content thereof is preferably It is 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. In more detail, when it is a thin cell gap, it is preferably 0.10~0.13 corresponding to it, and when it is a thick cell gap, it is preferably 0.08~0.10 corresponding to it. η at 20 °C Preferably it is 10~45mPa. s, more preferably 10~25mPa. s, especially good for 10~20mPa. s. Further, T _{ni is} preferably 60 ° C to 120 ° C, more preferably 70 ° C to 100 ° C, and particularly preferably 70 ° C to 85 ° C.

The liquid crystal composition 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 order to produce a liquid crystal display element such as a PS (Polymer Stabilized) mode, a PSA (Polymer Sustained Alignment) mode, or a Polymer Stabilized Vertically Alignment (PSVA) mode One or two or more kinds of polymerizable compounds may be contained in the liquid crystal composition of the present invention. 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 biphenyl derivative, and a plurality of six members. A polymerizable compound of a liquid crystal skeleton of a ring 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 set to be 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 of the 1,4-phenylene groups in the formula may be subjected to fluorine. Atomic substitution).

X ⁵¹ and X ⁵² are each preferably a diacrylate derivative each having a hydrogen atom and 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. The rate of polymerization of these compounds is the fastest in diacrylate derivatives, the slower in dimethacrylate derivatives, and the presence of asymmetric compounds, depending on the application. Among the PSA display elements, 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 -, but in the PSA display element, at least one of them is preferably a single bond. Further, it is preferably a compound which each represents a single bond, or one of which 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, preferably a 1,4-phenylene group or a single bond. When 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 formula (V), M ⁵¹ represents a single bond, and when the ring structure is formed by two rings, it preferably represents the following formula (Va-1) to formula (Va-5), more preferably a formula ( Va-1)~Formula (Va-3), and more preferably represents the formula (Va-1).

(where the two ends are set to be combined with Sp ¹ or Sp ² )

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

In the above aspect, the polymerizable compound is preferably a compound of the formula (V-1) to the formula (V-4), and among them, the formula (V-2) is most preferable.

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

When a polymerizable compound is added to the liquid crystal composition of the present invention, the polymerization is carried out 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 fluorenylphosphine oxides.

The liquid crystal composition containing a polymerizable compound of the present invention is polymerized by ultraviolet irradiation to impart a liquid crystal alignment ability, and can be used for controlling the light transmittance by utilizing the birefringence of the liquid crystal composition. Liquid crystal display element. The liquid crystal display element can be used for an AM-LCD (Active Matrix-Liquid Crystal Display), a TN (Nematic Liquid Crystal Display Element), an STN-LCD (Super Torsional Nematic Liquid Crystal Display Element), OCB-LCD and IPS-LCD (coplanar switching liquid crystal display elements) are especially useful for AM-LCDs and can be used for transmissive or reflective liquid crystal display elements.

(color filter)

The color filter of the present invention is composed of a black matrix and at least RGB three-color pixel portion, and the RGB three-color pixel portion contains a halogenated metal indigo pigment as a colorant in the G pixel portion, and the halogenated metal indigo pigment has a selected from Al a metal in a group consisting of Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn, and Pb as a central metal, and when the central metal When it is trivalent, one of a halogen atom, a hydroxyl group or a sulfonic acid group is bonded to the central metal, or an oxo or thio crosslink is carried out. When the central metal is a tetravalent metal, Any one of two oxygen atoms, a hydroxyl group or a sulfonic acid group which may be the same or different may be bonded to the central metal. Further, the RGB three-color pixel portion preferably contains a diketopyrrolopyrrole pigment and/or an anionic red organic dye as a colorant in the R pixel portion, and an ε-type copper phthalocyanine pigment and/or a cation in the B pixel portion. Sexual blue organic dyes are used as colorants.

(G pixel part)

Examples of the above-mentioned halogenated metal indigo pigment in the G pixel portion include the following two groups of halogenated metal indigo pigments.

(first group)

It is a halogenated metal indigo pigment having a composition selected from the group consisting of Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sr, and Pb. The metal in the group acts as a central metal, and 8 to 16 halogen atoms in each indigo molecule are bonded to the benzene ring of the indocyanine molecule; when the central metal is trivalent, the metal is bonded to the central metal. Any one of a halogen atom, a hydroxyl group or a sulfonic acid group (-SO ₃ H), when the central metal is a tetravalent metal, one oxygen atom may be bonded to the central metal or may be the same or different. Any of two halogen atoms, hydroxyl groups or sulfonic acid groups.

(second group)

It is a pigment composed of a halogenated metal indigo dimer which is composed of two molecules of a halogenated metal indigo which is selected from the group consisting of Al, Sc, and Ga. a trivalent metal in the group consisting of Y and In as a central metal, and 8 to 16 halogen atoms in each indocyanine molecule are bonded to the benzene ring of the indocyanine molecule, and the structural units are Each of the center metals is bonded via a divalent atomic group selected from the group consisting of an oxygen atom, a sulfur atom, a sulfinyl group (-SO-), and a sulfonyl group (-SO ₂ -).

In the halogenated metal indigo pigment used in the present invention, the halogen bonded to the benzene ring The prime atoms may all be the same or different. Further, a halogen atom may be bonded to a benzene ring.

Here, 9 to 15 of the 8 to 16 halogen atoms in each indocyanine molecule are bonded to the benzene ring of the indocyanine molecule, and the halogenated metal indigo pigment used in the present invention exhibits a bright yellow color. Green, ideal for green pixels in color filters. The halogenated metal indigo pigment used in the present invention is insoluble or poorly soluble in water or an organic solvent. The halogenated metal indigo pigment used in the present invention also contains both a pigment (also referred to as a crude pigment) which has not been subjected to the following finishing treatment, and a pigment which has been subjected to finishing treatment.

