WO2017183683A1 - 液晶表示素子及びその製造方法 - Google Patents
液晶表示素子及びその製造方法 Download PDFInfo
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- WO2017183683A1 WO2017183683A1 PCT/JP2017/015845 JP2017015845W WO2017183683A1 WO 2017183683 A1 WO2017183683 A1 WO 2017183683A1 JP 2017015845 W JP2017015845 W JP 2017015845W WO 2017183683 A1 WO2017183683 A1 WO 2017183683A1
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- 0 C*(C)c(ccc(*)c1F)c1F Chemical compound C*(C)c(ccc(*)c1F)c1F 0.000 description 3
- UNROARZYSQWMFQ-YSURURNPSA-N C=CC(OCCCCCCOc(cc1)ccc1-c1ccc(/C=C/C(Oc(cc2)ccc2-c(cc2)ccc2C(OCCOC(C=C)=O)=O)=O)cc1F)=O Chemical compound C=CC(OCCCCCCOc(cc1)ccc1-c1ccc(/C=C/C(Oc(cc2)ccc2-c(cc2)ccc2C(OCCOC(C=C)=O)=O)=O)cc1F)=O UNROARZYSQWMFQ-YSURURNPSA-N 0.000 description 1
- YPDAHRTUPVECHJ-WYMPLXKRSA-N C=CC(OCCCCCCOc(cc1)ccc1-c1ccc(/C=C/C(Oc(cc2)ccc2C(Oc2ccc(CCOC(C=C)=O)cc2)=O)=O)cc1F)=O Chemical compound C=CC(OCCCCCCOc(cc1)ccc1-c1ccc(/C=C/C(Oc(cc2)ccc2C(Oc2ccc(CCOC(C=C)=O)cc2)=O)=O)cc1F)=O YPDAHRTUPVECHJ-WYMPLXKRSA-N 0.000 description 1
- VYAVSWXYTMCABL-UHFFFAOYSA-N C=CC([ClH]c(cc1)ccc1-c(cc1)ccc1C([ClH]c(cc1)ccc1C([ClH]CCc(cc1)cc([ClH]C(C=C)=O)c1[ClH]C(C=C)=O)=O)=O)=O Chemical compound C=CC([ClH]c(cc1)ccc1-c(cc1)ccc1C([ClH]c(cc1)ccc1C([ClH]CCc(cc1)cc([ClH]C(C=C)=O)c1[ClH]C(C=C)=O)=O)=O)=O VYAVSWXYTMCABL-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
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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
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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
- C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
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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
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
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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
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
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- C—CHEMISTRY; METALLURGY
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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
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
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- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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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
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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
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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
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
Definitions
- the present invention relates to a liquid crystal display element useful as a constituent member for a liquid crystal TV or the like and a method for manufacturing the same.
- Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, etc., including clocks and calculators.
- Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment type (vertical alignment; VA) using TFT (thin film transistor), and IPS. (In-plane switching) type.
- the liquid crystal composition used in these liquid crystal display elements is stable against external factors such as moisture, air, heat, and light, and exhibits a liquid crystal phase in the widest possible temperature range centering on room temperature. It is required to be viscous and have a low driving voltage.
- the liquid crystal composition is composed of several to several tens of kinds of compounds in order to optimize dielectric anisotropy ( ⁇ ), refractive index anisotropy ( ⁇ n), etc. for each liquid crystal display element. It is composed of
- a liquid crystal composition having a negative ⁇ is used, which is widely used for liquid crystal TVs and the like.
- low voltage driving, high-speed response, and a wide operating temperature range are required. That is, the absolute value of ⁇ is large, the viscosity ( ⁇ ) is small, and a high nematic phase-isotropic liquid phase transition temperature (T ni ) is required.
- T ni nematic phase-isotropic liquid phase transition temperature
- T ni nematic phase-isotropic liquid phase transition temperature
- ⁇ n ⁇ d which is the product of ⁇ n and the cell gap (d)
- it is necessary to adjust ⁇ n of the liquid crystal composition to an appropriate range according to the cell gap when applying a liquid crystal display element to a television or the like, since high-speed response is important, a liquid crystal composition having a low rotational viscosity ( ⁇ 1 ) is required.
- an MVA (multi-domain vertical alignment) type that divides the alignment direction of liquid crystal molecules in a pixel into a plurality of parts by providing a protrusion structure on the substrate.
- Liquid crystal display elements have been widely used.
- the MVA type liquid crystal display element is excellent in view angle characteristics, the response speed of liquid crystal molecules is different between the vicinity of the protrusion structure on the substrate and the part away from the protrusion structure, and the liquid crystal having a slow response speed away from the protrusion structure.
- the response speed as a whole is insufficient due to the influence of molecules, and there is a problem of a decrease in transmittance due to the protruding structure.
- PSA is a method for providing a uniform pretilt angle in a divided pixel without providing a non-transparent protrusion structure in a cell, unlike a normal MVA liquid crystal display element.
- Liquid crystal display elements including polymer sustained alignment: polymer sustaining alignment and PS liquid crystal display elements (polymer stabilized) have been developed.
- a PSA liquid crystal display element is obtained by adding a small amount of a reactive monomer to a liquid crystal composition, introducing the liquid crystal composition into a liquid crystal cell, and then irradiating active energy rays while applying a voltage between the electrodes. It is produced by polymerizing the reactive monomer.
- a reactive monomer is mixed into the alignment film material. Then, after introducing the liquid crystal composition into the liquid crystal cell, a method of polymerizing the reactive monomer in the alignment film by applying active energy rays while applying a voltage between the electrodes has been developed (for example, Patent Document 2, 3 and 4).
- the manufacturing method of the liquid crystal display element has also undergone great changes. That is, in the conventional vacuum injection method, when a large panel is manufactured, the manufacturing process takes a lot of time. Therefore, in the manufacture of a large panel, a manufacturing method using an ODF (one-drop-fill) method is mainly used. (For example, see Patent Document 5). Since this method can shorten the injection time compared with the vacuum injection method, it has become the mainstream method for manufacturing liquid crystal display elements. However, a phenomenon in which a drop mark in which a liquid crystal composition is dropped remains in the liquid crystal display element in a dropped shape after the liquid crystal display element is produced has become a new problem.
- ODF one-drop-fill
- a dripping mark is defined as a phenomenon in which a mark in which a liquid crystal composition is dripped appears white when displaying black.
- the reactive monomer that is a foreign substance is present in the alignment film when the liquid crystal composition is dropped onto the substrate. Therefore, the problem of dripping marks is likely to occur.
- the occurrence of dripping marks is often caused by the selection of a liquid crystal material, and the cause is not clear.
- the polymerizable compound mixed in the liquid crystal composition is polymerized to form a polymer layer in the liquid crystal composition layer, thereby suppressing the drop mark generated in relation to the alignment control film.
- this method alone has a problem of display burn-in caused by the reactive monomer added to the liquid crystal composition, as in the PSA method and the like, and the effect on the suppression of dripping marks is insufficient.
- the liquid crystal display element is exposed to UV light at the time of manufacture and use, it is important that the UV irradiation does not cause deterioration or the like even if it does not deteriorate.
- Patent Document 12 Japanese Patent No. 05299595 (Patent Document 12) and the like, a reactive monomer is contained in the vertical alignment film, and after introducing the liquid crystal composition into the liquid crystal cell, the voltage is applied between the electrodes,
- the liquid crystal display element which combined the specific liquid crystal composition in the system which superposes
- various characteristics as a liquid crystal display element such as dielectric anisotropy, viscosity, nematic phase upper limit temperature, rotational viscosity ( ⁇ 1 ) and the image sticking characteristic of the liquid crystal display element are not deteriorated.
- the present invention has been made in view of the above circumstances, and has various characteristics as a liquid crystal display device such as dielectric anisotropy, viscosity, nematic phase upper limit temperature, rotational viscosity ( ⁇ 1 ), and image sticking of the liquid crystal display device.
- An object of the present invention is to provide a liquid crystal display element that does not easily cause dripping marks at the time of manufacture, does not deteriorate characteristics, has various characteristics as a liquid crystal display element, and is stably provided with a pretilt angle, and a method for manufacturing the same.
- the present invention includes a first substrate, a second substrate, and a liquid crystal composition layer sandwiched between the first group and the second substrate, and the first substrate and the second substrate.
- a polymer of a compound having an electrode on at least one and having a polymerizable group for controlling the orientation direction of liquid crystal molecules in the liquid crystal composition layer on at least one of the first substrate and the second substrate And an alignment film containing a thermally decomposable polymer having a thermally decomposable group, wherein the liquid crystal composition constituting the liquid crystal composition layer has a negative dielectric anisotropy ( ⁇ ).
- ⁇ dielectric anisotropy
- high-speed response as a liquid crystal display element is excellent, there is little occurrence of image sticking, there are few occurrences of dripping marks during its manufacture, and various characteristics as a liquid crystal display element are excellent, and the pretilt angle is stable.
- Embodiments of the liquid crystal display element and the manufacturing method thereof according to the present invention will be described.
- the liquid crystal display element of the present invention is a liquid crystal display element having a liquid crystal composition layer sandwiched between a pair of substrates, and a voltage is applied to the liquid crystal composition layer to displace the liquid crystal molecules in the liquid crystal composition layer. This is based on the principle of acting as an optical switch by transferring, and a well-known and conventional technique can be used in this respect.
- a method of applying a charge vertically between the two substrates is generally employed.
- one electrode is a common electrode and the other electrode is a pixel electrode. The most typical embodiment of this scheme is shown below.
- FIG. 1 is a schematic perspective view showing an embodiment of the liquid crystal display element of the present invention.
- the liquid crystal display element 10 of this embodiment includes a first substrate 11, a second substrate 12, a liquid crystal composition layer 13 sandwiched between the first substrate 11 and the second substrate 12, and a first
- the common electrode 14 provided on the surface of the substrate 11 facing the liquid crystal composition layer 13, the pixel electrode 15 provided on the surface of the second substrate 12 facing the liquid crystal composition layer 13, and the common electrode 14, a vertical alignment film 16 provided on the surface facing the liquid crystal composition layer 13, a vertical alignment film 17 provided on the surface of the pixel electrode 15 facing the liquid crystal composition layer 13, and as necessary.
- the first substrate 11 and the second substrate 12 a glass substrate or a plastic substrate is used.
- a substrate made of a resin such as acrylic resin, methacrylic resin, polyethylene terephthalate, polycarbonate, or cyclic olefin resin is used as the plastic substrate.
- the common electrode 14 is usually made of a transparent material such as indium-added tin oxide (ITO).
- ITO indium-added tin oxide
- the pixel electrode 15 is usually made of a transparent material such as indium-added tin oxide (ITO).
- ITO indium-added tin oxide
- the pixel electrodes 15 are arranged in a matrix on the second substrate 12.
- the pixel electrode 15 is controlled by a drain electrode of an active element typified by a TFT switching element, and the TFT switching element has a gate line as an address signal line and a source line as a data line in a matrix.
- the configuration of the TFT switching element is not shown.
- slits having striped or V-shaped patterns are formed in each pixel.
- a pixel electrode having a portion that is not provided) may be provided.
- FIG. 2 is a schematic plan view showing a typical form of a slit electrode (comb electrode) when the inside of a pixel is divided into four regions.
- the slit electrode has comb-like slits in four directions from the center of the pixel, so that the liquid crystal molecules in each pixel that are substantially perpendicularly aligned with respect to the substrate when no voltage is applied are applied with voltage application.
- the liquid crystal molecules are directed in four different directions, approaching horizontal alignment.
- the orientation direction of the liquid crystal in the pixel can be divided into a plurality of parts, so that the viewing angle characteristic is extremely wide.
- a method for dividing the pixel in addition to a method of providing a slit in the pixel electrode, a method of providing a structure such as a linear protrusion in the pixel, a method of providing an electrode other than the pixel electrode and the common electrode, and the like are used. .
- a configuration using a slit electrode is preferable from the viewpoint of transmittance and ease of production. Since the pixel electrode provided with the slit does not have a driving force for the liquid crystal molecules when no voltage is applied, the pretilt angle cannot be given to the liquid crystal molecules. However, when the alignment film material used in the present invention is used in combination, a pretilt angle can be given, and a wide viewing angle by pixel division can be achieved by combining with a slit electrode obtained by pixel division.
- having a pretilt angle means that the liquid crystal molecules are perpendicular to the substrate surface (the surface adjacent to the liquid crystal composition layer 13 in the first substrate 11 and the second substrate 12) in the state where no voltage is applied.
- the director is slightly different.
- VA vertical alignment
- the director of the liquid crystal molecules is aligned substantially perpendicular to the substrate surface when no voltage is applied.
- a (vertical) alignment film is generally used.
- polyimide When polyimide is used as the alignment film material for forming the vertical alignment film, a mixture of tetracarboxylic dianhydride and diisocyanate, polyamic acid, or a polyimide solution in which polyimide is dissolved or dispersed in a solvent is used as the polymer compound precursor.
- the content of polyimide in the polyimide solution is preferably 1% by mass or more and 10% by mass or less, more preferably 3% by mass or more and 5% by mass or less, and more preferably 10% by mass or less. Is more preferable.
- a polysiloxane material when used as an alignment film material for forming a vertical alignment film, it is manufactured by mixing and heating a silicon compound having an alkoxy group, an alcohol derivative, and an oxalic acid derivative at a predetermined blending ratio.
- a polysiloxane solution in which the prepared polysiloxane is dissolved can be used.
- the vertical alignment films 16 and 17 formed of polyimide or the like include a polymer formed by polymerization of a polymerizable compound having a polymerizable group.
- This polymerizable compound imparts a function of fixing the pretilt angle of the liquid crystal molecules. That is, it is possible to tilt the director of the liquid crystal molecules in the pixel in different directions when a voltage is applied, using a slit electrode or the like.
- the liquid crystal molecules are aligned almost perpendicularly to the substrate surface and no pretilt angle is generated, but a voltage is applied between the electrodes to slightly displace the liquid crystal molecules.
- ultraviolet rays or the like are irradiated to polymerize the reactive monomer in the liquid crystal composition, thereby giving an appropriate pretilt angle.
- the polymer layers 20 and 21 can be polymerized by sandwiching a polymerizable compound contained in a liquid crystal composition between substrates and then curing the polymerizable compound while applying a voltage.
- the compound can be formed as a polymer on the surfaces of the vertical alignment films 16 and 17 while phase-separating.
- the polymer contained in the vertical alignment films 16 and 17 and the polymer layers 20 and 21 formed on the surfaces of the vertical alignment films 16 and 17 that are formed as necessary provide the alignment of liquid crystal molecules. High, less occurrence of image sticking, and less generation of dripping marks during the production.
- substantially vertical means a state in which the directors of vertically aligned liquid crystal molecules are slightly tilted from the vertical direction to give a pretilt angle.
- substantially vertical is preferably 89.5 to 85 °. More preferably, it is 5 to 87 °.
- the vertical alignment films 16 and 17 containing a polymer of a polymerizable compound having a polymerizable group are formed by the effect of the polymerizable compound mixed in the vertical alignment film material. Therefore, it is presumed that the vertical alignment film and the polymerizable compound are intertwined in a complicated manner to form a kind of polymer alloy, but the exact structure cannot be shown.
- the polymer layers 20 and 21 that are formed as necessary are formed on the vertical alignment films 16 and 17 while phase-separating from the liquid crystal composition when the polymerizable compound contained in the liquid crystal composition is polymerized. Although it is formed on the surface, whether it is formed uniformly on the entire surface of the vertical alignment film or nonuniform sea-island structure is considered to differ depending on the manufacturing conditions, and the exact structure is shown I can't.
- FIG. 1 shows the case where it is formed uniformly.
- the alignment film used in the present invention needs to have an alignment control ability for controlling the alignment direction of the liquid crystal molecules as well as a vertical alignment ability for aligning liquid crystal molecules in the liquid crystal composition layer in a direction perpendicular to the substrate surface. Further, in order to stably provide the pretilt angle, it is necessary to smooth the surface of the alignment film so as not to affect the alignment of the liquid crystal composition in contact with the alignment film.
- the present invention is characterized in that the alignment film contains at least one polymer having a thermally decomposable group.
- the polymer having a thermally decomposable group is used by being added to the alignment film material, and the alignment film surface can be smoothed by a heating step.
- the pretilt angle formed by the polymer of the compound having a polymerizable group which controls the alignment direction of the liquid crystal molecules in the liquid crystal composition layer described later, is uniformly and stably imparted on the alignment film layer. It is considered to have.
- polymers having a thermally decomposable group include polymers in which the thermally decomposable group contains a fluorine atom and / or a silicon atom.
