JP6291724B2 - Liquid crystal display - Google Patents

Description

  The present invention relates to a liquid crystal display device.

  Liquid crystal display devices are used in various electric appliances for home use, measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, etc., including clocks and calculators. Typical liquid crystal display methods include TN (twisted nematic), STN (super twisted nematic), DS (dynamic light scattering), GH (guest / host), and IPS (in-plane switching). Type, OCB (optical compensation birefringence) type, ECB (voltage controlled birefringence) type, VA (vertical alignment) type, CSH (color super homeotropic) type, FLC (ferroelectric liquid crystal), etc. . As a driving method, multiplex driving is generally used instead of conventional static driving, and the active matrix (AM) method driven by a TFT (thin film transistor), TFD (thin film diode) or the like has become mainstream recently. ing.

As shown in FIG. 1, a general color liquid crystal display device has a transparent electrode layer (a common electrode) between one alignment film of two substrates (1) each having an alignment film (4) and the substrate. 3a) and a color filter layer (2), a pixel electrode layer (3b) is provided between the other alignment film and the substrate, these substrates are arranged so that the alignment films face each other, and a liquid crystal layer ( 5) is sandwiched.
The color filter layer is composed of a color filter composed of a black matrix, a red colored layer (R), a green colored layer (G), a blue colored layer (B), and, if necessary, a yellow colored layer (Y). The
The liquid crystal material constituting the liquid crystal layer has been subjected to a high degree of management because impurities have a great influence on the electrical characteristics of the display device if the impurities remain in the material. In addition, regarding the material for forming the alignment film, it is already known that the alignment film directly affects the liquid crystal layer and the impurities remaining in the alignment film move to the liquid crystal layer, thereby affecting the electrical characteristics of the liquid crystal layer. The characteristics of the liquid crystal display device due to the impurities in the alignment film material are being studied.

  On the other hand, the material such as the organic pigment used for the color filter layer is also assumed to have an influence on the liquid crystal layer due to impurities contained in the same manner as the alignment film material. However, since an alignment film and a transparent electrode are interposed between the color filter layer and the liquid crystal layer, it has been considered that the direct influence on the liquid crystal layer is significantly less than that of the alignment film material. However, the alignment film is usually only 0.1 μm or less in thickness, and the common electrode used on the color filter layer side for the transparent electrode is usually 0.5 μm or less even if the film thickness is increased to increase the conductivity. . Therefore, it cannot be said that the color filter layer and the liquid crystal layer are placed in a completely isolated environment, and the color filter layer is formed by impurities contained in the color filter layer through the alignment film and the transparent electrode. There is a possibility that display defects such as white spots due to a decrease in voltage holding ratio (VHR), an increase in ion density (ID), uneven alignment, and burn-in may occur. As a method of solving display defects caused by impurities contained in pigments constituting the color filter, the elution of impurities into the liquid crystal is controlled by using pigments whose ratio of the extract of ethyl formate is not more than a specific value. A method (Patent Document 1) and a method (Patent Document 2) for controlling the elution of impurities into a liquid crystal by specifying a pigment in a blue colored layer have been studied. However, these methods are not significantly different from simply reducing impurities in the pigment, and are insufficient as an improvement to solve display defects even in the current state of progress in pigment purification technology. Met.

On the other hand, paying attention to the relationship between the organic impurities contained in the color filter and the liquid crystal composition, the difficulty of dissolving the organic impurities in the liquid crystal layer is expressed by the hydrophobic parameter of the liquid crystal molecules contained in the liquid crystal layer. Since there is a correlation between the parameter value of a certain value or more and the hydrophobic parameter and the -OCF ₃ group at the liquid crystal molecule terminal, a liquid crystal compound having a -OCF ₃ group at the liquid crystal molecule terminal is contained in a certain ratio or more. A method for producing a liquid crystal composition (Patent Document 3) is disclosed.
However, in the disclosure of the cited document as well, it is the essence of the invention to suppress the influence of impurities in the pigment on the liquid crystal layer, and the structure of the coloring material such as dyes and pigments used in the color filter and the structure of the liquid crystal material The direct relationship with the above has not been studied, and the problem of display defects of liquid crystal display devices that have been advanced has not been solved.

JP 2000-19321 A JP 2009-109542 A JP 2000-192040 A

  The present invention uses a color filter using a specific liquid crystal composition and a specific dye and / or pigment to prevent a decrease in voltage holding ratio (VHR) and an increase in ion density (ID) of the liquid crystal layer, An object of the present invention is to provide a liquid crystal display device that solves the problem of display defects such as white spots, uneven alignment, and baking.

In order to solve the above-mentioned problems, the inventors of the present application have made extensive studies on the combination of the coloring material and the like for constituting the color filter and the structure of the liquid crystal material constituting the liquid crystal layer. In addition, a liquid crystal display device using a color filter using a dye and / or pigment having a specific structure prevents a decrease in voltage holding ratio (VHR) and an increase in ion density (ID) of the liquid crystal layer, thereby causing white spots and uneven orientation. The inventors have found that the problem of display defects such as image sticking is solved, and have completed the present invention.
That is, the present invention
A color filter composed of 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 an RGB three-color pixel portion, A pixel electrode and a common electrode;
The liquid crystal composition layer has the general formula (LC1) and the general formula (LC2).

(In the formula, each R ₁ independently represents an alkyl group having 1 to 15 carbon atoms, and one or two or more CH ₂ groups in the alkyl group are —O—so that oxygen atoms are not directly adjacent to each other. -, - CH = CH -, - CO -, - OCO -, - COO -, - C≡C -, - CF 2 O -, - OCF 2 - may be replaced by one in the alkyl group or Two or more hydrogen atoms may be optionally halogen-substituted, and A ₁ and A ₂ are each independently any one of the following structures:

(One or more CH ₂ groups of the cyclohexane ring in the structure may be substituted with an oxygen atom, and one or two or more CH groups of the benzene ring in the structure are substituted with a nitrogen atom. And one or more hydrogen atoms in the structure may be substituted with F, Cl, CF ₃ or OCF ₃ ), and X _{1 to} X ₅ are each independently Each represents a hydrogen atom, Cl, F, CF ₃ or OCF ₃ , Y independently represents a hydrogen atom, Cl, F, CF ₃ , OCH ₂ F, OCHF ₂ or OCF ₃ , and Z _{1 to} Z ₃ represent Each independently a single bond, —CH═CH—, —CF═CF—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O— , —OCF ₂ —, —CF ₂ O—, —COO— or —OCO—, m ₁ And m ₂ each independently represents an integer of 0 to 3, and m ₁ + m ₂ represents 1, 2 or 3. )
A liquid crystal composition containing one or more compounds selected from the group of compounds represented by the formula (1) in a liquid crystal compound having a dielectric anisotropy of 2 or more and more than 90% by mass,
The RGB three-color pixel portion includes, as a color material, a diketopyrrolopyrrole pigment and / or an anionic red organic dye in the R pixel portion, a copper halide phthalocyanine pigment, a phthalocyanine green dye, and a phthalocyanine type in the G pixel portion. A liquid crystal display device comprising at least one selected from the group consisting of a mixture of a blue dye and an azo yellow organic dye, the B pixel portion containing an ε-type copper phthalocyanine pigment and / or a cationic blue organic dye I will provide a.

  The liquid crystal display device of the present invention uses a color filter that uses a specific liquid crystal composition and a specific dye and / or pigment, thereby reducing the voltage holding ratio (VHR) of the liquid crystal layer and increasing the ion density (ID). Thus, it is possible to prevent display defects such as white spots, uneven alignment, and baking.

