TW201908470A - Liquid crystal display device - Google Patents

Abstract

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

Description

   Liquid crystal display device   

The invention relates to a liquid crystal display device.

The liquid crystal display device is used for various household electrical appliances, such as clocks and calculators, measuring equipment, automobile panels, word processors, electronic notebooks, printers, computers, and televisions. As the liquid crystal display mode, representative examples include: TN (Twisted Nematic, twisted nematic) type, STN (Super Twisted Nematic, super twisted nematic) type, DS (Dynamic Scattering) type, GH (Guest -Host (guest-host) type, IPS (In-Plane Switching) type, OCB (Optically Compensated Birefringence) type, ECB (Electrically Controlled Birefringence) type, VA (Vertical Aligned) , Vertical alignment) type, CSH (Color Super Homeotropic) type, or FLC (Ferroelectric Liquid Crystal, ferroelectric liquid crystal). In addition, as a driving method, the previous static driving has generally become a multiplex driving, a simple matrix method, and recently a thin film transistor (TFT) or a thin film diode (TFD). ) And other active matrix (AM, Active Matrix) methods are becoming mainstream.

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

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

If impurities are left in the liquid crystal material constituting the liquid crystal layer, the electrical characteristics of the display device will be greatly affected. Therefore, impurities have been highly managed. In addition, as for the material forming the alignment film, it is also known that the alignment film will directly contact the liquid crystal layer, and impurities remaining in the alignment film will be transferred to the liquid crystal layer, thereby affecting the electrical characteristics of the liquid crystal layer, and the industry is facing The characteristics of the liquid crystal display device caused by impurities in the alignment film material are studied.

On the other hand, regarding materials such as an organic pigment used for a color filter layer, it is expected that the same effect as that of the alignment film material on the liquid crystal layer due to impurities contained therein. However, since an alignment film and a 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 much smaller than that of the alignment film material. However, the alignment film is usually only a film thickness of 0.1 μm or less. Regarding the transparent electrode, even if the common electrode used for the color filter layer side is increased in order to increase the conductivity, the film thickness is usually 0.5 μm or less. Therefore, it cannot be considered that the color filter layer and the liquid crystal layer are in a completely isolated environment. The color filter layer may be caused by impurities contained in the color filter layer through the alignment film and the transparent electrode. The liquid crystal layer has a reduced voltage retention rate (VHR) and an increased display of ion density (ID), which results in poor display such as whitening, uneven alignment, and residual image.

As a method for solving display failure caused by impurities contained in pigments constituting a color filter, the industry has studied the following methods: using pigments in which the ratio of the extract of the pigment obtained by using ethyl formate is less than a specific value, A method of controlling the dissolution of impurities into the liquid crystal (Patent Document 1); or a method of controlling the dissolution of impurities into the liquid crystal by specifying a pigment in the blue colored layer (Patent Document 2). However, these methods are not much different from simply reducing impurities in pigments. Even in the current situation where the purification technology of pigments has improved in recent years, improvements to solve display defects are still insufficient.

On the other hand, the industry focuses on the relationship between the organic impurities contained in the color filter and the liquid crystal composition, and has revealed the following method: The hydrophobicity parameter of the liquid crystal molecules contained in the liquid crystal layer indicates that the organic impurities are in the liquid crystal layer. In the difficulty of dissolution, the method of setting the value of the hydrophobicity parameter above a certain value; or because the hydrophobicity parameter is related to the -OCF ₃ group at the end of the liquid crystal molecule, it is made to contain a certain proportion of A method for a liquid crystal composition of a liquid crystal compound having -OCF ₃ group at the molecular end (Patent Document 3).

However, even in the disclosure of the cited document, it is the essence of the invention to suppress the influence of impurities in the pigment on the liquid crystal layer, but it does not directly affect the structure of colorants such as dyes and pigments used in color filters and the structure of liquid crystal materials. The research on the relationship has failed to solve the problem of poor display of the continuously improved liquid crystal display device.

[Advanced technical literature]

[Chartered Literature]

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

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

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

An object of the present invention is to provide a liquid crystal display device that prevents a decrease in voltage retention (VHR) and an ion density (ID) of a liquid crystal layer by using a color filter using a specific liquid crystal composition and a specific pigment. Increase, to solve the problem of poor display such as anti-whitening, uneven alignment, and residual image.

In order to solve the above-mentioned problems, the present inventor conducted intensive research on the combination of the color materials such as dyes and pigments constituting a color filter and the liquid crystal material constituting the liquid crystal layer. As a result, it was found that a liquid crystal material having a specific structure and a specific The liquid crystal display device of the structured pigment and compound color filter can prevent the voltage holding ratio (VHR) of the liquid crystal layer from decreasing and increase the ion density (ID), and solve the problems of poor display such as whitening, uneven alignment, and residual image. To complete the invention of this case.

That is, the present invention provides a liquid crystal display device including a first substrate, a second substrate, a liquid crystal layer sandwiched between the first substrate and the second substrate, and a color filter including at least three RGB pixel portions. A light sheet, a pixel electrode, and a common electrode. The liquid crystal layer contains a liquid crystal composition. The liquid crystal composition contains one or two or more compounds represented by the general formula (I-1). Compounds in the group consisting of compounds represented by formula (II-a) to formula (II-f),

(Wherein R ³¹ represents an alkyl group, alkoxy group having 1 to 10 carbon atoms, alkenyl group or alkenyl group having 2 to 10 carbon atoms, and M ³¹ to M ³² independently represent trans-1,4 -Cyclohexyl or 1,4-phenylene, one or two of the trans-1,4-cyclohexyl -CH ₂ -can also be substituted with -O- in a way that the oxygen atoms are not directly adjacent One of the hydrogen atoms in the phenylene group may also be substituted by a fluorine atom. M ³³ represents trans-1,4-cyclohexyl or 1,4-phenylene. One or two -CH ₂ -groups in the hexyl group can also be substituted with -O- in a way that the oxygen atoms are not directly adjacent, and one or two hydrogen atoms in the phenyl group can also be substituted with fluorine atoms, X ³¹ And X ³² independently represent a hydrogen atom or a fluorine atom, Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group, n ³¹ and n ³² independently represent 0, 1 or 2, n ³¹ + n ³² It means 0, 1, or 2. When there are multiple M ³¹ and M ³³ , they may be the same or different.)

(Wherein R ¹⁹ to R ³⁰ independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and X ²¹ represents a hydrogen atom or (Fluorine atom), regarding the above-mentioned RGB three-color pixel portion, the G pixel portion contains at least one or more selected from the first group represented by the following general formula (PIG-1) and / or the following general formula ( The metal phthalocyanine pigment in the second group represented by PIG-2), the metal phthalocyanine pigment has an average primary particle diameter of 5 to 50 nm obtained by a small-angle X-ray scattering method,

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

In (Formula ^{(PIG-2), X 17i} ~ X 32i each independently represent a halogen atom, a nitro group, may also have phthalimide (PEI) methyl substituent, the substituent may also have an amine group of the sulfonylureas Group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may also have a substituent, An aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may also have a substituent. M represents a member selected from the group consisting of Ga, Al, Sc, Y, and In. Trivalent metal. Y ²ⁱ represents -O-, -O-SiR6R7-O-, -O-SiR6R7-O-SiR8R9-O-, or -OP (= O) R10-O-, and R6 ~ R10 are each independently expressed A hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may also have a substituent).

The liquid crystal display device of the present invention uses a color filter using a specific liquid crystal composition, a specific pigment, and a specific compound to prevent a decrease in voltage retention (VHR) of the liquid crystal layer and a decrease in ion density (ID). The increase can prevent poor display such as whitening, uneven alignment, and residual image.

1‧‧‧ substrate

2‧‧‧ color filter layer

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

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

3b‧‧‧pixel electrode layer

4‧‧‧alignment film

5‧‧‧LCD layer

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

FIG. 1 is a diagram showing an example of a conventional conventional liquid crystal display device.

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

An example of the liquid crystal display device of the present invention is shown in FIG. 2. It is provided between the first substrate and the second substrate having an alignment film (4), and a transparent electrode layer (3a) serving as a common electrode between the alignment film and the substrate, and a specific pigment. A color filter layer (2a) of a specific compound and a pixel electrode layer (3b) are provided between the other alignment film and the substrate, and the substrates are arranged so that the alignment films face each other, and sandwiched therebetween It consists of a liquid crystal layer (5a) containing a specific liquid crystal composition.

In the above display device, the two substrates are bonded by a sealing material and a sealing material arranged in the peripheral area. In most cases, a granular spacer or a light lithography is arranged between them in order to maintain the distance between the substrates. Spacers made of resin.

(Liquid crystal layer)

The liquid crystal layer in the liquid crystal display device of the present invention is composed of a liquid crystal composition containing one or two or more compounds represented by the general formula (I-1).

(In the formula, R ³¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, M ³¹ ~ M ³² independently represent trans-1,4-cyclohexyl or 1,4-phenylene, and one of the trans-1,4-cyclohexyl groups -CH ₂ -can also be oxygen The atoms are not directly adjacent to each other by -O-. One or two hydrogen atoms in the phenyl group can also be replaced by a fluorine atom. M ³³ represents trans-1,4-cyclohexyl or 1,4- Phenylene, one or two of the trans-1,4-cyclohexyl groups -CH ₂ -can also be substituted with -O- in a way that oxygen atoms are not directly adjacent, one of the phenylene Or two hydrogen atoms may be substituted by a fluorine atom. X ³¹ and X ³² each independently represent a hydrogen atom or a fluorine atom, Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group, and n ³¹ and n ³² each other It independently represents 0, 1, or 2, and n ³¹ + n ³² represents 0, 1, or 2. In the case where a plurality of M ³¹ and M ³³ exist, they may be the same or different).

In the general formula (I-1), when R ³¹ is a phenyl (aromatic) ring structure, it is preferably a linear alkyl group having 1 to 5 carbon atoms and a linear alkyl group. When the alkoxy group having 1 to 4 carbon atoms (or more) and the alkenyl group having 4 to 5 carbon atoms are bonded, the ring structure is more saturated when the ring structure is saturated, such as cyclohexane and pyran. It is preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkyl group having 1 to 4 (or more) alkoxy groups, and a linear alkyl group having 2 to 5 carbon atoms.

When good chemical stability to heat or light is valued, R ^{31 is} preferably an alkyl group. In addition, if it is important to produce a liquid crystal display device having a small viscosity and a fast response speed, R ^{31 is} preferably an alkenyl group. Furthermore, if the viscosity is small, the nematic-isotropic phase transition temperature (Tni) is high, and the response speed is further shortened, it is preferable to use an alkenyl group whose terminal is not unsaturated, especially It is preferred that a methyl group be located at the ortho position of the alkenyl group as a terminal. In addition, if good solubility at low temperature is important, as one of the solutions, R ^{31 is} preferably an alkoxy group. As another solution, it is preferable to use a plurality of types of R ^{31 in combination} . For example, it is preferable to use a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms as R ³¹ , more preferably a compound having 3 and 5 carbon atoms, and it is more preferable to use 3, 5 or 2 carbon atoms in combination. Compounds of 4 and 5.

M ³¹ ~ M ^{32 is} preferably

M ^{31 is} preferably M ^{31 is} better

M ^{32 is} preferably M ^{32 is} better M ^{32 is} better

M ^{33 is} preferred M ^{33 is} better M ^{33 is} better

At least one of X ³¹ and X ^{32 is} preferably a fluorine atom, and more preferably, both of them are fluorine atoms.

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

As a combination of X ³¹ , X ^32, and Z ³¹ , one embodiment is X ³¹ = F, X ³² = F, and Z ³¹ = F. In other embodiments, X ³¹ = F, X ³² = H, and Z ³¹ = F. In another embodiment, X ³¹ = F, X ³² = H, and Z ³¹ = OCF ₃ . In another embodiment, X ³¹ = F, X ³² = F, and Z ³¹ = OCF ₃ . In another embodiment, X ³¹ = H, X ³² = H, and Z ³¹ = OCF ₃ .