- the polymer having a thermally decomposable group preferably contains a structural unit represented by the following general formula (I-1-1) or general formula (I-1-2) as a side chain.
- R 1 and R 2 are each independently a hydrogen atom or a straight or branched carbon atom having 1 to 18 carbon atoms. Represents an organic group, Y 1 represents an oxygen atom or a sulfur atom, R 4 represents an organic group having a fluorine atom and / or a silicon atom, and * represents a bonding site. It is preferable.
- R 1 is a hydrogen atom or a linear or branched organic group having a carbon number of 1 ⁇ 18, R 1 Is preferably a hydrogen atom or a methyl group, and R 1 is more preferably a hydrogen atom.
- R 2 is a hydrogen atom or a linear or branched organic group having a carbon number of 1 ⁇ 18, R 2 Is preferably a linear alkyl group having 1 to 12 carbon atoms, and R 2 is more preferably a methyl group.
- Y 1 represents an oxygen atom or a sulfur atom, and Y 1 is preferably an oxygen atom.
- R 4 represents an organic group having a fluorine atom and / or a silicon atom, but R 4 exhibits excellent smoothness. Therefore, a fluorinated alkyl group, a fluorinated alkenyl group, a fluorinated aromatic group, a poly (perfluoroalkylene ether) group, one or more hydrogen atoms bonded to a silicon atom are each independently a methyl group and a phenylene group
- a polysiloxane group which may be substituted with a group selected from: a fluorinated alkyl group having 1 to 12 carbon atoms to which a fluorine atom is directly bonded, one or more hydrogen atoms bonded to a silicon atom More preferred is a polysiloxane group in which the atoms are each independently substituted with a group selected from a methyl group and a phenylene group, and a fluorine atom having 1 to 8 carbon atom
- R 4 for example, groups represented by the following formulas (I-R4-1) to (I-R4-19) are preferable.
- * represents a bonding site to Y 1
- R 51 to R 56 each independently represent a hydrogen atom, a methyl group, or a phenyl group
- R57 to R59 each independently represent 1 to 3 carbon atoms.
- n5 represents an integer of 1 to 150.
- the polymer having a thermally decomposable group of the present invention is a polymer other than the structural unit represented by the general formula (I-1-1) or the general formula (I-1-2) as long as the effects of the present invention are not impaired. It may contain a structural unit. Specifically, side chains can be exemplified by the following general formula (I-2-1) or general formula (I-2-2).
- R 11 and R 21 are each independently a hydrogen atom or a linear or branched carbon atom having 1 to 18 carbon atoms. Represents an organic group, Y 11 represents an oxygen atom or a sulfur atom, R 41 represents an organic group having 1 to 18 carbon atoms, and R 21 and R 41 are bonded to each other to form a hetero atom having Y 11 as a hetero atom. A ring may be formed, and * represents a binding site.
- R 11 represents a hydrogen atom
- R 21 represents a methyl group
- Y 11 is an oxygen atom or a sulfur atom.
- the side chain represented by the general formula (I-2-1) or (I-2-2) includes the following formula (I-2-1-1) or formula (I-2-2)
- the side chain represented by -1) is more preferable.
- the polymer having a thermally decomposable group of the present invention can be efficiently produced by, for example, the following method.
- Production method 1 Polymerizable monomer ( ⁇ ) having a hydroxyl group or a carboxyl group and the following general formula (IA)
- R 1 , R 21 and R 22 are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R 4 is an organic group having a fluorine atom and / or a silicon atom. .
- Production method 2 A method of reacting a polymer obtained by using a polymerizable monomer ( ⁇ ) having a hydroxyl group or a carboxyl group with a vinyl ether compound represented by the general formula (IA).
- Examples of the polymerizable monomer ( ⁇ ) having a hydroxyl group or a carboxyl group include (meth) acrylic acid, itaconic acid, mesaconic acid, maleic acid, fumaric acid, carboxyethyl (meth) acrylate, carboxypentyl (meta ) Acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyl Preferred examples include loxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid and the like. Among them, (meth) acrylic acid
- (meth) acrylate refers to one or both of methacrylate and acrylate
- (meth) acryloyl group refers to one or both of methacryloyl group and acryloyl group
- “Acrylic acid” refers to one or both of methacrylic acid and acrylic acid.
- the polymerizable monomer (A) include acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like.
- acrylic esters examples include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydro And furfuryl acrylate.
- methacrylic acid esters examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, furfuryl methacrylate, tetrahydro And furfuryl methacrylate.
- acrylamides examples include acrylamide, N-alkylacrylamide (alkyl groups having 1 to 3 carbon atoms, such as methyl group, ethyl group, propyl group), N, N-dialkylacrylamide (as alkyl group). Are those having 1 to 3 carbon atoms), N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like.
- methacrylamides examples include methacrylamide, N-alkylmethacrylamide (alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, propyl), N, N-dialkylmethacrylamide ( Examples of the alkyl group include those having 1 to 3 carbon atoms), N-hydroxyethyl-N-methylmethacrylamide, N-2-acetamidoethyl-N-acetylmethacrylamide and the like.
- allyl compound examples include allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.)
- allyl esters eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.
- vinyl ethers examples include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, Hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc., vinyl esters: vinyl vinylate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate , Vini Bareto, vinyl caproate, vinyl chloroacetate, vinyl di- chloroacetate, vinyl methoxyacetate
- dialkyl itaconates examples include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.
- dialkyl esters or monoalkyl esters of fumaric acid examples include dibutyl fumarate and the like, and also crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleilonitrile, styrene, and the like.
- a radical polymerizable monomer having an oxyalkylene group can also be used as the polymerizable monomer (A).
- the radical polymerizable monomer having an oxyalkylene group include polypropylene glycol mono (meth) acrylate, polytetramethylene glycol (meth) acrylate, poly (ethylene glycol / propylene glycol) mono (meth) acrylate, polyethylene glycol / Polypropylene glycol mono (meth) acrylate, poly (ethylene glycol / tetramethylene glycol) mono (meth) acrylate, polyethylene glycol / polytetramethylene glycol mono (meth) acrylate, poly (propylene glycol / tetramethylene glycol) mono (meth) acrylate , Polypropylene glycol polytetramethylene glycol mono (meth) acrylate, poly (propylene glycol butylene Cole) mono (meth) acrylate, polypropylene glycol /
- poly (ethylene glycol / propylene glycol) means a random copolymer of ethylene glycol and propylene glycol
- polyethylene glycol / polypropylene glycol means a block copolymer of ethylene glycol and propylene glycol. The same is true for the others.
- radical polymerizable monomers having an oxyalkylene group examples include “NK Ester AMP-10G”, “NK Ester AMP-20G”, and “NK Ester AMP-60G” manufactured by Shin-Nakamura Chemical Co., Ltd. "Blemmer PME-100”, “Blemmer PME-200”, “Blemmer PME-400”, “Blemmer PME-4000”, “Blemmer PP-1000", “Blemmer PP-500”, manufactured by NOF Corporation “Blemmer PP-800”, “Blemmer 70PEP-350B”, “Blemmer 55PET-800”, “Blemmer 50POEP-800B”, “Blemmer 10PPB-500B”, “Blemmer NKH-5050”, “Blemmer AP-400”, Sartomer "SR604" made by company It is.
- the radical polymerizable monomer ( ⁇ ) can be used alone or in combination of two or more.
- a radical polymerizable monomer having a fluorinated alkyl group or a poly (perfluoroalkylene ether) chain can be used as long as the effects of the present invention are not impaired.
- Preferred examples of the radical polymerizable monomer include those represented by the following general formula (A0).
- R represents a hydrogen atom or a methyl group
- L represents one of the following formulas (L-1) to (L-10)
- Rf represents the following formula (Rf -1) to any one of (Rf-7).
- n represents an integer of 1 to 8.
- m represents an integer of 1 to 8
- n represents an integer of 0 to 8.
- Rf ′′ represents any one of the following formulas (Rf-1) to (Rf-7).
- n is, for example, an integer of 1 to 6, and preferably an integer of 4 to 6.
- m in the above formula (Rf-5) is For example, it is an integer of 1 to 18, n is an integer of 0 to 5, and the sum of m and n is 1 to 23.
- m is an integer of 1 to 5, and n is 0 to 4 And the sum of m and n is 4 to 5.
- m is an integer of 1 to 6, for example, n is an integer of 1 to 3, and l is And an integer of 1 to 20, p is an integer of 0 to 5, and m, p and the sum of products of n and l are 2 to 71.
- m is an integer of 1 to 3.
- N is an integer of 1 to 3
- l is an integer of 1 to 6
- p is an integer of 0 to 2
- the sum of m, p, and the product of n and l is 2 to 23 .
- Specific examples of the radical polymerizable monomer having a fluorinated alkyl group or a poly (perfluoroalkylene ether) chain include, for example, the following polymerizable monomers (A-1) to (A-15). It can be illustrated preferably.
- N in Formula (A-13) to Formula (A-15) is, for example, 0 to 20.
- Examples of the vinyl ether compound represented by the general formula (IA) include 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1 -Vinyloxyoctane, 3,3,4,4,5,5,6,6,6-nonafluoro-1-vinyloxyhexane, and the like. Among them, it is preferable because the reaction with the polymer obtained using the polymerizable monomer ( ⁇ ) easily proceeds and the difference in polarity before and after heating increases.
- a vinyl ether compound other than the compound represented by the general formula (IA) is converted into a vinyl ether compound represented by the general formula (IA) and It can also be used in combination as long as the effects of the present invention are not impaired.
- vinyl ether compounds include aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether; Aliphatic vinyl thioether compound; 2,3-dihydrofuran, 3,4-dihydrofuran, 2,3-dihydro-2H-pyran, 3,4-dihydro-2H-pyran, 3,4-dihydro-2-methoxy- 2H-pyran, 3,4-dihydro-4,4-dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy-2H-pyran, 3,4-dihydro-2H-pyran-2- Cyclic vinyl such as sodium carboxylate Ether compounds, cyclic vinyl thioether compounds corresponding to these.
- the polymerizable monomer ( ⁇ ) having a carboxyl group is reacted with the vinyl ether compound represented by the general formula (IA).
- a polymerizable monomer having a blocked carboxyl group is obtained.
- the reaction conditions include heating to about 20 to 100 ° C. in the presence of an acid catalyst. And when polymerizing the polymerizable monomer which has the blocked carboxyl group, it can carry out on the conditions on which the polymerizable monomer ((alpha)) mentioned later is polymerized.
- the method for obtaining the polymer using the polymerizable monomer ( ⁇ ) is not particularly limited.
- the polymerizable monomer ( ⁇ ) and, if necessary, the radically polymerizable monomer examples thereof include a method of polymerizing ( ⁇ ) in an organic solvent using a radical polymerization initiator.
- a radical polymerization initiator As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons are preferable.
- acetone methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate
- examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility, and polymerizability.
- radical polymerization initiator examples include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile.
- a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid or the like can be used as necessary.
- the polymer and the vinyl ether compound represented by the general formula (IA) can be reacted, for example, by heating to about 20 to 100 ° C. in the presence of an acid catalyst. .
- the carboxyl group of the polymer is blocked, and a polymer having a structure represented by the general formula (I-1-1) or the general formula (I-1-2) is obtained.
- the blocked carboxyl group is released from the blocked vinyl ether in a high temperature environment, for example, in an environment of 150 to 300 ° C., and the carboxyl group is regenerated.
- the polymer having a thermally decomposable group is preferably a polymer having a structural unit selected from the following general formula (I-1-1-1) to general formula (I-1-2-2).
- R 1 represents a hydrogen atom or a linear or branched organic group having 1 to 18 carbon atoms.
- R 41 and R 5 each independently represents an alkylene group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an alicyclic hydrocarbon group having 4 to 12 carbon atoms.
- R 6 represents a hydrogen atom or a methyl group
- R 42 represents an organic group having a fluorine atom and / or a silicon atom
- n represents an integer of 0 to 12.
- a preferable group of R 42 is the general formula (I-1-1) or the general formula (I-1 The same as the preferable group of R 4 described in 2).
- the alignment film material containing the polymer having a thermally decomposable group When the alignment film material containing the polymer having a thermally decomposable group is applied to a substrate, the polymer having a thermally decomposable group containing fluorine atoms and / or silicon atoms is segregated on the coating film surface.
- the surface of the film obtained by the group having fluorine atoms and / or silicon atoms being detached from the polymer in a state of being segregated on the surface becomes smooth.
- the pretilt angle formed by the polymer of the compound having a polymerizable group that controls the alignment direction of liquid crystal molecules in the liquid crystal composition layer described later is uniformly stabilized on the alignment film layer. Can be granted.
- the number average molecular weight (Mn) of the polymer having a thermally decomposable group used in the present invention represented by the general formula (I-1-1-1) to the general formula (I-1-2-2) is as follows.
- the range of 1,000 to 50,000 is preferred, the range of 1,500 to 20,000 is more preferred, and the range of 2,000 to 8,000 is even more preferred.
- the weight average molecular weight (Mw) is preferably in the range of 1,000 to 100,000, and more preferably in the range of 5,000 to 70,000.
- the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement.
- GPC gel permeation chromatography
- the polymer having a thermally decomposable group used in the alignment film of the present invention can be used alone or in combination of two or more.
- the total amount blended in the alignment film material of the polymer having a thermally decomposable group used in the present invention is preferably 0.01 to 5% by mass with respect to the total solid content of the alignment film material.
- the amount is preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass, and further preferably 0.2 to 1% by mass.
- Method of blending a polymer having a thermally decomposable group and a polymerizable compound having a polymerizable group in the alignment film material As a method of blending the polymer having a thermally decomposable group and the polymerizable compound having a polymerizable group in the alignment film material, the above-mentioned thermally decomposable group is added to the polymer compound precursor as an alignment film material.
- blending the polymer which has a polymer which has and a polymeric group which has and a polymeric group is mentioned. Then, the alignment film surface can be smoothed by the heating step (firing) of the polymer compound precursor.
- the pretilt angle formed by the polymer of the compound having a polymerizable group can be stably imparted on the alignment film layer, and the alignment direction of the liquid crystal molecules in the liquid crystal composition layer to be described later can be uniformly controlled. can do.
- the polymerizable compound having a reactive group contained in the alignment film material may or may not contain a mesogenic site.
- the polymer of the polymerizable compound having a reactive group preferably has a cross-linked structure from the viewpoint of durability. From the viewpoint of durability, the polymerizable compound having a reactive group is bifunctional or trifunctional. A polymerizable compound having two or more reactive groups such as a functional group is preferred.
- 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.
- X 7 and X 8 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 —X— (CH 2 ) s —
- U represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms, a linear or branched polyvalent alkenylene group having 3 to 20 carbon atoms, or a polyvalent cyclic substituent having 5 to 30 carbon atoms.
- the alkylene group in the polyvalent alkylene group or the alkenylene group in the polyvalent alkenylene group may be substituted with —O—, —CO—, —CF 2 — within the range in which the oxygen atom is not adjacent,
- the oxygen group may be substituted with an oxygen atom in the range where the oxygen atoms are not adjacent to each other)), or may be substituted with a cyclic substituent, and k represents an integer of 0 to 5.) are preferred.
- X 7 and X 8 each independently represent a hydrogen atom or a methyl group.
- a hydrogen atom is preferable, and importance is placed on reducing the residual amount of the 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 8 carbon atoms, or —X— (CH 2 ) s — (wherein s is 2 to 7 X represents O, OCOO, or COO, and X is bonded to an aromatic ring present in U.), but the carbon chain is preferably not so long, and a single bond or An alkylene group having 1 to 5 carbon atoms is preferable, and a single bond or an alkylene group having 1 to 3 carbon atoms is more preferable.
- Sp 1 and Sp 2 represent —X— (CH 2 ) s —
- s is preferably 1 to 5, more preferably 1 to 3, and at least one of Sp 1 and Sp 2 is a single bond. More preferably, it is particularly preferable that both are single bonds.
- k represents an integer of 0 to 5.
- k represents an integer of 1 to 5. It is more preferable that k represents an integer of 1 to 3, and it is more preferable that k represents 1 or 2.
- U represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms, a linear or branched polyvalent alkenylene group having 3 to 20 carbon atoms, or a polyvalent having 5 to 30 carbon atoms.
- An alkyl group (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 may be substituted with two or more cyclic substituents; It is preferable.
- U specifically preferably represents the following formulas (Va-1) to (Va-6), and the formulas (Va-1), (Va-2), It is more preferable to represent the formula (Va-6), and it is particularly preferable to represent the formula (Va-1).
