WO2015045440A1 - 液晶表示装置 - Google Patents
液晶表示装置 Download PDFInfo
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- WO2015045440A1 WO2015045440A1 PCT/JP2014/056464 JP2014056464W WO2015045440A1 WO 2015045440 A1 WO2015045440 A1 WO 2015045440A1 JP 2014056464 W JP2014056464 W JP 2014056464W WO 2015045440 A1 WO2015045440 A1 WO 2015045440A1
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- 0 *C1CCC(*c(ccc(*)c2F)c2F)CC1 Chemical compound *C1CCC(*c(ccc(*)c2F)c2F)CC1 0.000 description 2
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- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
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- 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
- C09K19/3001—Cyclohexane rings
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- 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
- C09K19/3001—Cyclohexane rings
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- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
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- 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
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133512—Light shielding layers, e.g. black matrix
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- 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
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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- C09K19/00—Liquid crystal materials
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- 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
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
- C09K2019/123—Ph-Ph-Ph
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- 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
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/3004—Cy-Cy
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- 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
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
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- 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
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/301—Cy-Cy-Ph
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- 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
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/3016—Cy-Ph-Ph
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- C09K19/00—Liquid crystal materials
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- 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
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/3027—Compounds comprising 1,4-cyclohexylene and 2,3-difluoro-1,4-phenylene
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- 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
- G02F1/133742—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers for homeotropic alignment
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 that constitutes the liquid crystal layer has been subjected to advanced management of impurities because impurities remaining in the material greatly affect the electrical characteristics of the display device.
- 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.
- an alignment film and a transparent electrode are interposed between the color filter layer and the liquid crystal layer, it has been considered that the direct influence on the liquid crystal layer is significantly less than that of the alignment film material.
- 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. .
- 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.
- 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
- burn-in may occur.
- the difficulty of dissolving the organic impurities in the liquid crystal layer is expressed by the hydrophobic parameter of the liquid crystal molecules contained in the liquid crystal layer. Since there is a correlation between the hydrophobic parameter and the —OCF 3 group at the end of the liquid crystal molecule, the 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
- the present invention prevents a decrease in voltage holding ratio (VHR) and an increase in ion density (ID) of a liquid crystal layer by using a color filter containing a specific liquid crystal composition and an organic pigment having a specific particle size distribution.
- VHR voltage holding ratio
- ID ion density
- Another object of the present invention is to provide a liquid crystal display device that solves the problem of display defects such as white spots, uneven alignment, and baking.
- a liquid crystal display device using a color filter containing an organic pigment prevents a decrease in voltage holding ratio (VHR) and an increase in ion density (ID) of the liquid crystal layer, and causes display defects such as white spots, alignment unevenness, and image sticking.
- VHR voltage holding ratio
- ID ion density
- the present invention A color filter composed of a first substrate, a second substrate, a liquid crystal composition layer sandwiched between the first substrate and the second substrate, a black matrix and at least an RGB three-color pixel portion, A pixel electrode and a common electrode;
- the liquid crystal composition layer has the general formula (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 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
- R 4 represents an alkyl group, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group or an alkenyloxy group having 3-8 carbon atoms of 1 to 8 carbon atoms of 1 to 8 carbon atoms
- Z 3 is 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 contained, and the compound represented by the general formula (II-2)
- R 5 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
- R 6 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
- B represents a fluorine-substituted group
- Z 4 is a single bond, —CH ⁇ CH—, —C ⁇ C—, —CH 2 CH 2 —, A compound represented by — (CH 2 ) 4 —, —COO—, —OCO—, —OCH 2 —, —CH 2 O—, —OCF 2 — or
- the color filter is a color filter containing an organic pigment,
- the volume fraction occupied by particles having a particle diameter of more than 1000 nm out of all particles of the organic pigment is 1% or less, and the volume fraction occupied by particles of 40 nm or more and 1000 nm or less is 25% or less.
- a liquid crystal display device which is a color filter is provided.
- the liquid crystal display device of the present invention uses a color filter containing a specific liquid crystal composition and an organic pigment having a specific particle size distribution, thereby reducing the voltage holding ratio (VHR) of the liquid crystal layer and the ion density (ID). Can be prevented, and display defects such as white spots, alignment unevenness, and burn-in can be prevented.
- 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 and a specific particle diameter 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 an organic pigment having a distribution 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 between them.
- 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 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
- R 4 represents an alkyl group, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group or an alkenyloxy group having 3-8 carbon atoms of 1 to 8 carbon atoms of 1 to 8 carbon atoms
- Z 3 is 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 contained, and the compound represented by the general formula (II-2)
- R 5 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
- R 6 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
- B represents a fluorine-substituted group
- Z 4 is a single bond, —CH ⁇ CH—, —C ⁇ C—, —CH 2 CH 2 —, A compound represented by — (CH 2 ) 4 —, —COO—, —OCO—, —OCH 2 —, —CH 2 O—, —OCF 2 — or
- the liquid crystal layer in the liquid crystal display device of the present invention contains 30 to 50% of the compound represented by the general formula (I), preferably 32 to 48%, more preferably 34 to 46%. .
- 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% or more, more preferably 70% or more, and further preferably 80% 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% or more, more preferably 70% or more, further preferably 80% or more, and most preferably 100%.
- 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.
- the content of the compound represented by the general formula (I) in which A represents a trans-1,4-cyclohexylene group is preferably 50% or more of the compound represented by the general formula (I). 70% or more is more preferable, and 80% or more is more 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 represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group 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 (Ic) and general formula (Ig) are preferable, general formula (Ia) and general formula (Ig) are more preferable, and general formula (Ia) is particularly preferable, but general formula (Ib) is also preferable when response speed is important, and general formula (Ib), general formula (Ic), and general formula (Ie) when response speed is more important.
- general formula (Ik) are preferable, general formula (Ic) and general formula (Ik) are more preferable, and dialkenyl compounds represented by general formula (Ik) are particularly preferable when the response speed is important.
- the content of the compound represented by the general formula (Ia) and the general formula (Ic) is 50% or more in the compound represented by the general formula (I), and 70% or more. Is more preferably 80% or more, and most preferably 100%. Further, the content of the compound represented by the general formula (Ia) is preferably 50% or more in the compound represented by the general formula (I), more preferably 70% or more, and 80% or more. More preferably.
- the liquid crystal layer in the liquid crystal display device of the present invention contains 5 to 30% of the compound represented by the general formula (II-1), preferably 8 to 27%, and preferably 10 to 25%. More preferred.
- 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 alkenyl having 2 to 8 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 3 carbon atoms. It is more preferable to represent an alkyl group having 3 or an alkoxy group having 2 carbon atoms, and it is particularly preferable to represent an alkoxy group having 2 carbon atoms.
- Z 3 is 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 2 — or —CF 2 O -Is preferably represented, more preferably a single bond or -CH 2 O-.
- 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 one or two compounds.
- the compound represented by the general formula (II-1) is preferably a compound represented by the following general formula (II-1a) to (II-1d).
- 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.
- general formula (II-1a) to (II-1d) are preferable for increasing the absolute value of dielectric anisotropy. And general formula (II-1a) is preferred.
- 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).
- the liquid crystal layer in the liquid crystal display device of the present invention contains 25 to 45% of the compound represented by the general formula (II-2), preferably 28 to 42%, preferably 30 to 40%. More preferred.
- R 5 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 alkenyl having 2 to 8 carbon atoms.
