WO2016021582A1 - Dispositif d'affichage à cristaux liquides - Google Patents

Dispositif d'affichage à cristaux liquides Download PDF

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WO2016021582A1
WO2016021582A1 PCT/JP2015/072051 JP2015072051W WO2016021582A1 WO 2016021582 A1 WO2016021582 A1 WO 2016021582A1 JP 2015072051 W JP2015072051 W JP 2015072051W WO 2016021582 A1 WO2016021582 A1 WO 2016021582A1
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liquid crystal
group
carbon atoms
crystal display
general formula
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PCT/JP2015/072051
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English (en)
Japanese (ja)
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小川　真治
芳典 岩下
近藤　仁
博志 牧
淳一郎 小池
宍倉　正視
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Dic株式会社
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Priority to CN201580040088.2A priority Critical patent/CN106537238A/zh
Priority to KR1020167035814A priority patent/KR101911281B1/ko
Priority to JP2016540239A priority patent/JP6083492B2/ja
Publication of WO2016021582A1 publication Critical patent/WO2016021582A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/60—Pleochroic dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

  • 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, automotive 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.
  • TFT thin film transistor
  • TFD thin film diode
  • 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 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.
  • 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.
  • 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.
  • the alignment film is usually only 0.1 ⁇ m or less in thickness, and the common electrode used on the color filter layer side for the transparent electrode is usually 0.5 ⁇ m 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.
  • VHR voltage holding ratio
  • ID increase in ion density
  • 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.
  • 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. Because of the correlation between the parameter value and the hydrophobic parameter and the —OCF 3 group at the end of the liquid crystal molecule, a liquid crystal compound having —OCF 3 group at the end of the liquid crystal molecule is contained in a certain proportion or more.
  • Patent Document 3 A method for producing a liquid crystal composition
  • An object of the present invention is to provide a liquid crystal display device that solves the problem of display defects such as unevenness and burn-in.
  • the inventors of the present application have made extensive studies on a combination of a coloring material and the like for constituting a color filter and a structure of a liquid crystal material constituting a liquid crystal layer, and as a result, a liquid crystal material having a specific structure.
  • a liquid crystal display device using a color filter using a pigment and a compound having a specific structure prevents a decrease in voltage holding ratio (VHR) and an increase in ion density (ID) of the liquid crystal layer, and causes white spots and uneven alignment.
  • VHR voltage holding ratio
  • ID ion density
  • the present invention A first substrate; a second substrate; a liquid crystal layer sandwiched between the first substrate and the second substrate; a color filter comprising a black matrix and at least an RGB three-color pixel portion; and a pixel electrode And a common electrode,
  • the liquid crystal layer has the general formula (I)
  • R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms
  • 8 represents an alkenyloxy group
  • A represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group
  • R 3 and R 4 are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 8 carbon atoms.
  • Z 3 and Z 4 are each independently a single bond, —CH ⁇ CH—, —C ⁇ C—, —CH 2 CH 2 —, — (CH 2 ) 4 —, —COO—.
  • R 1 to R 10 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, an alkoxy group, —CO 2 — (carboxylate ion group), —CO 2.
  • R 21, -SO 3 - (sulfonic acid ion group), - SO 3 M, .R 21 and R 22 represents an -SO 2 NR 21 R 22 are each independently a hydrogen atom, a branched structure having 1 to 12 carbon atoms Represents a good alkyl group or a cyclic alkyl group having 1 to 10 carbon atoms, and R 21 and R 22 may form a ring structure.
  • R 11 is -CO 2 - (carboxylate ion group), - CO 2 R 21, -SO 3 - ( sulfonic acid ion group), - SO 3 M, represents a -SO 2 NR 23 R 24.
  • R 23 and R 24 each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, or a cyclic alkyl group having 1 to 10 carbon atoms, and R 23 and R 24 form a ring structure. Also good.
  • M represents a hydrogen atom, a sodium atom or a potassium atom.
  • one or more of R 1 to R 10 are —SO 2 NR 21 R 22 .
  • the liquid crystal display device characterized by containing the xanthene compound represented by this.
  • the liquid crystal display device of the present invention uses a color filter that uses a specific liquid crystal composition, a specific pigment, and a specific compound, thereby reducing the voltage holding ratio (VHR) of the liquid crystal layer and increasing the ion density (ID).
  • VHR voltage holding ratio
  • ID ion density
  • FIG. 1 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 pigment, and a specific pigment between one of the two substrates (1) of the first substrate and the second substrate (1) having the alignment film (4)
  • a color filter layer (2a) containing a specific compound is provided, a pixel electrode layer (3b) is provided 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 (5a) 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 in the liquid crystal display device of the present invention has the general formula (I)
  • R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms
  • 8 represents an alkenyloxy group
  • A represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group
  • R 3 and R 4 are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 8 carbon atoms.
  • Z 3 and Z 4 are each independently a single bond, —CH ⁇ CH—, —C ⁇ C—, —CH 2 CH 2 —, — (CH 2 ) 4 —, —COO—.
  • the liquid crystal layer in the liquid crystal display device of the present invention contains 10 to 50% by weight of the compound represented by the general formula (I), preferably 15 to 48% by weight, and preferably 20 to 46% by weight. Is more preferable.
  • R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a carbon atom.
  • R 1 represents an alkyl group having 3 carbon atoms
  • R 2 is preferably an alkyl group having 2, 4 or 5 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms
  • R 2 is More preferred is an alkyl group having 2 carbon atoms.
  • A represents a 1,4-phenylene group
  • It preferably represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an alkenyloxy group having 3 to 5 carbon atoms
  • R 1 preferably represents an alkyl group, and in this case, an alkyl group having 1, 3 or 5 carbon atoms is particularly preferred.
  • R 2 preferably represents an alkoxy group having 1 to 2 carbon atoms.
  • the content of the compound represented by the general formula (I) in which at least one substituent of R 1 and R 2 is an alkyl group having 3 to 5 carbon atoms is in the compound represented by the general formula (I) It is preferably 50% by weight or more, more preferably 70% by weight or more, and further preferably 80% by weight or more.
  • the content of the compound represented by the general formula (I) in which at least one substituent of R 1 and R 2 is an alkyl group having 3 carbon atoms is in the compound represented by the general formula (I) It is preferably 50% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, and most preferably 100% by weight.
  • the compound represented by the general formula (I) may be contained alone or in combination of two or more, but A represents a trans-1,4-cyclohexylene group, and A represents a 1,4-phenylene group. It is preferable to contain at least one compound. Further, the content of the compound represented by the general formula (I) in which A represents a trans-1,4-cyclohexylene group may be 50% by weight or more in the compound represented by the general formula (I). Preferably, 70% by weight or more is more preferable, and 80% by weight or more is further preferable.
  • the compound represented by the general formula (I) is preferably a compound represented by the following general formula (Ia) to general formula (Ik).
  • R 1 and R 2 each independently represent an alkyl group or an alkoxy group having 1 to 5 carbon atoms having 1 to 5 carbon atoms, and R 1 and R 2 in the general formula (I) Similar embodiments are preferred.
  • general formula (Ia) to general formula (Ik) general formula (Ia), general formula (Ib), general formula (Ic), and general formula (Ig) are preferable, and general formula (Ia), general formula (Ib) )
  • general formula (Ic) are more preferable, and general formula (Ia) and general formula (Ib) are more preferable. Yes.
  • the general formula (Ib) and the general formula (Ic) are preferable, and the general formula (Ib) and the general formula (Ic) are more preferably used in combination.
  • the general formula (Ia) is preferable.
  • the content of the compound represented by the general formula (Ia), the general formula (Ib) and the general formula (Ic) is 80% by weight or more in the compound represented by the general formula (I). It is preferably 90% by weight or more, more preferably 95% by weight or more, and most preferably 100% by weight.
  • the content of the compound represented by the general formula (Ia) is 65% by weight to 100% by weight in the compound represented by the general formula (I), and the general formula (Ib) and the general formula (Ic)
  • the content of the compound represented by general formula (I) is 0% to 35% by weight in the compound represented by general formula (I), or the content of the compound represented by general formula (Ia) is
  • the content of the compound represented by the general formula (Ib) and the general formula (Ic) is 0% by weight to 10% by weight in the compound represented by the formula (I). It is preferably 90 to 100% by weight in the compound.
  • the liquid crystal layer in the liquid crystal display device of the present invention contains 35 to 80% by weight of the compound represented by the general formula (II), preferably 40 to 75% by weight, and preferably 45 to 70% by weight. Is more preferable.
  • R 3 represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms.
  • it represents an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 or 3 carbon atoms, and more preferably represents an alkyl group having 2 or 3 carbon atoms or an alkenyl group having 2 carbon atoms. It is particularly preferred to represent an alkyl group having 2 or 3 carbon atoms.