The halogenated metal indigo pigment belonging to the first group and the second group described above can be represented by the following formula (PIG-1).

Among the above formula (PIG-1), the halogenated metal indigo pigments belonging to the first group are as follows.

In the formula (PIG-1), X ₁ to X ₁₆ represent a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom. The four X atoms bonded to one benzene ring may be the same or different. Among the X ₁ to X ₁₆ bonded to the four benzene rings, 8 to 16 are chlorine atoms, bromine atoms or iodine atoms. M represents the center metal. In the range of the following Y and the number m of the halogenated metal indigo pigment, the total of the chlorine atoms, the bromine atom and the iodine atom in the six X ₁ to X ₁₆ are not blue, and the same is true. When the total of the chlorine atom, the bromine atom, and the iodine atom in the sixteen X ₁ to X ₁₆ is 8 or more, the larger the total value, the stronger the yellow color becomes. The Y group bonded to the central metal M is selected from a monovalent atomic group in a group consisting of any one of fluorine, chlorine, bromine or iodine, an oxygen atom, a hydroxyl group and a sulfonic acid group, and m represents a bond at the center. The number of Y on the metal M is an integer from 0 to 2.

The value of m depends on the valence of the central metal M. When the central metal M is as trivalent as Al, Sc, Ga, Y, In, m=1, and one of the bonds on the central metal is selected from the group consisting of fluorine, chlorine, bromine, iodine, hydroxyl and sulfonic acid groups. The base of the group. When the central metal M is tetravalent, such as Si, Ti, V, Ge, Zr, Sn, the valence is tetravalent, m=2, and one oxygen is bonded to the central metal, or two are bonded to the central metal. a group of fluorine, chlorine, bromine, iodine, hydroxyl, and sulfonic acid groups. When the central metal M is divalent, such as Mg, Fe, Co, Ni, Zn, Zr, Sn, and Pb, Y does not exist.

Further, in the above formula (PIG-1), the halogenated metal indigo pigment belonging to the second group is as follows.

In the above formula (PIG-1), X ₁ to X ₁₆ have the same meanings as defined above, and the central metal M represents a trivalent metal selected from the group consisting of Al, Sc, Ga, Y, and In, and m represents 1. Y represents the following atomic group.

Y=

Furthermore, the chemical structure of the atomic group Y, the central metal M above the same meanings as defined, on X ₁₇ ~ X _32, in the general formula (PIG-1) are the same as defined above X ₁ ~ X ₁₆ of meaning. A represents a divalent atomic group selected from the group consisting of an oxygen atom, a sulfur atom, a sulfinyl group (-SO-), and a sulfonyl group (-SO ₂ -). The M in the formula (PIG-1) and the M group of the atomic group Y are bonded via a divalent atomic group A.

That is, the halogenated metal indigo pigment belonging to the second group is a halogenated metal indigo dimer obtained by bonding two molecules of a halogenated metal indigo as a structural unit and bonding the above-mentioned divalent atomic groups.

Specific examples of the halogenated metal indigo pigment represented by the formula (PIG-1) include the following (1) to (4).

(1) a divalent valence selected from the group consisting of Mg, Fe, Co, Ni, Zn, Zr, Sn, and Pb, such as a tin halide antimony pigment, a nickel halide indigo pigment, or a zinc halide indigo pigment. A metal halide as a center metal, and 8 to 16 halogen atoms per one indocyanine molecule are bonded to a metal halide indigo pigment on four benzene rings. Further, among them, the zinc bromide indigo pigment is preferably C.I. Pigment Green 58.

(2) A trivalent metal selected from the group consisting of Al, Sc, Ga, Y, and In as a central metal such as a halogenated chloroaluminum phthalocyanine having a halogen atom, a hydroxyl group or a sulfonic acid on the center metal Any of the groups, and 8 to 16 halogen atoms per one indigo molecule are bonded to the metal halide indigo pigment on the four benzene rings.

(3) a tetravalent metal having a group selected from the group consisting of Si, Ti, V, Ge, Zr, and Sn as a center metal, such as a titanium oxyhalide halide or a vanadyl halide, having a center metal An oxygen atom or any of two halogen atoms, a hydroxyl group or a sulfonic acid group which may be the same or different, and a halogenation of 8 to 16 halogen atoms bonded to 4 benzene rings per indigo molecule Metal indigo pigment.

(4) A pigment composed of a halogenated μ-oxo-aluminum phthalocyanine dimer, a halogenated μ-thio-aluminum phthalocyanine dimer, or the like: a halogenated metal The metal indigo dimer system is a structural unit composed of two molecules of a metal halide, which is a central metal selected from the group consisting of trivalent metals selected from the group consisting of Al, Sc, Ga, Y, and In. Every one indigo molecule 8 to 16 halogen atoms are bonded to 4 benzene rings; and each of the central metals of the structural units is divalently selected from the group consisting of an oxygen atom, a sulfur atom, a sulfinyl group and a sulfonyl group. The atomic group is bonded.

(R pixel section)

Preferably, the R pixel portion contains a diketopyrrolopyrrole pigment and/or an anionic red organic dye. As the diketopyrrolopyrrole pigment, specifically, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 272, CI Pigment Orange 71, CI Pigment Orange 73, and more preferably CI Pigment are preferred. Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 272, and especially CI Pigment Red 254. Specific examples of the anionic red organic dye are C.I. Solvent Red 124, C.I. Acid Red 52, C.I. Acid Red 289, and particularly preferably C.I. Solvent Red 124.