- R 6 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 3 carbon atoms. It is more preferable to represent an alkyl group having 3 or an alkoxy group having 2 carbon atoms, and it is particularly preferable to represent an alkoxy group having 2 carbon atoms.
- B represents a 1,4-phenylene group or trans-1,4-cyclohexylene group, which may be fluorine-substituted, and an unsubstituted 1,4-phenylene group or trans-1,4-cyclohexylene group A trans-1,4-cyclohexylene group is preferable.
- Z 4 is 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 2 — or —CF 2 O -Is preferably represented, more preferably a single bond or -CH 2 O-.
- the compound represented by the general formula (II-2) is preferably a compound represented by the following general formula (II-2a) to general formula (II-2f).
- R 5 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms
- R 6a represents an alkyl group having 1 to 5 carbon atoms. Preferred is the same embodiment as R 5 and R 6 in 2).
- R 5 is preferably the same embodiment as in general formula (II-2).
- R 6a 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 5 is preferably the same embodiment as in general formula (II-2).
- R 6a 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 formula (II-2a) to (II-2f) in order to increase the absolute value of dielectric anisotropy, general formula (II-2a), general formula (II-2b) and general formula Formula (II-2e) is preferred.
- the compound represented by the general formula (II-2) can be contained alone or in combination of two or more, wherein B represents a 1,4-phenylene group, and B represents a trans-1,4-cyclohexylene group. It is preferable to contain at least one compound each representing
- 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 preferably included).
- the compound represented by the general formula (III) is preferably contained in an amount of 3 to 35%, preferably 5 to 33%, more preferably 7 to 30%.
- 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- A 1,4-phenylene group and a 1,4-phenylene group are more preferable, and a 2,3-difluoro-1,4-phenylene group and a 1,4-phenylene group are particularly 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 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-1a) to the general formula (III-1e) from the viewpoint of increasing the negative dielectric anisotropy.
- 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-2i) 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
- 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-3a) from the viewpoint of increasing the negative dielectric anisotropy when n represents 0, and the response speed From the viewpoint of speeding up the reaction, a compound represented by the general formula (III-3b) is 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 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 compounds represented by general formula (II-1) and general formula (II-2) are both compounds having a negative dielectric anisotropy and a relatively large absolute value.
- the amount is preferably 30 to 65%, more preferably 40 to 55%, and particularly preferably 43 to 50%.
- the compound represented by the general formula (III) includes both a positive compound and a negative compound with respect to the dielectric anisotropy, but the dielectric anisotropy is negative and the absolute value thereof is 0.3.
- the total content of the compounds represented by formulas (II-1), (II-2) and (III) is preferably 35 to 70%, preferably 45 to 65%. Is more preferable, and 50 to 60% is particularly preferable.
- the total content of the compounds represented by the general formula (I), the general formula (II-1), the general formula (II-2) and the general formula (III) is 80 to 100% with respect to the entire composition. Preferably, 90 to 100% is more preferable, and 95 to 100% is particularly preferable.
- 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.
- 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.
- diacrylate derivatives are the fastest, dimethacrylate derivatives are slow, asymmetric compounds are in the middle, 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
- —COO—, —OCO— or a single bond is more preferred, and a single bond is particularly preferred.
- 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 the alignment regulating power after polymerization, and a good alignment state can be 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 containing a polymerizable monomer is useful for a liquid crystal display device, particularly useful for a liquid crystal display device for driving an active matrix, and for a liquid crystal display device for a PSA mode, PSVA mode, VA mode, IPS mode or ECB mode. Can be used.
- the liquid crystal layer containing a polymerizable monomer is a liquid crystal that provides liquid crystal alignment ability by polymerizing the polymerizable monomer contained therein by ultraviolet irradiation, and controls the amount of light transmitted using the birefringence of the liquid crystal composition.
- Used for display elements As liquid crystal display elements, 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 IPS-LCD (in-plane switching liquid crystal display element)
- 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 in the present invention refers to a filter that contains an organic pigment, absorbs a specific wavelength, and transmits light of a specific wavelength other than that.
- a base material what is necessary is just to transmit light, and what is necessary is just to select suitably according to a use.
- resin and inorganic material are mentioned, and glass is particularly preferable.
- the color filter includes a base material and an organic pigment, and the organic pigment may be dispersed in the base material or may exist only on the surface of the base material.
- An organic pigment may be dispersed and molded in the resin, or may be dispersed as a coating film on the surface of the substrate.
- a color filter in which a pigment dispersion is applied to the surface of a glass substrate can be suitably used for a light-emitting display element such as a liquid crystal display element or an organic EL display element.
- the shape of the color filter is arbitrary, and may be any shape, such as a plate, film, lens, sphere, one having a three-dimensional unevenness on the surface, or one having a fine unevenness on the surface. .
- organic pigments examples include phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyrimidine, anthanthrone, indanthrone, flavanthrone, perinone , Perylene, thioindigo, triarylmethane, isoindolinone, isoindoline, metal complex, quinophthalone, dyed lake, and the like.
- the pigment type may be selected as appropriate according to the wavelength to be transmitted.
- a red pigment may be used, and specifically, a pigment having a high transmittance at a transmission wavelength of 600 nm to 700 nm is mentioned.
- the said pigment may be only 1 type and may use 2 or more types together.
- Specific examples of pigments that can be preferably used include C.I. I. Pigment Red 81, 122, 177, 209, 242, 254, and Pigment Violet 19. Among them, C.I. I. Pigment Red 254 is particularly preferred, and its maximum transmission wavelength is between 660 nm and 700 nm.
- red color filter is further used for toning, C.I. I. Pigment Orange 38, 71, C.I. I. It is also possible to contain at least one organic pigment selected from the group consisting of Pigment Yellow 150, 215, 185, 138, and 139.
- a green pigment may be used, and examples thereof include pigments having a maximum transmission wavelength of 500 nm to 600 nm.
- the said pigment may be only 1 type and may use 2 or more types together.
- Specific examples of pigments that can be preferably used include C.I. I. Pigment Green 7, Tatsumi 36, Tatsumi 58. Among them, the same 58 is particularly preferable, and the maximum transmission wavelength is between 510 nm and 550 nm.
- the green color filter is further used for toning, C.I. I. It is also possible to contain at least one organic pigment selected from the group consisting of Pigment Yellow 150, 215, 185, and 138.
- a blue pigment may be used, and examples thereof include pigments having a maximum transmission wavelength of 400 nm to 500 nm.
- the said pigment may be only 1 type and may use 2 or more types together.
- Specific examples of pigments that can be preferably used include C.I. I. Pigment Blue 15: 3, 15: 6, C.I. I.
- Pigment Blue 1 and / or the following general formula (1) (wherein R 1 to R 6 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, or a substituent)
- R 1 to R 6 represent an alkyl group which may have a substituent
- R 1 and R 2 , R 3 and R 4 , R 5 and R 6 may be bonded to form a ring structure
- X 1 and X 2 each independently represent a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 8 carbon atoms.
- a plurality of formulas (1) are contained in one molecule, they may be the same structure or different structures.
- the triarylmethane pigments represented.
- R 1 to R 6 may be the same or different. Accordingly, the —NRR (RR represents any combination of R 1 R 2 , R 3 R 4 , and R 5 R 6 ) group may be symmetric or asymmetric.
- the maximum transmission wavelength of Pigment Blue 15: 3 is between 440 nm and 480 nm, the maximum transmission wavelength of 15: 6 is between 430 nm and 470 nm, and the maximum transmission wavelength of the triarylmethane pigment is 410 nm to 450 nm. Between.
