WO2017026479A1 - 液晶表示素子 - Google Patents
液晶表示素子 Download PDFInfo
- Publication number
- WO2017026479A1 WO2017026479A1 PCT/JP2016/073423 JP2016073423W WO2017026479A1 WO 2017026479 A1 WO2017026479 A1 WO 2017026479A1 JP 2016073423 W JP2016073423 W JP 2016073423W WO 2017026479 A1 WO2017026479 A1 WO 2017026479A1
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- Prior art keywords
- liquid crystal
- group
- carbon atoms
- general formula
- crystal display
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- 0 CC(*)C(NC)=O Chemical compound CC(*)C(NC)=O 0.000 description 19
- GSMQGKBIUJXJPK-UHFFFAOYSA-N CC(C(ONC)=O)=C Chemical compound CC(C(ONC)=O)=C GSMQGKBIUJXJPK-UHFFFAOYSA-N 0.000 description 1
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- KKTHNHDEZARQMB-UHFFFAOYSA-N CC(C)(C)c(cc1)cc(F)c1F Chemical compound CC(C)(C)c(cc1)cc(F)c1F KKTHNHDEZARQMB-UHFFFAOYSA-N 0.000 description 1
- FWRAFJPYLSKDHJ-UHFFFAOYSA-N CC(CC1)CCC1C(CC1)CCC1C(C)(C)C Chemical compound CC(CC1)CCC1C(CC1)CCC1C(C)(C)C FWRAFJPYLSKDHJ-UHFFFAOYSA-N 0.000 description 1
- PGXNQWRWIFMVDP-UHFFFAOYSA-N CC(CC1)CCC1C(CC1)CCC1c(cc1)cc(F)c1F Chemical compound CC(CC1)CCC1C(CC1)CCC1c(cc1)cc(F)c1F PGXNQWRWIFMVDP-UHFFFAOYSA-N 0.000 description 1
- RFAFVAPNXFBQJX-UHFFFAOYSA-N CC(CC1)CCC1C1COC(CCC2COC(C)OC2)CC1 Chemical compound CC(CC1)CCC1C1COC(CCC2COC(C)OC2)CC1 RFAFVAPNXFBQJX-UHFFFAOYSA-N 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N CC1CCCCC1 Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- ZTLZJZSCNZWXQD-UHFFFAOYSA-N CC1COC(CCC2COC(C)CC2)OC1 Chemical compound CC1COC(CCC2COC(C)CC2)OC1 ZTLZJZSCNZWXQD-UHFFFAOYSA-N 0.000 description 1
- CYISMTMRBPPERU-UHFFFAOYSA-N CCC1CCC(C)CC1 Chemical compound CCC1CCC(C)CC1 CYISMTMRBPPERU-UHFFFAOYSA-N 0.000 description 1
- SPBBSQHISUDMFA-UHFFFAOYSA-N Cc(ccc(-c(ccc(C)c1F)c1F)c1)c1F Chemical compound Cc(ccc(-c(ccc(C)c1F)c1F)c1)c1F SPBBSQHISUDMFA-UHFFFAOYSA-N 0.000 description 1
- WJAVYWPXOXAOBS-UHFFFAOYSA-N Cc1cc(F)c(C)cc1 Chemical compound Cc1cc(F)c(C)cc1 WJAVYWPXOXAOBS-UHFFFAOYSA-N 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Cc1ccc(C)cc1 Chemical compound Cc1ccc(C)cc1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- XWKFPIODWVPXLX-UHFFFAOYSA-N Cc1cnc(C)cc1 Chemical compound Cc1cnc(C)cc1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 1
- RHOOLJLEYYXKTK-UHFFFAOYSA-N Cc1cnc(C)nc1 Chemical compound Cc1cnc(C)nc1 RHOOLJLEYYXKTK-UHFFFAOYSA-N 0.000 description 1
- SPLACXJTZMJGQJ-UHFFFAOYSA-N Fc(ccc(C(CC1)CCC1C(CC1)CCC1C1CC1)c1)c1F Chemical compound Fc(ccc(C(CC1)CCC1C(CC1)CCC1C1CC1)c1)c1F SPLACXJTZMJGQJ-UHFFFAOYSA-N 0.000 description 1
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- 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
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- 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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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3028—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon single bonds
- C09K2019/3037—Cy-Cy-C2H4-Ph
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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
- G02F1/133365—Cells in which the active layer comprises a liquid crystalline polymer
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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
- G02F1/133707—Structures for producing distorted electric fields, e.g. bumps, protrusions, recesses, slits in pixel electrodes
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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
- G02F1/1343—Electrodes
- G02F1/134309—Electrodes characterised by their geometrical arrangement
- G02F1/134381—Hybrid switching mode, i.e. for applying an electric field with components parallel and orthogonal to the substrates
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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
- G02F2203/00—Function characteristic
- G02F2203/30—Gray scale
Definitions
- the present invention relates to a liquid crystal display element.
- the field sequential full-color display method that does not require a color filter is characterized by the use of a backlight that is lit in order of “red ⁇ green ⁇ blue”.
- the frame time In a normal CRT or liquid crystal display, the frame time is 16.7 ms, but in the field sequential full color display system, the frame time is 5.6 ms, and high-speed response is required.
- ⁇ d is the fall response time of the liquid crystal
- ⁇ r is the rise response time of the liquid crystal.
- the sum of ⁇ d and ⁇ r is less than 1.5 ms.
- nematic liquid crystal in the market is generally used in flat panel displays such as televisions, monitors, mobile phones, smartphones, and tablet terminals.
- nematic liquid crystals have a response speed as low as about several tens of milliseconds to several milliseconds, and hence improvement is desired. Since the response speed is greatly influenced by the rotational viscosity ⁇ 1 of the liquid crystal and the elastic constant, improvement has been studied by developing new compounds and optimizing the composition, but the progress of the improvement is slow.
- a ferroelectric liquid crystal (FLC) using a smectic liquid crystal can respond at a high speed of several hundred microseconds.
- the Polymer Stabilized V shaped-FLC (PSV-FLC) element which is a mixture of FLC and monomer, forms a fine polymer network in a ferroelectric liquid crystal, and is a high-speed response characteristic of FLC.
- PSV-FLC Polymer Stabilized V shaped-FLC
- nematic liquid crystal and polymer in a composite material of nematic liquid crystal and polymer, a high-speed response of several tens of microseconds is obtained when 70% by mass or more of a polymerizable compound is added to the nematic liquid crystal medium, but the driving voltage exceeds about 80V. Since it is not suitable for practical use and the effective birefringence is one digit or more lower than the liquid crystal birefringence used, the transmittance of the element is lowered. On the other hand, one or more polymerizable compounds of 0.3% by mass or more and less than 1% by mass are added to the liquid crystal medium and polymerized on the glass substrate interface by UV photopolymerization with or without application of voltage.
- a PS (polymer-stable) or PSA (polymer-stained alignment) display has been proposed in which a fine protrusion structure obtained by crosslinking is formed to mainly induce pretilt.
- these devices also have room for improvement in terms of high-speed response.
- the liquid crystal composition has a low viscosity, a high dielectric constant, a low elastic constant, a pretilt angle, or an improved drive method such as an overdrive method.
- Various methods have been put into practical use, but regarding the falling rate, no effective method has been found other than lowering the viscosity of the liquid crystal composition, and improvement has been desired.
- JP 2002-31821 A Special table 2013-536271 gazette Special table 2013-538249 gazette Special table 2012-527495 gazette Special table 2012-513482 gazette JP 2012-219270 A Japanese Patent Laying-Open No. 2015-099344
- the problem to be solved by the present invention is that it improves the fall time of the liquid crystal and has excellent high-speed response, and does not deteriorate the voltage holding ratio (VHR), and is highly sensitive even at relatively long UV irradiation wavelengths. It is to provide a liquid crystal display element that can form a polymer network and is excellent in production efficiency.
- the present inventor has prepared a polymer or copolymer that is a cured product of a polymerizable composition containing a polymerizable compound and a photopolymerization initiator having a maximum peak of an absorption wavelength in a specific wavelength range in the liquid crystal composition.
- the content of the polymerizable composition in the total weight of the polymerizable composition and the liquid crystal composition is found to be 1% by mass or more and less than 40% by mass, and the present invention can be solved. It came to be completed.
- liquid crystal composition containing one or more liquid crystal compounds sandwiched between two transparent substrates having electrodes on at least one side, one or more polymerizable compounds and an absorption wavelength
- a polymer or copolymer that is a cured product of a polymerizable composition containing a photopolymerization initiator having a maximum peak at 310 to 380 nm, and the polymer composition and the liquid crystal composition in the total weight The liquid crystal display element whose content of polymeric composition is 1 mass% or more and less than 40 mass%.
- the liquid crystal display device wherein the polymer or copolymer in the liquid crystal composition forms a polymer network and has an alignment layer for aligning the liquid crystal composition on a transparent substrate.
- Zp1 represents a fluorine atom, a cyano group, a hydrogen atom, a hydrogen atom in which a hydrogen atom may be substituted with a halogen atom, or a hydrogen atom in which a hydrogen atom is substituted.
- An alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 1 to 15 carbon atoms in which a hydrogen atom may be substituted with a halogen atom, and 1 to 15 carbon atoms in which a hydrogen atom may be substituted with a halogen atom Represents an alkenyloxy group of -Spp2-Rp2, Rp1 and Rp2 are each independently the following formulas (RI) to (R-IX):
- R2 to R6 are independently of each other a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 halogenated alkyl groups
- W is a single bond, —O— or a methylene group
- T is a single bond or —COO—
- p, t and q are each independently 0, 1 or 2 Spp1 and Spp2 each represent a spacer group
- Spp1 and Spp2 each independently represent a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH2) s— (wherein s is an integer of 1 to 11).
- Mp3 represents the following formulas (i-13) to (ix-13):
- mp2 to mp4 each independently represents 0, 1, 2 or 3
- mp1 and mp5 each independently represent 1, 2 or 3, but when there are a plurality of Zp1, they are the same.
- mp1 and mp5 each independently represent 1, 2 or 3, but when there are a plurality of Zp1, they are the same.
- Rp1 when there are a plurality of Rp1, they may be the same or different, and when there are a plurality of Rp2, they may be the same or different. They may be the same or different, and when there are multiple Spp2, they may be the same or different, and when there are multiple Lp1 May be the same or different, and when a plurality of Mp2 are present, they may be the same or different.
- LC liquid crystal display device according to any one of [1] to [7], wherein the liquid crystal composition contains a liquid crystal compound represented by the following general formula (LC).
- RLC represents an alkyl group having 1 to 15 carbon atoms.
- One or two or more CH 2 groups in the alkyl group may be —O —, —CH ⁇ CH—, —CO—, —OCO—, —COO— or —C ⁇ C— may be substituted, and one or more hydrogen atoms in the alkyl group are optionally halogen atoms.
- ALC1 and ALC2 each independently represent a group selected from the group consisting of the following group (a), group (b) and group (c).
- trans-1,4-cyclohexylene group one CH2 group present in this group or two or more CH2 groups not adjacent to each other may be substituted with an oxygen atom or a sulfur atom
- B 1,4-phenylene group (one CH group present in this group or two or more non-adjacent CH groups may be substituted with a nitrogen atom)
- C 1,4-bicyclo (2.2.2) octylene group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2 , 6-Diyl group or Chroman-2,6-diyl group.
- One or more hydrogen atoms contained in the group (a), group (b) or group (c) may be substituted with a fluorine atom, a chlorine atom, —CF 3 or —OCF 3, respectively.
- ZLC is a single bond, —CH ⁇ CH—, —CF ⁇ CF—, —C ⁇ C—, —CH 2 CH 2 —, — (CH 2) 4 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O—, —COO— or —OCO— is represented.
- YLC represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, and an alkyl group having 1 to 15 carbon atoms.
- One or more CH2 groups in the alkyl group are —O—, —CH ⁇ CH—, —CO—, —OCO—, —COO—, —C ⁇ so that the oxygen atom is not directly adjacent.
- C—, —CF 2 O—, —OCF 2 — may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom.
- a represents an integer of 1 to 4.
- a represents 2, 3 or 4, and when there are a plurality of ALC1s in the general formula (LC), the plurality of ALC1s may be the same or different, and when there are a plurality of ZLCs, The ZLC to be performed may be the same or different.
- the liquid crystal display element formed by superposing
- a polymer network can be formed with high sensitivity even at a relatively long UV irradiation wavelength, it can be efficiently produced without deteriorating VHR, and the fall time of the liquid crystal can be improved. Therefore, a liquid crystal display element excellent in high-speed response can be provided.
- the liquid crystal composition used in the present invention preferably contains a liquid crystal compound represented by the general formula (LC).
- R LC represents an alkyl group having 1 to 15 carbon atoms.
- One or more CH 2 groups in the alkyl group are —O—, —CH ⁇ CH—, —CO—, —OCO—, —COO— or —C, so that the oxygen atom is not directly adjacent.
- ⁇ C— may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom.
- Alkyl group R LC may be respectively branched chain groups, may be straight chain groups, but is preferably a linear group.
- a LC1 and A LC2 each independently represent a group selected from the group consisting of the following group (a), group (b) and group (c).
- C 1,4-bicyclo (2.2.2) octylene group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2 , 6-Diyl group or Chroman-2,6-diyl group.
- One or two or more hydrogen atoms contained in the group (a), the group (b) or the group (c) may be substituted with a fluorine atom, a chlorine atom, —CF 3 or —OCF 3 , respectively. Good.
- Z LC is a single bond, —CH ⁇ CH—, —CF ⁇ CF—, —C ⁇ C—, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —. , -CH 2 O -, - OCF 2 -, - CF 2 O -, - COO- or an -OCO-.
- Y LC represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 15 carbon atoms.
- One or more CH 2 groups in the alkyl group may be —O—, —CH ⁇ CH—, —CO—, —OCO—, —COO—, —C, so that the oxygen atom is not directly adjacent.
- ⁇ C—, —CF 2 O—, —OCF 2 — may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom.
- a represents an integer of 1 to 4.
- a represents 2, 3 or 4
- the plurality of ALC1s may be the same or different
- there are a plurality of ZLCs A plurality of Z LCs may be the same or different.
- the compound represented by the general formula (LC) is preferably one or more compounds selected from the group of compounds represented by the following general formula (LC1) and general formula (LC2).
- R LC11 and R LC21 each independently represent an alkyl group having 1 to 15 carbon atoms, and one or more CH 2 groups in the alkyl group are One of the alkyl groups may be substituted with —O—, —CH ⁇ CH—, —CO—, —OCO—, —COO— or —C ⁇ C— so that the oxygen atom is not directly adjacent. Alternatively, two or more hydrogen atoms may be optionally substituted with a halogen atom.
- R LC11 and R LC21 are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or the number of carbon atoms.
- An alkenyl group having 2 to 7 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms are more preferable, and it is further linear.
- the alkenyl group preferably represents the following structure.
- a LC11 and A LC21 each independently represent any one of the following structures.
- one or more CH 2 groups in the cyclohexylene group may be substituted with an oxygen atom
- one or more CH groups in the 1,4-phenylene group are nitrogen atoms.
- one or more hydrogen atoms in the structure may be substituted with a fluorine atom, a chlorine atom, —CF 3, or —OCF 3 .
- ALC11 and ALC21 each independently preferably have one of the following structures.
- X LC11, X LC12, X LC21 ⁇ X LC23 are each independently a hydrogen atom, a chlorine atom, a fluorine atom, a -CF 3 or -OCF 3
- Y LC11 and Y LC21 each independently represents a hydrogen atom, a chlorine atom, a fluorine atom, a cyano group, —CF 3 , —OCH 2 F, —OCHF 2 or —OCF 3 .
- Y LC11 and Y LC21 are each independently preferably a fluorine atom, a cyano group, —CF 3 or —OCF 3 , and a fluorine atom or —OCF 3 is More preferred is a fluorine atom.
- Z LC11 and Z LC21 are each independently a single bond, —CH ⁇ CH—, —CF ⁇ CF— , —C ⁇ C— , —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O—, —COO— or —OCO— is represented.
- Z LC11 and Z LC21 are each independently a single bond, —CH 2 CH 2 —, —COO— , —OCO— , —OCH 2 —, —CH 2 O—, —OCF 2 — or —CF 2 O— is preferred, and a single bond, —CH 2 CH 2 —, —OCH 2 —, —OCF 2 — or —CF 2 O— is more preferred, and a single bond -OCH 2 -or -CF 2 O- is more preferable.
- m LC11 and m LC21 each independently represents an integer of 1 to 4.
- mLC11 and mLC21 are preferably independently 1, 2 or 3, respectively, and when importance is attached to storage stability at low temperature and response speed. 1 or 2 is more preferable, and 2 or 3 is more preferable when improving the upper limit of the nematic phase upper limit temperature.
- a LC11 , A LC21 , Z LC11 and Z LC21 are present in the general formula (LC1) or (LC2), they may be the same or different.
- the compound represented by the general formula (LC1) is one or more compounds selected from the group consisting of compounds represented by the following general formulas (LC1-a) to (LC1-c) Is preferred.
- R LC11 each independently represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, An alkenyl group having 2 to 7 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms are more preferable.
- a hydrogen atom or a fluorine atom X LC11 and X LC12 each independently, Y LC11 each independently a fluorine atom, -CF 3 or -OCF 3 are preferred.
- a LC1a1 , ALC1a2 and ALC1b1 are trans-1,4-cyclohexylene group, tetrahydropyran-2,5-diyl group, 1,3-dioxane. Represents a -2,5-diyl group.
- X LC1b1 , X LC1b2 and X LC1c1 to X LC1c4 each independently represent a hydrogen atom, a chlorine atom, a fluorine atom, —CF 3 or —OCF 3 .
- X LC1b1 , X LC1b2 and X LC1c1 to X LC1c4 are each independently preferably a hydrogen atom or a fluorine atom.
- the general formula (LC1) is also preferably one or more compounds selected from the group consisting of compounds represented by the following general formula (LC1-d) to general formula (LC1-p).
- R LC11 is in formula each independently (LC1), Y LC11, X LC11 and X LC12 Represents the same meaning.
- R LC11 is independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or the number of carbon atoms.
- alkenyl group having 2 to 7 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms are more preferable.
- X LC11 and X LC12 is preferably a hydrogen atom or a fluorine atom independently.
- Y LC11 is preferably independently a fluorine atom, —CF 3 or —OCF 3 .
- a LC1d1 , A LC1f1 , A LC1g1 , A LC1j1 , A LC1k1 , A LC1k2 , A LC1m1 to A LC1m3 are each independently a 1,4-phenylene group Represents a trans-1,4-cyclohexylene group, a tetrahydropyran-2,5-diyl group, or a 1,3-dioxane-2,5-diyl group.
- X LC1d1 to X LC1m2 are preferably each independently a hydrogen atom or a fluorine atom.
- Z LC1d1 , Z LC1e1 , Z LC1j1 , Z LC1k1 and Z LC1m1 are each independently a single bond, —CH ⁇ CH—, —CF ⁇ CF— , — C ⁇ C—, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O—, —COO— or —OCO— To express.
- Z LC1d1 to Z LC1m1 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —CF 2 O— or —OCH 2 — is preferred.
- R LC11 independently represents an alkyl group having 1 to 7 carbon atoms.
- the general formula (LC2) is preferably one or more compounds selected from the group consisting of compounds represented by the following general formula (LC2-a) to general formula (LC2-g).
- R LC21 is independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or the number of carbon atoms.
- X LC21 to X LC23 are each independently preferably a hydrogen atom or a fluorine atom, and Y LC21 is preferably independently a fluorine atom, —CF 3 or —OCF 3 .
- X LC2d1 to X LC2d4 , X LC2e1 to X LC2e4 , X LC2f1 to X LC2f4 and X LC2g1 to X LC2g4 are each independently hydrogen atom, chlorine atom, fluorine Represents an atom, —CF 3 or —OCF 3 ;
- X LC2d1 to X LC2g4 are each independently preferably a hydrogen atom or a fluorine atom.
- Z LC2a1 , Z LC2b1 , Z LC2c1 , Z LC2d1 , Z LC2e1 , Z LC2f1 and Z LC2g1 are each independently a single bond, —CH ⁇ CH—, — CF ⁇ CF—, —C ⁇ C—, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O—, —COO -Or -OCO- is represented.
- Z LC2a1 to Z LC2g4 are preferably each independently —CF 2 O— or —OCH 2 —.
- the compound represented by the general formula (LC) is preferably one or more compounds selected from the group of compounds represented by the following general formula (LC3) to general formula (LC5).
- R LC31, R LC32, R LC41 , R LC42, R LC51 and R LC52 is 1 to 15 carbon atoms independently, one in the alkyl group or two or more —CH 2 — may be substituted with —O—, —CH ⁇ CH—, —CO—, —OCO—, —COO— or —C ⁇ C— so that the oxygen atom is not directly adjacent.
- one or more hydrogen atoms in the group may be optionally substituted by a halogen atom, a LC31, a LC32, a LC41, a LC42, a LC51 and a LC52 each independently any of the following Structure
- one or more —CH 2 — in the cyclohexylene group may be substituted with an oxygen atom
- one or more —CH— in the 1,4-phenylene group is Any one of which may be substituted with a nitrogen atom
- one or more hydrogen atoms in the structure may be substituted with a fluorine atom, a chlorine atom, —CF 3 or —OCF 3 ).
- Z LC31, Z LC32, Z LC41, Z LC42, Z LC51 and Z LC51 each independently represent a single bond
- -CH CH -, - C ⁇ C -, - CH 2 CH 2 -, - ( CH 2 ) 4 —, —COO—, —OCH 2 —, —CH 2 O—, —OCF 2 — or —CF 2 O—
- Z 5 represents —CH 2 — or an oxygen atom
- X LC41 represents Represents a hydrogen atom or a fluorine atom
- m LC31 , m L C32, m LC41, m LC42, m LC51 and m LC52 each independently represent 0 ⁇ 3, m LC31 + m LC32, m LC41 + m LC42 and m LC51 + m LC52 is 1, 2 or 3,
- a LC31 ⁇ When a plurality of A LC52 and Z
- R LC31 to R LC52 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms. Most preferably,
- a LC31 to A LC52 each independently preferably has the following structure:
- Z LC31 to Z LC51 each independently has a single bond, —CH 2 O—, —COO—, —OCO— , —CH 2 CH 2 —, —CF 2 O—, —OCF 2 — or —OCH 2 —. preferable.
- Compounds represented by general formula (LC3), general formula (LC4), and general formula (LC5) include general formula (LC3-1), general formula (LC4-1), and general formula (LC5-1).
- R 31 to R 33 are alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, or alkenyloxy groups having 2 to 8 carbon atoms.
- R 41 to R 43 represent 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.
- Z 31 to Z 33 are 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—,
- X 41 represents a hydrogen atom or a fluorine atom
- Z 34 represents —CH 2 — or an oxygen atom. It is preferable to contain at least one compound selected from the group .
- R 31 to R 33 are alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, and 1 to 8 carbon atoms. Represents an alkoxy group or an alkenyloxy group having 2 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and an alkyl group having 2 to 5 carbon atoms.
- R 41 to R 43 represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, It preferably represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms.
- it represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, more preferably represents an alkyl group having 3 carbon atoms or an alkoxy group having 2 carbon atoms, and has 2 carbon atoms. It is particularly preferred to represent an alkoxy group.
- Z 31 to Z 33 are 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 — It preferably represents CF 2 O—, and more preferably represents a single bond or —CH 2 O—.
- the liquid crystal composition contains 5% by mass to 50% by mass of a compound selected from the group of compounds represented by general formula (LC3-1), general formula (LC4-1), and general formula (LC5-1). It is preferably 5 to 40% by mass, more preferably 5 to 30% by mass, more preferably 8 to 27% by mass, and more preferably 10 to 25% by mass. % Content is more preferable.
- the compound represented by the general formula (LC3-1) is preferably a compound represented by the following general formula (LC3-11) to general formula (LC3-15).
- the compound represented by the general formula (LC4-1) is preferably a compound represented by the following general formula (LC4-11) to general formula (LC4-14).
- the compound represented by the general formula (LC5-1) is preferably a compound represented by the following general formula (LC5-11) to general formula (LC5-14).
- R 33 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms
- R 43a represents an alkyl group having 1 to 5 carbon atoms
- Z 34 represents —CH 2 -Or represents an oxygen atom.
- R 31 to R 33 are preferably the same embodiments as in formulas (LC3-1) to (LC5-1).