(B pixel section)

Preferably, the B pixel portion contains an ε-type copper phthalocyanine pigment and/or a cationic blue organic dye. The ε-type copper phthalocyanine pigment is C.I. Pigment Blue 15:6. Specific examples of the cationic blue organic dye are CI solvent blue 2, CI solvent blue 3, CI solvent blue 4, CI solvent blue 5, CI solvent blue 6, CI solvent blue 7, CI solvent blue 23, CI Solvent Blue 43, CI Solvent Blue 72, CI Solvent Blue 124, CI Basic Blue 7, CI Basic Blue 26, more preferably CI Solvent Blue 7, CI Basic Blue 7, and more preferably CI Solvent Blue 7.

Preferably, the RGB three-color pixel portion includes a CI solvent red 124 as a colorant in the R pixel portion, and a halogenated metal indigo pigment as a color material in the G pixel portion, the halogenated metal indigo pigment having a selected from the group consisting of Al and Si. a metal in a group consisting of Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn, and Pb as a central metal, when the central metal is trivalent In the case where one of a halogen atom, a hydroxyl group or a sulfonic acid group is bonded to the central metal, or an oxo or thiocrosslinking is carried out, when the central metal is a tetravalent metal, The central metal has one oxygen atom or one of two halogen atoms, a hydroxyl group or a sulfonic acid group which may be the same or different, or an oxo or thio crosslink; and is contained in the B pixel portion. CI solvent Blue 7 is used as a colorant.

Further, the RGB three-color pixel portion preferably includes CI Pigment Red 254 as a color material in the R pixel portion, and a halogenated metal indigo pigment as a color material in the G pixel portion: the pigment has a color selected from the group consisting of Al, Si, and a metal in a group consisting of Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn, and Pb as a central metal, when the central metal is trivalent And bonding one of a halogen atom, a hydroxyl group or a sulfonic acid group to the central metal, or performing oxo or thiocrosslinking, when the central metal is a tetravalent metal, on the central metal The bond has one oxygen atom or one of two halogen atoms, a hydroxyl group or a sulfonic acid group which may be the same or different, and contains a CI Pigment Blue 15:6 as a colorant in the B pixel portion.

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, CI Pigment Orange 38, and 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, CI Solvent At least one organic dye of the group consisting of 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 contains, 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, CI Solvent Yellow 82, CI Solvent. At least one organic dye of the group consisting of yellow 83:1 and CI solvent yellow 33 is used as a colorant.

Preferably, the RGB three-color pixel portion further includes, 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, CI Acid Blue 1, CI Acid Blue 90, At least one organic dye of the group consisting of CI Acid Blue 83 and CI Direct Blue 86 is used as a colorant.

Further, it is preferable that 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 C.I. Pigment Yellow 150, C.I. Pigment Yellow 215, and C.I. At least one yellow organic group consisting of 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 Dyeing pigments as coloring materials.

The color filter of the present invention is used in view of preventing a decrease in the voltage holding ratio (VHR) of the liquid crystal layer, an increase in the ion density (ID), and suppressing occurrence of display defects such as whitening, misalignment, and afterimage. The chromaticity x and the chromaticity y of each of the pixel portions 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. The chromaticity x is 0.58 to 0.69 and the chromaticity y is 0.30 to 0.36, more 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 0.32, more preferably 0.20 to 0.26, and the chromaticity y is preferably 0.60 to 0.76, more preferably 0.68 to 0.74. The chromaticity x is 0.19 to 0.32 and the chromaticity y is 0.60 to 0.76, more preferably the chromaticity x is 0.20 to 0.26 and the chromaticity y is 0.68 to 0.74.

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. The chromaticity x is 0.11 to 0.16 and the chromaticity y is 0.04 to 0.15, more 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 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. The chromaticity x is 0.46 to 0.50 and the chromaticity y is 0.48 to 0.53, more preferably the chromaticity x is 0.47 to 0.48 and the chromaticity y is 0.50 to 0.52.

Here, the XYZ color system refers to a table that was identified as a standard color system on CIE (International Commission on Illumination) in 1931. Color system.

The chromaticity in each of the above pixel portions can be adjusted by changing the kind of the dyed pigment 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 pigment to the red dye. In the case of G pixels, it is possible to add an appropriate amount of yellow dye to the green dye. The pigment is adjusted, and in the case of B pixels, it can be adjusted by adding an appropriate amount of purple dye to the blue dye. Further, it can also 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 typical method for forming a pixel portion is a photolithography method in which a photocurable composition is applied to a surface of a transparent substrate for a color filter provided on a side of a black matrix. After heat drying (prebaking), pattern exposure is performed by irradiating ultraviolet rays through a mask, and the photocurable compound corresponding to the pixel portion is cured, and then the unexposed portion is developed by the developer to remove non-pixels. The pixel portion is fixed to the transparent substrate. In this method, a pixel portion composed of a hardened colored film of a photocurable composition is formed on a transparent substrate.

By arranging the following photocurable composition for each of pixels of other colors such as R pixels, G pixels, B pixels, and Y pixels as needed, and repeating the above operation, it is possible to manufacture R pixels and G pixels at specific positions. a color filter of a color pixel portion of 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 slit coating method, a roll coating method, or an inkjet method.

The drying conditions of the coating film of the photocurable composition coated on the transparent substrate are also different depending on the type of each component, the blending ratio, and the like, and are usually carried out at 50 to 150 ° C for about 1 to 15 minutes. Further, as the light used for photohardening of the photocurable composition, ultraviolet light or visible light in a wavelength range of 200 to 500 nm is preferably used. 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 of the desired color has been formed is washed with water and dried. By subjecting the color filter thus obtained to a specific time heat treatment (post-baking) at 90 to 280 ° C by a heating means such as a hot plate or an oven, the volatile component in the colored coating film is removed while leaving the residue. The unreacted photocurable compound in the hardened coloring film of the photocurable composition is thermally cured to complete a color filter.