It is a figure which shows an example of the conventional common liquid crystal display device. It is a figure which shows an example of the liquid crystal display device of this invention.

1 Substrate 2 Color filter layer 2a Color filter layer 3a containing a specific dye and / or pigment Transparent electrode layer (common electrode)
3b Pixel electrode layer 4 Alignment film 5 Liquid crystal layer 5a Liquid crystal layer containing a specific liquid crystal composition

An example of the liquid crystal display device of the present invention is shown in FIG. A transparent electrode layer (3a) serving as a common electrode, a specific dye, and one of the two substrates (1) of the first substrate and the second substrate having the alignment film (4) and the substrate And / or a color filter layer (2) containing a pigment, a pixel electrode layer (3b) between the other alignment film and the substrate, and these substrates are arranged so that the alignment films face each other, A liquid crystal layer (5) containing a specific liquid crystal composition is sandwiched.
The two substrates in the display device are bonded together by a sealing material and a sealing material disposed in the peripheral region, and in many cases, formed by a granular spacer or a photolithography method in order to maintain a distance between the substrates. Spacer pillars made of the prepared resin are arranged.

(Liquid crystal layer)
The liquid crystal layer in the liquid crystal display device of the present invention has the general formula (LC1) and the general formula (LC2).

(In the formula, each R ₁ independently represents an alkyl group having 1 to 15 carbon atoms, and one or two or more CH ₂ groups in the alkyl group are —O—so that oxygen atoms are not directly adjacent to each other. -, - CH = CH -, - CO -, - OCO -, - COO -, - C≡C -, - CF 2 O -, - OCF 2 - may be replaced by one in the alkyl group or Two or more hydrogen atoms may be optionally halogen-substituted, and A ₁ and A ₂ are each independently any one of the following structures:

(One or more CH ₂ groups of the cyclohexane ring in the structure may be substituted with an oxygen atom, and one or two or more CH groups of the benzene ring in the structure are substituted with a nitrogen atom. And one or more hydrogen atoms in the structure may be substituted with F, Cl, CF ₃ or OCF ₃ ), and X _{1 to} X ₅ are each independently Each represents a hydrogen atom, Cl, F, CF ₃ or OCF ₃ , Y independently represents a hydrogen atom, Cl, F, CF ₃ , OCH ₂ F, OCHF ₂ or OCF ₃ , and Z _{1 to} Z ₃ represent Each independently a single bond, —CH═CH—, —CF═CF—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O— , —OCF ₂ —, —CF ₂ O—, —COO— or —OCO—, m ₁ And m ₂ each independently represents an integer of 0 to 3, and m ₁ + m ₂ represents 1, 2 or 3. The liquid crystal composition contains more than 90% by mass of one or more compounds selected from the group of compounds represented by (2) in a liquid crystal compound having a dielectric anisotropy of 2 or more.

R ₁ is preferably independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. More preferably an alkoxy group having 2 to 5 carbon atoms,
A ₁ and A ₂ each independently preferably have the following structure:

Y is independently preferably F, CF ₃ or OCF ₃ , F is particularly preferred,
Z _{1 to} Z ₃ are each independently a single bond, —CH ₂ CH ₂ —, —COO—, —OCO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—. Preferably, a single bond, —CH ₂ CH ₂ —, —OCF ₂ — or —CF ₂ O— is more preferable,
m ₁ and m ₂ are each independently preferably 1 or 2.

  The liquid crystal composition further has the general formula (LC5)

(In the formula, R ₃ and R ₄ each independently represent an alkyl group having 1 to 15 carbon atoms, and one or two or more CH ₂ groups in the alkyl group are so arranged that oxygen atoms are not directly adjacent to each other. , —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF ₂ O—, or —OCF ₂ —, One or more hydrogen atoms may be optionally halogen-substituted, and B _{1 to} B ₃ are each independently

(Wherein one or more CH ₂ CH ₂ groups in the cyclohexane ring may be substituted with —CH═CH—, —CF ₂ O—, —OCF ₂ —, Z ₄ or Z ₅ each independently represents a single bond, —CH═CH—, —CF═CF—, wherein one or two or more CH groups may be substituted with a nitrogen atom. , —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, m ₃ represents the 0-3. A liquid crystal composition containing one or more compounds represented by formula (1) is preferred.

R ₃ and R ₄ are each independently preferably 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. , An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms are more preferable.
B _{1 to} B ₃ each independently preferably have the following structure:

Z ₄ and Z ₅ are each independently a single bond, —CH ₂ CH ₂ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, preferably a single bond , _-CH 2 CH ₂ - are more preferable,
m ₃ is preferably 0, 1 or 2.

  The general formula (LC1) is represented by the following general formula (LC1) -1 to general formula (LC1) -4.

(In the formula, each R ₁ independently represents an alkyl group having 1 to 15 carbon atoms, and one or two or more CH ₂ groups in the alkyl group are —O —, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF ₂ O— or —OCF ₂ — may be substituted, and X ₂ and X ₆ are Each independently represents a hydrogen atom, Cl, F, CF ₃ or OCF _3, and when there are a plurality of X _{6 s,} they may be the same or different; Y is independently Cl, F, CF ₃ , represents OCH ₂ F, OCHF ₂ or OCF ₃ ), and is preferably one or more compounds selected from the group consisting of compounds represented by:

R ₁ is preferably independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. And an alkenyl group having 2 to 5 carbon atoms is more preferable.
X ₂ and X ₆ are each independently preferably a hydrogen atom or F,
Y is preferably independently F, CF ₃ or OCF ₃ .

  The general formula (LC1) is changed from the following general formula (LC1) -5 to general formula (LC1) -22.

(In the formula, each R ₁ independently represents an alkyl group having 1 to 15 carbon atoms, and one or two or more CH ₂ groups in the alkyl group are —O —, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF ₂ O— or —OCF ₂ — may be substituted. One or two or more hydrogen atoms may be optionally halogen-substituted, X ₂ and X ₇ each independently represent a hydrogen atom, Cl, F, CF ₃ or OCF _3, and there are a plurality of X ₇ In this case, they may be the same or different, and each Z ₁ is independently a single bond, —CH═CH—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —. _{, -OCH 2 -, - CH 2} O -, - OCF 2 - or _-CF 2 O-a represents, Y Waso Each independently _{Cl, F, CF 3, OCH} 2 F, represents OCHF ₂ or OCF _3, ^{A 1} is independently of the following structures

Represents one of the following. It is preferable that it is 1 type, or 2 or more types of compounds chosen from the group which consists of a compound represented by this.

R ₁ is preferably independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. And an alkenyl group having 2 to 5 carbon atoms is more preferable.
X ₂ and X ₇ are each independently preferably a hydrogen atom or F,
Y is preferably independently F, CF ₃ or OCF ₃ .

  The general formula (LC2) is represented by the following general formula (LC2) -1 to general formula (LC2) -11.

(In the formula, each R ₁ independently represents an alkyl group having 1 to 15 carbon atoms, and one or two or more CH ₂ groups in the alkyl group are —O—so that oxygen atoms are not directly adjacent to each other. —, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF ₂ O— or —OCF ₂ — may be substituted, and X ₄ and X ₈ are Each independently represents a hydrogen atom, Cl, F, CF ₃ or OCF _3, and when there are a plurality of X _{8 s,} they may be the same or different; Y is independently Cl, F, CF ₃ , OCH ₂ F, OCHF ₂ or OCF ₃ ). It is preferably one or more compounds selected from the group consisting of compounds represented by:

R ₁ is preferably independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. And an alkenyl group having 2 to 5 carbon atoms is more preferable.
X ₄ and X ₈ are each independently preferably a hydrogen atom or F,
Y is preferably independently F, CF ₃ or OCF ₃ .