  • R 4 represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms, It preferably represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. More preferably, it represents an alkoxy group of 2-4.
  • Z 3 and Z 4 are each independently a single bond, —CH ⁇ CH—, —C ⁇ C—, —CH 2 CH 2 —, — (CH 2 ) 4 —, —COO—, —OCO—, —OCH 2 —, —CH 2 O—, —OCF 2 — or —CF 2 O—, represents a single bond, —CH 2 CH 2 —, —COO—, —OCH 2 —, —CH 2 O—, —OCF It preferably represents 2 — or —CF 2 O—, and more preferably represents a single bond or —CH 2 O—.
  • the liquid crystal layer in the liquid crystal display device of the present invention can contain 3 to 10 compounds represented by the general formula (II), preferably 4 to 9 compounds, and preferably 5 to 8 compounds. It is preferable to contain.
  • the compound represented by the general formula (II) is preferably a compound represented by the following general formula (II-1) or (II-2).
  • R 3 and R 4 are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms.
  • An alkenyloxy group, wherein Z 5 and Z 6 are each independently a single bond, —CH ⁇ CH—, —C ⁇ C—, —CH 2 CH 2 —, — (CH 2 ) 4 —, —COO—, —OCO—, —OCH 2 —, —CH 2 O—, —OCF 2 — or —CF 2 O— is represented, and m1, m2 and n2 each independently represents 0 or 1.
  • R 3 preferably represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and an alkyl group having 2 to 5 carbon atoms or the number of carbon atoms It is more preferably an alkenyl group having 2 to 4 carbon atoms, more preferably an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 carbon atoms, and particularly preferably an alkyl group having 3 carbon atoms.
  • R 4 preferably represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. More preferably, it represents an alkyl group having 3 carbon atoms or an alkoxy group having 2 carbon atoms, more preferably represents an alkoxy group having 2 carbon atoms, Z 5 represents a single bond,- It preferably represents CH 2 CH 2 —, —COO—, —OCH 2 —, —CH 2 O—, —OCF 2 — or —CF 2 O—, and more preferably represents a single bond or —CH 2 O—. preferable.
  • the liquid crystal layer in the liquid crystal display device of the present invention preferably contains 15% to 60% by weight, and preferably contains 17% to 50% by weight of the compound represented by the general formula (II-1).
  • the content is preferably from 40% by weight to 40% by weight, more preferably from 19% by weight to 30% by weight.
  • the liquid crystal layer in the liquid crystal display device of the present invention can contain one or more compounds represented by the general formula (II-1), but preferably contains 1 to 6 types. It is preferable to contain 5 types, and it is preferable to contain 3 types or 4 types.
  • R 3 preferably represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and the alkyl group having 2 to 5 carbon atoms or the number of carbon atoms More preferably, it represents an alkenyl group having 2 to 4 carbon atoms, more preferably represents an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 carbon atoms, and represents an alkyl group having 2 or 3 carbon atoms.
  • R 4 represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. And more preferably an alkyl group having 3 carbon atoms or an alkoxy group having 2 carbon atoms, and Z 6 represents a single bond, —CH 2 CH 2 —, —COO—, —OCH 2 —. , -CH 2 O -, - OCF 2 - or preferably representing a -CF 2 O-, and more preferably represents a single bond or -CH 2 O-.
  • the liquid crystal layer in the liquid crystal display device of the present invention preferably contains 10% by weight to 50% by weight of the compound represented by the general formula (II-2), preferably 15% by weight to 45% by weight, The content is preferably 20 to 40% by weight, more preferably 25 to 35% by weight.
  • the liquid crystal layer in the liquid crystal display device of the present invention may contain one or more compounds represented by the general formula (II-2), but preferably contains 1 to 6 types. It is preferable to contain 5 types, and it is preferable to contain 3 types or 4 types.
  • R 3 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms
  • R 4a represents an alkyl group having 1 to 5 carbon atoms.
  • R 3 is preferably the same embodiment as in general formula (II-1).
  • R 4a is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably an alkyl group having 2 carbon atoms.
  • R 3 is preferably the same embodiment as in general formula (II-1).
  • R 4a is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 3 carbon atoms, and particularly preferably an alkyl group having 3 carbon atoms.
  • the liquid crystal layer in the liquid crystal display device of the present invention preferably contains one or more compounds represented by the general formulas (II-1a) to (II-1d). It is preferable to contain 1 type or 2 types of compounds represented by general formula (II-1a).
  • R 3 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms
  • R 4b represents an alkyl group having 1 to 5 carbon atoms.
  • R 3 is preferably the same embodiment as in general formula (II-1).
  • R 4b is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably an alkyl group having 2 carbon atoms.
  • R 3 is preferably the same embodiment as in general formula (II-1).
  • R 4b is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 3 carbon atoms, and particularly preferably an alkyl group having 3 carbon atoms.
  • general formulas (II-1e) to (II-1h) general formula (II-1e) and general formula (II-1g) are preferable in order to increase the absolute value of dielectric anisotropy. .
  • R 3 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms
  • R 4c represents an alkyl group having 1 to 5 carbon atoms. Preferred is the same embodiment as R 3 and R 4 in 2).
  • R 3 is preferably the same embodiment as in general formula (II-2).
  • R 4c is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably an alkyl group having 2 carbon atoms.
  • R 3 is preferably the same embodiment as in general formula (II-2).
  • R 4c is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 3 carbon atoms, and particularly preferably an alkyl group having 3 carbon atoms.
  • general formulas (II-2a) to (II-2d) general formula (II-2a) and general formula (II-2c) are preferable for increasing the absolute value of dielectric anisotropy.
  • the general formula (II-2a) is preferable.
  • R 3 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms
  • R 4d represents an alkyl group having 1 to 5 carbon atoms.
  • An embodiment similar to R 3 and R 4 in 2) is preferred.
  • R 3 is preferably the same embodiment as in general formula (II-2).
  • R 4d is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably an alkyl group having 2 carbon atoms.
  • R 3 is preferably the same embodiment as in general formula (II-2).
  • R 4d is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 3 carbon atoms, and particularly preferably an alkyl group having 2 carbon atoms.
  • general formulas (II-2e) to (II-2i) general formula (II-2e) and general formula (II-2h) are preferable.
  • the total content of the compounds represented by the general formula (I) and the general formula (II) is preferably 75% by weight to 100% by weight, and 80% by weight to 100%. % By weight is preferable, 85% by weight to 100% by weight is preferable, 90% by weight to 100% by weight is preferable, and 95% by weight to 100% by weight is preferable.
  • the liquid crystal layer in the liquid crystal display device of the present invention further has the general formula (III)
  • R 7 and R 8 are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 8 represents an alkenyloxy group
  • D, E and F each independently represent a fluorine-substituted 1,4-phenylene group or trans-1,4-cyclohexylene
  • Z 2 represents a single bond.
  • the general formula (I), the general formula (II-1 And the compound represented by the general formula (II-2) are excluded.
  • the compound represented by the general formula (III) is preferably contained in an amount of 1 to 20%, more preferably 2 to 15%, and more preferably 4 to 10%.
  • R 7 is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms.
  • D represents trans-1,4-cyclohexylene
  • it preferably represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and an alkyl group or carbon having 2 to 5 carbon atoms More preferably, it represents an alkenyl group having 2 to 4 atoms, more preferably represents an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 or 3 carbon atoms, and represents an alkyl group having 3 carbon atoms.
  • D represents a 1,4-phenylene group optionally substituted with fluorine
  • D preferably represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 or 5 carbon atoms, More preferably, it represents a 5 alkyl group or an alkenyl group having 4 carbon atoms, and more preferably represents an alkyl group having 2 to 4 carbon atoms.
  • R 8 represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms
  • F represents trans-1,4-cyclohexylene
  • it preferably represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and an alkyl group or carbon having 2 to 5 carbon atoms
  • it represents an alkenyl group having 2 to 4 atoms More preferably represents an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 or 3 carbon atoms, and represents an alkyl group having 3 carbon atoms.
  • F represents a 1,4-phenylene group optionally substituted with fluorine
  • it preferably represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 or 5 carbon atoms, More preferably, it represents a 5 alkyl group or an alkenyl group having 4 carbon atoms, and more preferably represents an alkyl group having 2 to 4 carbon atoms.
  • R 7 and R 8 represent an alkenyl group and the bonded D or F represents a 1,4-phenylene group optionally substituted with fluorine
  • the alkenyl group having 4 or 5 carbon atoms includes A structure is preferred.