- Z 1 , Z 2 and Z 3 are each independently —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-, -O (CH 2) m
- At least one of Sp 1 and Sp 2 preferably represents a single bond, and it is also preferable that both are single bonds.
- k represents an integer of 0 to 5, and is preferably a bifunctional compound in which k is 1 or a trifunctional compound in which k is 2.
- the compound represented by the general formula (V) is preferably a compound represented by the following general formulas (Va-1-1) to (Va-5-3).
- the content of the compound represented by the general formula (V) in the alignment film material forming the alignment film is based on the total solid content of the alignment film material.
- the amount is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 25% by mass.
- the polymerizable compound having a polymerizable group contained in the alignment film material contains a polymerizable compound represented by the following general formula (V-1) in addition to the compound represented by the general formula (V). Also good.
- X 10 and X 11 each independently represent a hydrogen atom or a methyl group
- Sp 3 and Sp 4 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or —X— (CH 2 ) t — (wherein t represents an integer of 2 to 7, X represents —O—, —OCOO—, —OCO—, or —COO—, and X represents a bond to the phenanthrene ring.
- any hydrogen atom may be substituted with a fluorine atom.
- X 10 and X 11 each independently represent a hydrogen atom or a methyl group.
- a hydrogen atom is preferable, and the residual amount of the reaction is reduced. In the case where importance is attached to methyl, a methyl group is preferred.
- Sp 3 and Sp 4 are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, or —X— (CH 2 ) t — (wherein t is 2 Represents an integer of ⁇ 7, X represents —O—, —OCOO—, or —COO—, and X represents a bond to the phenanthrene ring), but the carbon chain is preferably not so long, A single bond or an alkylene group having 1 to 5 carbon atoms is preferable, and a single bond or an alkylene group having 1 to 3 carbon atoms is more preferable.
- t is preferably 1 to 5, more preferably 1 to 3, and at least one of Sp 3 and Sp 4 is a single bond. More preferably, it is particularly preferable that both are single bonds.
- the compound represented by the general formula (V-1) is preferably a compound represented by the following general formulas (V-1-1) to (V-1-52).
- the content of the compound represented by the general formula (V-1) in the alignment film material forming the alignment film is the total solid content of the alignment film material. On the other hand, it is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and further preferably 10 to 25% by mass.
- the total content of the polymerizable compound having a polymerizable group (the total amount of the compounds represented by the general formula (V) and / or the general formula (V-1)) is The amount is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 25% by mass.
- the total blending amount of the polymer having the thermally decomposable group in the alignment film material is preferably 0.01 to 5% by mass with respect to the total amount of the alignment film material.
- the content is preferably from 05 to 3% by mass, more preferably from 0.1 to 2% by mass, and further preferably from 0.2 to 1% by mass.
- Method of blending a polymer having a thermally decomposable group using a polymer of a polymerizable compound having a crosslinkable functional group in the side chain portion as an alignment film material As a method for obtaining an alignment film having two functions of the vertical alignment ability and the alignment control ability, a method using a polymer of a polymerizable compound having a crosslinkable functional group in the side chain portion as the alignment film material is also preferable. Moreover, also when using the said method, the alignment film surface can be smooth
- the pretilt angle formed by the polymer of the compound having a polymerizable group can be stably imparted on the alignment film layer, and the alignment direction of the liquid crystal molecules in the liquid crystal composition layer to be described later can be uniformly controlled. can do.
- the polymerizable compound having a crosslinkable functional group in the side chain portion is not particularly limited as long as it has a crosslinkable functional group (polymerizable group) in the side chain portion. It is preferable to use a compound having an imide skeleton or a siloxane skeleton, and it is more preferable to use a compound having a polyimide skeleton in the main chain portion.
- Examples of the polymerizable compound having a polyimide skeleton in the main chain portion and a crosslinkable functional group as a side chain include compounds having a crosslinkable functional group as a side chain in the repeating unit (main chain portion) constituting the polyimide structure. It is done. And the said crosslinkable functional group becomes a polymerization reaction start point, and the polymerizable compound which has a polymerizable group mix
- R 1 represents an alkyl group having 1 to 5 carbon atoms.
- the crosslinkable functional group only needs to be bonded to the main chain portion via a covalent bond, and may be directly bonded to the main chain portion or may be bonded to the main chain portion via a linking group.
- As the linking group —O—C 6 H 4 — or —O—C 6 H 4 — (R 2 O) r— is preferably used (R 2 represents an alkylene group having 1 to 20 carbon atoms). R represents an integer of 1 or more.)
- a polymerizable compound having a polyimide skeleton as a main chain and a crosslinkable functional group as a side chain for example, a compound represented by the following general formula (V-3) can be exemplified.
- R 3 represents any one of the groups represented by the following (V-3-A) to (V-3-F)
- R 4 and R 5 are each independently represent an alkylene group having a carbon number of 1 ⁇ 20, R 6 and R 7, any of the independently a group represented by the above (P2-1) ⁇
- 1 represents an integer
- n represents an integer of 1 or more
- m1 and m2 each represents 0 or 1
- m3 and m4 each represents 0 or an integer of 1 or more
- m5 and m6 represent 0 or 1 respectively.
- M5 and m6 each represents 1.
- a polymerizable compound having a polymerizable group to be blended in an alignment film material together with a polymerizable compound having a polyimide skeleton in the main chain portion and a crosslinkable functional group as a side chain is represented by the general formula (V). And the same compounds as those represented by the general formula (V-1).
- the total blending amount of the compound represented by the general formula (V) and the compound represented by the general formula (V-1) in the alignment film material is 1 to It is preferably 40% by mass, preferably 3 to 35% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 25% by mass.
- the total blending amount of the polymer having the thermally decomposable group in the alignment film material is preferably 0.01 to 5% by mass with respect to the total amount of the alignment film material.
- the content is preferably from 05 to 3% by mass, more preferably from 0.1 to 2% by mass, and further preferably from 0.2 to 1% by mass.
- Method using cured product of polymerizable liquid crystal compound as alignment film As a method for obtaining an alignment film having two functions of the vertical alignment ability and the alignment control ability, a method using a cured product of a polymerizable liquid crystal compound as the alignment film is also preferable.
- an alignment film is obtained by heating (baking) the polymerizable liquid crystal composition, which is an alignment film material containing the polymerizable liquid crystal compound and the polymer having the thermally decomposable group.
- the surface can be smoothed.
- the pretilt angle formed by the polymer of the compound having a polymerizable group can be stably imparted on the alignment film layer, and the alignment direction of the liquid crystal molecules in the liquid crystal composition layer to be described later can be uniformly controlled. can do.
- an alignment film made of the above-described polyimide material or polysiloxane material may be used as the undercoat alignment film.
- the polymerizable liquid crystal compound forming the alignment film contains one or more polymerizable liquid crystal compounds represented by the following general formula (V3).
- X 1 represents a hydrogen atom or a methyl group
- Sp 1 and Sp 2 are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH 2 ) s —
- Z 1 represents —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 CH 2 —, —OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —CH 2 CH
- X 2 represents a hydrogen atom or a methyl group
- the C ring represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, -Any hydrogen atom of the phenylene group may be substituted with a fluorine atom.
- X 1 and X 2 are independently focused on represent a hydrogen atom or a methyl group, preferably a hydrogen atom in the case of emphasizing the reaction rate, to reduce the residual reaction volume 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 8 carbon atoms, or —O— (CH 2 ) s — (wherein s is 2 to 7 Wherein the oxygen atom is bonded to the aromatic ring), the carbon chain is preferably not so long, a single bond or an alkylene group having 1 to 5 carbon atoms is preferable, and a single bond or An alkylene group having 1 to 3 carbon atoms is more preferred.
- Sp 1 and Sp 2 represent —O— (CH 2 ) s —
- s is preferably 1 to 5, more preferably 1 to 3, and at least one of Sp 1 and Sp 2 is a single bond. More preferably, it is particularly preferable that both are single bonds.
- 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 is preferably a linking group other than a single bond.
- Z 1 is preferably a single bond.
- Y is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, a hydrogen atom, a fluorine atom, or
- a compound representing a cyano group is a monofunctional polymerizable liquid crystal compound, and Y does not have a polymerizable skeleton.
- the compound in which Y represents the above-described polymerizable skeleton is a bifunctional polymerizable liquid crystal compound.
- either a monofunctional polymerizable liquid crystal compound or a bifunctional polymerizable liquid crystal compound can be used, but a bifunctional polymerizable liquid crystal compound is preferable from the viewpoint of heat resistance, and both of them are used simultaneously. You can also.
- a compound represented by the general formula (V) (excluding a compound represented by the general formula (V3)), and Alternatively, one or more compounds represented by the general formula (V-1) may be used in combination.
- the total blending amount of the polymer having the thermally decomposable group in the alignment film material is preferably 0.01 to 5% by mass with respect to the total amount of the alignment film material.
- the content is preferably from 05 to 3% by mass, more preferably from 0.1 to 2% by mass, and further preferably from 0.2 to 1% by mass.
- the vertical alignment film includes a polymer formed by polymerization of a polymerizable compound having a reactive group, and the polymer can give an appropriate pretilt angle.
- the polymerizable compound is contained in the liquid crystal composition, and after sandwiching the liquid crystal composition between the substrates, the polymerizable compound is cured by applying the voltage to cure the polymerizable compound.
- the polymerizable compound for forming the polymerization layer is a monofunctional polymerizable compound having one reactive group, a polyfunctional polymerizable compound having two or more reactive groups such as bifunctional or trifunctional, etc. However, a polyfunctional polymerizable compound having two or more reactive groups such as bifunctional or trifunctional is preferable.
- the polymerizable compound used may be one type or two or more types.
- the polymerizable compound for forming the polymer layer preferably contains at least one compound represented by the above general formula (V) and / or the above general formula (V-1).
- the liquid crystal composition in the present invention contains one or more compounds represented by general formula (N-1), general formula (N-2), and general formula (N-3).
- R N11 , R N12 , R N21 , R N22 , R N31 and R N32 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two non-adjacent groups in the alkyl group
- the above —CH 2 — may be independently substituted with —CH ⁇ CH—, —C ⁇ C—, —O—, —CO—, —COO— or —OCO—
- a N11 , A N12 , A N21 , A N22 , A N31, and A N32 are each independently (a) a 1,4-cyclohexylene group (one —CH 2 — or adjacent to each other in this group).
- —CH 2 — may be replaced by —O—
- the group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom, Z N11 , Z N12 , Z N21 , Z N22 , Z N31 and Z N32 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—.
- XN21 represents a hydrogen atom or a fluorine atom
- T N31 represents —CH 2 — or —O—.
- n N11 , n N12 , n N21 , n N22 , n N31, and n N32 each independently represent an integer of 0 to 3, but n N11 + n N12 , n N21 + n N22, and n N31 + n N32 are each independently When there are a plurality of A N11 to A N32 and Z N11 to Z N32 , they may be the same or different.
- the compounds represented by the general formulas (N-1), (N-2) and (N-3) are preferably compounds having a negative ⁇ and an absolute value larger than 3.
- R N11 , R N12 , R N21 , R N22 , R N31 and R N32 each independently represent 1 to 8 carbon atoms.
- An alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms preferably an alkyl group having 1 to 5 carbon atoms.
- An alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is preferable.
- an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is more preferable, and an alkenyl group having 3 carbon atoms (propenyl group
- the ring structure to which it is bonded is a phenyl group (aromatic)
- An alkenyl group having 4 to 5 atoms is preferable
- the ring structure to which the alkenyl group is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane
- a straight-chain alkoxy group having 1 to 4 carbon atoms and a straight-chain alkenyl group having 2 to 5 carbon atoms are preferred.
- the total of carbon atoms and oxygen atoms, if present is preferably 5 or less, and is preferably linear.
- the alkenyl group is preferably selected from groups represented by any of the formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure.)
- a N11 , A N12 , A N21 , A N22 , A N31, and A N32 are preferably aromatic when it is required to increase ⁇ n independently, and in order to improve the response speed, fat
- fat Preferably a trans-1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5 -Difluoro-1,4-phenylene group, 2,3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1 , 4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group Preferred, it is more preferable that represents the following
- it represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group.
- Z N11, Z N12, Z N21 , Z N22, Z N31 and Z N32 -CH 2 each independently O -, - CF 2 O - , - CH 2 CH 2 -, - CF 2 CF 2 - or a single bond preferably represents an, -CH 2 O -, - CH 2 CH 2 - or a single bond is more preferable, -CH 2 O-or a single bond is particularly preferred.
- XN21 is preferably a fluorine atom.
- T N31 is preferably —O—.
- n N11 + n N12 , n N21 + n N22 and n N31 + n N32 are preferably 1 or 2, a combination in which n N11 is 1 and n N12 is 0, a combination in which n N11 is 2 and n N12 is 0, n A combination in which N11 is 1 and n N12 is 1, a combination in which n N11 is 2 and n N12 is 1, a combination in which n N21 is 1 and n N22 is 0, n N21 is 2 and n N22 is n A combination in which n N31 is 1 and n N32 is 0, and a combination in which n N31 is 2 and n N32 is 0 are preferable.
- the lower limit of the preferable content of the compound represented by the general formula (N-1) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter referred to simply as%), 10%, 20%, 30%, 40%, 50%, 55%, 60% Yes, 65%, 70%, 75%, 80%.
- the upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% It is.
- the lower limit of the preferable content of the compound represented by the general formula (N-2) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%), 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%.
- the upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% It is.
- the lower limit of the preferable content of the compound represented by the general formula (N-3) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%.
- the upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% It is.
- the above lower limit value is preferably low and the upper limit value is preferably low. Furthermore, when the composition of the present invention keeps Tni high and a composition having good temperature stability is required, the above lower limit value is preferably low and the upper limit value is preferably low. When it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the above lower limit value is increased and the upper limit value is high.
- the compound represented by the general formula (N-1) is preferably a compound selected from the group of compounds represented by the general formulas (N-1-1) to (N-1-21).
- the compound represented by the general formula (N-1-1) is the following compound.
- R N111 and R N112 each independently represent the same meaning as R N11 and R N12 in formula (N-1)).
- R N111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably a propyl group or a pentyl group.
- RN112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group or a butoxy group.
- the compound represented by the general formula (N-1-1) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the formula (N-1-1) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%). 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33% 35%.
- the upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 30% with respect to the total amount of the liquid crystal composition of the present invention. 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3%.
- the compound represented by the general formula (N-1-1) is a compound selected from the group of compounds represented by the formula (N-1-1.1) to the formula (N-1-1.14).
- it is a compound represented by the formulas (N-1-1.1) to (N-1-1.4), and the formula (N-1-1.1) and the formula (N
- the compound represented by -1-1.3) is preferable.
- the compounds represented by the formulas (N-1-1.1) to (N-1-1.4) can be used alone or in combination, but the liquid crystal composition of the present invention
- the lower limit of the preferred content of these compounds alone or with respect to the total amount is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, and 15%. 17%, 20%, 23%, 25%, 27%, 30%, 33%, and 35%.
- the upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 30% with respect to the total amount of the liquid crystal composition of the present invention. 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3%.
- the compound represented by the general formula (N-1-2) is the following compound.
- R N121 and R N122 each independently represent the same meaning as R N11 and R N12 in formula (N-1)).
- RN121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group, a butyl group or a pentyl group.
- RN122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and includes a methyl group, a propyl group, a methoxy group, an ethoxy group, or a propoxy group. preferable.
- the compound represented by the general formula (N-1-2) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the formula (N-1-2) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%). 7%, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30% 33%, 35%, 37%, 40%, 42%.
- the upper limit of the preferred content is 50%, 48%, 45%, 43%, 40%, 38%, with respect to the total amount of the liquid crystal composition of the present invention, 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6%, 5%.
- the compound represented by the general formula (N-1-2) is a compound selected from the group of compounds represented by the formula (N-1-2.1) to the formula (N-1-2.13).
- the compound represented by (N-1-2.13) is preferable, and when importance is placed on the improvement of ⁇ , the formula (N-1-2.3) to the formula (N-1-2.7) in the compounds represented, when emphasizing improvements in T NI formula (N-1-2.10), formula (N-1-2.11) and formula (N-1-2.13) It is preferable that it is a compound represented by these.
- the compounds represented by the formulas (N-1-2.1) to (N-1-2.13) can be used alone or in combination.
- the lower limit of the preferred content of these compounds alone or with respect to the total amount of the product is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, 15% Yes, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%.
- the upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 30% with respect to the total amount of the liquid crystal composition of the present invention. 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3%.