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

More specifically, the compound represented by the general formula (I-1) is preferably a compound represented by the following general formula (I-a) to (I-f).

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

In the general formulae (Ia) to (If), when R ³² is a phenyl (aromatic) ring structure, a linear alkyl group having 1 to 5 carbon atoms, Straight-chain alkoxy groups having 1 to 4 carbon atoms (or more) and alkenyl groups having 4 to 5 carbon atoms. The bonded ring structures are cyclohexane, pyran, and In the case of a saturated ring structure such as an alkane, a linear alkyl group having 1 to 5 carbon atoms, a linear alkyl group having 1 to 4 carbon atoms (or more), and a linear alkyl group are preferred. Alkenyl group having 2 to 5 carbon atoms.

When importance is attached to good chemical stability to heat or light, R ^{32 is} preferably an alkyl group. In addition, if it is important to produce a liquid crystal display element having a small viscosity and a fast response speed, R ^{32 is} preferably an alkenyl group. Further, if the purpose is to reduce the viscosity, increase the nematic-homogeneous phase transition temperature (Tni), and further shorten the response speed, it is preferable to use an alkenyl group whose terminal is not unsaturated, and it is more preferably an ortho position of the alkenyl group. There are methyl groups at the ends. In addition, if importance is given to good solubility at low temperature, as one of the solutions, it is preferable to use R ³² as an alkoxy group. As another solution, it is preferable to use a plurality of types of R ^{32 in combination} . For example, a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms as R ³² is preferably used in combination, a compound having 3 and 5 carbon atoms is more preferably used in combination, and a combination of 3 and 5 carbon atoms is more preferable. Compounds of 4 and 5.

At least one of X ³¹ and X ^{32 is} preferably a fluorine atom, and more preferably, both of them are fluorine atoms.

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

As a combination of X ³¹ , X ^32, and Z ³¹ , one embodiment is X ³¹ = F, X ³² = F, and Z ³¹ = F. In other embodiments, X ³¹ = F, X ³² = H, and Z ³¹ = F. In another embodiment, X ³¹ = F, X ³² = H, and Z ³¹ = OCF ₃ . In another embodiment, X ³¹ = F, X ³² = F, and Z ³¹ = OCF ₃ . In another embodiment, X ³¹ = H, X ³² = H, and Z ³¹ = OCF ₃ .

At least one of X ³³ and X ^{34 is} preferably a fluorine atom, and more preferably, both of them are fluorine atoms.

It is preferable that at least one of X ³⁵ and X ³⁶ is a fluorine atom. When both of them are fluorine atoms, it is effective when Δε is increased, but it is soluble in Tni, low temperature, or when it is made into a liquid crystal display element. It is not good from the viewpoint of chemical stability.

It is preferable that at least one of X ³⁷ and X ³⁸ is a hydrogen atom, and it is preferable that both are a hydrogen atom. In the case where at least one of X ³⁷ and X ³⁸ is a fluorine atom, it is not preferable from the viewpoints of Tni, solubility at low temperature, or chemical stability when forming a liquid crystal display element.

The compound group represented by the general formula (I-1) preferably contains 1 to 8 species, particularly preferably 1 to 5 species, and the content thereof is preferably 3 to 60% by mass, and more preferably 5 to 50% by mass. %.

The liquid crystal layer in the liquid crystal display device of the present invention may be composed of a liquid crystal composition containing one or two or more compounds selected from the group consisting of compounds represented by the general formula (I-2). Compounds in the group as arbitrary components,

(In the formula, R ³³ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, M ³⁴ to M ³⁵ independently represent trans-1,4-cyclohexyl or 1,4-phenylene, and one or two of the trans-1,4-cyclohexyl groups are -CH _2- It can also be substituted with -O- in a way that the oxygen atoms are not directly adjacent. One or two hydrogen atoms in the phenyl group can also be substituted with fluorine atoms. Among them, at least M ³⁴ and M ³⁵ are present. One represents trans-1,4-cyclohexyl, and two of the trans-1,4-cyclohexyl groups -CH ₂ -can be substituted with -O- in a manner that oxygen atoms are not directly adjacent, and M ³⁶ represents Trans-1,4-cyclohexyl or 1,4-phenylene, one or two of the trans-1,4-cyclohexyl groups -CH ₂ -can also be directly adjacent to each other with an oxygen atom The method is substituted with -O-, and one or two hydrogen atoms in the phenyl group can also be substituted with fluorine atoms. X ⁵¹ and X ⁵² independently represent a hydrogen atom or a fluorine atom, and Z ³² represents a fluorine atom and a trifluoro Methoxy or trifluoromethyl, Z ³³ represents -CF ₂ O- or a single bond, n ³⁴ and n ³⁶ independently represent 0, 1 or 2, n ³⁴ + n ³⁶ Shows 0, 1, or 2, when there are multiple M ³⁴ and M ³⁶ , they may be the same or different).

In the general formula (I-2), when R ³³ is a phenyl (aromatic) ring structure, it is preferably a straight-chain alkyl group having 1 to 5 carbon atoms and a straight-chain alkyl group. The alkoxy group having 1 to 4 carbon atoms (or more) and the alkenyl group having 4 to 5 carbon atoms have ring structures bonded to them such as cyclohexane, pyran and In the case of a saturated ring structure such as an alkane, a linear alkyl group having 1 to 5 carbon atoms, a linear alkyl group having 1 to 4 carbon atoms (or more), and a linear alkyl group are preferred. Alkenyl having 2 to 5 carbon atoms.

When good chemical stability to heat or light is valued, R ^{33 is} preferably an alkyl group. In addition, if it is important to produce a liquid crystal display element having a small viscosity and a fast response speed, R ^{33 is} preferably an alkenyl group. Further, if the purpose is to reduce the viscosity, increase the nematic-homogeneous phase transition temperature (Tni), and further shorten the response speed, it is preferable to use an alkenyl group whose terminal is not unsaturated, and it is more preferably an ortho position to the alkenyl There are methyl groups at the ends. In addition, if importance is given to good solubility at low temperature, as one of the solutions, it is preferable to use R ³³ as an alkoxy group. As another solution, it is preferable to use a plurality of types of R ^{33 in combination} . For example, a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms as R ³³ is preferably used, a compound having 3 and 5 carbon atoms is more preferably used in combination, and a combination of 3 and 5 carbon atoms is more preferable. Compounds of 4 and 5.

M ³⁴ ~ M ^{35 is} preferred

M ^{34 is} preferred

M ^{34 is} better

M ^{35 is} better

M ^{35 is} better

M ^{36 is} preferred

M ^{36 is} better

M ^{36 is} better

At least one of X ⁵¹ and X ^{52 is} preferably a fluorine atom, and more preferably, both of them are fluorine atoms.

Z ^{32 is} preferably a fluorine atom or a trifluoromethoxy group.

As a combination of X ⁵¹ , X ⁵² and Z ³² , one embodiment is X ⁵¹ = F, X ⁵² = F, and Z ³² = F. In other embodiments, X ⁵¹ = F, X ⁵² = H, and Z ³² = F. In another embodiment, X ⁵¹ = F, X ⁵² = H, and Z ³² = OCF ₃ . In another embodiment, X ⁵¹ = F, X ⁵² = F, and Z ³¹ = OCF ₃ . In another embodiment, X ⁵¹ = H, X ⁵² = H, and Z ³¹ = OCF ₃ .

n ^{34 is} preferably 1 or 2, n ^{36 is} preferably 0 or 1, more preferably 0, and n ³⁴ + n ^{36 is} preferably 1 or 2, and more preferably 2. More specifically, the compound represented by general formula (I-2) is preferably a compound represented by general formula (Ig) to general formula (Ij) below.

(Wherein R ³³ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, X ⁵¹ to X ⁵⁸ each independently represent a hydrogen atom or a fluorine atom, and Z ³² represents a fluorine atom, a trifluoromethoxy group, or a trifluoromethyl group).

In general formula (Ig) to general formula (Ij), the ring structure to which R ³³ is bonded is cyclohexane, pyran and di In the case of a saturated ring structure such as an alkane, a linear alkyl group having 1 to 5 carbon atoms, a linear alkyl group having 1 to 4 carbon atoms (or more), and a linear alkyl group are preferred. Alkenyl having 2 to 5 carbon atoms.

When good chemical stability to heat or light is valued, R ^{33 is} preferably an alkyl group. In addition, if it is important to produce a liquid crystal display element having a small viscosity and a fast response speed, R ^{32 is} preferably an alkenyl group. Further, if the purpose is to reduce the viscosity, increase the nematic-homogeneous phase transition temperature (Tni), and further shorten the response speed, it is preferable to use an alkenyl group whose terminal is not unsaturated, and it is more preferably an ortho position of the alkenyl group. There are methyl groups at the ends. In addition, if good solubility at low temperature is important, as one of the solutions, R ^{33 is} preferably an alkoxy group. As another solution, it is preferable to use a plurality of types of R ^{33 in combination} . For example, a compound having an alkyl group or an alkenyl group having 2, 3, and 4 carbon atoms as R ³³ is preferably used, a compound having 3 and 5 carbon atoms is more preferably used, and 3, 4 carbon atoms are more preferably used in combination. And the compound of 5.

At least one of X ⁵¹ and X ^{52 is} preferably a fluorine atom, and more preferably, both of them are fluorine atoms.

Z ^{32 is} preferably a fluorine atom or a trifluoromethoxy group.

As a combination of X ⁵¹ , X ⁵² and Z ³² , one embodiment is X ⁵¹ = F, X ⁵² = F, and Z ³² = F. In other embodiments, X ⁵¹ = F, X ⁵² = H, and Z ³² = F. In another embodiment, X ⁵¹ = F, X ⁵² = H, and Z ³² = OCF ₃ . In another embodiment, X ⁵¹ = F, X ⁵² = F, and Z ³² = OCF ₃ . In another embodiment, X ⁵¹ = H, X ⁵² = H, and Z ³² = OCF ₃ .

X ⁵³ and X ^{54 are each} preferably a fluorine atom.

It is preferable that at least one of X ⁵³ and X ⁵⁴ is a fluorine atom. When both of them are fluorine atoms, it is effective when Δε is increased. It is not good from the viewpoint of chemical stability.

X ⁵⁵ and X ^{56 are each} preferably a hydrogen atom. In the case where at least one of X ⁵⁵ and X ⁵⁶ is a fluorine atom, it is not preferable from the viewpoints of Tni, solubility at low temperature, or chemical stability when forming a liquid crystal display element.

X ⁵⁷ and X ^{58 are each} preferably a hydrogen atom. In the case where at least one of X ⁵⁷ and X ⁵⁸ is a fluorine atom, it is not preferable from the viewpoints of Tni, solubility at low temperature, or chemical stability when forming a liquid crystal display element.

More specifically, the compound group represented by the general formula (I-2) preferably contains one to five compounds represented by the general formula (Ig) to the general formula (Ij), and particularly preferably one to three compounds. Species, the content of which is preferably 2 to 30% by mass, more preferably 4 to 25% by mass, and even more preferably 5 to 20% by mass.

Further, the liquid crystal layer in the liquid crystal display device of the present invention is composed of a liquid crystal composition, and the liquid crystal composition contains one or two or more selected from the group consisting of the formulae (II-a) to (II-f). A compound in a group of compounds as an essential ingredient,

(Wherein R ¹⁹ to R ³⁰ independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and X ²¹ represents a hydrogen atom or Fluorine atom).

In the general formulae (II-a) to (II-f), when R ¹⁹ to R ³⁰ is a phenyl (aromatic) ring structure, the number of linear carbon atoms is preferred. Alkyl groups of 1 to 5, linear alkoxy groups of 1 to 4 (or more) carbon atoms, and alkenyl groups of 4 to 5 carbon atoms, the ring structures to which they are bonded are cyclohexane, pyridine Mum and two In the case of a saturated ring structure such as an alkane, a linear alkyl group having 1 to 5 carbon atoms, a linear alkyl group having 1 to 4 carbon atoms (or more), and a linear alkyl group are preferred. Alkenyl having 2 to 5 carbon atoms.