By using the color filter coloring material of the present invention together with the liquid crystal composition of the present invention, it is possible to provide a reduction in voltage holding ratio (VHR) of the liquid crystal layer, an increase in ion density (ID), and a solution to the reverse A liquid crystal display device that exhibits a problem of poor display such as misalignment and afterimage.

The method for producing the photocurable composition is usually a method in which a dye for a color filter and/or a pigment composition, an organic solvent, and a dispersant of the present invention are used as an essential component, and these are mixed and stirred and dispersed. In order to make it uniform, first, a pigment dispersion liquid for forming a pixel portion of a color filter is prepared, and thereafter, a photocurable compound, an optional thermoplastic resin, a photopolymerization initiator, or the like is added thereto to prepare the above. Photocurable composition.

Examples of the organic solvent usable herein include aromatic solvents such as toluene or xylene and methoxybenzene; ethyl acetate, propyl acetate or butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol. An acetate solvent such as diethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol diethyl ether acetate, diethylene glycol propyl ether acetate or diethylene glycol butyl ether acetate; a propionate solvent such as ethoxyethyl propionate; an alcohol solvent such as methanol or ethanol; an ether solvent such as butyl racelusu, propylene glycol monomethyl ether, diethylene glycol diethyl ether or diethylene glycol dimethyl ether; a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; an aliphatic hydrocarbon solvent such as hexane; N,N-dimethylformamide, γ-butylimamine, N - a solvent such as a methyl compound such as methyl-2-pyrrolidone, aniline or pyridine; a solvent such as a lactone such as γ-butyrolactone; a mixture of methyl carbamate and ethyl urethane at 48:52; Various urethanes and the like.

As a dispersing agent usable herein, for example, it may contain BYK-Chemie Disperbyk 130, Disperbyk 161, Disperbyk 162, Disperbyk 163, Disperbyk 170, Disperbyk 171, Disperbyk 174, Disperbyk 180, Disperbyk 182, Disperbyk 183, Disperbyk 184, Disperbyk 185, Disperbyk 2000, Disperbyk 2001, Disperbyk 2020, Disperbyk 2050, Disperbyk 2070 , Disperbyk 2096, Disperbyk 2150, Disperbyk LPN21116, Disperbyk LPN6919; Efka 46, Efka 47, Efka 452, Efka LP4008, Efka 4009, Efka LP4010, 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 Solsperse 3000, Solsperse 9000, Solsperse 13240, Solsperse 13650, Solsperse 13940, Solsperse 17000, Solsperse 18000, Solsperse 20000, Solsperse 21000, Solsperse 20000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, Solsperse 32000, Solsperse 36000, Solsperse 37000, Solsperse 38000, Solsperse 41000, Solsperse 4 2000, Solsperse 43000, Solsperse 46000, Solsperse 54000, Solsperse 71000; Ajisper PB711, Ajisper PB821, Ajisper PB822, Ajisper PB814, Ajisper PN411, Ajisper PA111 and other dispersing agents; or acrylic resin; urethane Resin; alkyd resin; natural rosin such as wood rosin, rosin gum, tall oil rosin; modified rosin such as polymerized rosin, disproportionated rosin, hydrogenated rosin, oxidized rosin, maleic rosin; rosin amine, lime rosin A synthetic resin such as a rosin alkylene oxide adduct, a rosin alkyd adduct, a rosin-modified phenol, and the like, and a liquid-like and water-insoluble synthetic resin at room temperature. The addition of such dispersants or resins 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 a phthalimine methylamine derivative, an organic pigment derivative such as a sulfonic acid derivative, or an organic pigment derivative such as N-(dioxane) may be contained. A methylamine derivative, an organic pigment derivative such as an N-(dialkylaminoalkyl)sulfonamide derivative, or the like. Of course, these derivatives may also be used in combination of two or more different types.

Examples of the thermoplastic resin used for the preparation of the photocurable composition include an urethane resin, an acrylic resin, a polyamine resin, a polyimide resin, and styrene butene. A diacid 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). a difunctional monomer such as ethoxy)bisphenol A or 3-methylpentanediol diacrylate; trimethylolpropane triacrylate, neopentyl alcohol triacrylate, isocyanuric acid three [2] a polyfunctional monomer having a relatively small molecular weight such as (meth) propylene methoxyethyl ester, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate; polyester acrylate, poly acrylate A polyfunctional monomer having a relatively large molecular weight such as a carbamic acid ester or a polyether acrylate.

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'-diaziridine-2,2'-disulfonic acid and the like. As a commercially available photopolymerization initiator, for example, "Irgacure (trade name)-184", "Irgacure (trade name)-369", "Darocure (trade name)-1173" manufactured by BASF Corporation; manufactured by BASF Corporation "Lucirin-TPO";"kayacure (trade name) DETX" and "kayacure (trade name) OA" manufactured by Nippon Kayaku Co., Ltd.; "Vicure 10" manufactured by Staunffer, "Vicure 55", "Trigonal" manufactured by Akzo "PI", "Sandoray 1000" manufactured by Sandoz, "Deap" manufactured by Upjohn, and "Biimidazole" manufactured by Heijin Chemical Company.

Further, a known photosensitizer may be used in combination with the above photopolymerization initiator. Examples of the photosensitizer include amines, ureas, compounds having a sulfur atom, compounds having a phosphorus atom, compounds having a chlorine atom or nitriles, or compounds having other nitrogen atoms. 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 compound having a photopolymerizable or photocurable functional group. When it is less than 0.1%, the sensitivity at the time of photocuring tends to decrease, and when it exceeds 30%, when the coating film of the pigment dispersion resist is dried, crystals of the photopolymerization initiator are precipitated to cause a coating film. The situation of physical deterioration.