- the compound represented by the general formula (N-1-3) is the following compound.
- R N131 and R N132 each independently represent the same meaning as R N11 and R N12 in formula (N-1)).
- R N131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group.
- R N132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.
- the compound represented by the general formula (N-1-3) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the formula (N-1-3) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%). 10%, 13%, 15%, 17%, 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.
- the compound represented by the general formula (N-1-3) is a compound selected from the group of compounds represented by the formula (N-1-3.1) to the formula (N-1-3.11).
- it is a compound represented by the formulas (N-1-3.1) to (N-1-3.7), and the formula (N-1-3.1) and the formula (N -1-3.2), formula (N-1-3.3), formula (N-1-3.4) and compounds represented by formula (N-1-3.6) are preferred.
- the compounds represented by formula (N-1-3.1) to formula (N-1-3.4) and formula (N-1-3.6) may be used alone or in combination. Is possible, but the combination of formula (N-1-3.1) and formula (N-1-3.2), formula (N-1-3.3), formula (N-1-3.4) ) And a combination of two or three selected from formula (N-1-3.6) are preferred.
- the lower limit of the preferred content of these compounds alone or with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, and 13%. Yes, 15%, 17%, 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the liquid crystal composition of the present invention. 18%, 15% and 13%.
- the compound represented by the general formula (N-1-4) is the following compound.
- R N141 and R N142 each independently represents the same meaning as R N11 and R N12 in the general formula (N-1).
- R N141 and R N142 are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group or an alkoxy group having 1 to 4 carbon atoms carbon atoms 4-5 preferably a methyl group, a propyl group, an ethoxy Group or butoxy group is preferred.
- the compound represented by the general formula (N-1-4) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the formula (N-1-4) with respect to the total amount of the liquid crystal composition of the present invention is 3% by mass (hereinafter, mass% is simply expressed as%). 5%, 7%, 10%, 13%, 15%, 17%, 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the liquid crystal composition of the present invention. 18%, 15%, 13%, 11%, 10%, 8%.
- the compound represented by the general formula (N-1-4) is a compound selected from the group of compounds represented by the formula (N-1-4.1) to the formula (N-1-4.14).
- it is a compound represented by the formulas (N-1-4.1) to (N-1-4.4), and the formula (N-1-4.1) and the formula (N
- the compound represented by -1-4.2) is preferable.
- the compounds represented by the formulas (N-1-4.1) to (N-1-4.4) can be used alone or in combination, but the liquid crystal composition of the present invention
- the lower limit of the preferable content of these compounds alone or with respect to the total amount of 3% is 3% by mass (hereinafter, mass% is simply expressed as%), 5%, 7%, and 10%. 13%, 15%, 17%, 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the liquid crystal composition of the present invention. 18%, 15%, 13%, 11%, 10%, 8%.
- the compound represented by the general formula (N-1-5) is the following compound.
- R N151 and R N152 each independently represent the same meaning as R N11 and R N12 in formula (N-1).
- R N151 and R N152 are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethyl group, a propyl group, or a butyl group. Is preferred.
- the compound represented by the general formula (N-1-5) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the formula (N-1-5) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%). 8%, 10%, 13%, 15%, 17%, 20%.
- the upper limit of the preferable content is 35%, 33%, 30%, 28%, 25%, and 23% with respect to the total amount of the liquid crystal composition of the present invention, 20%, 18%, 15%, 13%.
- the compound represented by the general formula (N-1-5) is a compound selected from the group of compounds represented by the formula (N-1-5.1) to the formula (N-1-5.6). It is preferable that a compound represented by the formula (N-1-3.2 and the formula (N-1-3.4) is preferable.
- the compounds represented by formula (N-1-3.2) and formula (N-1-3.4) can be used alone or in combination, but the liquid crystal composition of the invention
- the lower limit value of the preferred content of these compounds alone or with respect to the total amount of is 5% by mass (hereinafter, mass% is simply expressed as%), 8%, 10%, and 13%. 15%, 17%, and 20%
- the upper limit of the preferred content is 35%, 33%, and 30% with respect to the total amount of the liquid crystal composition of the present invention. 28%, 25%, 23%, 20%, 18%, 15%, 13%.
- the compound represented by the general formula (N-1-10) is the following compound.
- R N1101 and R N1102 each independently represent the same meaning as R N11 and R N12 in formula (N-1).
- R N1101 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group.
- R N1102 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.
- the compound represented by the general formula (N-1-10) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the formula (N-1-10) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%). 10%, 13%, 15%, 17%, 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.
- the compound represented by the general formula (N-1-10) is a compound selected from the group of compounds represented by the formula (N-1-10.1) to the formula (N-1-10.11).
- it is a compound represented by the formulas (N-1-10.1) to (N-1-10.5), and the formula (N-1-10.1) and the formula (N
- the compound represented by (1-10.2) is preferable.
- the compounds represented by the formula (N-1-10.1) and the formula (N-1-10.2) can be used alone or in combination.
- the lower limit of the preferred content of these compounds alone or with respect to the total amount of the product is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, 15% Yes, 17%, 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the liquid crystal composition of the present invention. 18%, 15% and 13%.
- the compound represented by the general formula (N-1-11) is the following compound.
- R N1111 and R N1112 each independently represent the same meaning as R N11 and R N12 in formula (N-1).
- R N1111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group.
- R N1112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.
- the compound represented by the general formula (N-1-11) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the formula (N-1-11) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%). 10%, 13%, 15%, 17%, 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the liquid crystal composition of the present invention. 18%, 15% and 13%.
- the compound represented by the general formula (N-1-11) is a compound selected from the group of compounds represented by the formula (N-1-11.1) to the formula (N-1-11.15).
- it is a compound represented by the formulas (N-1-11.1) to (N-1-11.15), and is preferably a compound represented by the formula (N-1-11.2) or the formula (N-- The compound represented by 1-11.4) is preferable.
- the compounds represented by the formulas (N-1-11.2 and (N-1-11.4) can be used alone or in combination, but the liquid crystal composition of the present invention
- the lower limit of the preferred content of these compounds alone or with respect to the total amount is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, and 15%.
- the upper limit of the preferable content is 35%, 30%, 28%, and 25% with respect to the total amount of the liquid crystal composition of the present invention. 23%, 20%, 18%, 15%, 13%.
- the compound represented by the general formula (N-1-12) is the following compound.
- R N1121 and R N1122 each independently represent the same meaning as R N11 and R N12 in formula (N-1)).
- RN1121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group.
- RN1122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.
- the compound represented by the general formula (N-1-12) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the formula (N-1-12) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, the mass% is simply expressed as%). 10%, 13%, 15%, 17%, 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the liquid crystal composition of the present invention. 18%, 15% and 13%.
- the compound represented by the general formula (N-1-13) is the following compound.
- R N1131 and R N1132 each independently represent the same meaning as R N11 and R N12 in formula (N-1)).
- R N1131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group.
- R N1132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.
- the compound represented by the general formula (N-1-13) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the formula (N-1-13) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%). 10%, 13%, 15%, 17%, 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.
- the compound represented by the general formula (N-1-14) is the following compound.
- R N1141 and R N1142 each independently represent the same meaning as R N11 and R N12 in formula (N-1)).
- R N1141 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group.
- R N1142 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.
- the compound represented by the general formula (N-1-14) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the formula (N-1-14) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%). 10%, 13%, 15%, 17%, 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the liquid crystal composition of the present invention. 18%, 15% and 13%.
- the compound represented by the general formula (N-1-15) is the following compound.
- R N1151 and R N1152 each independently represent the same meaning as R N11 and R N12 in formula (N-1)).
- RN1151 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group.
- R N1152 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.
- the compound represented by the general formula (N-1-15) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the formula (N-1-15) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%). 10%, 13%, 15%, 17%, 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the liquid crystal composition of the present invention. 18%, 15% and 13%.
- the compound represented by the general formula (N-1-16) is the following compound.
- R N1161 and R N1162 each independently represent the same meaning as R N11 and R N12 in formula (N-1).
- R N1161 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group.
- R N1162 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.
- the compound represented by the general formula (N-1-16) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the formula (N-1-16) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, the mass% is simply expressed as%). 10%, 13%, 15%, 17%, 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the liquid crystal composition of the present invention. 18%, 15% and 13%.
- the compound represented by the general formula (N-1-17) is the following compound.
- R N1171 and R N1172 each independently represent the same meaning as R N11 and R N12 in formula (N-1)).
- RN1171 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group.
- R N1172 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.
- the compound represented by the general formula (N-1-17) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the formula (N-1-17) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%). 10%, 13%, 15%, 17%, 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the liquid crystal composition of the present invention. 18%, 15% and 13%.
- the compound represented by the general formula (N-1-18) is the following compound.
- R N1181 and R N1182 each independently represent the same meaning as R N11 and R N12 in General Formula (N)).
- RN1181 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group.
- R N1182 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.
- the compound represented by the general formula (N-1-18) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the formula (N-1-18) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, the mass% is simply expressed as%). 10%, 13%, 15%, 17%, 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the liquid crystal composition of the present invention. 18%, 15% and 13%.
- the compound represented by the general formula (N-1-20) is the following compound.
- R N1201 and R N1202 each independently represent the same meaning as R N11 and R N12 in formula (N)).
- the compound represented by the general formula (N-1-21) is the following compound.
- R N1211 and R N1212 each independently represent the same meaning as R N11 and R N12 in formula (N-1).
- the compound represented by the general formula (N-2) is preferably a compound selected from the group of compounds represented by the general formulas (N-2-1) to (N-2-3).
- the compound represented by the general formula (N-2-1) is the following compound.
- R N211 and R N212 each independently represents the same meaning as R N21 and R N22 in the general formula (N-2).
- the compound represented by the general formula (N-2-2) is the following compound.
- R N221 and R N222 each independently represents the same meaning as R N21 and R N22 in the general formula (N-2).
- the compound represented by the general formula (N-2-3) is the following compound.
- the compound represented by the general formula (N-3) is preferably a compound selected from the group of compounds represented by the general formulas (N-3-1) to (N-3-2).
- the compound represented by the general formula (N-3-1) is the following compound.
- R N311 and R N312 each independently represent the same meaning as R N11 and R N12 in formula (N-1)).
- the compound represented by the general formula (N-3-2) is the following compound.
- R N321 and R N322 each independently represent the same meaning as R N11 and R N12 in formula (N-1).
- General formula (N-1), general formula (N-2), and general formula (N-3) with respect to the total amount of the liquid crystal composition of the present invention total amount of liquid crystal compounds contained in the liquid crystal composition
- the total amount of the compound represented by the formula is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, further preferably 20 to 70% by mass, further preferably 20 to 60% by mass, Is more preferably 55 to 55% by mass, further preferably 25 to 55% by mass, and particularly preferably 30 to 55% by mass.
- the total amount of the compounds represented by the general formula (N-1), the general formula (N-2), and the general formula (N-3) is a lower limit in the liquid crystal composition.
- mass% is simply expressed as%), preferably 5% or more, preferably 10% or more, preferably 13% or more, 15 %, Preferably 18% or more, preferably 20% or more, preferably 23% or more, preferably 25% or more, 28% or more. 30% or more, preferably 33% or more, preferably 35% or more, preferably 38% or more, preferably 40% or more Masui.
- the upper limit value is preferably 95% or less, preferably 90% or less, preferably 88% or less, preferably 85% or less, and preferably 83% or less. 80% or less, preferably 78% or less, preferably 75% or less, preferably 73% or less, preferably 70% or less, preferably 68% or less Preferably 65% or less, preferably 63% or less, preferably 60% or less, preferably 55% or less, preferably 50% or less, It is preferable to contain 40% or less.
- the liquid crystal composition in the present invention preferably contains one or more compounds represented by the general formula (L).
- the compound represented by the general formula (L) corresponds to a dielectrically neutral compound ( ⁇ value is ⁇ 2 to 2).
- R L1 and R L2 each independently represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH 2 — in the alkyl group are each independently Optionally substituted by —CH ⁇ CH—, —C ⁇ C—, —O—, —CO—, —COO— or —OCO—, n L1 represents 0, 1, 2 or 3,
- a L1 , A L2 and A L3 each independently represent (a) a 1,4-cyclohexylene group (one —CH 2 — present in the group or two or more —CH 2 — not adjacent to each other).
- the group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom
- the compound represented by general formula (L) may be used independently, it can also be used in combination.
- the types of compounds that can be combined but they are used in appropriate combinations according to desired properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention.
- the content of the compound represented by the general formula (L) is low-temperature solubility, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, image sticking, It is necessary to appropriately adjust according to required performance such as dielectric anisotropy.
- the lower limit of the preferable content of the compound represented by the formula (L) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%), which is 10%. Yes, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% is there.
- the upper limit of the preferable content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, and 25%.
- the above lower limit value is preferably high and the upper limit value is preferably high. Furthermore, when the composition of the present invention maintains a high Tni and requires a composition having good temperature stability, the above lower limit value is preferably high and the upper limit value is preferably high. Further, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the above lower limit value is lowered and the upper limit value is low.
- R L1 and R L2 are preferably both alkyl groups, and when importance is placed on reducing the volatility of the compound, it is preferably an alkoxy group, and importance is placed on viscosity reduction. In this case, at least one is preferably an alkenyl group.
- R L1 and R L2 are each a linear alkyl group having 1 to 5 carbon atoms or a linear alkyl group having 1 to 4 carbon atoms when the ring structure to which R L1 is bonded is a phenyl group (aromatic).
- a phenyl group aromatic
- Alkyl groups, linear alkoxy groups having 1 to 4 carbon atoms and linear alkenyl groups having 2 to 5 carbon atoms are preferred.
- the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.
- the alkenyl group is preferably selected from groups represented by any of the formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure.)
- n L1 is preferably 0 when importance is attached to the response speed, 2 or 3 is preferred for improving the upper limit temperature of the nematic phase, and 1 is preferred for balancing these. In order to satisfy the properties required for the composition, it is preferable to combine compounds having different values.
- a L1 , A L2, and A L3 are preferably aromatic when it is required to increase ⁇ n, and are preferably aliphatic for improving the response speed, and are each independently trans- 1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6 -It preferably represents a diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably represents the following structure:
- it represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group.
- Z L1 and Z L2 are preferably single bonds when the response speed is important.
- the compound represented by the general formula (L) is preferably a compound selected from the group of compounds represented by the general formulas (L-1) to (L-7).
- the compound represented by the general formula (L-1) is the following compound.
- R L11 and R L12 each independently represent the same meaning as R L1 and R L2 in the general formula (L).
- R L11 and R L12 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .
- the compound represented by the general formula (L-1) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content is 1% by mass (hereinafter, mass% is simply expressed as%), 2%, 3%, and 5% with respect to the total amount of the liquid crystal composition of the present invention. Yes, 7%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% Yes, 55%.
- the upper limit of the preferable content is 95%, 90%, 85%, 80%, 75%, 70%, 65%, based on the total amount of the composition of the present invention. %, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%.
- the above lower limit value is preferably high and the upper limit value is preferably high. Furthermore, when the composition of the present invention requires a high Tni and a composition having good temperature stability, it is preferable that the lower limit value is moderate and the upper limit value is moderate. When it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the lower limit value is low and the upper limit value is low.
- the compound represented by the general formula (L-1) is preferably a compound selected from the group of compounds represented by the general formula (L-1-1).
- the compound represented by the general formula (L-1-1) is a compound selected from the group of compounds represented by the formula (L-1-1.1) to the formula (L-1-1.3). And is preferably a compound represented by formula (L-1-1.2) or formula (L-1-1.3), and particularly represented by formula (L-1-1.3). It is preferable that it is a compound.
- the lower limit of the preferable content of the compound represented by the formula (L-1-1.3) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass% is simply expressed as%). 2% 3% 5% 7% 10%
- the upper limit of the preferable content is 20%, 15%, 13%, 10%, 8%, 7%, and 6% with respect to the total amount of the composition of the present invention. %, 5%, 3%.
- the compound represented by the general formula (L-1) is preferably a compound selected from the group of compounds represented by the general formula (L-1-2).
- R L12 represents the same meaning as in general formula (L-1).
- the lower limit of the preferable content of the compound represented by the formula (L-1-2) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). 5%, 10%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 35% .
- the upper limit of the preferable content is 60%, 55%, 50%, 45%, 42%, 40%, and 38% with respect to the total amount of the composition of the present invention. %, 35%, 33%, and 30%.
- the compound represented by the general formula (L-1-2) is a compound selected from the group of compounds represented by the formula (L-1-2.1) to the formula (L-1-2.4).
- it is a compound represented by the formula (L-1-2.2) to the formula (L-1-2.4).