  • D, E, and F each independently represents a fluorine-substituted 1,4-phenylene group or trans-1,4-cyclohexylene, and represents a 2-fluoro-1,4-phenylene group, 2 , 3-difluoro-1,4-phenylene group, 1,4-phenylene group or trans-1,4-cyclohexylene, preferably 2-fluoro-1,4-phenylene group or 2,3-difluoro- 1,4-phenylene group and 1,4-phenylene group are more preferable, and 2,3-difluoro-1,4-phenylene group and 1,4-phenylene group are preferable.
  • Z 2 is a single bond, -OCH 2 -, - OCO - , - CH 2 O- or represents a -COO-, single bond, it is preferable to represent a -CH 2 O-or -COO-, a single bond is more preferable.
  • n represents 0, 1 or 2, but preferably represents 0 or 1. Also, if Z 2 represents a substituent other than a single bond, preferably it represents 1.
  • the compound represented by the general formula (III) is represented by the general formula (III-1c) to the general formula (III-1e) from the viewpoint of increasing the negative dielectric anisotropy when n represents 1.
  • the compounds represented by formulas (III-1f) to (III-1j) are preferred from the viewpoint of increasing the response speed.
  • R 7 and R 8 each independently represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms
  • An embodiment similar to R 7 and R 8 in (III) is preferred.
  • the compound represented by the general formula (III) is represented by the general formula (III-2a) to the general formula (III-2h) from the viewpoint of increasing the negative dielectric anisotropy when n is 2. From the viewpoint of increasing the response speed, compounds represented by general formula (III-2j) to general formula (III-2l) are preferable.
  • R 7 and R 8 each independently represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms
  • R 7 and R 8 each independently represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms
  • An embodiment similar to R 7 and R 8 in (III) is preferred.
  • the compound represented by the general formula (III) is preferably a compound represented by the general formula (III-3b) from the viewpoint of increasing the response speed when n is 0.
  • R 7 and R 8 each independently represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms
  • R 7 is preferably an alkyl group having 2 to 5 carbon atoms, more preferably an alkyl group having 3 carbon atoms.
  • R 8 is preferably an alkoxy group having 1 to 3 carbon atoms, more preferably an alkoxy group having 2 carbon atoms.
  • the liquid crystal layer in the liquid crystal display device of the present invention can use a nematic phase-isotropic liquid phase transition temperature (T ni ) in a wide range, but is preferably 60 to 120 ° C., 70 To 100 ° C is more preferable, and 70 to 85 ° C is particularly preferable.
  • T ni nematic phase-isotropic liquid phase transition temperature
  • the dielectric anisotropy is preferably ⁇ 2.0 to ⁇ 6.0 at 25 ° C., more preferably ⁇ 2.5 to ⁇ 5.0, and ⁇ 2.5 to ⁇ 4. Particularly preferred is 0.
  • the refractive index anisotropy is preferably 0.08 to 0.13 at 25 ° C., more preferably 0.09 to 0.12. More specifically, it is preferably 0.10 to 0.12 when corresponding to a thin cell gap, and preferably 0.08 to 0.10 when corresponding to a thick cell gap.
  • the rotational viscosity ( ⁇ 1) is preferably 150 or less, more preferably 130 or less, and particularly preferably 120 or less.
  • Z as a function of rotational viscosity and refractive index anisotropy shows a specific value.
  • ⁇ 1 represents rotational viscosity and ⁇ n represents refractive index anisotropy.
  • Z is preferably 13000 or less, more preferably 12000 or less, and particularly preferably 11000 or less.
  • the liquid crystal layer in the liquid crystal display device of the present invention is required to have a specific resistance of 10 12 ( ⁇ ⁇ m) or more, preferably 10 13 ( ⁇ ⁇ m), when used for an active matrix display element. 10 14 ( ⁇ ⁇ m) or more is more preferable.
  • the liquid crystal layer in the liquid crystal display device of the present invention may contain a normal nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, an antioxidant, an ultraviolet absorber, a polymerizable monomer, etc., in addition to the above-described compound, depending on the application. good.
  • a polymerizable monomer general formula (V)
  • X 1 and X 2 each independently represent a hydrogen atom or a methyl group
  • Sp 1 and Sp 2 are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH 2 ) s — (wherein s represents an integer of 2 to 7, Represents an aromatic ring).
  • Z 1 is —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, —CF 2 CF 2 —, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO—CH ⁇ CH—, —OCO—CH ⁇ CH—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —CH 2 CH 2 —OCO—, —COO—CH 2 —, —OCO—CH 2 —, —CH 2 —COO—, —CH 2 —OCO—, —CY 1 ⁇ CY 2 — (Wherein Y 1 and Y 2 each independently represents a fluorine atom or a hydrogen atom), —C ⁇ C— or a single bond; C represents a 1,4-phenylene group,
  • X 1 and X 2 are each preferably a diacrylate derivative that represents a hydrogen atom, or a dimethacrylate derivative that has a methyl group, and a compound in which one represents a hydrogen atom and the other represents a methyl group.
  • the polymerization rate of these compounds is the fastest for diacrylate derivatives, slow for dimethacrylate derivatives, and intermediate for asymmetric compounds, and a preferred embodiment can be used depending on the application.
  • a dimethacrylate derivative is particularly preferable.
  • Sp 1 and Sp 2 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or —O— (CH 2 ) s —, but at least one of them is a single bond in a PSA display element.
  • a compound in which both represent a single bond or one in which one represents a single bond and the other represents an alkylene group having 1 to 8 carbon atoms or —O— (CH 2 ) s — is preferable.
  • 1 to 4 alkyl groups are preferable, and s is preferably 1 to 4.
  • Z 1 is —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, —CF 2 CF 2 — or a single bond
  • C represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond in which any hydrogen atom may be substituted with a fluorine atom, and a 1,4-phenylene group or a single bond is preferred.
  • Z 1 is preferably a linking group other than a single bond.
  • Z 1 is preferably a single bond.
  • the ring structure between Sp 1 and Sp 2 is specifically preferably the structure described below.
  • C represents a single bond and the ring structure is formed of two rings
  • both ends shall be bonded to Sp 1 or Sp 2.
  • the polymerizable compounds containing these skeletons are optimal for PSA-type liquid crystal display elements because of their alignment restriction power after polymerization, and a good alignment state is obtained, so that display unevenness is suppressed or does not occur at all.
  • general formula (V-1) to general formula (V-4) are particularly preferable, and general formula (V-2) is most preferable.
  • Sp 2 represents an alkylene group having 2 to 5 carbon atoms.
  • the polymerization proceeds even in the absence of a polymerization initiator, but a polymerization initiator may be contained in order to accelerate the polymerization.
  • the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides, and the like.
  • a stabilizer may be added in order to improve storage stability.
  • Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, ⁇ -naphthylamines, ⁇ -naphthols, nitroso compounds, and the like. It is done.
  • the liquid crystal layer in the present invention is useful for a liquid crystal display element, and includes AM-LCD (active matrix liquid crystal display element), TN (nematic liquid crystal display element), STN-LCD (super twisted nematic liquid crystal display element), OCB-LCD and Although it is useful for IPS-LCD (in-plane switching liquid crystal display element), it is particularly useful for AM-LCD and can be used for liquid crystal display elements for PSA mode, PSVA mode, VA mode, IPS mode or ECB mode.
  • AM-LCD active matrix liquid crystal display element
  • TN nematic liquid crystal display element
  • STN-LCD super twisted nematic liquid crystal display element
  • OCB-LCD OCB-LCD
  • IPS-LCD in-plane switching liquid crystal display element
  • the color filter according to the present invention includes a black matrix and at least an RGB three-color pixel portion.
  • the following general formula (1) is used as a color material.
  • R 1 to R 10 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, an alkoxy group, —CO 2 — (carboxylate ion group), —CO 2.
  • R 21, -SO 3 - (sulfonic acid ion group), - SO 3 M, .R 21 and R 22 represents an -SO 2 NR 21 R 22 are each independently a hydrogen atom, a branched structure having 1 to 12 carbon atoms Represents a good alkyl group or a cyclic alkyl group having 1 to 10 carbon atoms, and R 21 and R 22 may form a ring structure.
  • R 11 is -CO 2 - (carboxylate ion group), - CO 2 R 21, -SO 3 - ( sulfonic acid ion group), - SO 3 M, represents a -SO 2 NR 23 R 24.
  • R 23 and R 24 each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, or a cyclic alkyl group having 1 to 10 carbon atoms, and R 23 and R 24 form a ring structure. Also good.
  • M represents a hydrogen atom, a sodium atom or a potassium atom.
  • R 1 to R 10 are —SO 2 NR 21 R 22 .
  • the xanthene compound represented by this is contained. Especially, it is preferable to contain the xanthene compound represented by the said General formula (1) in at least 1 pixel part of R pixel part and B pixel part.