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 per 100 parts of the color filter dye and/or pigment composition of the present invention may be used on a mass basis. The above-mentioned dyeing liquid was obtained by stirring and dispersing to make it uniform. Then, a total of 3 to 20 parts of a thermoplastic resin, a photocurable compound, and a photocurable compound per 1 part of the pigment composition for a color filter of the present invention are added to the pigment dispersion. In a portion, 0.05 to 3 parts of a photopolymerization initiator is added, and if necessary, an organic solvent is added, and the mixture is stirred and dispersed to make it uniform, and a photocurable composition for forming a pixel portion of the color filter is obtained.

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 exhibits alkali solubility, cleaning with an alkaline aqueous solution is applied to the pixel portion of the color filter. Formed effectively.

Although the method of manufacturing the color filter pixel portion by the photolithography method has been described in detail, the color filter pixel portion prepared by using the pigment composition for a color filter of the present invention may be further electroplated. , 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 to form pixel portions of respective colors to produce color filter sheet.

(alignment film)

In the liquid crystal display device of the present invention, since the liquid crystal composition is aligned on the surface of the first substrate and the second substrate which are in contact with the liquid crystal composition, the alignment film is disposed in the color filter in the liquid crystal display device requiring the alignment film. Between the light sheet and the liquid crystal layer, even if the film thickness of the alignment film is thick, it is thinner than 100 nm, and the color of the pigment constituting the color filter cannot be completely blocked. The interaction of the element with the liquid crystal compound constituting the liquid crystal layer.

Further, in the liquid crystal display device in which the alignment film is not used, the interaction between the dye such as the pigment constituting the color filter and the liquid crystal compound constituting the liquid crystal layer becomes larger.

As the alignment film material, a transparent organic material such as polyimine, polyamine, benzocyclobutene polymer, benzocyclobutene polymer or polyvinyl alcohol can be used, and it is particularly preferably a polymer synthesized from the following compounds. Polyimine alignment film obtained by hydrazine imidization: diamine such as p-phenylenediamine or 4,4'-diaminodiphenylmethane or an aliphatic or alicyclic diamine, and butane An aromatic tetracarboxylic anhydride such as tetracarboxylic anhydride or an aliphatic or alicyclic tetracarboxylic anhydride such as 2,3,5-tricarboxycyclopentyl acetic anhydride or pyromic acid dianhydride. In this case, the method of imparting alignment is usually a method of rubbing, but when it is used for a vertical alignment film or the like, it may be used without imparting alignment.

As the alignment film material, a material containing chalcone, cinnamate, cinnamon or azo in the compound may be used, or may be used in combination with a material such as polyimine or polyamine. In this case, alignment The film can be rubbed or optically aligned.

In the alignment film, the alignment film material is usually applied onto a substrate by a spin coating method or the like to form a resin film, but a uniaxial stretching method or a Langmuir-Blodgett method may be used. Wait.

(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), cerium-added titanium dioxide (Ti _1-x Nb _x O ₂ ), fluorine-doped tin oxide, graphite The olefin band 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 a photolithography method or a method using a photomask.

The liquid crystal display device of the invention can be especially used for liquid crystal display for active matrix driving The display device can be applied to a liquid crystal display device for TN mode, IPS mode, polymer stabilized IPS mode, FFS (Fringe Field Switching) mode, OCB mode, VA mode or ECB mode.

The liquid crystal display device and the backlight device can be combined and used for various purposes such as a liquid crystal television, a computer screen, a mobile phone, a smart phone display, or a notebook personal computer, a personal digital assistant, a digital signage, and the like. As the backlight device, there are a cold cathode tube type backlight device, an analog white backlight device using a two-wavelength peak of an organic material light-emitting diode or an organic EL element, and a three-wavelength peak backlight device.

[Examples]

The invention is further illustrated by the following examples, but the 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 properties measured were as follows.

T _ni : nematic phase-average liquid phase transfer temperature (°C)

Δn: refractive index anisotropy at 25 ° C

△ ε: dielectric anisotropy at 25 ° C

η: viscosity at 20 ° C (mPa.s)

Rotational viscosity at γ 1:25°C (mPa.s)

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

(A value in which the ratio of the measured voltage to the initial applied voltage is measured in % when a liquid crystal composition is injected into a cell having a cell thickness of 3.5 μm and subjected to measurement under a condition of applying 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 )

(Ion density value when a liquid crystal composition was injected into a cell having a cell thickness of 3.5 μm, and MTR-1 (manufactured by TOYO Corporation) was used to measure at a voltage of 20 V and a frequency of 0.05 Hz)

Afterimage: The afterimage evaluation of the liquid crystal display element was performed after displaying a specific fixed pattern for 1000 hours in the display area, and the level of the afterimage of the fixed pattern when the entire screen was uniformly displayed was visually evaluated by the following four levels.

◎ no afterimage

○ There are very few afterimages, but they can also be tolerated.

△There is an afterimage and cannot be tolerated

× has afterimage and 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 the plastic bottle, and 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 polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toagosei Chemical Co., Ltd.) 5.50 parts, dipentaerythritol hexaacrylate (KAYARAD (trade name) DPHA, Japan Pharmacological Co., Ltd. manufactures 5.00 parts, benzophenone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.) 1.00 parts, UCAR Ester EEP 13.5 parts is stirred by a dispersing mixer, and the pore diameter is utilized. A 1.0 μm filter was filtered to obtain a red dye coloring composition 1.

[Red dye coloring composition 2]

Red 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 1 (CI solvent yellow 21) were used instead of the above red dye coloring composition 1 of 10 parts of red dye 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 coloring composition 1 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 10 parts of red pigment 1 of the above red pigment 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 blue dye 1 (C.I. Solvent Blue 7) was used instead of the above-mentioned red dye coloring composition 1 of 10 parts of the red dye 1.

[Blue dye coloring composition 2]

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

[Blue dye coloring composition 3]

The 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 the above-mentioned blue dye coloring composition 2 of 7 parts of blue dye 1 and 3 parts of purple dye 1. .