  General formula (LC5) is general formula (LC5) -1 to general formula (LC5) -14.

(In the formula, R ₃ and R ₄ are each independently 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. It is more preferable that it is 1 type, or 2 or more types of compounds chosen from the group which consists of a compound represented by this. R ₃ and R ₄ are more preferably each independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms.

The liquid crystal composition layer may contain one or more polymerizable compounds.
Specifically, the polymerizable compound is represented by the general 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 mesogenic supporting group, R ₁₀ represents a halogen atom, a cyano group or a carbon atom number of 1 to 25 Represents an alkyl group, and one or more CH ₂ groups in the alkyl group are —O—, —S—, —NH—, —N (CH ₃ ) — so that the oxygen atom is not directly adjacent. , -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡ C ₁₀ may be substituted, or R ₁₀ is P ₂ -Sp ₂ -Q _2- (wherein P ₂ , Sp ₂ and Q ₂ are independently the same as P ₁ , Sp ₁ and Q _1). It is preferably a polymerizable compound represented by the following formula:

  More preferably, in the general formula (PC1), MG has the following structure:

(Wherein C _{1 to} C ₃ are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3 -Dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2 , 5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene -2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group or fluorene 2,7 -Represents a diyl group The 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2 , 7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group and fluorene 2,7-diyl group are substituted with one or more F, Cl, CF ₃ , OCF ₃ , cyano group, alkyl group having 1 to 8 carbon atoms, alkoxy group, alkanoyl group, alkanoyloxy group, alkenyl group having 2 to 8 carbon atoms, alkenyloxy group, alkenoyl group or alkenoyloxy group may have, _{Y 1} and _{Y 2} are each independently _{-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, and 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, and one or two or more CH ₂ groups present in the group may be —O—, —S— so that the oxygen atom is not directly adjacent. , —NH—, —N (CH ₃ ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS— or —C≡C—, P ₁ and _{P 2} are each independently Under the formula (R-1) ~ formula (R-15)

It is preferable that it is a structure represented by these. These polymerizable groups are cured by radical polymerization, radical addition polymerization, cationic polymerization, and anionic polymerization. In particular, when performing ultraviolet polymerization as a polymerization method, the formula (R-1), formula (R-2), formula (R-4), formula (R-5), formula (R-7), formula (R -11), formula (R-13) or formula (R-15) are preferred, and formula (R-1), formula (R-2), formula (R-7), formula (R-11) or formula ( R-13) is more preferable, and formula (R-1) and formula (R-2) are more preferable.

  Examples of the polymerizable compound having one polymerizable functional group in the molecule include general formula (PC1) -0.

(In Formula (PC1) -0, R ₁₁ represents a hydrogen atom or a methyl group, and each of the six-membered rings T ₁ , T _2, and T ₃ is independently

(Where m represents an integer of 1 to 4),
n ⁴ represents an integer of 0 or 1,
Y ₀ , Y ₁ and Y ₂ are each independently 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 - represents,
Y ₃ represents a single bond, —O—, —COO—, or —OCO—,
R ₁₂ is a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. Represents a hydrocarbon group. At least one polymerizable compound selected from the group consisting of

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

(P ₁ , Sp ₁ , Q ₁ , P ₂ , Sp ₂ , Q ₂ and MG represent the same meaning 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 changed from the general formula (PC1) -3 to the general formula (PC1) -11.

(In the formula, P ₁ , P ₂ , Sp ₁ , Sp ₂ , Q ₁ and Q ₂ represent the same meaning as in the general formula (PC1), and W ₁ independently represents F, CF ₃ , OCF ₃ , CH _3. , OCH ₃ , an alkyl group having 2 to 5 carbon atoms, an alkoxy group, an alkenyl group, COOW ₂ , OCOW ₂ or OCOW ₂ (wherein W ₂ is each independently a straight chain having 1 to 10 carbon atoms) Or a branched alkyl group or an alkenyl group having 2 to 5 carbon atoms), n ₃ independently represents 1, 2 or 3, n ₄ independently represents 1, 2 or 3; n ₆ each independently represents 0, 1, 2, 3 or 4, and n ₃ + n ₆ and n ₄ + n ₆ on the same ring are 5 or less.) Preferably it is one or more polymerizable compounds .

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 1 to 3, and preferably 1 or 2. P ₁ and P ₂ are preferably 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 following compounds are preferred.

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

  The polymerizable compound is a discotic liquid crystal compound represented by the following general formula (PC1) -9.

(In the formula, each R ₇ independently represents a substituent of P ₁ -Sp ₁ -Q ₁ or general formula (PC1-e) (wherein P ₁ , Sp ₁ and Q ₁ are general formula (PC1) R ₈₁ and R ₈₂ each independently represent a hydrogen atom, a halogen atom or a methyl group, R ₈₃ represents an alkoxy group having 1 to 20 carbon atoms, and at least one hydrogen in the alkoxy group It is also preferred that the atom is substituted with a substituent represented by the above formulas (R-1) to (R-15).

The amount of the polymerizable compound used is preferably 0.05 to 2.0% by mass.
The liquid crystal composition can be used alone for the above applications, and can further contain one or more antioxidants, and can further contain one or more UV absorbers.

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

The RGB three-color pixel portion is a color material that contains C.I. I. Solvent Red 124 with C.I. I. Solvent Blue 67 and C.I. I. The mixture with Solvent Yellow 162 was added to C.I. I. Preferably it contains Solvent Blue 7.
In addition, the RGB three-color pixel portion includes C.I. I. Pigment Red 254 in the G pixel portion. I. Pigment Green 7 and / or 36 in the B pixel portion. I. It is also preferable to contain Pigment Blue 15: 6.

The RGB three-color pixel portion is further provided with C.I. I. Pigment Red 177, 242, 166, 167, 179, C.I. I. Pigment Orange 38, 71, C.I. I. Pigment Yellow 150, 215, 185, 138, 139, C.I. I. Solvent Red 89, C.I. I. Solvent Orange 56, C.I. I. It is preferable to contain at least one organic dye / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1, 33, 162.
The RGB three-color pixel portion is further provided with C.I. I. Pigment Yellow 150, 215, 185, 138, C.I. I. It is preferable to contain at least one organic dye / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1, and 33.
The RGB three-color pixel portion is further provided with C.I. I. Pigment Blue 1, C.I. I. Pigment Violet 23, C.I. I. Basic Blue 7, C.I. I. Basic Violet 10, C.I. I. Acid Blue 1, 90, 83, C.I. I. It is preferable to contain at least one organic dye / pigment selected from the group consisting of Direct Blue 86.

  The color filter is composed of a black matrix, an RGB three-color pixel portion, and a Y pixel portion. I. Pigment Yellow 150, 215, 185, 138, 139, C.I. I. It is also preferable to contain at least one yellow organic dye / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1, 33, 162.

  The color filter can form the color filter pixel portion by a conventionally known method. A typical method for forming the pixel portion is a photolithography method, which applies and heats a photocurable composition to be described later on the surface of the transparent substrate for the color filter provided with the black matrix. After drying (pre-baking), pattern exposure is performed by irradiating ultraviolet rays through a photomask to cure the photo-curable compound at the location corresponding to the pixel portion, and then developing the unexposed portion with a developer. In this method, the non-pixel portion is removed and the pixel portion is fixed to the transparent substrate. In this method, a pixel portion made of a cured colored film of a photocurable composition is formed on a transparent substrate.