- R 41a to R 41c are 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 31 to R 33 are preferably the same embodiments as in formulas (LC3-1) to (LC5-1).
- R 41a to R 41c are preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 3 carbon atoms, and particularly preferably an alkyl group having 3 carbon atoms.
- general formulas (LC3-11) to (LC5-14) in order to increase the absolute value of dielectric anisotropy, general formula (LC3-11), general formula (LC4-11), Formula (LC5-11), general formula (LC3-13), general formula (LC4-13) and general formula (LC5-13) are preferred, and general formula (LC3-11), general formula (LC4-11), general formula Formula (LC5-11) is more preferred.
- the liquid crystal layer in the liquid crystal display element of the present invention preferably contains one or more compounds represented by the general formulas (LC3-11) to (LC5-14), and contains one or two compounds. It is more preferable to include one or two compounds represented by the general formula (LC3-1).
- R 51 to R 53 are 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 61 to R 63 represent 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.
- B 1 to B 3 each represents a 1,4-phenylene group or trans-1,4-cyclohexylene group which may be fluorine-substituted
- Z 41 to Z 43 each represents 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— the stands
- X 42 represents a hydrogen atom or a fluorine atom
- Z 4 It is -CH 2 - represents an or an oxygen atom). It is preferable to contain at least one compound selected from the group of compounds represented by:
- R 51 to R 53 are each an alkyl group having 1 to 8 carbon atoms, and an alkenyl having 2 to 8 carbon atoms.
- Group, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. More preferably, it represents an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, and more preferably represents an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 carbon atoms. And particularly preferably an alkyl group having 3 carbon atoms.
- R 61 to R 63 represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, It preferably represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms.
- it represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, more preferably represents an alkyl group having 3 carbon atoms or an alkoxy group having 2 carbon atoms, and has 2 carbon atoms. It is particularly preferred to represent an alkoxy group.
- B 31 to B 33 each represents a 1,4-phenylene group or trans-1,4-cyclohexylene group, which may be substituted with fluorine, but is an unsubstituted 1,4-phenylene group or trans-1,4- A cyclohexylene group is preferred, and a trans-1,4-cyclohexylene group is more preferred.
- Z 41 to Z 43 are 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 — It preferably represents CF 2 O—, and more preferably represents a single bond or —CH 2 O—.
- the compound represented by the general formula (LC3-2), the general formula (LC3-3), the general formula (LC4-2), and the general formula (LC5-2) is contained in an amount of 10 to 60% by mass in the liquid crystal composition. However, it is preferable to contain 20 to 50% by mass, more preferably 25 to 45% by mass, more preferably 28 to 42% by mass, and more preferably 30 to 40% by mass. Further preferred.
- the compound represented by the general formula (LC3-2) is preferably a compound represented by the following general formula (LC3-21) to general formula (LC3-29).
- the compounds represented by the following general formula (LC3-31) to general formula (LC3-33) are also preferable.
- R 51 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms
- R 61a represents an alkyl group having 1 to 5 carbon atoms.
- the compound represented by the general formula (LC4-2) is preferably a compound represented by the following general formula (LC4-21) to general formula (LC4-26).
- the compound represented by the general formula (LC5-2) is preferably a compound represented by the following general formula (LC5-21) to general formula (LC5-26).
- R 53 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms
- R 63a represents an alkyl group having 1 to 5 carbon atoms
- W 2 represents —CH 2 -Represents an oxygen atom
- R 61a to R 63a are 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 51 to R 53 represent general formula (LC3-2), general formula (LC4-2), and general formula (LC5- Similar embodiments in 2) are preferred.
- R 61a to R 63a are 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 (LC3-21), general formula (Lc3-22) and general formula Formula (LC3-25) in order to increase the absolute value of dielectric anisotropy, general formula (LC3-21), general formula (Lc3-22) and general formula Formula (LC3-25), Formula (LC4-21), Formula (LC4-22) and Formula (LC4-25), Formula (LC5-21), Formula (LC5-22) and Formula (LC LC5-25) is preferred.
- the compounds represented by the general formula (LC3-2), the general formula (Lc4-2) and the general formula (LC5-2) can be contained in one kind or two or more kinds, but B 1 to B 3 are 1, It is preferable to contain at least one compound each representing a 4-phenylene group and a compound in which B 1 to B 3 represent a trans-1,4-cyclohexylene group.
- R LC31 , R LC32 , A LC31 and Z LC31 each independently represent the same meaning as R LC31 , R LC32 , A LC31 and Z LC31 in the general formula (LC3)
- X LC3b1 to X LC3b6 are Represents a hydrogen atom or a fluorine atom, and at least one of X LC3b1 and X LC3b2 or X LC3b3 and X LC3b4 represents a fluorine atom, m LC3a1 is 1, 2 or 3, and m LC3b1 is 0 or 1 and when there are a plurality of A LC31 and Z LC31 , they may be the same or different.) Or one or more compounds selected from the group of compounds represented by Is preferred.
- R LC31 and R LC32 each independently represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms. Is preferably represented.
- a LC31 preferably represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group, a tetrahydropyran-2,5-diyl group, or a 1,3-dioxane-2,5-diyl group.
- 4-phenylene group and trans-1,4-cyclohexylene group are more preferable.
- Z LC31 is a single bond, -CH 2 O -, - COO -, - OCO -, - CH 2 CH 2 - is preferred to represent, and more preferably a single bond.
- the general formula (LC3-a) preferably represents the following general formula (LC3-a1).
- R LC31 and R LC32 each independently represent the same meaning as R LC31 and R LC32 in General Formula (LC3).
- R LC31 and R LC32 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and R LC31 has 1 carbon atom. More preferably, it represents an alkyl group of ⁇ 7 , and R LC32 represents an alkoxy group of 1 to 7 carbon atoms.
- the general formula (LC3-b) is preferably represented by the following general formula (LC3-b1) to general formula (LC3-b12).
- the general formula (LC3-b1), the general formula (LC3-b6), the general formula (LC3-b8) and general formula (LC3-b11) are more preferable, general formula (LC3-b1) and general formula (LC3-b6) are more preferable, and general formula (LC3-b1) is Most preferably it represents.
- R LC31 and R LC32 each independently represent the same meaning as R LC31 and R LC32 in General Formula (LC3).
- R LC31 and R LC32 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and R LC31 has 2 carbon atoms. Or an alkyl group having 3 carbon atoms, and more preferably R LC32 represents an alkyl group having 2 carbon atoms.
- the compound represented by the general formula (LC4) is preferably a compound represented by the following general formula (LC4-a) to general formula (LC4-c), and the compound represented by the general formula (LC5) is Compounds represented by the following general formula (LC5-a) to general formula (LC5-c) are preferable.
- R LC41, R LC42 and X LC41 each independently represent the same meaning as R LC41, R LC42 and X LC41 in the general formula (LC4)
- R LC51 and R LC52 is the formula each independently represents the same meaning as R LC51 and R LC52 in (LC5)
- Z LC4a1, Z LC4b1, Z LC4c1, Z LC5a1, Z LC5b1 and Z LC5c1 each independently represent a single bond
- -CH CH -, - C ⁇ C It represents —, —CH 2 CH 2 —, — (CH 2 ) 4 —, —COO—, —OCH 2 —, —CH 2 O—, —OCF 2 — or —CF 2 O—.
- R LC41, R LC42, R LC51 and R LC52 each independently represents an alkyl group of 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, the number alkenyl group or a carbon atom of 2 to 7 carbon atoms 2 It preferably represents ⁇ 7 alkenyloxy groups.
- Z LC4a1 to Z LC5c1 each independently preferably represents a single bond, —CH 2 O—, —COO—, —OCO— , —CH 2 CH 2 —, and more preferably represents a single bond.
- the compound represented by the general formula (LC) is selected from the compounds represented by the following general formula (LC6) (excluding compounds represented by the general formula (LC1) to the general formula (LC5)). It is also preferable that it is 1 type, or 2 or more types of compounds.
- R LC61 and R LC62 each independently represent an alkyl group having 1 to 15 carbon atoms.
- One or more CH 2 groups in the alkyl group are —O—, —CH ⁇ CH—, —CO—, —OCO—, —COO— or —C, so that the oxygen atom is not directly adjacent.
- ⁇ C— may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally halogen substituted.
- R LC61 and R LC62 are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or 2 to 7 carbon atoms.
- the alkenyl group is preferably represented by any one of the following structures.
- a LC61 to A LC63 each independently represent any one of the following structures.
- one or more CH 2 CH 2 groups in the cyclohexylene group may be substituted with —CH ⁇ CH—, —CF 2 O—, —OCF 2 —.
- One or two or more CH groups in the phenylene group may be substituted with a nitrogen atom.
- a LC61 to A LC63 each independently preferably have any one of the following structures.
- Z LC61 and Z LC62 are each independently a single bond, —CH ⁇ CH—, —C ⁇ C— , —CH 2 CH 2 —, — (CH 2 ) 4 —, —COO—. , -OCH 2 -, - CH 2 O -, - OCF 2 - or -CF 2 O-a represents, MLC61 represents 0-3.
- Z LC61 and Z LC62 are each independently a single bond, —CH 2 CH 2 —, —COO— , —OCH 2 —, —CH 2 O—, —OCF 2 -Or -CF 2 O- is preferred.
- the compound represented by the general formula (LC6) is one or more compounds selected from the group consisting of compounds represented by the following general formula (LC6-a) to general formula (LC6-v) Is preferred.
- R LC61 and R LC62 each independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, carbon An alkenyl group having 2 to 7 atoms or an alkenyloxy group having 2 to 7 carbon atoms is represented.
- polymerizable compound examples include a monofunctional polymerizable compound having one reactive group, and a polyfunctional polymerizable compound having two or more reactive groups such as bifunctional or trifunctional. Can be mentioned.
- the polymerizable compound having a reactive group may or may not contain a mesogenic moiety.
- the reactive group is preferably a substituent having photopolymerizability.
- the reaction of the polymerizable compound having a reactive group can be suppressed during the thermal polymerization of the vertical alignment film material. Substituents are particularly preferred.
- the polymerizable compound according to the present invention includes the following general formula (P)
- Z p1 represents a fluorine atom, a cyano group, a hydrogen atom, an alkyl group having 1 to 15 carbon atoms in which a hydrogen atom may be substituted with a halogen atom, and a hydrogen atom in a halogen atom.
- An optionally substituted alkoxy group having 1 to 15 carbon atoms, a hydrogen atom optionally substituted with a halogen atom, and an alkenyl group having 1 to 15 carbon atoms optionally substituted with a halogen atom Represents an alkenyloxy group having 1 to 15 carbon atoms or —Sp p2 —R p2 ;
- R p1 and R p2 are each independently the following formulas (RI) to (R-IX):
- R 2 to R 6 are independently of each other a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the number of carbon atoms. 1 to 5 halogenated alkyl groups, W is a single bond, —O— or a methylene group, T is a single bond or —COO—, and p, t and q are each independently 0, Represents 1 or 2, Sp p1 and Sp p2 each represent a spacer group, and each of Sp p1 and Sp p2 independently represents a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH 2 ) s — (wherein s is L p1 and L p2 each independently represent a single bond, —O—, —S—, —CH 2 —, an integer of 1 to 11 and an oxygen atom is bonded to an aromatic ring.
- M p3 represents the following formulas (i-13) to (ix-13):
- m p2 to m p4 each independently represents 0, 1, 2 or 3
- m p1 and m p5 each independently represent 1, 2 or 3, but when there are a plurality of Z p1 May be the same or different.
- R p1 When a plurality of R p1 are present, they may be the same or different.
- R p2 When a plurality of R p2 are present, they may be the same.
- Z p1 is preferably -Sp p2 -R p2
- R 11 and R 12 are each independently represented by the formulas (R-1) to (R-3). Either is preferable.
- m p1 + m p5 is preferably 2 or more.
- L p1 represents a single bond, —OCH 2 —, —CH 2 O—, —CO—, —C 2 H 4 —, —COO—, —OCO—, —COOC 2.
- H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO -, - C 2 H 4 COO -, - CH CH -, - CF 2 -, - CF 2 O -, - (CH 2) z —C ( ⁇ O) —O—, — (CH 2 ) z—O— (C ⁇ O) —, —O— (C ⁇ O) — (CH 2 ) z—, —CH ⁇ CH—COO—, —COO—CH ⁇ CH—, —OCOCH ⁇ CH—, — (C ⁇ O) —O— (CH 2 ) z—, —OCF 2 — or —C ⁇ C—, and L p2 represents
- At least one of L p1 and L p2 in the general formula (P) is — (CH 2 ) z —C ( ⁇ O) —O— or — (CH 2 ) z—O— (C ⁇ O). It is preferably at least one selected from the group consisting of — and —O— (C ⁇ O) — (CH 2 ) z— and — (C ⁇ O) —O— (CH 2 ) z—.
- R p1 and R p2 are each independently the following formulas (R-1) to (R-15):
- m p3 represents 0, 1, 2, or 3.
- L p1 is a single bond
- m p2 is 2 or 3, a plurality of L p1 is present. At least one is preferably a single bond.
- m p3 represents 0, 1, 2 or 3, and when m p3 is 1, M p2 is a 1,4-phenylene group, and when m p3 is 2 or 3, a plurality of them are present.
- m p3 in the general formula (P) represents 0, 1, 2, or 3, and at least one of M p2 is a 1,4-phenylene group substituted with one or two or more fluorines. It is preferable.
- m p4 in the general formula (P) represents 0, 1, 2 or 3, and at least one of M p3 is a 1,4-phenylene group substituted with one or two or more fluorines. It is preferable.
- the spacer group (Sp p1 , Sp p2 , Sp p4 ) in the general formula (P) is a single bond, —OCH 2 —, — (CH 2 ) z O—, —CO—, —C 2 H 4.
- the polymerizable compound of the general formula (P) according to the present invention is represented by the general formula (Pa), the general formula (Pb), the general formula (Pc), and the general formula (Pd). It is preferably at least one compound selected from the group consisting of compounds.
- R p1 and R p2 are each independently the following formulas (RI) to (R-IX):
- R 2 to R 6 are independently of each other a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the number of carbon atoms. 1 to 5 halogenated alkyl groups, W is a single bond, —O— or a methylene group, T is a single bond or —COO—, and p, t and q are each independently 0, Represents 1 or 2, Ring A and Ring B are each independently 1,4-phenylene group, 1,4-cyclohexylene group, anthracene-2,6-diyl group, phenanthrene-2,7-diyl group, pyridine-2,5- Diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, indan-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or 1, Represents
- Sp p1 and Sp p4 each represent a spacer group
- X p1 to X p4 preferably each independently represent a hydrogen atom or a halogen atom
- L p3 is preferably —CH ⁇ CHCOO—, —COOCH ⁇ CH— or —OCOCH ⁇ CH—.
- R p1 When a plurality of R p1 are present, they may be the same or different.
- R p1 When a plurality of R p1 are present, they may be the same or different, and a plurality of R p2 are present. In some cases, they may be the same or different.
- a plurality of Sp p1 When a plurality of Sp p1 are present, they may be the same or different.
- Sp p4 When there are a plurality of Sp p4 , they are the same. They may be the same or different when there are a plurality of L p4 and L p5, and they may be the same when there are a plurality of rings A to C Or different.
- Preferred examples of the compound represented by the general formula (Pa) according to the present invention include polymerizable compounds represented by the following formulas (Pa-1) to (Pa-31).
- Preferred examples of the compound represented by the general formula (Pb) according to the present invention include polymerizable compounds represented by the following formulas (Pb-1) to (Pb-34).
- Preferred examples of the compound represented by the general formula (Pc) according to the present invention include polymerizable compounds represented by the following formulas (Pc-1) to (Pc-52).
- the compound represented by the general formula (Pd) according to the present invention is preferably a compound represented by the following general formula (P-d ').
- mp10 is more preferably 2 or 3.
- the other symbols are the same as those in the general formula (pd) and are omitted.
- Preferable examples of the compound represented by the general formula (Pd) according to the present invention include polymerizable compounds represented by the following formulas (Pd-1) to (Pd-31).
- the “alkyl group having 1 to 15 carbon atoms” is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
- R 1 and R 2 are each independently an alkyl group having 1 to 15 carbon atoms, and R 1 and R 2 are each independently 1 to 1 carbon atoms. Eight alkyl groups are preferred, and alkyl groups having 1 to 6 carbon atoms are more preferred.
- alkyl group having 1 to 15 carbon atoms examples include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, t-butyl group, 3-pentyl group, isopentyl group.
- examples of alkyl groups are common and are appropriately selected from the above examples depending on the number of carbon atoms of each alkyl group.
- Examples of the “alkoxy group having 1 to 15 carbon atoms” according to the present invention are preferably present at a position where at least one oxygen atom in the substituent is directly bonded to the ring structure.
- Group, propoxy group (n-propoxy group, i-propoxy group), butoxy group, pentyloxy group, octyloxy group and decyloxy group are more preferable.
- the example of an alkoxy group is common and is suitably selected from the said illustration according to the number of carbon atoms of each alkoxy group.
- alkenyl group having 2 to 15 carbon atoms examples include vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl. Group, 2-pentenyl group, 3-pentenyl group, 2-hexenyl group and the like. More preferable alkenyl groups according to the present invention include the following formula (i) (vinyl group), formula (ii) (1-propenyl group), formula (iii) (3-butenyl group) and formula (iv) ) (3-pentenyl group):
- examples of the polymerizable compound having a monofunctional reactive group that is preferable for increasing the solubility with a low-molecular liquid crystal and suppressing crystallization include the following general formula (VI):
- V represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic group having 5 to 30 carbon atoms.
- the alkylene group in the polyvalent alkylene group may be substituted with an oxygen atom in the range where the oxygen atom is not adjacent to each other, and the alkyl group having 5 to 20 carbon atoms (the alkylene group in the group is an oxygen atom) Or may be substituted with a cyclic substituent, and W represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 15 carbon atoms. All 1,4-phenylene groups of Meaning hydrogen atoms -CH 3, -OCH 3, fluorine atom, or a cyano group may be substituted.
- the polymerizable compound represented by) are preferred.
- X 3 represents a hydrogen atom or a methyl group.
- a hydrogen atom is preferred, and when importance is placed on reducing the residual amount of reaction, a methyl group is preferred. preferable.
- Sp 3 represents a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH 2 ) t — (wherein t represents an integer of 2 to 11, Represents the bond to the aromatic ring), but the length of the carbon chain affects Tg, so when the polymerizable compound content is less than 10% by weight, it is preferably not too long.
- a bond or an alkylene group having 1 to 5 carbon atoms is preferred.
- the polymerizable compound content is less than 6% by weight, a single bond or an alkylene group having 1 to 3 carbon atoms is more preferred.
- an alkylene group having 5 to 10 carbon atoms is preferable.
- t is preferably 1 to 5, and more preferably 1 to 3. Furthermore, it is preferable to use a mixture of a plurality of number of carbon atoms of Sp 3 are different polymerizable compounds such that the desired pre-tilt angle as needed so affects the pretilt angle can be obtained carbon atoms.
- V represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic substituent having 5 to 30 carbon atoms, and an alkylene group in the polyvalent alkylene group. May be substituted with an oxygen atom in the range where the oxygen atom is not adjacent, and an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be substituted with an oxygen atom within the range where the oxygen atom is not adjacent) .) Or may be substituted with a cyclic substituent, and is preferably substituted with two or more cyclic substituents.
- polymerizable compound represented by the general formula (VI) is represented by the general formula (X1a).
- a 1 represents a hydrogen atom or a methyl group
- a 2 represents a single bond or an alkylene group having 1 to 8 carbon atoms (one or two or more methylene groups in the alkylene group are each independently an oxygen atom, assuming that oxygen atoms are not directly bonded to each other, -CO-, -COO- or -OCO- may be substituted, and one or more hydrogen atoms in the alkylene group are each independently substituted with a fluorine atom, a methyl group or an ethyl group.
- a 3 and A 6 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group are such that oxygen atoms are not directly bonded to each other) And each independently may be substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more hydrogen atoms in the alkyl group are each independently a halogen atom. Which may be substituted with an atom or an alkyl group having 1 to 17 carbon atoms).
- a 4 and A 7 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group are such that oxygen atoms are not directly bonded to each other) And each independently may be substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more hydrogen atoms in the alkyl group are each independently a halogen atom. Which may be substituted with an atom or an alkyl group having 1 to 9 carbon atoms).
- B 1 , B 2 and B 3 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group are).
- each may be independently substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more of the alkyl groups may be substituted.
- each of the hydrogen atoms may be independently substituted with a halogen atom or a trialkoxysilyl group having 3 to 6 carbon atoms.
- the general formula (X1a) is preferably a compound represented by the general formula (II-b).
- the compounds represented by the general formula (II-b) are specifically compounds represented by the following formulas (II-q) to (II-z), (II-aa) to (II-al). It is preferable.
- the compounds represented by the above general formula (VI), general formula (XaI) and general formula (II-b) may be one kind or two or more kinds.
- a 8 represents a hydrogen atom or a methyl group
- the 6-membered rings T 1 , T 2 and T 3 are each independently
- Y 1 and Y 2 are each independently a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —C ⁇ C—, —CH ⁇ CH—.
- Y 3 and Y 4 are each independently a single bond, an alkylene group having 1 to 12 carbon atoms (one or two or more methylene groups in the alkylene group are such that oxygen atoms are not directly bonded to each other, Each independently may be substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more hydrogen atoms in the alkylene group are each independently a fluorine atom, a methyl group, Or may be substituted with an ethyl group).
- B 8 represents a hydrogen atom, a cyano group, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkylene group having a terminal acryloyl group or methacryloyl group.
- polymerizable compound represented by the general formula (VI) is specifically the general formula (X1c).
- R 70 represents a hydrogen atom or a methyl group
- R 71 represents a hydrocarbon group having a condensed ring
- examples of the polymerizable compound having a multifunctional reactive group that is preferable for increasing the solubility with a low-molecular liquid crystal and suppressing crystallization include the following general formula (V):
- X 1 and X 2 each independently represent a hydrogen atom or a methyl group
- Sp 1 and Sp 2 each independently represent a single bond
- U represents a linear or branched chain having 2 to 20 carbon atoms
- alkyl group of ⁇ 20 May be substituted with an alkyl group of ⁇ 20 (the alkylene group in the group may be substituted with an oxygen atom in the range where the oxygen atom is not adjacent) or a cyclic substituent, and k is an integer of 1 to 5 All 1,4-phenyle in the formula Groups, any hydrogen atom is -CH 3, -OCH 3, fluorine atom, or may be substituted by a cyano group.)
- the polymerizable compound represented by are preferred.
- X 1 and X 2 each independently represent a hydrogen atom or a methyl group.
- a hydrogen atom is preferable, and importance is placed on reducing the amount of residual reaction. In this case, a methyl group is preferred.
- Sp 1 and Sp 2 are each independently a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH 2 ) s — (wherein s is 2 to 11). In which the oxygen atom is bonded to an aromatic ring.)
- the pretilt angle in the liquid crystal display element of the present invention is the number of carbon atoms, the content with liquid crystal, and the alignment film used. It is affected by the type and orientation processing conditions.
- the carbon chain is preferably not so long, a single bond or an alkylene group having 1 to 5 carbon atoms is more preferable, and a single bond Alternatively, an alkylene group having 1 to 3 carbon atoms is more preferable.
- a polymerizable compound having 6 to 12 carbon atoms, and more preferably 8 to 10 carbon atoms.
- Sp 1 and Sp 2 represent —O— (CH 2 ) s —, it affects the pretilt angle, so it is preferable to adjust the lengths of Sp 1 and Sp 2 as necessary.
- s is preferably from 1 to 5, and more preferably from 1 to 3.
- s is preferably 6 to 10.
- at least one of Sp 1 and Sp 2 is a single bond, a molecular asymmetry is exhibited, which is preferable because pretilt is induced.
- a compound in which Sp 1 and Sp 2 are the same in the general formula (V) is also preferable, and it is preferable to use two or more compounds in which Sp 1 and Sp 2 are the same. In this case, it is more preferable to use two or more different Sp 1 and Sp 2 from each other.
- U represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic substituent having 5 to 30 carbon atoms
- an alkylene group in the polyvalent alkylene group May be substituted with an oxygen atom in the range where the oxygen atom is not adjacent, and an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be substituted with an oxygen atom within the range where the oxygen atom is not adjacent)
- May be substituted with a cyclic substituent and is preferably substituted with two or more cyclic substituents.
- U preferably specifically represents the following formulas (Va-1) to (Va-13).