[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 1 (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 dye coloring 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 1 of the above yellow dye coloring composition 1.

[Red Pigment Coloring Composition 1]

10 parts of red pigment 1 (CI Pigment Red 254, "IRGAPHOR RED BT-CF" manufactured by BASF Corporation) were added to the plastic bottle, 55 parts of propylene glycol monomethyl ether acetate was added, and Disperbyk LPN21116 (manufactured by BYK-Chemie Co., Ltd.) was added. 7.0 parts, manufactured by Saint-Gobain, 0.3-0.4mm The zirconia beads "ER-120S" were dispersed by a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, and then filtered through a filter of 1 μm to obtain a pigment dispersion liquid. 75.00 parts of the pigment dispersion liquid and a polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toagosei Chemical Co., Ltd.) 5.50 parts, dipentaerythritol hexaacrylate (KAYARAD (trade name) DPHA, Japan Pharmacological Co., Ltd. manufactures 5.00 parts, benzophenone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.) 1.00 parts, UCAR Ester EEP 13.5 parts is stirred by a dispersing mixer, and the pore diameter is utilized. 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, 2 parts of 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. 10 parts of red pigment 1, a red pigment coloring composition 2 was obtained in the same manner as above.

[Green Pigment Coloring Composition 1]

The green pigment coloring composition 1 was obtained in the same manner as above except that 10 parts of the green pigment 1 (aluminum phthalocyanine (AlClPcBr14ClH)) was used instead of the red pigment 1 of the above red pigment coloring composition 1.

[Green Pigment Coloring Composition 2]

Green pigment coloring composition 2 was obtained in the same manner as above except that 10 parts of green pigment 2 (zinc halide indigo (ZnPcBr14ClH)) was used instead of 10 parts of green pigment 1 of the above green pigment coloring composition 1.

[Green Pigment Coloring Composition 3]

6 parts of green pigment 3 (CI Pigment Green 58, FASTOGEN GREEN A110 manufactured by DIC Corporation) and 4 parts of yellow pigment 1 (CI Pigment Yellow 150, FANCHON FAST YELLOW E4GN manufactured by LANXESS Co., Ltd.) were used instead of the above green pigment coloring composition. 10 parts of green pigment 1 was obtained in the same manner as above to obtain green pigment coloring composition 3.

[Green Pigment Coloring Composition 4]

4 parts of green pigment 4 (CI Pigment Green 58, Manufactured by DIC Corporation FASTOGEN GREEN A310) and 6 parts of Yellow Pigment 3 (CI Pigment Yellow 138) were used instead of the above green pigment coloring composition 3 of 6 parts of green pigment 3 and 4 The yellow pigment 1 was obtained in the same manner as above to obtain a green pigment coloring composition 4.

[Blue pigment coloring composition 1]

9 parts of blue pigment 1 (CI Pigment Blue 15:6, "FASTOGEN BLUE EP-210" manufactured 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, a blue pigment coloring composition 1 was obtained in the same manner as above.

[Blue pigment dye coloring composition 2]

The blue pigment dye coloring composition 2 was obtained in the same manner as above except that 1 part of the purple dye 1 (C.I. Basic Violet 10) was used instead of the above-mentioned blue pigment coloring composition 1 of the violet pigment 1.

[Yellow Pigment Coloring Composition 1]

Yellow pigment coloring composition 1 was obtained in the same manner as above except that 10 parts of yellow pigment 1 (C.I. Pigment Yellow 150, FANCHON FAST YELLOW E4GN manufactured by LANXESS Co., Ltd.) was used instead of 10 parts of red pigment 1 of the above red pigment coloring composition 1.

[Production of color filter]

On the glass substrate on which the black matrix was formed in advance, the red colored composition was applied by spin coating so that the film thickness became 2 μm. 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 with an alkaline developing solution 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 which is a striped colored layer on the transparent substrate.

Next, the green colored composition was applied in the same manner by spin coating so that the film thickness became 2 μm. After drying, the portion shifted from the red pixel is exposed by an exposure machine to develop a striped color layer, thereby forming a green pixel adjacent to the red pixel.

Next, similarly to 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 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 was formed by spin coating in a film thickness of 2 μm as needed. Thereby, a color filter including stripes of red, green, blue, and yellow colors on a transparent substrate is obtained.

The color filter composition 1 or 4 and the comparative color filter 1 were produced using the dye coloring composition or the pigment coloring composition shown in Table 2.

For each pixel portion of the color filter, a microscope MX-50 manufactured by Olympus and a spectrophotometer MCPD-3000 microspectrophotometer manufactured by Otsuka Electronics were used to measure the x value and y of the C light source of the CIE 1931 XYZ color system. value. The results are shown in the table 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 each opposite side, and performing a weak rubbing treatment to form an IPS unit, sandwiching between the first substrate and the second substrate The liquid crystal composition 1 shown below was held. The physical property values of the liquid crystal composition 1 are shown in Table 4. Next, 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. Moreover, the afterimage of the obtained liquid crystal display device was evaluated. The results are shown in 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 low viscosity and optimum Δn.

The liquid crystal display devices of Examples 1 to 4 can realize high VHR and small ID. In addition, there is no afterimage in the afterimage evaluation, or even if there is little, the allowable level is not allowed.

(Examples 5 to 12)

The liquid crystal compositions 2 to 3 shown in Table 5 were sandwiched in the same manner as in Example 1, and the color filters shown in Table 2 were used to fabricate the liquid crystal display devices of Examples 5 to 12, and the VHR and ID thereof were measured. . Further, the afterimage of the liquid crystal display device was evaluated. The results are shown in Tables 7 to 8.

The liquid crystal display devices of Examples 5 to 12 can realize high VHR and small ID. In addition, there is no afterimage in the afterimage evaluation, or even if there is little, the allowable level is not allowed.