- the compound represented by the formula (L-1-2.2) is preferable because the response speed of the composition of the present invention is particularly improved.
- it is preferable to use a compound represented by the formula (L-1-2.3) or the formula (L-1-2.4).
- the content of the compounds represented by formula (L-1-2.3) and formula (L-1-2.4) is not preferably 30% by mass or more in order to improve the solubility at low temperatures. .
- the lower limit of the preferable content of the compound represented by the formula (L-1-2.2) with respect to the total amount of the liquid crystal composition of the present invention is 10% by mass (hereinafter, mass% is simply expressed as%). 15%, 18%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 38% And 40%.
- the upper limit of the preferable content is 60%, 55%, 50%, 45%, 43%, 40%, and 38% with respect to the total amount of the composition of the present invention. %, 35%, 32%, 30%, 27%, 25%, and 22%.
- the preferred total content of the compound represented by the formula (L-1-1.3) and the compound represented by the formula (L-1-2.2) with respect to the total amount of the liquid crystal composition of the present invention The lower limit is 10% by mass (hereinafter, mass% is simply expressed as%), 15%, 20%, 25%, 27%, 30%, and 35%. 40%.
- the upper limit of the preferable content is 60%, 55%, 50%, 45%, 43%, 40%, and 38% with respect to the total amount of the composition of the present invention. %, 35%, 32%, 30%, 27%, 25%, and 22%.
- the compound represented by the general formula (L-1) is preferably a compound selected from the group of compounds represented by the general formula (L-1-3).
- R L13 and R L14 each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.
- R L13 and R L14 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .
- the lower limit of the preferable content of the compound represented by the formula (L-1-3) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). 5%, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 30%.
- the upper limit of the preferable content is 60%, 55%, 50%, 45%, 40%, 37%, and 35% with respect to the total amount of the composition of the present invention. %, 33%, 30%, 27%, 25%, 23%, 23%, 20%, 17%, 15%, 13%, 10% %.
- the compound represented by the general formula (L-1-3) is a compound selected from the group of compounds represented by the formula (L-1-3.1) to the formula (L-1-3.12).
- it is a compound represented by formula (L-1-3.1), formula (L-1-3.3) or formula (L-1-3.4).
- the compound represented by the formula (L-1-3.1) is preferable because the response speed of the composition of the present invention is particularly improved.
- the equation (L-1-3.3), the equation (L-1-3.4), the equation (L-1-3.11), and the equation (L ⁇ It is preferable to use a compound represented by 1-3.12).
- Sum of compounds represented by formula (L-1-3.3), formula (L-1-3.4), formula (L-1-3.11) and formula (L-1-3.12) The content of is not preferably 20% by mass or more in order to improve the solubility at low temperatures.
- the lower limit of the preferable content of the compound represented by the formula (L-1-3.1) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass% is simply expressed as%). 2%, 3%, 5%, 7%, 10%, 13%, 15%, 18%, and 20%. The upper limit of the preferable content is 20%, 17%, 15%, 13%, 10%, 8%, and 7% with respect to the total amount of the composition of the present invention. % And 6%.
- the compound represented by the general formula (L-1) is preferably a compound selected from the group of compounds represented by the general formula (L-1-4) and / or (L-1-5).
- R L15 and R L16 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.
- R L15 and R L16 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .
- the lower limit of the preferable content of the compound represented by the formula (L-1-4) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). 5%, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 25%, 23%, 20%, 17%, 15%, 13%, and 10% with respect to the total amount of the composition of the present invention. %.
- the lower limit of the preferable content of the compound represented by the formula (L-1-5) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). 5%, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 25%, 23%, 20%, 17%, 15%, 13%, and 10% with respect to the total amount of the composition of the present invention. %.
- the compounds represented by the general formulas (L-1-4) and (L-1-5) are represented by the formulas (L-1-4.1) to (L-1-5.3).
- a compound represented by the formula (L-1-4.2) or the formula (L-1-5.2) is preferable.
- the lower limit of the preferable content of the compound represented by the formula (L-1-4.2) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass% is simply expressed as%). 2%, 3%, 5%, 7%, 10%, 13%, 15%, 18%, and 20%. The upper limit of the preferable content is 20%, 17%, 15%, 13%, 10%, 8%, and 7% with respect to the total amount of the composition of the present invention. % And 6%.
- the compound represented by the general formula (L-2) is the following compound.
- R L21 and R L22 each independently represent the same meaning as R L1 and R L2 in the general formula (L).
- R L21 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms
- R L22 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom.
- An alkoxy group of 1 to 4 is preferable.
- the compound represented by the general formula (L-1) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the formula (L-2) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). %, 3%, 5%, 7%, 10%.
- the upper limit of the preferable content is 20%, 15%, 13%, 10%, 8%, 7% with respect to the total amount of the liquid crystal composition of the present invention, 6%, 5%, 3%.
- the compound represented by the general formula (L-2) is preferably a compound selected from the group of compounds represented by the formulas (L-2.1) to (L-2.6).
- a compound represented by formula (L-2.1), formula (L-2.3), formula (L-2.4) and formula (L-2.6) is preferred.
- the compound represented by the general formula (L-3) is the following compound.
- R L31 and R L32 each independently represent the same meaning as R L1 and R L2 in General Formula (L).
- R L31 and R L32 are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
- the compound represented by the general formula (L-3) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the formula (L-3) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass, 2%, 3%, 5% 7% and 10%.
- the upper limit of the preferable content is 20%, 15%, 13%, 10%, 8%, 7% with respect to the total amount of the liquid crystal composition of the present invention, 6%, 5%, 3%.
- the effect is high when the content is set to be large.
- the effect is high when the content is set low.
- the compound represented by the general formula (L-3) is preferably a compound selected from the group of compounds represented by the formulas (L-3.1) to (L-3.4).
- a compound represented by the formula (L-3.7) from (L-3.2) is preferable.
- the compound represented by the general formula (L-4) is the following compound.
- R L41 and R L42 each independently represent the same meaning as R L1 and R L2 in General Formula (L).
- R L41 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms
- R L42 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom.
- An alkoxy group of 1 to 4 is preferable.
- the compound represented by the general formula (L-4) can be used alone, or two or more compounds can be used in combination.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the content of the compound represented by the general formula (L-4) is low-temperature solubility, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, It is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.
- the lower limit of the preferable content of the compound represented by the formula (L-4) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass% is simply expressed as%). %, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30% %, 35%, and 40%.
- the upper limit of the preferable content of the compound represented by the formula (L-4) with respect to the total amount of the liquid crystal composition of the present invention is 50%, 40%, 35%, and 30%. Yes, 20%, 15%, 10%, 5%.
- the compound represented by general formula (L-4) is preferably a compound represented by formula (L-4.1) to formula (L-4.3), for example.
- the formula (L-4.2) Even if it contains a compound represented by formula (L-4.1), it contains both a compound represented by formula (L-4.1) and a compound represented by formula (L-4.2). Or all of the compounds represented by formulas (L-4.1) to (L-4.3) may be included.
- the lower limit of the preferable content of the compound represented by the formula (L-4.1) or the formula (L-4.2) with respect to the total amount of the liquid crystal composition of the present invention is 3%, and 5% 7%, 9%, 11%, 12%, 13%, 18%, 21%, and a preferred upper limit is 45, 40%. Yes, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8% is there.
- both the compound represented by the formula (L-4.1) and the compound represented by the formula (L-4.2) are contained, both compounds relative to the total amount of the liquid crystal composition of the present invention
- the lower limit of the preferable content of is 15% by mass (hereinafter, mass% is simply expressed as%), 19%, 24%, 30%, and the preferable upper limit is 45. 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%.
- the compound represented by the general formula (L-4) is preferably, for example, a compound represented by the formula (L-4.4) to the formula (L-4.6). It is preferable that it is a compound represented by this.
- the formula (L -4.5) contains both the compound represented by formula (L-4.4) and the compound represented by formula (L-4.5). May be.
- the lower limit of the preferable content of the compound represented by the formula (L-4.4) or the formula (L-4.5) with respect to the total amount of the liquid crystal composition of the present invention is 3% by mass (hereinafter referred to as mass%). Is simply expressed as%), 5%, 7%, 9%, 11%, 12%, 13%, 18%, and 21%. Preferred upper limit values are 45, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13% %, 10%, and 8%.
- both the compound represented by formula (L-4.4) and the compound represented by formula (L-4.5) are contained, both compounds relative to the total amount of the liquid crystal composition of the present invention
- the lower limit of the preferable content of is 15% by mass (hereinafter, mass% is simply expressed as%), 19%, 24%, 30%, and the preferable upper limit is 45. 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%.
- the compound represented by the general formula (L-4) is preferably a compound represented by the formula (L-4.7) to the formula (L-4.10), and particularly the formula (L-4.
- the compound represented by 9) is preferred.
- the compound represented by the general formula (L-5) is the following compound.
- R L51 and R L52 each independently represent the same meaning as R L1 and R L2 in the general formula (L).
- R L51 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms
- R L52 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom.
- An alkoxy group of 1 to 4 is preferable.
- the compound represented by the general formula (L-5) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the content of the compound represented by the general formula (L-5) includes solubility at low temperature, transition temperature, electrical reliability, birefringence index, process suitability, dripping marks, It is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.
- the lower limit of the preferable content of the compound represented by the formula (L-5) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). %, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30% %, 35%, and 40%.
- the upper limit of the preferable content of the compound represented by the formula (L-5) with respect to the total amount of the liquid crystal composition of the present invention is 50%, 40%, 35%, 30% Yes, 20%, 15%, 10%, 5%
- the compound represented by the general formula (L-5) is represented by the formula (L-5.1) or the formula (L-5.
- the compound represented by 2) is preferred, and the compound represented by the formula (L-5.1) is particularly preferred.
- the lower limit of the preferable content of these compounds with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%), 2%, 3%, 5% and 7%.
- the upper limit of the preferable content of these compounds is 20%, 15%, 13%, 10%, and 9%.
- the compound represented by the general formula (L-5) is preferably a compound represented by the formula (L-5.3) or the formula (L-5.4).
- the lower limit of the preferable content of these compounds with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%), 2%, 3%, 5% and 7%.
- the upper limit of the preferable content of these compounds is 20%, 15%, 13%, 10%, and 9%.
- the compound represented by the general formula (L-5) is preferably a compound selected from the group of compounds represented by the formulas (L-5.5) to (L-5.7).
- the compound represented by L-5.7) is preferred.
- the lower limit of the preferable content of these compounds with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%), 2%, 3%, 5% and 7%.
- the upper limit of the preferable content of these compounds is 20%, 15%, 13%, 10%, and 9%.
- the compound represented by the general formula (L-6) is the following compound.
- R L61 and R L62 each independently represent the same meaning as R L1 and R L2 in the general formula (L), and X L61 and X L62 each independently represent a hydrogen atom or a fluorine atom.
- R L61 and R L62 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and one of X L61 and X L62 is a fluorine atom and the other is a hydrogen atom. Is preferred.
- the compound represented by the general formula (L-6) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the formula (L-6) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). %, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30% %, 35%, and 40%.
- the upper limit of the preferable content of the compound represented by the formula (L-6) with respect to the total amount of the liquid crystal composition of the present invention is 50%, 40%, 35%, 30% Yes, 20%, 15%, 10%, 5%.
- the compound represented by the general formula (L-6) is preferably a compound represented by the formula (L-6.1) to the formula (L-6.9).
- the compound represented by the general formula (L-6) is preferably, for example, a compound represented by the formula (L-6.10) to the formula (L-6.17).
- a compound represented by L-6.11) is preferable.
- the lower limit of the preferable content of these compounds with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%), 2%, 3%, 5% and 7%.
- the upper limit of the preferable content of these compounds is 20%, 15%, 13%, 10%, and 9%.
- the compound represented by the general formula (L-7) is the following compound.
- R L71 and R L72 each independently represent the same meaning as R L1 and R L2 in Formula (L), A L71 and A L72 is A L2 and in the general formula (L) independently A L3 represents the same meaning, but the hydrogen atoms on A L71 and A L72 may be each independently substituted with a fluorine atom, Z L71 represents the same meaning as Z L2 in formula (L), X L71 and X L72 each independently represent a fluorine atom or a hydrogen atom.
- R L71 and R L72 are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and
- a L71 and A L72 Are each independently preferably a 1,4-cyclohexylene group or a 1,4-phenylene group, the hydrogen atoms on A L71 and A L72 may be each independently substituted with a fluorine atom, and
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, and four kinds.
- the content of the compound represented by the general formula (L-7) includes solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, dropping trace Therefore, it is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.
- the lower limit of the preferable content of the compound represented by the formula (L-7) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). %, 3%, 5%, 7%, 10%, 14%, 16%, 20%.
- the upper limit of the preferable content of the compound represented by the formula (L-7) with respect to the total amount of the composition of the present invention is 30%, 25%, 23%, and 20%. 18%, 15%, 10%, 5%.
- the content of the compound represented by formula (L-7) is preferably increased, and when an embodiment with low viscosity is desired, the content is It is preferable to reduce the amount.
- the compound represented by the general formula (L-7) is preferably a compound represented by the formula (L-7.1) to the formula (L-7.4), and the formula (L-7. It is preferable that it is a compound represented by 2).
- the compound represented by the general formula (L-7) is preferably a compound represented by the formula (L-7.11) to the formula (L-7.13). It is preferable that it is a compound represented by 11).
- the compound represented by the general formula (L-7) is a compound represented by the formula (L-7.21) to the formula (L-7.23).
- a compound represented by formula (L-7.21) is preferable.
- the compound represented by the general formula (L-7) is preferably a compound represented by the formula (L-7.31) to the formula (L-7.34), and the formula (L-7. 31) or / and a compound represented by the formula (L-7.32).
- the compound represented by the general formula (L-7) is preferably a compound represented by the formula (L-7.41) to the formula (L-7.44), and the formula (L-7. 41) or / and a compound represented by formula (L-7.42).
- the additive (antioxidant, UV absorber, etc.) in the liquid crystal composition according to the present invention is preferably 100 ppm to 1% by mass.
- the liquid crystal composition of the present invention can use a nematic phase-isotropic liquid phase transition temperature (Tni) in a wide range, but the nematic phase-isotropic liquid phase transition temperature (Tni) is 60. It is preferably from ⁇ 120 ° C., more preferably from 70 to 100 ° C., particularly preferably from 70 to 85 ° C.
- the dielectric anisotropy ⁇ of the liquid crystal composition in the present invention is preferably ⁇ 2.0 to ⁇ 6.0, more preferably ⁇ 2.5 to ⁇ 5.0 at 25 ° C. A value of ⁇ 2.5 to ⁇ 3.5 is particularly preferable.
- the refractive index anisotropy ⁇ n of the liquid crystal composition in the present invention is preferably 0.08 to 0.13 at 25 ° C., more preferably 0.09 to 0.12. More specifically, the refractive index anisotropy of the liquid crystal composition in the present invention is preferably 0.10 to 0.12 at 25 ° C. when dealing with a thin cell gap. When it corresponds to a cell gap (cell gap of 3.4 ⁇ m or less), it is preferably about 0.9 to about 0.12, and when it corresponds to a thick cell gap (cell gap of 3.5 ⁇ m or more), it is about 0. It is preferably about 08 to about 0.1.
- the upper limit of the rotational viscosity ( ⁇ 1 ) of the liquid crystal composition according to the present invention is preferably 150 (mPa ⁇ s) or less, more preferably 130 (mPa ⁇ s) or less, and particularly preferably 120 (mPa ⁇ s) or less.
- the lower limit of the rotational viscosity ( ⁇ 1 ) is preferably 20 (mPa ⁇ s) or more, more preferably 30 (mPa ⁇ s) or more, still more preferably 40 (mPa ⁇ s) or more, and 50 (mPa ⁇ s). s) or more is more preferable, 60 (mPa ⁇ s) or more is further more preferable, and 70 (mPa ⁇ s) or more is particularly preferable.
- Z as a function of rotational viscosity and refractive index anisotropy shows a specific value.
- ⁇ 1 represents rotational viscosity and ⁇ n represents refractive index anisotropy.
- Z is preferably 13000 or less, more preferably 12000 or less, and particularly preferably 11000 or less.
- the liquid crystal composition according to the present invention needs to have a specific resistance of 10 11 ( ⁇ ⁇ m) or more, preferably 10 12 ( ⁇ ⁇ m). 13 ( ⁇ ⁇ m) or more is more preferable.