- biphenyl having high linearity is preferable, and it is preferable to express the formula (Va-1) to the formula (Va-6).
- the structure representing the formula (Va-6) to the formula (Va-11) is preferable in terms of high solubility with liquid crystal, and is used in combination with the formula (Va-1) to the formula (Va-6). preferable.
- C ⁇ C- or all of the 1,4-phenylene group represents in formula single bond
- Any hydrogen atom is —CH 3 , —OCH 3 , a fluorine atom, or a cyano group
- one or more CH 2 CH 2 groups in the cyclohexylene group may be substituted with —CH ⁇ CH—, —CF 2 O—, —OCF 2 —. May be good.
- U has a ring structure, at least one of Sp 1 and Sp 2 is —O— (CH 2 ) s — (wherein s represents an integer of 1 to 7, and an oxygen atom is bonded to an aromatic ring) It is preferable that both are —O— (CH 2 ) s —.
- k represents an integer of 1 to 5, but k is preferably a bifunctional compound of 1 or k is a trifunctional compound of 2, more preferably a bifunctional compound. .
- the compound represented by the general formula (V) is preferably a compound represented by the following general formula (Vb).
- Z 1 and ZZ 2 represent —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—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —CH 2 CH 2 -OCO -, - COO-
- X 1 and X 2 each independently represent a hydrogen atom or a methyl group, both of which are diacrylate derivatives each representing a hydrogen atom, or both are dimethacrylate derivatives having a methyl group.
- a compound in which one represents a hydrogen atom and the other represents a methyl group is also preferable.
- 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.
- Sp 1 and Sp 2 each independently represent a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH 2 ) s—, at least one of which is —O -(CH 2 ) s- is preferred, and an embodiment in which both represent -O- (CH 2 ) s- is more preferred.
- s is preferably 1-6.
- Z 1 and Z 2 are —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 — (Y 1 and Y 2 each independently represents a hydrogen atom or a fluorine atom), —C ⁇ C— or a single bond, —OCH 2 — (Y 1 and Y
- 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.
- -A phenylene group or a single bond is preferred.
- Z 1 and Z 2 are also preferably a linking group other than a single bond, and when C is a single bond, Z 1 and Z 2 are preferably a single bond.
- C represents a single bond and the ring structure is formed of two rings.
- Specific examples of the polymerizable compound having a ring structure include the following general formula: Compounds represented by (V-1) to (V-6) are preferred, compounds represented by general formulas (V-1) to (V-4) are particularly preferred, and compounds represented by general formula (V-2) Most preferred are the compounds
- the compounds represented by the following general formulas (V1-1) to (V1-5) are preferable for improving the solubility in the liquid crystal composition, and the general formula (V1-1) ) Is particularly preferred.
- the general formula (Vb) is preferably used when it is formed of three ring structures, and the compounds represented by the general formulas (V1-6) to (V1-13) have a solubility in the liquid crystal composition. It is preferable in terms of enhancement. Further, the compounds represented by the general formulas (V-1) to (V-6) having a strong anchoring force with the liquid crystal have a weak general anchoring force and a good compatibility with the liquid crystal composition (V1- It is also preferable to use a mixture with the compound represented by 1) to (V1-5).
- q1 and q2 each independently represents an integer of 1 to 12, and R 3 represents a hydrogen atom or a methyl group.
- a compound represented by the following general formula (Vc) is preferable in terms of increasing the reaction rate, and the pretilt angle is thermally stable. This is preferable.
- a desired pretilt angle can be obtained by adjusting the number of carbon atoms of Sp 1 , Sp 2 and Sp 3 as necessary. The relationship between pretilt and the number of carbon atoms shows the same tendency as in the case of two functional groups.
- X 1 , X 2 and X 3 each independently represent a hydrogen atom or a methyl group
- Sp 1 , Sp 2 and Sp 3 each independently represent a single bond, having 1 to 12 carbon atoms.
- X 1 and X 2 each independently represent a hydrogen atom or a methyl group
- 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 2 (wherein s represents an integer of 1 to 7 and an oxygen atom is bonded to an aromatic ring)
- Z 1 represents —N ⁇ N—
- C represents 1,4-phenylene.
- a group, a trans-1,4-cyclohexylene group (any hydrogen atom may be substituted by a fluorine atom) or a compound representing a single bond is preferable.
- the photopolymerization initiator used in the present invention has a maximum absorption wavelength peak at 310 to 380 nm. From the viewpoint of efficiently polymerizing a polymerizable compound contained in a liquid crystal composition to form a polymer network,
- the lower limit of the maximum peak of the absorption wavelength is preferably 320 nm, and the upper limit of the maximum peak of the absorption wavelength is preferably 370 nm.
- anthraquinone, 2-sulfone anthraquinone monohydrate, benzyl, benzoin isobutyl ether, benzoin methyl ether, benzoin, benzoin ethyl ether, benzophenone, 4,4′-bisdimethylaminobenzophenone, 2-benzyl-2- Dimethylamino-4′-monoforinobutylketone, dibenzosuberone, 4-dimethylaminobenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 3′hydroxyacetophenone, ethylanthraquinone, ferrocene, 3-hydroxybenzophenone, 1 -Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-methylbenzophenone, phenanthrenequino and benzyldimethyl ketal are preferred.
- one or more photopolymerization initiators are preferably used, and two or more photoinitiators are also preferably used.
- a polymerization initiator that does not volatilize in the process.
- a polymerization initiator having a molecular weight of 120 or more is preferable.
- a polymerization initiator having a molecular weight of 180 or more is preferable.
- VHR voltage holding ratio
- VHR voltage holding ratio
- a polymerization initiator having a structure having no metal atom or phosphorus atom is used. More preferably, a polymerization initiator composed of carbon atoms, hydrogen atoms, and oxygen atoms is used. Moreover, it is preferable to use the polymerization initiator which does not color a panel after UV irradiation from a viewpoint of ensuring the external appearance of the manufactured liquid crystal display element.
- a polymerization initiator having a structure having no metal atom is preferred. More preferred is a polymerization initiator having a structure having no metal atom and benzophenone skeleton.
- the content of the photopolymerization initiator used in the present invention is preferably 0.001 to 1% by mass, preferably 0.005 to 0.5% by mass, and preferably 0.008 to 0.3% by mass.
- the polymerizable liquid crystal composition used in the present invention preferably contains the liquid crystal composition exemplified above and 1% by mass or more and less than 10% by mass polymerizable compound exemplified above.
- the lower limit of the content is preferably 2% by mass or more, and the upper limit is preferably less than 9% by mass, more preferably less than 7% by mass, more preferably less than 5% by mass, and more preferably less than 4% by mass.
- the polymerizable liquid crystal composition used in the present invention preferably contains the liquid crystal composition exemplified above and 10% by mass or more and less than 40% by mass polymerizable compound exemplified above.
- the lower limit of the content of the polymerizable compound is preferably 9% by mass or more, more preferably 10% by mass or more, and the upper limit is preferably less than 30% by mass, more preferably less than 25% by mass, and less than 20% by mass. More preferably, it is less than 15% by mass.
- the polymerizable liquid crystal composition used in the present invention preferably contains the liquid crystal composition exemplified above and the polymerizable compound exemplified above in an amount of 5% by mass or more and less than 15% by mass, and 7% by mass. It is more preferable to contain a polymerizable compound in an amount of not less than 12% and less than 12%.
- the polymerizable liquid crystal composition used in the present invention contains 1% by mass or more and less than 40% by mass of a polymerizable compound, so that uniaxial optical anisotropy or uniaxial refractive index anisotropy or easy alignment is achieved. It is preferable to form a polymer network having an axial direction, and it is more preferable that the optical axis or the easy alignment axis of the polymer network and the easy alignment axis of the low-molecular liquid crystal are substantially aligned.
- the polymer network includes a polymer binder in which a polymer thin film is formed by aggregating a plurality of polymer networks.
- the polymer binder has refractive index anisotropy indicating uniaxial orientation, low molecular liquid crystal is dispersed in the thin film, and the uniaxial optical axis of the thin film and the optical axis of the low molecular liquid crystal are in substantially the same direction.
- the feature is that it is complete. Therefore, unlike a polymer dispersion type liquid crystal or polymer network type liquid crystal which is a light scattering type liquid crystal, light scattering does not occur and a high contrast display can be obtained in a liquid crystal element using polarized light.
- the polymerizable liquid crystal composition used in the present invention is a PSA (Polymer Sustained Alignment) that forms a polymer network layer on the entire liquid crystal element and induces a pretilt by forming a polymer thin film layer on the liquid crystal element substrate. ) Type liquid crystal composition.
- PSA Polymer Sustained Alignment
- Type liquid crystal composition In any concentration, it is preferable to contain at least two kinds of polymerizable compounds having different Tg and adjust Tg as necessary.
- the polymerizable compound that is a precursor of a polymer having a high Tg is a polymerizable compound having a molecular structure that increases the crosslink density, and preferably has 2 or more functional groups.
- the precursor of the polymer having a low Tg preferably has a structure in which the number of functional groups is 1 or 2 or more, and an alkylene group or the like is provided as a spacer between the functional groups to increase the molecular length.
- Tg is also related to thermal mobility at the molecular level in the main chain and side chain of the polymer network, and has an influence on electro-optical properties.
- the crosslink density when the crosslink density is increased, the molecular mobility of the main chain is lowered, the anchoring force with the low molecular liquid crystal is increased, the drive voltage is increased, and the fall time is shortened.
- the crosslinking density is lowered so that Tg is lowered, the thermal mobility of the polymer main chain is increased, so that the anchoring force with the low-molecular liquid crystal is lowered, the driving voltage is lowered, and the fall time is increased.
- the anchoring force at the polymer network interface is influenced by the molecular mobility of the polymer side chain in addition to the above Tg, and the polymer is obtained by using a polymerizable compound having a polyvalent branched alkylene group and a polyvalent alkyl group.
- the anchoring force of the interface is lowered.
- the polymerizable compound having a polyvalent branched alkylene group and a polyvalent alkyl group is effective in inducing a pretilt angle and acts in the direction of reducing the polar anchoring force.
- the polymerizable liquid crystal composition exhibits a liquid crystal phase
- the polymerizable compound in the polymerizable liquid crystal composition is polymerized to increase the molecular weight of the polymerizable compound to cause phase separation of the liquid crystal composition and the polymerizable compound. .
- the form of separation into two phases varies greatly depending on the type of liquid crystal compound contained and the type of polymerizable compound.
- a phase separation structure may be formed by binodal decomposition in which an infinite number of polymerizable compound phases are generated and grown as island-like nuclei in the liquid crystal phase, and phase separation is caused by fluctuations in concentration between the liquid crystal phase and the polymerizable compound phase.
- a phase separation structure may be formed by spinodal decomposition.
- the content of at least low-molecular liquid crystal is 85% by mass or more, and the size is smaller than the wavelength of visible light by using a compound having a high reaction rate of the polymerizable compound.
- Innumerable nuclei of the polymerizable compound are generated to form a nano-order phase separation structure, which is preferable.
- the polymerization in the polymerizable compound phase proceeds, a polymer network having a void interval shorter than the wavelength of visible light is formed depending on the phase separation structure, whereas the voids in the polymer network are caused by phase separation of the low-molecular liquid crystal phase.
- the size of the void is smaller than the wavelength of visible light, the liquid crystal display device has high contrast, no light scattering, high contrast, strong influence of anchoring force from the polymer network, and short fall time. Is particularly preferable.
- the nucleation of the polymerizable compound phase in the binodal decomposition is preferably adjusted as needed as affected by changes in compatibility depending on the type and combination of compounds, reaction rate, temperature and other parameters.
- the reaction rate in the case of ultraviolet polymerization, may be adjusted as appropriate to the ultraviolet exposure conditions so as to promote the reactivity depending on the functional group of the polymerizable compound, the type and content of the photoinitiator, and the ultraviolet exposure intensity.
- An ultraviolet exposure intensity of 20 mW / cm 2 or more is preferable.
- spinodal decomposition a phase separation fine structure is obtained due to fluctuations in the concentration of two phases with periodicity. This is preferable because a uniform gap interval smaller than the wavelength can be easily formed. It is preferable to form the polymer network.
- phase separation structure When the proportion of the polymerizable compound is less than 15% by mass, it is preferable to form a phase separation structure by binodal decomposition, and when it is 15% by mass or more, it is preferable to form a phase separation structure by spinodal decomposition.
- content of the polymerizable compound When the content of the polymerizable compound is increased, there exists a phase transition temperature at which the low-molecular liquid crystal phase and the polymerizable compound phase are separated into two phases due to the influence of temperature. An isotropic phase is exhibited at a temperature higher than the two-phase separation transition temperature, but if it is low, separation occurs and a uniform phase separation structure cannot be obtained.
- a phase separation structure When two-phase separation is performed according to temperature, it is preferable to form a phase separation structure at a temperature higher than the two-phase separation temperature.
- a polymer network is formed while maintaining the same alignment state as that of the low-molecular liquid crystal.
- the formed polymer network exhibits optical anisotropy so as to follow the orientation of the low-molecular liquid crystal.
- As the form of the liquid crystal layer in the polymer network a structure in which the liquid crystal composition forms a continuous layer in the three-dimensional network structure of the polymer, a structure in which droplets of the liquid crystal composition are dispersed in the polymer, or both are mixed.
- a pretilt angle of 0 to 90 ° is preferably induced with respect to the liquid crystal element substrate interface by the action of the polymer network.
- the polymer network to be formed preferably has a function of aligning the coexisting low molecular liquid crystal in the alignment direction indicated by the alignment film of the liquid crystal cell, and further has a function of pretilting the low molecular liquid crystal with respect to the polymer interface direction. It is also preferable.
- a polymerizable compound that pretilts a low-molecular liquid crystal with respect to the polymer interface is useful and preferable for lowering the driving voltage of the liquid crystal element.
- it may have refractive index anisotropy, and it is preferable to use a polymerizable compound having a mesogenic group for the function of aligning the liquid crystal in the alignment direction.
- a polymerizable compound having a polyvalent alkyl group that does not have a mesogenic group that induces vertical alignment or a polyvalent branched alkylene group may be used, and a polymerizable compound having a mesogenic group Is also preferred in combination.
- the fibrous or columnar polymer network is in the vertical direction of the low molecular liquid crystal with respect to the liquid crystal cell substrate. It is preferable that they are formed in substantially the same direction.
- the liquid crystal is pretilted and aligned. It is preferable that a fiber-like or columnar polymer network is inclined in the same direction as the low-molecular liquid crystal.
- the optical axis direction or the easy alignment axis direction of the columnar polymer network is a desired pretilt angle, preferably vertical alignment
- a pretilt angle of 0.1 to 30 ° with respect to the normal direction of the transparent substrate is used for horizontal alignment.
- a pretilt angle of 0.1 to 30 ° with respect to the horizontal direction of the transparent substrate is formed, which is more preferable.
- the fibrous or columnar polymer network formed by any method is characterized in that the two cell substrates are connected to each other.
- the thermal stability of the pretilt angle is improved, and the reliability of the liquid crystal display element can be increased.
- the alkylene group between the functional group and the mesogenic group has 6 or more carbon atoms.
- a desired pretilt angle can be induced by adjusting the compounding ratio of these compounds.
- the trans form has a rod-like shape similar to that of the low-molecular liquid crystal and affects the alignment state of the low-molecular liquid crystal.
- the trans isomer contained in the polymerizable liquid crystal composition of the present invention has a low molecular weight that is aligned so that the direction of ultraviolet light travels parallel to the long axis direction of the rod-shaped molecule when ultraviolet light is exposed as parallel light from the top surface of the cell.
- the liquid crystal is aligned so as to be aligned in the molecular long axis direction of the trans form.
- the molecular long axis of the trans body is oriented in the inclined direction, and the liquid crystal is oriented in the inclined direction of the ultraviolet rays. That is, a pre-tilt angle is induced and a photo-alignment function is exhibited.
- the pretilt angle induced by crosslinking the polymerizable compound at this stage is fixed by a fibrous or columnar polymer network formed by polymerization phase separation.
- the pretilt angle that is important in the VA mode can be induced by a method of separating the polymerization phase while applying a voltage, a method of adding a plurality of polymerizable compounds having different induced pretilt angles, and a reversible photo-alignment function.
- the liquid crystal element of the present invention can be produced using a method of aligning low-molecular liquid crystals and polymerizable liquid crystal compounds in the direction in which ultraviolet rays travel by using the photo-alignment function exhibited by the polymerizable compound, and separating the polymerization phase as necessary. .
- the polymerizable compound having a photo-alignment function is preferably a photoisomeric compound that absorbs ultraviolet rays to become a trans isomer, and further, the polymerizable compound having a photo-alignment function has a reaction rate of the polymerizable compound having the photo-alignment function. It is preferably slower than the reaction rate of the polymerizable compound other than the above.
- UV exposure is performed, the polymerizable compound having a photo-alignment function immediately becomes a trans isomer, and when aligned in the light traveling direction, the surrounding liquid crystal compound including the polymerizable property is aligned in the same direction.
- the pretilt angle in the direction in which the UV light travels when the polymer phase separation proceeds and the long axis direction of the low molecular liquid crystal and the easy axis direction of the polymer network are aligned with the easy axis of the polymerizable compound having a photo-alignment function. Is induced.
- the polymer liquid crystal composition is used for the alignment direction of the alignment film having a fibrous or columnar polymer network on the liquid crystal cell substrate surface by phase separation polymerization.
- the low-molecular liquid crystals are aligned in parallel, but they are formed in the same direction as the refractive index anisotropy or easy-orientation axis direction of the formed fibrous or columnar polymer network and the alignment direction of the low-molecular liquid crystals. Is preferred. Furthermore, it is more preferable that the fibrous or columnar polymer network is present in substantially the entire cell except for the voids in which the low-molecular liquid crystal is dispersed.
- the pretilt angle with respect to the polymer interface direction it is preferable to use a polyvalent alkyl group having no mesogenic group, or a polymerizable compound having a polyvalent alkylene group and a polymerizable compound having a mesogenic group.
- the electro-optical characteristics are affected by the surface area of the polymer network interface and the gap spacing of the polymer network, it is important not to cause light scattering, and the average gap spacing is preferably smaller than the wavelength of visible light. For example, there is a method of increasing the monomer composition content in order to increase the surface area of the interface and reduce the gap interval.
- the polymer phase is formed so that the surface area of the interface is increased by changing the polymerization phase separation structure and making the gap interval fine, and the drive voltage and the fall time are shortened.
- the polymerization phase separation structure is also affected by the polymerization temperature.
- the phase separation rate is greatly influenced by the compatibility between the low-molecular liquid crystal and the polymerizable compound and the polymerization rate. Since it largely depends on the molecular structure and content of the compound, it is preferable to adjust the composition as appropriate. When the compatibility is high, it is preferable to use a polymerizable compound having a high polymerization rate.
- the ultraviolet polymerization it is preferable to increase the ultraviolet intensity. It is also preferable to increase the content of the polymerizable compound in the polymerizable liquid crystal composition.
- the compatibility is low, the phase separation rate is sufficiently high, which is preferable for producing the liquid crystal element of the present invention.
- a method for reducing the compatibility a method of polymerizing at a low temperature can be mentioned. When the temperature is lowered, the degree of alignment order of the liquid crystal is increased and the compatibility between the liquid crystal and the monomer is decreased, so that the polymerization phase separation rate can be increased.
- Still another method includes a method in which the polymerizable liquid crystal composition is polymerized at a temperature showing a supercooled state.
- the phase separation can be accelerated only by lowering the temperature by several degrees.
- the polymer phase separation structure corresponding to the case where a monomer composition content of several tens of percent is added to the liquid crystal, that is, the surface area of the polymer network interface, which is a structure that acts to shorten the fall time, has a large gap spacing. A fine polymer network structure is formed. Therefore, it is preferable that the polymerizable liquid crystal composition of the present invention is appropriately adjusted in consideration of the alignment function, the crosslinking density, the anchoring force, and the gap interval so that the fall time is shortened.
- a liquid crystal device using the polymerizable liquid crystal composition of the present invention it is necessary to prevent light scattering in order to obtain a high contrast display. It is important to control the phase separation structure to obtain an appropriate polymer network layer structure so as to obtain switching characteristics.
- the polymer network layer structure will be specifically described as follows. ⁇ Continuous structure of polymer network layer> A structure in which a polymer network layer is formed on the entire surface of the liquid crystal display element in the liquid crystal phase and the liquid crystal phase is continuous, and the orientation axis of the polymer network and the uniaxial optical axis are substantially in the same direction as the orientation axis of the low-molecular liquid crystal The polymer network is preferably formed so as to induce the pretilt angle of the low-molecular liquid crystal.
- the average gap distance of the polymer network is preferably smaller than the wavelength of visible light, preferably 800 nm or less, preferably 650 nm or less, and 450 nm or less. Is preferred. Furthermore, in order to make the fall time of the response shorter than the response time of the low-molecular liquid crystal alone due to the interaction effect (anchoring force) between the polymer network and the low-molecular liquid crystal, it is preferable to be in the range of 50 nm to 450 nm.
- the average gap interval is in the range of around 200 nm and the upper limit is around 450 nm. It is preferable to enter.
- the cell thickness refers to the distance between the surfaces of two substrates. Increasing the drive gap increases the average gap spacing. However, in order to suppress the increase in drive voltage to 25 V or less and shorten the fall response time, it is sufficient to enter the range from about 250 nm to 450 nm.
- the fall response time can be improved in the range of about 5 msec to about 1 msec, which is preferable.
- the average gap interval is in the range of about 300 nm to 450 nm. Furthermore, it is also possible to control the average gap interval of the polymer network so that the falling response time is a high-speed response of 1 msec or less.
- the drive voltage may increase to 30 V or more, the average gap interval may be set between about 50 nm and about 250 nm, and in order to reduce it to 0.5 msec or less, it is preferable to set from about 50 nm to about 200 nm.
- the average diameter of the polymer network is in the range of 20 nm to 700 nm, contrary to the average gap spacing.
- the average diameter tends to increase.
- Increasing the polymerization phase separation rate by increasing the reactivity increases the density of the polymer network and decreases the average diameter of the polymer network. Therefore, the phase separation conditions may be adjusted as necessary.
- the average diameter is preferably 20 nm to 160 nm, and when the average gap distance is 200 nm to 450 nm, the average diameter is 40 nm to 160 nm. preferable.
- the polymerizable compound content is greater than 10%, a range of 50 nm to 700 nm is preferable, and a range of 50 nm to 400 nm is more preferable.
- ⁇ Discontinuous structure of polymer network layer> The distance d between two opposing substrates is determined so that the product (retardation) of the cell thickness (d) and the effective birefringence ( ⁇ n) of the liquid crystal is about 0.275 to 0.33.
- the content of the polymerizable compound is low, and the polymer network layer is required to cover the entire cell.
- the polymer network layer is formed discontinuously.
- the polymerizable compound tends to gather near the liquid crystal cell substrate interface, and the polymer network layer is formed so that the polymer network grows from the substrate surface and adheres to the substrate interface.
- a polymer network layer, a liquid crystal layer, a polymer network layer, and a counter substrate are stacked in this order from the surface.
- Polymer having a laminated structure of polymer network layer / liquid crystal layer / polymer network layer and having a thickness of at least 0.5%, preferably 1%, more preferably 5% or more of the cell thickness in the cell cross-sectional direction
- the cell thickness refers to the distance between the surfaces of two substrates.
- the thickness of the polymer network layer may be increased as necessary.
- the polymer network structure in the polymer network layer is such that the low-molecular liquid crystal and the easy-orientation axis or uniaxial optical axis are aligned in substantially the same direction, and the low-molecular liquid crystal is formed so as to induce a pretilt angle. Just do it.
- the average gap distance is preferably in the range of 90 nm to 450 nm.
- the content of the polymerizable compound is 1% by mass to 6% by mass, it is preferable to use a bifunctional monomer having a mesogenic group having a high anchoring force, and the polymerization rate is low with a structure having a short distance between the functional groups.
- a fast bifunctional monomer it is preferable to form a polymer phase separation structure at a low temperature of 0 ° C. or lower.
- the content of the polymerizable compound is from 6% by mass to less than 10% by mass, a combination of the bifunctional monomer and a monofunctional monomer having a low anchoring force is preferable, and a range of 25 ° C. to ⁇ 20 ° C. is necessary. It is preferable to form a polymer phase separation structure.
- the melting point is room temperature or higher, it is preferable to lower the melting point by about 5 ° C. because the same effect as low temperature polymerization can be obtained.
