TWI554599B - Liquid crystal display device - Google Patents

Description

Liquid crystal display device

The present invention relates to a liquid crystal display device.

The liquid crystal display device starts with a clock and a calculator, and is gradually applied to various household electrical appliances, measuring machines, automobile panels, word processors, electronic notebooks, printers, computers, televisions, and the like. Typical examples of the liquid crystal display method include TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, DLS (Dynamic Light Scattering) type, and GH ( Guest-Host, IPS (In-Plane Switching), OCB (Optically Compensated Birefringence), ECB (Electrically Controlled Birefringence), VA (Vertical) Alignment, vertical alignment, CSH (Color Super Homeotropic), or FLC (Ferroelectric Liquid Crystal). Moreover, as a driving method, it has become common from the previous static driving to the multiplex driving, and in the simple matrix method, a TFT (Thin Film Transistor) or a TFD (Thin Film Diode) has recently been used. The Driven Active Matrix (AM) approach has gradually become mainstream.

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

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

If the liquid crystal material constituting the liquid crystal layer has impurities remaining in the material, it will be mounted on the display. The electrical characteristics of the device have a great influence, so the management of the height of the impurities has been carried out. Further, regarding the material for forming the alignment film, it is also known that the alignment film directly contacts the liquid crystal layer, and the impurities remaining in the alignment film are transferred to the liquid crystal layer, thereby affecting the electrical characteristics of the liquid crystal layer, and the industry is facing the alignment film material. The characteristics of the liquid crystal display device caused by impurities in the study were investigated.

On the other hand, materials such as organic pigments used in color filter layers are also The influence on the liquid crystal layer caused by impurities contained in the same manner as the alignment film material is conceivable. However, since the alignment film and the transparent electrode are interposed between the color filter layer and the liquid crystal layer, it is considered that the direct influence on the liquid crystal layer is significantly reduced as compared with the alignment film material. However, the film thickness of the alignment film is usually only 0.1 μm or less, and the common electrode for the color filter layer side, which is a transparent electrode, is usually 0.5 μm or less in order to increase the film thickness in order to increase the conductivity. Therefore, it is not possible to say that the color filter layer and the liquid crystal layer are completely isolated. The color filter layer may pass through the alignment film and the transparent electrode, and the impurity contained in the color filter layer may be represented by the liquid crystal layer. The decrease in voltage holding ratio (VHR) and the increase in ion density (ID, Ion Density) cause display defects such as void, misalignment, and afterimage. As a method for solving the display defect caused by the impurities contained in the pigment constituting the color filter, the industry is investigating the use of a pigment having a ratio of an extract of ethyl acetate to a specific value or less to control the impurity to the liquid crystal. A method of eluting (Patent Document 1) or a method of controlling elution of impurities into liquid crystal by specifying a pigment in a blue colored layer (Patent Document 2). However, these methods are not significantly different from the method of simply reducing the impurities in the pigment. In recent years, in the current state of progress in the purification of the pigment, the improvement to solve the display defect is insufficient.

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

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

[Patent Document 1]

Japanese Special Report No. 2000-19321

[Patent Document 2]

Japanese Special Open 2009-109542

[Patent Document 3]

Japanese Special Report No. 2000-192040

The present invention provides a liquid crystal display device which prevents a decrease in voltage holding ratio (VHR) of a liquid crystal layer and an increase in ion density (ID) by using a specific liquid crystal composition and a color filter using a specific pigment. To solve the problem of poor display, such as whiteness, uneven alignment, and residual image.

In order to solve the above problems, the inventors of the present invention have made an effort to study the combination of a coloring material such as a dye for forming a color filter and a liquid crystal material constituting a liquid crystal layer, and as a result, found that the structure and use of a specific liquid crystal material are used. A liquid crystal display device having a color filter of a dye having a specific structure can prevent a decrease in voltage holding ratio (VHR) of a liquid crystal layer, and an ion density The increase of (ID) solves the problem of poor display, such as whiteness, uneven alignment, and residual image, thereby completing the invention of the present invention.

That is, the present invention provides a liquid crystal display device including a first substrate, a second substrate, a liquid crystal composition layer sandwiched between the first substrate and the second substrate, a black matrix, and at least RGB three colors a color filter, a pixel electrode, and a common electrode, wherein the liquid crystal composition layer contains one or more selected from the group consisting of a compound represented by the formula (LC1) to the formula (LC4). a liquid crystal composition of the compound,

(wherein R ₁ and R ₂ each independently represent an alkyl group having 1 to 15 carbon atoms, and one or more of the CH ₂ groups in the alkyl group may be via O-, in a manner in which the oxygen atoms are not directly adjacent to each other; -CH=CH-, -CO-, -OCO-, -COO-, -C≡C-, -CF ₂ O- or -OCF ₂ -, one or more hydrogen atoms in the alkyl group It may be optionally substituted by halogen, and A ₁ and A ₂ each independently represent any of the following structures,

(In this structure, one or two or more CH ₂ groups of the cyclohexane ring may be substituted with an oxygen atom, and in this structure, one or two or more CH groups of the benzene ring may be substituted by a nitrogen atom, and, in the structure, One or more hydrogen atoms may be substituted by Cl, CF ₃ or OCF ₃ ), and Z ₁ to Z ₄ each independently represent a single bond, -CH=CH-, -C≡C-, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -COO-, -OCH ₂ -, -CH ₂ O-, -OCF ₂ - or -CF ₂ O-, Z ₅ represents a CH ₂ group or an oxygen atom, and is present in Z At least one of ₁ and Z ₂ is not a single bond, l ₁ represents 0 or 1, m ₁ and m ₂ independently represent 0 to 3, and m ₁ + m ₂ is 1, 2 or 3)

The RGB three-color pixel portion contains a triarylmethane pigment represented by the following formula (1) as a color material in the B pixel portion.

(wherein R ¹ to R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, or an aryl group which may have a substituent; and R ¹ to R ⁶ may have a substituent; In the case of an alkyl group, adjacent R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to form a ring structure; X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, Or an alkyl group having 1 to 8 carbon atoms which may have a substituent; the Z ^- series is selected from an integer represented by (P ₂ Mo _y W _18-y O ₆₂ ) ^6- /6 and y = 0, 1, 2 or 3. Heteropolyoxometalate anion, or (SiMoW ₁₁ O ₄₀ ) ^4- /4 heteropolyoxometalate anion, or defect Dawson type phosphotungstic acid heteropolyoxometalate anion At least one anion; when a plurality of formulas (1) are contained in one molecule, they may be the same structure or different structures.

The liquid crystal display device of the present invention uses a specific liquid crystal composition and uses The color filter having a specific pigment can prevent a decrease in the voltage holding ratio (VHR) of the liquid crystal layer and an increase in the ion density (ID), thereby preventing occurrence of display defects such as whiteness, uneven alignment, and afterimage.

1‧‧‧Substrate

2‧‧‧Color filter layer

2a‧‧‧Color filter layer with specific pigments

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

3b‧‧‧pixel electrode layer

4‧‧‧Alignment film

5‧‧‧Liquid layer

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

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

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

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

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

(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 more compounds selected from the group consisting of the compounds represented by the formulae (LC1) to (LC4).

(wherein R ₁ and R ₂ each independently represent an alkyl group having 1 to 15 carbon atoms, and one or more of the CH ₂ groups in the alkyl group may be via O-, in a manner in which the oxygen atoms are not directly adjacent to each other; -CH=CH-, -CO-, -OCO-, -COO-, -C≡C-, -CF ₂ O- or -OCF ₂ -, one or more hydrogen atoms in the alkyl group It may be optionally substituted by halogen, and A ₁ and A ₂ each independently represent any of the following structures,

(In this structure, one or two or more CH ₂ groups of the cyclohexane ring may be substituted with an oxygen atom, and in this structure, one or two or more CH groups of the benzene ring may be substituted by a nitrogen atom, and, in the structure, One or more hydrogen atoms may be substituted by Cl, CF ₃ or OCF ₃ ), and Z ₁ to Z ₄ each independently represent a single bond, -CH=CH-, -C≡C-, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -COO-, -OCH ₂ -, -CH ₂ O-, -OCF ₂ - or -CF ₂ O-, Z ₅ represents a CH ₂ group or an oxygen atom, and is present in Z At least one of ₁ and Z ₂ is not a single bond, l ₁ represents 0 or 1, m ₁ and m ₂ independently represent 0 to 3, and m ₁ + m ₂ is 1, 2 or 3). R ₁ and R ₂ are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, and an alkenyl group having 2 to 7 carbon atoms, and A ₁ and A _{2 are} preferably independently independent. The ground is the following structure,

Z ₁ to Z _{4 are} preferably each independently a single bond, -CH ₂ CH ₂ -, -COO-, -OCH ₂ -, -CH ₂ O-, -OCF ₂ - or -CF ₂ O-.

The liquid crystal composition preferably further contains one or two or more liquid crystal compositions of a compound represented by the formula (LC5).

(wherein R ₁ and R ₂ each independently represent an alkyl group having 1 to 15 carbon atoms, and one or more of the CH ₂ groups in the alkyl group may be via O-, in a manner in which the oxygen atoms are not directly adjacent to each other; -CH=CH-, -CO-, -OCO-, -COO-, -C≡C-, -CF ₂ O- or -OCF ₂ -, one or more hydrogen atoms in the alkyl group It may be optionally substituted by halogen, and B ₁ to B ₃ each independently represent any of the following structures,

(wherein, one or more CH ₂ CH ₂ groups in the cyclohexane ring may be substituted by -CH=CH-, -CF ₂ O-, -OCF ₂ -, one or two of the benzene rings More than one CH group may be substituted by a nitrogen atom), and Z ₃ and Z ₄ each independently represent a single bond, -CH=CH-, -C≡C-, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ - , -COO-, -OCH ₂ -, -CH ₂ O-, -OCF ₂ - or -CF ₂ O-, m ₁ represents 0 to 3).