When importance is attached to good chemical stability to heat or light, R ¹⁹ to R ^{30 are} preferably alkyl groups. In addition, if it is important to produce a liquid crystal display device having a small viscosity and a fast response speed, R ¹⁹ to R ^{30 are} preferably alkenyl groups. Further, if the purpose is to reduce the viscosity, increase the nematic-homogeneous phase transition temperature (Tni), and further shorten the response speed, it is preferable to use an alkenyl group whose terminal is not unsaturated, and it is more preferably an ortho position of the alkenyl group. There are methyl groups at the ends. In addition, if good solubility at low temperature is important, as one of the solutions, it is preferable to use R ¹⁹ to R ³⁰ as an alkoxy group. As another solution, it is preferable to use a plurality of R ¹⁹ to R ^{30 in combination} . For example, it is preferable to use a compound having an alkyl group or an alkenyl group having a carbon number of 2, 3, and 4 as R ¹⁹ to R ³⁰ , it is more preferable to use a compound having a carbon number of 3 and 5, and it is more preferable to use a carbon atom in combination Numbers 3, 4 and 5.

R ¹⁹ to R ^{20 are} preferably an alkyl group or an alkoxy group, and at least one of them is preferably an alkoxy group. More preferably, R ¹⁹ is an alkyl group, and R ²⁰ is an alkoxy group. Further preferably, R ¹⁹ is an alkyl group having 3 to 5 carbon atoms, and R ²⁰ is an alkoxy group having 1 to 2 carbon atoms.

R ²¹ to R ^{22 are} preferably an alkyl group or an alkenyl group. In the case of accelerating the response speed, it is preferable that at least one is an alkenyl group. In the case of attaching importance to chemical reliability, it is preferable that both are alkyl groups. In the case of achieving a balance between response speed and reliability, It is preferable to use both a compound having only one alkenyl group and a compound having both alkyl groups.

It is preferable that at least one of R ²³ to R ²⁴ is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an alkenyl group having 4 to 5 carbon atoms. If the balance between response speed and Tni is required, at least one of R ²³ to R ²⁴ is preferably alkenyl. If the balance between response speed and solubility at low temperature is good, R ²³ to R ²⁴ is preferred. At least one of them is an alkoxy group.

It is preferable that at least one of R ²⁵ to R ²⁶ is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. When the response speed is important, at least one of R ²⁵ to R ²⁶ is preferably an alkenyl group. When a balance between response speed and solubility at low temperature is required, compounds in which all of R ²⁵ to R ²⁶ are alkyl groups, or compounds in which R ²⁵ is an alkyl group and R ²⁶ is an alkoxy group may be used. When an alkenyl group is used, R ²⁵ is preferably an alkenyl group, and in this case, R ²⁶ is an alkyl group. In particular, when the balance between response speed and solubility at low temperature is important, it is preferable to use a compound having an alkenyl group and a compound not having an alkenyl group in combination.

It is preferable that at least one of R ²⁷ to R ²⁸ is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. If a good balance between the response speed and Tni is required, at least one of R ²⁷ to R ²⁸ is preferably an alkenyl group. If a good balance between the response speed and solubility at low temperature is preferred, R ²⁷ to R ²⁸ is preferred. At least one of them is an alkoxy group. It is more preferred that R ²⁷ is alkyl or alkenyl and R ²⁸ is alkyl. It is also preferable 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 preferable that at least one of R ²⁹ to R ³⁰ is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 to 5 carbon atoms. If the balance between response speed and Tni is required to be good, at least one of R ²⁹ to R ³⁰ is preferably an alkenyl group. If good reliability is required, at least one of R ²⁹ to R ³⁰ is preferably an alkyl group. It is more preferred that R ²⁹ is alkyl or alkenyl and R ³⁰ is alkyl or alkenyl. And, R ²⁹ is alkyl and R ³⁰ is an alkenyl group is also preferred, R ²⁹ is an alkenyl group and R ³⁰ is an alkyl group are also preferred. Furthermore, it is also preferable that R ²⁹ is an alkyl group and R ³⁰ is an alkyl group.

The compound group represented by the general formula (II-a) to the general formula (II-f) preferably contains 1 to 10 kinds, particularly preferably 1 to 8 kinds, and the content thereof is preferably 5 to 80% by mass. , More preferably 10 to 75% by mass, and even more preferably 20 to 70% by mass.

In particular, in the case where a high-speed response is achieved by reducing γ1 of the liquid crystal composition, it is preferable to use one or two of the compound groups represented by the general formula (II-b) or (II-d). Above, it is more preferable to use two or more of the compound group represented by the general formula (II-b), and it is more preferable to use two or more of the compound group represented by the general formula (II-b) and further use (II -d) one or more of the compound groups. The content of the compound group represented by the general formula (II-b) or (II-d) is preferably 5 to 75% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 65% by mass.

In the case where the cell is narrowed to achieve high-speed response, it is preferred to use one or two or more of the compound group represented by the general formula (II-f), and the content is preferably 2 to 35 mass. %, More preferably 4 to 30% by mass, particularly preferably 6 to 25% by mass, and most preferably 6 to 20% by mass.

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

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

In the general formulae (III-a) to (III-f), when R ⁴¹ is a phenyl (aromatic) ring structure, the linear carbon number is preferably 1 to 5 Alkyl groups, linear alkoxy groups having 1 to 4 carbon atoms (or more), and alkenyl groups having 4 to 5 carbon atoms, and the ring structures to which they are bonded are cyclohexane, pyran, and two In the case of a saturated ring structure such as an alkane, a linear alkyl group having 1 to 5 carbon atoms, a linear alkyl group having 1 to 4 carbon atoms (or more), and a linear alkyl group are preferred. Alkenyl having 2 to 5 carbon atoms.

When good chemical stability to heat or light is valued, R ^{41 is} preferably an alkyl group. In addition, if it is important to produce a liquid crystal display element having a small viscosity and a fast response speed, R ^{41 is} preferably an alkenyl group. Furthermore, if the purpose is to reduce the viscosity, increase the nematic-homogeneous phase transition temperature (Tni), and further shorten the response speed, it is preferable to use an alkenyl group whose terminal is not unsaturated, and it is more preferably an alkenyl group. There is a methyl group at the end as a terminal. In addition, if good solubility at low temperature is important, as one of the solutions, R ^{41 is} preferably an alkoxy group. As another solution, 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 a carbon number of 2, 3, and 4 as R ⁴¹ is preferably used in combination, a compound having a carbon number of 3 and 5 is more preferably used in combination, and a combination of a carbon number of 3 and 3 is more preferable. Compounds of 4 and 5.

At least one of X ⁴¹ and X ^{42 is} preferably a fluorine atom, and further preferably, both of them are fluorine atoms.

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

As a combination of X ⁴¹ , X ^42, and Z ⁴¹ , one embodiment is X ⁴¹ = F, X ⁴² = F, and Z ⁴¹ = F. In other embodiments, X ⁴¹ = F, X ⁴² = H, and Z ⁴¹ = F. In another embodiment, X ⁴¹ = F, X ⁴² = H, and Z ⁴¹ = OCF ₃ . In another embodiment, X ⁴¹ = F, X ⁴² = F, and Z ⁴¹ = OCF ₃ . In another embodiment, X ⁴¹ = H, X ⁴² = H, and Z ⁴¹ = OCF ₃ .

At least one of X ⁴³ and X ^{44 is} preferably a fluorine atom. When both of them are fluorine atoms, it is preferable to obtain a large Δε. However, on the contrary, the solubility at low temperature becomes good. The situation is not good.

At least one of X ⁴⁵ and X ^{46 is} preferably a hydrogen atom, and more preferably, both of them are hydrogen atoms. From the standpoint of Tni, solubility at low temperature, or chemical stability when made into a liquid crystal display element, the use of a large amount of fluorine atoms is not satisfactory.

At least one of X ⁴⁷ and X ^{48 is} preferably a hydrogen atom, and more preferably, both of them are hydrogen atoms. In the case where at least one of X ⁴⁷ and X ⁴⁸ is a fluorine atom, it is not preferable from the viewpoints of Tni, solubility at low temperature, or chemical stability when forming a liquid crystal display element.

The compound selected from the compound group represented by the general formula (III-a) to the general formula (III-f) preferably contains 1 to 10 kinds, more preferably 1 to 8 kinds, and the content thereof is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.

The liquid crystal composition of the liquid crystal layer in the liquid crystal display device of the present invention is preferably Δε at 25 ° C. is +3.5 or more, and more preferably +3.5 to +15.0. In addition, Δn at 25 ° C is preferably 0.08 to 0.14, and more preferably 0.09 to 0.13. In more detail, when it is a thin cell gap, it is preferably 0.10 to 0.13, and when it is a thick cell gap, it is preferably 0.08 to 0.10. Η at 20 ° C is preferably 10 to 45 mPa‧s, more preferably 10 to 25 mPa‧s, and even more preferably 10 to 20 mPa‧s. T _{ni is} preferably 60 ° C. to 120 ° C., more preferably 70 ° C. to 100 ° C., and even more preferably 70 ° C. to 85 ° C.

The liquid crystal composition in the invention may contain a normal nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, and the like in addition to the aforementioned compounds.

In the liquid crystal composition of the present invention, in order to produce a liquid crystal display element such as a PS (Polymer Stabilized) mode, a transverse electric field type PSA (Polymer Stabilized Alignment) mode, or a transverse electric field type PSVA (Polymer Stabilized Vertical-Alignment) mode, it may contain a Or two or more polymerizable compounds. Examples of the polymerizable compound that can be used include photopolymerizable monomers that are polymerized by energy lines such as light. Examples of the structure include biphenyl derivatives and bitriphenyl derivatives having a plurality of six-membered ring linkages. Polymerizable compounds of the resulting liquid crystal skeleton. More specifically, it is preferably a difunctional monomer represented by the general formula (V),

(In the formula, 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 -(Where s represents an integer from 2 to 7, and an oxygen atom is bonded to an aromatic ring), 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 A bond, M ⁵¹ represents 1,4-phenylene, trans-1,4-cyclohexyl, or a single bond, and any hydrogen atom of all 1,4-phenylene in the formula may be substituted with a fluorine atom).

Preferably X ⁵¹ and X ⁵² each represents a hydrogen atom diacrylate derivative of, X ⁵¹ and X ⁵² each represents a person dimethacrylate derivative according to any one of methyl, also preferably represents one of a hydrogen The atom and the other represent a methyl compound. Regarding the polymerization speed of these compounds, the diacrylate derivative is the fastest, and the dimethacrylate derivative is slower. The asymmetric compound is in between, and a better aspect can be used according to its application. Among 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- . In the PSA display element, it is preferable that at least one of them is a single bond, and It is preferable that the compounds each represent a single bond or one represents a single bond and the other represents an alkylene group having 1 to 8 carbon atoms or -O- (CH ₂ ) _s- . In this case, an alkyl group of 1 to 4 is preferred, 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 single Bond, more preferably -COO-, -OCO- or a single bond, particularly preferably a single bond.

M ⁵¹ represents 1,4-phenylene, trans-1,4-cyclohexyl, or a single bond in which any hydrogen atom may be substituted with a fluorine atom, and preferably 1,4-phenylene or a single bond. When M ⁵¹ 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 represents a single bond, Z ^{51 is} preferably a single bond.

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

In the general formula (V), when M ⁵¹ represents a single bond and the ring structure is formed by two rings, the following formulas (Va-1) to (Va-5) are preferred, and the formula (Va) is more preferred -1) to the formula (Va-3), particularly preferably the expression (Va-1).

(Where both ends are bonded to Sp ¹ or Sp ² )

The alignment limiting force after polymerization of a polymerizable compound containing these skeletons is optimal for a PSA type liquid crystal display element, and a good alignment state can be obtained, so display unevenness is suppressed or display unevenness is not generated at all.