A photocurable composition to be described later is prepared for each pixel of other colors such as an R pixel, a G pixel, a B pixel, and a Y pixel as necessary. A color filter having colored pixel portions of pixels, G pixels, B pixels, and Y pixels can be manufactured.
Examples of a method for applying a photocurable composition described later on a transparent substrate such as glass include a spin coat method, a roll coat method, and an ink jet method.
Although the drying conditions of the coating film of the photocurable composition apply | coated to the transparent substrate differ also with the kind of each component, a compounding ratio, etc., they are 50-150 degreeC and are about 1 to 15 minutes normally. Moreover, as light used for photocuring of a photocurable composition, it is preferable to use the ultraviolet-ray of a wavelength range of 200-500 nm, or visible light. Various light sources that emit light in this wavelength range can be used.
Examples of the developing method include a liquid piling method, a dipping method, and a spray method. After exposure and development of the photocurable composition, the transparent substrate on which the necessary color pixel portion is formed is washed with water and dried. The color filter thus obtained is subjected to heat treatment (post-baking) at 90 to 280 ° C. for a predetermined time by a heating device such as a hot plate or an oven to remove volatile components in the colored coating film, and at the same time, light The unreacted photocurable compound remaining in the cured colored film of the curable composition is thermally cured to complete the color filter.

By using the color material for a color filter of the present invention with the liquid crystal composition of the present invention, the voltage holding ratio (VHR) of the liquid crystal layer is reduced and the ion density (ID) is prevented from being increased. It is possible to provide a liquid crystal display device that solves the problem of display defects such as baking.
As the method for producing the photocurable composition, the color filter dye and / or pigment composition of the present invention, an organic solvent and a dispersant are used as essential components, and these are mixed and stirred so as to be uniform. First, a pigment dispersion for forming the pixel portion of the color filter is prepared by dispersion, and then a photocurable compound and, if necessary, a thermoplastic resin or a photopolymerization initiator are added. The method of making the said photocurable composition is common.

  Examples of the organic solvent used here include aromatic solvents such as toluene, xylene, methoxybenzene, ethyl acetate, propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol methyl ether acetate. , Acetate solvents such as diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol butyl ether acetate, propionate solvents such as ethoxyethyl propionate, alcohol solvents such as methanol and ethanol, butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl Ether, diethylene glycol dimethyl ether Ether solvents such as methyl, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, aniline And nitrogen compound solvents such as pyridine, lactone solvents such as γ-butyrolactone, and carbamic acid esters such as a 48:52 mixture of methyl carbamate and ethyl carbamate.

  Dispersants used here include, for example, Big Chemie's Dispersic 130, Dispersic 161, Dispersic 162, Dispersic 163, Dispersic 170, Dispersic 171, Dispersic 174, Dispersic 180, Dispersic 182, Dispersic 183, Dispersic 184, Dispersic 185, Dispersic 2000, Dispersic 2001, Dispersic 2020, Dispersic 2050, Dispersic 2070, Dispersic 2096, Dispersic 2150, Dispersic LPN21116, Dispersic LPN6919 Efka EFKA46, EFKA47, EFKA452, EFKALP4008, EFKA4 09, EFKA LP4010, EFKA LP4050, LP4055, EFKA400, EFKA401, EFKA402, EFKA403, EFKA450, EFKA451, EFKA453, EFKA4540, EFKA4550, EFKALP4560, EFKA120, EFKA150, EFKA1501, EFKA1501 1502, Efka 1503, Lubrizol's Sol Sparse 3000, Sol Sparse 9000, Sol Sparse 13240, Sol Sparse 13650, Sol Sparse 13940, Sol Sparse 17000, 18000, Sol Sparse 20000, Sol Sparse 21000, Sol Sparse 20000, Sol Sparse 24000, Sol Sparse 26000, Sol Sparse 28000, Sol Sparse 28000, Solsparse 32000, Solsparse 36 00, Solsperse 37000, Solsperse 38000, Solsperse 41000, Solsperse 42000, Solsperse 43000, Solsperse 44000, Solsperse 71000, Ajinomoto Co., Inc. Agents, natural rosin such as acrylic resin, urethane resin, alkyd resin, wood rosin, gum rosin, tall oil rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, oxidized rosin, modified rosin such as maleated rosin, Rosin derivatives such as rosinamine, lime rosin, rosin alkylene oxide adduct, rosin alkyd adduct, rosin modified phenol, etc. A synthetic resin that is liquid and water-insoluble at room temperature can be contained. Addition of these dispersants and resins also contributes to reduction of flocculation, improvement of pigment dispersion stability, and improvement of viscosity characteristics of the dispersion.

Further, as a dispersion aid, organic pigment derivatives such as phthalimidomethyl derivatives, sulfonic acid derivatives, N- (dialkylamino) methyl derivatives, N- (dialkylaminoalkyl) sulfonic acid amide derivatives, etc. You can also. Of course, two or more of these derivatives can be used in combination.
Examples of the thermoplastic resin used for the preparation of the photocurable composition include urethane resins, acrylic resins, polyamide resins, polyimide resins, styrene maleic acid resins, styrene maleic anhydride resins, and the like. .

Examples of the photocurable compound include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol di Bifunctional monomers such as acrylate, trimethylol propaton triacrylate, pentaerythritol triacrylate, tris [2- (meth) acryloyloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. Relatively high molecular weight such as low molecular weight polyfunctional monomer, polyester acrylate, polyurethane acrylate, polyether acrylate, etc. Functional monomer.
Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethylketanol, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4′-azidobenzal) -2-propane, 1,3-bis (4 ′). -Azidobenzal) -2-propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid and the like. Examples of commercially available photopolymerization initiators include “Irgacure (trade name) -184”, “Irgacure (trade name) -369”, “Darocur (trade name) -1173” manufactured by BASF, and “Lucirin-” manufactured by BASF. "TPO", Nippon Kayaku Co., Ltd. "Kayacure (trade name) DETX", "Kayacure (trade name) OA", Stofer "Bicure 10", "Bicure 55", Akzo "Trigonal PI", Sand "Sandray 1000" manufactured by Upjohn, "Deep" manufactured by Upjohn, and "Biimidazole" manufactured by Kurokin Kasei.

Moreover, a well-known and usual photosensitizer can also be used together with the said photoinitiator. Examples of the photosensitizer include amines, ureas, compounds having a sulfur atom, compounds having a phosphorus atom, compounds having a chlorine atom, nitriles or other compounds having a nitrogen atom. These can be used alone or in combination of two or more.
The blending ratio of the photopolymerization initiator is not particularly limited, but is preferably in the range of 0.1 to 30% with respect to the compound having a photopolymerizable or photocurable functional group on a mass basis. If it is less than 0.1%, the photosensitivity at the time of photocuring tends to decrease, and if it exceeds 30%, crystals of the photopolymerization initiator are precipitated when the pigment-dispersed resist coating film is dried. May cause deterioration of film properties.