R ₁ and R ₂ are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, and an alkenyl group having 2 to 7 carbon atoms, and B ₁ to B _{3 are} preferably independently independent. The ground is the following structure,

Z ₃ and Z _{4 are} preferably each independently a single bond, -CH ₂ CH ₂ -, -COO-, -OCH ₂ -, -CH ₂ O-, -OCF ₂ - or -CF ₂ O-.

The formula (LC1) is more preferably one or more compounds selected from the group consisting of compounds represented by the following formula (LC1)-1 to formula (LC1)-7,

(wherein R ¹ and R ² each independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, and an alkenyloxy group having 2 to 7 carbon atoms. ).

The formula (LC2) is more preferably one or more compounds selected from the group consisting of compounds represented by the following formula (LC2)-1 to formula (LC2)-15,

(wherein R ₁ and R ₂ each independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; , Z ₁ represents -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ - or -CF ₂ O-, and A ¹ represents any of the following structures, ).

The formula (LC3) is more preferably one or more compounds selected from the group consisting of compounds represented by the following formula (LC3)-1 to (LC3)-6, and the formula (LC4) is more It is preferably one or more compounds selected from the group consisting of compounds represented by the following formula (LC4)-1 to (LC4)-4,

(wherein R ₁ and R ₂ each independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; ).

The formula (LC5) is more preferably one or more compounds selected from the group consisting of compounds represented by the formula (LC5)-1 to the formula (LC5)-13,

(wherein R ₁ and R ₂ each independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; ).

The liquid crystal composition layer may contain one or more polymerizable compounds.

Specifically, the polymerizable compound is preferably a polymerizable compound represented by the formula (PC1).

(wherein P ₁ represents a polymerizable functional group, Sp ₁ represents a spacer group having 0 to 20 carbon atoms, and Q ₁ represents a single bond, -O-, -NH-, -NHCOO-, -OCONH- , -CH=CH-, -CO-, -COO-, -OCO-, -OCOO-, -OOCO-, -CH=CH-, -CH=CH-COO-, -OCO-CH=CH- or- C≡C-, n ₁ , n ₂ represents 1, 2 or 3, MG represents a mesogenic group or a liquid crystal-derived support group, and R ₁₀ represents a halogen atom, a cyano group or an alkyl group having 1 to 25 carbon atoms. One or more than two or more CH ₂ groups in the alkyl group may be via O-, -S-, -NH-, -N(CH ₃ )-, -CO-, in a manner in which the oxygen atoms are not directly adjacent to each other. -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-substituted, or R ₁₀ represents P ₂ -Sp ₂ -Q ₂ - (wherein P ₂ , Sp ₂ , Q ₂ independently represents the same meaning as P ₁ , Sp ₁ , and Q ₁ )).

More preferably, the MG in the formula (PC1) is preferably represented by the following structure.

(wherein C ₁ to C ₃ each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenyl group, a tetrahydropyran-2,5-diyl group, 1,3-two Alkano-2,5-diyl, tetrahydrothiopyran-2,5-diyl, 1,4-dicyclo(2,2,2)octyl, decahydronaphthalene-2,6-diyl, pyridine- 2,5-diyl, pyrimidine-2,5-diyl, pyridyl -2,5-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 2,6-anthranyl, phenanthrene-2,7-diyl, 9,10-dihydro Phenanthrene-2,7-diyl, 1,2,3,4,4a,9,10a-octahydrophenanthrene-2,7-diyl or indole-2,7-diyl, the 1,4-phenylene 1,1,2,3,4-tetrahydronaphthalene-2,6-diyl, 2,6-anthranyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7- Dibasic, 1,2,3,4,4a,9,10a-octahydrophenanthrene-2,7-diyl and indole-2,7-diyl may also have more than one F, Cl, CF ₃ , OCF ₃ , cyano group, alkyl group having 1 to 8 carbon atoms, alkoxy group, alkyl fluorenyl group, alkyl alkoxy group, alkenyl group having 2 to 8 carbon atoms, alkenyloxy group, olefin group or olefin group The base serves as a substituent, and Y ₁ and Y ₂ each independently represent -COO-, -OCO-, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH=CH-, -C≡C -, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -CH ₂ CH ₂ OCO-, -COOCH ₂ CH ₂ -, -OCOCH ₂ CH ₂ -, -CONH-, -NHCO Or a single bond, n ₅ represents 0, 1 or 2), and Sp ₁ and Sp ₂ each independently represent an alkylene group, and the alkylene group may be substituted by one or more halogen atoms or cyano groups. the presence of one or two or more of the CH ₂ group not directly adjacent oxygen atom by way of -O -, - S -, - NH- _{-N (CH 3) -, -} CO -, - COO -, - OCO -, - OCOO -, - SCO -, - COS- or -C≡C-, P ₁ and P ₂ is preferably independently The structure represented by the following formula (R-1) to formula (R-15).

These polymeric groups are hardened by radical polymerization, radical addition polymerization, cationic polymerization, and anionic polymerization. In particular, when ultraviolet polymerization is carried out as a polymerization method, it is preferably a formula (R-1), a formula (R-2), a formula (R-4), a formula (R-5), and a formula (R-7). , the formula (R-11), the formula (R-13) or the formula (R-15), more preferably the formula (R-1), the formula (R-2), the formula (R-7), the formula (R- 11) or formula (R-13), more preferably formula (R-1), formula (R-2).

The polymerizable compound having one polymerizable functional group in the molecule may, for example, be a formula (PC1)-0.

Preferably selected from

(In the formula (PC1)-0, R ₁₁ represents a hydrogen atom or a methyl group, and the 6-membered rings T ₁ , T ₂ and T ₃ are independently represented

Any one of them (where m represents an integer from 1 to 4), n ⁴ represents an integer of 0 or 1, and Y ₀ , Y ₁ and Y ₂ each independently represent a single bond, -O-, -OCH ₂ -, -OCH ₂ -, -C ₂ H ₄ -, -COO-, -OCO-, -CH=CH-, -CO-, -OCOO-, -NH-, -NHCOO-, -OCONH-, -OCOCH ₂ - , -CH ₂ OCO-, -COOCH ₂ -, -CH ₂ COO-, -CH=CH-COO-, -OCO-CH=CH-, -CH=CH-OCO-, -COO-CH=CH-, -CH=CCH ₃ -COO-, -COO-CCH ₃ =CH-, -COOC ₂ H ₄ -, -OCOC ₂ H ₄ -, -C ₂ H ₄ OCO-, -C ₂ H ₄ COO-, -C ≡C-, -CF ₂ O- and -OCF ₂ -, Y ³ represents a single bond, -O-, -COO-, or -OCO-, and R ₁₂ represents a hydrogen atom, a halogen atom, a cyano group, and a carbon atom number of 1. At least one polymerizable compound of the group consisting of an alkyl group of 20, an alkenyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms.

Examples of the polymerizable compound having two or more polymerizable functional groups in the molecule include a formula (PC1)-1 or a formula (PC1)-2.

(P ₁ , Sp ₁ , Q ₁ , P ₂ , Sp ₂ , Q ₂ and MG have the same meanings as in the general formula (PC1), and n ₃ and n ₄ each independently represent 1, 2 or 3).

Specifically, the general formula (PC1) is preferably one or two or more polymerizable compounds selected from the group consisting of compounds represented by the general formula (PC1)-3 to the general formula (PC1)-11.

Wherein P ₁ , P ₂ , Sp ₁ , Sp ₂ , Q ₁ and Q _{2 have the} same meanings as in the formula (PC1), and W ₁ independently represents F, CF ₃ , OCF ₃ , CH ₃ , OCH, respectively. ₃ , an alkyl group having 2 to 5 carbon atoms, an alkoxy group, an alkenyl group, COOW ₂ , OCOW ₂ or OCOOW ₂ (wherein, W ₂ independently represents a linear or branched alkane having 1 to 10 carbon atoms; a base or an alkenyl group having 2 to 5 carbon atoms), n ₃ each independently represents 1, 2 or 3, and n ₄ independently represents 1, 2 or 3, respectively, and n ₆ independently represents 0, 1, 2, and 3 Or 4, n ₃ + n ₆ and n ₄ + n ₆ on the same ring are 5 or less).

In the general formula (PC1) and the general formula (PC1)-1 to the general formula (PC1)-11, Sp ₁ , Sp ₂ , Q ₁ and Q _{2 are} preferably a single bond. n ₃ + n _{4 is} preferably from 1 to 3, more preferably 1 or 2. P ₁ and P _{2 are} preferably of the formula (R-1) or (R-2). W _{1 is} preferably F, CF ₃ , OCF ₃ , CH ₃ or OCH ₃ . n ₆ is 1, 2, 3 or 4.

Specifically, the compound described below is preferred.

Further, the hydrogen atom of the benzene ring of the above (PC1-3a) to (PC1-3i) may be further substituted with a fluorine atom.

Further, the polymerizable compound is also preferably a discotic liquid crystal compound represented by the following formula (PC1)-9.