  • the RGB three-color pixel portion includes, as coloring materials, a diketopyrrolopyrrole pigment and / or an anionic red organic dye in the R pixel portion, a metal halide phthalocyanine pigment, a phthalocyanine green dye, and a phthalocyanine in the G pixel portion. It is preferable that at least one selected from the group consisting of a mixture of a blue-based dye and an azo-based yellow organic dye contains an ⁇ -type phthalocyanine pigment or a cationic blue organic dye in the B pixel portion.
  • the alkyl groups represented by R 1 to R 10 are methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group.
  • Examples of the alkyl group represented by R 21 and R 22 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a heptyl group.
  • Examples of the C1-C10 cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 2-cyclohexylethyl group, and the like.
  • R 21 and R 22 is preferably other than hydrogen.
  • R 11 is -CO 2 - (carboxylate ion group), - CO 2 R 21, -SO 3 - ( sulfonic acid ion group), - SO 3 M, represents a -SO 2 NR 23 R 24.
  • R 23 and R 24 each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, or a cyclic alkyl group having 1 to 10 carbon atoms, and R 23 and R 24 form a ring structure. Also good.
  • Examples of the alkyl group represented by R 23 and R 24 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a heptyl group.
  • Examples of the C1-C10 cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclohexylmethyl group, and the like.
  • a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, and the like can be given.
  • a heptyl group, a cyclooctyl group, and a 2-cyclohexylethyl group are preferable.
  • R 23 and R 24 form a ring structure
  • specific examples include the following structures.
  • Either one of R 23 and R 24 is preferably other than hydrogen.
  • xanthene compound represented by the general formula (1) include, for example, the compounds described below, but the present invention is not limited to these unless it exceeds the gist.
  • Ra dodecyl
  • R a 2-ethylhexyl
  • R a 2-cyclohexylethyl
  • R a 2-ethylhexyl
  • R b 2-ethylhexyl
  • R a decyl
  • R b decyl
  • R a dodecyl
  • R a 2-ethylhexyl
  • R a 2-cyclohexylethyl
  • R a 2-ethylhexyl
  • R b 2-ethylhexyl
  • No.15: R a decyl
  • R b decyl
  • the G pixel portion preferably contains at least one selected from the group consisting of metal halide phthalocyanine pigments, phthalocyanine green dyes, and mixtures of phthalocyanine blue dyes and azo yellow organic dyes.
  • the metal halide phthalocyanine pigment is 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 Pb.
  • Metal halide phthalocyanine pigments that are bonded together are preferred. Examples of the metal halide phthalocyanine pigment include the following two groups of metal halide phthalocyanine pigments.
  • (First group) It has a metal 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 Pb as a central metal.
  • a halogenated metal phthalocyanine pigment in which 8 to 16 halogen atoms per phthalocyanine molecule are bonded to the benzene ring of the phthalocyanine molecule, and when the central metal is trivalent, the central metal has one halogen atom
  • the central metal when a hydroxyl group or a sulfonic acid group (—SO 3 H) is bonded and the central metal is a tetravalent metal, the central metal has one oxygen atom or two halogens which may be the same or different.
  • a halogenated metal phthalocyanine pigment to which any one of an atom, a hydroxyl group and a sulfonic acid group is bonded.
  • a pigment composed of a metal phthalocyanine dimer In the metal halide phthalocyanine pigment, all the halogen atoms bonded to the benzene ring may be the same or different. Different halogen atoms may be bonded to one benzene ring.
  • the halogenated metal phthalocyanine pigment in which 9 to 15 bromine atoms out of 8 to 16 halogen atoms per phthalocyanine molecule are bonded to the benzene ring of the phthalocyanine molecule exhibits a yellowish bright green color, It is most suitable for use in the green pixel portion of the color filter.
  • the metal halide phthalocyanine pigment is insoluble or hardly soluble in water or an organic solvent.
  • the halogenated metal phthalocyanine pigment includes both a pigment that has not been subjected to a finishing treatment described later (also referred to as a crude pigment) and a pigment that has been subjected to a finishing treatment.
  • halogenated metal phthalocyanine pigments belonging to the first group and the second group can be represented by the following general formula (PIG-1).
  • the metal halide phthalocyanine pigments belonging to the first group are as follows.
  • X 1 to X 16 each represents 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.
  • 8 to 16 are chlorine, bromine or iodine atoms.
  • M represents a central metal.
  • a pigment having a total of less than 8 chlorine atoms, bromine atoms and iodine atoms out of 16 X 1 to X 16 is blue.
  • Y bonded to the central metal M is a monovalent atomic group selected from the group consisting of a halogen atom of any one of fluorine, chlorine, bromine or iodine, an oxygen atom, a hydroxyl group and a sulfonic acid group, and m is bonded to the central metal M. Represents the number of Y to be represented, and is an integer of 0-2.
  • m The value of m is determined by the valence of the central metal M.
  • One of the groups is attached to the central metal.
  • the central metal M is divalent like Mg, Fe, Co, Ni, Zn, Cu, Zr, Sn, Pb, Y does not exist.
  • the halogenated metal phthalocyanine pigment belonging to the second group is as follows in the general formula (PIG-1).
  • X 1 to X 16 are as defined above, and the central metal M represents a trivalent metal selected from the group consisting of Al, Sc, Ga, Y and In, m represents 1.
  • Y represents the following atomic group.
  • the central metal M has the same definition as described above, and X 17 to X 32 have the same definition as X 1 to X 16 in the general formula (PIG-1).
  • A represents a divalent atomic group selected from the group consisting of an oxygen atom, a sulfur atom, sulfinyl (—SO—) and sulfonyl (—SO 2 —).
  • M in the general formula (PIG-1) and M in the atomic group Y are bonded via the divalent atomic group A. That is, the metal halide phthalocyanine pigment belonging to the second group is a metal halide phthalocyanine dimer in which two molecules of metal halide phthalocyanine are constituent units and these are bonded via the divalent atomic group.
  • halogenated metal phthalocyanine pigment represented by the general formula (PIG-1) include the following (1) to (4).
  • chlorinated brominated zinc phthalocyanine pigments include C.I. I. Pigment Green 58, particularly preferred.
  • a halogenated metal phthalocyanine pigment having any of the groups and having 8 to 16 halogen atoms bonded to 4 benzene rings per phthalocyanine molecule.
  • the center metal has a tetravalent metal selected from the group consisting of Si, Ti, V, Ge, Zr and Sn, such as halogenated oxytitanium phthalocyanine and halogenated oxyvanadium phthalocyanine. 8 to 16 halogen atoms bonded to four benzene rings per one phthalocyanine molecule, having one oxygen atom or two halogen atoms which may be the same or different, a hydroxyl group or a sulfonic acid group Halogenated metal phthalocyanine pigment.
  • a tetravalent metal selected from the group consisting of Si, Ti, V, Ge, Zr and Sn, such as halogenated oxytitanium phthalocyanine and halogenated oxyvanadium phthalocyanine. 8 to 16 halogen atoms bonded to four benzene rings per one phthalocyanine molecule, having one oxygen atom or two halogen atoms which may be the same or different
  • a halogenated ⁇ -oxo-aluminum phthalocyanine dimer and a halogenated ⁇ -thio-aluminum phthalocyanine dimer.
  • the valence metal is the central metal
  • the halogenated metal phthalocyanine is composed of two molecules of 8-16 halogen atoms bonded to 4 benzene rings per phthalocyanine molecule. Each central metal of these structural units is an oxygen atom.
  • a pigment comprising a metal halide phthalocyanine dimer bonded through a divalent atomic group selected from the group consisting of sulfur atom, sulfinyl and sulfonyl.
  • the metal halide phthalocyanine pigment include C.I. I. One or more selected from Pigment Green 7, 36 and 58 are preferred, and one or two selected from Green 36 and 58 are more preferred.
  • Specific examples of the phthalocyanine green dye include C.I. I. One or more selected from Solvent Green 4, 5, 7, and 28 are preferred.
  • Specific examples of phthalocyanine blue dyes include C.I. I. Solvent Blue 4, 5, 25, 35, 36, 38, 58, 59, 67 and 70 are preferred, and Blue 25, 38, 67 are preferred. And one or more selected from 70 are more preferred.
  • Specific examples of the azo yellow organic dye include C.I. I. Solvent Yellow 2, 4, 14, 16, 18, 21, 56, 72, 82, 124, 162, and 163 are preferred, preferably Yellow 82 And one or two selected from 162 are more preferred.
  • the R pixel portion preferably contains a diketopyrrolopyrrole pigment and / or an anionic red organic dye.