- a polymerizable compound having a mesogenic group having an orientation function and a relatively weak anchoring force is effective to increase the number of carbon atoms of an alkylene group between the functional group and the mesogenic group, and preferably has 5 to 10 carbon atoms.
- liquid crystal droplets may be dispersed in the polymer binder.
- the polymer binder has a refractive index anisotropy and is oriented on the substrate surface. It is preferable that the orientation direction indicated by the film is aligned with the optical axis direction of the polymer binder.
- concentration of the polymerizable compound in the polymerizable liquid crystal composition the greater the anchoring force between the liquid crystal composition and the polymer interface, and the higher the ⁇ d.
- ⁇ r decreases.
- the concentration of the polymerizable compound in the polymerizable liquid crystal composition is 1% by mass or more and less than 40% by mass, and 2% by mass or more and 15% by mass or less. Preferably, 3 mass% or more and 8 mass% or less are more preferable.
- the voltage holding ratio is an important characteristic.
- the cause of lowering the voltage holding ratio is considered to be ionic impurities contained in the polymerizable liquid crystal composition.
- mobile ions strongly influence the voltage holding ratio. Therefore, it is preferable to remove the mobile ions by performing a purification treatment or the like so that at least a specific resistance of 10 14 ⁇ ⁇ cm or more is obtained.
- the liquid crystal display element of the present invention contains a polymer or copolymer in the liquid crystal composition, and the content of the polymer or copolymer is 1 mass of the total mass of the liquid crystal composition and the polymer or copolymer.
- the liquid crystal display device has the same structure as the liquid crystal display device according to the prior art except that the content is less than 40% and less than 40% by mass.
- the liquid crystal display device has a structure in which a liquid crystal layer is sandwiched between two transparent substrates having electrodes on at least one side.
- the liquid crystal display element of the present invention preferably has an alignment layer for aligning the liquid crystal composition on at least one transparent substrate. By applying a voltage to the alignment layer provided on the substrate and the electrode provided on the substrate, the alignment of the liquid crystal molecules is controlled.
- the polymer network or polymer binder has a uniaxial refractive index anisotropy or an easy axis direction, and the optical axis direction or the easy axis direction of the polymer network or the polymer binder and the easy axis direction of the low molecular liquid crystal are the same direction. Preferably there is.
- the orientation easy axis direction of the alignment layer is the same as the orientation easy axis direction of the polymer network or the polymer binder.
- the liquid crystal display element can be applied to operation modes such as TN, STN, ECB, VA, VA-TN, IPS, FFS, ⁇ cell, OCB, and cholesteric liquid crystal.
- the liquid crystal display element of the present invention is a PSA (Polymer Sustained Alignment) type liquid crystal display element having a polymer or copolymer on the alignment film in that the liquid crystal composition contains a polymer or copolymer. Is different.
- PSA Polymer Sustained Alignment
- the distance (d) between the substrates of the liquid crystal display element of the present invention is preferably in the range of 2 to 5 ⁇ m, more preferably 3.5 ⁇ m or less.
- the birefringence is adjusted so that the product of the birefringence of the liquid crystal composition and the cell thickness is close to 0.275.
- a polymer network is formed after the polymerization phase separation. Therefore, the birefringence of the liquid crystal display element when an electric field is applied is lowered due to the anchoring force action of the polymer network and the optical properties of the polymer network, so that it is included in the liquid crystal composition, the polymerization composition, or the polymerizable liquid crystal composition.
- the product of the birefringence ( ⁇ n) and the distance (d) between the substrates is particularly preferably in the range of 0.3 to 0.4 ⁇ m when the driving voltage is increased within about 5 V due to the formation of the polymer network.
- a range of 0.30 to 0.35 ⁇ m is more preferable for an increase within a range, and a range of 0.29 to 0.33 ⁇ m is particularly preferable for an increase within a drive voltage of 1 V.
- the birefringence of the liquid crystal composition used for the polymerizable liquid crystal composition may be set so that the product of the cell thickness (d) and the birefringence index ( ⁇ n) is 1 to 1.9 times with respect to 0.275. preferable.
- the driving voltage of the liquid crystal display element of the present invention is not determined only by the dielectric anisotropy or elastic constant of the liquid crystal composition, but is greatly influenced by the anchoring force acting between the liquid crystal composition and the polymer interface.
- Japanese Patent Application Laid-Open No. 6-222320 discloses the relationship of the following formula as a description relating to the driving voltage of a polymer dispersed liquid crystal display element.
- Vth represents a threshold voltage
- 1Kii and 2Kii represent elastic constants
- i represents 1, 2 or 3
- ⁇ represents dielectric anisotropy
- ⁇ r> represents a transparent polymer substance interface.
- A indicates the anchoring force of the transparent polymer substance to the liquid crystal composition
- d indicates the distance between the substrates having transparent electrodes.
- the driving voltage of the light scattering type liquid crystal display element is determined by the average gap distance at the interface of the transparent polymer substance, the distance between the substrates, the elastic constant / dielectric anisotropy of the liquid crystal composition, and Determined by the anchoring energy between the conductive polymer materials.
- parameters that can be controlled by the liquid crystal display device of the present invention are liquid crystal properties and anchoring force between polymers. Since the anchoring force largely depends on the molecular structure of the polymer and the molecular structure of the low-molecular liquid crystal, if a polymerizable compound having a strong anchoring force is selected, the response time can be shortened to 1.5 ms or less. At the same time, since the driving voltage increases to 30 V or higher, it is preferable to adjust the composition by appropriately selecting the liquid crystal compound and the polymerizable compound so that the driving voltage is 30 V or lower and the response speed is 1.5 ms or lower. .
- the composition so that the driving voltage and the response speed are balanced by appropriately blending a polymer precursor having a strong anchoring force and a polymer precursor having a weak anchoring force.
- the dielectric anisotropy is 6 or more for the P-type liquid crystal and -3 or less for the N-type liquid crystal.
- the birefringence is preferably 0.09 or more. Furthermore, it is more preferable to make the birefringence of the liquid crystal composition and the refractive index of the fibrous or columnar polymer network as close as possible to eliminate light scattering.
- the liquid crystal display element of the present invention is irradiated with energy rays while the above-mentioned liquid crystal composition is at ⁇ 50 ° C. to 30 ° C. to polymerize the polymerizable compound and have a refractive index anisotropy or an easy orientation axis in the liquid crystal composition. It is preferably obtained by forming a polymer network having a direction.
- the upper limit of the polymerization temperature is 30 ° C, preferably 20 ° C to -10 ° C.
- ⁇ d is further accelerated by low temperature polymerization and normal temperature polymerization depending on the composition of the polymerizable compound. This is because 1) the polymerization is performed in a state where the orientation degree of the liquid crystal molecules is increased at a low temperature, and 2) the phase separation is facilitated by reducing the compatibility between the polymer polymerized by the low temperature polymerization and the liquid crystal composition. The phase separation speed is increased and the gap distance of the polymer network becomes fine. 3) Even if a polymerizable compound having a relatively low anchoring force is used, the influence of the anchoring force seems to be strong because the gap gap is fine.
- the optical axis direction or the easy alignment axis direction of the polymer network or polymer binder having uniaxial refractive index anisotropy or easy alignment axis direction forms a pretilt angle with respect to the transparent substrate. It is preferable to adjust the strength of the electric field to control the orientation of the low-molecular liquid crystal, and by tilting it with respect to the substrate surface, the energy rays are applied while applying a voltage to the liquid crystal layer described above.
- the composition is obtained by polymerizing the polymerizable compound by irradiation to obtain a polymer having a refractive index anisotropy or an orientation easy axis direction in the liquid crystal composition.
- a voltage is applied so that the pretilt angle is 20 degrees or less with respect to the normal direction of the substrate, and polymerization is performed, so that the portulsion currently used in the VA mode cell is used.
- This is particularly preferable because it not only has an effect corresponding to the fine polymer protrusions of the PSA liquid crystal, but also exhibits a high-speed response that cannot be realized by PSA.
- the alignment direction of the low-molecular liquid crystal is regulated by applying photo-alignment treatment or rubbing alignment treatment to the low-molecular liquid crystal to induce a pretilt angle at the substrate interface vertical alignment film interface.
- the occurrence of orientation defects is preferably suppressed, and it is also preferable to perform the orientation treatment so as to incline in a plurality of directions.
- the liquid crystal layer is applied with an alternating electric field in a temperature range of ⁇ 50 ° C. to 30 ° C.
- a liquid crystal composition containing a polymerizable compound containing a polymerizable compound, and irradiated with ultraviolet rays or an electron beam, thereby providing refractive index anisotropy.
- This pretilt angle is a liquid crystal element in which the polymer axis after polymerization is tilted with respect to the substrate surface when the polymer phase is separated in an alignment state induced by applying an electric field due to the dielectric anisotropy of the low-molecular liquid crystal It is more preferable that the polymerizable compound has a high molecular weight.
- the two substrates used in the liquid crystal display element of the present invention can be made of a transparent material having flexibility such as glass or plastic.
- a transparent substrate having a transparent electrode layer can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.
- ITO indium tin oxide
- the color filter can be prepared by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method.
- a method for producing a color filter by a pigment dispersion method will be described as an example.
- a curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be created.
- a pixel electrode provided with an active element such as a TFT or a thin film diode may be provided on the substrate.
- the substrate is opposed so that the transparent electrode layer is on the inside.
- the thickness of the obtained light control layer is 1 to 100 ⁇ m. 1.5 to 10 ⁇ m is more preferable.
- the product of the refractive index anisotropy ⁇ n of the liquid crystal and the cell thickness d is adjusted so that the contrast is maximized, and 1/550 nm is reduced depending on the display mode. It is preferable to make it 2 or 1/4.
- the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good.
- a retardation film for widening the viewing angle can also be used.
- the spacer include columnar spacers made of glass particles, plastic particles, alumina particles, a photoresist material, and the like.
- a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant.
- a normal vacuum injection method or an ODF method can be used as a method of sandwiching the polymerizable liquid crystal composition between the two substrates.
- a sealant such as epoxy photothermal curing is drawn on a backplane or frontplane substrate using a dispenser in a closed-loop bank shape, and then removed.
- a liquid crystal display element can be produced by bonding a front plane and a back plane after dropping a predetermined amount of the polymerizable liquid crystal composition under air.
- the polymerizable liquid crystal composition used in the present invention can be suitably used because the liquid crystal / monomer composite material can be stably dropped in the ODF process.
- an appropriate polymerization rate is desirable in order to obtain good alignment performance of liquid crystals. Therefore, ultraviolet rays or electron beams, which are active energy rays, are irradiated singly or in combination or sequentially.
- the method of polymerizing by is preferred.
- a polarized light source or a non-polarized light source may be used.
- polymerization is performed in a state where the polymerizable liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy rays. .
- the liquid crystal composition containing a polymerizable compound it is preferable to apply an alternating electric field to the polymerizable liquid crystal composition in a temperature range of ⁇ 50 ° C. to 20 ° C. and irradiate ultraviolet rays or electron beams.
- the alternating electric field to be applied is preferably an alternating current having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 100 Hz to 5 kHz, and the voltage is selected depending on a desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage.
- the pretilt angle is preferably controlled from 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.
- the temperature during irradiation is preferably in the temperature range of ⁇ 50 ° C. to 30 ° C. for the polymerizable liquid crystal composition.
- a lamp for generating ultraviolet rays a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used.
- a wavelength of the ultraviolet rays to be irradiated it is preferable to irradiate ultraviolet rays in a wavelength region other than the absorption wavelength region of the liquid crystal composition, and it is preferable to cut and use ultraviolet rays of less than 365 nm as necessary.
- Intensity of ultraviolet irradiation is preferably from 0.1mW / cm 2 ⁇ 100W / cm 2, 2mW / cm 2 ⁇ 50W / cm 2 is more preferable.
- the amount of energy of ultraviolet rays to be irradiated can be adjusted as appropriate, but is preferably 10 mJ / cm 2 to 500 J / cm 2, and more preferably 100 mJ / cm 2 to 200 J / cm 2 .
- the intensity may be changed.
- the time for irradiating with ultraviolet rays is appropriately selected depending on the intensity of the irradiated ultraviolet rays, but is preferably from 10 seconds to 3600 seconds, and more preferably from 10 seconds to 600 seconds.
- FIG. 1 is a schematic sectional view showing an example of the liquid crystal display element of the present invention.
- a liquid crystal display element 10 according to an embodiment of the present invention includes a first substrate 2 having an alignment layer 4 formed on the surface thereof, a space away from the first substrate, and a photo-alignment layer formed on the surface. And a liquid crystal layer 5 filled between the first substrate 2 and the second substrate 7 and in contact with the pair of alignment layers, the alignment layer 4 (4a, 4b). ) And the first substrate 2 have an electrode layer 3 including a thin film transistor, a common electrode 22 and a pixel electrode as an active element.
- FIG. 1 is a diagram schematically showing a configuration of a liquid crystal display element.
- the configuration of the liquid crystal display element 10 according to the embodiment of the present invention is sandwiched between a first transparent insulating substrate 2 and a second transparent insulating substrate 7 that are arranged to face each other.
- a liquid crystal display element of a lateral electric field type (an FFS mode as one form of IPS as an example in the figure) having the polymerizable liquid crystal composition (or liquid crystal layer 5).
- the first transparent insulating substrate 2 has an electrode layer 3 formed on the surface on the liquid crystal layer 5 side.
- the liquid crystal molecules in the polymerizable liquid crystal composition are aligned so as to be substantially parallel to the substrates 2 and 7 when no voltage is applied.
- the second substrate 7 and the first substrate 2 may be sandwiched between a pair of polarizing plates 1 and 8.
- a color filter 6 is provided between the second substrate 7 and the alignment film 4.
- the liquid crystal display element according to the present invention may be a so-called color filter on array (COA), or a color filter may be provided between an electrode layer including a thin film transistor and a liquid crystal layer, or the thin film transistor.
- COA color filter on array
- a color filter may be provided between the electrode layer containing and the second substrate.
- the liquid crystal display element 10 of one embodiment of the present invention includes the first polarizing plate 1, the first substrate 2, the electrode layer 3 including a thin film transistor, the alignment film 4, and the polymerizable liquid crystal composition.
- the liquid crystal layer 5, the alignment film 4, the color filter 6, the second substrate 7, and the second polarizing plate 8 are sequentially stacked.
- the first substrate 2 and the second substrate 7 can be made of a transparent material having flexibility such as glass or plastic, and one of them can be an opaque material such as silicon.
- the two substrates 2 and 7 are bonded together by a sealing material and a sealing material such as an epoxy thermosetting composition disposed in the peripheral region, and in order to maintain the distance between the substrates, for example, Spacer columns made of resin formed by granular spacers such as glass particles, plastic particles, alumina particles, or the photolithography method may be arranged.
- FIG. 2 is an enlarged plan view of a region surrounded by the II line of the electrode layer 3 formed on the substrate 2 in FIG.
- FIG. 3 is a cross-sectional view of the liquid crystal display element shown in FIG. 1 cut along the line III-III in FIG.
- the electrode layer 3 including a thin film transistor formed on the surface of the first substrate 2 includes a plurality of gate lines 24 for supplying scanning signals and a plurality of data for supplying display signals.
- the wirings 25 are arranged in a matrix so as to cross each other. In FIG. 2, only a pair of gate lines 24 and a pair of data lines 25 are shown.
- a unit pixel of a liquid crystal display device is formed by a region surrounded by a plurality of gate lines 24 and a plurality of data lines 25, and a pixel electrode 21 and a common electrode 22 are formed in the unit pixel.
- a thin film transistor including a source electrode 27, a drain electrode 26, and a gate electrode 28 is provided in the vicinity of the intersection where the gate wiring 24 and the data wiring 25 intersect each other.
- the thin film transistor is connected to the pixel electrode 21 as a switch element that supplies a display signal to the pixel electrode 21.
- a common line (not shown) is provided in parallel with the gate wiring 24. The common line is connected to the common electrode 22 in order to supply a common signal to the common electrode 22.
- a preferred embodiment of the structure of the thin film transistor is provided, for example, as shown in FIG. 3 so as to cover the gate electrode 11 formed on the surface of the substrate 2 and the gate electrode 11 and cover the substantially entire surface of the substrate 2.
- a source electrode 17 which covers the other side edge of the layer 14 and the semiconductor layer 13 and is in contact with the gate insulating layer 12 formed on the surface of the substrate 2; and the drain Has an insulating protective layer 18 provided to cover the electrode 16 and the source electrode 17, a.
- An anodic oxide film may be formed on the surface of the gate electrode 11 for reasons such as eliminating a step with the gate electrode.
- Amorphous silicon, polycrystalline polysilicon, or the like can be used for the semiconductor layer 13, but when a transparent semiconductor film such as ZnO, IGZO (In—Ga—Zn—O), ITO, or the like is used, it results from light absorption. It is also preferable from the viewpoint of suppressing the adverse effect of optical carriers and increasing the aperture ratio of the element.
- an ohmic contact layer 15 may be provided between the semiconductor layer 13 and the drain electrode 16 or the source electrode 17 for the purpose of reducing the width and height of the Schottky barrier.
- a material in which an impurity such as phosphorus such as n-type amorphous silicon or n-type polycrystalline polysilicon is added at a high concentration can be used.
- the gate wiring 26, the data wiring 25, and the common line 29 are preferably metal films, more preferably Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni, or an alloy thereof, and Al or an alloy thereof. It is particularly preferable to use this wiring.
- the insulating protective layer 18 is a layer having an insulating function, and is formed of silicon nitride, silicon dioxide, silicon oxynitride film, or the like.
- the common electrode 22 is a flat electrode formed on almost the entire surface of the gate insulating layer 12, while the pixel electrode 21 is an insulating protective layer 18 covering the common electrode 22. It is a comb-shaped electrode formed on the top. That is, the common electrode 22 is disposed at a position closer to the first substrate 2 than the pixel electrode 21, and these electrodes are disposed so as to overlap each other via the insulating protective layer 18.
- the pixel electrode 21 and the common electrode 22 are formed of a transparent conductive material such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), IZTO (Indium Zinc Tin Oxide), and the like. Since the pixel electrode 21 and the common electrode 22 are formed of a transparent conductive material, the area opened by the unit pixel area increases, and the aperture ratio and transmittance increase.
- the pixel electrode 21 and the common electrode 22 have an interelectrode distance (also referred to as a minimum separation distance): R between the pixel electrode 21 and the common electrode 22 in order to form a fringe electric field between the electrodes.
- the distance between the first substrate 2 and the second substrate 7 is smaller than G.
- the distance between electrodes: R represents the distance in the horizontal direction on the substrate between the electrodes.
- the distance between the first substrate 7 and the second substrate 7 is smaller than G, so that a fringe electric field E is formed. Therefore, the FFS type liquid crystal display element can use a horizontal electric field formed in a direction perpendicular to a line forming the comb shape of the pixel electrode 21 and a parabolic electric field.
- the electrode width of the comb-shaped portion of the pixel electrode 21: l and the width of the gap of the comb-shaped portion of the pixel electrode 21: m are such that all the liquid crystal molecules in the liquid crystal layer 5 can be driven by the generated electric field. It is preferable to form. Further, the minimum separation distance R between the pixel electrode and the common electrode can be adjusted as the (average) film thickness of the gate insulating layer 12.
- an inter-electrode distance (also referred to as a minimum separation distance) between the pixel electrode 21 and the common electrode 22: R is different from that of the first substrate 2 and the second substrate.
- the distance from the substrate 7 may be larger than G (IPS method).
- IPS method a configuration in which comb-like pixel electrodes and comb-like common electrodes are provided alternately in substantially the same plane can be cited.
- a preferred form of the liquid crystal display element according to the present invention is preferably an FFS mode liquid crystal display element using a fringe electric field, and the shortest separation distance d between the common electrode 22 and the pixel electrode 21 is set to be the alignment film 4.
- the distance is shorter than the shortest distance D between the substrates (distance between substrates)
- a fringe electric field is formed between the common electrode and the pixel electrode, and the horizontal and vertical alignments of the liquid crystal molecules can be used efficiently.
- the FFS mode liquid crystal display element of the present invention when a voltage is applied to the liquid crystal molecules arranged so that the long axis direction is parallel to the alignment direction of the alignment layer, the pixel electrode 21 and the common electrode 22 are interposed.
- Parabolic electric field equipotential lines are formed up to the top of the pixel electrode 21 and the common electrode 22 and are arranged along the electric field in which the long axes of the liquid crystal molecules in the liquid crystal layer 5 are formed. Therefore, liquid crystal molecules can be driven even with a low dielectric anisotropy.
- the color filter 6 it is preferable to form a black matrix (not shown) in a portion corresponding to the thin film transistor and the storage capacitor 23 from the viewpoint of preventing light leakage.
- the color filter 6 is usually composed of one dot of video or image from three filter pixels of R (red), G (green), and B (blue). For example, these three filters are arranged in the extending direction of the gate wiring. Yes.
- the color filter 6 can be produced by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. A method for producing a color filter by a pigment dispersion method will be described as an example.
- a curable coloring composition for a color filter is applied onto the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be manufactured.
- a so-called color filter-on-array in which pixel electrodes provided with active elements such as TFTs and thin film diodes are provided on the substrate may be used.
- a pair of alignment films 4 that are in direct contact with the polymerizable liquid crystal composition constituting the liquid crystal layer 5 and induce homogeneous alignment are provided.
- the polarizing plate 1 and the polarizing plate 8 can be adjusted so that the viewing angle and the contrast are good by adjusting the polarizing axis of each polarizing plate, and the transmission axes thereof operate in the normally black mode.
- any one of the polarizing plate 1 and the polarizing plate 8 is preferably arranged so as to have a transmission axis parallel to the alignment direction of the liquid crystal molecules.
- a retardation film for widening the viewing angle can also be used.
- the shortest separation distance d between the adjacent common electrode and the pixel electrode is longer than the shortest separation distance G between the liquid crystal alignment films.
- the electrode and the pixel electrode are formed on the same substrate, and the common electrode and the pixel electrode are alternately arranged, and the shortest separation distance d between the adjacent common electrode and the pixel electrode is the liquid crystal alignment Examples include a structure longer than the shortest separation distance G between the films.
- the pair of substrates are separated and faced so that the film is inside, and then the liquid crystal It is preferred to fill the composition between the substrates. In that case, it is preferable to adjust the space
- the distance between the substrates (the average thickness of the obtained liquid crystal layer, also referred to as the separation distance between the coatings) is preferably adjusted to be 1 to 100 ⁇ m.
- the average distance between the coatings is more preferably 1.5 to 10 ⁇ m.
- examples of the spacer used for adjusting the distance between the substrates include columnar spacers made of glass particles, plastic particles, alumina particles, a photoresist material, and the like.
- the FFS type liquid crystal display element described with reference to FIGS. 1 to 3 is an example, and can be implemented in various other forms without departing from the technical idea of the present invention.
- FIG. 4 is another embodiment of the plan view in which the region surrounded by the II line of the electrode layer 3 formed on the substrate 2 in FIG. 1 is enlarged.
- the pixel electrode 21 may have a slit.
- the slit pattern may be formed so as to have an inclination angle with respect to the gate wiring 24 or the data wiring 25.
- the pixel electrode 21 shown in FIG. 4 has a shape in which a substantially rectangular flat plate electrode is cut out by a notch portion having a substantially rectangular frame shape. Further, a comb-like common electrode 22 is formed on one surface of the back surface of the pixel electrode 21 via an insulating protective layer 18 (not shown). When the shortest separation distance R between the adjacent common electrode and the pixel electrode is shorter than the shortest separation distance G between the alignment layers, the FFS method is used.
- the surface of the pixel electrode is preferably covered with a protective insulating film and an alignment film layer.
- a storage capacitor 23 for storing a display signal supplied via the data line 25 may be provided in an area surrounded by the plurality of gate lines 24 and the plurality of data lines 25.
- the shape of the notch is not particularly limited, and is not limited to the substantially rectangular shape shown in FIG. 4, and a notch having a known shape such as an ellipse, a circle, a rectangle, a rhombus, a triangle, or a parallelogram. Can be used.
- a notch having a known shape such as an ellipse, a circle, a rectangle, a rhombus, a triangle, or a parallelogram.
- FIG. 5 is another embodiment different from FIG. 3, and is another example of a cross-sectional view of the liquid crystal display element shown in FIG. 1 taken along the line III-III in FIG.
- the liquid crystal layer 5 containing the liquid crystal composition is filled in this space.