Wherein R ₇ independently represents _a substituent of P ₁ -Sp ₁ -Q ₁ or (PC1-e) (wherein P ₁ , Sp ₁ and Q ₁ represent the same as the formula (PC1)) And R ₈₁ and R ₈₂ each independently represent a hydrogen atom, a halogen atom or a methyl group, and R ₈₃ represents an alkoxy group having 1 to 20 carbon atoms, and at least one hydrogen atom of the alkoxy group is subjected to the above formula (R- 1) The substituent represented by ~(R-15) is substituted).

The amount of the polymerizable compound used is preferably from 0.05 to 2.0% by mass.

The liquid crystal composition may be used singly in the above-mentioned applications, and may further contain one or more kinds of antioxidants, and may further contain one or more kinds of UV absorbers.

(color filter)

The color filter of the present invention is composed of a black matrix and at least RGB three-color pixel portion, and the RGB three-color pixel portion contains a triarylmethane pigment represented by the following formula (1) as a color material in the B pixel portion.

(wherein R ¹ to R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, or an aryl group which may have a substituent; and R ¹ to R ⁶ may have a substituent; In the case of an alkyl group, adjacent R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to form a ring structure; X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, Or an alkyl group having 1 to 8 carbon atoms which may have a substituent; the Z ^- series is selected from an integer represented by (P ₂ Mo _y W _18-y O ₆₂ ) ^6- /6 and y = 0, 1, 2 or 3. a heteropolyoxometalate anion, or at least one anion of (SiMoW ₁₁ O ₄₀ ) ^4- /4 heteropolyoxometalate anion, or a defect Dawson-type phosphotungstic acid polyoxometalate anion; When a plurality of formulas (1) are contained in the molecule, they may be the same structure or different structures. Further, the RGB three-color pixel portion preferably contains a diketo-pyrolo-pyrrole pigment and/or an anionic red organic dye as a colorant in the R pixel portion, and is selected from the G pixel portion. At least one of a group consisting of a halogenated metal anthraquinone pigment, an anthraquinone-based green dye, an anthraquinone-based blue dye, and an azo-based yellow organic dye is used as a colorant.

(G pixel part)

Preferably, the G pixel portion contains a pigment selected from the group consisting of halogenated metal anthraquinone pigments and ruthenium At least one of a group consisting of a mixture of a green dye, an anthrain blue dye, and an azo yellow organic dye. As the halogenated metal anthraquinone pigment, it is preferable to have a selected from the group consisting of Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Cu, Ga, Ge, Y, Zr, Nb, In, Sn, and The metal in the group consisting of Pb is used as a central metal, and when the central metal is trivalent, one of a halogen atom, a hydroxyl group or a sulfonic acid group is bonded to the central metal, or is crosslinked by oxygen. Or sulfur cross-linking, in the case where the central metal is a tetravalent metal, one of the oxygen atoms or the two halogen atoms, hydroxyl groups or sulfonic acid groups which may be the same or different may be bonded to the central metal. . Examples of the halogenated metal ruthenium pigment pigment include the following two groups of halogenated metal ruthenium pigments.

(first group)

It is a halogenated metal ruthenium pigment selected from the group consisting of Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Cu, Ga, Ge, Y, Zr, Nb, In, Sn, and The metal in the group consisting of Pb acts as a central metal, and 8 to 16 halogen atoms in each of the isatin molecules are bonded to the benzene ring of the indocyanin molecule, and when the central metal is trivalent, The central metal bond has one of a halogen atom, a hydroxyl group or a sulfonic acid group (-SO ₃ H). When the central metal is a tetravalent metal, one oxygen atom is bonded to the central metal. Or any of two halogen atoms, a hydroxyl group or a sulfonic acid group which may be the same or different.

(second group)

a pigment composed of a halogenated metal anthraquinone dimer having 2 molecules of a trivalent metal selected from the group consisting of Al, Sc, Ga, Y, and In as a center metal. And a metal halide of 8 to 16 halogen atoms bonded to the benzene ring of the indoline molecule per one of the isatin molecules is a structural unit, and each of the central metals of the structural units is selected from the group consisting of oxygen atoms A divalent atomic group in a group consisting of a sulfur atom, a sulfinyl group (-SO-), and a sulfonyl group (-SO ₂ -) is bonded.

In the halogenated metal ruthenium pigment, all of the halogen atoms bonded to the benzene ring may be The same or different. Further, a different halogen atom may be bonded to a benzene ring.

Here, 9 to 15 bromines of 8 to 16 halogen atoms per one of the indocyanin molecules The halogenated metal anthraquinone pigment bonded to the benzene ring of the indocyanin molecule is a bright yellowish green color, and is most suitably applied to the green pixel portion of the color filter. The halogenated metal anthraquinone pigment is insoluble or poorly soluble in water or an organic solvent. The halogenated metal ruthenium pigment contains both a pigment (also referred to as a crude pigment) which has not been subjected to the following finishing treatment, and a pigment which has been subjected to finishing treatment.

The halogenated metal phthalocyanine pigments belonging to the first group and the second group described above may be as follows Expressed by the formula (PIG-1).

In the above formula (PIG-1), the first group of halogenated metal indocyanine pigments It is as follows.

In the formula (PIG-1), X ₁ to X ₁₆ represent a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom. The four X atoms bonded to one benzene ring may be the same or different. Among the X ₁ to X ₁₆ bonded to the four benzene rings, 8 to 16 are chlorine atoms, bromine atoms or iodine atoms. M represents the center metal. In the range of Y and the halogenated metal anthraquinone pigment having the same number m, the pigments of 16 X ₁ to X ₁₆ having a total of chlorine atoms, bromine atoms and iodine atoms of less than 8 are blue, similarly The pigment having a total of 8 or more chlorine atoms, bromine atoms, and iodine atoms in 16 X ₁ to X ₁₆ is larger as the total value is yellow. The Y bonded to the central metal M is a one-valent atomic group selected from the group consisting of any halogen atom, oxygen atom, hydroxyl group and sulfonic acid group of fluorine, chlorine, bromine or iodine, and m represents a bond to the central metal M. The number of Y is an integer from 0 to 2.

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

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

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

Further, in the chemical structure of the atomic group Y, the central metal M has the same meaning as defined above, and with respect to X ₁₇ to X ₃₂ , the meanings of X ₁ to X ₁₆ described above in the general formula (PIG-1) have the same meaning. . A represents a divalent atomic group selected from the group consisting of an oxygen atom, a sulfur atom, a sulfinyl group (-SO-), and a sulfonyl group (-SO ₂ -). It is shown that M in the general formula (PIG-1) and the M group of the atomic group Y are bonded via a divalent atomic group A.

That is, the halogenated metal ruthenium pigment belonging to the second group is composed of 2 molecules of halogenated metal. An anthocyanin dimer which is a structural unit and which is bonded via the above-mentioned divalent atomic group.

As the halogenated metal phthalocyanine pigment represented by the formula (PIG-1), specifically, The following (1) to (4) can be cited.

(1) The halogenated copper phthalocyanine pigment, the tin halide anthraquinone pigment, the nickel halide phthalocyanine pigment, the zinc halide phthalocyanine pigment or the like having a selected from the group consisting of Mg, Fe, Co, Ni, Zn, Cu, A divalent metal in a group consisting of Zr, Sn, and Pb is used as a central metal, and 8 to 16 halogen atoms in each of the indocyanin molecules are bonded to the metal halide anthocyanin pigment on the four benzene rings. Further, among them, the zinc bromide phthalocyanine pigment is preferably C.I. Pigment Green 58.

(2) A trivalent metal selected from the group consisting of Al, Sc, Ga, Y, and In as a central metal, such as a halogenated chloroaluminium phthalocyanine, having a halogen atom, a hydroxyl group, or a sulfonate in the center metal Any of the acid groups, and 8 to 16 halogen atoms per 1 indocyanin molecule are bonded to 4 A halogenated metal anthraquinone pigment on a benzene ring.

(3) It is a central metal having a tetravalent metal selected from the group consisting of Si, Ti, V, Ge, Zr, and Sn as a central metal such as oxytitanium oxyhalide or oxyvanadium oxalate. Any one of two halogen atoms, a hydroxyl group or a sulfonic acid group which may have one oxygen atom or may be the same or different, and 8 to 16 halogen atoms per one cordierin molecule are bonded to four benzene rings A halogenated metal anthraquinone pigment.

(4) It is a pigment composed of a halogenated metal anthraquinone dimer which is a halogenated μ-oxo-alumina anthraquinone dimer, halogenated μ- a thio-aluminium anthraquinone dimer or the like, wherein two molecules are selected from a trivalent metal selected from the group consisting of Al, Sc, Ga, Y, and In as a central metal and each of the indocyanin molecules is 8~ 16 halogenated metal phthalocyanins bonded to four benzene rings are defined as structural units, and each central metal of the structural units is selected from the group consisting of an oxygen atom, a sulfur atom, a sulfinyl group and a sulfonium group. The divalent atomic group in the group is bonded.