  • a diketopyrrolopyrrole pigment include C.I. I. One or two or more selected from Pigment Red 254, 255, 264, 272, Orange 71 and 73 are preferred, and one or more selected from Red 254, 255, 264 and 272 Is more preferred, and C.I. I. Pigment Red 254 is particularly preferred.
  • Specific examples of the anionic red organic dye include C.I. I. One or more selected from Solvent Red 124, Acid Red 52 and 289 are preferred. I. Solvent Red 124 is particularly preferred.
  • the B pixel portion preferably contains an ⁇ -type phthalocyanine pigment or a cationic blue organic dye.
  • an ⁇ -type phthalocyanine pigment Pigment Blue 15: 6 is preferable, and as the cationic blue organic dye, a triarylmethane-based dye is preferably contained.
  • the RGB three-color pixel portion is a color material that contains C.I. I. Solvent Red 124 in the G pixel portion.
  • I. Solvent Blue 67 and C.I. I. Solvent Yellow 82 or a mixture thereof with 162 contains Pigment Blue 15: 6 in the B pixel portion, and the xanthene compound represented by the general formula (1) in the R pixel portion and / or the B pixel portion. It is preferable to contain.
  • the RGB three-color pixel portion includes C.I. I. Pigment Red 254 in the G pixel portion. I.
  • 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. Acid Red 52, C.I. I. Basic Red 1, 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 and 162.
  • the RGB three-color pixel portion is further provided with C.I. I. Pigment Yellow 150, 215, 185, 138, C.I. I.
  • the RGB three-color pixel portion further includes C.I. I. Pigment Violet 23, C.I. I. Basic Violet 10, C.I. I. Acid Blue 1, 90, 83, C.I. I. Direct Blue 86, C.I. I. It is preferable to contain at least one organic dye / pigment selected from the group consisting of Pigment Blue 15, 15: 1, 15: 2, 15: 3 and 15: 4.
  • the color filter is composed of a black matrix, an RGB three-color pixel portion, and a Y pixel portion.
  • the chromaticity x and chromaticity y in the XYZ color system under the C light source of each pixel portion prevent a decrease in voltage holding ratio (VHR) and an increase in ion density (ID) of the liquid crystal layer. From the viewpoint of suppressing the occurrence of display defect problems such as white spots, uneven alignment, and baking, the following are preferable.
  • the chromaticity x in the XYZ color system under the C light source of the R pixel portion is preferably 0.58 to 0.69, more preferably 0.62 to 0.68, and the chromaticity y is 0.
  • chromaticity x is 0.58 to 0.69
  • chromaticity y is 0.30 to 0. More preferably, the chromaticity x is 0.62 to 0.68, and the chromaticity y is more preferably 0.31 to 0.35.
  • the chromaticity x in the XYZ color system under the C light source of the G pixel portion is preferably 0.19 to 0.35, more preferably 0.20 to 0.26, and the chromaticity y is 0. .54 to 0.76 is preferred, 0.64 to 0.74 is more preferred, chromaticity x is 0.19 to 0.35, and chromaticity y is 0.54 to 0. More preferably, the chromaticity x is 0.20 to 0.26, and the chromaticity y is 0.64 to 0.74.
  • the chromaticity x in the XYZ color system under the C light source of the B pixel portion is preferably 0.12 to 0.20, more preferably 0.13 to 0.18, and the chromaticity y is 0. 0.04 to 0.12 is preferable, 0.05 to 0.09 is more preferable, chromaticity x is 0.12 to 0.18, and chromaticity y is 0.04 to 0. More preferably, the chromaticity x is 0.13 to 0.17, and the chromaticity y is 0.04 to 0.09.
  • the chromaticity x in the XYZ color system under the C light source of the Y pixel portion is preferably 0.46 to 0.50, more preferably 0.47 to 0.48, and the chromaticity y is 0.
  • the XYZ color system means a color system approved as a standard color system by the CIE (International Lighting Commission) in 1931.
  • the chromaticity in each of the pixel portions can be adjusted by changing the type of dyes and pigments used and their mixing ratio.
  • a yellow dye and / or orange pigment is used as the red dye / pigment
  • the yellow dye / pigment is used as the green dye / pigment
  • a purple dye or yellowish dye is used as the blue dye / pigment. It is possible to adjust by adding an appropriate amount of the blue dye / pigment. It can also be adjusted by appropriately adjusting the particle size of the pigment.
  • 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 coating method, a slit coating method, a roll coating method, and an ink jet method.
  • the drying conditions of the coating film of the photocurable composition applied to the transparent substrate are usually about 50 to 150 ° C. for about 1 to 15 minutes, although it varies depending on the type of each component, the blending ratio and the like.
  • the light used for photocuring the photocurable composition it is preferable to use ultraviolet rays or visible light in the wavelength range of 200 to 500 nm.
  • 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 a 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, thereby removing volatile components in the colored coating film and simultaneously applying light.
  • the unreacted photocurable compound remaining in the cured colored film of the curable composition is thermally cured to complete the color filter.
  • VHR voltage holding ratio
  • ID ion density
  • the color filter dye and / or pigment composition of the present invention 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.
  • 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.
  • organic solvent used here examples 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.
  • 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, ⁇ -butyrolactam, N-methyl-2-pyrrolidone, aniline And nitrogen compound solvents such as pyridine, lactone solvents such as ⁇ -butyrolactone, and carbamate esters such as a 48:52 mixture of methyl
  • 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 EFKA 46, EFKA 47, EFKA 452, EFKA LP4008, EFKA 009, Efka LP4010, Efka LP4050, LP4055, Efka400, Efka401, Evka402, Efka403, Efka450, Efka451, Efka453, Evka4540, Efka4550, EfkaLP4560, Efka120, Efka150, Evka
  • 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
  • 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.
  • 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.
  • thermoplastic resin used for the preparation of the photocurable composition examples include urethane resins, acrylic resins, polyamide resins, polyimide resins, styrene maleic acid resins, styrene maleic anhydride resins, and the like.
  • thermocurable compound examples include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, and 3-methylpentanediol diacrylate.
  • 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.
  • photopolymerization initiator examples 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.
  • photopolymerization initiators include, for example, “Irgacure (trade name) -184”, “Irgacure (trade name) -369”, “Darocur (trade name) -1173” manufactured by BASF, “Lucirin- "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.
  • a well-known and usual photosensitizer can also be used together with the said photoinitiator.
  • 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.
  • 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.
  • the materials as described above 300 to 1000 parts of an organic solvent and 1 to 100 parts of a dispersant per 100 parts of the color filter dye and / or pigment composition of the present invention on a mass basis.
  • the dye / pigment solution can be obtained by stirring and dispersing so as to be uniform.
  • the pigment dispersion is combined with 3 to 20 parts in total of the thermoplastic resin and the photocurable compound per 1 part of the pigment composition for a color filter of the present invention and 0.05 to 3 parts per 1 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.
  • the developer a known and commonly used organic solvent or alkaline aqueous solution can be used.
  • 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.
  • 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.
  • a color filter may be used in a state where an organic pigment is applied to a substrate and dried, and when a curable resin is contained in the pigment dispersion, a color filter may be obtained by curing with heat or active energy rays.
  • a volatile component in the coating film may be removed by heat treatment (post-baking) at 100 to 280 ° C. for a predetermined time using a heating device such as a hot plate or an oven.
  • particles having an ⁇ -type phthalocyanine pigment which is an organic pigment
  • particles having an ⁇ -type phthalocyanine pigment have a volume fraction of 1% or less of particles greater than 1000 nm and 25% or less of 40 nm to 1000 nm.
  • the state of the organic pigment in the state of the color filter contributes to the suppression of display defects such as white spots, alignment unevenness, and burn-in.
  • the particles having a particle size of 40 nm or more and 1000 nm or less are high-order particles in which primary particles are aggregated, such as secondary particles or tertiary and quaternary particles, and more preferably have a volume fraction of 15% or less. Moreover, when there are many particles of 100 nm or more and 1000 nm or less, the display state is affected.
  • the volume fraction of particles of 100 nm or more and 1000 nm or less is preferably 7% or less, more preferably 3% or less.
  • coarse particles larger than 1000 nm are not preferable because they may adversely affect the display state. This can be done by observing the color filter surface with an appropriate optical microscope or the like.
  • Ultra-small angle X-ray scattering profile In order to measure the volume fraction of particles of 1000 nm or less, it can be obtained by analyzing an ultra small angle X-ray scattering profile based on the ultra small angle X-ray scattering method.
  • the step (B) of obtaining a theoretical scattering profile from the value of the temporary radius R 1 and the temporary normalized dispersion value by simulation, and the theoretical scattering profile and the measured scattering profile are: Step (C) for obtaining a residual square sum Z value between the theoretical scattering profile and the measured scattering profile by curve fitting, and the residual square sum Z value obtained in step (C) is 2% or less.