From the above, as the polymerizable compound, the general formula (V-1) to the general formula (V-4) are particularly preferable, and among them, the general formula (V-2) is the most preferable.

(In the formula, 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, polymerization can be performed even when no polymerization initiator is present, but it may contain a polymerization initiator to promote polymerization. Examples of the polymerization initiator include benzoin ethers, diphenyl ketones, acetophenones, benzyl ketals, and fluorenyl phosphine oxides.

The liquid crystal composition containing a polymerizable compound in the present invention is used to control the amount of transmitted light by utilizing the birefringence of the liquid crystal composition to impart liquid crystal alignment energy by polymerizing the polymerizable compound contained therein by ultraviolet irradiation. Liquid crystal display element. As liquid crystal display elements, AM-LCD (active matrix liquid crystal display element), TN (twisted nematic liquid crystal display element), STN-LCD (super twisted nematic liquid crystal display element), OCB-LCD and IPS-LCD ( Co-planar switching type liquid crystal display element), especially for AM-LCD, can be used for transmissive or reflective liquid crystal display elements.

(Color filter)

The color filter in the present invention is composed of a black matrix and at least three RGB pixel portions. As the color material, the RGB three-color pixel portion contains an average primary particle measured by a small-angle X-ray scattering method. Gallium, aluminum, scandium, yttrium, or indium phthalocyanine pigments with a diameter of 5 to 50 nm are used as G colorants. The RGB three-color pixel portion is preferably such that the R pixel portion contains a diketopyrrolopyrrole pigment and / or an anionic red organic dye, and the B pixel portion contains an ε-type copper phthalocyanine pigment and / or a cationic blue organic material. Dyes are used as colorants.

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

In addition, the normalized dispersion which indicates the particle size distribution measured by the small-angle X-ray scattering method can be calculated by a method described in Japanese Patent Application Laid-Open No. 2013-96944, and is preferably 20 to 50%. In addition, the smaller the value of the standardized dispersion, the sharper the particle size distribution is, the better it is. If it exceeds 50%, coarse particles will increase, which will appear on the surface of the color filter, which will reduce the voltage holding ratio (VHR) of the liquid crystal layer, resulting in an increase in ion density (ID), whitening, and uneven alignment. , Afterimages, and other poor display problems.

(G pixel section)

Examples of the gallium, aluminum, scandium, yttrium, or indium phthalocyanine pigment in the G pixel portion include a pigment represented by the following general formula (PIG-1) or a pigment represented by the following general formula (PIG-2). The phthalocyanine pigments conforming to the general formula (PIG-1) or the general formula (PIG-2) can be used alone, and multiple pigments conforming to the general formula (PIG-1) can also be used. -2) For the pigment, both the pigment according to the general formula (PIG-1) and the pigment according to the general formula (PIG-2) can be used.

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

In (Formula ^{(PIG-2), X 17i} ~ X 32i each independently represent a halogen atom, a nitro group, may also have phthalimide (PEI) methyl substituent, the substituent may also have an amine group of the sulfonylureas Group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may also have a substituent, An aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may also have a substituent. M represents a member selected from the group consisting of Ga, Al, Sc, Y, and In. Trivalent metal. Y ²ⁱ represents, -O-, -O-SiR6R7-O-, -O-SiR6R7-O-SiR8R9-O-, or -OP (= O) R10-O-, and R6 ~ R10 are each independently Represents a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may also have a substituent).

In the general formula (PIG-1) and general formula (PIG-2), as the phthalimide imine methyl group which may have a substituent, specifically, phthalimide imine methyl Methyl, 3-chlorophthalimide methyl, 4-chlorophthalimide methyl, 3-nitrophthalimide methyl, 4-nitrophthalimide methyl Fluorenimine methyl, 3-sulfonyl phthalimidomethyl, 4-sulfonyl phthalimidomethyl, and the like.

In the general formula (PIG-1) and general formula (PIG-2), examples of the aminesulfonyl group which may have a substituent include dimethylaminomethylsulfonylamine and diethylamine Methylsulfonamido, dimethylaminoethylsulfoamido, diethylaminoethylsulfoamido, dimethylaminopropylsulfoamido, diethylaminopropyl Sulfoamido and the like.

In the general formula (PIG-1) and general formula (PIG-2), the alkyl group is more preferably an alkyl group having 1 to 8 carbon atoms, and more specifically, methyl, ethyl, Unsubstituted alkyl such as propyl, isopropyl, butyl, isobutyl, second butyl, pentyl, hexyl, 2-ethylhexyl; 2-methoxyethyl, 2-ethoxy Alkoxyalkyl groups such as ethyl; alkoxyalkyl groups such as 2-ethoxyethyl; cyanoalkyl groups such as 2-cyanoethyl; 2,2,2-trifluoroethyl, 4,4, Fluoroalkyl and the like such as 4-trifluorobutyl. When the alkyl group has a substituent, examples include trichloromethyl, 2,2-dibromoethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, and 4-tert-butyl. Benzyl, 4-methoxybenzyl, 4-nitrobenzyl, 2,4-dichlorobenzyl and the like.

In the general formula (PIG-1) and general formula (PIG-2), examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group. When the aryl group has a substituent, examples include chlorophenyl, bromophenyl, tolyl, nitrophenyl, methoxyphenyl, 2,4-dichlorophenyl, and pentafluorophenyl. , 2-methyl-4-chlorophenyl, 2-aminophenyl, 4-hydroxy-1-naphthyl, 6-methyl-2-naphthyl, 4,5,8-trichloro-2-naphthalene Group, anthraquinone group, 2-aminoanthraquinone group, and the like.

In the general formula (PIG-1) and general formula (PIG-2), examples of the cycloalkyl group which may have a substituent include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and adamantane. Examples of the "cycloalkyl group having a substituent" include cyclohexylmethyl, cyclohexylethyl, 2,5-dimethylcyclopentyl, 4-thirdbutylcyclohexyl, and the like.

In the general formula (PIG-1) and general formula (PIG-2), the heterocyclic group which may have a substituent is preferably an aromatic or fat containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples of the heterocyclic group include thienyl group, benzo [b] thienyl group, and naphtho [2,3-b] thienyl group. [2,3-b] thienyl group), thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group, benzopiperanyl ( chromenyl group), Base (xanthenyl group), brown Phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyridine (Pyrazinyl group), pyrimidyl group (pyrimidinyl group), (Pyridazinyl group), indole (Indolizinyl group), isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purine group ( purinyl group), 4H-quine (4H-quinolizinyl group), isoquinolyl group, quinolyl group, fluorene (Phthalazinyl group), Naphthyridinyl group, quinine Quinoxalinyl group, quinazolinyl group, Cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, morphinyl (phenanthridinyl group), acridinyl group (acridinyl group), Perimidinyl group, phenanthrolinyl group, (Phenazinyl group), morphine (Phenarsazinyl group), isothiazolyl group, phenothiazine Base (phenothiazinyl group), iso Isoxazolyl group, furazanyl group, brown (Phenoxazinyl group), isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl (imidazolidinyl group), imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperidyl Piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and thioxantholyl group) 基 等.

In the general formula (PIG-1) and general formula (PIG-2), as the alkoxy group which may have a substituent, an alkoxy group having 1 to 8 carbon atoms is more preferable, and more specifically, Examples: methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, second butoxy, third butoxy, trichloromethoxy, trifluoromethoxy, 2, 2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 2,2-ditrifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethyl Oxy, 2-nitropropoxy, benzyloxy and the like.

In the general formula (PIG-1) and general formula (PIG-2), examples of the aryloxy group which may have a substituent include a phenoxy group, a naphthyloxy group, an anthracenyloxy group, and a 3-tert-butyl group. Phenylphenoxy, 2,4-di-tert-butylphenoxy, p-methylphenoxy, p-nitrophenoxy, p-methoxyphenoxy, 2,4-dichlorophenoxy, Pentafluorophenoxy, 2-methyl-4-chlorophenoxy, etc.

In the general formula (PIG-1) and general formula (PIG-2), examples of the alkylthio group which may have a substituent include methylthio, ethylthio, propylthio, butylthio, and pentyl. Thio, hexylthio, heptylthio, decylthio, dodecylthio, octadecylthio, methoxyethylthio, aminoethylthio, benzylaminoethylthio, methyl Carbonylaminoethylthio, phenylcarbonylaminoethylthio, and the like.

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

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

^(1k, n 1k 1l in the n ^1l and is an integer of 1 to 16)

Specific examples of the metal phthalocyanine pigment represented by the general formula (PIG-2) include the compounds described below, but the present invention is not limited to these as long as it does not exceed the gist thereof.

(N ^2g1 and n ^2g2 in the general formula (2g) are each independently an integer of 1 to 16).

The G pixel portion preferably contains a pigment derivative as a dispersion aid. The pigment derivative preferably contains at least one of a phthalocyanine pigment derivative and a quinoline yellow pigment derivative. Derivatives include phthalimidomethyl, sulfonic acid, iso-N- (dialkylamino) methyl, and iso-N- (dialkylaminoalkyl) sulfoamido . These derivatives may be used in combination of two or more different kinds.

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

Further, in terms of hue adjustment, it is also preferable that the G pixel portion contains one or more pigments selected from the group consisting of a quinoline yellow compound represented by the general formula (3), the general formula (4), and the general formula (5).

(In the general formulae (3) to (5), R ₁₀ to R ₂₄ , R ₂₅ to R ₃₉ , and R ₄₀ to R ₅₅ each independently represent a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent. , Alkoxy groups which may have a substituent, aryl groups which may also have a substituent, -SO ₃ H group, -COOH group, -SO ₃ H group or -COOH group monovalent to trivalent metal salt; Ammonium salt, phthalimidoimide methyl group which may have a substituent, or sulfamoyl group which may also have a substituent).

In the general formulae (3) to (5), R ₁₀ to R ₂₄ , R ₂₅ to R ₃₉ , and R ₄₀ to R _{55 are} preferably each independently a hydrogen atom, a halogen atom, or a substituent which may have a substituent. Alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms which may have a substituent, aryl group having 1 to 4 carbon atoms which may have a substituent, -SO ₃ H group,- A monovalent to trivalent metal salt of a COOH group, -SO ₃ H group, or -COOH group; an alkylammonium salt, an phthalimidoimide methyl group which may have a substituent, or a Examples of the sulfamoyl group include a dimethylaminopropylaminosulfonyl group and a diethylaminopropylaminosulfonyl group.

Specific examples of the quinoline yellow pigments represented by the general formula (3), the general formula (4), and the general formula (5) include the following formulae (3a) to (5a) Compounds, but the present invention is not limited to them as long as the gist thereof is not exceeded.

(R pixel section)

The R pixel portion preferably contains a diketopyrrolopyrrole pigment and / or an anionic red organic dye. The diketopyrrolopyrrole pigment is specifically selected from 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 Brominated One or two or more of diketopyrrolopyrrole, more preferably one or two or more selected from CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, and CI Pigment Red 272, particularly preferably CI Pigment Red 254. As an anionic red organic dye, one or two or more selected from C.I. Solvent Red 124, Acid Red 52, and Acid Red 289 are particularly preferable, and C.I. Solvent Red 124 is particularly preferable.

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

The amount of the pigment derivative used is preferably 4 parts or more and 20 parts or less, more preferably 6 parts or more and 16 parts with respect to 100 parts of the diketopyrrolopyrrole-based red pigment and / or the anionic red organic dye. the following.

(B pixel section)

It is preferable that the ε-type phthalocyanine pigment or the cationic blue organic dye is contained in the B pixel portion. The ε-type phthalocyanine pigment is preferably Pigment Blue 15: 6, and the cationic blue organic dye is preferably one containing a triarylmethane dye or a triarylmethane lake pigment.

The triarylmethane lake pigment is preferably a triarylmethane lake pigment represented by the following general formula (6).