As the halogenated metal anthraquinone pigment, specifically, it is preferably selected from the group consisting of C.I. pigments One or two or more of Green 7, C.I. Pigment Green 36 and C.I. Pigment Green 58 are more preferably one or two selected from the group consisting of C.I. Pigment Green 36 and C.I. Pigment Green 58. Specifically, the anthocyanin-based green dye is preferably one or more selected from the group consisting of C.I. Solvent Green 4, C.I. Solvent Green 5, C.I. Solvent Green 7, and C.I. Solvent Green 28. As the anthraquinone blue dye, specifically, it is preferably selected from CI Solvent Blue 4, CI Solvent Blue 5, CI Solvent Blue 25, CI Solvent Blue 35, CI Solvent Blue 36, CI Solvent. One or more of Blue 38, CI Solvent Blue 58, CI Solvent Blue 59, CI Solvent Blue 67, and CI Solvent Blue 70, more preferably CI Solvent Blue 25, CI Solvent Blue 38, CI Solvent Blue 67, and CI One or two or more of Solvent Blue 70. As the azo yellow organic dye, specifically, it is preferably selected from CI Solvent Yellow 2, CI Solvent Yellow 4, CI Solvent Yellow 14, CI Solvent Yellow 16, CI Solvent Yellow 18, CI Solvent Yellow. 21, CI Solvent Yellow 56, CI Solvent Yellow 72, CI Solvent Yellow 124, CI Solvent Yellow 162 And one or more of C.I. Solvent Yellow 163, more preferably one or two selected from the group consisting of C.I. Solvent Yellow 82 and C.I. Solvent Yellow 162.

(R pixel section)

It is preferred to contain a diketopyrrolopyrrole pigment and/or a yin in the R pixel portion. Ionic red organic dye. The diketopyrrolopyrrole pigment is specifically selected from the group consisting of CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 272, CI Pigment Orange 71, and CI Pigment. One or more of the oranges 73, more preferably one or more selected from the group consisting of CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, and CI Pigment Red 272, and more preferably CI Pigment Red 254. Specifically, the anionic red organic dye is preferably one or more selected from the group consisting of CI Solvent Red 124, CI Acid Red 52, and CI Acid Red 289, and more preferably CI Solvent Red. 124.

(B pixel section)

The B pixel portion contains a triarylmethane pigment represented by the following formula (1).

(wherein R ¹ to R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, or an aryl group which may have a substituent; and R ¹ to R ⁶ may have a substituent; In the case of an alkyl group, adjacent R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to form a ring structure; X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, Or an alkyl group having 1 to 8 carbon atoms which may have a substituent; the Z ^- series is selected from an integer represented by (P ₂ Mo _y W _18-y O ₆₂ ) ^6- /6 and y = 0, 1, 2 or 3. a heteropolyoxometalate anion, or at least one anion of (SiMoW ₁₁ O ₄₀ ) ^4- /4 heteropolyoxometalate anion, or a defect Dawson-type phosphotungstic acid polyoxometalate anion; When a plurality of formulas (1) are contained in the molecule, they may be the same structure or different structures.

In the formula (1), R ¹ to R ⁶ may be the same or different. Therefore, -NRR (RR represents any combination of R ¹ R ² , R ³ R ⁴ , and R ⁵ R ⁶ ) may be symmetric or asymmetric.

In the case where adjacent R (R represents any of R ¹ to R ⁶ ) is bonded to form a ring, these may also be rings crosslinked by a hetero atom. Specific examples of the ring include the following. The rings may also have a substituent.

Further, in terms of chemical stability, R ¹ to R ⁶ are each preferably an independently substituted hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.

Wherein R ¹ to R ^{6 are more} preferably independently hydrogen atoms; methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, secondary butyl, tert-butyl An alkyl group such as a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group or a 2-ethylhexyl group; or an aryl group such as a phenyl group or a naphthyl group.

In the case where R ¹ to R ⁶ represent an alkyl group or an aryl group, the alkyl group or the aryl group may further have any substituent. The alkyl group or the aryl group may further have any substituent, and examples thereof include the following [substituent group Y].

[Substituent group Y]

Methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, secondary Butyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl An alkyl group; an aryl group such as a phenyl group or a naphthyl group; a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; a hydroxyl group; and a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like having 1 to 8 carbon atoms. Alkoxy group; amine group which may have a substituent such as an amine group, a diethylamino group, a dibutylamino group or an ethyl fluorenylamino group; an anthracenyl group such as an ethyl fluorenyl group or a benzamidine group; And an anthraceneoxy group such as a benzyl methoxy group.

R ¹ to R ^{6 are more} preferably an alkyl group having 1 to 8 carbon atoms which may have a substituent, and more specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and the like. An unsubstituted alkyl group such as isobutyl, secondary butyl, pentyl, hexyl or 2-ethylhexyl; alkoxyalkyl group such as 2-methoxyethyl or 2-ethoxyethyl; - anthracenyloxy group such as acetoxyethyl; cyanoalkyl such as 2-cyanoethyl; fluoroalkyl group such as 2,2,2-trifluoroethyl or 4,4,4-trifluorobutyl Wait.

When X ¹ and X ² are the above alkyl groups, they may further have any substituent. Examples of the substituents include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; and an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group. Specific examples of X ¹ and X ² include a haloalkyl group such as a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, and a 2,2,2-trifluoroethyl group; and an alkyl group such as a methoxymethyl group; Oxyalkyl and the like.

X ¹ and X ^{2 are} preferably a substituent having a moderate steric hindrance such as a hydrogen atom, a methyl group, a chlorine atom or a trifluoromethyl group which does not affect the torsion. In terms of color tone and heat resistance, X ¹ and X ^{2 are} most preferably a hydrogen atom, a methyl group or a chlorine atom.

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

Specific examples of the triarylmethane pigment represented by the above formula (1), for example The compounds described in the following Tables 1 to 7 can be mentioned, but the present invention does not exceed the gist thereof, and Not limited to these.

Preferably, the RGB three-color pixel portion contains C.I. solvent red in the R pixel portion. In the G pixel portion, a mixture of CI solvent blue 67 and CI solvent yellow 82 or CI solvent yellow 162 is contained as a coloring material, and the triarylmethane pigment represented by the above formula (1) is contained in the B pixel portion. Color material.

Further, the RGB three-color pixel portion preferably contains C.I. The material red 254 is a coloring material, and one or two or more selected from the group consisting of CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58 are contained in the G pixel portion as a color material, and the above-described formula is contained in the B pixel portion. (1) A triarylmethane pigment represented as a colorant.

Preferably, the RGB three-color pixel portion further includes, in the R pixel portion, CI Pigment Red 177, CI Pigment Red 242, CI Pigment Red 166, CI Pigment Red 167, CI Pigment Red 179, CI Pigment Orange 38, CI Pigment Orange 71, CI Pigment Yellow (CIPigment Yellow) 150, CI Pigment Yellow 215, CI Pigment Yellow 185, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Solvent Red 89, CI Solvent Orange 56, CI Solvent Yellow 21, CI Solvent Yellow 82, CI Solvent Yellow 83:1, CI Solvent Yellow 33 and CI Solvent Yellow At least one organic dyed pigment of the group consisting of 162 is used as a colorant.

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

Preferably, the RGB three-color pixel portion further includes, in the B pixel portion, 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 At least one organic dye of the group consisting of CI Pigment Blue 15:3, CI Pigment Blue 15:4, and CI Pigment Blue 15:6 is used as a colorant.

Moreover, the color filter is composed of a black matrix, RGB three-color pixel portion, and Y pixel. Preferably, the Y pixel portion is selected from the group consisting of CI Pigment Yellow 150, CI Pigment Yellow 215, CI Pigment Yellow 185, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Solvent Yellow 21, CI Solvent Yellow 82, CI. At least one yellow organic dye pigment of the group consisting of Solvent Yellow 83:1, CI Solvent Yellow 33 and CI Solvent Yellow 162 is used as a colorant.

The color filter can be formed into a color filter pixel by a conventionally known method. unit. A typical method for forming a pixel portion is a photolithography method in which a photocurable composition described later is applied to a surface of a transparent substrate for a color filter provided with a black matrix side. After heat drying (prebaking), pattern exposure is performed by irradiating ultraviolet rays through a mask, and the photocurable compound corresponding to the pixel portion is cured, and then the unexposed portion is developed by the developer to remove the non-pixel portion. The pixel portion is fixed on the transparent substrate. In this method, a pixel portion composed of a hard colored film of a photocurable composition is formed on a transparent substrate.

For other colors such as R pixels, G pixels, B pixels, and Y pixels as needed Each of the color pixels is prepared with a photocurable composition described later, and the above operation is repeated, whereby a color filter having a colored pixel portion of R pixels, G pixels, B pixels, and Y pixels at a specific position can be manufactured.

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

Drying condition root of coating film of photocurable composition coated on transparent substrate It varies depending on the type of each component, the blending ratio, etc., and is usually carried out at 50 to 150 ° C for about 1 to 15 minutes. Further, as the light used for photohardening of the photocurable composition, it is preferred to use ultraviolet light having a wavelength range of 200 to 500 nm or visible light. Various light sources that emit light in this wavelength range can be used.

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

The color filter coloring material of the present invention is used by the liquid crystal composition of the present invention. When used, it is possible to provide a liquid crystal display device which prevents a decrease in the voltage holding ratio (VHR) of the liquid crystal layer and an increase in the ion density (ID), and solves the problems of display failure such as whitening, misalignment, and afterimage.

As a method for producing the photocurable composition, a method is generally used as follows: A dye and/or a pigment composition, an organic solvent, and a dispersing agent for a color filter of the present invention are used as an essential component, and these are mixed and stirred to be dispersed to be uniform, and first prepared to form a color filter. The photocurable composition is prepared by adding a photocurable compound, a thermoplastic resin or a photopolymerization initiator as needed, and the like, to a pigment dispersion liquid in a pixel portion of the sheet.