- the liquid crystal composition according to the present invention can use a nematic phase-isotropic liquid phase transition temperature (T NI ) in a wide range, and the phase transition temperature (T NI ) is 60 to 120 ° C. It is preferably 70 to 110 ° C, particularly preferably 75 to 100 ° C.
- T NI nematic phase-isotropic liquid phase transition temperature
- the vertical alignment films 16 and 17 are formed by applying a compound and heating.
- a normal alignment film may be provided as the base alignment film.
- an alignment film material containing a polymer having a thermally decomposable group is prepared by any one of the three methods described above.
- examples of the polymer compound precursor include a mixture of tetracarboxylic dianhydride and diisocyanate, polyamic acid, and a polyimide solution in which polyimide is dissolved or dispersed in a solvent. Etc.
- the polyimide content in the polyimide solution is preferably 1% by mass or more and 10% by mass or less, and more preferably 3% by mass or more and 5% by mass or less.
- examples of the polymer compound precursor include a silicon compound having an alkoxy group, a silicon compound having a halogenated alkoxy group, alcohol, and oxalic acid.
- examples thereof include a polysiloxane solution prepared by synthesizing polysiloxane by mixing at a quantitative ratio and heating, and dissolving it in a solvent.
- the alignment film material is applied to each of the first substrate 11 and the second substrate 12 so as to cover the common electrode 14, the pixel electrode 15, and its slit portion (not shown). Or print. Moreover, it will be in the state which the polymer which has a thermally decomposable group containing a fluorine atom and / or a silicon atom segregated on the application
- heat treatment is performed in an environment of 120 to 300 ° C.
- the polymer compound precursor and / or the compound represented by the general formula (V-3) or the polymerizable liquid crystal compound contained in the coated or printed alignment film material is polymerized and cured to form a polymer.
- the thermally decomposable group portion containing fluorine atoms and / or silicon atoms is optically anisotropic. It is detached from the polymer contained in the body, and the coated surface is smoothed.
- a baking treatment is preferably performed at 150 to 300 ° C. for 5 to 120 minutes, and at 180 to 250 ° C. for 10 to 60 minutes. It is more preferable to perform a baking treatment for a minute.
- the vertical alignment ability to align the liquid crystal molecules in the liquid crystal composition layer in the direction perpendicular to the substrate surface is formed. Thereafter, a process such as rubbing may be performed as necessary.
- the first substrate 11 and the second substrate 12 are overlapped, and the liquid crystal composition layer 13 containing liquid crystal molecules is sealed between them.
- the seal portion is printed using an epoxy adhesive or the like by a screen printing method.
- first substrate 11 and the second substrate 12 are bonded together through spacer protrusions and a seal portion so that the vertical alignment films 16 and 17 are opposed to each other, and liquid crystal molecules and, if necessary, polymerizable.
- a liquid crystal composition containing the compound is injected.
- liquid crystal composition is sealed between the first substrate 11 and the second substrate 12 by curing the seal portion by heating or the like.
- a voltage is applied between the common electrode 14 and the pixel electrode 15 using voltage applying means.
- the voltage is applied with a magnitude of 5 to 30 (V), for example.
- the application may apply a charge substantially perpendicularly to the first substrate and the second substrate.
- the tilt angle of the liquid crystal molecules 19 is approximately equal to the pretilt ⁇ given to the liquid crystal molecules 19 in a process described later. Therefore, the magnitude of the pretilt ⁇ of the liquid crystal molecules 19 can be controlled by appropriately adjusting the magnitude of the voltage (see FIG. 3).
- liquid crystal composition layer in the vertical alignment films 16 and 17 for example, by irradiating the liquid crystal composition layer 13 with ultraviolet light UV from the outside of the first substrate 11 with the voltage applied.
- a polymer having a polymerizable group for controlling the alignment direction of the liquid crystal molecules or the polymerizable liquid crystal compound and the polymerizable compound in the liquid crystal composition are polymerized to form a polymer.
- the intensity of the ultraviolet light UV to be irradiated may or may not be constant, and the irradiation time at each intensity when the irradiation intensity is changed is arbitrary, but two or more stages of irradiation processes are performed.
- the average irradiation light intensity in the first half of the entire irradiation process time is stronger than the average irradiation intensity in the second half, and the intensity immediately after the start of irradiation is the strongest. More desirably, it is further preferable that the irradiation intensity always decreases to a certain value as the irradiation time elapses.
- the ultraviolet UV intensity is preferably 2 mW / cm ⁇ 2 to 100 mW / cm ⁇ 2 , but the first stage in the case of multi-stage irradiation or the entire irradiation process in the case of changing the irradiation intensity discontinuously.
- the maximum irradiation intensity is 10 mW / cm ⁇ 2 to 100 mW / cm ⁇ 2
- the minimum irradiation intensity is 2 mW / cm ⁇ after the second stage in the case of multistage irradiation or when the irradiation intensity is changed discontinuously. More preferably, it is 2 to 50 mW / cm ⁇ 2 .
- the total irradiation energy is preferably 10 J to 300 J, more preferably 50 J to 250 J, and even more preferably 100 J to 250 J.
- the applied voltage may be alternating current or direct current.
- This alignment control unit has a function of imparting a pretilt ⁇ to the liquid crystal molecules 19 located in the vicinity of the interface of the liquid crystal composition layer 13 with the polymer layers 20 and 21 (vertical alignment films 16 and 17) in the non-driven state (alignment). Controllability).
- the ultraviolet light UV is irradiated from the outside of the first substrate 11, it may be irradiated from the outside of the second substrate 12, and both the first substrate 11 and the second substrate 12 may be irradiated. You may irradiate from the outer side of a board
- the liquid crystal molecules 19 in the liquid crystal composition layer 13 have a predetermined pretilt ⁇ .
- the response speed to the drive voltage can be greatly improved as compared with a liquid crystal display element that has not been subjected to any pretilt processing and a liquid crystal display device having the liquid crystal display element.
- the polymer compound precursor constituting the vertical alignment films 16 and 17 is preferably a non-photosensitive polyimide precursor.
- Tni, ⁇ n, ⁇ , ⁇ , ⁇ 1 respectively are defined as follows.
- T ni Nematic phase-isotropic liquid phase transition temperature (° C.)
- T cn solid phase-nematic phase transition temperature (° C.)
- ⁇ n refractive index anisotropy at 25 ° C.
- ⁇ dielectric anisotropy ⁇ 1 at 25 ° C .
- K 33 Elastic constant of bending at 20 ° C.
- the burn-in evaluation of the liquid crystal display element is based on the following four-level evaluation of the afterimage level of the fixed pattern when the predetermined fixed pattern is displayed in the display area for 1000 hours and then the entire screen is uniformly displayed. went. ⁇ : No afterimage ⁇ : Level of afterimage is slightly acceptable but acceptable ⁇ : Level of afterimage is unacceptable ⁇ : Image retention is quite poor (drop mark) Evaluation of the drop marks of the liquid crystal display device was performed by the following four-stage evaluation of the drop marks that appeared white when the entire surface was displayed in black.
- a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 50 g of propylene glycol monomethyl ether acetate as a solvent, and the temperature was raised to 80 ° C. while stirring in a nitrogen stream.
- PGMEA propylene glycol monomethyl ether acetate
- a radical polymerization initiator As a polymerization initiator solution prepared by dissolving 1.5 g of 2,2′-azobis (methyl isobutyrate) in 17 g of propylene glycol monomethyl ether acetate, each was set in a separate dropping device, and the flask was filled with 80 While maintaining the temperature at 0 ° C., the dropwise addition was started at the same time, and each was dropped over 3 hours.
- the mixture was stirred at 80 ° C. for 10 hours, and then propylene glycol monomethyl ether acetate was further added to obtain a propylene glycol monomethyl ether acetate solution containing 20% by mass of the polymer (A-1) having a thermally decomposable group. .
- GPC polystyrene equivalent molecular weight
- the number average molecular weight was 9,900
- the weight average molecular weight was 21,800
- the maximum molecular weight was 70,000. there were.
- Example 1 A first substrate (common electrode substrate) having a transparent electrode layer and a color filter layer made of a transparent common electrode, and a second substrate (pixel) having a pixel electrode layer having a transparent pixel electrode driven by an active element Electrode substrate).
- each pixel electrode was obtained by etching ITO so that a slit having no electrode was present in the pixel electrode in order to divide the orientation of liquid crystal molecules.
- a vertical alignment film material containing a polyimide precursor and a polymerizable compound having a polymerizable group is applied to each of the common electrode substrate and the pixel electrode substrate by spin coating, and the applied film is heated at 200 ° C.
- the polyimide precursor in the alignment film material was cured to form a vertical alignment film of 100 nm ⁇ 20 nm on the surface of each substrate.
- the polymerizable compound having a polymerizable group in the vertical alignment film is not cured.
- a compound represented by the above formula (Va-1-3) is added to a polyimide solution (trade name: JALS2131-R6, manufactured by JSR) containing 3% by mass of a polyimide precursor as a solid content. And a solution containing 0.01% by weight of the polymer (A-1) having a thermally decomposable group was used.
- the liquid crystal composition (LC-A1) was sandwiched between the common electrode substrate and the pixel electrode substrate on which the vertical alignment film was formed, and then the sealing material was cured to form a liquid crystal composition layer. At this time, a spacer having a thickness of 3.0 ⁇ m was used, and the thickness of the liquid crystal composition layer was set to 3.0 ⁇ m.
- the obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular alternating electric field was applied to cure the compound represented by the formula (Va-1-3).
- the irradiation device UIS-S2511RZ manufactured by USHIO INC. And USH-250BY manufactured by USHIO ELECTRIC CO., LTD. are used as UV lamps, and the liquid crystal display device is irradiated with UV rays at 20 mW for 300 seconds. Got.
- a vertical alignment film containing the compound represented by the formula (Va-1-3) is formed, and a pretilt angle is given to the liquid crystal molecules in the liquid crystal composition layer.
- the pretilt angle is defined as shown in FIG. In the case of complete vertical alignment, the pretilt angle ( ⁇ ) is 90 °, and when the pretilt angle is given, the pretilt angle ( ⁇ ) is smaller than 90 °.
- the liquid crystal display element of Example 1 has pretilt angles in different directions in the four sections according to the slits of the pixel electrode as shown in FIG. 2, and the AC electric field is turned off after the polymerizable compound is cured.
- the pretilt angle was maintained.
- the pretilt angle hardly changed even after stress.
- liquid crystal composition used in the liquid crystal display element of Example 1 shows no significant change in the pretilt angle before and after stress. This is because the alignment film is made smoother by the polymer (A-1) having a thermally decomposable group in the alignment film material, and the pretilt angle is also stable because the polymer is stable to the liquid crystal composition. It is considered to have become.
- Example 2-11 Comparative Examples 1-2
- the compound having a polymerizable group to be used the polymer having a thermally decomposable group to be used, the polymer having no thermally decomposable group, and the liquid crystal composition to be used were changed to those described in the above table, respectively.
- liquid crystal display elements of Examples 2 to 11 and Comparative Examples 1 and 2 were produced.
- Various physical properties of the liquid crystal composition used in the obtained liquid crystal display element VHR after UV irradiation, drop mark evaluation of the obtained liquid crystal display element, burn-in evaluation, pretilt angle before stress, pretilt change after stress And shown in the above table.
- Example 12 A first substrate (common electrode substrate) having a transparent electrode layer and a color filter layer made of a transparent common electrode, and a second substrate (pixel) having a pixel electrode layer having a transparent pixel electrode driven by an active element Electrode substrate).
- each pixel electrode was obtained by etching ITO so that a slit having no electrode was present in the pixel electrode in order to divide the orientation of liquid crystal molecules.
- a vertical alignment film material containing a polyimide precursor, a polymerizable compound having a polymerizable group, and a polymer having a thermally decomposable group is applied to each of the common electrode substrate and the pixel electrode substrate by spin coating, and the application is performed.
- the polyimide precursor in the vertical alignment film material was cured by heating the film at 200 ° C., and a 100 nm vertical alignment film was formed on the surface of each substrate. At this stage, the polymerizable compound having a polymerizable group is not cured in the vertical alignment film.
- a polyimide derivative represented by the following formula has a solid content of 3% by mass, a polymerizable compound represented by the formula (Va-1-3) 0.5% by mass, and thermal decomposability.
- An N-methyl-2-pyrrolidone / 2-butoxyethanol 70/30 (mass ratio) solution containing 0.01% by mass of the polymer (A-1) having a group was used.
- the liquid crystal composition (LC-A1) was sandwiched between the common electrode substrate and the pixel electrode substrate on which the vertical alignment film was formed, and then the sealing material was cured to form a liquid crystal composition layer. At this time, a spacer having a thickness of 3.0 ⁇ m was used, and the thickness of the liquid crystal composition layer was set to 3.0 ⁇ m.
- the obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular alternating electric field was applied to cure the compound represented by the formula (Va-1-3).
- the irradiation device UIS-S2511RZ manufactured by Ushio Electric Co., Ltd. and USH-250BY manufactured by Ushio Electric Co., Ltd. are used as an ultraviolet lamp, and the liquid crystal display element is irradiated with ultraviolet rays at 20 mW for 300 seconds.
- a vertical alignment film containing a polymer of a polymerizable compound having a polyimide skeleton as a main chain and a polymerizable group as a side chain is formed, and a pretilt angle is given to the liquid crystal molecules in the liquid crystal composition layer.
- the liquid crystal display element of Example 12 has pretilt angles in different directions in the four sections according to the slits of the pixel electrode as shown in FIG. 2, and the AC electric field is turned off after the polymerizable compound is cured.
- the pretilt angle was maintained.
- the pretilt angle hardly changed even after stress.
- liquid crystal composition used in the liquid crystal display element of Example 12 shows no significant change in pretilt angle before and after stress. This is because the alignment film is made smoother by the polymer (A-1) having a thermally decomposable group in the alignment film material, and the pretilt angle is also stable because the polymer is stable to the liquid crystal composition. It is considered to have become.
- Example 13 to 18, Comparative Examples 3 to 4 Except that the compound having a polymerizable group to be used, the polymer having a thermally decomposable group to be used, the polymer having no thermally decomposable group, and the liquid crystal composition to be used were changed to those described in the above table, respectively. Under the same conditions as Example 12, liquid crystal display elements of Examples 13 to 18 and Comparative Examples 3 to 4 were produced. Various physical properties of the liquid crystal composition used in the obtained liquid crystal display element, VHR after UV irradiation, drop mark evaluation of the obtained liquid crystal display element, burn-in evaluation, pretilt angle before stress, pretilt change after stress And shown in the above table.
- a first substrate having a transparent electrode layer and a color filter layer made of a transparent common electrode
- a second substrate having a pixel electrode layer having a transparent pixel electrode driven by an active element Electrode substrate.
- a vertical alignment film material containing a polymerizable liquid crystal compound and a polymerization initiator was applied to each of the common electrode substrate and the pixel electrode substrate by a spin coating method to form a precursor layer of a vertical alignment film having a thickness of 200 nm.
- the polymerizable compound represented by the formula (Va-1-3) is 5.0% by mass
- the polymer (A-1) having a thermally decomposable group is 0.1% by mass. %
- And 95.0% by mass of UCL-011-K1 (manufactured by DIC Corporation) polymerizable compound is 5.0% by mass
- the polymer (A-1) having a thermally decomposable group is 0.1% by mass. %
- UCL-011-K1 manufactured by DIC Corporation
- Each of the substrates coated with the vertical alignment film forming material is heated in a constant temperature bath at 70 ° C. for 5 minutes, and then further heated on a hot plate at 180 ° C. for 15 minutes, so that the polymerizable property in the applied vertical alignment film forming material
- the liquid crystal compound was an isotropic liquid.
- the temperature was lowered to room temperature at a rate of 10 ° C./min, and the alignment of the polymerizable liquid crystal compound in the vertical alignment film forming material was set to the vertical alignment.
- a magnetic field inclined by 70 ° from the substrate surface was applied to each of the pixel electrode substrate and the common electrode substrate to give a pretilt angle to the polymerizable liquid crystal compound.
- ultraviolet rays were irradiated to cure the polymerizable liquid crystal compound, and a vertical alignment film was formed.
- the liquid crystal composition (LC-A1) was sandwiched between the common electrode substrate and the pixel electrode substrate on which the vertical alignment film was formed, and then the sealing material was cured to form a liquid crystal composition layer. At this time, a spacer having a thickness of 3.0 ⁇ m was used, and the thickness of the liquid crystal composition layer was set to 3.0 ⁇ m.
- the obtained liquid crystal display element was irradiated with ultraviolet rays in a state where a rectangular alternating electric field was applied to cure the compound represented by the formula (Va-1-3).