(In the general formula (6), R ^11j to R ^16j each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbons which may have a substituent, or an aryl group having 1 to 8 carbons which may have a substituent. When R ^11j to R ^16j represent an alkyl group which may have a substituent, adjacent R ^11j and R ^12j , R ^13j and R ^14j , R ^15j and R ^16j may be bonded to form a ring structure. X ^11j and X ^12j each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms which may have a substituent. Z ^- is selected from (P ₂ Mo _y W _18-y O ₆₂ ) ^6- / 6 Heteropolyoxometalate anion represented by an integer of y = 0, 1, 2 or 3, or heteropolyoxometalate anion as (SiMoW ₁₁ O ₄₀ ) ^4- / 4, or missing Dawson-type phosphorus tungsten At least one of the acid heteropolyoxometalate anions. When a plurality of formula (1) is contained in one molecule, these may have the same structure or different structures).

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

In the general formula (6), when adjacent R (R represents any of R ^11j to R ^16j ) is bonded to form a ring, these may be a ring cross-linked by a hetero atom. Specific examples of the ring include the following. These rings may also have a substituent.

In terms of chemical stability, in the general formula (6), it is preferable that R ^11j to R ^16j are each independently a hydrogen atom, an alkyl group which may have a substituent, or an alkyl group which may also have a substituent. Aryl.

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

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

[Substituent Group Y]

Methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl Alkyl groups such as alkyl, 2-ethylhexyl; aryl groups such as phenyl and naphthyl; halogen atoms such as fluorine and chlorine atoms; cyano; hydroxyl; methoxy, ethoxy, propoxy, butoxy, etc. Alkoxy groups having 1 to 8 carbon atoms; amino groups, diethylamino groups, dibutylamino groups, ethylamino groups, and the like may also have substituents; ethylamino groups, benzamidine groups, etc. Fluorenyl; fluorenyl, such as ethynyl, benzyl, and the like.

In the general formula (6), R ^11j to R ^{16j is more} preferably an alkyl group having 1 to 8 carbon atoms which may have a substituent. More specifically, methyl, ethyl, and propyl are listed. Unsubstituted alkyl groups such as alkyl, isopropyl, butyl, isobutyl, second butyl, pentyl, hexyl, 2-ethylhexyl; 2-methoxyethyl, 2-ethoxyethyl Alkoxyalkyl groups such as alkyl; alkoxyalkyl groups such as 2-ethoxyethyl; cyanoalkyl groups such as 2-cyanoethyl; 2,2,2-trifluoroethyl, 4,4,4 -A fluoroalkyl group such as trifluorobutyl.

In the case where X ^11j and X ^12j are the aforementioned alkyl groups in the general formula (6), they may further have arbitrary substituents. Examples of such substituents include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; and alkoxy groups such as a methoxy group, an ethoxy group, and a propoxy group. Specifically, examples of X ^11j and X ^12j include haloalkyl groups such as fluoromethyl, trifluoromethyl, trichloromethyl, and 2,2,2-trifluoroethyl; and alkyl groups such as methoxymethyl. Oxyalkyl, etc.

In the general formula (6), as X ^11j and X ^12j , a hydrogen atom, a methyl group, a chlorine atom, or a trifluoromethyl group is preferably a substituent having an appropriate steric hindrance to the extent that it does not affect the twist. In terms of color tone and heat resistance, X ^11j and X ^{12j are} preferably a hydrogen atom, a methyl group, or a chlorine atom.

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

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

In the above-mentioned RGB three-color pixel portion, as the colorant, CI solvent red 124 is preferably contained in the R pixel portion, gallium or aluminum phthalocyanine is contained in the G pixel portion, and pigment blue 15: 6 is contained in the B pixel portion. Contained in R pixel portion and / or B pixel portion Compound.

As Specific examples of the compound include, for example, compounds represented by the following general formula (7a) to general formula (7b), but the present invention is not limited to these as long as the subject matter is not exceeded.

(In the general formulae (7a) to (7b), R ^a represents a dodecyl group, R ^b represents a 2-ethylhexyl group, and R ^c represents a 2-ethylhexyl group).

In the above-mentioned RGB three-color pixel portion, it is preferable that the R pixel portion further contains a pigment selected from the group consisting of CI Pigment Red 177, CI Pigment Red 242, CI Pigment Red 166, CI Pigment Red 167, CI Pigment Red 179, and CI Pigment. Red 269, CI Pigment Orange 38, CI Pigment Orange 71, CI Pigment Yellow 150, CI Pigment Yellow 215, CI Pigment Yellow 185, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Acid Red 52, Basic Red 1, CI Solvent Red 89, CI solvent orange 56, CI solvent yellow 21, CI solvent yellow 82, CI solvent yellow 83: 1, CI solvent yellow 33 and CI solvent yellow 162, at least one organic dye pigment in the group.

In the above-mentioned RGB three-color pixel portion, it is preferable that the G pixel portion further contains a material selected from CI Pigment Yellow 150, CI Pigment Yellow 215, CI Pigment Yellow 185, CI Pigment Yellow 138, CI Solvent Yellow 21, and CI Solvent. Yellow 82, CI Solvent Yellow 83: 1, and CI Solvent Yellow 33, at least one organic dye pigment.

In the above RGB three-color pixel portion, it is preferable that the B pixel portion further contains a material selected from the group consisting of CI Pigment Violet 23, CI Basic Violet 10, CI Acid Blue 1, CI Acid Blue 90, CI Acid Blue 83, CI. Direct Blue 86, CI Pigment Blue 15, CI Pigment Blue 15: 1, CI Pigment Blue 15: 2, CI Pigment Blue 15: 3, and CI Pigment Blue 15: 4C.I. At least one organic group Dyes and pigments.

It is also preferable that the color filter is composed of a black matrix, RGB three-color pixel portions, and a Y pixel portion, and the Y pixel portion contains, as a colorant, selected from the group consisting of CI Pigment Yellow 150, CI Pigment Yellow 215, and CI Pigment Yellow. 185, CI pigment yellow 138, CI pigment yellow 139, CI solvent yellow 21, 82, CI solvent yellow 83: 1, CI solvent yellow 33 and CI solvent yellow 162, at least one yellow organic dye pigment in the group.

From the viewpoint of preventing a decrease in the voltage holding ratio (VHR) and an increase in the ion density (ID) of the liquid crystal layer and suppressing problems such as whitening, uneven alignment, and afterimages, the color filter in the present invention The chromaticity x and chromaticity y of each pixel portion 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, and more preferably The chromaticity x is 0.58 to 0.69, and the chromaticity y is 0.30 to 0.36, and more preferably the chromaticity x is 0.62 to 0.68, and the chromaticity y is 0.31 to 0.35.

The chromaticity x of the G pixel portion in the XYZ color system under the C light source is preferably 0.19 to 0.35, more preferably 0.20 to 0.29, and the chromaticity y is preferably 0.54 to 0.76, more preferably 0.64 to 0.74, and more preferably The chromaticity x is 0.19 to 0.35, and the chromaticity y is 0.54 to 0.76, and the chromaticity x is 0.20 to 0.29, and the chromaticity y is 0.64 to 0.74.

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

The chromaticity x 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, and more preferably The chromaticity x is 0.46 to 0.50 and the chromaticity y is 0.48 to 0.53, and 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 color system recognized by the CIE (International Commission for Illumination) as a standard color system in 1931.

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

The color filter can be formed into a color filter pixel portion by a conventionally known method. A typical method for forming a pixel portion is a photolithography method, which is a method in which the following photocurable composition is applied to a surface of a transparent substrate for a color filter on the side provided with a black matrix. After heating and drying (pre-baking), the substrate is irradiated with ultraviolet rays through a photomask to perform pattern exposure, thereby curing the photo-curable compound at a portion corresponding to the pixel portion, and then developing the unexposed portion using a developing solution. Except for the pixel portion, the pixel portion is fixed on a transparent substrate. By this method, a pixel portion made of a cured colored film of a photocurable composition is formed on a transparent substrate.

For pixels of other colors such as R pixels, G pixels, B pixels, and Y pixels as needed, the following photo-hardenable compositions can be prepared one by one and the above operations are repeated to manufacture R pixels and G pixels at predetermined positions. Color filters for colored pixel sections of, B, and Y pixels.

Examples of a method for applying the following photocurable composition to a transparent substrate such as glass include a spin coating method, a slit coating method, a roll coating method, and an inkjet method.

The drying conditions of the coating film of the photocurable composition applied on the transparent substrate also vary according to the type of each component, the blending ratio, etc., and it is usually dried at 50 to 150 ° C for about 1 to 15 minutes. In addition, as the light for light curing of the photocurable composition, it is preferable to use ultraviolet rays or visible light in a wavelength range of 200 to 500 nm. Various light sources that emit light in this wavelength range can be used.

Examples of the development method include a puddle method, a dipping method, and a spray method. After the photocurable composition is exposed and developed, the transparent substrate on which the pixel portion having the necessary color is formed is washed with water and dried. The color filter thus obtained is subjected to a heating treatment (post-baking) at a temperature of 90 to 280 ° C for a predetermined time by a heating device such as a hot plate and an oven, thereby removing volatile components from the colored coating film and simultaneously The unreacted photocurable compound remaining in the cured colored film of the photocurable composition is thermally cured to complete a color filter.

By using the color filter material of the present invention and the liquid crystal composition of the present invention, it is possible to prevent a decrease in voltage retention (VHR) and an increase in ion density (ID) of the liquid crystal layer, and solve the problem of anti-whitening and alignment Liquid crystal display device having poor display problems such as uniformity and afterimage.

As a method for producing the above-mentioned photocurable composition, a method is generally used in which the pigment composition for a color filter of the present invention, an organic solvent, and a dispersant are used as essential components, and these are mixed and dispersed with stirring to change To obtain uniformity, first prepare a pigment dispersion liquid for forming a pixel portion of a color filter, and then add a photocurable compound, and optionally a thermoplastic resin or a photopolymerization initiator to the above-mentioned photohardenability.组合 物。 Composition.

Examples of the organic solvent used here include aromatic solvents such as toluene, xylene, and methoxybenzene; ethyl acetate, propyl acetate or butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol mono Acetic acid ester solvents such as diethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol butyl ether acetate; Propionate solvents such as ethoxyethyl propionate; Alcohol solvents such as methanol and ethanol; Ether solvents such as butylcellulose, propylene glycol monomethyl ether, diethylene glycol ether, and diethylene glycol dimethyl ether ; Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; aliphatic hydrocarbon solvents such as hexane; N, N-dimethylformamide, γ-butyrolactam, N -Methyl-2-pyrrolidone, aniline, pyridine and other nitrogen compound solvents; γ-butyrolactone and other lactone solvents; such as a 48:52 amine mixture of methyl carbamate and ethyl carbamate Carbamate, etc.

Examples of the dispersant used herein include: Disperbyk 130, Disperbyk 161, Disperbyk 162, Disperbyk 163, Disperbyk 170, Disperbyk 171, Disperbyk 174, Disperbyk 180, Disperbyk 182, Disperbyk 183, Disperbyk 184, BYK-Chemie Disperbyk 185, Disperbyk 2000, Disperbyk 2001, Disperbyk 2020, Disperbyk 2050, Disperbyk 2070, Disperbyk 2096, Disperbyk 2150, Disperbyk LPN21116, Disperbyk LPN6919, Lubrizol's Solsperse 3000, Solsperse 9000, Solsperse 13 13240 , 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 41000, Solsperse 54000, Solsperse 71000, Ajisper PB711, Ajisper PB821, Ajisper PB822, Ajisper PB814, Ajisper PN411, Ajisper of Ajinomoto Co., Ltd. Dispersants such as PA111, or natural rosins such as acrylic resins, urethane resins, alkyd resins, wood rosin, rosin gum, tall oil rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin Modified rosin, such as oxidized rosin, malay rosin, rosin amine, lime rosin, rosin alkylene oxide adduct, rosin alkyd adduct, rosin modified phenol and other rosin derivatives at room temperature It is a liquid and water-insoluble synthetic resin. The addition of these dispersants or resins also helps to reduce floculation, improve the dispersion stability of the pigment, and improve the viscosity characteristics of the dispersion.