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

As the dispersing agent used herein, for example, it may contain: BYK-Chemie DISPERBYK 130, DISPERBYK 161, DISPERBYK 162, DISPERBYK 163, DISPERBYK 170, DISPERBYK 171, DISPERBYK 174, DISPERBYK 180, DISPERBYK 182, DISPERBYK 183, DISPERBYK 184, DISPERBYK 185, DISPERBYK 2000, DISPERBYK 2001, DISPERBYK 2020, DISPERBYK 2050, DISPERBYK 2070, DISPERBYK 2096, DISPERBYK 2150, DISPERBYK 2164, DISPERBYK LPN21116, DISPERBYK LPN6919, EFKA 46 of EFKA, EFKA 47, EFKA 452, EFKA LP4008, EFKA 4009, EFKA LP4010, EFKA LP4050, EFKA LP4055, EFKA 400, EFKA 401 , EFKA 402, EFKA 403, EFKA 450, EFKA 451, EFKA 453, EFKA 4540, EFKA 4550, EFKA LP4560, EFKA 120, EFKA 150, EFKA 1501, EFKA 1502, EFKA 1503, Solsperse 3000, Solsperse 9000, Solsperse by Lubrizol 13240, Solsperse 13650, Solsperse 13940, Solsperse 17000, Solsperse 18000, Solsperse 20000, Solsperse 21000, Solsperse 20000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, Solsperse 32000, Solsperse 36000, Solsperse 37000, Solsperse 38000, S Olsperse 41000, Solsperse 42000, Solsperse 43000, Solsperse 46000, Solsperse 54000, Solsperse 71000, Ajisper PB711, Ajisper PB821, Ajisper PB822, Ajisper PB814, Ajisper PN411, Ajisper PA111, etc., or acrylic resin , urethane resin, alkyd resin, wood rosin, rosin gum, oil rosin and other natural rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, oxidized rosin, maleic rosin and other modified pine Rosin, rosin amine, lime rosin, rosin alkylene oxide adduct, rosin alkyd adduct, rosin modified phenol and other rosin derivatives are equivalent to a liquid and water-insoluble synthetic resin at room temperature. The addition of such dispersants or resins also contributes to a reduction in flocculation, an increase in the dispersion stability of the pigment, and an increase in the viscosity characteristics of the dispersion.

Further, as a dispersing aid, an organic pigment derivative such as phthalic acid may also be contained. Methyl carbamide methyl derivative, phthalimide sulfonic acid derivative, phthalimide N-(dialkylamino)methyl derivative, phthalimide N a -(dialkylaminoalkyl)sulfonamide derivative or the like. Of course, these derivatives may also be used in combination of two or more different types.

As the thermoplastic resin used in the preparation of the photocurable composition, for example, Examples thereof include a urethane-based resin, an acrylic resin, a polyamine-based resin, a polyimide-based resin, a styrene maleic acid-based resin, and a styrene maleic anhydride-based resin.

Examples of the photocurable compound include, for example, 1,6-hexanediol dipropylene. Acid ester, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis(acryloxyethoxy)bisphenol A, 3-methylpentanediol diacrylate Difunctional monomers such as trimethylolpropane triacrylate, neopentyl alcohol triacrylate, tris[2-(methyl) propylene oxyethyl ester], two new Molecular weights such as pentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and the like having relatively small molecular weight, polyester acrylate, polyacrylic acid urethane, polyether acrylate, etc. Large polyfunctional monomer.

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

Further, a known photosensitizer may be used in combination with the above photopolymerization initiator. Make The photosensitizer may, for example, be an amine, a urea, a compound having a sulfur atom, a compound having a phosphorus atom, a compound having a chlorine atom or a nitrile or another compound having a nitrogen atom. These may be used singly or in combination of two or more.

The blending ratio of the photopolymerization initiator is not particularly limited, and is relative to the mass basis. The compound having a photopolymerizable or photocurable functional group is preferably in the range of 0.1 to 30%. When it is less than 0.1%, the sensitivity at the time of photocuring tends to be lowered, and when it exceeds 30%, the crystal of the photopolymerization initiator is precipitated when the coating film of the pigment-dispersed resist is dried, and the physical properties of the coating film are deteriorated. The situation.

Various materials as described above may be used, on a mass basis, relative to the color of the present invention The dye and/or pigment composition for the filter is stirred and dispersed in an amount of from 300 to 1,000 parts by weight per 100 parts of the organic solvent and from 1 to 100 parts of the dispersing agent to make it uniform, thereby obtaining the above-mentioned dyeing liquid. Then, a total of 3 to 20 parts of a thermoplastic resin and a photocurable compound, and a photocurable compound per 1 part of the pigment composition for a color filter of the present invention are added to the pigment dispersion liquid. In a portion, 0.05 to 3 parts of a photopolymerization initiator is added, and if necessary, an organic solvent is further added, and the mixture is stirred and dispersed to make it uniform, and a photocurable composition for forming a pixel portion of the color filter is obtained.

As the developer, a known organic solvent or an alkaline aqueous solution can be used. especially When the photocurable composition contains a thermoplastic resin or a photocurable compound, and at least one of them has an acid value and is alkali-soluble, it is washed with an alkaline aqueous solution to a color filter pixel. The formation of the ministry is effective.

A method of manufacturing a color filter pixel portion using photolithography has been performed. In detail, the color filter pixel portion prepared by using the pigment composition for a color filter of the present invention may be further subjected to electroplating, transfer, microelectrolysis, PVED (photovoltaic electrodeposition). A color filter is produced by forming a pixel portion of each color by a method such as a method, an inkjet method, a reverse printing method, or a thermosetting method.

(alignment film)

In the liquid crystal display device of the present invention, the liquid on the first substrate and the second substrate Since the liquid crystal composition is aligned on the surface on which the crystal composition contacts, the alignment film is disposed between the color filter and the liquid crystal layer in the liquid crystal display device requiring the alignment film, but the film thickness of the alignment film is thinner. When it is 100 nm or less, the interaction between the pigment of the pigment or the like constituting the color filter and the liquid crystal compound constituting the liquid crystal layer cannot be completely blocked.

Further, in a liquid crystal display device which does not use an alignment film, a color filter is formed The interaction between the pigment such as a pigment and the liquid crystal compound constituting the liquid crystal layer becomes larger.

As an alignment film material, polyimine, polyamine, BCB can be used. (benzocyclobutene polymer, benzocyclobutene polymer), transparent organic material such as polyvinyl alcohol, and more preferably an aliphatic or alicyclic ring such as p-phenylenediamine or 4,4'-diaminodiphenylmethane a diamine such as a diamine, an aliphatic or alicyclic tetracarboxylic anhydride such as butane tetracarboxylic anhydride or 2,3,5-tricarboxycyclopentyl acetic anhydride, or an aromatic tetracarboxylic anhydride such as pyromellitic dianhydride. The synthesized polylysine is subjected to a ruthenium imidization of a polyimide film. In this case, the alignment imparting method is usually a rubbing method, but when it is used for a vertical alignment film or the like, it may be used without imparting alignment.

As an alignment film material, a compound containing chalcones, cinnamic acid ester, A material such as cassia sulfhydryl or azo group may be used in combination with a material such as polyimine or polyamine. In this case, the alignment film may be rubbed or a photo-alignment technique may be used.

The alignment film is usually coated on the substrate by a spin coating method or the like. A resin film is formed on the film material, but a uniaxial stretching method, a Langmuir-Blodgett method, or the like can also be used.

(transparent electrode)

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

[Examples]

Hereinafter, a part of the best mode of the present invention will be described in detail by way of examples, but The invention is not limited to the embodiments. In addition, "%" in the composition of the following examples and comparative examples means "% by mass".

The physical properties of the liquid crystal composition are as follows.

T _NI : the nematic phase-isotropic liquid phase transfer temperature (°C) is the upper limit temperature of the liquid crystal phase

△ ε: dielectric anisotropy

△n: refractive index anisotropy

η: viscosity at 20 ° C (mPa.s)

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

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

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

ID: ion density at 70 ° C (pC/cm ² )

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

For the description of the compounds, the following abbreviations are used.

End n (number) C _n H _2n+1 -

-2- -CH ₂ CH ₂ -

-10- -CH ₂ O-

-01- -OCH ₂ -

-0n -OC _n H _2n+1

-1=1- -HC=CH-

-V0- -COO-

Ndm- C _n H _2n+1 -HC=CH-(CH ₂ ) _m-1 -

The afterimage evaluation of the liquid crystal display element causes a specific fixed pattern to be displayed on the display area After 1000 hours of display, the level of the afterimage of the fixed pattern when the entire screen was uniformly displayed was evaluated visually in accordance with the following four levels.

◎ no afterimage

○ There are very few afterimages, but they are also acceptable levels.

△ There is an afterimage and it is an unacceptable level

× There is an afterimage and it is quite bad

[Production of color filter]

[Preparation of coloring composition]

[Red dye coloring composition 1]

Add 10 parts of red dye 1 (CI solvent red 124) to a plastic bottle, add 55 parts of propylene glycol monomethyl ether acetate, 0.3-0.4mm The Sepr beads were dispersed by a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, and then filtered using a 5 μm filter to obtain a dye coloring liquid. 75.00 parts of the dye coloring liquid and 5.50 parts of polyester acrylate resin (ARONIX (trade name) M7100, manufactured by Toagosei Chemical Co., Ltd.), dipentaerythritol hexaacrylate (KAYARAD (trade name) DPHA, Japan Pharmacological Co., Ltd. manufactured by 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 using a dispersing mixer for stirring, and using the aperture 1.0 The filter of μm was filtered to obtain a red dye coloring composition 1.