- the blue color filter is a C.I. I. Pigment Violet 23, 37, C.I. I. It is also possible to contain at least one organic pigment selected from the group consisting of Pigment Blue 15, 15: 1, 15: 2, and 15: 4.
- the pigment dispersion may be a known pigment dispersant or solvent in addition to the organic pigment. It may be contained. A dispersion in which an organic pigment is dispersed in advance with a solvent or a pigment dispersant is prepared, and the obtained dispersion may be applied to a substrate. Examples of the application method include spin coating, roll coating, and inkjet methods. , Spray coating method, printing method and the like.
- a color filter may be used in a state where an organic pigment is applied to a substrate and dried, or 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.
- the color filter of the present invention is characterized in that the organic pigment particles have a volume fraction of 1% or less of particles larger than 1000 nm and 25% or less of 40 nm or more and 1000 nm or less.
- 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 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.
- the volume fraction of particles of 100 nm to 1000 nm is preferably 7% or less, more preferably 3% or less.
- 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 result 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 for simultaneously measuring diffuse scattering and diffraction that occurs in the ultra-small angle region of 1 °.
- 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.
- 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 device is 10 6 Brilliance (photons / sec / mm 2 / mrad 2 /0.1% bandwidth) or more, sufficient scattering intensity Can be measured, and is preferably 10 7 Brilliance or more.
- the luminance of incident X-rays is preferably 10 16 Brilliance or more, more preferably 10 18 Brilliance or more.
- a light source such as the large synchrotron radiation facility 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.
- several kinds of metal absorbing plates called attenuators are used on the incident side, and the exposure time is set to 0. 0.
- 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 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.
- M 1 is a first type particle size distribution spread parameter.
- M 2 is a second type of particle size distribution spread parameter.
- 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. . Further, 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).
- 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.
- This liquid crystal display device and backlight are used in various applications such as LCD TVs, personal computer monitors, mobile phones, smartphone displays, notebook personal computers, personal digital assistants, and digital signage.
- the backlight include a cold cathode tube type backlight, a two-wavelength peak pseudo-white backlight and a three-wavelength peak backlight using a light emitting diode or an organic EL element using an inorganic material.
- 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) d gap : gap between the first substrate and the second substrate of the cell ( ⁇ m) VHR: Voltage holding ratio at 70 ° C.
- xylene was added to adjust the non-volatile content to obtain a polymer A which was a modified polyamine having a non-volatile content of 40%.
- the resin had a weight average molecular weight of 10,000 and an amine value of 22.0 mgKOH / g.
- Powder Pigment 1 FASTOGEN Green A110 (CI Pigment Green 58, brominated chlorinated zinc phthalocyanine) manufactured by DIC Corporation was used as Powder Pigment 1.
- ⁇ Production Example 2 Production of powder pigment 2 100 parts of powder pigment 1 obtained in Production Example 1, 300 parts of heptane and 10 parts of polymer A were mixed, and 300 parts of 1.25 mm zirconia beads were added. Toyo Seiki Co., Ltd.) was stirred at room temperature for 1 hour, diluted with 200 parts of heptane, and zirconia beads were separated by filtration to obtain a pigment mixture.
- Dispersion 1 5 parts of the powder pigment 1 obtained in Production Example 1, 33.3 parts of propylene glycol monomethyl ether (PGMA), and 3 parts of Polymer A were mixed, and 65 mm 0.5 mm Sepra beads were mixed. In addition, the mixture was stirred with a paint shaker (manufactured by Toyo Seiki Co., Ltd.) for 4 hours. Sepra beads were separated from the obtained mixed solution by filtration to obtain dispersion 1.
- PGMA propylene glycol monomethyl ether
- Dispersion 3 In Production Example 5, except that 5 parts of powder pigment 2, 33.3 parts of PGMA, 3 parts of BYK6919, and 0.1 part of pyridine were further added. Dispersion 3 was obtained.
- Dispersion 5 was obtained in the same manner as in Production Example 6, except that pyridine was changed to piperidine.
- Diketopyrrolopyrrole red pigment PR254 (“Irgafore Red B-CF”; R-1 manufactured by Ciba Specialty Chemicals) was used as powder pigment 5, and powder pigment 5 5 parts, 33.3 parts of propylene glycol monomethyl ether (PGMA) and 3 parts of polymer A were added, 65 parts of 0.5 mm Sepra beads were added, and the mixture was stirred for 4 hours with a paint shaker (manufactured by Toyo Seiki Co., Ltd.). Sepra beads were separated from the obtained mixture by filtration to obtain dispersion 8.
- PGMA propylene glycol monomethyl ether
- ⁇ Production Example 15 Production of color filter 5 Cover glass (manufactured by Tokyo Glass Instrument Co., Ltd., borosilicate cover glass) was set on a spin coater (manufactured by Mikasa Co., Ltd., Opticoat MS-A100), and obtained in Production Example 7. 1.5 ml of the dispersion 4 was applied and coated at 600 rpm. The obtained coated product was dried at 90 ° C. for 3 minutes in a thermostatic device to obtain a color filter 5. The maximum transmission wavelength of the color filter 5 was 521 nm. The transmission spectrum is shown in FIG.
- Color filters 1 to 11 were attached to an Al sample holder with tape and set on a transmission sample stage.
- three particle size distributions are obtained.
- particles represented by a distribution having an average particle size of 1 to 40 nm are primary particles, and similarly 40 to 100 nm.
- Table 1 shows the distribution of the secondary particles and the distribution of 100 to 1000 nm as the tertiary particles. The total of the secondary particles and the tertiary particles is shown in Table 1 as high-order particles.
- 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. Details of the analysis example are as follows.
- the particles are set as C 32 N 8 ZnBr 16 (density 3.2) and the matrix is set as C 6 H 12 O 3 (density 1).
- Z value 10% or less when calculating only primary particles, 5% or less when setting up to secondary particles and calculating, and 0.5% or less when setting up and calculating up to tertiary particles.
- Examples 1 to 8 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 A liquid crystal composition 1 shown in Table 2 below was sandwiched between them.
- the liquid crystal composition 1 has a practical liquid crystal layer temperature range of 81 ° C. as a TV liquid crystal composition, 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 8 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 9 to 24 In the same manner as in Example 1, the liquid crystal compositions shown in Table 4 were sandwiched, and the liquid crystal display devices of Examples 9 to 24 were prepared using the color filters 1 to 6, 8, and 10 shown in Table 1, and the VHR and ID was measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 5 and 6.
- liquid crystal display devices of Examples 9 to 24 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 25 to 48 In the same manner as in Example 1, the liquid crystal composition shown in Table 7 was held, and the color filters 1 to 6, 8, and 10 shown in Table 1 were used to prepare the liquid crystal display devices of Examples 25 to 24, and their VHR and ID was measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 8-10.
- liquid crystal display devices of Examples 25 to 48 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 49 to 72 In the same manner as in Example 1, the liquid crystal composition shown in Table 11 was sandwiched, and the liquid crystal display devices of Examples 49 to 72 were prepared using the color filters 1 to 6, 8, and 10 shown in Table 1. The VHR and ID was measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 12-14.
- liquid crystal display devices of Examples 49 to 72 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.