In addition, as a dispersing aid, organic pigment derivatives such as phthalimide methyl derivatives, organic pigment derivatives of sulfonic acid derivatives, and organic pigment derivatives of N- (dialkylamine) may be contained. Methyl) derivatives, N- (dialkylaminoalkyl) sulfonamide derivatives of organic pigment derivatives, and the like. Of course, these derivatives may be used in combination of two or more different kinds.

Examples of the thermoplastic resin used for the preparation of the photocurable composition include amine ester resins, acrylic resins, polyamido resins, polyamido resins, styrene maleic acid resins, Styrene maleic anhydride resin and the like.

Examples of the photocurable compound include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, and bis (acrylic acid) Ethoxy) Bifunctional monomers such as bisphenol A, 3-methylpentanediol diacrylate, trimethylolpropane triacrylate, neopentaerythritol triacrylate, isocyanurate tri [2 -(Meth) acryloxyethyl] ester, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and other relatively small molecular weight polyfunctional monomers, such as polyester acrylate, polyacrylic acid Polyfunctional monomers having relatively large molecular weights such as amine esters and polyether acrylates.

Examples of the photopolymerization initiator include acetophenone, diphenyl ketone, benzyl dimethyl ketal, benzamidine peroxide, and 2-chloro-9-oxysulfur. , 1,3-bis (4'-azidobenzylidene) -2-propane, 1,3-bis (4'-azidobenzylidene) -2-propane-2'-sulfonic acid, 4 , 4'-diazide stilbene-2,2'-disulfonic acid and the like. Examples of commercially available photopolymerization initiators include "Irgacure (trade name) -184", "Irgacure (trade name) -369", "Darocure (trade name) -1173", manufactured by BASF Corporation), and "Lucirin-TPO", "Kayacure (trade name) DETX" manufactured by Nippon Kayaku Co., Ltd., "Kayacure (trade name) OA", "Vicure 10", "Vicure 55" manufactured by Stouffer, "Trigonal" manufactured by AKZO "PI", "Sandoray 1000" manufactured by Sandoz, "DEAP" manufactured by Upjohn, "Biimidazole" manufactured by Black Gold Chemical Co., etc.

A known and commonly used photosensitizer may be used in combination with the photopolymerization initiator. Examples of the photosensitizer include amines, ureas, compounds having a sulfur atom, compounds having a phosphorus atom, compounds having a chlorine atom, or nitriles or other compounds having a nitrogen atom. These may be used alone or in combination of two or more.

The blending ratio of the photopolymerization initiator is not particularly limited, and it is preferably in the range of 0.1 to 30% based on the mass basis with respect to the compound having a photopolymerizable or photocurable functional group. If it is less than 0.1%, the photosensitivity tends to decrease during photo-hardening. If it exceeds 30%, when the coating film of the pigment-dispersed photoresist is dried, crystals of the photopolymerization initiator are precipitated, causing coating Deterioration of film physical properties.

Using each of the materials described above, 300 to 1,000 parts of the organic solvent and 1 to 100 parts of the dispersant are stirred and dispersed with respect to each 100 parts of the pigment composition for a color filter of the present invention on a mass basis in a uniform manner. Parts, and the above-mentioned dye pigment liquid can be obtained. Next, in this pigment dispersion liquid, a thermoplastic resin and a photocurable compound in a total amount of 3 to 20 parts are added for each part of the pigment composition for a color filter of the present invention, and 1 part, adding 0.05 to 3 parts of a photopolymerization initiator, and further adding an organic solvent as needed, and stirring and dispersing to make it uniform, thereby obtaining a photocurable composition for forming a pixel portion of a color filter.

As the developing solution, a known and commonly used organic solvent or an alkaline aqueous solution can be used. In particular, when a thermoplastic resin or a photocurable compound is contained in the photocurable composition, and at least one of them has an acid value and is alkali-soluble, the color filter pixels are washed with an alkaline aqueous solution. The formation of parts is more effective.

The manufacturing method of the color filter pixel portion using 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 can also be processed by other plating methods. , A transfer method, a cell electrolysis method, a PVED (Photovoltaic Electrodeposition) method, an inkjet method, a reverse printing method, a thermosetting method, and the like to form pixel units of various colors to produce a color filter.

An organic pigment can be coated on a substrate and dried to form a color filter. When a pigment dispersion contains a curable resin, it can be hardened by heat or active energy rays. Thereby, a color filter is formed. In addition, the following steps may be performed: by using a heating device such as a hot plate and an oven, heat treatment (post-baking) is performed at 100 to 280 ° C for a predetermined time, thereby removing volatile components in the coating film.

(Alignment film)

In the liquid crystal display device of the present invention, in order to align the liquid crystal composition on the surface where the first substrate and the liquid crystal composition on the second substrate are in contact, the alignment film is disposed in a color filter in a liquid crystal display device requiring an alignment film. The thickness of the alignment film between the light sheet and the liquid crystal layer is even less than 100 nm and is relatively thin, which does not completely block the interaction between the pigments such as pigments constituting the color filter and the liquid crystal compounds constituting the liquid crystal layer.

Further, in a liquid crystal display device without using an alignment film, the interaction between a pigment such as a pigment constituting a color filter and a liquid crystal compound constituting a liquid crystal layer becomes larger.

As the alignment film material, transparent organic materials such as polyimide, polyimide, BCB (benzocyclobutene, benzocyclobutene polymer), and polyvinyl alcohol can be used. Particularly preferably, p-phenylenediamine, 4,4 '-Diamino diphenylmethane and other aliphatic or alicyclic diamines and other diamines, butane tetracarboxylic anhydride and 2,3,5-tricarboxycyclopentyl acetic anhydride and other aliphatic or alicyclic four Polyimide alignment film formed by polyimide acid synthesized from aromatic tetracarboxylic anhydrides such as carboxylic anhydride, pyromellitic dianhydride, and the like. In this case, the rubbing method is generally used for the alignment application method, and it can also be used without providing alignment when it is used in the case of a vertical alignment film or the like.

As the alignment film material, chalcone, cinnamate, a material containing a cinnamyl group or an azo group in the compound, or a combination with materials such as polyimide, polyimide, etc. may be used in this case. , The alignment film can use friction, and can also use light alignment technology.

The alignment film is usually formed by coating the above-mentioned alignment film material on a substrate by a method such as a spin coating method to form a resin film. A uniaxial stretching method, a Langmuir-Blodgett method, or the like may also be used.

(Transparent electrode)

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

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

The liquid crystal display device is combined with a backlight to be used in various applications such as an LCD television, a monitor of a personal computer, a display of a mobile phone, a smart phone, a notebook personal computer, a personal digital assistant, and a digital signage. As the backlight source, there are a cold-cathode tube-type backlight source, an analog white backlight source using a two-wavelength peak of a light-emitting diode using an inorganic material or an organic EL element, and a backlight source having a three-wavelength peak.

[Example]

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to these examples. In addition, "%" in the composition of the following examples and comparative examples means "mass%."

In the examples, the characteristics measured are as follows.

T _ni : nematic phase-homogeneous liquid phase transition temperature (° C)

△ n: refractive index anisotropy at 25 ° C

△ ε: Dielectric anisotropy at 25 ° C

η: viscosity at 20 ° C (mPa‧s)

γ1: Rotary viscosity at 25 ° C (mPa‧s)

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

(The liquid crystal composition will be injected into a cell with a cell thickness of 3.5 μm, and the ratio of the measured voltage to the initial applied voltage when measuring under the conditions of 5 V voltage, 200 ms frame time, and 64 μs pulse width will be expressed in%. )

ID: ion density at 70 ° C (pC / cm ² )

(Ion density value when a liquid crystal composition is injected into a cell having a cell thickness of 3.5 μm and measured by MTR-1 (manufactured by Toyo Technology Co., Ltd.) under a condition of applying a voltage of 20 V and a frequency of 0.05 Hz)

Afterimage:

The residual image evaluation of the liquid crystal display element is performed after a predetermined fixed pattern is displayed in the display area for 1000 hours, and the residual image of the fixed pattern is uniformly evaluated when the entire screen is uniformly displayed according to the following 4 levels.

◎ No afterimage

○ There are very few afterimages, which is an allowable level

△ There is an afterimage, which is an unacceptable level

× Afterimages exist, very poor

In the examples, the following symbols are used to describe the compounds.

(Ring structure)

(Side chain structure and connection structure)

[Production of color filters]

[Preparation of coloring composition]

[Green pigment coloring composition 1]

4.8 parts of the gallium phthalocyanine pigment of the general formula (1a) having an average primary particle size of 25 nm and a standardized dispersibility of 40% obtained by the small-angle X-ray scattering method 1, an average primary particle size of 30 nm and standardized dispersibility 47% of 40% yellow pigment 1 (CI Pigment Yellow 138), 5 parts of yellow 138 sulfonic acid derivative, 7.0 parts of Disperbyk LPN6919 (manufactured by BYK-Chemie Co., Ltd.) was added to a polymer container, and propylene glycol monomethyl ether was added 55 parts of acetate, 0.3-0.4mm manufactured by Saint-Gobain The zirconia beads "ER-120S" were dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, and then filtered through a 5 μm filter to obtain a pigment coloring solution.

75.00 parts of the pigment coloring solution and 5.50 parts of polyester acrylate resin (ARONIX (trade name) M7100, manufactured by Toa Synthetic Chemical Industry Co., Ltd.) and dipentaerythritol hexaacrylate (KAYARAD (trade name)) using a dispersion mixer. DPHA, manufactured by Nippon Kayaku Co., Ltd.) 5.00 parts, diphenyl ketone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.) 1.00 parts, UCAR ESTER EEP 13.5 parts were stirred, and the pore diameter was 1.0 The filter of μm was filtered to obtain green pigment colored composition 1.

Furthermore, in the examples of the present invention, the average primary particle size and particle size distribution of the organic pigments are the small-angle X-ray scattering of the organic pigment dispersion by the small-angle X-ray scattering method according to Japanese Patent Application Laid-Open No. 2006-113042. The spectrum (measurement of the scattering spectrum) was obtained. The normalized dispersion of the particle size distribution obtained by the small-angle X-ray scattering method is calculated using a method described in Japanese Patent Application Laid-Open No. 2013-96944.

[Green pigment coloring composition 2]

4.5 parts of the aluminum phthalocyanine pigment of the above-mentioned general formula (1b) having an average primary particle diameter of 40 nm and standardized dispersion of 50% and 2,3 parts of the copper phthalocyanine sulfonic acid derivative were used instead of 4.8 parts of the green pigment coloring composition. The gallium phthalocyanine pigment of 1 was replaced with the yellow pigment 1 (CI pigment yellow 138) by using a quinoline yellow pigment of the above general formula (3a) having an average primary particle diameter of 30 nm and a standardized dispersibility of 40%. Green pigment coloring composition 2.

[Green pigment coloring composition 3]

4.5 parts of an aluminum phthalocyanine pigment having an average primary particle diameter of 20 nm, a standardized dispersibility of 35% of the above general formula (11), and an average number of bromine substituents of 8 and 3 parts of copper phthalocyanine sulfonic acid derivatives were used to replace 4.8 Parts of the gallium phthalocyanine pigment of the above-mentioned green pigment coloring composition 1, using 20 parts of the quinoline yellow pigment of the general formula (3a) having an average primary particle diameter of 30 nm and a standardized dispersibility of 40% instead of the yellow pigment 1 (CI pigment Yellow 138) 47 parts, and the green pigment coloring composition 3 was obtained in the same manner as described above.

[Green pigment coloring composition 4]

4.5 parts of an aluminum phthalocyanine pigment with a mixture of the above-mentioned general formula (1b) / (2a) = 95/5 with an average primary particle size of 25 nm and a standardized dispersibility of 45%, and 0.3 parts of a copper phthalocyanine sulfonic acid derivative In place of 4.8 parts of the gallium phthalocyanine pigment of the above-mentioned green pigment coloring composition 1, the yellow pigment 1 (CI Pigment Yellow 138) was replaced with a quinoline yellow pigment having a compound (4a) having an average primary particle diameter of 20 nm and a standardized dispersion of 35%. ), A green pigment coloring composition 4 was obtained in the same manner as described above.