- the liquid crystal display element of Example 19 was irradiated with UV light at 20 mW for 300 seconds using USH-250BY made by USHIO ELECTRIC CO., LTD. Got.
- a vertical alignment film containing the polymer of the formula (Va-1-3) is formed, and a pretilt angle is given to the liquid crystal molecules in the liquid crystal composition layer.
- the liquid crystal display element of Example 19 has pretilt angles in different directions in four sections according to the slits of the pixel electrode as shown in FIG. 2, and the AC electric field is turned off after the polymerizable liquid crystal compound is cured. But the pretilt angle was maintained. In addition, the pretilt angle hardly changed even after stress.
- liquid crystal composition used in the liquid crystal display element of Example 19 shows no significant change in the pretilt angle before and after stress. This is because the alignment film is made smoother by the polymer (A-1) having a thermally decomposable group in the alignment film material, and the pretilt angle is also stable because the polymer is stable to the liquid crystal composition. It is considered to have become.
- Example 20 to 25 Except that the compound having a polymerizable group to be used, the polymer having a thermally decomposable group to be used, the polymer having no thermally decomposable group, and the liquid crystal composition to be used were changed to those described in the above table, respectively. Under the same conditions as in Example 19, liquid crystal display elements of Examples 20 to 25 and Comparative Examples 5 to 6 were produced.
- Various physical properties of the liquid crystal composition used in the obtained liquid crystal display element VHR after UV irradiation, drop mark evaluation of the obtained liquid crystal display element, burn-in evaluation, pretilt angle before stress, pretilt change after stress And shown in the above table.
- SYMBOLS 10 Liquid crystal display element, 11 ... 1st board
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Abstract
Description
[液晶表示素子]
本発明の液晶表示素子は、一対の基板の間に挟持された液晶組成物層を有する液晶表示素子であって、液晶組成物層に電圧を印加し、液晶組成物層中の液晶分子をフレデリクス転移させることにより、光学的なスイッチとして働かせる原理に基づくものであり、この点では周知慣用技術を用いることができる。
(配向膜)
本発明の液晶表示素子は、垂直配向(VA)型液晶表示素子であるので、電圧無印加時に液晶分子のダイレクターは基板面に対して略垂直配向しているものである。液晶分子を垂直配向させるためには、一般的に(垂直)配向膜が用いられる。垂直配向膜を形成する材料(垂直配向膜材料)としては、ポリイミド、ポリアミド、ポリシロキサン、重合性液晶化合物の硬化物等が用いられる。
(配向膜に配合する熱分解性基を有する熱分解性重合体)
本発明において用いる配向膜には、液晶組成物層中の液晶分子を基板面に対して垂直方向に配向させる垂直配向能と共に、液晶分子の配向方向を制御する配向制御能を有する必要がある。さらに、安定してプレチルト角が付与されるためには、配向膜表面を平滑にし、配向膜に接する液晶組成物の配向性に影響を及ぼさないようにする必要がある。
前記、一般式(I-2-1)及び一般式(I-2-2)中、R11は水素原子を表し、R21はメチル基を表し、Y11は酸素原子またはイオウ原子であるものが、ブロック化されたカルボキシル基と復活したカルボキシル基の極性の差が大きく好ましい。また、前記一般式(I-2-1)又は一般式(I-2-2)で表される側鎖としては、下記式(I-2-1-1)又は式(I-2-2-1)で表される側鎖がより好ましい。
で表されるビニルエーテル化合物とを反応させてブロック化されたカルボキシル基を有する重合性単量体を得た後、該重合性単量体を重合させる方法。
前記フッ素化アルキル基やポリ(パーフルオロアルキレンエーテル)鎖を有するラジカル重合性単量体の具体的な例として、例えば下記の重合性単量体(A-1)~(A-15)等を好ましく例示することができる。
上記一般式(I-1-1-1)~一般式(I-1-2-2)中、R42の好ましい基は、上記一般式(I-1-1)又は一般式(I-1-2)に記載したR4の好ましい基と同一である。
(配向膜材料中に熱分解性基を有する重合体及び、重合性基を有する重合性化合物を配合する方法)
配向膜材料中に、上記熱分解性基を有する重合体及び、重合性基を有する重合性化合物を配合する方法としては、配向膜材料として前記高分子化合物前駆体に、上記熱分解性基を有する重合体及び重合性基を有する重合性化合物を配合する方法が挙げられる。そして、当該高分子化合物前駆体の加熱工程(焼成)により、配向膜表面を平滑にすることができる。その結果、重合性基を有する化合物の重合体によって形成されたプレチルト角を配向膜層上に安定して付与することができ、後述する液晶組成物層中の液晶分子の配向方向を均一に制御することができる。
上記Uにおいて、Z1、Z2及びZ3はそれぞれ独立して、-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-又は単結合が好ましく、-COO-、-OCO-、-OCH2CH2O-又は単結合がより好ましい。
上記一般式(V-1)において、X10及びX11はそれぞれ独立して、水素原子又はメチル基を表すが、反応速度を重視する場合には水素原子が好ましく、反応残留量を低減することを重視する場合にはメチル基が好ましい。
(配向膜材料として、側鎖部分に架橋性官能基を有する重合性化合物の重合体を用い、さらに上記熱分解性基を有する重合体を配合する方法)
前記垂直配向能及び配向制御能の2つの機能を有する配向膜を得る方法としては、配向膜材料として側鎖部分に架橋性官能基を有する重合性化合物の重合体を用いる方法も好ましい。また、当該方法を用いる場合も、上記熱分解性基を有する重合体を用いその後の加熱工程(焼成)により、配向膜表面を平滑にすることができる。その結果、重合性基を有する化合物の重合体によって形成されたプレチルト角を配向膜層上に安定して付与することができ、後述する液晶組成物層中の液晶分子の配向方向を均一に制御することができる。 側鎖部分に架橋性官能基を有する重合性化合物としては、側鎖部分に架橋性官能基(重合性基)を有していれば、主鎖部分は特に限定されないが、主鎖部分として前述のイミド骨格やシロキサン骨格を有する化合物を用いることが好ましく、主鎖部分にポリイミド骨格を有する化合物を用いることがより好ましい。
上記架橋性官能基は、主鎖部分と共有結合を介して結合していればよく、主鎖部分に直接結合していても、主鎖部分に連結基を介して結合していても良いが、連結基としては、-O-C6H4-又は-O-C6H4-(R2O)r-を用いることが好ましい(R2は炭素原子数1~20のアルキレン基を表し、rは1以上の整数を表す。)。
(配向膜として重合性液晶化合物の硬化物を用いる方法)
前記垂直配向能及び配向制御能の2つの機能を有する配向膜を得る方法としては、配向膜として重合性液晶化合物の硬化物を用いる方法も好ましい。また、当該方法を用いる場合も、前記重合性液晶化合物、及び、上記熱分解性基を有する重合体を含有する配向膜材料である重合性液晶組成物を加熱(焼成)することにより、配向膜表面を平滑にすることができる。その結果、重合性基を有する化合物の重合体によって形成されたプレチルト角を配向膜層上に安定して付与することができ、後述する液晶組成物層中の液晶分子の配向方向を均一に制御することができる。
上記一般式(V3)において、X1及びX2はそれぞれ独立して、水素原子又はメチル基を表すが、反応速度を重視する場合には水素原子が好ましく、反応残留量を低減することを重視する場合にはメチル基が好ましい。
また、上記一般式(V3)で表される重合性液晶化合物以外にも、上記一般式(V)で表される化合物(ただし、一般式(V3)で表される化合物を除く。)、及び/又は、上記一般式(V-1)で表される化合物を1種以上併用しても良い。
(配向膜表面に重合体層を形成させるために液晶組成物に含有させる重合性化合物)
本発明の液晶表示素子において、垂直配向膜は、反応性基を有する重合性化合物の重合により形成される重合体を含み、当該重合体により、適切なプレチルト角を付与することができるが、更に、必要に応じて、液晶組成物中に重合性化合物を含有させ、当該液晶組成物を基板間に挟持した後、電圧を印加しながら該重合性化合物を硬化させることにより、重合性化合物が相分離しながら、前記垂直配向膜の表面に重合体層として形成され、更に液晶分子の配向性やプレチルト角の安定性が高く、焼き付きの発生が少なく、その製造時における滴下痕の発生が少ない液晶表示素子を得ることができる。
(液晶組成物)
本発明における液晶組成物には、一般式(N-1)、一般式(N-2)、及び一般式(N-3)で表される化合物を1種または2種以上含有する。
AN11、AN12、AN21、AN22、AN31及びAN32はそれぞれ独立して
(a) 1,4-シクロヘキシレン基(この基中に存在する1個の-CH2-又は隣接していない2個以上の-CH2-は-O-に置き換えられてもよい。)及び
(b) 1,4-フェニレン基(この基中に存在する1個の-CH=又は隣接していない2個以上の-CH=は-N=に置き換えられてもよい。)
(c) 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-ジイル基又はデカヒドロナフタレン-2,6-ジイル基(ナフタレン-2,6-ジイル基又は1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基中に存在する1個の-CH=又は隣接していない2個以上の-CH=は-N=に置き換えられても良い。)
からなる群より選ばれる基を表し、上記の基(a)、基(b)及び基(c)はそれぞれ独立してシアノ基、フッ素原子又は塩素原子で置換されていても良く、
ZN11、ZN12、ZN21、ZN22、ZN31及びZN32はそれぞれ独立して単結合、-CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-、-CH=N-N=CH-、-CH=CH-、-CF=CF-又は-C≡C-を表し、
XN21は水素原子又はフッ素原子を表し、
TN31は-CH2-又は-O-を表し、
nN11、nN12、nN21、nN22、nN31及びnN32はそれぞれ独立して0~3の整数を表すが、nN11+nN12、nN21+nN22及びnN31+nN32はそれぞれ独立して1、2又は3であり、AN11~AN32、ZN11~ZN32が複数存在する場合は、それらは同一であっても異なっていても良い。
RN111は炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基が好ましく、プロピル基又はペンチル基が好ましい。RN112は炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましく、エトキシ基又はブトキシ基が好ましい。
RN121は炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基が好ましく、エチル基、プロピル基、ブチル基又はペンチル基が好ましい。RN122は炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましく、メチル基、プロピル基、メトキシ基、エトキシ基又はプロポキシ基が好ましい。
RN131は炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基が好ましく、エチル基、プロピル基又はブチル基が好ましい。RN132は炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましく、エトキシ基、プロポキシ基又はブトキシ基が好ましい。
RN141及びRN142はそれぞれ独立して、炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましく、メチル基、プロピル基、エトキシ基又はブトキシ基が好ましい。
RN151及びRN152はそれぞれ独立して、炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましくエチル基、プロピル基又はブチル基が好ましい。
RN1101は炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基が好ましく、エチル基、プロピル基又はブチル基が好ましい。RN1102は炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましく、エトキシ基、プロポキシ基又はブトキシ基が好ましい。
RN1111は炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基が好ましく、エチル基、プロピル基又はブチル基が好ましい。RN1112は炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましく、エトキシ基、プロポキシ基又はブトキシ基が好ましい。
RN1121は炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基が好ましく、エチル基、プロピル基又はブチル基が好ましい。RN1122は炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましく、エトキシ基、プロポキシ基又はブトキシ基が好ましい。
RN1131は炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基が好ましく、エチル基、プロピル基又はブチル基が好ましい。RN1132は炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましく、エトキシ基、プロポキシ基又はブトキシ基が好ましい。
RN1141は炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基が好ましく、エチル基、プロピル基又はブチル基が好ましい。RN1142は炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましく、エトキシ基、プロポキシ基又はブトキシ基が好ましい。
RN1151は炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基が好ましく、エチル基、プロピル基又はブチル基が好ましい。RN1152は炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましく、エトキシ基、プロポキシ基又はブトキシ基が好ましい。
RN1161は炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基が好ましく、エチル基、プロピル基又はブチル基が好ましい。RN1162は炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましく、エトキシ基、プロポキシ基又はブトキシ基が好ましい。
RN1171は炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基が好ましく、エチル基、プロピル基又はブチル基が好ましい。RN1172は炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましく、エトキシ基、プロポキシ基又はブトキシ基が好ましい。
RN1181は炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基が好ましく、エチル基、プロピル基又はブチル基が好ましい。RN1182は炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましく、エトキシ基、プロポキシ基又はブトキシ基が好ましい。
一般式(N-1-21)で表される化合物は下記の化合物である。
一般式(N-2)で表される化合物は一般式(N-2-1)~(N-2-3)で表される化合物群から選ばれる化合物であることが好ましい。
一般式(N-2-2)で表される化合物は下記の化合物である。
一般式(N-2-3)で表される化合物は下記の化合物である。
一般式(N-3)で表される化合物は一般式(N-3-1)~(N-3-2)で表される化合物群から選ばれる化合物であることが好ましい。
一般式(N-3-2)で表される化合物は下記の化合物である。
本発明の液晶組成物の総量(液晶組成物中に含まれる液晶化合物の総量。)に対しての一般式(N-1)、一般式(N-2)、及び一般式(N-3)で表される化合物の含有量の総量は10~90質量%であることが好ましく、20~80質量%が更に好ましく、20~70質量%が更に好ましく、20~60質量%が更に好ましく、20~55質量%が更に好ましく、25~55質量%が更に好ましく、30~55質量%が特に好ましい。
nL1は0、1、2又は3を表し、
AL1、AL2及びAL3はそれぞれ独立して
(a) 1,4-シクロヘキシレン基(この基中に存在する1個の-CH2-又は隣接していない2個以上の-CH2-は-O-に置き換えられてもよい。)及び
(b) 1,4-フェニレン基(この基中に存在する1個の-CH=又は隣接していない2個以上の-CH=は-N=に置き換えられてもよい。)
(c) 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-ジイル基又はデカヒドロナフタレン-2,6-ジイル基(ナフタレン-2,6-ジイル基又は1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基中に存在する1個の-CH=又は隣接していない2個以上の-CH=は-N=に置き換えられても良い。)