  • Steps (B) to (C) are repeated n times, and from the results of curve fitting the theoretical scattering profile and the measured scattering profile, the primary particle diameter of organic pigment and the average particle diameter of higher order particles, normalized dispersion value, A step (D) of determining at least one of the volume fractions.
  • the ultra-small angle X-ray scattering method (Ultra-Small Angle X-ray Scattering: USAXS) is not only a small angle region where the scattering angle is 0.1 ° ⁇ (2 ⁇ ) ⁇ 10 °, but also 0 ° ⁇ (2 ⁇ ) ⁇ 0. It is a method that simultaneously measures diffuse scattering and diffraction occurring in the ultra-small angle region of 1 °. In the small-angle X-ray scattering method, if there are regions with different electron densities of about 1 to 100 nm in the material, the diffuse scattering of X-rays can be measured by the difference in electron density.
  • the main technology for realizing the ultra-small angle X-ray scattering method is to reduce the background scattering intensity in the ultra-small angle region by reducing the wavelength width and beam diameter of incident X-rays, and from the sample to the detector as much as possible. This is achieved by two techniques for measuring a portion having a small scattering angle with high accuracy by increasing a distance, that is, a so-called camera length. In the small laboratory apparatus, this is mainly achieved by the former technique. Further, as a program for obtaining the particle size distribution from the X-ray small angle scattering curve, it is preferable to use a program such as NANO-solver (manufactured by Rigaku Corporation) or GIF (manufactured by PANalytical).
  • NANO-solver manufactured by Rigaku Corporation
  • GIF manufactured by PANalytical
  • the luminance of the incident X-ray of the X-ray scattering apparatus is 10 6 Brilliance (photons / sec / mm 2 / mrad 2 /0.1% bandwidth) or more.
  • the scattering intensity can be measured, and is preferably 10 7 Brilliance or higher.
  • the luminance of the incident X-ray is preferably 10 16 Brilliance or higher, more preferably 10 18 Brilliance or higher.
  • a large-scale synchrotron radiation facility such as a light source such as SPring-8 in Hyogo Prefecture or Photon Factory in Ibaraki Prefecture can be used.
  • a desired scattering region can be set by selecting an arbitrary camera length. Further, in order to obtain sufficient scattering intensity, to prevent sample damage, and to protect the detector, several kinds of metal absorbing plates called attenuators are used on the incident side, and the exposure time is set to 0. 0. By arbitrarily adjusting in 5 to 60 seconds, the optimum measurement conditions can be selected from a wide range of purposes. Examples of the attenuator include a thin film made of Au, Ag, or molybdenum.
  • step (A) after setting the color filter on the sample holder, sample stage, etc. of a commercially available X-ray diffractometer, each of the scattering angles (2 ⁇ ) in the range of less than 10 °.
  • the scattering intensity I at the scattering angle (2 ⁇ ) is measured to measure a small-angle X-ray scattering profile (measured scattering profile).
  • the ultra-small-angle scattering device using synchrotron radiation used when the substrate is a glass coating uses a double crystal spectrometer to monochromatic white light extracted from a circular accelerator called a storage ring, and changes the wavelength in the X-ray region (for example, 1 ⁇ ).
  • the step (A) is an operation for converting to a scattering intensity I at each scattering angle (2 ⁇ ) in a range of less than 0 ° to obtain a small-angle X-ray scattering profile (measured scattering profile).
  • step (B) from the measured scattering profile obtained, it is assumed that the organic pigment is a spherical particle with a radius R and there is a variation in the particle size distribution, and the value of the temporary radius R 1 and the temporary standard A theoretical scattering profile is obtained from the normalized dispersion value using a commercially available analysis software.
  • the scattering intensity I can be approximated as the following formula (1).
  • q represents a scattering vector
  • V represents a volume integration region, and means that the entire material is integrated.
  • F (q) is a shape factor
  • S (q) is a structure factor
  • S (q) 1 when the particles are randomly present in the substance.
  • the scattering vector q is expressed by the following formula (2).
  • ⁇ is the X-ray wavelength
  • 2 ⁇ is the scattering angle.
  • the shape factor F (q) is represented by the following formula (3).
  • the scattering intensity I can be described if the shape factor F (q) is calculated assuming a temporary radius R value.
  • the scattering intensity I is assumed only when the particles in the substance have a certain size (the radius R is constant).
  • the particles are rarely present in a certain size, and there is generally some variation (particle size distribution variation) in the particle size.
  • the object of the present invention is to accurately and accurately measure the particle size distribution of organic pigments having such a particle size distribution variation, it is necessarily assumed that the particle size distribution varies. Will be needed.
  • the scattering intensity I is given by a superposition of scattering generated from particles having various sizes.
  • a known distribution function used in statistics can be used.
  • the ⁇ distribution function is used. Is preferred. This ⁇ distribution function is expressed by the following formula (4).
  • R 0 is an average radius of the spherical particles
  • M is a spread parameter of the particle size distribution.
  • M which is a spread parameter of the particle size distribution in Expression (5), is output as a normalized dispersion value ⁇ (%) as a result of the conversion of Expression (6) as an analysis result.
  • step (B) the scattering intensity I at the scattering angle (2 ⁇ ) is calculated by simulation from the value of the temporary radius R 1 and the temporary normalized dispersion value to obtain the theoretical scattering profile.
  • step (C) curve fitting between the theoretical scattering profile calculated from the scattering intensity I and the measured scattering profile is performed by the method of least squares.
  • the variables to be refined in profile fitting are the average particle diameter (nm) and the normalized dispersion value (%).
  • Profile fitting is performed so that the residual square sum Z value between the measurement profile and the theoretical scattering profile is minimized by the method of least squares. The smaller the residual square sum Z value, the higher the accuracy of particle size analysis. The In general, when the Z value decreases to less than 2%, it may be determined that the two profiles almost overlap and converge at the visual level.
  • the Z value is preferably less than 1%, more preferably less than 0.5%.
  • step (A) When X-ray scattering is measured in the step (A) including the ultra-small angle scattering region, a relatively large particle size is included in the analysis range, so one kind of particle size distribution assumed in the step (B), that is, one kind of average.
  • step C In the fitting analysis of step C assuming the primary particle size and the normalized dispersion value, the residual sum of squares Z value does not sufficiently decrease, and the measurement profile and the theoretical scattering profile may not show good agreement. The reason for this is that the particle size distribution is not a single type, and pigment particles having a larger particle size and particles aggregated in a higher order are included. Introduce a diameter distribution model.
  • step (D) until the residual sum of squares Z value obtained in step (C) becomes 2% or less, a new value of radius R n + 1 (n is an integer, R n ⁇ R n + 1 ) and temporary
  • the normalized dispersion value is added to set a plurality of particle size distribution models, and the steps (B) to (C) are repeated n times.
  • a new particle size distribution model having a larger average particle size is assumed, the radius is R 2 (in this case, R 2 > R 1 ), and the scattering intensity I of each component is I (1 ) And I (2), the left term of the pre-scattering intensity equation (5) is corrected as in equations (7) and (8).
  • M 1 is a first type particle size distribution spread parameter.
  • M 2 is a second type of particle size distribution spread parameter. Similarly, when assuming a distribution of the third radius R3 or higher, it can be described as I (3), I (4)... I (n).
  • the total scattering intensity I Total of the particle size distribution model system having two average particle sizes is expressed by Equation (9).
  • I Total k (1) I (1) + k (2) I (2) (9)
  • k (1) and k (2) are scale factors representing the composition ratio of each component.
  • the total scattering intensity can be described as in equation (10) with a total of n particle size distribution models.
  • I Total k (1) I (1) + k (2) I (2) +... + K (n) I (n) (10)
  • the volume fractions w (1), w (2)... W (n) of each of the n particle size distribution components are represented by the ratio shown in Equation (11). .
  • w (1): w (2): ...: w (n) k (1): k (2): ...: k (n) (11)
  • the variables to be refined in profile fitting are the average particle size (nm) of each particle size distribution component, the normalized dispersion value (%) representing the width of each particle size distribution, and the volume fraction (%) of each component. .
  • profile fitting is performed so that the Z value, which is the residual sum of squares of the measurement profile and the total theoretical scattering profile, is minimized, and each of the variables is determined.
  • the normalized dispersion value of each particle size distribution component may be fixed with reference to the normalized dispersion value obtained in the step (C). By this operation, the profile fitting by the least square method with fewer variables becomes easier to converge. In this way, the average particle diameter, normalized dispersion value (%), and volume fraction (%) of each component are obtained as analysis results.
  • 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.