- Example 73 to 96 As in Example 1, the liquid crystal compositions shown in Table 15 were sandwiched, and the color filters 1 to 6, 8, and 10 shown in Table 1 were used to produce the liquid crystal display devices of Examples 73 to 96, and their VHR and ID Was measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 16-18.
- liquid crystal display devices of Examples 73 to 96 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.
- Example 97 to 120 In the same manner as in Example 1, the liquid crystal composition shown in Table 19 was sandwiched, and the liquid crystal display devices of Examples 97 to 120 were prepared using the color filters 1 to 6, 8, and 10 shown in Table 1. The VHR and ID was measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 20-22.
- liquid crystal display devices of Examples 97 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 144 In the same manner as in Example 1, the liquid crystal composition shown in Table 23 was sandwiched, and the liquid crystal display devices of Examples 121 to 144 were prepared using the color filters 1 to 6, 8, and 10 shown in Table 1, and the VHR and ID was measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 24-26.
- liquid crystal display devices of Examples 121 to 144 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.
- Example 145 to 168 In the same manner as in Example 1, the liquid crystal composition shown in Table 27 was held, and the color filters 1 to 6, 8, and 10 shown in Table 1 were used to prepare liquid crystal display devices of Examples 145 to 168, and their VHR and ID Was measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 28-30.
- liquid crystal display devices of Examples 145 to 168 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 169 to 192 In the same manner as in Example 1, the liquid crystal composition shown in Table 31 was sandwiched, and the liquid crystal display devices of Examples 169 to 192 were prepared using the color filters 1 to 6, 8, and 10 shown in Table 1, and the VHR and ID was measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 32-34.
- liquid crystal display devices of Examples 169 to 192 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 193 to 216 In the same manner as in Example 1, the liquid crystal composition shown in Table 35 was sandwiched, and the liquid crystal display devices of Examples 193 to 216 were prepared using the color filters 1 to 6, 8, and 10 shown in Table 1, and their VHR and ID Was measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 36-38.
- liquid crystal display devices of Examples 193 to 216 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 217 to 224 were prepared using the color filters 1 to 6, 8, and 10 shown in Table 1, and their VHR and ID were measured.
- the burn-in evaluation of the liquid crystal display device was performed. The results are shown in Table 39.
- liquid crystal display devices of Examples 217 to 224 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 225 to 232 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 225 to 232 were prepared using the color filters 1 to 6, 8, and 10 shown in Table 1, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Table 40.
- liquid crystal display devices of Examples 225 to 232 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 233 to 240 were prepared using the color filters 1 to 6, 8, and 10 shown in Table 1, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Table 41.
- the liquid crystal display devices of Examples 233 to 240 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 24 The liquid crystal display devices of Comparative Examples 1 to 24 were produced using the color filters 1 to 6, 8, and 10 shown in Table 1 by sandwiching the comparative liquid crystal composition shown in Table 42 as in Example 1, and the VHR And ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 43 to 45.
- the liquid crystal display devices of Comparative Examples 1 to 24 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 25 to 48 The liquid crystal display devices of Comparative Examples 25 to 48 were prepared using the color filters 1 to 6, 8, and 10 shown in Table 1 by sandwiching the comparative liquid crystal composition shown in Table 46 as in Example 1, and the VHR thereof. And ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 47-49.
- the liquid crystal display devices of Comparative Examples 25 to 48 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 49-72 In the same manner as in Example 1, the comparative liquid crystal composition shown in Table 50 is sandwiched, and the liquid crystal display devices of Comparative Examples 49 to 72 are produced using the color filters 1 to 6, 8, and 10 shown in Table 1, and the VHR is obtained. And ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 51 to 53.
- the liquid crystal display devices of Comparative Examples 49 to 72 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 73-88 In the same manner as in Example 1, the comparative liquid crystal composition shown in Table 54 is sandwiched, and the liquid crystal display devices of Comparative Examples 73 to 88 are manufactured using the color filters 1 to 6, 8, and 10 shown in Table 1, and the VHR is obtained. And ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 55 to 56.
- the liquid crystal display devices of Comparative Examples 73 to 88 have 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 89-112 In the same manner as in Example 1, the comparative liquid crystal composition shown in Table 57 is sandwiched, and the liquid crystal display devices of Comparative Examples 89 to 112 are manufactured using the color filters 1 to 6, 8, and 10 shown in Table 1, and the VHR is obtained. And ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 58-60.
- the liquid crystal display devices of Comparative Examples 89 to 112 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 113 to 120 The liquid crystal display devices of Comparative Examples 113 to 120 were produced using the color filters 1 to 6, 8, and 10 shown in Table 1 by sandwiching the comparative liquid crystal composition shown in Table 61 as in Example 1, and the VHR And ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Table 62.
- the liquid crystal display devices of Comparative Examples 113 to 120 have 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.
- the liquid crystal display devices of Comparative Examples 121 to 144 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.
- Examples 241 to 264 In the same manner as in Example 1, the liquid crystal composition shown in Table 66 is sandwiched, and the liquid crystal display devices of Examples 241 to 264 are prepared using the color filters 1 to 6, 8, and 10 shown in Table 1, and the VHR and ID are obtained. Was measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 67-69.
- liquid crystal display devices of Examples 241 to 264 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 265 to 280 In the same manner as in Example 1, the liquid crystal composition shown in Table 70 was sandwiched, and the liquid crystal display devices of Examples 265 to 280 were prepared using the color filters 1 to 6, 8, and 10 shown in Table 1, and their VHR and ID Was measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 71-72.
- liquid crystal display devices of Examples 265 to 280 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.