Using each material as described above, on a mass basis, 300 to 1000 parts of an organic solvent and 1 to 100 parts of a dispersant per 100 parts of the dye and / or pigment composition for a color filter of the present invention. The dye / pigment solution can be obtained by stirring and dispersing so as to be uniform. Next, in this pigment dispersion, the total amount of the thermoplastic resin and the photocurable compound is 3 to 20 parts per part of the pigment composition for a color filter of the present invention, and 0.05 to 3 parts per part of the photocurable compound. A photopolymerization initiator and, if necessary, an organic solvent may be further added, and a photocurable composition for forming a color filter pixel portion can be obtained by stirring and dispersing so as to be uniform.
As the developer, a known and commonly used organic solvent or alkaline aqueous solution can be used. In particular, when the photocurable composition contains a thermoplastic resin or a photocurable compound, and at least one of them has an acid value and exhibits alkali solubility, the color filter can be washed with an alkaline aqueous solution. It is effective for forming the pixel portion.
Although the manufacturing method of the color filter pixel part by the photolithographic method was described in detail, the color filter pixel part prepared by using the pigment composition for the color filter of the present invention can be used in other electrodeposition methods, transfer methods, and micelle electrolysis methods. A color filter may be manufactured by forming each color pixel portion by a PVED (Photovoltaic Electrodeposition) method, an inkjet method, a reverse printing method, a thermosetting method, or the like.

(Alignment film)
In the liquid crystal display device of the present invention, the liquid crystal composition is aligned on the first substrate and the surface in contact with the liquid crystal composition on the second substrate. Although arranged between the liquid crystal layers, even if the alignment film is thick, it is as thin as 100 nm or less, and completely blocks the interaction between the pigment such as a pigment constituting the color filter and the liquid crystal compound constituting the liquid crystal layer. It is not a thing.
Further, in a liquid crystal display device that does not use an alignment film, the interaction between a pigment such as a pigment constituting a color filter and a liquid crystal compound constituting a liquid crystal layer becomes larger.

As the alignment film material, transparent organic materials such as polyimide, polyamide, BCB (Penzocyclobutene Polymer), and polyvinyl alcohol can be used. In particular, p-phenylenediamine, 4,4′-diaminodiphenylmethane, etc. Aliphatic or alicyclic tetracarboxylic anhydrides such as aliphatic or alicyclic diamines, and butanetetracarboxylic anhydrides, 2,3,5-tricarboxycyclopentylacetic anhydride, pyromellitic dianhydride A polyimide alignment film obtained by imidizing a polyamic acid synthesized from an aromatic tetracarboxylic anhydride such as a product is preferable. In this case, rubbing is generally used as a method for imparting orientation, but when used for a vertical orientation film or the like, it can be used without imparting orientation.
As the alignment film material, a material containing chalcone, cinnamate, cinnamoyl or azo group in the compound can be used, and it may be used in combination with materials such as polyimide and polyamide. In this case, the alignment film is rubbed. Or a photo-alignment technique may be used.
The alignment film is generally formed by applying the alignment film material on a substrate by a method such as spin coating to form a resin film, but a uniaxial stretching method, Langmuir-Blodgett method, or the like can also be used. .

(Transparent electrode)
In the liquid crystal display device of the present invention, a conductive metal oxide can be used as a material for the transparent electrode. Examples of the metal oxide include indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), and zinc oxide. (ZnO), indium tin oxide (In ₂ O ₃ —SnO ₂ ), indium zinc oxide (In ₂ O ₃ —ZnO), niobium-doped titanium dioxide (Ti _1-x Nb _x O ₂ ), fluorine-doped tin oxide, graphene Although nanoribbons or metal nanowires can be used, zinc oxide (ZnO), indium tin oxide (In ₂ O ₃ —SnO ₂ ), or indium zinc oxide (In ₂ O ₃ —ZnO) is preferable. For patterning these transparent conductive films, a photo-etching method or a method using a mask can be used.

EXAMPLES Hereinafter, although an Example is given and a part of best form of this invention is explained in full detail, this invention is not limited to these Examples. Further, “%” in the compositions of the following examples and comparative examples means “mass%”.
The physical properties of the liquid crystal composition are expressed as follows.
T _NI : Nematic phase-isotropic liquid phase transition temperature (° C.), liquid crystal phase upper limit temperature Δε: dielectric anisotropy Δn: refractive index anisotropy η: viscosity at 20 ° C. (mPa · s)
d _gap : _gap between the first substrate and the second substrate of the cell (μm)
VHR: Voltage holding ratio at 70 ° C. (%)
(The ratio of the measured voltage to the initial applied voltage in% when the liquid crystal composition was injected into a cell having a cell thickness of 3.5 μm and measured under the conditions of 5 V applied, frame time 200 ms, and pulse width 64 μs)
ID: Ion density at 70 ° C. (pC / cm ² )
(Ion density value measured by injecting a liquid crystal composition into a cell having a cell thickness of 3.5 μm and applying 20 V with MTR-1 (manufactured by Toyo Corporation) at a frequency of 0.05 Hz)

The following abbreviations are used in compound descriptions.
Terminal n (number) C _n H _{2n + 1-}
-2- -CH ₂ CH ₂ -
-1O- -CH ₂ O-
-O1- -OCH _2-
-V- -CO-
-VO- -COO-
-CFFO- -CF ₂ O-
-F -F
-Cl -Cl
-CN -C≡N
-OCFFF -OCF ₃
-CFFF -CF ₃
-OCFF -OCHF ₂
-On -OC _n H _{2n + 1}
-T- -C≡C-
ndm- C _n H _{2n + 1} -HC = CH- (CH ₂ ) _m-1-

The burn-in evaluation of the liquid crystal display device is based on the following four-stage evaluation of the afterimage level of the fixed pattern when the predetermined fixed pattern is displayed in the display area for 1000 hours and then the entire screen is displayed uniformly. went.
◎ No afterimage ○ Very little afterimage but acceptable level △ With afterimage unacceptable level × Afterimage fairly bad

[Create color filter]
[Preparation of colored composition]
[Red dye coloring composition 1]
Put 10 parts of Red Dye 1 (CI Solvent Red 124) in a plastic bottle, add 55 parts of propylene glycol monomethyl ether acetate and 0.3-0.4 mmφ Sepul beads, and use paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours. After dispersion, the mixture was filtered through a 5 μm filter to obtain a dye coloring liquid. 75.00 parts of this dye coloring liquid, 5.50 parts of polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Gosei Chemical Co., Ltd.), dipentaerystol hexaacrylate (KAYARAD (trade name) DPHA, Nippon Kayaku) 5.00 parts of Yakuhin Co., Ltd., 1.00 parts of benzophenone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.) and 13.5 parts of Euker Ester EEP are stirred with a dispersion stirrer. Filtration through a 0 μm filter gave a red dye coloring composition 1.

[Red dye coloring composition 2]
Instead of 10 parts of red dye 1 of the red dye coloring composition 1, 8 parts of red dye 1 (CI Solvent Red 124) and 2 parts of yellow dye 2 (CI Solvent Yellow 21) are used. In the same manner as above, a red dye coloring composition 2 was obtained.

[Red dye coloring composition 3]
Instead of 10 parts of the red dye 1 of the red dye coloring composition 1, 10 parts of red dye 2 (CI Solvent Red 1) was used to obtain a red dye coloring composition 3 in the same manner as described above.

[Green Dye Coloring Composition 1]
Instead of 10 parts of the red dye 1 of the red dye coloring composition 1, 3 parts of blue dye 1 (CI Solvent Blue 67) and 7 parts of yellow dye 1 (CI Solvent Yellow 162) are used. In the same manner as above, a green dye coloring composition 1 was obtained.

[Green Dye Coloring Composition 2]
7 parts of the yellow dye 1 of the green dye coloring composition 1 are replaced with 4 parts of yellow dye 1 (CI Solvent Yellow 162) and 3 parts of yellow dye 3 (CI Solvent Yellow 82). Similarly, a green dye coloring composition 2 was obtained.