  • alignment film material transparent organic materials such as polyimide, polyamide, BCB (Penzocyclobutene Polymer), polyvinyl alcohol and the like can be used. Particularly, p-phenylenediamine, 4,4′-diaminodiphenylmethane, etc.
  • Aliphatic or alicyclic tetracarboxylic anhydrides such as aliphatic or alicyclic diamines, butanetetracarboxylic anhydride, 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.
  • 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.
  • 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. .
  • a conductive metal oxide can be used as a material for the transparent electrode.
  • 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
  • niobium-doped titanium dioxide Ti 1-x Nb x O 2
  • fluorine-doped tin oxide graphene
  • ZnO zinc oxide
  • In 2 O 3 —SnO 2 indium tin oxide
  • In 2 O 3 —ZnO indium zinc oxide
  • a photo-etching method or a method using a mask can be used.
  • the liquid crystal display device of the present invention has a feature that prevents a decrease in voltage holding ratio (VHR) and an increase in ion density (ID) of the liquid crystal layer and suppresses the occurrence of display defects such as image sticking. It is useful for liquid crystal display devices for driving VA mode, PSVA mode, and FSS mode, and can be applied to liquid crystal display devices such as liquid crystal TVs, monitors, mobile phones, and smartphones.
  • VHR voltage holding ratio
  • ID ion density
  • T ni Nematic phase-isotropic liquid phase transition temperature (° C.) ⁇ n: refractive index anisotropy at 25 ° C. ⁇ : dielectric anisotropy at 25 ° C. ⁇ : viscosity at 20 ° C. (mPa ⁇ s) ⁇ 1: rotational viscosity at 25 ° C. (mPa ⁇ s) VHR: Voltage holding ratio at 70 ° C.
  • 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 1 (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 Instead of 7 parts of the yellow dye 1 of the green dye coloring composition 1, 4 parts of yellow dye 1 (CI Solvent Yellow 162) and 3 parts of yellow dye 3 (CI Solvent Yellow 82) are used. In the same manner as above, a green dye coloring composition 2 was obtained.
  • Green dye coloring composition 3 Instead of 3 parts of blue dye 1 and 7 parts of yellow dye 1 in the green dye coloring composition 1, 10 parts of green dye 1 (CI Solvent Green 7) is used in the same manner as described above to give a green dye coloring composition. Product 3 was obtained.
  • Blue dye coloring composition 1 Blue dye coloring composition 1 was obtained in the same manner as described above using 10 parts of blue dye 2 (CI Solvent Blue 12) instead of 10 parts of red dye 1 of red dye coloring composition 1 above. .
  • 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 1 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) is placed in a polybin, 55 parts of propylene glycol monomethyl ether acetate, Dispersic LPN21116 (manufactured by BYK Chemie) 7.0 Add 0.3-0.4mm ⁇ zirconia beads “ER-120S” manufactured by Saint-Gobain, and disperse with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, and then filter through a 1 ⁇ m filter to obtain a pigment dispersion. Obtained.
  • a paint conditioner manufactured by Toyo Seiki Co., Ltd.
  • Red pigment coloring composition 2 instead of 10 parts of red pigment 1 of the above-mentioned 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 Using 2 parts of (C.I. Pigment Yellow 139), a red pigment coloring composition 2 was obtained in the same manner as described above.
  • Red pigment coloring composition 3 Instead of 10 parts of the red pigment 1 of the red pigment coloring composition 1, 8 parts of the red pigment 1 and 2 parts of the xanthene compound represented by the general formula (1) (compound No. 16: CI Acid Red 289) In the same manner as above, a red pigment composition 3 was obtained.
  • 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 1 CI Pigment Green 36, “FASTOGEN GREEN 2YK-CF” manufactured by DIC Corporation
  • yellow pigment 1 C.I. Pigment Yellow 150, 4 parts of FANCHON FAST YELLOW E4GN manufactured by BAYER
  • 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 58, FASTOGEN GREEN A110 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 Blue pigment 1 (CI Pigment Blue 15: 6, FASTOGEN Blue A510 manufactured by DIC Corporation) 1.80 parts, xanthene compound (Compound No. 2) represented by the general formula (1) 0.18 parts, BYK-LPN21116 (Bic Chemie) 2.84 parts, cyclohexanone 10.19 parts, 0.3-0.4 mm ⁇ Sepul beads are placed in a polybin and dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours. Obtained.
  • a paint conditioner manufactured by Toyo Seiki Co., Ltd.
  • Blue pigment coloring composition 2 In place of the xanthene compound of the blue pigment coloring composition 1, the xanthene compound (compound No. 4) represented by the general formula (1) was used to obtain a blue pigment coloring composition 2 in the same manner as described above.
  • Blue pigment coloring composition 3 In place of the xanthene compound of the blue pigment coloring composition 1, the xanthene compound (compound No. 1) represented by the general formula (1) was used to obtain a blue pigment coloring composition 3 in the same manner as described above.
  • yellow pigment coloring composition 1 In place 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 LANXESS) was used in the same manner as described above, and yellow pigment 1 A colored composition 1 was obtained.
  • yellow pigment 1 CI Pigment Yellow 150, FANCHON FAST YELLOW E4GN manufactured by LANXESS
  • 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 ⁇ m by spin coating. After drying at 70 ° C. for 20 minutes, a striped pattern was exposed to ultraviolet rays through a photomask in 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 ⁇ m.
  • 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.
  • red pixels and blue pixels adjacent to the green pixels were formed by spin coating with a film thickness of 2 ⁇ m.
  • a color filter having striped pixels of three colors of red, green, and blue on the transparent substrate was obtained.
  • the yellow coloring composition was similarly formed by spin coating to form a yellow pixel adjacent to the red pixel and the green pixel with a film thickness of 2 ⁇ m.
  • 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 pigment coloring composition shown in the following table.
  • the primary particle volume fraction represented by the distribution of the average particle diameter of 1 nm or more and less than 40 nm in the B pixel portion of the color filters 1 to 5 is 88.4% and the distribution of 40 nm or more and less than 100 nm
  • the volume fraction of secondary particles represented is 11.6%
  • the volume fraction of tertiary particles represented by a distribution of 100 nm to 1000 nm is 0.0%
  • the volume fraction occupied by particles of 40 nm to 1000 nm is The rate was 11.6%.
  • Measuring instruments and measuring methods are as follows.
  • Analysis software Fit2D for two-dimensional data imaging and one-dimensionalization (obtained from the homepage of the European Synchron Radiation Facility [http://www.esrf.eu/computing/scientific/FIT2D/]) The analysis of the particle size distribution was performed with software NANO-Solver (Ver 3.6) manufactured by Rigaku Corporation.
  • Examples 1 to 5 An electrode structure is formed on the first and second substrates, a vertical alignment film is formed on each facing side, and then a weak rubbing process is performed to create a VA cell.
  • the first substrate and the second substrate The liquid crystal composition 1 shown in the following table was sandwiched between them.
  • the liquid crystal composition 1 has a practical liquid crystal phase temperature range of 81 ° C. as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, has a low viscosity, and an optimal ⁇ n. I understand that.
  • the liquid crystal display devices of Examples 1 to 5 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.
  • Example 6 to 15 In the same manner as in Example 1, the liquid crystal compositions shown in the following table were sandwiched, and the liquid crystal display devices of Examples 6 to 15 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • the liquid crystal display devices of Examples 6 to 15 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.
  • Example 16 to 30 In the same manner as in Example 1, the liquid crystal compositions shown in the following table were sandwiched, and the liquid crystal display devices of Examples 16 to 30 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • liquid crystal display devices of Examples 16 to 30 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 31 to 45 In the same manner as in Example 1, the liquid crystal compositions shown in the following table were sandwiched, and the liquid crystal display devices of Examples 31 to 45 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • the liquid crystal display devices of Examples 31 to 45 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.
  • Example 46 to 60 In the same manner as in Example 1, the liquid crystal compositions shown in the following table were sandwiched, and the liquid crystal display devices of Examples 46 to 60 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • liquid crystal display devices of Examples 46 to 60 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 61 to 75 In the same manner as in Example 1, the liquid crystal compositions shown in the following table were sandwiched, and the liquid crystal display devices of Examples 61 to 75 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • liquid crystal display devices of Examples 61 to 75 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.
  • Example 76 to 90 In the same manner as in Example 1, the liquid crystal compositions shown in the following table were sandwiched, and the liquid crystal display devices of Examples 76 to 90 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • liquid crystal display devices of Examples 76 to 90 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.
  • Example 91 to 105 In the same manner as in Example 1, the liquid crystal compositions shown in the following table were sandwiched, and the liquid crystal display devices of Examples 91 to 105 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • liquid crystal display devices of Examples 91 to 105 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.