からなる群より選ばれる基を表し、上記の基(a)、基(b)及び基(c)はそれぞれ独立してシアノ基、フッ素原子又は塩素原子で置換されていても良く、
ZL1及びZL2はそれぞれ独立して単結合、-CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-、-CH=N-N=CH-、-CH=CH-、-CF=CF-又は-C≡C-を表し、
nL1が2又は3であってAL2が複数存在する場合は、それらは同一であっても異なっていても良く、nL1が2又は3であってZL3が複数存在する場合は、それらは同一であっても異なっていても良いが、一般式(N-1)、一般式(N-2)及び一般式(N-3)で表される化合物を除く。)
一般式(L)で表される化合物は単独で用いてもよいが、組み合わせて使用することもできる。組み合わせることができる化合物の種類に特に制限は無いが、低温での溶解性、転移温度、電気的な信頼性、複屈折率などの所望の性能に応じて適宜組み合わせて使用する。使用する化合物の種類は、例えば本発明の一つの実施形態としては1種類である。あるいは本発明の別の実施形態では2種類であり、3種類であり、4種類であり、5種類であり、6種類であり、7種類であり、8種類であり、9種類であり、10種類以上である。
RL11及びRL12は、直鎖状の炭素原子数1~5のアルキル基、直鎖状の炭素原子数1~4のアルコキシ基及び直鎖状の炭素原子数2~5のアルケニル基が好ましい。
一般式(L-1-1)で表される化合物は、式(L-1-1.1)から式(L-1-1.3)で表される化合物群から選ばれる化合物であることが好ましく、式(L-1-1.2)又は式(L-1-1.3)で表される化合物であることが好ましく、特に、式(L-1-1.3)で表される化合物であることが好ましい。
本発明の液晶組成物の総量に対しての式(L-1-2)で表される化合物の好ましい含有量の下限値は、1質量%(以下質量%を単に%と表す。)であり、5%であり、10%であり、15%であり、17%であり、20%であり、23%であり、25%であり、27%であり、30%であり、35%である。好ましい含有量の上限値は、本発明の組成物の総量に対して、60%であり、55%であり、50%であり、45%であり、42%であり、40%であり、38%であり、35%であり、33%であり、30%である。
RL13及びRL14は、直鎖状の炭素原子数1~5のアルキル基、直鎖状の炭素原子数1~4のアルコキシ基及び直鎖状の炭素原子数2~5のアルケニル基が好ましい。
さらに、一般式(L-1-3)で表される化合物は、式(L-1-3.1)から式(L-1-3.12)で表される化合物群から選ばれる化合物であることが好ましく、式(L-1-3.1)、式(L-1-3.3)又は式(L-1-3.4)で表される化合物であることが好ましい。特に、式(L-1-3.1)で表される化合物は本発明の組成物の応答速度を特に改善するため好ましい。また、応答速度よりも高いTniを求めるときは、式(L-1-3.3)、式(L-1-3.4)、式(L-1-3.11)及び式(L-1-3.12)で表される化合物を用いることが好ましい。式(L-1-3.3)、式(L-1-3.4)、式(L-1-3.11)及び式(L-1-3.12)で表される化合物の合計の含有量は、低温での溶解度を良くするために20質量%以上にすることは好ましくない。
RL15及びRL16は、直鎖状の炭素原子数1~5のアルキル基、直鎖状の炭素原子数1~4のアルコキシ基及び直鎖状の炭素原子数2~5のアルケニル基が好ましい。
RL21は炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基が好ましく、RL22は炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましい。
RL31及びRL32はそれぞれ独立して炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましい。
RL41は炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基が好ましく、RL42は炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましい。)
一般式(L-4)で表される化合物は単独で使用することもできるが、2以上の化合物を組み合わせて使用することもできる。組み合わせることができる化合物の種類に特に制限は無いが、低温での溶解性、転移温度、電気的な信頼性、複屈折率などの求められる性能に応じて適宜組み合わせて使用する。使用する化合物の種類は、例えば本発明の一つの実施形態としては1種類であり、2種類であり、3種類であり、4種類であり、5種類以上である。
RL51は炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基が好ましく、RL52は炭素原子数1~5のアルキル基、炭素原子数4~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましい。
一般式(L-5)で表される化合物は、式(L-5.1)又は式(L-5.2)で表される化合物であることが好ましく、特に、式(L-5.1)で表される化合物であることが好ましい。
RL61及びRL62はそれぞれ独立して炭素原子数1~5のアルキル基又は炭素原子数2~5のアルケニル基が好ましく、XL61及びXL62のうち一方がフッ素原子他方が水素原子であることが好ましい。
式中、RL71及びRL72はそれぞれ独立して炭素原子数1~5のアルキル基、炭素原子数2~5のアルケニル基又は炭素原子数1~4のアルコキシ基が好ましく、AL71及びAL72はそれぞれ独立して1,4-シクロヘキシレン基又は1,4-フェニレン基が好ましく、AL71及びAL72上の水素原子はそれぞれ独立してフッ素原子によって置換されていてもよく、QL71は単結合又はCOO-が好ましく、単結合が好ましく、XL71及びXL72は水素原子が好ましい。
Zは、13000以下が好ましく、12000以下がより好ましく、11000以下が特に好ましい。
[液晶表示素子の製造方法]
次に、図1を参照して、本発明の液晶表示素子の製造方法を説明する。
Tni :ネマチック相-等方性液体相転移温度(℃)
Tcn :固相-ネマチック相転移温度(℃)
Δn :25℃における屈折率異方性
Δε :25℃における誘電率異方性
γ1 :25℃における回転粘度(mPa・s)
K33 :20℃における曲がりの弾性定数(pN)
UV照射前電圧保持率(初期VHR):周波数60Hz,印加電圧1Vの条件下で343Kにおける電圧保持率(%)
UV照射後VHR:以下の実施例・比較例の液晶表示素子にUV照射した後、周波数60Hz、印加電圧1Vの条件下で343Kにおける電圧保持率(%)
以下の実施例及び比較例において、下記の方法により、液晶表示素子の焼き付き、滴下痕およびプレチルト角を評価した。
(焼き付き)
液晶表示素子の焼き付き評価は、表示エリア内に所定の固定パターンを1000時間表示させた後に、全画面均一な表示を行ったときの固定パターンの残像のレベルを目視にて以下の4段階評価で行った。
◎:残像無し
○:残像ごく僅かに有るも許容できるレベル
△:残像有り許容できないレベル
×:残像有りかなり劣悪
(滴下痕)
液晶表示装置の滴下痕の評価は、全面黒表示した場合における白く浮かび上がる滴下痕を目視にて以下の4段階評価で行った。
◎:残像無し
○:残像ごく僅かに有るも許容できるレベル
△:残像有り許容できないレベル
×:残像有りかなり劣悪
(プレチルト角)
液晶表示素子の面内をランダムに5箇所計測し、平均値をプレチルト角とした。また、プレチルト角の安定性を評価する場合は、ストレス前後のプレチルト角の変化を比較した。ストレスは、液晶表示装置を70℃に保持されたオーブンに投入し、1kHz、30Vの矩形波を168時間印加することで与えた。
プレチルト変化角(°):ストレス後のプレチルト角-ストレス前のプレチルト角
なお、実施例において化合物の記載について以下の略号を用いた。なお、nは自然数を表す。
(側鎖)
-n -CnH2n+1 炭素原子数nの直鎖状のアルキル基
n- CnH2n+1- 炭素原子数nの直鎖状のアルキル基
-On -OCnH2n+1 炭素原子数nの直鎖状のアルコキシル基
nO- CnH2n+1O- 炭素原子数nの直鎖状のアルコキシル基
-V -CH=CH2
V- CH2=CH-
-V1 -CH=CH-CH3
1V- CH3-CH=CH-
-2V -CH2-CH2-CH=CH3
V2- CH3=CH-CH2-CH2-
-2V1 -CH2-CH2-CH=CH-CH3
1V2- CH3-CH=CH-CH2-CH2
(連結基)
-n- -CnH2n-
-nO- -CnH2n-O-
-On- -O-CnH2n-
-COO- -C(=O)-O-
-OCO- -O-C(=O)-
-CF2O- -CF2-O-
-OCF2- -O-CF2-
D -C=C-
T -C≡C-
(環構造)
〔熱分解性基を有する重合体(A-1)の合成〕
撹拌装置、温度計、冷却管、滴下装置を備えたガラスフラスコに、アクリル酸26.8gと3,3,4,4,5,5,6,6,7,7,8,8,8-トリデカフルオロ-1-ビニルオキシオクタン30.0gとを仕込み、乾燥空気気流下、室温にて21時間攪拌した。次いで、メトキノン0.003gとジイソプロピルエーテル107.6gを加え、飽和炭酸ナトリウム水溶液161.4g、イオン交換水161.4gを加えて分液した。次いで、上層を取り出した後、イオン交換水161.4gを加えて分液した。更に、上層を取り出した後、脱溶剤し、前記一般式(1)で表されるブロック化されたカルボキシル基を有する重合性単量体を得た。
(合成例2)
〔熱分解性基を有する重合体(A-2)の合成〕
攪拌装置、温度計、滴下装置を備えたガラスフラスコに、ヒドロキシフェニルメタクリレート25.0g、と3,3,4,4,5,5,6,6,7,7,8,8,8-トリデカフルオロ-1-ビニルオキシオクタン82.0g、トリフルオロ酢酸1.6g、及び、テトラヒドロフラン200gを仕込み、窒素雰囲気下、60℃で9時間保持して反応させた。冷却後、反応液にピリジン1.7gを加えた後、得られた反応液を水洗、分液、脱溶剤し、減圧蒸留により未反応成分を除去することでアセタール化生成物を得た。
(液晶組成物)
本発明の実施例及び比較例においては、以下の液晶組成物(LC-A1)~(LC-A6)、(LC-B1)、(LC-B2)を用いた。
液晶組成物層中の液晶分子の配向方向を制御する重合性基を有する化合物としては、以下の式で表される化合物を使用した。
透明な共通電極からなる透明電極層及びカラーフィルター層を具備した第一の基板(共通電極基板)と、アクティブ素子により駆動される透明画素電極を有する画素電極層を具備した第二の基板(画素電極基板)とを作製した。
用いる重合性基を有する化合物、用いる熱分解性基を有する重合体又は熱分解性基を有さない重合体、用いる液晶組成物を、それぞれ、上記表に記載したものに変更した以外は、実施例1と同一条件で、実施例2~11、比較例1~2の液晶表示素子を作製した。得られた液晶表示素子に用いられた液晶組成物の各物性、UV照射後のVHR及び、得られた液晶表示素子の滴下痕評価、焼き付き評価、ストレス前のプレチルト角、ストレス後のプレチルト変化を、上記の表に合わせて示す。
(実施例12)
透明な共通電極からなる透明電極層及びカラーフィルター層を具備した第一の基板(共通電極基板)と、アクティブ素子により駆動される透明画素電極を有する画素電極層を具備した第二の基板(画素電極基板)とを作製した。
用いる重合性基を有する化合物、用いる熱分解性基を有する重合体又は熱分解性基を有さない重合体、用いる液晶組成物を、それぞれ、上記表に記載したものに変更した以外は、実施例12と同一条件で、実施例13~18、比較例3~4の液晶表示素子を作製した。得られた液晶表示素子に用いられた液晶組成物の各物性、UV照射後のVHR及び、得られた液晶表示素子の滴下痕評価、焼き付き評価、ストレス前のプレチルト角、ストレス後のプレチルト変化を、上記の表に合わせて示す。
(実施例19)
透明な共通電極からなる透明電極層及びカラーフィルター層を具備した第一の基板(共通電極基板)と、アクティブ素子により駆動される透明画素電極を有する画素電極層を具備した第二の基板(画素電極基板)とを作製した。
用いる重合性基を有する化合物、用いる熱分解性基を有する重合体又は熱分解性基を有さない重合体、用いる液晶組成物を、それぞれ、上記表に記載したものに変更した以外は、実施例19と同一条件で、実施例20~25、比較例5~6の液晶表示素子を作製した。得られた液晶表示素子に用いられた液晶組成物の各物性、UV照射後のVHR及び、得られた液晶表示素子の滴下痕評価、焼き付き評価、ストレス前のプレチルト角、ストレス後のプレチルト変化を、上記の表に合わせて示す。
Claims (16)
- 第一基板と第二基板と、前記第一基及び第二基板の間に挟持された液晶組成物層とを有し、前記第一の基板と前記第二の基板の少なくとも一方に電極を有しており、前記第一の基板と前記第二の基板の少なくとも一方に、前記液晶組成物層中の液晶分子の配向方向を制御する重合性基を有する化合物の重合体、及び、熱分解性基を有する重合体を含有する配向膜を有し、前記液晶組成物層を構成する液晶組成物の誘電率異方性(Δε)が負であることを特徴とする液晶表示素子。
- 前記液晶組成物層を構成する液晶組成物が、下記一般式(N-1)、一般式(N-2)、及び一般式(N-3)
AN11、AN12、AN21、AN22、AN31及びAN32はそれぞれ独立して、
(a) 1,4-シクロヘキシレン基(この基中に存在する1個の-CH2-又は隣接していない2個以上の-CH2-は-O-に置き換えられてもよい。)及び
(b) 1,4-フェニレン基(この基中に存在する1個の-CH=又は隣接していない2個以上の-CH=は-N=に置き換えられてもよい。)
(c) 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-ジイル基又はデカヒドロナフタレン-2,6-ジイル基(ナフタレン-2,6-ジイル基又は1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基中に存在する1個の-CH=又は隣接していない2個以上の-CH=は-N=に置き換えられても良い。)
からなる群より選ばれる基を表し、上記の基(a)、基(b)及び基(c)はそれぞれ独立してシアノ基、フッ素原子又は塩素原子で置換されていても良く、
ZN11、ZN12、ZN21、ZN22、ZN31及びZN32はそれぞれ独立して単結合、-CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-、-CH=N-N=CH-、-CH=CH-、-CF=CF-又は-C≡C-を表し、
XN21は水素原子又はフッ素原子を表し、
TN31は-CH2-又は-O-を表し、
nN11、nN12、nN21、nN22、nN31及びnN32はそれぞれ独立して0~3の整数を表すが、nN11+nN12、nN21+nN22及びnN31+nN32はそれぞれ独立して1、2又は3であり、AN11~AN32、ZN11~ZN32が複数存在する場合は、それらは同一であっても異なっていても良い。)で表される化合物群から選ばれる1種又は2種以上の化合物を含有する、請求項1に記載の液晶表示素子。 - 前記熱分解性基がフッ素原子及び/又はケイ素原子を含有する、請求項1又は請求項2に記載の液晶表示素子。
- 複数の画素を有し、該画素中にプレチルト角が異なる2以上の領域を有する請求項1~請求項4のいずれか一項に記載の液晶表示素子。
- 前記第一の基板が共通電極を有し、第二の基板が画素電極を有する請求項1~請求項5のいずれか一項に記載の液晶表示素子。
- 前記共通電極と前記画素電極間に、前記第一の基板と前記第二の基板に略垂直に電荷を印加し、前記液晶組成物層中の液晶分子を制御する前記配向膜を有する請求項6に記載の液晶表示素子。
- 前記配向膜が前記液晶組成物層中の液晶分子の配向方向を制御する重合体を含むか、又は、重合性液晶化合物の硬化物から形成される請求項1~請求項7のいずれか一項に記載の液晶表示素子。
- 前記前記液晶組成物層中の液晶分子の配向方向を制御する重合体として、重合性基を有する化合物の重合体を含むか、又は、主鎖としてポリイミド骨格を有し側鎖として架橋性官能基を有する重合性化合物の重合体を含む請求項8に記載の液晶表示素子。
- 前記配向膜表面に液晶分子の配向を制御し安定化する1種又は2種以上の重合性化合物の重合体を更に有する請求項1~請求項9のいずれか一項に記載の液晶表示素子。
- 第一の基板と第二の基板の少なくとも一方に、熱分解性基を有する重合体を含有する配向材料を塗布し、配向膜材料を形成した後、少なくとも一方に電極を有する前記第一の基板と前記第二の基板により液晶組成物を挟持し、前記電極に、電圧を印加した状態で活性エネルギー線を照射することにより、前記配向膜材料中に含まれる重合性基を有する化合物の重合性基を重合して前記液晶組成物層中の液晶分子の配向方向を制御する配向膜を有し、前記液晶組成物が、下記一般式(N-1)、一般式(N-2)、及び一般式(N-3)
AN11、AN12、AN21、AN22、AN31及びAN32はそれぞれ独立して
(a) 1,4-シクロヘキシレン基(この基中に存在する1個の-CH2-又は隣接していない2個以上の-CH2-は-O-に置き換えられてもよい。)及び
(b) 1,4-フェニレン基(この基中に存在する1個の-CH=又は隣接していない2個以上の-CH=は-N=に置き換えられてもよい。)
(c) 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-ジイル基又はデカヒドロナフタレン-2,6-ジイル基(ナフタレン-2,6-ジイル基又は1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基中に存在する1個の-CH=又は隣接していない2個以上の-CH=は-N=に置き換えられても良い。)
からなる群より選ばれる基を表し、上記の基(a)、基(b)及び基(c)はそれぞれ独立してシアノ基、フッ素原子又は塩素原子で置換されていても良く、
ZN11、ZN12、ZN21、ZN22、ZN31及びZN32はそれぞれ独立して単結合、-CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-、-CH=N-N=CH-、-CH=CH-、-CF=CF-又は-C≡C-を表し、
XN21は水素原子又はフッ素原子を表し、
TN31は-CH2-又は-O-を表し、
nN11、nN12、nN21、nN22、nN31及びnN32はそれぞれ独立して0~3の整数を表すが、nN11+nN12、nN21+nN22及びnN31+nN32はそれぞれ独立して1、2又は3であり、AN11~AN32、ZN11~ZN32が複数存在する場合は、それらは同一であっても異なっていても良い。)で表される化合物群から選ばれる1種又は2種以上の化合物を含有する、液晶表示素子の製造方法。 - 前記配向膜材料が、前記液晶組成物層中の液晶分子の配向方向を制御する重合体を含むか、又は、前記配向膜材料が、重合性液晶化合物の硬化物である請求項11に記載の液晶表示素子の製造方法。
- 前記前記液晶組成物層中の液晶分子の配向方向を制御する重合体として、重合性基を有する化合物の重合体を含むか、又は、主鎖としてポリイミド骨格を有し側鎖として架橋性官能基を有する重合性化合物の重合体を含む請求項12に記載の液晶表示素子の製造方法。
- 前記配向膜表面に液晶分子の配向を制御し安定化する1種又は2種以上の重合性化合物の重合体を更に有する請求項12又は請求項13に記載の液晶表示素子の製造方法。
- 前記活性エネルギー線が紫外線であり、その強度が2mW/cm-2~100mW/cm-2であり、照射総エネルギー量が10J~300Jである請求項12~請求項14のいずれか一項に記載の液晶表示素子の製造方法。
- 液晶分子の配向方向を制御する重合性基を有する化合物の重合体、及び、熱分解性基を有する重合体を含有する配向膜材料。
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