[Green dye coloring composition 3]
In the same manner as described above, using 10 parts of green dye 1 (CI Solvent Green 7) instead of 3 parts of blue dye 1 and 7 parts of yellow dye 1 of green dye coloring composition 1 3 was obtained.

[Blue dye coloring composition 1]
Instead of 10 parts of the red dye 1 of the red dye coloring composition 1, 10 parts of blue dye 1 (CI Solvent Blue 7) was used to obtain a blue dye coloring composition 1 in the same manner as described above.

[Blue dye coloring composition 2]
Instead of 10 parts of blue dye 1 of the blue dye coloring composition 1, 7 parts of blue dye 1 (CI Solvent Blue 7) and 3 parts of purple dye 1 (CI Basic Violet 10) are used. In the same manner as above, a blue dye coloring composition 2 was obtained.

[Blue dye coloring composition 3]
The blue dye coloring composition 2 is replaced with 7 parts of the blue dye 1 and 3 parts of the purple dye 1, and 10 parts of blue dye 2 (CI Solvent Blue 12) is used in the same manner as described above. Product 3 was obtained.

[Yellow dye coloring composition 1]
Instead of 10 parts of the red dye 1 of the red dye coloring composition 1, 10 parts of a yellow dye 2 (CI Solvent Yellow 21) was used to obtain a yellow dye coloring composition 1 in the same manner as described above.

[Yellow dye coloring composition 2]
A yellow dye coloring composition 2 was obtained in the same manner as described above using 10 parts of yellow dye 4 (CI Solvent Yellow 2) instead of 10 parts of yellow dye 2 of the yellow dye coloring composition 1.

[Red pigment coloring composition 1]
10 parts of red pigment 1 (CI Pigment Red 254, “IRGAPHOR RED BT-CF” manufactured by BASF Corporation) is placed in a polybin, 55 parts of propylene glycol monomethyl ether acetate, 7.0 parts of Disp. 0.3-0.4 mmφ Sepul beads were added and dispersed for 4 hours with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.), followed by filtration with a 5 μm filter to obtain a pigment dispersion. 75.00 parts of this pigment dispersion, 5.50 parts of polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Gosei Chemical Co., Ltd.), dipentaerystol hexaacrylate (KAYARAD (trade name) DPHA, Nippon Kayaku) 5.00 parts of Yakuhin Co., Ltd., 1.00 parts of benzophenone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.) and 13.5 parts of Euker Ester EEP are stirred with a dispersion stirrer. Filtration through a 0 μm filter gave a red pigment coloring composition 1.

[Red pigment coloring composition 2]
Instead of 10 parts of the red pigment 1 of the red pigment coloring composition 1, 6 parts of red pigment 1 and 2 parts of red pigment 2 (FASTOGEN SUPER RED ATY-TR manufactured by CI Pigment Red 177 DIC Corporation), yellow pigment 2 (C.I. Pigment Yellow 139) was used in the same manner as above to obtain a red pigment coloring composition 2.

[Green pigment coloring composition 1]
Instead of 10 parts of the red pigment 1 of the red pigment coloring composition 1, 6 parts of green pigment 1 (CI Pigment Green 36, “FASTOGEN GREEN 2YK-CF” manufactured by DIC Corporation) and yellow pigment 1 (C.I. Pigment Yellow 150, 4 parts of FANCHON FAST YELLOW E4GN manufactured by BAYER) was used in the same manner as above to obtain a green pigment coloring composition 1.

[Green pigment coloring composition 2]
Instead of 6 parts of green pigment 1 and 4 parts of yellow pigment 1 of the green pigment coloring composition 1, 4 parts of green pigment 2 (CI Pigment Green 7, FASTOGEN GREEN S manufactured by DIC Corporation) and yellow pigment 3 (C Green pigment coloring composition 2 was obtained in the same manner as described above using 6 parts of I. Pigment YELLOW 138).

[Blue pigment coloring composition 1]
Instead of 10 parts of the red pigment 1 of the red pigment coloring composition 1, 9 parts of blue pigment 1 (CI Pigment Blue 15: 6, “FASTOGEN BLUE EP-210” manufactured by DIC Corporation) and purple pigment 1 (C Blue pigment coloring composition 1 was obtained in the same manner as described above using 1 part of I. Pigment VIOLET 23).

[Blue Pigment Dye Coloring Composition 2]
A blue pigment dye coloring composition 2 was obtained in the same manner as described above using 1 part of purple dye 1 (CI Basic Violet 10) instead of 1 part of purple pigment 1 of the blue pigment coloring composition 1. .

[Yellow pigment coloring composition 1]
Instead of 10 parts of the red pigment 1 of the red pigment coloring composition 1, 10 parts of yellow pigment 1 (CI Pigment Yellow 150, FANCHON FAST YELLOW E4GN manufactured by BAYER) was used in the same manner as above, and the yellow pigment was used. A colored composition 1 was obtained.

[Production of color filter]
The red coloring composition was applied to a glass substrate on which a black matrix had been formed in advance so as to have a film thickness of 2 μm by spin coating. After drying at 70 ° C. for 20 minutes, striped pattern exposure was performed using a photomask with ultraviolet rays using an exposure machine equipped with an ultrahigh pressure mercury lamp. Spray development with an alkali developer for 90 seconds, washing with ion exchange water, and air drying. Further, post-baking was performed at 230 ° C. for 30 minutes in a clean oven to form red pixels, which are striped colored layers, on a transparent substrate.
Next, the green coloring composition is similarly applied by spin coating so that the film thickness becomes 2 μm. After drying, the striped colored layer was exposed and developed at a place different from the above-mentioned red pixel by an exposure machine, thereby forming a green pixel adjacent to the above-mentioned red pixel.
Next, similarly for the blue coloring composition, red pixels and blue pixels adjacent to the green pixels were formed by spin coating with a film thickness of 2 μm. Thus, a color filter having striped pixels of three colors of red, green, and blue on the transparent substrate was obtained.
As necessary, for the yellow coloring composition, a red pixel and a blue pixel adjacent to the green pixel were similarly formed by spin coating with a film thickness of 2 μm. As a result, a color filter having striped pixels of four colors of red, green, blue and yellow on the transparent substrate was obtained.
Color filters 1 to 4 and comparative color filter 1 were prepared using the dye coloring composition or the pigment coloring composition shown in Table 1.

(Examples 1-4)
An electrode structure is formed on the first and second substrates, a horizontal alignment film is formed on each opposing side, and then a rubbing process is performed to create a TN cell, and the first and second substrates are formed. A liquid crystal composition 1 having positive dielectric anisotropy shown in Table 2 was sandwiched therebetween. Next, the liquid crystal display device of Example 1 was produced using the color filters 1 to 4 shown in Table 1 (d _gap = 3.5 μm, alignment film AL-1051). VHR and ID of the obtained liquid crystal display device were measured. The obtained liquid crystal display device was evaluated for burn-in. The results are shown in Table 3.

  The liquid crystal display devices of Examples 1 to 4 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Comparative Examples 1-8)
The comparative liquid crystal composition 1 and the comparative liquid crystal composition 2 having positive dielectric anisotropy shown in Table 4 are sandwiched between the TN cells used in Example 1, and the color filters 1 to 4 shown in Table 1 are used as comparative examples. 1 to 8 liquid crystal display devices were produced, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 5 and 6.

  The liquid crystal display devices of Comparative Examples 1 to 8 had lower VHR and larger ID than the liquid crystal display devices of the present invention. Also, in the burn-in evaluation, afterimages were observed and the level was not acceptable.