(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 color filters shown in Table 2 were used to fabricate the liquid crystal display devices of Examples 13 to 24, and the VHR thereof was measured. ID. Further, the afterimage of the liquid crystal display device was evaluated. The results are shown in Tables 10 to 12.

The liquid crystal display devices of Examples 13 to 24 can realize high VHR and small ID. In addition, there is no afterimage in the afterimage evaluation, or even if there is little, the allowable level is not allowed.

(Examples 25 to 36)

An electrode structure is formed on the first and second substrates, and a horizontally oriented alignment film is formed on each of the opposite sides, and then subjected to a weak rubbing treatment to form a TN cell, and the first substrate and the second substrate are sandwiched between the first substrate and the second substrate. The liquid crystal composition is 7~9. Next, liquid crystal display devices (d _gap = 3.5 μm, alignment film SE-7492) of Examples 25 to 36 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. Moreover, the afterimage of the obtained liquid crystal display device was evaluated. The results are shown in Tables 14 to 16.

The liquid crystal display devices of Examples 25 to 36 can realize high VHR and small ID. In addition, there is no afterimage in the afterimage evaluation, or even if there is little, the allowable level is not allowed.

(Examples 37 to 44)

And forming an electrode structure on at least one of the first substrate and the second substrate, forming a horizontal alignment alignment film on each opposite side, and performing a weak rubbing treatment to form an FFS unit, and sandwiching between the first substrate and the second substrate The liquid crystal compositions 10 to 11 shown in Table 17. Next, 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. Moreover, the afterimage of the obtained liquid crystal display device was evaluated. The results are shown in Tables 18 to 19.

The liquid crystal display devices of Examples 37 to 44 can realize high VHR and small ID. In addition, there is no afterimage in the afterimage evaluation, or even if there is little, the allowable level is not allowed.

(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 produced using the color filters shown in Table 2, and the VHR and ID thereof were measured. . Further, the afterimage of the liquid crystal display device was evaluated. The results are shown in Tables 21 to 23.

The liquid crystal display devices of Examples 45 to 56 can realize high VHR and small ID. In addition, there is no afterimage in the afterimage evaluation, or even if there is little, the allowable level is not allowed.

(Examples 57 to 60)

In the liquid crystal composition 10 used in Example 37, 0.3% by mass of biphenyl methacrylate-4,4'-diester was mixed to prepare a liquid crystal composition 15. The liquid crystal composition 15 was sandwiched between the electrodes in a TN cell, and a driving voltage was applied between the electrodes. In this state, ultraviolet rays were irradiated for 600 seconds (3.0 J/cm ² ) for polymerization treatment, and secondly, color filters shown in Table 2 were used. For the sheets 1 to 4, liquid crystal display devices of Examples 57 to 60 were produced, and their VHR and ID were measured. Further, the afterimage of the liquid crystal display device was evaluated. The results are shown in Table 24.

The liquid crystal display devices of Examples 57 to 60 can realize high VHR and small ID. In addition, there is no afterimage in the afterimage evaluation, or even if there is little, the allowable level is not allowed.

(Examples 61 to 64)

In the liquid crystal composition 8 used in Example 29, 0.3% by mass of biphenyl methacrylate-4,4'-diester was mixed to prepare a liquid crystal composition 16. The liquid crystal composition 16 was sandwiched between the electrodes in the IPS unit, and a driving voltage was applied between the electrodes. In this state, ultraviolet rays were irradiated for 600 seconds (3.0 J/cm ² ) for polymerization treatment, and secondly, color filters shown in Table 2 were used. For the sheets 1 to 4, liquid crystal display devices of Examples 61 to 64 were produced, and their VHR and ID were measured. Further, the afterimage of the liquid crystal display device was evaluated. The results are shown in Table 25.

The liquid crystal display devices of Examples 61 to 64 can realize high VHR and small ID. In addition, there is no afterimage in the afterimage evaluation, or even if there is little, the allowable level is not allowed.

(Examples 65 to 68)

Into the liquid crystal composition 6 used in Example 21, 0.3% by mass of 3-fluorobiphenyl-4,4'-diester methacrylate was mixed to prepare a liquid crystal composition 17. The liquid crystal composition 17 was sandwiched between the electrodes in the FFS unit, and a driving voltage was applied between the electrodes. In this state, ultraviolet rays were irradiated for 600 seconds (3.0 J/cm ² ) for polymerization treatment, and secondly, color filters shown in Table 2 were used. For the sheets 1 to 4, liquid crystal display devices of Examples 65 to 68 were produced, and their VHR and ID were measured. Further, the afterimage of the liquid crystal display device was evaluated. The results are shown in Table 26.

The liquid crystal display devices of Examples 65 to 68 can realize high VHR and small ID. In addition, there is no afterimage in the afterimage evaluation, or even if there is little, the allowable level is not allowed.

(Comparative examples 11 to 4)

The comparative liquid crystal composition 1 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. Using the color filters 1 to 4 shown in Table 2, liquid crystal display devices of Comparative Examples 1 to 4 were produced, and their VHR and ID were measured. Further, the afterimage of the liquid crystal display device was evaluated. The results are shown in Table 28.

Compared with the liquid crystal display device of the present invention, the liquid crystal display devices of Comparative Examples 1 to 4 have a low VHR and an increased ID. Further, the generation of afterimages was also confirmed in the afterimage evaluation, which is not an allowable level.

(Comparative examples 5 to 12)

The comparative liquid crystal compositions 2 and 3 shown in Table 29 were sandwiched in the same manner as in Example 1, 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 were measured. Its VHR and ID. Further, the afterimage of the liquid crystal display device was evaluated. The results are shown in Tables 30 to 31.