- a gate insulating layer 12, a common electrode 22, an insulating protective layer 18, a pixel electrode 21, and an alignment layer 4 are stacked in this order on part of the surface of the first substrate 2. As shown in FIG.
- the pixel electrode 21 has a shape in which the center and both ends of the flat plate are cut out by a triangular cutout, and the remaining region is cut out by a rectangular cutout.
- the common electrode 22 has a structure in which a comb-like common electrode is disposed on the first substrate side from the pixel electrode substantially in parallel with the substantially elliptical cutout portion of the pixel electrode 21.
- FIG. 5 shows an example in which the common electrode 22 is formed on the gate insulating layer 12, but as shown in FIG. 5, the common electrode 22 is formed on the first substrate 2,
- the pixel electrode 21 may be provided through the gate insulating layer 12.
- the electrode width of the pixel electrode 21: l, the electrode width of the common electrode 22: n, and the interelectrode distance: R are appropriately adjusted to such a width that all liquid crystal molecules in the liquid crystal layer 5 can be driven by the generated electric field. It is preferable.
- the shortest separation distance R between the adjacent common electrode and the pixel electrode is shorter than the shortest separation distance G between the alignment layers, the FFS method is used, and when it is longer, the IPS method is used.
- the positions in the thickness direction of the pixel electrode 21 and the common electrode 22 are different, but the positions in the thickness direction of both electrodes may be the same or the common electrode may be provided on the liquid crystal layer 5 side.
- FIG. 6 is a diagram schematically showing a configuration of a vertical electric field type liquid crystal display element. Moreover, in FIG. 7, for convenience of explanation, each component is illustrated separately.
- FIG. 7 is an enlarged plan view of a region surrounded by a line VII of an electrode layer 300 including a thin film transistor (or also referred to as a thin film transistor layer 300) formed on the substrate in FIG.
- FIG. 8 is a cross-sectional view of the liquid crystal display element shown in FIG. 6 taken along the line VIII-VIII in FIG.
- the liquid crystal display element 1000 includes a second substrate 800 provided with a transparent electrode (layer) 600 (also referred to as a common electrode 600) made of a transparent conductive material, as shown in FIG.
- a transparent electrode (layer) 600 also referred to as a common electrode 600
- the polymerizable liquid crystal composition (or the liquid crystal layer 500) is sandwiched between the liquid crystal molecules in the polymerizable liquid crystal composition, and the alignment when no voltage is applied is substantially perpendicular to the substrates 200 and 800.
- the second substrate 800 and the first substrate 200 may be sandwiched between a pair of polarizing plates 100 and 900.
- a color filter 700 is provided between the first substrate 200 and the common electrode 600.
- a pair of alignment films 400 are formed on the surfaces of the transparent electrodes (layers) 600 and 1400 so as to be adjacent to the liquid crystal layer 500 according to the present invention and in direct contact with the polymerizable liquid crystal composition constituting the liquid crystal layer 500.
- the liquid crystal display element 1000 according to the present invention includes a first polarizing plate 100, a first substrate 200, an electrode layer (also referred to as a thin film transistor layer) 300 including a thin film transistor, a photo-alignment film 400, and a liquid crystal composition.
- a layer 500 containing an object, an alignment film 400, a common electrode 600, a color filter 700, a second substrate 800, and a second polarizing plate 900 are sequentially stacked.
- the alignment film 400 is preferably a photo-alignment film.
- FIG. 10 is a schematic cross-sectional view showing an embodiment of the VA mode liquid crystal display device according to the present invention, in which an alignment film is formed in a liquid crystal layer of a liquid crystal cell manufactured using alignment treatment (mask rubbing or photo-alignment).
- 3 shows a polymer network structure and a liquid crystal molecular arrangement structure.
- a vertical alignment film slightly inclined (0.1 to 5.0 °) from the normal direction of the glass substrate is formed on the inner side (liquid crystal layer side) of the transparent electrode of the liquid crystal cell.
- the molecule has a twisted structure of approximately 90 ° between the upper and lower substrates.
- the polymerizable monomers are arranged in the vertical direction, and the polymerizable monomer is polymerized and fixed by UV light irradiation to form a polymer network.
- the polymer network formed in this way is (V1) a polymer network that extends over the upper and lower substrates, (V2) a polymer network that forms the polymer network from the upper (lower) substrate toward the liquid crystal direction, but halfway ( V3) A polymer network is formed only near the surface of the alignment film. (Mainly in the case of a monofunctional monomer), (V4) It is estimated that the polymer network has approximately four types of structures in which the polymer networks are bonded (not floating).
- the polymer polymer network having anisotropy formed in this manner is almost completely separated from the liquid crystal layer, and the liquid crystal molecules are considered to be aligned between these polymer networks.
- the molecular alignment structure of the so-called polymer network type liquid crystal, in which liquid crystal molecules and polymer networks coexist and cause light scattering when no voltage is applied, is clearly different from that of the alignment maintaining layer that is unevenly distributed in the vicinity of the alignment film used in PSA etc. It has a completely different structure.
- a polymer network and a liquid crystal molecule alignment structure by a method using an alignment film have been shown, but even in a so-called MVA method having a structure such as a rib or a slit, a polymer network or liquid crystal molecule pretilt in the vicinity of the substrate interface is It is only slightly different depending on the intensity of the oblique electric field applied through the structure or slit, and it is presumed that the structure essentially has the structure shown in the above figure.
- the anchoring force for the liquid crystal molecules when no voltage is applied is due to the synergistic action of the anchoring force of the liquid crystal alignment film and the polymer network.
- FIG. 11 is a plan view schematically showing a minimum unit structure in one pixel PX of a TFT liquid crystal display element using the above technique.
- the structure and operation of the horizontal / diagonal electric field mode liquid crystal display device will be briefly described below.
- the pixel electrode PE has a main pixel electrode PA and a sub-pixel electrode PB.
- the main pixel electrode PA and the sub-pixel electrode PB are electrically connected to each other, and both the main pixel electrode PA and the sub-pixel electrode PB are provided on the array substrate AR.
- the main pixel electrode PA extends along the second direction Y, and the subpixel electrode PB extends along the first direction X different from the second direction Y.
- the pixel electrode PE is formed in a substantially cross shape.
- the sub-pixel electrode PB is coupled to a substantially central portion of the main pixel electrode PA, and extends from the main pixel electrode PA toward both sides thereof, that is, the left side and the right side of the pixel PX.
- the main pixel electrode PA and the sub pixel electrode PB are substantially orthogonal to each other.
- the pixel electrode PE is electrically connected to a switching element (not shown) in the pixel electrode PB.
- the common electrode CE has a main common electrode CA and a sub-common electrode CB, and the main common electrode CA and the sub-common electrode CB are electrically connected to each other.
- the common electrode CE is electrically insulated from the pixel electrode PE.
- at least a part of the main common electrode CA and the sub-common electrode CB is provided on the counter substrate CT.
- the main common electrode CA extends along the second direction Y.
- the main common electrode CA is disposed on both sides of the main pixel electrode PA. At this time, none of the main common electrodes CA overlaps with the main pixel electrode PA in the XY plane, and a substantially equal interval is formed between each of the main common electrodes CA and the main pixel electrode PA. Yes.
- the main pixel electrode PA is located approximately in the middle of the adjacent main common electrode CA.
- the sub-common electrode CB extends along the first direction X.
- the sub-common electrode CB is disposed on both sides of the sub-pixel electrode PB.
- none of the sub-common electrodes CB overlaps the sub-pixel electrode PB in the XY plane, and a substantially equal interval is formed between each of the sub-common electrodes CB and the sub-pixel electrode PB.
- the sub-pixel electrode PB is located approximately in the middle of the adjacent sub-common electrode CB.
- the main common electrode CA is formed in a strip shape extending linearly along the second direction Y.
- the sub-common electrode CB is formed in a strip shape extending linearly along the first direction X.
- the two main common electrodes CA are arranged in parallel at intervals along the first direction X.
- the main common electrode on the left side in the drawing is referred to as CAL.
- the right main common electrode is called CAR.
- the two sub-common electrodes CB are arranged in parallel along the second direction Y at intervals, and in the following, in order to distinguish these, the upper main common electrode in the drawing is referred to as CBU.
- the lower main common electrode is called CBB.
- the main common electrode CAL and the main common electrode CAR are at the same potential as the sub-common electrode CBU and the sub-common electrode CBB.
- the main common electrode CAL and the main common electrode CAR are connected to the sub-common electrode CBU and the sub-common electrode CBB, respectively.
- the main common electrode CAL and the main common electrode CAR are respectively disposed between the pixel PX and the adjacent pixels on the left and right. That is, the main common electrode CAL is disposed across the boundary between the illustrated pixel PX and the left pixel (not shown), and the main common electrode CAR is the illustrated pixel PX and the right pixel (not shown). ).
- the sub-common electrode CBU and the main common electrode CBB are disposed between pixels adjacent to the pixel PX in the vertical direction. That is, the sub-common electrode CBU is disposed across the boundary between the illustrated pixel PX and the upper pixel (not illustrated), and the sub-common electrode CBB is illustrated with the illustrated pixel PX and the lower pixel (not illustrated). Z)).
- the initial alignment direction of the liquid crystal molecules LM is a direction substantially parallel to the second direction Y.
- the first alignment film AL1 is disposed on the surface of the array substrate AR that faces the counter substrate CT, and extends over substantially the entire active area ACT.
- the first alignment film AL1 covers the pixel electrode PE and is also disposed on the second interlayer insulating film 13. Such a first alignment film AL1 is formed of a material exhibiting horizontal alignment.
- the array substrate AR may further include a first main common electrode and a first sub-common electrode as part of the common electrode.
- FIG. 12 is a schematic diagram of an electrode structure of an eight-division oblique electric field mode liquid crystal cell. In this way, a wider viewing angle can be realized by dividing one pixel into eight.
- the operation of the liquid crystal display panel having the above configuration will be described.
- the liquid crystal molecules LM of LQ are aligned such that the major axis thereof faces the first alignment processing direction PD1 of the first alignment film AL1 and the second alignment processing direction PD2 of the second alignment film AL2.
- Such OFF time corresponds to the initial alignment state
- the alignment direction of the liquid crystal molecules LM at the OFF time corresponds to the initial alignment direction.
- the liquid crystal molecules LM are not always aligned parallel to the XY plane, and are often pretilted. Therefore, the strict initial alignment direction of the liquid crystal molecules LM is a direction obtained by orthogonally projecting the alignment direction of the liquid crystal molecules LM at the OFF time on the XY plane.
- the first alignment treatment direction PD1 and the second alignment treatment direction PD2 are both substantially parallel to the second direction Y.
- the liquid crystal molecules LM are initially aligned so that the major axis thereof is oriented in a direction substantially parallel to the second direction Y, as indicated by a broken line in FIG. That is, the initial alignment direction of the liquid crystal molecules LM is parallel to the second direction Y (or 0 ° with respect to the second direction Y).
- the liquid crystal molecules LM in the cross section of the liquid crystal layer LQ are substantially horizontal in the vicinity of the intermediate portion of the liquid crystal layer LQ. Alignment is performed with a pretilt angle of approximately zero, and alignment is performed with a pretilt angle that is symmetrical in the vicinity of the first alignment film AL1 and the vicinity of the second alignment film AL2 (spray alignment).
- the liquid crystal molecules LM in the vicinity of the first alignment film AL1 and the second alignment film in the direction inclined from the normal direction of the substrate are the liquid crystal molecules LM in the vicinity of AL2.
- the liquid crystal molecules LM are in the vicinity of the first alignment film AL1, in the second alignment film AL2 in the cross section of the liquid crystal layer LQ. And in the middle part of the liquid crystal layer LQ with a substantially uniform pretilt angle (homogeneous alignment). Part of the backlight light from the backlight 4 passes through the first polarizing plate PL1 and enters the liquid crystal display panel LPN.
- the light incident on the liquid crystal display panel LPN is linearly polarized light orthogonal to the first polarization axis AX1 of the first polarizing plate PL1.
- Such a polarization state of linearly polarized light hardly changes when it passes through the liquid crystal display panel LPN in the OFF state. Therefore, the linearly polarized light transmitted through the liquid crystal display panel LPN is absorbed by the second polarizing plate PL2 having a crossed Nicol positional relationship with the first polarizing plate PL1 (black display).
- the substrate is interposed between the pixel electrode PE and the common electrode CE.
- a horizontal electric field (or an oblique electric field) substantially parallel to the line is formed.
- the liquid crystal molecules LM are affected by the electric field and rotate in a plane whose major axis is substantially parallel to the XY plane as indicated by the solid line in the figure.
- the liquid crystal molecules LM in the lower half of the region between the pixel electrode PE and the main common electrode CAL rotate clockwise with respect to the second direction Y in the drawing.
- the liquid crystal molecules LM in the upper half region rotate counterclockwise with respect to the second direction Y and are oriented so as to face the upper left in the figure.
- the liquid crystal molecules LM in the lower half region rotate counterclockwise with respect to the second direction Y and face the lower right in the drawing.
- the liquid crystal molecules LM in the upper half region are aligned so as to rotate clockwise with respect to the second direction Y and to face the upper right in the drawing.
- each pixel PX in the state where an electric field is formed between the pixel electrode PE and the common electrode CE, the alignment direction of the liquid crystal molecules LM is divided into a plurality of directions with the position overlapping the pixel electrode PE as a boundary. , A domain is formed in each orientation direction. That is, a plurality of domains are formed in one pixel PX.
- linearly polarized light orthogonal to the first polarization axis AX1 of the first polarizing plate PL1 is incident on the liquid crystal display panel LPN, and the polarization state is the alignment of the liquid crystal molecules LM when passing through the liquid crystal layer LQ. It changes according to the state.
- the second polarizing plate PL2 (white display). According to such a structure, since four domains can be formed in one pixel, viewing angles in the four directions can be optically compensated, and a wide viewing angle can be achieved.
- liquid crystal display device with high display quality, which can realize display with high transmittance without gradation inversion. Further, by setting the area of the opening portion to be substantially the same for each of the four regions partitioned by the pixel electrode PE and the common electrode CE within one pixel, the transmittance of each region becomes substantially equal, The light transmitted through the part optically compensates for each other, and a uniform display can be realized over a wide viewing angle range.
- Example 1 97% of N-type liquid crystal composition (LCN-1), 2.94% of polymerizable compound (V1) and 0.06% of photopolymerization initiator No. 1 shown in Table 10 below (photopolymerization with these polymerizable compounds) Polymeric composition 3%) was mixed as a mixture of initiators to prepare composition 1.
- the pretilt angle is 1 ° to 2 ° with respect to the normal direction of the substrate.
- a rubbing alignment treatment was performed to produce a rubbing alignment cell with ITO.
- the composition 1 was heated to 60 ° C. to dissolve the solid polymerizable compound (V1).
- Composition 1 was confirmed that the polymerizable compound (V1) was uniformly dissolved at room temperature and showed a nematic liquid crystal phase with a polarizing microscope.
- the polymerizable liquid crystal composition 1 was heated to 60 ° C. and injected into the glass cell by a vacuum injection method.
- the glass cell was taken out and the inlet was sealed with a sealing agent 3026E (manufactured by ThreeBond).
- An ultraviolet ray having an irradiation intensity of 365 nm of 15 mW / cm 2 was irradiated for 300 seconds at 25 ° C. through an ultraviolet cut filter L-37 (manufactured by Hoya Candeo Optronics) to polymerize the polymerizable compound of the polymerizable liquid crystal composition. .
- a VA mode liquid crystal display element in which a phase separation structure was formed in the entire cell was obtained.
- the cell prepared between two orthogonal polarizing plates When the cell prepared between two orthogonal polarizing plates is placed, it becomes black and the dark field does not change even if the cell is rotated in the azimuth direction, and the optical axis direction of the polymer network and the liquid crystal alignment easy axis direction are the same direction. It was confirmed. Further, it was confirmed from the retardation measurement that the liquid crystal was aligned in a state where the pretilt angle was 2 ° with respect to the normal spring direction of the substrate. When a response time was measured by applying a rectangular wave of 60 Hz to the obtained VA mode liquid crystal display element, ⁇ off was 3.4 msec. The composition used for cell preparation was allowed to stand at 20 ° C. for 1 week, and it was confirmed that there was no crystallization due to the polymerizable compound.
- Examples 2 to 23, Comparative Examples 1 to 3 A VA mode liquid crystal display device was prepared in the same manner as in Example 1 except that the liquid crystal composition, the polymerizable compound, and the initiator were adjusted as shown in Table 1 below. Placing the prepared cell between two orthogonal polarizing plates using a polarizing microscope results in a dark field, and the black level of the dark field does not change even when the cell is rotated in the azimuth direction. It was confirmed that the optical axis direction of the liquid crystal composition and the easy axis direction of the liquid crystal composition were the same direction.
- the composition used for cell preparation was allowed to stand at 20 ° C. for 1 week, and it was confirmed that there was no crystallization due to the polymerizable compound.
- a 60 Hz rectangular wave was applied to the obtained VA mode liquid crystal display element, and the response time was measured.
- the results are shown in Table 1.
- ⁇ off was slow because it did not contain a polymerizable composition and an initiator.
- Comparative Example 2 the content of the polymerizable composition is low and a photopolymerization initiator having a maximum absorption wavelength peak at 310 nm to 380 nm is not used, so that a polymer network structure cannot be formed efficiently and ⁇ off is slow. It was.
- Comparative Example 3 the liquid crystal composition was cured during the cell formation process, and ⁇ off could not be measured.
- the content of the polymerizable composition was 1% to 40%, and ⁇ off was improved because a photopolymerization initiator having a maximum absorption wavelength peak at 310 nm to 380 nm was used.
- Examples 24 to 25, Comparative Examples 4 to 5 A VA mode liquid crystal display device was prepared in the same manner as in Example 1 except that the liquid crystal composition, the polymerizable compound, and the photopolymerization initiator were adjusted as shown in Table 2 below. Placing the prepared cell between two orthogonal polarizing plates using a polarizing microscope results in a dark field, and the black level of the dark field does not change even when the cell is rotated in the azimuth direction. It was confirmed that the optical axis direction of the liquid crystal composition and the easy axis direction of the liquid crystal composition were the same direction. The composition used for cell preparation was allowed to stand at 20 ° C. for 1 week, and it was confirmed that there was no crystallization due to the polymerizable compound. A 60 Hz rectangular wave was applied to the obtained VA mode liquid crystal display element, and the response time was measured. The results are shown in Table 2.
- Comparative Example 4 ⁇ off was slow because it did not contain a polymerizable composition and an initiator.
- Comparative Example 5 the content of the polymerizable composition is low and a photopolymerization initiator having a maximum absorption wavelength peak at 310 nm to 380 nm is not used, so that a polymer network structure cannot be formed efficiently and ⁇ off is slow. It was.
- the content of the polymerizable composition was 1% to 40%, and a photopolymerization initiator having a maximum absorption wavelength peak at 310 nm to 380 nm was used, so ⁇ off was improved.
- Examples 26 to 27, Comparative Examples 6 to 7 A VA mode liquid crystal display device was prepared in the same manner as in Example 1 except that the liquid crystal composition, the polymerizable compound, and the photopolymerization initiator were adjusted as shown in Table 3 below. Placing the prepared cell between two orthogonal polarizing plates using a polarizing microscope results in a dark field, and the black level of the dark field does not change even when the cell is rotated in the azimuth direction. It was confirmed that the optical axis direction of the liquid crystal composition and the easy axis direction of the liquid crystal composition were the same direction. The composition used for cell preparation was allowed to stand at 20 ° C. for 1 week, and it was confirmed that there was no crystallization due to the polymerizable compound. A 60 Hz rectangular wave was applied to the obtained VA mode liquid crystal display element, and the response time was measured. The results are shown in Table 3.
- Comparative Example 6 ⁇ off was slow because it did not contain a polymerizable composition and an initiator.
- Comparative Example 7 the content of the polymerizable composition was low and a photopolymerization initiator having a maximum absorption wavelength peak at 310 nm to 380 nm was not used, so that a polymer network structure could not be formed efficiently and ⁇ off was slow. .
- the content of the polymerizable composition was 1% to 40%, and ⁇ off was improved because a photopolymerization initiator having a maximum absorption wavelength peak at 310 nm to 380 nm was used.
- Examples 28 to 29, Comparative Examples 8 to 9 A VA mode liquid crystal display device was prepared in the same manner as in Example 1 except that the liquid crystal composition, the polymerizable compound, and the photopolymerization initiator were adjusted as shown in Table 4 below. Placing the prepared cell between two orthogonal polarizing plates using a polarizing microscope results in a dark field, and the black level of the dark field does not change even when the cell is rotated in the azimuth direction. It was confirmed that the optical axis direction of the liquid crystal composition and the easy axis direction of the liquid crystal composition were the same direction. The composition used for cell preparation was allowed to stand at 20 ° C. for 1 week, and it was confirmed that there was no crystallization due to the polymerizable compound.
- a 60 Hz rectangular wave was applied to the obtained VA mode liquid crystal display element, and the response time was measured.
- the results are shown in Table 4.
- ⁇ off was slow because it did not contain a polymerizable composition and an initiator.
- the content of the polymerizable composition was low, and a photopolymerization initiator having a maximum absorption wavelength peak at 310 to 380 nm was not used, so that a network structure could not be formed efficiently and ⁇ off was slow.
- the liquid crystal composition was cured during the cell formation process and ⁇ off could not be measured.
- the content of the polymerizable composition was 1% to 40%, and the absorption wavelength maximum peak ⁇ off was improved due to the use of a photopolymerization initiator having a thickness of 310 nm to 380 nm.
- Examples 30 to 36, Comparative Examples 10 to 11 An ECB mode liquid crystal display device was prepared in the same manner as in Example 1 except that the liquid crystal composition, the polymerizable compound, and the photopolymerization initiator were adjusted as shown in Table 5 below. Placing the prepared cell between two orthogonal polarizing plates using a polarizing microscope results in a dark field, and the black level of the dark field does not change even when the cell is rotated in the azimuth direction. It was confirmed that the optical axis direction of the liquid crystal composition and the easy axis direction of the liquid crystal composition were the same direction. The composition used for cell preparation was allowed to stand at 20 ° C. for 1 week, and it was confirmed that there was no crystallization due to the polymerizable compound.
- a 60 Hz rectangular wave was applied to the obtained VA mode liquid crystal display element, and the response time was measured.
- the results are shown in Table 5.
- ⁇ off was slow because it did not contain a polymerizable composition and an initiator.
- Comparative Example 11 since the content of the polymerizable composition was low and a photopolymerization initiator having a maximum absorption wavelength peak at 310 to 380 nm was not used, a network structure could not be formed efficiently and ⁇ off was slow.
- the content of the polymerizable composition was set to 1% to 40%, and a photopolymerization initiator having a maximum absorption wavelength peak at 310 nm to 380 nm was used, so ⁇ off was improved.
- Examples 37 to 39 A VA mode liquid crystal display device was prepared in the same manner as in Example 1 except that the liquid crystal composition, the polymerizable compound, and the photopolymerization initiator were adjusted as shown in Table 6 below. Placing the prepared cell between two orthogonal polarizing plates using a polarizing microscope results in a dark field, and the black level of the dark field does not change even when the cell is rotated in the azimuth direction. It was confirmed that the optical axis direction of the liquid crystal composition and the easy axis direction of the liquid crystal composition were the same direction. The composition used for cell preparation was allowed to stand at 20 ° C. for 1 week, and it was confirmed that there was no crystallization due to the polymerizable compound.
- a rectangular wave of 60 Hz was applied to the obtained VA mode liquid crystal display element, and the response time was measured.
- the results are shown in Table 6.
- the content of the polymerizable composition was set to 1% to 40%, and a photopolymerization initiator having a maximum absorption wavelength peak at 310 nm to 380 nm was used. Therefore, in all Examples, ⁇ off was improved. .
- Examples 40 to 41 A VA mode liquid crystal display device was prepared in the same manner as in Example 1 except that the liquid crystal composition, the polymerizable compound, and the photopolymerization initiator were adjusted as shown in Table 7 below. Placing the prepared cell between two orthogonal polarizing plates using a polarizing microscope results in a dark field, and the black level of the dark field does not change even when the cell is rotated in the azimuth direction. It was confirmed that the optical axis direction of the liquid crystal composition and the easy axis direction of the liquid crystal composition were the same direction. The composition used for cell preparation was allowed to stand at 20 ° C. for 1 week, and it was confirmed that there was no crystallization due to the polymerizable compound.
- a rectangular wave of 60 Hz was applied to the obtained VA mode liquid crystal display element, and the response time was measured.