[Red dye coloring composition 2]

Use 8 parts of red dye 1 (C.I. Solvent Red 124) and 2 parts of yellow dye 2 (C.I. Solvent Yellow 21) In place of the above-mentioned red dye coloring composition 1 of 10 parts of red dye 1, red dye coloring composition 2 was obtained in the same manner as above.

[Red dye coloring composition 3]

Use 10 parts of red dye 2 (C.I. Solvent Red 1) instead of the above red dye The red dye coloring composition 3 was obtained in the same manner as above for 10 parts of the red dye 1 of the color composition 1.

[Green dye coloring composition 1]

Use 3 parts of blue dye 1 (C.I. Solvent Blue 67) and 7 parts of yellow dye 1 (C.I. Solvent Yellow 162) In place of the above-mentioned red dye coloring composition 1 of 10 parts of red dye 1, a green dye coloring composition 1 was obtained in the same manner as above.

[Green dye coloring composition 2]

Replace 7 parts of yellow dye 1 of the above green dye coloring composition 1 with 4 parts Green dye coloring composition 2 was obtained in the same manner as above, with yellow dye 1 (C.I. Solvent Yellow 162) and 3 parts of yellow dye 3 (C.I. Solvent Yellow 82).

[Green dye coloring composition 3]

Use 10 parts of green dye 1 (C.I. Solvent Green 7) instead of the above green dye The green dye coloring composition 3 was obtained in the same manner as above, with 3 parts of the blue dye 1 and 7 parts of the yellow dye 1 of the color composition 1.

[Blue dye coloring composition 1]

Use 10 parts of blue dye 2 (C.I. Solvent Blue 12) instead of the above red dye The blue dye coloring composition 1 was obtained in the same manner as above for 10 parts of the red dye 1 of the color composition 1.

[Yellow dye coloring composition 1]

Use 10 parts of yellow dye 1 (C.I. Solvent Yellow 21) instead of the above red dye The yellow dye coloring composition 1 was obtained in the same manner as above for 10 parts of the red dye 1 of the color composition 1.

[Yellow dye coloring composition 2]

Use 10 parts of yellow dye 4 (C.I. Solvent Yellow 2) instead of the above yellow dye The yellow dye coloring composition 2 was obtained in the same manner as above for 10 parts of the yellow dye 1 of the color composition 1.

[Red Pigment Coloring Composition 1]

Add 10 parts of Red Pigment 1 (CI Pigment Red 254, "IRGAPHOR RED BT-CF" manufactured by BASF Corporation) to a plastic bottle, add 55 parts of propylene glycol monomethyl ether acetate, DISPERBYK LPN21116 (BYK-Chemie Co., Ltd. Manufactured in 7.0 parts, 0.3-0.4mm manufactured by Saint-Gobain The zirconia beads "ER-120S" was dispersed by a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, and then filtered through a filter of 1 μm to obtain a pigment dispersion liquid. 75.00 parts of the pigment dispersion and 5.50 parts of a polyester acrylate resin (ARONIX (trade name) M7100, manufactured by Toagosei Chemical Co., Ltd.), dipentaerythritol hexaacrylate (KAYARAD (trade name) DPHA, Japan Pharmacological Co., Ltd. manufactured by 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 using a dispersing mixer for stirring, and using the aperture 1.0 The filter of μm was filtered to obtain a red pigment coloring composition 1.

[Red Pigment Coloring Composition 2]

Use 6 parts of red pigment 1, 2 parts of red pigment 2 (C.I. Pigment Red 177, DIC FASTOGEN SUPER RED ATY-TR) manufactured by Co., Ltd., and 2 parts of yellow pigment 2 (CI Pigment Yellow 139) were substituted for 10 parts of red pigment 1 of the above red pigment coloring composition 1 to obtain red pigment coloring in the same manner as described above. Composition 2.

[Green Pigment Coloring Composition 1]

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

[Green Pigment Coloring Composition 2]

Use 4 parts of green pigment 2 (C.I. Pigment Green 58, DIC Corporation FASTOGEN GREEN A110) and 6 parts of yellow pigment 3 (CI Pigment Yellow 138) were used instead of the above green pigment coloring composition 1 of 6 parts of green pigment 1 and 4 parts of yellow pigment 1 to obtain a green pigment coloring composition in the same manner as above. Object 2.

[Blue pigment coloring composition 1]

1.80 parts of the triarylmethane pigment (Table 1 Compound No. 2) represented by the above formula (1), 2.10 parts of BYK-2164 (BYK-Chemie), 11.10 parts of propylene glycol monomethyl ether acetate, 0.3-0.4 mm Sepr beads were added to a plastic bottle, and dispersed by a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours to obtain a pigment dispersion. 75.00 parts of the dye coloring liquid and 5.50 parts of polyester acrylate resin (ARONIX (trade name) M7100, manufactured by Toagosei Chemical Co., Ltd.), dipentaerythritol hexaacrylate (KAYARAD (trade name) DPHA, Japan Pharmacological Co., Ltd.) 5.00 parts, 1.00 parts of diphenyl ketone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.), and 13.5 parts of UCAR Ester EEP (manufactured by Union Carbide Co., Ltd.) using a dispersing mixer The mixture was stirred and filtered using a filter having a pore size of 1.0 μm to obtain a blue pigment coloring composition 1.

[Blue pigment coloring composition 2]

A triarylmethane pigment represented by the formula (1) (Compound No. 5 of Table 1) was used. In place of the above-described blue pigment coloring composition 1, the triarylmethane pigment, the blue pigment coloring composition 2 was obtained in the same manner as described above.

[Blue pigment coloring composition 3]

A triarylmethane pigment represented by the formula (1) (Compound No. 1 of Table 1) was used. In place of the above-described blue pigment coloring composition 1, the triarylmethane pigment, the blue pigment coloring composition 3 was obtained in the same manner as described above.

[Blue pigment coloring composition 4]

A triarylmethane pigment represented by the formula (1) is used (Table 4, Compound No. 29) In place of the above-described blue pigment coloring composition 1, the triarylmethane pigment, the blue pigment coloring composition 4 was obtained in the same manner as described above.

[Yellow Pigment Coloring Composition 1]

Use 10 parts of yellow pigment 1 (C.I. Pigment Yellow 150, manufactured by LANXESS) FANCHON FAST YELLOW E4GN) In place of the above-mentioned red pigment coloring composition 1 of 10 parts of red pigment 1, a yellow pigment coloring composition 1 was obtained in the same manner as above.

[Production of color filter]

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

Next, the green coloring composition is similarly rotated by spin coating to have a film thickness of 2 Coating is carried out in the form of μm. After drying, the stripe-like coloring layer is exposed and developed at a portion shifted from the red pixel by an exposure machine, thereby forming a green pixel adjacent to the red pixel.

Next, the blue coloring composition is similarly applied by spin coating to a film thickness of 2 Mm forms a blue pixel adjacent to the red pixel and the green pixel. Thereby, a color filter having stripes of three colors of red, green, and blue on a transparent substrate is obtained.

The same is also applied to the yellow coloring composition by spin coating as needed. Mm forms a blue pixel adjacent to the red pixel and the green pixel. Thereby, a color filter having pixels of stripes of four colors of red, green, blue, and yellow on a transparent substrate is obtained.

Using the dye coloring composition or the pigment coloring composition shown in Table 8, Color filters 1 to 4 and comparison color filters 1.

(Examples 1 to 4)

An electrode structure is formed on the first and second substrates, and a vertical alignment alignment film is formed on the opposite side of each of the electrodes to perform a weak rubbing treatment to form a VA unit, and the table 9 is sandwiched between the first substrate and the second substrate. The liquid crystal composition 1 having a negative dielectric anisotropy is shown. Next, the liquid crystal display device of Example 1 (d _gap = 3.5 μm, alignment film SE-5300) was produced using the color filters 1 to 4 shown in Table 8. The VHR and ID of the obtained liquid crystal display device were measured. Moreover, the afterimage evaluation of the obtained liquid crystal display device was performed. The results are shown in Table 10.

The liquid crystal display devices of Embodiments 1 to 4 can achieve a higher VHR and a smaller one. ID. In addition, there is no residual image in the afterimage evaluation, or even if there are few, it is an allowable level.

(Comparative examples 1 to 8)

In the VA unit used in the embodiment 1, the clamping shown in Table 11 has a negative Comparison of Dielectric Anisotropy Liquid crystal composition 1 and comparative liquid crystal composition 2 were prepared using the color filters 1 to 4 shown in Table 8 to prepare liquid crystal display devices of Comparative Examples 1 to 8, and VHR and ID were measured. Moreover, the afterimage evaluation of this liquid crystal display device was performed. The results are shown in Table 12 and Table 13.

The liquid crystal display devices of Comparative Examples 1 to 8 and the liquid crystal display device of the present invention Compared, the VHR is lower and the ID is also increased. Further, the generation of the afterimage was also confirmed in the afterimage evaluation, and it was not an acceptable level.

(Comparative Example 9)

The liquid crystal composition 1 having negative dielectric anisotropy shown in Table 9 was sandwiched in the VA unit used in Example 1, and the liquid crystal display of Comparative Example 9 was produced using the comparative color filter 1 shown in Table 8. The device measures its VHR and ID. Moreover, the afterimage evaluation of this liquid crystal display device was performed. The results are shown in Table 14.

The liquid crystal display device of Comparative Example 9 and the liquid product display device of the present invention Compared, the VHR is lower and the ID is also increased. Further, the generation of the afterimage was also confirmed in the afterimage evaluation, and it was not an acceptable level.