(Comparative Example 9)
The liquid crystal composition 1 having positive dielectric anisotropy shown in Table 2 was sandwiched between the TN cells used in Example 1, and a liquid crystal display device of Comparative Example 9 was produced using the comparative color filter 1 shown in Table 1. The VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Table 7.

  The liquid crystal display device of Comparative Example 9 had a lower VHR and a larger ID than the liquid crystal display device of the present invention. Also, in the burn-in evaluation, afterimages were observed and the level was not acceptable.

(Examples 5 to 16)
As in Example 1, the positive dielectric anisotropic liquid crystal shown in Table 8 is sandwiched, and the liquid crystal display devices of Examples 5 to 12 are prepared using the color filter shown in Table 1, and the VHR and ID are measured. did. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 9-11.

  The liquid crystal display devices of Examples 5 to 16 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 17 to 28)
The negative dielectric anisotropic liquid crystal shown in Table 12 was held in the same manner as in Example 1, and the liquid crystal display devices of Examples 17 to 28 were prepared using the color filter shown in Table 1, and the VHR and ID were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 13-15.

  The liquid crystal display devices of Examples 17 to 28 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 29 to 40)
The positive dielectric anisotropic liquid crystal shown in Table 16 was sandwiched in the same manner as in Example 1, and the liquid crystal display devices of Examples 29 to 40 were prepared using the color filter shown in Table 1, and the VHR and ID were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 17-19.

  The liquid crystal display devices of Examples 29 to 40 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 41-56)
As in Example 1, the positive dielectric anisotropic liquid crystals shown in Tables 20 and 21 were sandwiched, and the liquid crystal display devices of Examples 41 to 56 were prepared using the color filters shown in Table 1, and the VHR and ID Was measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 22-25.

  The liquid crystal display device of Examples 41-56 has realized high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 57 to 72)
In the same manner as in Example 1, the positive dielectric anisotropic liquid crystal shown in Table 26 was sandwiched, and the liquid crystal display devices of Examples 57 to 72 were prepared using the color filter shown in Table 1, and the VHR and ID thereof were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 27-30.

  The liquid crystal display devices of Examples 57 to 72 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 73 to 80)
In the same manner as in Example 1, the positive dielectric anisotropic liquid crystal shown in Table 31 was sandwiched, and the liquid crystal display devices of Examples 73 to 80 were prepared using the color filter shown in Table 1, and the VHR and ID thereof were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 32 and 33.

  The liquid crystal display devices of Examples 73 to 80 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 81-88)
In the same manner as in Example 1, the positive dielectric anisotropic liquid crystal shown in Table 34 was sandwiched, and the liquid crystal display devices of Examples 81 to 88 were prepared using the color filter shown in Table 1, and the VHR and ID thereof were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 35-36.

  The liquid crystal display devices of Examples 81 to 88 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 89 to 96)
In the same manner as in Example 1, the positive dielectric anisotropic liquid crystal shown in Table 37 was sandwiched, and the liquid crystal display devices of Examples 89 to 96 were prepared using the color filter shown in Table 1, and the VHR and ID thereof were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 38-39.

  The liquid crystal display devices of Examples 89 to 96 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 97-104)
As in Example 1, the positive dielectric anisotropic liquid crystal shown in Table 40 was sandwiched, and the liquid crystal display devices of Examples 97 to 104 were prepared using the color filter shown in Table 1, and the VHR and ID were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 41-42.

  The liquid crystal display devices of Examples 97 to 104 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 105-112)
The liquid crystal display device of Examples 105-112 was created using the color filter shown in Table 1 while sandwiching the positive dielectric anisotropic liquid crystal shown in Table 43 as in Example 1, and the VHR and ID were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 44-45.

  The liquid crystal display device of Examples 105-112 has implement | achieved high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 113 to 120)
The positive dielectric anisotropic liquid crystal shown in Table 46 was held in the same manner as in Example 1, and the liquid crystal display devices of Examples 105 to 120 were prepared using the color filter shown in Table 1, and the VHR and ID were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 47-48.

  The liquid crystal display devices of Examples 113 to 120 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 121-128)
The liquid crystal display device of Examples 121-128 was created using the color filter shown in Table 1 while sandwiching the positive dielectric anisotropic liquid crystal shown in Table 49 in the same manner as in Example 1, and the VHR and ID thereof were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 50-51.

  The liquid crystal display devices of Examples 121 to 128 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 129 to 132)
The liquid crystal composition 1 having positive dielectric anisotropy used in Example 1 was added to 2-methyl-acrylic acid 4 ′-{2- [4- (2-acryloyloxy-ethyl) -phenoxycarbonyl] -ethyl}- A liquid crystal composition 33 was prepared by mixing 0.3% by mass of biphenyl-4-yl ester. The liquid crystal composition 33 was sandwiched between the TN cells used in Example 1, and ultraviolet rays were irradiated for 600 seconds (3.0 J / cm ² ) while applying a driving voltage between the electrodes, followed by a polymerization treatment. The liquid crystal display devices of Examples 129 to 132 were prepared using the color filters 1 to 4 shown in Table 1, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Table 52.

  The liquid crystal display devices of Examples 129 to 132 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 133-136)
A liquid crystal composition 34 was prepared by mixing 0.3% by mass of biphenyl-4,4′-diyl bismethacrylate with the liquid crystal composition 29 having positive dielectric anisotropy. The liquid crystal composition 34 was sandwiched between the TN cells used in Example 1, and irradiated with ultraviolet rays for 600 seconds (3.0 J / cm ² ) while applying a driving voltage between the electrodes, followed by polymerization treatment, The liquid crystal display devices of Examples 133 to 136 were prepared using the color filters 1 to 4 shown in Table 1, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Table 53.

  The liquid crystal display devices of Examples 133 to 136 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 137 to 140)
A liquid crystal composition 35 was prepared by mixing 0.3% by mass of bismethacrylic acid 3-fluorobiphenyl-4,4′-diyl with the liquid crystal composition 32 having positive dielectric anisotropy. The liquid crystal composition 35 was sandwiched between the TN cells used in Example 1, and ultraviolet light was irradiated for 600 seconds (3.0 J / cm ² ) with a driving voltage applied between the electrodes, followed by a polymerization treatment. The liquid crystal display devices of Examples 137 to 140 were prepared using the color filters 1 to 4 shown in Table 1, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Table 54.

  The liquid crystal display devices of Examples 137 to 140 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 141-144)
The liquid crystal display device of Examples 141-144 was created using the color filter shown in Table 1 while sandwiching the positive dielectric anisotropic liquid crystal shown in Table 55 as in Example 1, and the VHR and ID were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Table 56.

  The liquid crystal display devices of Examples 141 to 144 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 145 to 148)
The liquid crystal display device of Examples 145-148 was created using the color filter shown in Table 1 while sandwiching the positive dielectric anisotropic liquid crystal shown in Table 57 as in Example 1, and the VHR and ID thereof were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Table 58.

  The liquid crystal display devices of Examples 145 to 148 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 149 to 152)
As in Example 1, the positive dielectric anisotropic liquid crystal shown in Table 59 was sandwiched, and the liquid crystal display devices of Examples 149 to 152 were prepared using the color filter shown in Table 1, and the VHR and ID thereof were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Table 60.

  The liquid crystal display devices of Examples 149 to 152 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 153 to 156)
In the same manner as in Example 1, the positive dielectric anisotropic liquid crystal shown in Table 61 was held, and the liquid crystal display devices of Examples 153 to 156 were prepared using the color filter shown in Table 1, and the VHR and ID thereof were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Table 62.