Abstract
Description
前記カラーフィルタ層は、ブラックマトリックスと赤色着色層(R)、緑色着色層(G)、青色着色層(B)、及び必要に応じて黄色着色層(Y)から構成されるカラーフィルタにより構成される。
即ち、本発明は、
第一の基板と、第二の基板と、前記第一の基板と第二の基板間に挟持された液晶組成物層と、ブラックマトリックス及び少なくともRGB三色画素部から構成されるカラーフィルタと、画素電極と共通電極とを備え、
前記液晶組成物層が一般式(I)
前記カラーフィルタが、有機顔料を含有するカラーフィルタであって、
該有機顔料の全粒子のうち粒子径が1000nmより大きい粒子の占める体積分率が1%以下であって、40nm以上1000nm以下の粒子の占める体積分率が25%以下であることを特徴とするカラーフィルタである液晶表示装置を提供する。
2 カラーフィルタ層
2a 特定の粒子径分布を有する有機顔料を含有するカラーフィルタ層
3a 透明電極層(共通電極)
3b 画素電極層
4 配向膜
5 液晶層
5a 特定の液晶組成物を含有する液晶層
前記表示装置における2枚の基板は、周辺領域に配置されたシール材及び封止材によって貼り合わされていて、多くの場合その間には基板間距離を保持するために粒状スペーサーまたはフォトリソグラフィー法により形成された樹脂からなるスペーサー柱が配置されている。
本発明の液晶表示装置における液晶層は、一般式(I)
炭素原子数1~5のアルキル基、炭素原子数2~5のアルケニル基、炭素原子数1~5のアルコキシ基又は炭素原子数2~5のアルケニルオキシ基を表すことが好ましく、
炭素原子数2~5のアルキル基、炭素原子数2~4のアルケニル基、炭素原子数1~4のアルコキシ基又は炭素原子数2~4のアルケニルオキシ基を表すことがより好ましく、
R1がアルキル基を表すことが好ましいが、この場合炭素原子数2、3又は4のアルキル基が特に好ましい。R1が炭素原子数3のアルキル基を表す場合には、R2は炭素原子数2、4又は5のアルキル基、または炭素原子数2~3のアルケニル基である場合が好ましく、R2は炭素原子数2のアルキル基である場合がより好ましい。
Aが1,4-フェニレン基を表す場合には、
炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基、炭素原子数1~5のアルコキシ基又は炭素原子数3~5のアルケニルオキシ基を表すことが好ましく、
炭素原子数2~5のアルキル基、炭素原子数4~5のアルケニル基、炭素原子数1~4のアルコキシ基又は炭素原子数2~4のアルケニルオキシ基を表すことがより好ましく、
R1がアルキル基を表すことが好ましいが、この場合炭素原子数1、3又は5のアルキル基が特に好ましい。さらに、R2が炭素原子数1~2のアルコキシ基を表すことが好ましい。
又、Aがトランス-1,4-シクロヘキシレン基を表す一般式(I)で表される化合物の含有量が、一般式(I)で表される化合物中の50%以上で有ることが好ましく、70%以上がより好ましく、80%以上であることがさらに好ましい。
一般式(Ia)~一般式(Ik)において、一般式(Ia)、一般式(Ic)及び一般式(Ig)が好ましく、一般式(Ia)及び一般式(Ig)がより好ましく、一般式(Ia)が特に好ましいが、応答速度を重視する場合には一般式(Ib)も好ましく、より応答速度を重視する場合には、一般式(Ib)、一般式(Ic)、一般式(Ie)及び一般式(Ik)が好ましく、一般式(Ic)及び一般式(Ik)がより好ましく、一般式(Ik)で表されるジアルケニル化合物は特に応答速度を重視する場合に好ましい。
一般式(II-1a)及び一般式(II-1c)においてR3は、一般式(II-1)における同様の実施態様が好ましい。R4aは炭素原子数1~3のアルキル基が好ましく、炭素原子数1又は2のアルキル基がより好ましく、炭素原子数2のアルキル基が特に好ましい。
一般式(II-2a)、一般式(II-2b)及び一般式(II-2e)においてR5は、一般式(II-2)における同様の実施態様が好ましい。R6aは炭素原子数1~3のアルキル基が好ましく、炭素原子数1又は2のアルキル基がより好ましく、炭素原子数2のアルキル基が特に好ましい。
Dがトランス-1,4-シクロヘキシレンを表す場合、炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基を表すことが好ましく、炭素原子数2~5のアルキル基又は炭素原子数2~4のアルケニル基を表すことがより好ましく、炭素原子数3~5のアルキル基又は炭素原子数2又は3のアルケニル基を表すことがさらに好ましく、炭素原子数3のアルキル基を表すことが特に好ましく、
Dがフッ素置換されていてもよい、1,4-フェニレン基を表す場合、炭素原子数1~5のアルキル基又は炭素原子数4又は5のアルケニル基を表すことが好ましく、炭素原子数2~5のアルキル基又は炭素原子数4のアルケニル基を表すことがより好ましく、炭素原子数2~4のアルキル基を表すことがさらに好ましい。
Fがトランス-1,4-シクロヘキシレンを表す場合、炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基を表すことが好ましく、炭素原子数2~5のアルキル基又は炭素原子数2~4のアルケニル基を表すことがより好ましく、炭素原子数3~5のアルキル基又は炭素原子数2又は3のアルケニル基を表すことがさらに好ましく、炭素原子数3のアルキル基を表すことが特に好ましく、
Fがフッ素置換されていてもよい、1,4-フェニレン基を表す場合、炭素原子数1~5のアルキル基又は炭素原子数4又は5のアルケニル基を表すことが好ましく、炭素原子数2~5のアルキル基又は炭素原子数4のアルケニル基を表すことがより好ましく、炭素原子数2~4のアルキル基を表すことがさらに好ましい。
この場合においても、炭素原子数4のアルケニル基がさらに好ましい。
Z2は単結合、-OCH2-、-OCO-、-CH2O-又は-COO-を表すが、単結合、-CH2O-又は-COO-を表すことが好ましく、単結合がより好ましい。
一般式(III)で表される化合物は、nが2を表す場合、負の誘電率異方性を大きくする観点からは、一般式(III-2a)~一般式(III-2i)で表される化合物が好ましく、応答速度を速くする観点からは、一般式(III-2j)~一般式(III-2l)で表される化合物が好ましい。
一般式(III)で表される化合物は、nが0を表す場合、負の誘電率異方性を大きくする観点からは、一般式(III-3a)で表される化合物が好ましく、応答速度を速くする観点からは、一般式(III-3b)で表される化合物が好ましい。
R7は炭素原子数2~5のアルキル基が好ましく、炭素原子数3のアルキル基がより好ましい。R8は炭素原子数1~3のアルコキシ基が好ましく、炭素原子数2のアルコキシ基がより好ましい。
Zは、13000以下が好ましく、12000以下がより好ましく、11000以下が特に好ましい。
重合性モノマーとしては、一般式(V)
Sp1及びSp2はそれぞれ独立して、単結合、炭素原子数1~8のアルキレン基又は-O-(CH2)s-(式中、sは2から7の整数を表し、酸素原子は芳香環に結合するものとする。)を表し、
Z1は-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-、-CH=CH-COO-、-CH=CH-OCO-、-COO-CH=CH-、-OCO-CH=CH-、-COO-CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-CH2CH2-OCO-、-COO-CH2-、-OCO-CH2-、-CH2-COO-、-CH2-OCO-、-CY1=CY2-(式中、Y1及びY2はそれぞれ独立して、フッ素原子又は水素原子を表す。)、-C≡C-又は単結合を表し、
Cは1,4-フェニレン基、トランス-1,4-シクロヘキシレン基又は単結合を表し、式中の全ての1,4-フェニレン基は、任意の水素原子がフッ素原子により置換されていても良い。)で表されるニ官能モノマーが好ましい。
一般式(V)において、Cが単結合を表し、環構造が二つの環で形成される場合において、次の式(Va-1)から式(Va-5)を表すことが好ましく、式(Va-1)から式(Va-3)を表すことがより好ましく、式(Va-1)を表すことが特に好ましい。