Compared with the liquid crystal display device of the present invention, the liquid crystal display devices of Comparative Examples 5 to 12 have a low VHR and an increased ID. Further, the generation of afterimages was also confirmed in the afterimage evaluation, which is not an allowable level.

(Comparative examples 13 to 20)

The comparative liquid crystal compositions 4 to 5 shown in Table 32 were sandwiched in the same manner as in Example 1, and the liquid crystal display devices of Comparative Examples 13 to 24 were produced using the color filters 1 to 4 shown in Table 2, and were measured. Its VHR and ID. Further, the afterimage of the liquid crystal display device was evaluated. The results are shown in Tables 33 to 34.

Compared with the liquid crystal display device of the present invention, the liquid crystal display devices of Comparative Examples 13 to 20 have a low VHR and an increased ID. Further, the generation of afterimages was also confirmed in the afterimage evaluation, which is not an allowable level.

(Comparative examples 21 to 32)

The comparative liquid crystal compositions 6 to 8 shown in Table 35 were sandwiched in the same manner as in Example 1, and the color filters 1 to 4 shown in Table 2 were used to prepare liquid crystal display devices of Comparative Examples 21 to 32, and measured. Its VHR and ID. Further, the afterimage of the liquid crystal display device was evaluated. The results are shown in Tables 36 to 38.

Compared with the liquid crystal display device of the present invention, the liquid crystal display devices of Comparative Examples 21 to 32 have a low VHR and an increased ID. Further, the generation of afterimages was also confirmed in the afterimage evaluation, which is not an allowable level.

(Comparative Examples 33 to 44)

The comparative liquid crystal compositions 9 to 11 shown in Table 39 were sandwiched in the same manner as in Example 1, 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 were measured. Its VHR and ID. Further, the afterimage of the liquid crystal display device was evaluated. The results are shown in Tables 40 to 42.

Compared with the liquid crystal display device of the present invention, the liquid crystal display devices of Comparative Examples 33 to 44 have a low VHR and an increased ID. Further, the generation of afterimages was also confirmed in the afterimage evaluation, which is not an allowable level.

(Comparative Example 145~52)

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, and measure its VHR and ID. Further, the afterimage of the liquid crystal display device was evaluated. The results are shown in Tables 43 and 44.

Compared with the liquid crystal display device of the present invention, the liquid crystal display devices of Comparative Examples 45 to 52 have a low VHR and an increased ID. Moreover, the generation of afterimages was also confirmed in the afterimage evaluation. Not a tolerable level.

Claims (12)

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, and the liquid crystal composition contains one or two or more compounds represented by the formula (I), and one or more types thereof are selected from the group consisting of a compound of the group consisting of the compounds of 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 trans-1, 4 - a cyclohexyl group or a 1,4-phenylene group, wherein one or two -CH ₂ - groups of the trans-1,4-cyclohexylene group can be substituted by -O- in such a manner that the oxygen atoms are not directly adjacent to each other, One or two hydrogen atoms in the phenyl 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 may be the same or different when there are a plurality of M ³¹ and M ³³ ), (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 G pixel portion contains a halogenated metal indigo pigment as a coloring material selected from the group consisting of Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr. a metal in a group consisting of Nb, In, Sn, and Pb as a central metal. When the central metal is trivalent, one of a halogen atom, a hydroxyl group, or a sulfonic acid group is bonded to the central metal. Or oxo or thiocrosslinking. When the central metal is a tetravalent metal, one oxygen atom or two halogen atoms, a hydroxyl group or a sulfonate may be bonded to the central metal. Any of the acid groups. The liquid crystal display device of claim 1, wherein the RGB three-color pixel portion contains a diketopyrrolopyrrole pigment and/or an anionic red organic dye as a colorant in the R pixel portion, and contains ε in the B pixel portion. A type of copper phthalocyanine pigment and/or a cationic blue organic dye is used as a colorant. A liquid crystal display device according to claim 1 or 2, wherein the RGB three-color pixel portion contains C.I. solvent red 124 as a color material in the R pixel portion and C.I. Solvent Blue 7 as a color material in the B pixel portion. The liquid crystal display device of claim 1 or 2, wherein the RGB three-color pixel portion contains CI Pigment Red 254 as a color material in the R pixel portion and CI Pigment Blue 15:6 as a color material in the B pixel portion. . The liquid crystal display device according to any one of claims 1 to 4, wherein the G pixel portion contains 8 to 16 halogen atoms in each indocyanine molecule bonded to the benzene ring of the indocyanine molecule. A zinc halide indigo pigment having Zn as a central metal. The liquid crystal display device according to any one of claims 1 to 5, wherein C.I. Pigment Green 58 is contained in the G pixel portion. A liquid crystal display device according to any one of claims 1 to 6, wherein the image is The element further comprises a component 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, CI Solvent Yellow 82, CI Solvent Yellow 83:1, and CI Solvent Yellow 33. At least one organic dye in the group. The liquid crystal display device according to any one of claims 1 to 7, 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 yellow organic dye in the group is used as a colorant. The liquid crystal display device according to any one of claims 1 to 8, wherein the compound represented by the formula (I) is a compound represented by the formula (Ia) to the formula (If), (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 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 claims 1 to 9, wherein the liquid crystal composition layer further contains one or more selected from the group consisting of the formula (III-a) to the formula (III-f). a compound of the compound group shown, (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 10, wherein the liquid crystal composition layer is composed of a polymer obtained by polymerizing a liquid crystal composition containing one or two or more kinds of polymerizable compounds. The liquid crystal display device according to any one of claims 1 to 11, 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 set to be bonded to the aromatic ring), and Z ¹ represents -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, - CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO -CH=CH-, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -,- OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CY ¹ =CY ² - (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 1,4-phenylene groups in the formula may be subjected to fluorine. Atomic substitution).