  The liquid crystal display devices of Examples 153 to 156 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

(Examples 157 to 160)
In the same manner as in Example 1, the positive dielectric anisotropic liquid crystal shown in Table 63 was held, and the liquid crystal display devices of Examples 157 to 160 were prepared using the color filter shown in Table 1, and the VHR and ID thereof were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Table 64.

  The liquid crystal display devices of Examples 157 to 160 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.

Claims (13)

A color filter composed of 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 an RGB three-color pixel portion, A pixel electrode and a common electrode;
The liquid crystal composition layer has general formula (LC1) and general formula (LC2).

(In the formula, R ₁ represents an alkyl group having 1 to 15 carbon atoms, and one or two or more CH ₂ groups in the alkyl group are —O—, —CH, so that oxygen atoms are not directly adjacent to each other. ═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF ₂ O—, —OCF ₂ —, which may be substituted with one or more of the alkyl groups The hydrogen atom may be optionally halogen-substituted, and A ₁ and A ₂ are each independently any one of the following structures

(One or more CH ₂ groups of the cyclohexane ring in the structure may be substituted with an oxygen atom, and one or two or more CH groups of the benzene ring in the structure are substituted with a nitrogen atom. And one or more hydrogen atoms in the structure may be substituted with Cl, CF _3, or OCF ₃ ), and X _{1 to} X ₅ are each independently H , Cl, F, CF ₃ or OCF ₃ , Y represents Cl, F, CF ₃ or OCF ₃ , Z _{1 to} Z ₃ are each independently a single bond, —CH═CH—, —C≡C _{-, - CH 2 CH 2 -} , - (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - OCF 2 - or _-CF 2 O-a represents, _{m 1} and _{m 2} each independently Represents an integer of 0 to 3, and m ₁ + m ₂ represents 1, 2 or 3. )
A liquid crystal composition containing one or more compounds selected from the group of compounds represented by the formula (1) in a liquid crystal compound having a dielectric anisotropy of 2 or more and more than 90% by mass,
The RGB three-color pixel portion includes, as a color material, a diketopyrrolopyrrole pigment and / or an anionic red organic dye in the R pixel portion, a copper halide phthalocyanine pigment, a phthalocyanine green dye, and a phthalocyanine type in the G pixel portion. A liquid crystal display device comprising at least one selected from the group consisting of a mixture of a blue dye and an azo yellow organic dye, the B pixel portion containing an ε-type copper phthalocyanine pigment and / or a cationic blue organic dye . The RGB three-color pixel portion is used as a color material in the R pixel portion. I. Solvent Red 124 with C.I. I. Solvent Blue 67 and C.I. I. The mixture with Solvent Yellow 162 was added to C.I. I. The liquid crystal display device according to claim 1, comprising Solvent Blue 7. The RGB three-color pixel portion is used as a color material in the R pixel portion. I. Pigment Red 254 in the G pixel portion. I. Pigment Green 7 and / or 36 in the B pixel portion. I. The liquid crystal display device according to claim 1, comprising Pigment Blue 15: 6. In the R pixel portion, C.I. I. Pigment Red 177, 242, 166, 167, 179, C.I. I. Pigment Orange 38, 71, C.I. I. Pigment Yellow 150, 215, 185, 138, 139, C.I. I. Solvent Red 89, C.I. I. Solvent Orange 56, C.I. I. The liquid crystal display device according to claim 1, comprising at least one organic dye / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1, 33, and 162. In the G pixel portion, C.I. I. Pigment Yellow 150, 215, 185, 138, C.I. I. The liquid crystal display device according to claim 1, comprising at least one organic dye / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1, and 33. In the B pixel portion, C.I. I. Pigment Blue 1, C.I. I. Pigment Violet 23, C.I. I. Basic Blue 7, C.I. I. Basic Violet 10, C.I. I. Acid Blue 1, 90, 83, C.I. I. The liquid crystal display device according to claim 1, comprising at least one organic dye / pigment selected from the group consisting of Direct Blue 86. The color filter is composed of a black matrix, an RGB three-color pixel portion, and a Y pixel portion. I. Pigment Yellow 150, 215, 185, 138, 139, C.I. I. The liquid crystal display device according to any one of claims 1 to 6, comprising at least one yellow organic dye / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1, 33, and 162. The liquid crystal composition layer has a general formula (LC5)

(In the formula, R ₃ and R ₄ each independently represent an alkyl group having 1 to 15 carbon atoms, and one or two or more CH ₂ groups in the alkyl group are so arranged that oxygen atoms are not directly adjacent to each other. , —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF ₂ O—, or —OCF ₂ —, One or more hydrogen atoms may be optionally halogen-substituted, and B _{1 to} B ₃ are each independently

(Wherein one or more CH ₂ CH ₂ groups in the cyclohexane ring may be substituted with —CH═CH—, —CF ₂ O—, —OCF ₂ —, Z ₄ or Z ₅ each independently represents a single bond, —CH═CH—, —CF═CF—, wherein one or two or more CH groups may be substituted with a nitrogen atom. , —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, m ₃ represents the 0-3. The liquid crystal display device as described in any one of Claims 1-7 which uses the liquid crystal composition containing 1 type, or 2 or more types of compounds represented by this. The general formula (LC-1) is changed from the following general formula (LC1) -1 to general formula (LC1) -4.

(Wherein R ₁ represents an alkyl group having 1 to 15 carbon atoms, and one or two or more CH ₂ groups in the alkyl group are —O—, — CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF ₂ O— or —OCF ₂ — may be substituted, and X ₂ and X ₆ are each independently Represents a hydrogen atom, Cl, F, CF ₃ or OCF _3, and when a plurality of X ₆ are present, they may be the same or different, and Y is Cl, F, CF ₃ , OCH ₂ F, OCHF The liquid crystal display device according to claim 1, which is one or more compounds selected from the group consisting of compounds represented by: ₂ or OCF ₃ . General formula (LC2) is the following general formula (LC2) -1 to general formula (LC2) -11

(In the formula, R ₁ represents an alkyl group having 1 to 15 carbon atoms, and one or two or more CH ₂ groups in the alkyl group are —O—, —CH, so that oxygen atoms are not directly adjacent to each other. ═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF ₂ O— or —OCF ₂ — may be substituted, and X ₄ and X ₈ are a hydrogen atom, Cl , F, CF ₃ or OCF _3, and when a plurality of X ₈ are present, they may be the same or different, and Y represents Cl, F, CF ₃ , OCH ₂ F, OCHF ₂ or OCF ₃ . The liquid crystal display device according to claim 1, which is one or more compounds selected from the group consisting of compounds represented by: General formula (LC5) is changed from general formula (LC5) -1 to general formula (LC5) -14.

(In the formula, R ₃ and R ₄ are each independently 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 8 , which is one or more compounds selected from the group consisting of compounds represented by: The liquid crystal display device according to any one of claims 1 to 11, wherein the liquid crystal composition layer is composed of a polymer obtained by polymerizing a liquid crystal composition containing one or more polymerizable compounds. The polymerizable compound is represented by the general 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 mesogenic supporting group, R ₁₀ represents a halogen atom, a cyano group or a carbon atom number of 1 to 25 Represents an alkyl group, and one or more CH ₂ groups in the alkyl group are —O—, —S—, —NH—, —N (CH ₃ ) — so that the oxygen atom is not directly adjacent. , -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡ C ₁₀ may be substituted, or R ₁₀ is P ₂ -Sp ₂ -Q _2- (wherein P ₂ , Sp ₂ and Q ₂ are independently the same as P ₁ , Sp ₁ and Q _1). The liquid crystal display device according to claim 12, which is a polymerizable compound represented by the following formula:

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