これらの骨格を含む重合性化合物は重合後の配向規制力がPSA型液晶表示素子に最適であり、良好な配向状態が得られることから、表示ムラが抑制されるか、又は、全く発生しない。
重合性モノマーを添加する場合において、重合開始剤が存在しない場合でも重合は進行するが、重合を促進するために重合開始剤を含有していてもよい。重合開始剤としては、ベンゾインエーテル類、ベンゾフェノン類、アセトフェノン類、ベンジルケタール類、アシルフォスフィンオキサイド類等が挙げられる。また、保存安定性を向上させるために、安定剤を添加しても良い。使用できる安定剤としては、例えば、ヒドロキノン類、ヒドロキノンモノアルキルエーテル類、第三ブチルカテコール類、ピロガロール類、チオフェノール類、ニトロ化合物類、β-ナフチルアミン類、β-ナフトール類、ニトロソ化合物等が挙げられる。
本発明におけるカラーフィルタとは、有機顔料を含有することで、ある特定の波長を吸収することで、それ以外の特定の波長の光を透過するものをいう。
基材としては、光を透過するものであればよく、用途によって適時選択すればよい。例えば樹脂や無機材料が挙げられ、ガラスが特に好ましい。
カラーフィルタの形状は任意であり、板状、フィルム状、レンズ状、球体、一部に三次元の凹凸を有するものや、表面に微細な凹凸加工をしたものなど、どのような形状でも構わない。
本発明の有機顔料としては、フタロシアニン系、不溶性アゾ系、アゾレーキ系、アントラキノン系、キナクリドン系、ジオキサジン系、ジケトピロロピロール系、アントラピリミジン系、アンザンスロン系、インダンスロン系、フラバンスロン系、ペリノン系、ペリレン系、チオインジゴ系、トリアリールメタン系、イソインドリノン系、イソインドリン系、金属錯体系、キノフタロン系、染付レーキ系等が挙げられる。透過したい波長に合わせて、顔料種は適時選択すればよい。
本発明のカラーフィルタは、有機顔料の粒子の体積分率が、1000nmより大きい粒子が1%以下であって、40nm以上1000nm以下が25%以下であることを特徴とするものである。カラーフィルタにおいて、カラーフィルタの状態での有機顔料の状態が、もっとも白抜け、配向むら、焼き付けなどの表示不良の抑制に貢献する。カラーフィルタとなった状態での有機顔料粒子を規定することで、上記の表示不良を防止するカラーフィルタとなる。
1000nm以下の粒子の体積分率を測定するには、超小角エックス線散乱法に基づいた超小角エックス線散乱プロファイルを解析することで求めることができる。
ITotal=k(1)I(1)+k(2)I(2) ...(9)
k(1)、k(2)は、それぞれの成分の組成比を表すスケールファクターである。
ITotal=k(1)I(1)+k(2)I(2)+・・・+k(n)I(n)
...(10)
w(1):w(2):・・・:w(n)=k(1):k(2):・・・:k(n) ・・・(11)
本発明の液晶表示装置において、第一の基板と、第二の基板上の液晶組成物と接する面には液晶組成物を配向させるため、配向膜を必要とする液晶表示装置においてはカラーフィルタと液晶層間に配置するものであるが、配向膜の膜厚が厚いものでも100nm以下と薄く、カラーフィルタを構成する顔料等の色素と液晶層を構成する液晶化合物との相互作用を完全に遮断するものでは無い。
又、配向膜を用いない液晶表示装置においては、カラーフィルタを構成する顔料等の色素と液晶層を構成する液晶化合物との相互作用はより大きくなる。
本発明の液晶表示装置において、透明電極の材料としては、導電性の金属酸化物を用いることができ、金属酸化物としては酸化インジウム(In2O3)、酸化スズ(SnO2)、酸化亜鉛(ZnO)、酸化インジウムスズ(In2O3―SnO2)、酸化インジウム亜鉛(In2O3―ZnO)、ニオブ添加二酸化チタン(Ti1-xNbxO2)、フッ素ドープ酸化スズ、グラフェンナノリボン又は金属ナノワイヤー等が使用できるが、酸化亜鉛(ZnO)、酸化インジウムスズ(In2O3―SnO2)又は酸化インジウム亜鉛(In2O3―ZnO)が好ましい。これらの透明導電膜のパターニングには、フォト・エッチング法やマスクを用いる方法などを使用することができる。
Tni :ネマチック相-等方性液体相転移温度(℃)
Δn :25℃における屈折率異方性
Δε :25℃における誘電率異方性
η :20℃における粘度(mPa・s)
γ1 :25℃における回転粘度(mPa・s)
dgap:セルの第一基板と第二基板のギャップ(μm)
VHR :70℃における電圧保持率(%)
(セル厚3.5μmのセルに液晶組成物を注入し、5V印加、フレームタイム200ms、パルス幅64μsの条件で測定した時の測定電圧と初期印加電圧との比を%で表した値)
ID :70℃におけるイオン密度(pC/cm2)
(セル厚3.5μmのセルに液晶組成物を注入し、MTR-1(株式会社東陽テクニカ製)で20V印加、周波数0.05Hzの条件で測定した時のイオン密度値)
焼き付き :
液晶表示素子の焼き付き評価は、表示エリア内に所定の固定パターンを1000時間表示させた後に、全画面均一な表示を行ったときの固定パターンの残像のレベルを目視にて以下の4段階評価で行った。
◎残像無し
○残像ごく僅かに有るも許容できるレベル
△残像有り許容できないレベル
×残像有りかなり劣悪
尚、実施例において化合物の記載について以下の略号を用いる。
-n -CnH2n+1 炭素数nの直鎖状のアルキル基
n- CnH2n+1- 炭素数nの直鎖状のアルキル基
-On -OCnH2n+1 炭素数nの直鎖状のアルコキシル基
nO- CnH2n+1O- 炭素数nの直鎖状のアルコキシル基
-V -CH=CH2
V- CH2=CH-
-V1 -CH=CH-CH3
1V- CH3-CH=CH-
-2V -CH2-CH2-CH=CH3
V2- CH3=CH-CH2-CH2-
-2V1 -CH2-CH2-CH=CH-CH3
1V2- CH3-CH=CH-CH2-CH2
(環構造)
[顔料分散液の製造]
〈合成例1〉 共重合体aの合成
キシレン100部を、窒素気流中80℃に保ち、攪拌しながらメタクリル酸エチル68部、メタクリル酸2-エチルヘキシル29部、チオグリコール酸3部、および重合開始剤(「パーブチル(登録商標)O」〔有効成分ペルオキシ2-エチルヘキサン酸t-ブチル、日本油脂(株)製〕)0.2部からなる混合物を4時間かけて滴下した。滴下終了後、4時間ごとに「パーブチル(登録商標)O」0.5部を添加し、80℃で12時間攪拌した。反応終了後不揮発分調整のためキシレンを加え、不揮発分50%の共重合体aのキシレン溶液を得た。
キシレン100部を、窒素気流中80℃に保ち、攪拌しながらメタクリル酸エチル66部、メタクリル酸2-エチルヘキシル28部、チオグリコール酸6部、および重合開始剤(「パーブチル(登録商標)O」〔有効成分ペルオキシ2-エチルヘキサン酸t-ブチル、日本油脂(株)製〕)0.3部からなる混合物を4時間かけて滴下した。滴下終了後、4時間ごとに「パーブチル(登録商標)O」0.5部を添加し、80℃で12時間攪拌した。反応終了後、不揮発分調整のため適宜量のキシレンを添加し、不揮発分50%の、共重合体bのキシレン溶液を得た。
撹拌機,還流冷却器,窒素吹込み管、温度計を備えたフラスコに、キシレン54.5部、合成例2で得た共重合体aを19.0部、共重合体bを38.0部、およびポリアリルアミン20%水溶液(日東紡績(株)製「PAA-05」、数平均分子量約5,000)7.5部からなる混合物を仕込み、窒素気流下撹拌しながら140℃で撹拌し、分離装置を使用して水を溜去すると共に、キシレンを反応溶液に返流しながら8時間140℃で反応を行った。
DIC株式会社製のFASTOGEN Green A110(C.I.Pigment Green 58、臭素化塩素化亜鉛フタロシアニン)を、粉末顔料1とした。
製造例1で得た粉末顔料1を100部、ヘプタンを300部、ポリマーAを10部混合し、1.25mmジルコニアビーズを300部加えて、ペイントシェーカー(東洋精機株式会社製)で常温にて、1時間撹拌したのち、ヘプタン200部で希釈し、ジルコニアビーズを濾別し、顔料混合液を得た。
粉末顔料1を10部、粉砕した塩化ナトリウムを100部、ジエチレングリコール10部を双腕型ニーダーで100℃8時間混練した。混練後、80℃の水1000部を加え、一時間撹拌後、濾過、湯洗、乾燥、粉砕し、粉末顔料3を得た。