(Comparative examples 10 to 13)

In the same manner as in the first embodiment, the ratio of negative dielectric anisotropy shown in Table 15 was sandwiched. The liquid crystal display devices of Comparative Examples 10 to 13 were produced using the color filters 1 to 4 shown in Table 8 with respect to the liquid crystal composition 3, and the VHR and ID thereof were measured. Moreover, the afterimage evaluation of this liquid crystal display device was performed. The results are shown in Table 16.

Liquid crystal display device of Comparative Examples 10 to 13 and liquid crystal display device of the present invention In comparison, the VHR is lower and the ID is also increased. Moreover, the generation of afterimages was also confirmed in the afterimage evaluation, and Not a tolerable level.

(Examples 5 to 12)

The negative dielectric anisotropic liquid crystal shown in Table 17 was sandwiched in the same manner as in Example 1. The liquid crystal display devices of Examples 5 to 12 were produced using the color filters shown in Table 8, and their VHR and ID were measured. Moreover, the afterimage evaluation of this liquid crystal display device was performed. The results are shown in Tables 18 and 19.

The liquid crystal display devices of Embodiments 5 to 12 can achieve a higher VHR and a smaller one. ID. In addition, there is no residual image in the afterimage evaluation, or even if there are few, it is an allowable level.

(Examples 13 to 28)

The negative dielectric anisotropic liquid crystal shown in Table 20 was sandwiched in the same manner as in Example 1. The liquid crystal display devices of Examples 13 to 28 were produced using the color filters shown in Table 8, and their VHR and ID were measured. Moreover, the afterimage evaluation of this liquid crystal display device was performed. The results are shown in Tables 21 to 24.

The liquid crystal display devices of Embodiments 13 to 28 can achieve a higher VHR and smaller ID. In addition, there is no residual image in the afterimage evaluation, or even if there are few, it is an allowable level.

(Examples 29 to 40)

The negative dielectric anisotropic liquid crystal shown in Table 25 was sandwiched in the same manner as in Example 1. The liquid crystal display devices of Examples 29 to 40 were produced using the color filters shown in Table 8, and their VHR and ID were measured. Moreover, the afterimage evaluation of this liquid crystal display device was performed. The results are shown in Tables 26-28.

The liquid crystal display devices of Embodiments 29 to 40 can achieve a higher VHR and smaller ID. In addition, there is no residual image in the afterimage evaluation, or even if there are few, it is an allowable level.

(Examples 41 to 48)

The negative dielectric anisotropic liquid crystal shown in Table 29 was sandwiched in the same manner as in Example 1. The liquid crystal display devices of Examples 41 to 48 were produced using the color filters shown in Table 8, and their VHR and ID were measured. Moreover, the afterimage evaluation of this liquid crystal display device was performed. The results are shown in Tables 30 and 31.

The liquid crystal display devices of Embodiments 41 to 48 can achieve a higher VHR and smaller ID. In addition, there is no residual image in the afterimage evaluation, or even if there are few, it is an allowable level.

(Examples 49 to 60)

The negative dielectric anisotropic liquid crystal shown in Table 32 was sandwiched in the same manner as in Example 1. The liquid crystal display devices of Examples 49 to 60 were produced using the color filters shown in Table 8, and their VHR and ID were measured. Moreover, the afterimage evaluation of this liquid crystal display device was performed. The results are shown in Tables 33 to 35.

The liquid crystal display devices of Examples 49 to 60 can achieve a higher VHR and smaller ID. In addition, there is no residual image in the afterimage evaluation, or even if there are few, it is an allowable level.

(Examples 61 to 76)

The negative dielectric anisotropic liquid crystal shown in Table 36 was sandwiched in the same manner as in Example 1. The liquid crystal display devices of Examples 61 to 76 were produced using the color filters shown in Table 8, and their VHR and ID were measured. Moreover, the afterimage evaluation of this liquid crystal display device was performed. The results are shown in Tables 37 to 40.

The liquid crystal display devices of Embodiments 61 to 76 can achieve a higher VHR and smaller ID. In addition, there is no residual image in the afterimage evaluation, or even if there are few, it is an allowable level.

(Examples 77 to 92)

In the same manner as in the first embodiment, the negative dielectric anisotropic liquid crystal shown in Table 41 was sandwiched. The liquid crystal display devices of Examples 77 to 92 were produced using the color filters shown in Table 8, and their VHR and ID were measured. Moreover, the afterimage evaluation of this liquid crystal display device was performed. The results are shown in Tables 42 to 45.

The liquid crystal display devices of Embodiments 77 to 92 can achieve a higher VHR and smaller ID. In addition, there is no residual image in the afterimage evaluation, or even if there are few, it is an allowable level.

(Examples 93 to 100)

In the same manner as in the first embodiment, the negative dielectric anisotropic liquid crystal shown in Table 46 was sandwiched. The liquid crystal display devices of Examples 93 to 100 were produced using the color filters shown in Table 8, and their VHR and ID were measured. Moreover, the afterimage evaluation of this liquid crystal display device was performed. The results are shown in Tables 47 and 48.

The liquid crystal display devices of Embodiments 93 to 100 can achieve higher VHR and smaller ID. In addition, there is no residual image in the afterimage evaluation, or even if there are few, it is an allowable level.

(Examples 101 to 112)

In the same manner as in the first embodiment, the negative dielectric anisotropic liquid crystal shown in Table 49 was sandwiched. The liquid crystal display devices of Examples 101 to 112 were produced using the color filters shown in Table 8, and their VHR and ID were measured. Moreover, the afterimage evaluation of this liquid crystal display device was performed. The results are shown in Tables 50 to 52.

The liquid crystal display devices of Examples 101 to 112 can realize a higher VHR and a smaller ID. In addition, there is no residual image in the afterimage evaluation, or even if there are few, it is an allowable level.

(Examples 113 to 124)

In the same manner as in Example 1, the negative dielectric anisotropic liquid crystal shown in Table 53 was sandwiched, and the liquid crystal display devices of Examples 113 to 124 were produced using the color filters shown in Table 8, and the VHR and ID were measured. Moreover, the afterimage evaluation of this liquid crystal display device was performed. The results are shown in Tables 54 to 56.

The liquid crystal display devices of Examples 113 to 124 can realize a higher VHR and a smaller ID. In addition, there is no residual image in the afterimage evaluation, or even if there are few, it is an allowable level.

(Examples 125 to 128)

In the same manner as in Example 1, the negative dielectric anisotropic liquid crystal shown in Table 57 was sandwiched, and the liquid crystal display devices of Examples 125 to 128 were produced using the color filters shown in Table 8, and the VHR and ID were measured. Moreover, the afterimage evaluation of this liquid crystal display device was performed. The results are shown in Table 58.

The liquid crystal display devices of Embodiments 125 to 128 can realize a higher VHR and a smaller ID. In addition, there is no residual image in the afterimage evaluation, or even if there are few, it is an allowable level.

(Examples 129 to 132)

Mixing 2-methyl-acrylic acid 4'-{2-[4-(2-propenyloxy-ethyl)-benzene in liquid crystal composition 1 having negative dielectric anisotropy used in Example 1. The oxycarbyl]-ethyl}-biphenyl-4-yl ester was 0.3% by mass to prepare a liquid crystal composition 33. The liquid crystal composition 33 was sandwiched between the VA units used in Example 1, and ultraviolet rays were irradiated for 600 seconds (3.0 J/cm ² ) in a state where a driving voltage was applied between the electrodes, and polymerization treatment was carried out. Next, Table 8 was used. The liquid crystal display devices of Examples 129 to 132 were produced by the color filters 1 to 4 shown, and their VHR and ID were measured. Moreover, the afterimage evaluation of this liquid crystal display device was performed. The results are shown in Table 59.

The liquid crystal display devices of Examples 129 to 132 can realize a higher VHR and a smaller ID. In addition, there is no residual image in the afterimage evaluation, or even if there are few, it is an allowable level.

(Examples 133 to 136)

The liquid crystal composition 34 was prepared by mixing 0.3% by mass of bis(methacrylic acid) biphenyl-4,4'-diester in the liquid crystal composition 29 having a negative dielectric anisotropy. The liquid crystal composition 30 was sandwiched between the VA units used in Example 1, and ultraviolet rays were irradiated for 600 seconds (3.0 J/cm ² ) in a state where a driving voltage was applied between the electrodes, and polymerization treatment was carried out. Next, Table 8 was used. The liquid crystal display devices of Examples 133 to 136 were produced from the color filters 1 to 4 shown, and their VHR and ID were measured. Moreover, the afterimage evaluation of this liquid crystal display device was performed. The results are shown in Table 60.

The liquid crystal display devices of Examples 133 to 136 can realize a higher VHR and a smaller ID. In addition, there is no residual image in the afterimage evaluation, or even if there are few, it is an allowable level.

(Examples 137 to 140)

The liquid crystal composition 35 was prepared by mixing 0.3% by mass of 3-fluorobiphenyl-4,4'-diester of bis(methacrylic acid) in the liquid crystal composition 32 having negative dielectric anisotropy. The liquid crystal composition 35 was sandwiched between the VA units used in Example 1, and ultraviolet rays were irradiated for 600 seconds (3.0 J/cm ² ) in a state where a driving voltage was applied between the electrodes, and polymerization treatment was carried out. Next, Table 8 was used. The liquid crystal display devices of Examples 137 to 140 were produced for the color filters 1 to 4 shown, and their VHR and ID were measured. Moreover, the afterimage evaluation of this liquid crystal display device was performed. The results are shown in Table 61.

