WO2017115791A1 - 液晶配向剤、液晶配向膜、及び液晶表示素子 - Google Patents
液晶配向剤、液晶配向膜、及び液晶表示素子 Download PDFInfo
- Publication number
- WO2017115791A1 WO2017115791A1 PCT/JP2016/088869 JP2016088869W WO2017115791A1 WO 2017115791 A1 WO2017115791 A1 WO 2017115791A1 JP 2016088869 W JP2016088869 W JP 2016088869W WO 2017115791 A1 WO2017115791 A1 WO 2017115791A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- liquid crystal
- divalent
- aligning agent
- crystal aligning
- Prior art date
Links
- RYINMQTYSLHHLK-UHFFFAOYSA-N Brc1ccc(C(CC2)CCC2C2CCCCC2)cc1 Chemical compound Brc1ccc(C(CC2)CCC2C2CCCCC2)cc1 RYINMQTYSLHHLK-UHFFFAOYSA-N 0.000 description 1
- 0 CC(*)C(CCC1)CC1(c1cc(CO)cc(CO)c1)c1cc(CO)cc(CO)c1 Chemical compound CC(*)C(CCC1)CC1(c1cc(CO)cc(CO)c1)c1cc(CO)cc(CO)c1 0.000 description 1
- SGGVHVFWIUFDQG-AWNIVKPZSA-N CC(C(OCCOC(/C=C/c(cc1)ccc1OC(c(cc1)ccc1OCCCC(F)(F)F)=O)=O)=O)=C Chemical compound CC(C(OCCOC(/C=C/c(cc1)ccc1OC(c(cc1)ccc1OCCCC(F)(F)F)=O)=O)=O)=C SGGVHVFWIUFDQG-AWNIVKPZSA-N 0.000 description 1
- ZFSDWIASBGPOKB-LICLKQGHSA-N CC(C(OCCOC(/C=C/c1ccc(C(CC2)CCC2C2CCCCC2)cc1)=O)=O)=C Chemical compound CC(C(OCCOC(/C=C/c1ccc(C(CC2)CCC2C2CCCCC2)cc1)=O)=O)=C ZFSDWIASBGPOKB-LICLKQGHSA-N 0.000 description 1
- XDWYRANYCJPLGQ-RMKNXTFCSA-N CC(C)(C)OC(/C=C/c(cc1)ccc1O)=O Chemical compound CC(C)(C)OC(/C=C/c(cc1)ccc1O)=O XDWYRANYCJPLGQ-RMKNXTFCSA-N 0.000 description 1
- UURFZKGTVRILSD-VGOFMYFVSA-N CC(C)(C)OC(/C=C/c(cc1)ccc1OC(c(cc1)ccc1OCCCC(F)(F)F)=O)=O Chemical compound CC(C)(C)OC(/C=C/c(cc1)ccc1OC(c(cc1)ccc1OCCCC(F)(F)F)=O)=O UURFZKGTVRILSD-VGOFMYFVSA-N 0.000 description 1
- WHWMOMRHHQLBQQ-UHFFFAOYSA-N CC(C)(C)OC(c(cc1)ccc1O)=O Chemical compound CC(C)(C)OC(c(cc1)ccc1O)=O WHWMOMRHHQLBQQ-UHFFFAOYSA-N 0.000 description 1
- ZRIRUWWYQXWRNY-UHFFFAOYSA-N CC(C)(c(cc1CO)cc(CO)c1O)c(cc1CO)cc(CO)c1O Chemical compound CC(C)(c(cc1CO)cc(CO)c1O)c(cc1CO)cc(CO)c1O ZRIRUWWYQXWRNY-UHFFFAOYSA-N 0.000 description 1
- OJHWSLJYROENIQ-UHFFFAOYSA-N CC(C)C(C)(C)OC(c(cc1)ccc1OCCCC(F)(F)F)=O Chemical compound CC(C)C(C)(C)OC(c(cc1)ccc1OCCCC(F)(F)F)=O OJHWSLJYROENIQ-UHFFFAOYSA-N 0.000 description 1
- QYWKVJCDXGTXAW-UHFFFAOYSA-N CC(c1cc(CO)cc(CO)c1)(c1cc(CO)cc(CO)c1)c1cc(CO)cc(CO)c1 Chemical compound CC(c1cc(CO)cc(CO)c1)(c1cc(CO)cc(CO)c1)c1cc(CO)cc(CO)c1 QYWKVJCDXGTXAW-UHFFFAOYSA-N 0.000 description 1
- PMNLKHAHWOLBSL-UHFFFAOYSA-N COC(c(cc1)ccc1OCCCC(F)(F)F)=O Chemical compound COC(c(cc1)ccc1OCCCC(F)(F)F)=O PMNLKHAHWOLBSL-UHFFFAOYSA-N 0.000 description 1
- MBOOYFIAPXZRTK-UHFFFAOYSA-N Cc1cc(CO)cc(C2(CCCCC2)c2cc(CO)cc(C)c2)c1 Chemical compound Cc1cc(CO)cc(C2(CCCCC2)c2cc(CO)cc(C)c2)c1 MBOOYFIAPXZRTK-UHFFFAOYSA-N 0.000 description 1
- BVGLECMQARBFOT-UHFFFAOYSA-N Nc1cc(N)cc(C(NCc2cccnc2)=O)c1 Chemical compound Nc1cc(N)cc(C(NCc2cccnc2)=O)c1 BVGLECMQARBFOT-UHFFFAOYSA-N 0.000 description 1