製造例1で得た粉末顔料1を5部、プロピレングリコールモノメチルエーテル(PGMA)を33.3部、ポリマーAを3部混合し、0.5mmセプラビーズを65部加えて、ペイントシェーカー(東洋精機株式会社製)で4時間撹拌した。得られた混合液からセプラビーズを濾別し、分散液1を得た。
製造例4において、粉末顔料1を粉末顔料2に、ポリマーAをBYK6919(ビックケミージャパン株式会社製)に変えた以外は同様にして、分散液2を得た。
製造例5において、粉末顔料2を5部、PGMAを33.3部、BYK6919を3部に対し、さらにピリジンを0.1部添加した以外は同様にして、分散液3を得た。
製造例6において、ピリジンをモルホリンに変更した以外は同様にして、分散液4を得た。
製造例6において、ピリジンをピペリジンに変更した以外は同様にして、分散液5を得た。
ε型銅フタロシアニン顔料(DIC株式会社製「ファストゲン ブルー EP-193」)を粉末顔料4とし、粉末顔料4を5部、プロピレングリコールモノメチルエーテル(PGMA)を33.3部、ポリマーAを3部混合し、0.5mmセプラビーズを65部加えて、ペイントシェーカー(東洋精機株式会社製)で4時間撹拌した。得られた混合液からセプラビーズを濾別し、分散液6を得た
ジケトピロロピロール系赤色顔料PR254(チバスペシャリティケミカルズ社製「イルガフォアレッドB-CF」;R-1)を粉末顔料5とし、粉末顔料5を5部、プロピレングリコールモノメチルエーテル(PGMA)を33.3部、ポリマーAを3部混合し、0.5mmセプラビーズを65部加えて、ペイントシェーカー(東洋精機株式会社製)で4時間撹拌した。得られた混合液からセプラビーズを濾別し、分散液8を得た。
〈製造例11〉 カラーフィルタ1の製造
カバーガラス(東京硝子器械社製、硼珪酸製カバーガラス)をスピンコーター(ミカサ(株)社製、Opticoat MS-A100)にセットし、製造例4で得た分散液1を1.5ml供し、600rpmで塗工した。得られた塗工物を恒温機中で90度3分間乾燥させ、続けて230℃3時間加熱処理してカラーフィルタ1を得た。カラーフィルタ1の極大透過波長は、523nmであった。透過スペクトルを図3に示す。
製造例11において、分散液1を分散液2に変更した以外は同様にして、カラーフィルタ2を得た。カラーフィルタ2の極大透過波長は、522nmであった。透過スペクトルを図3に示す。
製造例11において、分散液1を分散液3に変更した以外は同様にして、カラーフィルタ3を得た。カラーフィルタ3の極大透過波長は、521nmであった。透過スペクトルを図3に示す。
製造例11において、分散液1を分散液4に変更した以外は同様にして、カラーフィルタ4を得た。カラーフィルタ4の極大透過波長は、523nmであった。透過スペクトルを図4に示す。
カバーガラス(東京硝子器械社製、硼珪酸製カバーガラス)をスピンコーター(ミカサ(株)社製、Opticoat MS-A100)にセットし、製造例7で得た分散液4を1.5ml供し、600rpmで塗工した。得られた塗工物を恒温機中で90度3分間乾燥させ、カラーフィルタ5を得た。カラーフィルタ5の極大透過波長は、521nmであった。透過スペクトルを図4に示す。
製造例11において、分散液1を分散液5に変更した以外は同様にして、カラーフィルタ6を得た。
製造例15において、分散液4を分散液3に変更した以外は同様にして、カラーフィルタ7を得た。カラーフィルタ7の極大透過波長は、515nmであった。透過スペクトルを図4に示す。
製造例11において、分散液1を分散液6に変更した以外は同様にして、カラーフィルタ8を得た。カラーフィルタ8の極大透過波長は、435nmであった。
製造例6において、粉末顔料2を製造例9の粉末顔料4に変えたものを分散液7とし、製造例11において、分散液1を分散液7に変更した以外は同様にして、カラーフィルタ9を得た。カラーフィルタ9の極大透過波長は、435nmであった。
製造例11において、分散液1を分散液8に変更した以外は同様にして、カラーフィルタ10を得た。
製造例6において、粉末顔料2を製造例11の粉末顔料5に変えたものを分散液9とし、製造例11において、分散液1を分散液9に変更した以外は同様にして、カラーフィルタ11を得た。
(顕微鏡での粗大粒子の測定)
得られたカラーフィルタ1~11について、任意の5点について、Nikon社製光学顕微鏡Optiphot2で、2000倍にて観察を行ったところ、いずれにおいても1000nm以上の粗大粒子は観察されなかった。
カラーフィルタ1~11をAl製試料ホルダーにテープで貼り付け、透過用の試料台にセットした。以下の条件で超小角エックス線散乱測定を行い、解析した結果、3つの粒子径分布が得られ、このうち平均粒子径1~40nmの分布で表される粒子を1次粒子、同様に40~100nmの分布を2次粒子、および100~1000nmの分布を3次粒子と表し、表1に示した。また、上記2次粒子と3次粒子の合計を高次粒子として表1に記した。
測定装置:大型放射光施設:SPring-8の中で、フロンティアソフトマター開発産学連合が所有するビームライン:BL03XU 第2ハッチ
測定モード:超小角X線散乱(USAXS)
測定条件:波長0.1nm、カメラ長6m、ビームスポットサイズ 140μm×80μm、アテネーター なし、露光時間 30秒、2θ= 0.01~1.5°
解析ソフト:2次元データの画像化と1次元化をFit2D (European Synchrotron Radiation Facilityのホームページ[http://www.esrf.eu/computing/scientific/FIT2D/]より入手)
粒度分布の解析を(株)リガク社製ソフトウェアNANO-Solver(Ver3.6)で行った。解析例の詳細は以下の通りである。
Z値:一次粒子のみ計算時に10%以下であり、2次粒子まで設定し計算した時に5%以下であり、3次粒子まで設定し計算した時に0.5%以下であること。
電極構造を第一及び第二の基板に作成し、各々の対向側に垂直配向性の配向膜を形成したのち弱ラビング処理を行い、VAセルを作成し、第一の基板と第二の基板の間に以下の表2に示す液晶組成物1を挟持した。次に、表1に示すカラーフィルタ1~6、8、10を用いて実施例1~8の液晶表示装置を作成した(dgap=3.5μm、配向膜SE-5300)。得られた液晶表示装置のVHR及びIDを測定した。また、得られた液晶表示装置の焼き付き評価を行った。その結果を表3に示す。
実施例1~8の液晶表示装置は、高いVHR及び小さいIDを実現できた。また、焼き付き評価においても残像がないか、又はあってもごく僅かであり許容できるレベルであった。
実施例1と同様に表4に示す液晶組成物を狭持し、表1に示すカラーフィルタ1~6、8、10を用いて実施例9~24の液晶表示装置を作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表5及び6に示す。
実施例1と同様に表7に示す液晶組成物を狭持し、表1に示すカラーフィルタ1~6、8、10を用いて実施例25~24の液晶表示装置作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表8~10に示す。
実施例1と同様に表11に示す液晶組成物を狭持し、表1に示すカラーフィルタ1~6、8、10を用いて実施例49~72の液晶表示装置作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表12~14に示す。
実施例1と同様に表15に示す液晶組成物を狭持し、表1に示すカラーフィルタ1~6、8、10を用いて実施例73~96の液晶表示装置作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表16~18に示す。
実施例1と同様に表19に示す液晶組成物を狭持し、表1に示すカラーフィルタ1~6、8、10を用いて実施例97~120の液晶表示装置作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表20~22に示す。
実施例1と同様に表23に示す液晶組成物を狭持し、表1に示すカラーフィルタ1~6、8、10を用いて実施例121~144の液晶表示装置作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表24~26に示す。