- the results are shown in Table 7.
- the content of the polymerizable composition was set to 1% to 40%, and a photopolymerization initiator having a maximum absorption wavelength peak at 310 nm to 380 nm was used. Therefore, ⁇ off was improved in all examples. did.
- Examples 42 to 45, Comparative Examples 12 to 13 The liquid crystal composition, the polymerizable compound, and the photopolymerization initiator were adjusted as shown in Table 8 below, and the VA mode was applied in the same manner as in Example 1 except that a 100 Hz rectangular wave was applied as shown in Table 8 below during UV irradiation.
- a liquid crystal display element was prepared.
- the composition used for cell preparation was allowed to stand at 20 ° C. for 1 week, and it was confirmed that there was no crystallization by the polymerizable compound.
- the pretilt angle from the normal direction of the fabricated cell was measured using RET-100 (Otsuka Electronics). The results are shown in Table 7. In Comparative Example 12, a pretilt induced by the alignment film was given.
- Examples 41 to 45 a photopolymerization initiator having a maximum absorption wavelength peak at 310 to 380 nm was used, and a voltage was applied during UV irradiation to give a larger pretilt angle compared to Comparative Example 12.
- Example 46 Comparative Example 14
- Example 46 A VA mode liquid crystal cell in the same manner as in Example 1 except that the liquid crystal composition, the polymerizable compound, and the photopolymerization initiator were adjusted as shown in Table 9 below, and the UV irradiation wavelength was changed to 365 nm and 254 nm without using a filter.
- the voltage holding ratio of the obtained cell was measured at 60 ° C., 0.6 Hz, and 1V.
- the results are shown in Table 9.
- the photopolymerization initiator of the present invention was not used, the composition could not be sufficiently cured by UV irradiation at a relatively long wavelength of 365 nm, as can be seen from Comparative Example 2, and ⁇ off was slow.
- Example 14 since the photopolymerization initiator that is not the photopolymerization initiator of the present invention is used, UV irradiation with a short wavelength of 254 nm is necessary to sufficiently cure the composition, and the voltage holding ratio (VHR) ) Has fallen.
- Example 46 since the content of the polymerizable composition was 1% to 40% and the photopolymerization initiator having the maximum absorption wavelength peak at 310 nm to 380 nm was used, ⁇ off was improved and the voltage holding ratio was improved. (VHR) also maintained a high value.
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Abstract
Description
FLCの内、FLCとモノマーの混合物からなるPolymer Stabilized V shaped-FLC(PSV-FLC)素子は、強誘電性液晶内に微細なポリマーネットワークを形成したものであり、FLCの特長である高速応答性のほかに中間階調表示が可能であり、また耐衝撃性も従来のFLCに比較して向上している(例えば、特許文献1参照。)。
[1] 少なくとも一方に電極を有する2枚の透明基板間に挟持した1種又は2種以上の液晶化合物を含有する液晶組成物中に、1種又は2種以上の重合性化合物と吸収波長の極大ピークが310nm~380nmに存在する光重合開始剤を含有する重合性組成物の硬化物である重合体又は共重合体を含み、該重合性組成物と該液晶組成物の全重量中の該重合性組成物の含有量が1質量%以上40質量%未満である液晶表示素子。
[2]該液晶組成物中の該重合体又は共重合体がポリマーネットワークを形成し、透明基板上に液晶組成物を配向させるための配向層を有する前記[1]記載の液晶表示素子。
[3]該ポリマーネットワークが一軸性の屈折率異方性を有し、該ポリマーネットワークの光軸方向又は配向容易軸方向と該液晶組成物の配向容易軸方向が同一方向である前記[2]記載に記載の液晶表示素子。
[4]透明基板の法線方向に対して該液晶組成物が0~90°のプレチルト角をなしている前記[1]~[3]のいずれかに記載の液晶表示素子。
[5]セル断面方向に対して少なくともセル厚の0.5%以上の厚さのポリマーネットワーク層が形成されている前記[2]~[5]のいずれかに記載の液晶表示素子。
[6]透明基板の法線方向に対して該ポリマーネットワークの光軸方向又は配向容易軸方向が0.1°~30°のプレチルト角をなしている前記[2]~[5]のいずれかに記載の液晶表示素子。
[7]重合性化合物として、下記一般式(P)で表される化合物から選ばれる1種又は2種以上の化合物を含有する前記[1]~[6]のいずれかに記載の液晶表示素子。
Rp1及びRp2はそれぞれ独立して以下の式(R-I)から式(R-IX):
Spp1及びSpp2はスペーサー基を表し、Spp1及びSpp2はそれぞれ独立して、単結合、炭素原子数1~12のアルキレン基又は-O-(CH2)s-(式中、sは1~11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
Lp1及びLp2はそれぞれ独立して、単結合、-O-、-S-、-CH2-、-OCH2-、-CH2O-、-CO-、-C2H4-、-COO-、-OCO-、-OCOOCH2-、-CH2OCOO-、-OCH2CH2O-、-CO-NRa-、-NRa-CO-、-SCH2-、-CH2S-、-CH=CRa-COO-、-CH=CRa-OCO-、-COO-CRa=CH-、-OCO-CRa=CH-、-COO-CRa=CH-COO-、-COO-CRa=CH-OCO-、-OCO-CRa=CH-COO-、-OCO-CRa=CH-OCO-、-(CH2)z-C(=O)-O-、-(CH2)z-O-(C=O)-、-O-(C=O)-(CH2)z-、-(C=O)-O-(CH2)z-、-CH=CH-、-CF=CF-、-CF=CH-、-CH=CF-、-CF2-、-CF2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-又は-C≡C-(式中、Raはそれぞれ独立して水素原子又は炭素原子数1~4のアルキル基を表し、前記式中、zは1~4の整数を表す。)を表し、
Mp2は、1,4-フェニレン基、1,4-シクロヘキシレン基、アントラセン-2,6-ジイル基、フェナントレン-2,7-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ナフタレン-2,6-ジイル基、インダン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基又は1,3-ジオキサン-2,5-ジイル基を表すが、Mp2は無置換であるか又は炭素原子数1~12のアルキル基、炭素原子数1~12のハロゲン化アルキル基、炭素原子数1~12のアルコキシ基、炭素原子数1~12のハロゲン化アルコキシ基、ハロゲン原子、シアノ基、ニトロ基又は-Rp1で置換されていても良く、
Mp1は以下の式(i-11)~(ix-11):
Mp3は以下の式(i-13)~(ix-13):
mp2~mp4はそれぞれ独立して、0、1、2又は3を表し、mp1及びmp5はそれぞれ独立して1、2又は3を表すが、Zp1が複数存在する場合にはそれらは同一であっても異なっていてもよく、Rp1が複数存在する場合にはそれらは同一であっても異なっていてもよく、Rp2が複数存在する場合にはそれらは同一であっても異なっていてもよく、Spp1が複数存在する場合にはそれらは同一であっても異なっていてもよく、Spp2が複数存在する場合にはそれらは同一であっても異なっていてもよく、Lp1が複数存在する場合にはそれらは同一であっても異なっていてもよく、Mp2が複数存在する場合にはそれらは同一であっても異なっていてもよい。)
[8]液晶組成物として、下記一般式(LC)で表される液晶化合物を含有する前記[1]~[7]のいずれか1項に記載の液晶表示素子。
(a)トランス-1,4-シクロヘキシレン基(この基中に存在する1個のCH2基又は隣接していない2個以上のCH2基は酸素原子又は硫黄原子で置換されていてもよい。)、
(b)1,4-フェニレン基(この基中に存在する1個のCH基又は隣接していない2個以上のCH基は窒素原子で置換されていてもよい。)、
(c)1,4-ビシクロ(2.2.2)オクチレン基、ナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、又はクロマン-2,6-ジイル基。
ZLCは単結合、-CH=CH-、-CF=CF-、-C≡C-、-CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-OCF2-、-CF2O-、-COO-又は-OCO-を表す。
YLCは、水素原子、フッ素原子、塩素原子、シアノ基、及び炭素原子数1~15のアルキル基を表す。該アルキル基中の1つ又は2つ以上のCH2基は、酸素原子が直接隣接しないように、-O-、-CH=CH-、-CO-、-OCO-、-COO-、-C≡C-、-CF2O-、-OCF2-で置換されてよく、該アルキル基中の1つ又は2つ以上の水素原子は任意にハロゲン原子によって置換されていてもよい。
aは1~4の整数を表す。aが2、3又は4を表し、一般式(LC)中にALC1が複数存在する場合、複数存在するALC1は、同一であっても異なっていてもよく、ZLCが複数存在する場合、複数存在するZLCは、同一であっても異なっていてもよい。)
[9]液晶組成物中の光重合開始剤の含有量が0.001~1%である前記[1]~[8]のいずれかに記載の液晶表示素子
[10]セル構造がVAモード、IPSモード、FFSモード、VA-TNモード、TNモード、ECBモードである前記[1]~[9]に記載の液晶表示素子。
[11]少なくとも一方に電極を有する2枚の透明基板間に挟持した1種又は2種以上の液晶化合物を含有する液晶組成物と、1種又は2種以上の重合性化合物と、吸収波長の極大ピークが310nm~380nmに存在する光重合開始剤とを含有する重合性組成物を含み、該重合性組成物と該液晶組成物の全重量中の該重合性組成物の含有量が1質量%以上40質量%未満である組成物中の重合性化合物をエネルギー線を照射することにより重合してなる液晶表示素子。
[12]該組成物中の重合性化合物を、-50℃~30℃の温度にてエネルギー線を照射することにより重合してなる前記[11]に記載の液晶表示素子。
[13]該組成物中の重合性化合物を、エネルギー線照射前の透明基板の法線方向に対するプレチルト角が0.1~30°になるような電圧を印加しながらエネルギー線を照射することにより重合してなる前記[11]又は[12]に記載の液晶表示素子。
[液晶化合物]
本発明に用いられる液晶組成物としては、一般式(LC)で表される液晶化合物を含有することが好ましい。
(a)トランス-1,4-シクロヘキシレン基(この基中に存在する1個のCH2基又は隣接していない2個以上のCH2基は酸素原子又は硫黄原子で置換されていてもよい。)、
(b)1,4-フェニレン基(この基中に存在する1個のCH基又は隣接していない2個以上のCH基は窒素原子で置換されていてもよい。)、
(c)1,4-ビシクロ(2.2.2)オクチレン基、ナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、又はクロマン-2,6-ジイル基。
一般式(LC1)又は(LC2)中、ALC11及びALC21はそれぞれ独立して下記の何れかの構造を表す。該構造中、シクロヘキシレン基中の1つ又は2つ以上のCH2基は酸素原子で置換されていてもよく、1,4-フェニレン基中の1つ又は2つ以上のCH基は窒素原子で置換されていてもよく、また、該構造中の1つ又は2つ以上の水素原子はフッ素原子、塩素原子、-CF3又は-OCF3で置換されていてもよい。
で表される化合物からなる群より選ばれる化合物を一種又は二種以上含むことが好ましい。
ALC31~ALC52はそれぞれ独立して下記の構造が好ましく、
一般式(LC4-1)で表される化合物は具体的には次に記載する一般式(LC4-11)~一般式(LC4-14)で表される化合物が好ましい。
一般式(LC5-1)で表される化合物は具体的には次に記載する一般式(LC5-11)~一般式(LC5-14)で表される化合物が好ましい。
一般式(LC3-11)、一般式(LC3-13)、一般式(LC4-11)、一般式(LC4-13)、一般式(LC5-11)、及び一般式(LC5-13)において、R31~R33は、一般式(LC3-1)~一般式(LC5-1)における同様の実施態様が好ましい。R41a~R41c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。
で表される化合物群から選ばれる化合物を少なくとも1種含有することが好ましい。
一般式(LC4-2)で表される化合物は具体的には次に記載する一般式(LC4-21)~一般式(LC4-26)で表される化合物が好ましい。
一般式(LC5-2)で表される化合物は具体的には次に記載する一般式(LC5-21)~一般式(LC5-26)で表される化合物が好ましい。
一般式(LC3-21)、一般式(LC3-22)、一般式(LC3-25)、一般式(LC4-21)、一般式(LC4-22)、一般式(LC4-25)、一般式(LC5-21)、一般式(LC5-22)、及び一般式(LC5-25)において、R51~R53は、一般式(LC3-2)、一般式(LC4-2)及び一般式(LC5-2)における同様の実施態様が好ましい。R61a~R63a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。
RLC31及びRLC32はそれぞれ独立して、炭素原子数1~7のアルキル基、炭素原子数1~7のアルコキシ基、炭素原子数2~7のアルケニル基が好ましく、RLC31が炭素原子数1~7のアルキル基を表し、RLC32が炭素原子数1~7のアルコキシ基を表すことがより好ましい。
RLC31及びRLC32はそれぞれ独立して、炭素原子数1~7のアルキル基、炭素原子数1~7のアルコキシ基、炭素原子数2~7のアルケニル基が好ましく、RLC31が炭素原子数2又は3のアルキル基を表し、RLC32が炭素原子数2のアルキル基を表すことがより好ましい。
RLC41、RLC42、RLC51及びRLC52はそれぞれ独立して炭素原子数1~7のアルキル基、炭素原子数1~7のアルコキシ基、炭素原子数2~7のアルケニル基又は炭素原子数2~7のアルケニルオキシ基を表すことが好ましい。
一般式(LC6)中、ALC61~ALC63はそれぞれ独立して下記の何れかの構造を表す。該構造中、シクロヘキシレン基中の1つ又は2つ以上のCH2CH2基は-CH=CH-、-CF2O-、-OCF2-で置換されていてもよく、1,4-フェニレン基中1つ又は2つ以上のCH基は窒素原子で置換されていてもよい。
本発明に係る重合性化合物としては、一つの反応性基を有する単官能性の重合性化合物、及び二官能又は三官能等の二つ以上の反応性基を有する多官能性の重合性化合物が挙げられる。反応性基を有する重合性化合物はメソゲン性部位を含んでいても、含んでいなくてもよい。
Rp1及びRp2はそれぞれ独立して以下の式(R-I)から式(R-IX):
Spp1及びSpp2はスペーサー基を表し、Spp1及びSpp2はそれぞれ独立して、単結合、炭素原子数1~12のアルキレン基又は-O-(CH2)s-(式中、sは1~11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
Lp1及びLp2はそれぞれ独立して、単結合、-O-、-S-、-CH2-、-OCH2-、-CH2O-、-CO-、-C2H4-、-COO-、-OCO-、-OCOOCH2-、-CH2OCOO-、-OCH2CH2O-、-CO-NRa-、-NRa-CO-、-SCH2-、-CH2S-、-CH=CRa-COO-、-CH=CRa-OCO-、-COO-CRa=CH-、-OCO-CRa=CH-、-COO-CRa=CH-COO-、-COO-CRa=CH-OCO-、-OCO-CRa=CH-COO-、-OCO-CRa=CH-OCO-、-(CH2)z-C(=O)-O-、-(CH2)z-O-(C=O)-、-O-(C=O)-(CH2)z-、-(C=O)-O-(CH2)z-、-CH=CH-、-CF=CF-、-CF=CH-、-CH=CF-、-CF2-、-CF2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-又は-C≡C-(式中、Raはそれぞれ独立して水素原子又は炭素原子数1~4のアルキル基を表し、前記式中、zは1~4の整数を表す。)を表し、
Mp2は、1,4-フェニレン基、1,4-シクロヘキシレン基、アントラセン-2,6-ジイル基、フェナントレン-2,7-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ナフタレン-2,6-ジイル基、インダン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基又は1,3-ジオキサン-2,5-ジイル基を表すが、Mp2は無置換であるか又は炭素原子数1~12のアルキル基、炭素原子数1~12のハロゲン化アルキル基、炭素原子数1~12のアルコキシ基、炭素原子数1~12のハロゲン化アルコキシ基、ハロゲン原子、シアノ基、ニトロ基又は-Rp1で置換されていても良く、
Mp1は以下の式(i-11)~(ix-11):
Mp3は以下の式(i-13)~(ix-13):
mp2~mp4はそれぞれ独立して、0、1、2又は3を表し、mp1及びmp5はそれぞれ独立して1、2又は3を表すが、Zp1が複数存在する場合にはそれらは同一であっても異なっていてもよく、Rp1が複数存在する場合にはそれらは同一であっても異なっていてもよく、Rp2が複数存在する場合にはそれらは同一であっても異なっていてもよく、Spp1が複数存在する場合にはそれらは同一であっても異なっていてもよく、Spp2が複数存在する場合にはそれらは同一であっても異なっていてもよく、Lp1が複数存在する場合にはそれらは同一であっても異なっていてもよく、Mp2が複数存在する場合にはそれらは同一であっても異なっていてもよい。)で表される化合物で表されることが好ましい。また、当該重合性化合物は1種又は2種以上含有することが好ましい。
環Aおよび環Bはそれぞれ独立して、1,4-フェニレン基、1,4-シクロヘキシレン基、アントラセン-2,6-ジイル基、フェナントレン-2,7-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ナフタレン-2,6-ジイル基、インダン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基又は1,3-ジオキサン-2,5-ジイル基を表すが、無置換であるか又は炭素原子数1~12のアルキル基、炭素原子数1~12のハロゲン化アルキル基、炭素原子数1~12のアルコキシ基、炭素原子数1~12のハロゲン化アルコキシ基、ハロゲン原子、シアノ基、ニトロ基又は-Rp1で置換されていていることが好ましく、
環Cは以下の式(c-i)~(c-ix):
Spp1及びSpp4はスペーサー基を表し、Xp1~Xp4は、それぞれ独立して、水素原子またはハロゲン原子を表すことが好ましく、
Lp4、Lp5およびLp6はそれぞれ独立して、単結合、-OCH2-、-CH2O-、-CO-、-C2H4-、-COO-、-OCO-、-COOC2H4-、-OCOC2H4-、-C2H4OCO-、-C2H4COO-、-CH=CH-、-CF2-、-CF2O-、-(CH2)z-C(=O)-O-、-(CH2)z-O-(C=O)-、-O-(C=O)-(CH2)z-、-(C=O)-O-(CH2)z-、-O-(CH2)z-O-、-OCF2-、-CH=CHCOO-、-COOCH=CH-、-OCOCH=CH-又は-C≡C-であることが好ましく、前記式中のzは、1~4の整数であることが好ましい。
本発明に係る一般式(P-d)で表される化合物の好ましい例として、下記式(P-d-1)~式(P-d-31)で表される重合性化合物が挙げられる。
で表されるが、本願発明の液晶組成物が重合性モノマーを含有する場合は、式(ii)および式(iv)で表される構造が好ましく、式(ii)で表される構造がより好ましい。なお、本明細書中において、アルケニル基の例は共通であり、各々のアルケニル基の炭素原子数の数によって適宜上記例示から選択される。
A2は単結合又は炭素原子数1~8のアルキレン基(該アルキレン基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよく、該アルキレン基中の1個又は2個以上の水素原子はそれぞれ独立してフッ素原子、メチル基又はエチル基で置換されていてもよい。)を表し、
A3及びA6はそれぞれ独立して水素原子、ハロゲン原子又は炭素原子数1~10のアルキル基(該アルキル基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよく、該アルキル基中の1個又は2個以上の水素原子は、それぞれ独立してハロゲン原子又は炭素原子数1~17のアルキル基で置換されていてもよい。)を表わし、
A4及びA7はそれぞれ独立して水素原子、ハロゲン原子又は炭素原子数1~10のアルキル基(該アルキル基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよく、該アルキル基中の1個又は2個以上の水素原子は、それぞれ独立してハロゲン原子又は炭素原子数1~9のアルキル基で置換されていてもよい。)を表し、
pは0~10を表し、
B1、B2及びB3は、それぞれ独立して水素原子、炭素原子数1~10の直鎖状若しくは分岐鎖状のアルキル基(該アルキル基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよく、該アルキル基中の1個又は2個以上の水素原子は、それぞれ独立してハロゲン原子又は炭素原子数3~6のトリアルコキシシリル基で置換されていてもよい。)を表わす化合物が挙げられる。
qは0又は1を表し、
Y1及びY2はそれぞれ独立して単結合、-CH2CH2-、-CH2O-、-OCH2-、-COO-、-OCO-、-C≡C-、-CH=CH-、-CF=CF-、-(CH2)4-、-CH2CH2CH2O-、-OCH2CH2CH2-、-CH=CHCH2CH2-又は-CH2CH2CH=CH-を表し、
Y3及びY4はそれぞれ独立して単結合、炭素原子数1~12のアルキレン基(該アルキレン基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよく、該アルキレン基中の1個又は2個以上の水素原子はそれぞれ独立してフッ素原子、メチル基又はエチル基で置換されていてもよい。)を表し、
B8は水素原子、シアノ基、ハロゲン原子又は炭素原子数1~8のアルキル基、又は、末端がアクリロイル基又はメタクリロイル基を有するアルキレン基を表す。)で表わす化合物も挙げられる。
Uが環構造を有する場合、前記Sp1及びSp2は少なくとも一方が-O-(CH2)s-(式中、sは1~7の整数を表し、酸素原子は芳香環に結合するものとする。)を表すことが好ましく、両方共に-O-(CH2)s-であることも好ましい。