The liquid crystal display devices of Examples 137 to 140 can realize a higher VHR and a smaller ID. In addition, there is no residual image in the afterimage evaluation, or even if there are few, it is an allowable level.

1‧‧‧Substrate

2a‧‧‧Color filter layer with specific pigments

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

3b‧‧‧pixel electrode layer

4‧‧‧Alignment film

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

Claims (14)

A liquid crystal display device comprising a first substrate, a second substrate, a liquid crystal composition layer sandwiched between the first substrate and the second substrate, a color filter composed of a black matrix and at least RGB three-color pixel portions, and a pixel The liquid crystal composition layer is composed of a liquid crystal composition containing one or two or more compounds selected from the group consisting of a compound represented by the formula (LC1) to the formula (LC4), and an electrode. (wherein R ₁ and R ₂ each independently represent an alkyl group having 1 to 15 carbon atoms, and one or more of the CH ₂ groups in the alkyl group may be via O-, in a manner in which the oxygen atoms are not directly adjacent to each other; -CH=CH-, -CO-, -OCO-, -COO-, -C≡C-, -CF ₂ O- or -OCF ₂ -, one or more hydrogen atoms in the alkyl group It may be optionally substituted by halogen, and A ₁ and A ₂ each independently represent any of the following structures, (In this structure, one or two or more CH ₂ groups of the cyclohexane ring may be substituted with an oxygen atom, and in this structure, one or two or more CH groups of the benzene ring may be substituted by a nitrogen atom, and, in the structure, One or more hydrogen atoms may be substituted by Cl, CF ₃ or OCF ₃ ), and Z ₁ to Z ₄ each independently represent a single bond, -CH=CH-, -C≡C-, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -COO-, -OCH ₂ -, -CH ₂ O-, -OCF ₂ - or -CF ₂ O-, Z ₅ represents a CH ₂ group or an oxygen atom, and is present in Z At least one of ₁ and Z ₂ is not a single bond, l ₁ represents 0 or 1, m ₁ and m ₂ independently represent 0 to 3, m ₁ + m ₂ is 1, 2 or 3) the RGB three colors The pixel portion contains a triarylmethane pigment represented by the following formula (1) as a colorant in the B pixel portion. (wherein R ¹ to R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, or an aryl group which may have a substituent; and R ¹ to R ⁶ may have a substituent; In the case of an alkyl group, adjacent R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to form a ring structure; X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, Or an alkyl group having 1 to 8 carbon atoms which may have a substituent; the Z ^- series is selected from an integer represented by (P ₂ Mo _y W _18-y O ₆₂ ) ^6- /6 and y = 0, 1, 2 or 3. Heteropolyoxometalate anion, or (SiMoW ₁₁ O ₄₀ ) ^4- /4 heteropolyoxometalate anion, or defect Dawson type phosphotungstic acid heteropolyoxometalate anion At least one anion; when a plurality of formulas (1) are contained in one molecule, they may be the same structure or different structures. The liquid crystal display device of claim 1, wherein the RGB three-color pixel portion The D pixel portion contains a diketo-pyrrolo-pyrrole pigment and/or an anionic red organic dye as a colorant, and the G pixel portion contains a pigment selected from the group consisting of a halogenated metal anthraquinone pigment and an anthraquinone. At least one of a group consisting of a mixture of a green dye, an anthrain-based blue dye, and an azo-based yellow organic dye is used as a colorant. The liquid crystal display device according to claim 1 or 2, wherein the B pixel portion contains the following triarylmethane pigment: in the formula (1), R ¹ to R ⁶ are each independently a hydrogen atom; a C 1~4 alkyl group having a substituent, or a phenyl group, X ¹ and X ² are a hydrogen atom, and the Z ⁻ system is selected from (P ₂ Mo _y W _18-y O ₆₂ ) ^6- /6 and a heteropolyoxometalate anion of an integer of y = 0, 1, 2 or 3, or a heteropolyoxometalate anion of (SiMoW ₁₁ O ₄₀ ) ⁴ / 4 or a Dawson type phosphotungstic anion (1) At least one anion of P ₂ W ₁₇ O ₆₁ ) ^10- /10. The liquid crystal display device of claim 1 or 2, wherein the G pixel portion contains a halogenated metal ruthenium pigment selected from the group consisting of Al, Si, Sc, Ti, V, Mg, Fe, Co, A metal in a group consisting of Ni, Zn, Cu, Ga, Ge, Y, Zr, Nb, In, Sn, and Pb is used as a center metal. When the center metal is trivalent, the center metal bond is 1 Any one of a halogen atom, a hydroxyl group or a sulfonic acid group, or crosslinked by oxygen or sulfur, in the case where the central metal is a tetravalent metal, one oxygen atom is bonded to the central metal or may be the same Any one of two halogen atoms, a hydroxyl group or a sulfonic acid group may be different. The liquid crystal display device of claim 1 or 2, wherein the R pixel portion contains CI Solvent Red 124, and the G pixel portion contains CI Solvent Blue 67 and CI solvent. A mixture of yellow (CI Solvent Yellow) 82 or CI Solvent Yellow 162. The liquid crystal display device according to claim 1 or 2, wherein the R pixel portion contains CI Pigment Red 254, and the G pixel portion contains a color selected from CI Pigment Green 7. One or two or more of CI Pigment Green 36 and CI Pigment Green 58. The liquid crystal display device of claim 1 or 2, wherein the color filter system The black matrix, the RGB three-color pixel portion, and the Y pixel portion are included in the Y pixel portion, and are selected from the group consisting of CI Pigment Yellow 150, CI Pigment Yellow 215, CI Pigment Yellow 185, CI Pigment Yellow 138, and CI. At least one yellow organic dye pigment of the group consisting of Pigment Yellow 139, CI Solvent Yellow 21, CI Solvent Yellow 82, CI Solvent Yellow 83:1, CI Solvent Yellow 33 and CI Solvent Yellow 162 is used as the colorant. A liquid crystal display device according to claim 1 or 2, wherein a liquid crystal composition containing one or more compounds represented by the formula (LC5) is used as the liquid crystal composition layer. (wherein R ₁ and R ₂ each independently represent an alkyl group having 1 to 15 carbon atoms, and one or more of the CH ₂ groups in the alkyl group may be via O-, in a manner in which the oxygen atoms are not directly adjacent to each other; -CH=CH-, -CO-, -OCO-, -COO-, -C≡C-, -CF ₂ O- or -OCF ₂ -, one or more hydrogen atoms in the alkyl group It may be optionally substituted by halogen, and B ₁ to B ₃ each independently represent any of the following structures, (wherein, one or more CH ₂ CH ₂ groups in the cyclohexane ring may be substituted by -CH=CH-, -CF ₂ O-, -OCF ₂ -, one or two of the benzene rings More than one CH group may be substituted by a nitrogen atom), and Z ₃ and Z ₄ each independently represent a single bond, -CH=CH-, -C≡C-, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ - , -COO-, -OCH ₂ -, -CH ₂ O-, -OCF ₂ - or -CF ₂ O-, m ₁ represents 0 to 3). The liquid crystal display device of claim 1 or 2, wherein the general formula (LC1) is one selected from the group consisting of compounds represented by the following general formula (LC1)-1 to (LC1)-7 Species or more than two compounds, (wherein R ¹ and R ² each independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, and an alkenyloxy group having 2 to 7 carbon atoms. ). The liquid crystal display device of claim 1 or 2, wherein the formula (LC2) is one selected from the group consisting of compounds represented by the following formula (LC2)-1 to (LC2)-15 Species or more than two compounds, (wherein R ₁ and R ₂ each independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; , Z ₁ represents -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -OCF ₂ - or -CF ₂ O-, and A ¹ represents any of the following structures, ). The liquid crystal display device of claim 1 or 2, wherein the general formula (LC3) is one selected from the group consisting of compounds represented by the following general formula (LC3)-1 to (LC3)-6 The compound of the formula (LC4) is one or two or more compounds selected from the group consisting of compounds represented by the following formula (LC4)-1 to (LC4)-4, (wherein R ₁ and R ₂ each independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; ). The liquid crystal display device of claim 8, wherein the general formula (LC5) is one or two selected from the group consisting of compounds represented by the general formula (LC5)-1 to the general formula (LC5)-13. The above compounds, (wherein R ₁ and R ₂ each independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; ). 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 more kinds of polymerizable compounds. The liquid crystal display device of claim 13, wherein the polymerizable compound is a polymerizable compound represented by the formula (PC1). (wherein P ₁ represents a polymerizable functional group, Sp ₁ represents a spacer group having 0 to 20 carbon atoms, and Q ₁ represents a single bond, -O-, -NH-, -NHCOO-, -OCONH- , -CH=CH-, -CO-, -COO-, -OCO-, -OCOO-, -OOCO-, -CH=CH-, -CH=CH-COO-, -OCO-CH=CH- or- C≡C-, n ₁ , n ₂ represents 1, 2 or 3, MG represents a mesogenic group or a liquid crystal-derived support group, and R ₁₀ represents a halogen atom, a cyano group or an alkyl group having 1 to 25 carbon atoms. One or more than two or more CH ₂ groups in the alkyl group may be via O-, -S-, -NH-, -N(CH ₃ )-, -CO-, in a manner in which the oxygen atoms are not directly adjacent to each other. -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-substituted, or R ₁₀ represents P ₂ -Sp ₂ -Q ₂ - (wherein P ₂ , Sp ₂ , Q ₂ independently represents the same meaning as P ₁ , Sp ₁ , and Q ₁ )).