[Green pigment coloring composition 5]

4.5 parts of the following aluminum phthalocyanine pigment 5, and 0.3 parts of copper phthalocyanine sulfonic acid derivative were used instead of 4.8 parts of the gallium phthalocyanine pigment of the green pigment coloring composition 1, and the aluminum phthalocyanine pigment 5 is an average primary particle size. Aluminum phthalocyanine pigment of 30 nm, standardized dispersion of 50%, and the above general formula (11) and an average number of bromine substituents of 8 / (2g) and an average number of bromine substituents of 8 = 97 / A mixture of 3; 47 parts of yellow pigment 1 (CI Pigment Yellow 138) was replaced with 20 parts of a quinoline yellow pigment having an average primary particle diameter of 20 nm and a standardized dispersion of 35% (4a) in the same manner as above A green pigment coloring composition 5 was obtained.

[Green pigment coloring composition 6]

4.8 parts of the gallium phthalocyanine pigment of the above-mentioned green pigment coloring composition 1 was replaced with 4.8 parts of the aluminum phthalocyanine pigment 6 of the above-mentioned general formula (1b) having an average primary particle size of 55 nm and standardized dispersibility of 65% to be the same as above. In this way, a green pigment coloring composition 6 was obtained.

[Red pigment coloring composition 1]

10 parts of Red Pigment 1 (CI Pigment Red 254) with an average primary particle size of 25 nm and a standardized dispersion of 40%, obtained by small-angle X-ray scattering method, were added to a polymer container, and propylene glycol monomethyl ether acetate 55 parts, Disperbyk LPN21116 (manufactured by BYK-Chemie Co., Ltd.) 7.0 parts, 0.3-0.4mm manufactured by Saint-Gobain The zirconia beads "ER-120S" were dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, and then filtered through a 1 μm filter to obtain a pigment coloring solution. 75.00 parts of the pigment coloring solution and 5.50 parts of polyester acrylate resin (ARONIX (trade name) M7100, manufactured by Toa Synthetic Chemical Industry Co., Ltd.) and dipentaerythritol hexaacrylate (KAYARAD (trade name)) using a dispersion mixer DPHA, manufactured by Nippon Kayaku Co., Ltd.) 5.00 parts, diphenyl ketone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.) 1.00 parts, UCAR ESTER EEP 13.5 parts were stirred, and the pore diameter was 1.0 A filter of μm was filtered to obtain a red pigment colored composition 1.

[Red pigment coloring composition 2]

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

[Blue pigment coloring composition 1]

1.80 parts of triarylmethane lake pigment (compound No. 2 in Table 1) represented by the general formula (6), 2.10 parts of BYK-2164 (manufactured by BYK-Chemie), and 11.10 parts of propylene glycol monomethyl ether acetate , 0.3-0.4mm The SEPR beads were put into a polymer container and dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours to obtain a pigment dispersion liquid. 75.00 parts of the pigment dispersion liquid and 5.50 parts of polyester acrylate resin (ARONIX (trade name) M7100, manufactured by Toa Synthetic Chemical Industry Co., Ltd.), dipentaerythritol hexaacrylate (KAYARAD (trade name)) using a dispersion mixer. DPHA, manufactured by Nippon Kayaku Co., Ltd.) 5.00 parts, diphenyl ketone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.) 1.00 parts, UCAR ESTER EEP (Union Carbide company) 13.5 parts The mixture was stirred and filtered through a filter having a pore size of 1.0 μm to obtain a blue pigment colored composition 1.

[Blue pigment coloring composition 2]

1.80 parts of a blue pigment (CI Pigment Blue 15: 6) having an average primary particle diameter of 20 nm and a standardized dispersion of 50%, obtained by the small-angle X-ray scattering method, and Compound 0.18 parts, BYK-LPN21116 (BYK-Chemie) 2.84 parts, propylene glycol monomethyl ether acetate 10.19 parts, 0.3-0.4mm manufactured by Saint-Gobain The zirconia beads "ER-120S" were put into a polymer container and dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours to obtain a pigment dispersion liquid. 75.00 parts of the pigment dispersion liquid and 5.50 parts of polyester acrylate resin (ARONIX (trade name) M7100, manufactured by Toa Synthetic Chemical Industry Co., Ltd.), dipentaerythritol hexaacrylate (KAYARAD (trade name)) using a dispersion mixer. DPHA, manufactured by Nippon Kayaku Co., Ltd.) 5.00 parts, diphenyl ketone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.) 1.00 parts, UCAR ESTER EEP (Union Carbide company) 13.5 parts The mixture was stirred and filtered through a filter having a pore size of 1.0 μm to obtain a blue pigment colored composition 2.

[Yellow pigment coloring composition 1]

Using 10 parts of yellow pigment 1 (CI Pigment Yellow 150, FANCHON FAST YELLOW E4GN manufactured by LANXESS) in place of 10 parts of red pigment 1 of red pigment coloring composition 1 described above, yellow pigment coloring composition 1 was obtained in the same manner as above. .

[Production of color filters]

A red coloring composition was applied on a glass substrate having a black matrix formed in advance so that the film thickness reached 2 μm by spin coating. After drying at 70 ° C for 20 minutes, a stripe-shaped pattern was exposed through a mask using an exposure machine equipped with an ultra-high pressure mercury lamp. 90-second spray development was performed using an alkaline developer, and the solution was washed with ion-exchanged water and air-dried. Furthermore, in a clean oven, baking was performed at 230 ° C. for 30 minutes, and a red pixel, that is, a stripe-shaped colored layer was formed on the transparent substrate.

Then, similarly, the green coloring composition was apply | coated so that film thickness might become 2 micrometers by spin coating. After drying, the stripe-shaped coloring layer is developed by exposing at an offset position from the red pixel by an exposure machine, thereby forming a green pixel adjacent to the red pixel.

Then, the blue coloring composition was formed into a blue pixel adjacent to a red pixel and a green pixel with a film thickness of 2 μm by spin coating in the same manner. Thereby, a color filter having striped pixels of three colors of red, green, and blue on a transparent substrate can be obtained.

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

Using the dye-colored composition or pigment-colored composition shown in the following table, color filters 1 to 5 and comparative color filters 1 were produced.

[Determination of the volume fraction of organic pigments in color filters]

(Measurement of coarse particles using a microscope)

Any 5 points of the G pixel portions of the obtained color filters 1 to 5 were observed at 2000 times using an optical microscope Optiphot 2 manufactured by Nikon Corporation, and as a result, no coarse particles of 1000 nm or more were observed.

(Measurement using USAXS color filters 1 to 6)

The G pixel portions of the color filters 1 to 5 were attached to a sample holder made of Al by using an adhesive tape, and set on a sample stand for penetration. Ultra-small angle X-ray scattering was measured and analyzed by the method described in Japanese Patent Application Laid-Open No. 2013-96944. As a result, three particle size distributions were obtained. Among them, the distribution with an average particle size of 1 nm or more and less than 40 nm was expressed. Particles are represented as primary particles, and similarly, a distribution of 40 nm or more and less than 100 nm is expressed as a secondary particle, and a distribution of 100 nm or more and 1000 nm or less is expressed as a tertiary particle. Add up as high-order particles.

As a result of the above measurement and analysis, the volume fraction of the primary particles represented by the distribution of the average particle diameter in the G pixel portion of the color filters 1 to 5 from 1 nm to 40 nm was 81 to 91% and 40 nm or more The volume fraction of the secondary particles represented by the distribution below 100nm is 9-19%, and the volume fraction of the tertiary particles represented by the distribution above 100nm and below 1000nm is 0.0%, and the volume fraction of above 40nm and below 1000nm The volume fraction of particles is 9 ~ 19%.

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

The measurement equipment and measurement method are as follows.

Measuring device: Large-scale radiation facility: Frontier Soft Matter developed in SPring-8. Beam line: BL03XU second shadow line

Measurement mode: Ultra-small angle X-ray scattering (USAXS)

Measurement conditions: Wavelength 0.1nm, camera length 6m, beam spot size 140μm × 80μm, no attenuator, exposure time 30 seconds, 2θ = 0.01 ~ 1.5 °

Analysis software: Set the visualization and one-dimensionalization of two-dimensional data to Fit2D (obtained from the homepage of European Synchrotron Radiation Facility [http // www.esrf.eu / computing / scientific / FIT2D /])

The software NANO-Solver (Ver3.6) manufactured by Rigaku Co., Ltd. was used to analyze the particle size distribution.

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

(Examples 1 to 5)

An electrode structure is fabricated on at least one of 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 friction treatment to produce an IPS unit, which is sandwiched between the first substrate and the second substrate The liquid crystal composition 1 shown below. The physical property values of the liquid crystal composition 1 are shown in the following table. Then, the color filters 1 to 5 shown in the above table were used to produce the liquid crystal display devices of Examples 1 to 5 (d _gap = 4.0 μm, alignment film AL-1051). The VHR of the obtained liquid crystal display device was measured. The residual image of the obtained liquid crystal display device was evaluated. The results are shown in the following table.

[TABLE 11]

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

The liquid crystal display devices of Examples 1 to 5 can achieve high VHR. In the evaluation of afterimages, no afterimages existed, or there were very few afterimages, which was an allowable level.

(Examples 6 to 15)

The liquid crystal compositions 2 to 3 shown in the following table were held in the same manner as in Example 1. The color filters 1 to 5 shown in the above table were used to produce the liquid crystal display devices of Examples 6 to 15 and the VHR of the liquid crystal display devices was measured. . The afterimage of this liquid crystal display device was evaluated. The results are shown in the following table.

The liquid crystal display devices of Examples 6 to 15 can achieve high VHR. In the evaluation of afterimages, no afterimages existed, or there were very few afterimages, which was an allowable level.

(Examples 16 to 30)

The liquid crystal compositions 4 to 6 shown in the following table were clamped in the same manner as in Example 1. The color filters 1 to 5 shown in the above table were used to produce the liquid crystal display devices of Examples 16 to 30, and the VHR was measured. . An afterimage of the liquid crystal display device was evaluated. The results are shown in the following table.

The liquid crystal display devices of Examples 16 to 30 can achieve high VHR. In the evaluation of afterimages, no afterimages existed, or there were very few afterimages, which was an allowable level.

(Examples 31 to 45)

An electrode structure was fabricated on the first and second substrates, and a horizontal alignment alignment film was formed on each of the opposite sides, and then subjected to a weak friction treatment to produce a TN unit. The following table was held between the first substrate and the second substrate The liquid crystal compositions 7 to 9 shown. Then, using the color filters 1 to 5 shown in the above table, the liquid crystal display devices of Examples 31 to 45 (d _gap = 3.5 μm, alignment film SE-7492) were produced. The VHR and ID of the obtained liquid crystal display device were measured. The residual image of the obtained liquid crystal display device was evaluated. The results are shown in the following table.

The liquid crystal display devices of Examples 31 to 45 can realize high VHR and small ID. In the evaluation of afterimages, no afterimages existed, or there were very few afterimages, which was an allowable level.

(Examples 46 to 50)

An electrode structure is fabricated on at least one of 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 friction treatment to produce an FFS unit, sandwiched between the first substrate and the second substrate The liquid crystal composition 10 shown in the following table is held. Then, using the color filters 1 to 5 shown in the above table, the liquid crystal display devices of Examples 46 to 55 (d _gap = 4.0 μm, alignment film AL-1051) were produced. The VHR of the obtained liquid crystal display device was measured. The residual image of the obtained liquid crystal display device was evaluated. The results are shown in the following table.

[TABLE 24]

The liquid crystal display devices of Examples 46 to 50 can achieve high VHR. In the evaluation of afterimages, no afterimages existed, or there were very few afterimages, which was an allowable level.