実施例1と同様に表27に示す液晶組成物を狭持し、表1に示すカラーフィルタ1~6、8、10を用いて実施例145~168の液晶表示装置作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表28~30に示す。
実施例1と同様に表31に示す液晶組成物を狭持し、表1に示すカラーフィルタ1~6、8、10を用いて実施例169~192の液晶表示装置作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表32~34に示す。
実施例1と同様に表35に示す液晶組成物を狭持し、表1に示すカラーフィルタ1~6、8、10を用いて実施例193~216の液晶表示装置作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表36~38に示す。
液晶組成物1に2-メチル-アクリル酸4-{2-[4-(2-アクリロイルオキシ-エチル)-フェノキシカルボニル]-エチル}-ビフェニル-4’-イルエステル0.3質量%を混合し液晶組成物28とした。実施例1で用いたVAセルにこの液晶組成物28を挟持し、電極間に駆動電圧を印加したまま、紫外線を600秒間照射(3.0J/cm2)し、重合処理を行い、次に、表1に示すカラーフィルタ1~6、8,10を用いて実施例217~224の液晶表示装置を作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表39に示す。
液晶組成物13にビスメタクリル酸ビフェニル‐4,4’‐ジイル 0.3質量%を混合し液晶組成物29とした。実施例1で用いたVAセルにこの液晶組成物29を挟持し、電極間に駆動電圧を印加したまま、紫外線を600秒間照射(3.0J/cm2)し、重合処理を行い、次に、表1に示すカラーフィルタ1~6、8、10を用いて実施例225~232の液晶表示装置を作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表40に示す。
液晶組成物19にビスメタクリル酸 3‐フルオロビフェニル‐4,4’‐ジイル 0.3質量%を混合し液晶組成物30とした。実施例1で用いたVAセルにこの液晶組成物30を挟持し、電極間に駆動電圧を印加したまま、紫外線を600秒間照射(3.0J/cm2)し、重合処理を行い、次に、表1に示すカラーフィルタ1~6、8、10を用いて実施例233~240の液晶表示装置を作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表41に示す。
実施例1と同様に表42に示す比較液晶組成物を狭持し、表1に示すカラーフィルタ1~6、8、10を用いて比較例1~24の液晶表示装置を作製し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表43~45に示す。
実施例1と同様に表46に示す比較液晶組成物を狭持し、表1に示すカラーフィルタ1~6、8、10を用いて比較例25~48の液晶表示装置を作製し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表47~49に示す。
実施例1と同様に表50に示す比較液晶組成物を狭持し、表1に示すカラーフィルタ1~6、8、10を用いて比較例49~72の液晶表示装置を作製し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表51~53に示す。
実施例1と同様に表54に示す比較液晶組成物を狭持し、表1に示すカラーフィルタ1~6、8、10を用いて比較例73~88の液晶表示装置を作製し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表55~56に示す。
実施例1と同様に表57に示す比較液晶組成物を狭持し、表1に示すカラーフィルタ1~6、8、10を用いて比較例89~112の液晶表示装置を作製し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表58~60に示す。
実施例1と同様に表61に示す比較液晶組成物を狭持し、表1に示すカラーフィルタ1~6、8、10を用いて比較例113~120の液晶表示装置を作製し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表62に示す。
実施例1で用いたVAセルに液晶組成物1、2、8、13、14、19、20及び26をそれぞれ挟持し、表1に示すカラーフィルタ7、9、11をそれぞれ用いて比較例121~144の液晶表示装置を作製し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表63及び64に示す。
実施例1と同様に表66に示す液晶組成物を狭持し、表1に示すカラーフィルタ1~6、8、10を用いて実施例241~264の液晶表示装置作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表67~69に示す。
実施例1と同様に表70に示す液晶組成物を狭持し、表1に示すカラーフィルタ1~6、8、10を用いて実施例265~280の液晶表示装置作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表71~72に示す。
Claims (16)
- 第一の基板と、第二の基板と、前記第一の基板と第二の基板間に挟持された液晶組成物層と、ブラックマトリックス及び少なくともRGB三色画素部から構成されるカラーフィルタと、画素電極と共通電極とを備え、前記液晶組成物層が一般式(I)
前記カラーフィルタが、有機顔料を含有するカラーフィルタであって、
該有機顔料の全粒子のうち粒子径が1000nmより大きい粒子の占める体積分率が1%以下であって、40nm以上1000nm以下の粒子の占める体積分率が25%以下であることを特徴とするカラーフィルタである液晶表示装置。 - 上記カラーフィルタが、有機顔料の全粒子のうち粒子径が40nm以上1000nm以下の粒子の占める体積分率が15%以下である、請求項1に記載の液晶表示装置。
- 上記カラーフィルタが、有機顔料の全粒子のうち粒子径が100nm以上1000nm以下の粒子の占める体積分率が7%以下である、請求項1または2に記載の液晶表示装置。
- 上記有機顔料の極大透過波長が600nm以上700nm以下である、請求項1~3のいずれか一項に記載の液晶表示装置。
- 上記有機顔料の極大透過波長が500nm以上600nm以下である、請求項1~3のいずれか一項に記載の液晶表示装置。
- 上記有機顔料の極大透過波長が400nm以上500nm以下である、請求項1~3のいずれか一項に記載の液晶表示装置。
- 上記有機顔料が、ガラス基板上で形成された塗膜に分散されたものである、請求項1~6のいずれか一項に記載の液晶表示装置。
- 前記液晶組成物層に、更に一般式(III)
- 一般式(I)において、Aがトランス-1,4-シクロヘキシレン基を表す化合物、及びAが1,4-フェニレン基を表す化合物をそれぞれ少なくとも1種以上含有する請求項1~8のいずれか一項に記載の液晶表示装置。
- 一般式(II-2)において、Bが1,4-フェニレン基を表す化合物、及びBがトランス-1,4-シクロヘキシレン基を表す化合物をそれぞれ少なくとも1種以上含有する請求項1~9のいずれか一項に記載の液晶表示装置。
- 一般式(II-1)、一般式(II-2)及び一般式(III)で表される化合物を35~70%含有する請求項1~10のいずれか一項に記載の液晶表示装置。
- 前記液晶組成物層を構成する液晶組成物の、ネマチック液晶相上限温度が60~120℃であり、ネマチック液晶相下限温度が‐20℃以下であり、ネマチック液晶相上限温度と下限温度の差が100~150である請求項1~12の何れか一項に記載の液晶表示装置。
- 前記液晶組成物層を構成する液晶組成物の比抵抗が1012(Ω・m)以上である請求項1~13の何れか一項に記載の液晶表示装置。
- 前記液晶組成物層が一般式(V)
- 一般式(V)において、Cが単結合を表しZ1が単結合を表す請求項15記載の液晶表示装置。
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