上記一般式(Vb)において、X1及びX2は、はそれぞれ独立して、水素原子又はメチル基を表すが、いずれも水素原子を表すジアクリレート誘導体、又はいずれもメチル基を有するジメタクリレート誘導体が好ましく、一方が水素原子を表し、もう一方がメチル基を表す化合物も好ましい。これらの化合物の重合速度は、ジアクリレート誘導体が最も早く、ジメタクリレート誘導体が遅く、非対称化合物がその中間であり、その用途により好ましい態様を用いることができる。
上記一般式(V)で表される化合物としては、具体的には、以下の一般式(Vc)で表される化合物が、反応速度を高める点で好ましく、又、プレチルト角を熱的に安定化させるので好ましい。更に、必要に応じてSp1、Sp2及びSp3の炭素原子数を調整して所望のプレチルト角を得ることもできる。プレチルトと該炭素原子数の関係は、官能基が2個の場合と同様の傾向を示す。
重合性化合物として、光配向機能を有する化合物を用いることも好ましい。中でも、光異性化を示す化合物を用いることが好ましい。
X1及びX2がそれぞれ独立して、水素原子又はメチル基を表し、Sp1及びSp2がそれぞれ独立して、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1~7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が-N=N-を表し、Cが1,4-フェニレン基、トランス-1,4-シクロヘキシレン基(任意の水素原子がフッ素原子により置換されていてもよい。)又は単結合を表す化合物が好ましい。
[重合開始剤]
本発明に用いられる光重合開始剤は310nm~380nmに吸収波長の極大ピークが存在するものであるが、効率よく液晶組成物に含まれる重合性化合物を重合させてポリマーネットワークを形成する観点から、吸収波長の極大ピークの下限値が320nmであるものが好ましく、吸収波長の極大ピークの上限値が370nmであるものが好ましい。
また、製造した液晶表示素子の画質を低下させない観点から、電圧保持率(VHR)を低下させない重合開始剤を用いることが好ましい。好ましくは金属原子を有さない構造の重合開始剤をもちいることが好ましい。より好ましくは金属原子又はりん原子を有さない構造の重合開始剤を用いることが好ましい。さらに好ましくは炭素原子、水素原子、酸素原子からなる重合開始剤を用いることが好ましい。
また、製造した液晶表示素子の外観を確保する観点から、UV照射後にパネルを着色させない重合開始剤を用いることが好ましい。好ましくは金属原子を有さない構造の重合開始剤が好ましい。より好ましくは金属原子及びベンゾフェノン骨格を有さない構造の重合開始剤が好ましい。
本発明に用いられる光重合開始剤の含有量は0.001~1質量%が好ましく、0.005~0.5質量%が好ましく、0.008~0.3質量%が好ましい。
[重合性液晶組成物]
本発明に用いられる重合性液晶組成物は、上記に例示される液晶組成物と、上記に例示される1質量%以上10質量%未満の重合性化合物を含有することが好ましいが、重合性化合物の含有量の下限値は2質量%以上が好ましく、上限値は9質量%未満が好ましく、7質量%未満がより好ましく、5質量%未満がより好ましく、4質量%未満がより好ましい。また、本発明に用いられる重合性液晶組成物は、上記に例示される液晶組成物と、上記に例示される10質量%以上40質量%未満の重合性化合物を含有することも好ましいが、この場合の重合性化合物の含有量の下限値は9質量%以上が好ましく、10質量%以上がより好ましく、上限値は30%質量未満が好ましく、25%質量未満がより好ましく、20%質量未満がより好ましく、15%質量未満がより好ましい。更に、本発明に用いられる重合性液晶組成物は、上記に例示される液晶組成物と、上記に例示される5質量%以上15質量%未満の重合性化合物を含有することが好ましく、7質量%以上12%未満の重合性化合物を含有することがより好ましい。本発明に用いられる重合性液晶組成物は、1質量%以上40質量%未満の重合性化合物を含有することで、一軸性の光学異方性、又は一軸性の屈折率異方性又は配向容易軸方向を有するポリマーネットワークを形成するものであることが好ましく、該ポリマーネットワークの光学軸又は配向容易軸と低分子液晶の配向容易軸が略一致するように形成されていることがより好ましい。
何れの濃度に於いてもTgの異なる重合性化合物を少なくとも二種類以上含有させて必要に応じてTgを調整することが好ましい。Tgが高いポリマーの前駆体である重合性化合物は、架橋密度が高くなる分子構造を有する重合性化合物であって、官能基数が2以上であることが好ましい。又、Tgが低いポリマーの前駆体は、官能基数が1であるか、又は2以上であって、官能基間にスペーサとしてアルキレン基等を有し分子長を長くした構造であることが好ましい。ポリマーネットワークの熱的安定性や耐衝撃性向上に対応することを目的にポリマーネットワークのTgを調整する場合、多官能モノマーと単官能モノマーの比率を適宜調整することが好ましい。又、Tgはポリマーネットワークの主鎖、及び側鎖に於ける分子レベルの熱的な運動性とも関連しており、電気光学特性にも影響を及ぼしている。例えば、架橋密度を高くすると主鎖の分子運動性が下がり低分子液晶とのアンカーリング力が高まり駆動電圧が高くなると共に立下り時間が短くなる。一方、Tgが下がるように架橋密度を下げるとポリマー主鎖の熱運動性が上がることにより、低分子液晶とのアンカーリング力が下がり駆動電圧が下がり立下り時間が長くなる傾向を示す。ポリマーネットワーク界面に於けるアンカーリング力は、上述のTgの他にポリマー側鎖の分子運動性にも影響され、多価分岐アルキレン基、及び多価アルキル基を有する重合性化合物を用いることでポリマー界面のアンカーリング力が下げられる。又、多価分岐アルキレン基、及び多価アルキル基を有する重合性化合物は、プレチルト角を誘起させるのに有効で極角方向のアンカーリング力を下げる方向に作用する。
重合性液晶組成物が液晶相を示した状態で、重合性液晶組成物中の重合性化合物を重合させることにより、重合性化合物の分子量が増加して液晶組成物と重合性化合物を相分離させる。二相に分離する形態は、含有する液晶化合物の種類や重合性化合物の種類に大きく依存して異なる。液晶相中に重合性化合物相が無数に島状の核として発生して成長するバイノーダル分解で相分離構造を形成しても良く、液晶相と重合性化合物相との濃度の揺らぎから相分離するスピノーダル分解により相分離構造を形成しても良い。バイノーダル分解によるポリマーネットワークを形成させるには、少なくとも低分子液晶の含有量を85質量%以上にするのが好ましく、重合性化合物の反応速度が速い化合物を用いることにより可視光の波長より小さい大きさの重合性化合物の核を無数に発生させてナノオーダーの相分離構造が形成されるので好ましい。結果として重合性化合物相に於ける重合が進むと相分離構造に依存して可視光の波長より短い空隙間隔のポリマーネットワークが形成され、一方、ポリマーネットワークの空隙は低分子液晶相の相分離によるもので、この空隙の大きさが可視光の波長より小さいと、光散乱性が無く高コントラストで、且つポリマーネットワークからのアンカーリング力の影響が強まり立下り時間が短くなり高速応答の液晶表示素子が得られるようになり特に好ましい。バイノーダル分解に於ける重合性化合物相の核生成は、化合物の種類や組合せによる相溶性の変化や、反応速度、温度等のパラメーターに影響され適宜必要に応じて調整することが好ましい。反応速度は、紫外線重合の場合は、重合性化合物の官能基や光開始剤の種類及び含有量、紫外線露光強度によるもので反応性を促進するように紫外線露光条件を適宜調整すれば良く、少なくとも20mW/cm2以上の紫外線露光強度が好ましい。低分子液晶が85質量%以上では、スピノーダル分解による相分離構造でポリマーネットワークを形成させることが好ましい、スピノーダル分解では周期性のある二相の濃度の揺らぎによる相分離微細構造が得られるので可視光波長より小さい均一な空隙間隔を容易に形成するので好ましい。ポリマーネットワークで形成させることが好ましい。重合性化合物の割合が15質量%未満ではバイノーダル分解による相分離構造を形成させることが好ましく、15質量%以上ではスピノーダル分解による相分離構造を形成させることが好ましい。重合性化合物含有量が増加すると、温度の影響で低分子液晶相と重合性化合物相との二相分離する相転移温度が存在する。二相分離転移温度より高い温度では等方相を示すが、低いと分離が起こり均一な相分離構造が得られず好ましくない。温度により二相分離する場合は、二相分離温度より高い温度に於いて相分離構造を形成させることが好ましい。上述した何れの場合も、低分子液晶の配向状態と同様の配向状態を保持しながらポリマーネットワークが形成される。形成されたポリマーネットワークは、低分子液晶の配向に倣うように光学異方性を示す。ポリマーネットワーク中の液晶層の形態としては、ポリマーの3次元ネットワーク構造中に液晶組成物が連続層をなす構造、液晶組成物のドロップレットがポリマー中に分散している構造、又は両者が混在する構造、更に、両基板面を起点にポリマーネットワーク層が存在し、対面基板との中心付近では液晶層のみである構造が挙げられる。何れもの構造もポリマーネットワークの作用により0~90°のプレチルト角が液晶素子基板界面に対して誘起されていることが好ましい。形成するポリマーネットワークは、共存する低分子液晶を液晶セルの配向膜が示す配向方向へ配向させる機能を有することが好ましく、更に、ポリマー界面方向に対して低分子液晶をプレチルトさせる機能を有していることも好ましい。ポリマー界面に対して低分子液晶をプレチルトさせる重合性化合物を導入すると液晶素子の駆動電圧を低くさせるのに有用で好ましい。又、屈折率異方性を有しても良く、配向方向へ液晶を配向させる機能は、メソゲン基を有する重合性化合物を用いることが好ましい。
VAモード等の垂直配向セルに対しては垂直配向を誘起するメソゲン基を有しない多価アルキル基、又は多価分岐アルキレン基を有する重合性化合物を用いても良く、メソゲン基を有する重合性化合物との併用でも好ましい。上述の重合性液晶組成物を用いて相分離重合により垂直配向セル内にポリマーネットワークが形成された場合は、繊維状、又は柱状のポリマーネットワークが液晶セル基板に対して低分子液晶の垂直方向と略同一の方向に形成されていることが好ましい。又、セル基板表面にある垂直配向膜に液晶が傾斜配向を誘起するようにラビング処理等を施してプレチルト角を誘起するようにした垂直配向膜が用いられた場合は、プレチルトして配向している低分子液晶と同方向に繊維状、又は柱状のポリマーネットワークが傾斜して形成されていることが好ましい。
更に、電圧を印加しながらプレチルト角を誘起する方法では、重合性液晶組成物の閾値電圧よりも0.9V程度低い電圧から2V程度高い電圧の範囲で電圧を印加しながら重合させると繊維状、又は柱状のポリマーネットワークの光軸方向又は配向容易軸方向が所望のプレチルト角、好ましくは垂直配向の場合は、透明基板の法線方向に対して0.1~30°のプレチルト角を、水平配向の場合は、透明基板の水平方向に対して0.1~30°のプレチルト角を形成するのでより好ましくなる。何れの方法で形成された繊維状、又は柱状のポリマーネットワークは、二枚のセル基板間を連結していることが特徴である。これにより、プレチルト角の熱的安定性が向上して液晶表示素子の信頼性を高められる。
他に、繊維状、又は柱状のポリマーネットワークを傾斜配向させて形成することにより低分子液晶のプレチルト角を誘起させる方法として、官能基とメソゲン基の間にあるアルキレン基の炭素原子数が6以上のプレチルト角の誘起角度が小さい二官能アクリレートと官能基と、メソゲン基の間にあるアルキレン基の炭素原子数が5以上のプレチルト角の誘起角度が大きい二官能アクリレートを組合せ用いる方法が挙げられる。これらの化合物の配合比を調整することにより所望のプレチルト角を誘起させることができる。
更に、可逆性の光配向機能を有する重合性化合物を少なくとも0.01%以上1%以下の範囲で添加して繊維状、又は柱状のポリマーネットワークを形成させる方法が挙げられる。この場合、トランス体に於いて低分子液晶と同様の棒状の形態になり低分子液晶の配向状態へ影響を及ぼす。本発明の重合性液晶組成物に含有されている該トランス体は、紫外線をセル上面から平行光として露光すると紫外線の進む方向と該棒状の分子長軸方向が平行になるように揃い、低分子液晶も同時に該トランス体の分子長軸方向へ揃うように配向する。セルに対して傾斜して紫外線を露光すると、該トランス体の分子長軸が傾斜方向に向き液晶を紫外線の傾斜方向へ配向させるようになる。即ち、プレチルト角を誘起するようになり光配向機能を示す。この段階で重合性化合物を架橋させると誘起したプレチルト角が重合相分離で形成された繊維状、又は柱状のポリマーネットワークにより固定化される。従って、VAモードで重要なプレチルト角の誘起は、電圧印加しながら重合相分離させる方法、誘起するプレチルト角が異なる重合性化合物を複数添加して重合相分離させる方法、可逆性の光配向機能を有する重合性化合物が示す光配向機能を用いて紫外線が進む方向へ低分子液晶及び重合性液晶化合物を配向させ重合相分離する方法を必要に応じて用い本発明の液晶素子を作製することができる。
光配向機能を有する重合性化合物は、紫外線を吸収してトランス体になる光異性化合物であることが好ましく、更に、光配向機能を有する重合性化合物の反応速度が光配向機能を有する重合性化合物以外の重合性化合物の反応速度より遅いことが好ましい。UV露光されると、直ちに光配向機能を有する重合性化合物はトランス体になり光の進む方向に配向すると、周囲の重合性を含む液晶化合物も同様の方向へ配向する。この時、重合相分離が進行して低分子液晶長軸方向とポリマーネットワークの配向容易軸方向が光配向機能を有する重合性化合物の配向容易軸と同一方向へ揃いUV光が進む方向へプレチルト角が誘起される。
更に、IPSやFFSモード等の平行配向セルに於いては、重合性液晶組成物を用いて相分離重合により繊維状、又は柱状のポリマーネットワークが液晶セル基板面に有る配向膜の配向方向に対して低分子液晶は平行配向するが、形成された繊維状、又は柱状のポリマーネットワークの屈折率異方性又は配向容易軸方向と低分子液晶の配向方向と略同一の方向に形成されていることが好ましい。更に、繊維状、又は柱状のポリマーネットワークは、低分子液晶が分散している空隙を除いて略セル全体に存在していることがより好ましい。ポリマー界面方向に対して該プレチルト角を誘起させることを目的に、メソゲン基を有しない多価アルキル基、又は多価アルキレン基を有する重合性化合物とメソゲン基を有する重合性化合物を用いることが好ましい。
更に、電気光学特性は、ポリマーネットワーク界面の表面積、及びポリマーネットワークの空隙間隔に影響されるが、光散乱を起こさないことが重要で、平均空隙間隔を可視光の波長より小さくすることが好ましい。例えば、該界面の表面積を広げて該空隙間隔を小さくさせるにはモノマー組成物含有量を増加させる方法がある。これにより、重合相分離構造が変化して該空隙間隔が微細になることにより該界面の表面積が増加するようにポリマーネットワークが形成され駆動電圧、及び立ち下がり時間が短くなる。重合相分離構造は、重合温度にも影響される。
本発明に於いては、相分離速度を速くして重合させることで微細な空隙を有する相分離構造が得られるようにすることが好ましい。相分離速度は、低分子液晶と重合性化合物との相溶性や重合速度に大きく影響される。化合物の分子構造や含有量に大きく依存するので適宜組成を調整して使用することが好ましい。該相溶性が高い場合は、該重合速度の高い重合性化合物を用いることが好ましく、紫外線重合の場合は、紫外線強度を高めることが好ましい。又、重合性液晶組成物中の重合性化合物の含有量を増やすことも好ましい。相溶性が低い場合は、相分離速度は十分に速くなるので本発明の液晶素子を作製するのに好ましい。相溶性を低くする方法として、低温で重合させる方法が挙げられる。低温にすると液晶の配向秩序度が上がり、液晶とモノマーの相溶性が下がるため、重合相分離速度を速くすることができる。更に別の方法として、重合性液晶組成物を過冷却状態を示す温度にして重合させる方法も挙げられる。この場合、重合性液晶組成物の融点よりも僅かに低くすれば良いので、数度温度を低くするだけで相分離を速くさせることも可能になり好ましい。これらにより、モノマー組成物含有量数十%を液晶へ添加した場合に相当する重合相分離構造、即ち、立ち下がり時間が短くなるように作用する構造であるポリマーネットワーク界面の表面積が多く該空隙間隔が微細なポリマーネットワーク構造が形成される。従って、本発明の重合性液晶組成物は、立ち下がり時間が短くなるように配向機能、架橋密度、アンカーリング力、空隙間隔、を考慮して重合性液晶組成を適宜調整することが好ましい。
本発明の重合性液晶組成物を用いた液晶素子において、高いコントラストの表示を得るには光散乱が起こらないようにする必要があるが、上述した方法を考慮して目的の電圧-透過率特性、及びスイッチング特性を得られるように相分離構造を制御して適切なポリマーネットワーク層構造を形成させることが重要である。ポリマーネットワーク層構造を具体的に説明すると次のようになる。
<ポリマーネットワーク層連続構造>
液晶相中に液晶表示素子全面にポリマーネットワーク層が形成され液晶相が連続している構造であって、ポリマーネットワークの配向容易軸や一軸の光学軸が低分子液晶の配向容易軸と略同一方向であることが好ましく、低分子液晶のプレチルト角を誘起するようにポリマーネットワークを形成させることが好ましい。また、光散乱を起こらなくさせるために、ポリマーネットワークの平均空隙間隔を可視光の波長より小さくすることが好ましく、800nm以下とすることが好ましく、650nm以下とすることが好ましく、450nm以下とすることが好ましい。更に、応答の立下り時間をポリマーネットワークと低分子液晶との相互作用効果(アンカーリング力)により低分子液晶単体の応答時間より短くするには、50nm~450nmの範囲にする事が好ましい。立下り時間が液晶のセル厚の影響が少なくなりセル厚が厚くても薄厚並の立下り時間を示すようにするには、少なくとも平均空隙間隔が下限は200nm付近で且つ上限は450nm付近の範囲に入るようにすることが好ましい。尚、ここでセル厚とは、2枚の基板表面間の距離を言う。平均空隙間隔を減少させると駆動電圧の増加が課題になるが、駆動電圧の増加を25V以下に抑制して立ち下がり応答時間を短くするには250nm近傍から450nmの範囲に入るようにすれば良く、立下り応答時間が約5msecから約1msecの範囲に改善ができるので好ましい。又、駆動電圧が5V程度以内の増加に抑制するには、平均空隙間隔が300nm付近から450nmの範囲にすることが好ましい。更に、ポリマーネットワークの平均空隙間隔を制御して立下り応答時間を1msec以下の高速応答にすることも可能である。駆動電圧が30V以上に増加する場合があるが、平均空隙間隔を50nm付近から250nm付近の間にすれば良く、0.5msec以下にするには50nm近傍から200nm付近にすることが好ましい。ポリマーネットワークの平均直径は、平均空隙間隔と相反し、20nmから700nmの範囲にあることが好ましい。重合性化合物の含有量が増えると平均直径は増加する傾向にある。反応性を高くして重合相分離速度を高めるとポリマーネットワークの密度が増加してポリマーネットワークの平均直径が減少するので必要に応じて相分離条件を調整すれば良い。重合性化合物含有量が10%以下の場合は、平均直径が20nmから160nmにあることが好ましく、平均空隙間隔が200nmから450nm範囲に於いては、平均直径が40nmから160nmの範囲であることが好ましい。重合性化合物含有量が10%より大きくなると50nmから700nmの範囲が好ましく、50nmから400nmの範囲がより好ましい。
<ポリマーネットワーク層不連続構造>
セル厚(d)と液晶の実効複屈折率(Δn)の積(リターデーション)が0.275~0.33程度になるよう二枚の対向する基板間の距離dを決めるが、十分な重合性化合物含有量があり液晶表示素子全面にポリマーネットワーク層が形成され液晶相が連続している構造に対して、重合性化合物含有量が低くなりセル全体にポリマーネットワーク層が被うのに必要な量が不足するとポリマーネットワーク層が不連続に形成される。ポリイミド配向膜等の基板表面の極性が高いと重合性化合物が液晶セル基板界面付近に集まり易く、基板表面からポリマーネットワークが成長して基板界面に付着するようにポリマーネットワーク層が形成され、セル基板表面からポリマーネットワーク層、液晶層、ポリマーネットワーク層、対向基板の順で積層されるように形成される。ポリマーネットワーク層/液晶層/ポリマーネットワーク層の積層構造を示し、且つセル断面方向に対して少なくともセル厚の0.5%以上、好ましくは1%以上、より好ましくは5%以上の厚さのポリマーネットワーク層が形成されているとポリマーネットワークと低分子液晶とのアンカーリング力の作用により立下り時間が短くなる効果が発現して好ましい傾向を示す。尚、ここでセル厚とは、2枚の基板表面間の距離を言う。但し、セル厚の影響が大きくなるのでセル厚を増すと立ち下がり時間が長くなる場合は、ポリマーネットワーク層の厚さを必要に応じて増加させれば良い。ポリマーネットワーク層に於けるポリマーネットワークの構造は、低分子液晶と配向容易軸や一軸の光学軸が略同一の方向へ揃っていれば良く、低分子液晶がプレチルト角を誘起するように形成されていれば良い。平均空隙間隔は90nmから450nmの範囲が好ましい。
例えば、重合性化合物含有量が1質量%から6質量%にする場合は、アンカーリング力の高いメソゲン基を有する二官能モノマーを用いることが好ましく、官能基間の距離が短い構造で重合速度が速い二官能モノマーを用いることが好ましく、0℃以下の低温で重合相分離構造を形成させることが好ましい。重合性化合物含有量を6質量%から10質量%未満にする場合は、該二官能モノマーとアンカーリング力が低い単官能モノマーとの組み合わせが好ましく、必要に応じて25℃から-20℃の範囲で重合相分離構造を形成させることが好ましい。更に、該融点が室温以上であれば該融点より5℃程度低くすると低温重合と同様な効果が得られるので好ましい。重合性化合物含有量を10質量%から40質量%にする場合は、ポリマーバインダ、又はポリマーネットワークの影響が低分子液晶の配向や駆動電圧に大きく影響を及ぼし駆動電圧を増大させるので、低分子液晶の配向機能を有し、且つアンカーリング力が比較的弱いメソゲン基を有する重合性化合物を用いることが好ましい。例えば、アンカーリング力が弱くメソゲン基を有する重合性化合物は、官能基とメソゲン基の間にあるアルキレン基の炭素数を増やすことが有効で炭素数が5~10が好ましい。又、重合性化合物が30質量%を超えるとポリマーバインダ中に液晶滴が分散した状態になることもあり、この場合でも屈折率異方性を有しているポリマーバインダであって基板面の配向膜が示す配向方向とポリマーバインダの光軸方向が揃うことが好ましい。
重合性液晶組成物中の重合性化合物の濃度が高いほど、液晶組成物とポリマー界面とのアンカーリング力は大きくなり、τdは高速化する。一方、液晶組成物とポリマー界面とのアンカーリング力は大きくなると、τrは低速化する。τdとτrの和を1.5ms未満とするためには、重合性液晶組成物中の重合性化合物の濃度は、1質量%以上40質量%未満であり、2質量%以上15質量%以下が好ましく、3質量%以上8質量%以下がより好ましい。
[液晶表示素子]
本発明の液晶表示素子は、液晶組成物中に重合体又は共重合体を含有し、重合体又は共重合体の含有量が液晶組成物及び重合体又は共重合体の合計の質量の1質量%以上40質量%未満である以外は、従来技術による液晶表示素子と同じ構造を有する。即ち、本発明に係る液晶表示素子は、少なくとも一方に電極を有する2枚の透明基板間に液晶層が狭持された構造を有している。そして、本発明の液晶表示素子は、少なくとも一方の透明基板上に液晶組成物を配向させるための配向層を有することが好ましい。基板に設けられたこの配向層と基板に設けられた電極に電圧を印加して、液晶分子の配向が制御される。ポリマーネットワーク又はポリマーバインダが一軸性の屈折率異方性又は配向容易軸方向を有し、ポリマーネットワーク又はポリマーバインダの光軸方向又は配向容易軸方向と低分子液晶の配向容易軸方向が同一方向であることが好ましい。この点で、一軸性の屈折率異方性又は配向容易軸方向を有さない光散乱型のポリマーネットワーク液晶や高分子分散型液晶とは異なる。更に、配向層の配向容易軸方向とポリマーネットワーク又はポリマーバインダの配向容易軸方向が同一であることが好ましい。偏光板、位相差フィルムなどを具備させることにより、この配向状態を利用して表示させる。液晶表示素子としては、TN、STN、ECB、VA、VA-TN、IPS、FFS、πセル、OCB、コレステリック液晶などの動作モードに適用できる。中でも、VA、IPS、FFS、VA-TN、TN、ECBが特に好ましい。尚、本発明の液晶表示素子は、液晶組成物中に重合体又は共重合体を含有する点で、配向膜上に重合体又は共重合体を有するPSA(Polymer Sustained Alignment)型液晶表示素子とは異なる。
本発明の液晶表示素子の駆動電圧は、液晶組成物の誘電異方性や弾性定数だけで決まるものではなく、液晶組成物とポリマー界面との間で作用するアンカーリング力に大きく影響される。
例えば高分子分散型液晶表示素子の駆動電圧に関する記述として、特開平6-222320号公報において次式の関係が示されている。
これによると、光散乱型液晶表示素子の駆動電圧は、透明性高分子物質界面の平均空隙間隔、基板間の距離、液晶組成物の弾性定数・誘電率異方性、及び液晶組成物と透明性高分子物質間のアンカーリングエネルギーによって決定される。
このうち本発明の液晶表示素子で制御できるパラメータは、液晶物性とポリマー間のアンカーリング力である。アンカーリング力は、該ポリマーの分子構造、及び低分子液晶の分子構造に大きく依存するため、アンカーリング力が強い重合性化合物を選定すれば応答時間を1.5ms以下に速くすることが可能であるが同時に、駆動電圧が30V以上に増加するので、駆動電圧が30V以下で応答速度が1.5ms以下になるように適宜液晶化合物、及び重合性化合物の選定を行い組成を調整することが好ましい。アンカーリング力の強いポリマー前駆体とアンカーリング力の弱いポリマー前駆体を適宜配合して駆動電圧と応答速度のバランスが取れるように組成を調整することが好ましい。一方、駆動電圧を低くするのに求められる液晶組成物の物性としては、P型液晶では誘電異方性が6以上で、N型液晶では誘電異方性が-3以下にすることが特に好ましい。又、複屈折率を0.09以上にすることが好ましい。更に、液晶組成物の複屈折率と繊維状、又は柱状ポリマーネットワークの屈折率を可能な限り近づけ光散乱を無くすとより好ましくなる。但し、ポリマー前駆体の濃度に液晶素子のリターデーションが影響されるので、適宜、必要なリターデーションが得られるように液晶組成物の複屈折率を増減させて使用することが好ましい。