(Examples 51 to 55)

In the liquid crystal composition 8 99.7 mass% used in Example 36, 0.3 mass% of biphenyl methacrylate-4,4′-diester was mixed to prepare a liquid crystal composition 11. The liquid crystal composition 11 was held in a TN unit, and ultraviolet rays (3.0 J / cm ² ) were irradiated for 600 seconds while a driving voltage was applied between the electrodes to perform a polymerization treatment. Then, the color filters shown in the above table were used. From 1 to 5, the liquid crystal display devices of Examples 51 to 55 were fabricated, and the VHR and ID were measured. An afterimage of the liquid crystal display device was evaluated. The results are shown in the following table.

The liquid crystal display devices of Examples 51 to 55 can realize high VHR and small ID. In the evaluation of afterimages, no afterimages existed, or there were very few afterimages, which was an allowable level.

(Examples 56 to 60)

The liquid crystal composition 9 99.7 mass% used in Example 41 was mixed with 0.3 mass% of biphenyl methacrylate-4,4′-diester to prepare a liquid crystal composition 12. The liquid crystal composition 12 is held in an IPS unit, and ultraviolet rays (3.0 J / cm ² ) are irradiated for 600 seconds while a driving voltage is applied between the electrodes to perform a polymerization treatment. Then, the color filter 1 shown in the above table is used. ~ 5. The liquid crystal display devices of Examples 56 to 60 were produced, and the VHR was measured. An afterimage of the liquid crystal display device was evaluated. The results are shown in the following table.

The liquid crystal display devices of Examples 56 to 60 can achieve high VHR. In the evaluation of afterimages, no afterimages existed, or there were very few afterimages, which was an allowable level.

(Examples 61 to 65)

The liquid crystal composition 10 of 99.7 mass% used in Example 46 was mixed with 0.3 mass% of 3-fluorobiphenyl-4,4'-diester bismethacrylate to prepare a liquid crystal composition 13. The liquid crystal composition 13 was held in an FFS unit, and ultraviolet rays (3.0 J / cm ² ) were irradiated for 600 seconds while a driving voltage was applied between the electrodes to perform a polymerization treatment. Then, the color filters shown in the above table were used. From 1 to 5, the liquid crystal display devices of Examples 61 to 65 were fabricated, and the VHR was measured. An afterimage of the liquid crystal display device was evaluated. The results are shown in the following table.

The liquid crystal display devices of the embodiments 61 to 65 can realize high VHR and small ID. In the evaluation of afterimages, there were no afterimages.

(Comparative Examples 1 to 5)

The comparative liquid crystal composition 1 shown below was held in the IPS unit used in Example 1. The liquid crystal display devices of Comparative Examples 1 to 5 were manufactured using the color filters 1 to 5 shown in the above table, and the VHR of the liquid crystal display devices was measured. An afterimage of the liquid crystal display device was evaluated. The results are shown in the following table.

[TABLE 29]

The liquid crystal display devices of Comparative Examples 1 to 5 have a lower VHR than the liquid crystal display device of the present invention. In the evaluation of afterimages, generation of afterimages was also observed, which is not an allowable level.

(Comparative Examples 6 to 10)

The comparative liquid crystal composition 2 shown in the following table was held in the same manner as in Example 1. The liquid crystal display devices of Comparative Examples 6 to 10 were manufactured using the color filters 1 to 5 shown in the above table, and the VHR of the liquid crystal display device was measured. An afterimage of the liquid crystal display device was evaluated. The results are shown in the following table.

[TABLE 31]

The liquid crystal display devices of Comparative Examples 6 to 10 have a lower VHR than the liquid crystal display device of the present invention. In the evaluation of afterimages, generation of afterimages was also observed, which is not an allowable level.

(Comparative Examples 11 to 15)

The comparative liquid crystal composition 3 shown in the following table was held in the same manner as in Example 1, and the liquid crystal display devices of Comparative Examples 11 to 15 were manufactured using the color filters 1 to 5 shown in the above table, and the VHR was measured. An afterimage of the liquid crystal display device was evaluated. The results are shown in the following table.

[TABLE 33]

In the liquid crystal display devices of Comparative Examples 11 to 15, compared with the liquid crystal display device of the present invention, in the afterimage evaluation, generation of afterimage was observed, which is not an allowable level.

(Comparative Examples 16 to 20)

The comparative liquid crystal composition 4 shown in the following table was held in the same manner as in Example 1, and the liquid crystal display devices of Comparative Examples 16 to 20 were manufactured using the color filters 1 to 5 shown in the above table, and the VHR was measured.

[TABLE 35]

The liquid crystal display devices of Comparative Examples 16 to 20 have a lower VHR than the liquid crystal display device of the present invention. In the evaluation of afterimages, generation of afterimages was also observed, which is not an allowable level.

(Comparative Examples 41 to 55)

The comparative liquid crystal compositions 9 to 11 shown in the following table were clamped in the same manner as in Example 1. The color filters 1 to 5 shown in the above table were used to prepare the liquid crystal display devices of Comparative Examples 41 to 55, and the VHR was measured. And ID. An afterimage of the liquid crystal display device was evaluated. The results are shown in the following table.

[TABLE 37]

The liquid crystal display devices of Comparative Examples 21 to 25 have a lower VHR than the liquid crystal display device of the present invention. In the evaluation of afterimages, generation of afterimages was also observed, which is not an allowable level.

(Comparative Examples 26 to 33)

In Comparative Examples 1, 16, 21, 26, 31, 36, 41, and 46, the comparative color filter 1 shown in the above table was used instead of the color filter 1, and a comparative example was produced in the same manner. For the liquid crystal display devices of 56 to 63, the VHR is measured, and the ID is further measured for the TN unit. An afterimage of the liquid crystal display device was evaluated. The results are shown in the following table.

The liquid crystal display devices of Comparative Examples 26 to 33 have a lower VHR than the liquid crystal display device of the present invention. In the evaluation of afterimages, generation of afterimages was also observed, which is not an allowable level.

Claims (8)

A liquid crystal display device includes a first substrate, a second substrate, a liquid crystal composition layer sandwiched between the first substrate and the second substrate, a color filter composed of at least three RGB pixel portions, a pixel electrode, and The common electrode, the liquid crystal composition layer contains a liquid crystal composition containing one or two or more compounds represented by the general formula (I-1), and one or two or more compounds selected from the general formula (II- a) a compound in the group consisting of a compound represented by the general formula (II-f), (In the formula, R ³¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, M ³¹ ~ M ³² independently represent trans-1,4-cyclohexyl or 1,4-phenylene, and one of the trans-1,4-cyclohexyl groups -CH ₂ -can also be oxygen The atoms are not directly adjacent to each other by -O-. One or two hydrogen atoms in the phenyl group can also be replaced by a fluorine atom. M ³³ represents trans-1,4-cyclohexyl or 1,4- Phenylene, one or two of the trans-1,4-cyclohexyl groups -CH ₂ -can also be substituted with -O- in a way that oxygen atoms are not directly adjacent, one of the phenylene Or two hydrogen atoms may be substituted by a fluorine atom. X ³¹ and X ³² each independently represent a hydrogen atom or a fluorine atom, Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group, and n ³¹ and n ³² each other Independently represents 0, 1, or 2, n ³¹ + n ³² represents 0, 1 or 2, which may be the same or different when there are multiple M ³¹ and M ³³ ); (Wherein R ¹⁹ to R ³⁰ independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and X ²¹ represents a hydrogen atom or Fluorine atom); regarding the above-mentioned RGB three-color pixel portion, as a coloring material, the G pixel portion contains at least one or more groups selected from the first group represented by the following general formula (PIG-1) and / or the following general formula ( The metal phthalocyanine pigment in the second group represented by PIG-2), the metal phthalocyanine pigment has an average primary particle diameter of 5 to 50 nm obtained by a small-angle X-ray scattering method, (In the general formula (PIG-1), X ¹ⁱ to X ¹⁶ⁱ each independently represent a halogen atom, a nitro group, a phthalimideimide methyl group which may have a substituent, and an sulfamonium which may also have a substituent. Group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may also have a substituent, An aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may also have a substituent, Y ¹ⁱ represents a hydroxyl group, a chlorine atom, -OP (= O) R1R2, or -O -SiR3R4R5, where R1 to R5 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or may have The aryloxy group of the substituent, R1 and R2, R3 to R5 may also be bonded to each other to form a ring, and M represents a trivalent metal selected from the group consisting of Ga, Al, Sc, Y, and In); In (Formula ^{(PIG-2), X 17i} ~ X 32i each independently represent a halogen atom, a nitro group, may also have phthalimide (PEI) methyl substituent, the substituent may also have an amine group of the sulfonylureas Group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may also have a substituent, An aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may also have a substituent, M represents a member selected from the group consisting of Ga, Al, Sc, Y, and In Trivalent metal, Y ²ⁱ represents -O-, -O-SiR6R7-O-, -O-SiR6R7-O-SiR8R9-O-, or -OP (= O) R10-O-, and R6 ~ R10 are each independently expressed A hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may also have a substituent).     The liquid crystal display device according to claim 1, wherein in the RGB three-color pixel portion, the R pixel portion contains a diketopyrrolopyrrole pigment and / or an anionic red organic dye as a colorant, and the B pixel portion contains an optional At least one of the group consisting of a free epsilon copper phthalocyanine pigment, a triarylmethane dye, a triarylmethane lake pigment, and a cationic blue organic dye is used as a colorant.         The liquid crystal display device according to claim 1 or 2, wherein the G pixel portion contains a pigment derivative.     The liquid crystal display device according to claim 1 or 2, wherein the G pixel portion contains one selected from the group consisting of a quinoline yellow compound represented by the general formula (3), the general formula (4), and the general formula (5). The above pigments, (In the general formulae (3) to (5), R ₁₀ to R ₂₄ , R ₂₅ to R ₃₉ , and R ₄₀ to R ₅₆ each independently represent a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent.) , Alkoxy groups which may have a substituent, aryl groups which may also have a substituent, -SO ₃ H group, -COOH group, -SO ₃ H group or -COOH group monovalent to trivalent metal salt; Ammonium salt, phthalimidoimide methyl group which may have a substituent, or sulfamoyl group which may also have a substituent). The liquid crystal display device according to claim 1 or 2, wherein the compound represented by the general formula (I-1) is a compound represented by the general formula (Ia) to (If), (Wherein R ³¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, X ³¹ to X ³⁸ each independently represent a hydrogen atom or a fluorine atom, and Z ³¹ represents a fluorine atom, a trifluoromethoxy group, or a trifluoromethyl group). The liquid crystal display device according to claim 1 or 2, further comprising one or two or more compounds selected from the group of compounds represented by the general formula (III-a) to the general formula (III-f) in the liquid crystal composition layer. Of compounds, (Wherein R ⁴¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, X ⁴¹ to X ⁴⁸ each independently represent a hydrogen atom or a fluorine atom, and Z ⁴¹ represents a fluorine atom, a trifluoromethoxy group, or a trifluoromethyl group).     The liquid crystal display device according to claim 1 or 2, wherein the liquid crystal composition layer is composed of a polymer obtained by polymerizing a liquid crystal composition containing one or two or more polymerizable compounds.     The liquid crystal display device according to claim 1 or 2, further comprising a bifunctional monomer represented by the general formula (V) in the liquid crystal composition layer, (Wherein X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or -O- (CH ₂ ) _s -(Where s represents an integer from 2 to 7, and an oxygen atom is bonded to the aromatic ring), Z ¹ represents -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O- , -OCF _2- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH _{-, - COO-CH 2 CH} 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, -CH ₂ -COO-, -CH ₂ -OCO-, -CY ¹ = CY ^2- (wherein Y ¹ and Y ² each independently represent a fluorine atom or a hydrogen atom), -C≡C- or a single Bond, C represents 1,4-phenylene, trans-1,4-cyclohexyl or single bond, and any hydrogen atom of all 1,4-phenylene in the formula may be substituted by fluorine atom).