  • Example 106 to 120 In the same manner as in Example 1, the liquid crystal compositions shown in the following table were sandwiched, and the liquid crystal display devices of Examples 106 to 120 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • the liquid crystal display devices of Examples 116 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.
  • Example 121 to 135 The liquid crystal compositions shown in the following table were sandwiched in the same manner as in Example 1, and the liquid crystal display devices of Examples 121 to 135 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • liquid crystal display devices of Examples 121 to 135 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.
  • Liquid crystal composition 1 was mixed with 0.3% by mass of 2-methyl-acrylic acid 4- ⁇ 2- [4- (2-acryloyloxy-ethyl) -phenoxycarbonyl] -ethyl ⁇ -biphenyl-4′-yl ester.
  • a liquid crystal composition 28 was obtained.
  • the liquid crystal composition 28 was sandwiched between the VA cells used in Example 1, and irradiated with ultraviolet rays (3.0 J / cm 2 ) for 600 seconds while applying a driving voltage between the electrodes, followed by polymerization treatment, Liquid crystal display devices of Examples 136 to 140 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • the liquid crystal display devices of Examples 136 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.
  • Example 141 to 145 The liquid crystal composition 13 was mixed with 0.3% by mass of bismethacrylic acid biphenyl-4,4′-diyl to obtain a liquid crystal composition 29.
  • the liquid crystal composition 29 was sandwiched between the VA cells used in Example 1, and irradiated with ultraviolet rays (3.0 J / cm 2 ) for 600 seconds while a driving voltage was applied between the electrodes, followed by polymerization treatment, Liquid crystal display devices of Examples 141 to 145 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • liquid crystal display devices of Examples 141 to 145 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.
  • Liquid crystal composition 30 was prepared by mixing 0.3% by mass of bismethacrylic acid 3-fluorobiphenyl-4,4′-diyl with liquid crystal composition 19. The liquid crystal composition 30 was sandwiched between the VA cells used in Example 1 and irradiated with ultraviolet rays (3.0 J / cm 2 ) for 600 seconds with a drive voltage applied between the electrodes, followed by a polymerization treatment. Liquid crystal display devices of Examples 146 to 150 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • liquid crystal display devices of Examples 146 to 150 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.
  • Example 151 to 165 In the same manner as in Example 1, the liquid crystal compositions shown in the following table were sandwiched, and the liquid crystal display devices of Examples 151 to 165 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • the liquid crystal display devices of Examples 151 to 165 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.
  • Example 166 to 175 In the same manner as in Example 1, the liquid crystal compositions shown in the following table were sandwiched, and the liquid crystal display devices of Examples 166 to 175 were prepared using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • liquid crystal display devices of Examples 166 to 175 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 to 15 As in Example 1, the liquid crystal display devices of Comparative Examples 1 to 15 were prepared by sandwiching the comparative liquid crystal compositions shown in the following table and using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. did. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • the liquid crystal display devices of Comparative Examples 1 to 15 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 Examples 16 to 30 As in Example 1, the liquid crystal display devices of Comparative Examples 16 to 30 were prepared by sandwiching the comparative liquid crystal compositions shown in the following table and using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. did. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • the liquid crystal display devices of Comparative Examples 16 to 30 had lower VHR and 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.
  • Comparative Examples 31 to 45 As in Example 1, the liquid crystal display devices of Comparative Examples 31 to 45 were prepared by sandwiching the comparative liquid crystal compositions shown in the following table and using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. did. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • the liquid crystal display devices of Comparative Examples 31 to 45 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 Examples 46-55 As in Example 1, the liquid crystal display devices of Comparative Examples 46 to 55 were prepared by sandwiching the comparative liquid crystal compositions shown in the following table and using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. did. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • the liquid crystal display devices of Comparative Examples 46 to 55 had a lower VHR and a 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 Examples 56 to 70 As in Example 1, the liquid crystal display devices of Comparative Examples 56 to 70 were prepared by sandwiching the comparative liquid crystal compositions shown in the following table and using the color filters 1 to 5 shown in the above table, and their VHR and ID were measured. did. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • the liquid crystal display devices of Comparative Examples 56 to 70 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 Examples 71-75 As in Example 1, the liquid crystal display devices of Comparative Examples 71 to 75 were prepared using the color filters 1 to 5 shown in the above table while holding the comparative liquid crystal compositions shown in the following table, and their VHR and ID were measured. did. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • the liquid crystal display devices of Comparative Examples 71 to 75 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 Examples 76-83 Liquid crystal compositions 1, 3, 7, 10, 15, 21, 30, and 34 were sandwiched between the VA cells used in Example 1, and the liquid crystals of Comparative Examples 76 to 83 were used by using the comparative color filter 1 shown in the above table.
  • a display device was manufactured and its VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in the table below.
  • the liquid crystal display devices of Comparative Examples 76 to 83 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.

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Abstract

La présente invention se rapporte à un dispositif d'affichage à cristaux liquides qui utilise un filtre coloré employant une composition de cristaux liquides précise, un pigment précis et un composé précis. La présente invention a trait à un afficheur à cristaux liquides qui évite une diminution du taux de maintien de tension (VHR) d'une couche de cristaux liquides et une augmentation de la densité ionique (ID), et qui résout les problèmes liés à des défauts d'affichage tels qu'une brûlure d'écran, une irrégularité d'alignement et des vides blancs. Les caractéristiques de ce dispositif d'affichage à cristaux liquides permettent d'éviter une diminution du taux de maintien de tension (VHR) d'une couche de cristaux liquides et une augmentation de la densité ionique (ID), et d'empêcher l'apparition de défauts d'affichage tels qu'une brûlure d'écran. Par conséquent, ledit dispositif d'affichage à cristaux liquides est particulièrement utile en tant que dispositif d'affichage à cristaux liquides à mode FSS, à mode PSVA ou à mode VA en ce qui concerne la commande d'une matrice active. De plus, il peut servir à des téléviseurs à cristaux liquides, à des moniteurs, à des téléphones mobiles, à des smartphones, et autres.
PCT/JP2015/072051 2014-08-06 2015-08-04 Dispositif d'affichage à cristaux liquides WO2016021582A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018003917A1 (fr) * 2016-06-29 2018-01-04 シャープ株式会社 Composition de cristaux liquides, panneau à cristaux liquides, appareil avec écran à cristaux liquides, et dispositif électronique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013037348A (ja) * 2011-07-08 2013-02-21 Sumitomo Chemical Co Ltd 着色感光性樹脂組成物
WO2014045371A1 (fr) * 2012-09-20 2014-03-27 Dic株式会社 Dispositif d'affichage à cristaux liquides
WO2014054133A1 (fr) * 2012-10-03 2014-04-10 Dic株式会社 Dispositif d'affichage à cristaux liquides
JP5561450B1 (ja) * 2013-11-29 2014-07-30 Ｄｉｃ株式会社 液晶表示装置

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09204074A (ja) * 1995-11-22 1997-08-05 Hodogaya Chem Co Ltd 静電荷像現像用トナー
JP2000019321A (ja) 1998-06-29 2000-01-21 Toray Ind Inc カラーフィルター用顔料、カラーペースト及びカラーフィルター
JP2000192040A (ja) 1998-12-25 2000-07-11 Toshiba Corp 液晶表示装置
JP5191194B2 (ja) * 2007-09-06 2013-04-24 富士フイルム株式会社 加工顔料、それを用いた顔料分散組成物、着色感光性組成物、及び、カラーフィルタ
JP5094315B2 (ja) * 2007-10-04 2012-12-12 富士フイルム株式会社 着色画素用硬化性組成物及びカラーフィルタ
JP2009109542A (ja) 2007-10-26 2009-05-21 Toppan Printing Co Ltd カラーフィルタおよびこれを備えた横電界方式の液晶表示装置
JP5273494B1 (ja) 2013-01-21 2013-08-28 Ｄｉｃ株式会社 液晶表示装置
US9441158B2 (en) 2013-05-28 2016-09-13 Dic Corporation Liquid crystal display device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013037348A (ja) * 2011-07-08 2013-02-21 Sumitomo Chemical Co Ltd 着色感光性樹脂組成物
WO2014045371A1 (fr) * 2012-09-20 2014-03-27 Dic株式会社 Dispositif d'affichage à cristaux liquides
WO2014054133A1 (fr) * 2012-10-03 2014-04-10 Dic株式会社 Dispositif d'affichage à cristaux liquides
JP5561450B1 (ja) * 2013-11-29 2014-07-30 Ｄｉｃ株式会社 液晶表示装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018003917A1 (fr) * 2016-06-29 2018-01-04 シャープ株式会社 Composition de cristaux liquides, panneau à cristaux liquides, appareil avec écran à cristaux liquides, et dispositif électronique

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