本発明の液晶表示素子は、上述した液晶組成物を-50℃から30℃としながらエネルギー線を照射して、重合性化合物を重合して液晶組成物中に屈折率異方性又は配向容易軸方向を有するポリマーネットワーク形成して得られたものであることが好ましい。重合温度の上限は、30℃であり、20℃~-10℃好ましい。実施例において後述するように、本発明者は、重合性化合物組成に依存して低温重合、及び常温重合により、τdが更に高速化することを見出した。この理由は、1)低温により液晶分子の配向度が上昇した状態で重合すること、2)低温重合により重合したポリマーと液晶組成物との相溶性が下がることで相分離が容易になり、重合相分離速度が速まりポリマーネットワークの空隙間隔が微細になること、3)比較的アンカーリング力が低い重合性化合物を用いても空隙間隔が微細なため、アンカーリング力の影響力が強くなるような屈折率異方性ポリマーネットワークの形成等によるものと考えられる。
更に、本発明の液晶表示素子は、一軸性の屈折率異方性又は配向容易軸方向を持つポリマーネットワーク又はポリマーバインダの光軸方向又は配向容易軸方向が透明基板に対してプレチルト角を成すように形成されたものであることが好ましく、電界の強さを調整して低分子液晶の配向制御行い、基板面に対して傾斜させることにより、上述した液晶層に電圧を印加しながらエネルギー線を照射することで、重合性化合物を高分子化せしめ、液晶組成物中の屈折率異方性又は配向容易軸方向を有する重合体を得てなる構成であることが好ましい。垂直配向のVAモードに於いては、基板法線方向に対してプレチルト角が20度以内になるように電圧を印加して重合させることにより、現行のVAモードセルの用いられているポルトリュージョン等やPSA液晶の微細なポリマー突起に相当する効果があるだけではなく、PSAでは実現できない高速応答を示すので特に好ましい。又、電界方向を複数の方向から印加して高分子化させることによりマルチドメインを形成させることができ、視野角向上が可能でより好ましくなる。更に、基板界面垂直配向膜界面に於いて低分子液晶がプレチルト角を誘起するように光配向処理やラビング配向処理等を該配向膜に施すことで低分子液晶配向の傾く方向が規定されスイッチング時の配向欠陥発生が抑制され好ましく、複数の方向へ傾くように該配向処理を施すとことも好ましい。前記液晶層は、重合性化合物を含有した液晶組成物に対し、適宜-50℃から30℃の温度範囲で交流電界を印加するとともに、紫外線もしくは電子線を照射することで、屈折率異方性を有するポリマーネットワークの光軸方向が基板面に対してプレチルト角を成すように液晶中に形成される。このプレチルト角は低分子液晶の誘電異方性により電界を印加することにより誘起された配向状態で重合相分離させると、重合後のポリマーネットワークの光軸を基板面に対して傾斜させた液晶素子を得ることができ、前記重合性化合物を高分子化せしめた構成であることがより好ましい。
重合性液晶組成物を-50℃から20℃の温度範囲で交流電界を印加するとともに、紫外線もしくは電子線を照射することが好ましい。印加する交流電界は、周波数10Hzから10kHzの交流が好ましく、周波数100Hzから5kHzがより好ましく、電圧は液晶表示素子の所望のプレチルト角に依存して選ばれる。つまり、印加する電圧により液晶表示素子のプレチルト角を制御することができる。横電界型MVAモードの液晶表示素子においては、配向安定性及びコントラストの観点からプレチルト角を80度から89.9度に制御することが好ましい。
(横電界型)
まず、本発明の一実施形態の液晶表示素子について図面を参照しながら説明する。図1は本発明の液晶表示素子の一例を示す概略断面図である。本発明の一実施形態の液晶表示素子10は、配向層4が表面に形成された第一の基板2と、前記第一の基板から離間して設けられ、かつ光配向層が表面に形成された第二の基板7と、前記第一の基板2および第二の基板7間に充填され、かつ前記一対の配向層と当接する液晶層5と、を備え、前記配向層4(4a,4b)と前記第一の基板2との間にアクティブ素子として薄膜トランジスタ、共通電極22および画素電極を備えた電極層3を有している。
例えば、図4は、図1における基板2上に形成された電極層3のII線で囲まれた領域を拡大した平面図の他の実施形態である。図4に示すように、画素電極21がスリットを有する構成としてもよい。また、スリットのパターンを、ゲート配線24又はデータ配線25に対して傾斜角を持つようにして形成してもよい。
(垂直電界型)
本発明の好ましい他の実施形態は、液晶組成物を用いた垂直電界型の液晶表示素子である。図6は、垂直電界型の液晶表示素子の構成を模式的に示す図である。また、図7では、説明のために便宜上各構成要素を離間して記載している。図7は、当該図6における基板上に形成された薄膜トランジスタを含む電極層300(または薄膜トランジスタ層300とも称する。)のVII線で囲まれた領域を拡大した平面図である。図8は、図7におけるVIII-VIII線方向に図6に示す液晶表示素子を切断した断面図である。以下、図6~8を参照して、本発明に係る垂直電界型の液晶表示素子を説明する。
すなわち、本発明に係る液晶表示素子1000は、第一の偏光板100と、第一の基板200と、薄膜トランジスタを含む電極層(又は薄膜トランジスタ層とも称する)300と、光配向膜400と、液晶組成物を含む層500と、配向膜400と、共通電極600と、カラーフィルター700と、第二の基板800と、第二の偏光板900と、が順次積層された構成である。尚、配向膜400は光配向膜であることが好ましい。
垂直配向膜の配向規制力を受け重合性モノマーが垂直方向に配列し、UV光照射によって重合性モノマーを重合・固定化させてポリマーネットワークを形成する。このようにして形成されたポリマーネットワークは、(V1)上下基板にまたがってポリマーネットワークを形成、(V2)上(下)基板から液晶方向に向かってポリマーネットワークを形成するも途中までのもの、(V3)配向膜の表面近傍のみポリマーネットワークを形成。(主に単官能モノマーの場合)、(V4)液晶層内でポリマーネットワーク同士が結合(Floatingはしていない)の、およそ4種類の構造を有するものと推定される。
この様にして形成された異方性を有するポリマーポリマネットワークは、液晶層とはほぼ完全に分離しており、これら高分子ネットワークの間に液晶分子は配向配列しているものと考えられる。液晶分子と高分子ネットワークが混在し、電圧無印加時に光散乱を起こす所謂ポリマーネットワーク型液晶の分子配列構造とは明らかに異なり、またPSA等で用いられる配向膜近傍に偏在する配向維持層のそれとも全く異なる構造を有するものである。
例示として、配向膜を用いた方法によるポリマーネットワークと液晶分子配列構造を示したが、リブやスリット等の構造物を有する所謂MVA方式においても、基板界面近傍のポリマーネットワークや液晶分子のプレティルトが、構造物やスリットを介して印加される斜め電界強度などによってやや異なるだけであり、本質的には、上図のような構造を有するものと推定される。
この様なポリマーネットワークと液晶分子による液晶分子配列を有するVA型液晶表示装置では、電圧無印加時の液晶分子に対するアンカーリング力が、液晶配向膜とポリマーネットワークの持つアンカーリング力の相乗作用により、より強く作用する事となって、結果的に電圧OFF時の応答速度を速くすることが可能となる。
(横・斜め電界型)
配向膜に対してマスクラビングやマスク露光等の煩雑な工程を行なわず、電極構造を工夫するだけの簡便な手法で液晶表示領域を配向分割できる新たな表示技術として、斜め電界と横電界を液晶層に作用させる方法が提案されている。
画素電極PEは、主画素電極PA及び副画素電極PBを有している。これらの主画素電極PA及び副画素電極PBは、互いに電気的に接続されており、これらの主画素電極PA及び副画素電極PBがともにアレイ基板ARに備えられている。主画素電極PAは、第2方 向Yに沿って延出しており、副画素電極PBは、第2方向Yとは異なる第1方向Xに沿って 延出している。図示した例では、画素電極PEは、略十字状に形成されている。副画素電極PBは、主画素電極PAの略中央部に結合し、主画素電極PAからその両側、即ち画素PXの左側及び右側に向かって延出している。これらの主画素電極PA及び副 画素電極PBは、互いに略直交している。画素電極PEは、画素電極PBにおいて図示を省略したスイッチング素子と電気的に接続されている。
(実施例1)
N型液晶組成物(LCN-1)を97%、重合性化合物(V1) 2.94%と下記表10に記載の光重合開始剤No.1 0.06%(これら重合性化合物と光重合開始剤の混合物として重合性組成物 3%)を混合し、組成物1を調製した。
液晶の垂直配向(ホメオトロピック配向)が得られるように、セルギャップ3μmのポリイミド配向膜をガラス基板に形成した後、基板の法線方向に対してプレチルト角が1°~2°になるようにラビング配向処理を施しITO付きラビング配向のセルを作成した。
組成物1を60℃に加熱して、固形の重合性化合物(V1)を溶解させた。組成物1は室温で重合性化合物(V1)が均一に溶解しており、ネマチック液晶相を示していることを偏光顕微鏡で確認した。重合性液晶組成物1を60℃に加熱して、真空注入法によりガラスセル内に注入した。注入後ガラスセルを取り出し、注入口を封口剤3026E(スリーボンド社製)で封止した。紫外線カットフィルターL-37(ホーヤ カンデオ オプトロニクス社製)を介して365nmの照射強度が15mW/cm2の紫外線を、25℃で300秒間照射し、重合性液晶組成物の重合性化合物を重合させた。これによりセル内全体に相分離構造を形成させたVAモードの液晶表示素子を得た。
得られたVAモードの液晶表示素子に60Hzの矩形波を印加して応答時間を測定したところ、τoffは3.4msecであった。セル作製に用いた組成物を20℃で1週間放置し重合性化合物による結晶化が無いことを確認した。
液晶組成物、重合性化合物、開始剤を下記表1のように調整した以外は実施例1と同様にして、VAモードの液晶表示素子を作成した。
偏光顕微鏡を用いて直交する二枚の偏光板の間に作製したセルを置くと暗視野になりセルを方位角方向へ回転しても暗視野の黒レベルが変化せずホメオトロピック配向であり、ポリマーネットワークの光軸方向と液晶組成物の配向容易軸方向が同一方向であることを確認した。
実施例1から23では重合性組成物の含有量を1%~40%とし、吸収波長の極大ピークが310nm~380nmに存在する光重合開始剤を用いたためτoffが改善した。
液晶組成物、重合性化合物、光重合開始剤を下記表2のように調整した以外は実施例1と同様にして、VAモードの液晶表示素子を作成した。
偏光顕微鏡を用いて直交する二枚の偏光板の間に作製したセルを置くと暗視野になりセルを方位角方向へ回転しても暗視野の黒レベルが変化せずホメオトロピック配向であり、ポリマーネットワークの光軸方向と液晶組成物の配向容易軸方向が同一方向であることを確認した。
セル作製に用いた組成物を20℃で1週間放置し、重合性化合物による結晶化が無い事を確認した。得られたVAモードの液晶表示素子に60Hzの矩形波を印加して、応答時間を測定した。結果を表2に示す。
液晶組成物、重合性化合物、光重合開始剤を下記表3のように調整する以外は実施例1と同様にして、VAモードの液晶表示素子を作成した。
偏光顕微鏡を用いて直交する二枚の偏光板の間に作製したセルを置くと暗視野になりセルを方位角方向へ回転しても暗視野の黒レベルが変化せずホメオトロピック配向であり、ポリマーネットワークの光軸方向と液晶組成物の配向容易軸方向が同一方向であることを確認した。
セル作製に用いた組成物を20℃で1週間放置し、重合性化合物による結晶化が無い事を確認した。得られたVAモードの液晶表示素子に60Hzの矩形波を印加して、応答時間を測定した。結果を表3に示す。
液晶組成物、重合性化合物、光重合開始剤を下記表4のように調整する以外は実施例1と同様にして、VAモードの液晶表示素子を作成した。
偏光顕微鏡を用いて直交する二枚の偏光板の間に作製したセルを置くと暗視野になりセルを方位角方向へ回転しても暗視野の黒レベルが変化せずホメオトロピック配向であり、ポリマーネットワークの光軸方向と液晶組成物の配向容易軸方向が同一方向であることを確認した。
セル作製に用いた組成物を20℃で1週間放置し、重合性化合物による結晶化が無い事を確認した。
比較例8では重合性組成物と開始剤を含まないためτoffは遅かった。比較例9では重合性組成物の含有量が低く、かつ吸収波長の極大ピークが310nm~380nmに存在する光重合開始剤を用いていないため、効率よくネットワーク構造が形成できずτoffが遅かった。比較例3ではセルの作成過程で液晶組成物が硬化してしまいτoffの測定ができなかった
実施例28から29では重合性組成物の含有量を1%~40%とし、吸収波長の極大ピークが310nm~380nmに存在する光重合開始剤を用いたためτoffが改善した。
液晶組成物、重合性化合物、光重合開始剤を下記表5のように調整する以外は実施例1と同様にして、ECBモードの液晶表示素子を作成した。
偏光顕微鏡を用いて直交する二枚の偏光板の間に作製したセルを置くと暗視野になりセルを方位角方向へ回転しても暗視野の黒レベルが変化せずホメオトロピック配向であり、ポリマーネットワークの光軸方向と液晶組成物の配向容易軸方向が同一方向であることを確認した。
セル作製に用いた組成物を20℃で1週間放置し、重合性化合物による結晶化が無い事を確認した。
比較例10では重合性組成物と開始剤を含まないためτoffは遅かった。比較例11では重合性組成物の含有量が低く、かつ吸収波長の極大ピークが310nm~380nmに存在する光重合開始剤を用いていないため、効率よくネットワーク構造が形成できずτoffが遅かった。
実施例30から36では重合性組成物の含有量を1%~40%とし、吸収波長の極大ピークが310nm~380nmに存在する光重合開始剤を用いたためτoffが改善した。
液晶組成物、重合性化合物、光重合開始剤を下記表6のように調整する以外は実施例1と同様にして、VAモードの液晶表示素子を作成した。
偏光顕微鏡を用いて直交する二枚の偏光板の間に作製したセルを置くと暗視野になりセルを方位角方向へ回転しても暗視野の黒レベルが変化せずホメオトロピック配向であり、ポリマーネットワークの光軸方向と液晶組成物の配向容易軸方向が同一方向であることを確認した。
セル作製に用いた組成物を20℃で1週間放置し、重合性化合物による結晶化が無い事を確認した。
液晶組成物、重合性化合物、光重合開始剤を下記表7のように調整する以外は実施例1と同様にして、VAモードの液晶表示素子を作成した。
偏光顕微鏡を用いて直交する二枚の偏光板の間に作製したセルを置くと暗視野になりセルを方位角方向へ回転しても暗視野の黒レベルが変化せずホメオトロピック配向であり、ポリマーネットワークの光軸方向と液晶組成物の配向容易軸方向が同一方向であることを確認した。
セル作製に用いた組成物を20℃で1週間放置し、重合性化合物による結晶化が無い事を確認した。
液晶組成物、重合性化合物、光重合開始剤を下記表8のように調整し、UV照射時に下記表8のように100Hzの矩形波を印加する以外は実施例1と同様にして、VAモードの液晶表示素子を作成した。
セル作製に用いた組成物を20℃で1週間放置し重合性化合物による結晶化が無い事を確認した。
作製したセルの法線方向からのプレチルト角をRET-100(大塚電子)を用いて測定した。結果を表7に示す。
比較例12では配向膜により誘起されるプレチルトが付与された。実施例41~45では吸収波長の極大ピークが310nm~380nmに存在する光重合開始剤を用いることで、UV照射時に電圧を印加することにより比較例12とくらべて大きなプレチルト角が付与された。
液晶組成物、重合性化合物、光重合開始剤を下記表9のように調整しUV照射波長をフィルターを介さずに365nm及び254nmとする以外は実施例1と同様の方法でVAモードの液晶セルを作製した。得られたセルの電圧保持率を60℃、0.6Hz、1Vで測定した。結果を表9に示す。
本願発明の光重合開始剤を用いない場合は、比較的長波長である365nmのUV照射では、比較例2から分かるように十分に組成物を硬化させることができず、τoffが遅かった。また、比較例14では本願発明の光重合開始剤ではない光重合開始剤を用いていることから、組成物を十分に硬化させるため254nmという短波長のUV照射が必要となり、電圧保持率(VHR)が低下してしまった。一方、実施例46では、重合性組成物の含有量を1%~40%とし、吸収波長の極大ピークが310nm~380nmに存在する光重合開始剤を用いたため、τoffが改善し、電圧保持率(VHR)も高い値を維持できた。
Claims (13)
- 少なくとも一方に電極を有する2枚の透明基板間に挟持した1種又は2種以上の液晶化合物を含有する液晶組成物中に、1種又は2種以上の重合性化合物と吸収波長の極大ピークが310nm~380nmに存在する光重合開始剤を含有する重合性組成物の硬化物である重合体又は共重合体を含み、該重合性組成物と該液晶組成物の全重量中の該重合性組成物の含有量が1質量%以上40質量%未満である液晶表示素子。
- 該液晶組成物中の該重合体又は共重合体がポリマーネットワークを形成し、透明基板上に液晶組成物を配向させるための配向層を有する請求項1記載の液晶表示素子。
- 該ポリマーネットワークが一軸性の屈折率異方性を有し、該ポリマーネットワークの光軸方向又は配向容易軸方向と該液晶組成物の配向容易軸方向が同一方向である請求項2に記載の液晶表示素子。
- 透明基板の法線方向に対して該液晶組成物が0~90°のプレチルト角をなしている請求項1~3のいずれか1項に記載の液晶表示素子。
- セル断面方向に対して少なくともセル厚の0.5%以上の厚さのポリマーネットワーク層が形成されている請求項2~4のいずれか1項に記載の液晶表示素子。
- 透明基板の法線方向又は水平方向に対して該ポリマーネットワークの光軸方向又は配向容易軸方向が0.1°~30°のプレチルト角をなしている請求項2~5のいずれか1項に記載の液晶表示素子。
- 重合性化合物として、下記一般式(P)で表される化合物から選ばれる1種又は2種以上の化合物を含有する請求項1~6のいずれか1項に記載の液晶表示素子。
Rp1及びRp2はそれぞれ独立して以下の式(R-I)から式(R-IX):
Spp1及びSpp2はスペーサー基を表し、Spp1及びSpp2はそれぞれ独立して、単結合、炭素原子数1~12のアルキレン基又は-O-(CH2)s-(式中、sは1~11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
Lp1及びLp2はそれぞれ独立して、単結合、-O-、-S-、-CH2-、-OCH2-、-CH2O-、-CO-、-C2H4-、-COO-、-OCO-、-OCOOCH2-、-CH2OCOO-、-OCH2CH2O-、-CO-NRa-、-NRa-CO-、-SCH2-、-CH2S-、-CH=CRa-COO-、-CH=CRa-OCO-、-COO-CRa=CH-、-OCO-CRa=CH-、-COO-CRa=CH-COO-、-COO-CRa=CH-OCO-、-OCO-CRa=CH-COO-、-OCO-CRa=CH-OCO-、-(CH2)z-C(=O)-O-、-(CH2)z-O-(C=O)-、-O-(C=O)-(CH2)z-、-(C=O)-O-(CH2)z-、-CH=CH-、-CF=CF-、-CF=CH-、-CH=CF-、-CF2-、-CF2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-又は-C≡C-(式中、Raはそれぞれ独立して水素原子又は炭素原子数1~4のアルキル基を表し、前記式中、zは1~4の整数を表す。)を表し、
Mp2は、1,4-フェニレン基、1,4-シクロヘキシレン基、アントラセン-2,6-ジイル基、フェナントレン-2,7-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ナフタレン-2,6-ジイル基、インダン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基又は1,3-ジオキサン-2,5-ジイル基を表すが、Mp2は無置換であるか又は炭素原子数1~12のアルキル基、炭素原子数1~12のハロゲン化アルキル基、炭素原子数1~12のアルコキシ基、炭素原子数1~12のハロゲン化アルコキシ基、ハロゲン原子、シアノ基、ニトロ基又は-Rp1で置換されていても良く、
Mp1は以下の式(i-11)~(ix-11):
Mp3は以下の式(i-13)~(ix-13):
mp2~mp4はそれぞれ独立して、0、1、2又は3を表し、mp1及びmp5はそれぞれ独立して1、2又は3を表すが、Zp1が複数存在する場合にはそれらは同一であっても異なっていてもよく、Rp1が複数存在する場合にはそれらは同一であっても異なっていてもよく、Rp2が複数存在する場合にはそれらは同一であっても異なっていてもよく、Spp1が複数存在する場合にはそれらは同一であっても異なっていてもよく、Spp2が複数存在する場合にはそれらは同一であっても異なっていてもよく、Lp1が複数存在する場合にはそれらは同一であっても異なっていてもよく、Mp2が複数存在する場合にはそれらは同一であっても異なっていてもよい。) - 液晶組成物として、下記一般式(LC)で表される液晶化合物を含有する請求項1~7のいずれか1項に記載の液晶表示素子。
(a)トランス-1,4-シクロヘキシレン基(この基中に存在する1個のCH2基又は隣接していない2個以上のCH2基は酸素原子又は硫黄原子で置換されていてもよい。)、
(b)1,4-フェニレン基(この基中に存在する1個のCH基又は隣接していない2個以上のCH基は窒素原子で置換されていてもよい。)、
(c)1,4-ビシクロ(2.2.2)オクチレン基、ナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、又はクロマン-2,6-ジイル基。
前記の基(a)、基(b)又は基(c)に含まれる1つ又は2つ以上の水素原子はそれぞれ、フッ素原子、塩素原子、-CF3又は-OCF3で置換されていてもよい。
ZLCは単結合、-CH=CH-、-CF=CF-、-C≡C-、-CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-OCF2-、-CF2O-、-COO-又は-OCO-を表す。
YLCは、水素原子、フッ素原子、塩素原子、シアノ基、及び炭素原子数1~15のアルキル基を表す。該アルキル基中の1つ又は2つ以上のCH2基は、酸素原子が直接隣接しないように、-O-、-CH=CH-、-CO-、-OCO-、-COO-、-C≡C-、-CF2O-、-OCF2-で置換されてよく、該アルキル基中の1つ又は2つ以上の水素原子は任意にハロゲン原子によって置換されていてもよい。
aは1~4の整数を表す。aが2、3又は4を表し、一般式(LC)中にALC1が複数存在する場合、複数存在するALC1は、同一であっても異なっていてもよく、ZLCが複数存在する場合、複数存在するZLCは、同一であっても異なっていてもよい。) - 該重合性組成物と該液晶組成物の全重量中の該光重合開始剤の含有量が0.001~1質量%である請求項1~8のいずれか1項に記載の液晶表示素子
- セル構造がVAモード、IPSモード、FFSモード、VA-TNモード、TNモード、ECBモードである請求項1~9記載の液晶表示素子。
- 少なくとも一方に電極を有する2枚の透明基板間に挟持した1種又は2種以上の液晶化合物を含有する液晶組成物と、1種又は2種以上の重合性化合物と、吸収波長の極大ピークが310nm~380nmに存在する光重合開始剤とを含有する重合性組成物を含み、該重合性組成物と該液晶組成物の全重量中の該重合性組成物の含有量が1質量%以上40質量%未満である組成物中の重合性化合物をエネルギー線を照射することにより重合してなる液晶表示素子。
- 該組成物中の重合性化合物を、-50℃~30℃の温度にてエネルギー線を照射することにより重合してなる請求項11に記載の液晶表示素子。
- 該組成物中の重合性化合物を、エネルギー線照射前の透明基板の法線方向に対するプレチルト角が0.1~30°になるような電圧を印加しながらエネルギー線を照射することにより重合してなる請求項11又は12に記載の液晶表示素子。
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JP2017534463A JP6358489B2 (ja) | 2015-08-11 | 2016-08-09 | 液晶表示素子 |
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WO2019102859A1 (ja) * | 2017-11-21 | 2019-05-31 | Dic株式会社 | 液晶組成物及び液晶表示素子 |
JP2019113675A (ja) * | 2017-12-22 | 2019-07-11 | Dic株式会社 | 液晶表示素子の製造方法 |
CN110317613A (zh) * | 2018-03-28 | 2019-10-11 | 江苏和成显示科技有限公司 | 一种液晶组合物及液晶显示器件 |
JP2022510013A (ja) * | 2018-12-03 | 2022-01-25 | メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | 重合性液晶材料および重合液晶フィルム |
US11760761B2 (en) | 2020-08-17 | 2023-09-19 | Aligos Therapeutics, Inc. | Methods and compositions for targeting PD-L1 |
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US10690952B2 (en) * | 2015-08-11 | 2020-06-23 | Dic Corporation | Liquid crystal display element |
JP6844749B2 (ja) * | 2018-10-11 | 2021-03-17 | Dic株式会社 | 重合性液晶組成物及び液晶表示素子 |
CN109445199B (zh) * | 2018-12-30 | 2021-11-23 | 厦门天马微电子有限公司 | 一种液晶装置及其制备方法 |
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US20180307069A1 (en) | 2018-10-25 |
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