- PTXMRQLIAQYLKJ-NYYWCZLTSA-N OC(/C=C/c(cc1)ccc1OC(c(cc1)ccc1OCCCC(F)(F)F)=O)=O Chemical compound OC(/C=C/c(cc1)ccc1OC(c(cc1)ccc1OCCCC(F)(F)F)=O)=O PTXMRQLIAQYLKJ-NYYWCZLTSA-N 0.000 description 1
- MLOMDXRYFMVEMO-OVCLIPMQSA-N OC(/C=C/c1ccc(C(CC2)CCC2C2CCCCC2)cc1)=O Chemical compound OC(/C=C/c1ccc(C(CC2)CCC2C2CCCCC2)cc1)=O MLOMDXRYFMVEMO-OVCLIPMQSA-N 0.000 description 1
- KMWBBCLPHGMNRU-UHFFFAOYSA-N OCc1cc(C(CC2)CCC2(c(cc2CO)cc(CO)c2O)c(cc2CO)cc(CO)c2O)cc(CO)c1O Chemical compound OCc1cc(C(CC2)CCC2(c(cc2CO)cc(CO)c2O)c(cc2CO)cc(CO)c2O)cc(CO)c1O KMWBBCLPHGMNRU-UHFFFAOYSA-N 0.000 description 1
- CLQWIZGOHRJBNS-UHFFFAOYSA-N OCc1cc(CO)nc(CO)c1 Chemical compound OCc1cc(CO)nc(CO)c1 CLQWIZGOHRJBNS-UHFFFAOYSA-N 0.000 description 1
- RXCXJIBFUHLERX-UHFFFAOYSA-N OCc1cc(Nc2cc(CO)cc(CO)c2)cc(CO)c1 Chemical compound OCc1cc(Nc2cc(CO)cc(CO)c2)cc(CO)c1 RXCXJIBFUHLERX-UHFFFAOYSA-N 0.000 description 1
- WWFMINHWJYHXHF-UHFFFAOYSA-N OCc1nc(CO)ccc1 Chemical compound OCc1nc(CO)ccc1 WWFMINHWJYHXHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
- C09K19/2021—Compounds containing at least one asymmetric carbon atom
- C09K19/2028—Compounds containing at least one asymmetric carbon atom containing additionally a linking group other than -COO- or -OCO-, e.g. -CH2-CH2-, -CH=CH-, -C=C-; containing at least one additional carbon atom in the chain containing -COO- or -OCO- groups, e.g. -COO-CH*-CH3
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/542—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
-
- 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
-
- 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
-
- 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
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
-
- 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
- G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
- C09K2019/2035—Ph-COO-Ph
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/3009—Cy-Ph
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/301—Cy-Cy-Ph
Definitions
- the present invention provides a liquid crystal aligning agent containing a polymer having a side chain having or expressing an isocyanate group, a side chain exhibiting photoreactivity, and a side chain having a hydroxyl group or an amino group, and thus obtained.
- the present invention relates to a liquid crystal alignment film and a liquid crystal display device including the obtained liquid crystal alignment film.
- the liquid crystal alignment film plays a role of aligning the liquid crystal in a certain direction.
- the main liquid crystal alignment film used industrially is a polyimide precursor (polyamic acid), a polyamic acid ester, or a polyimide-based liquid crystal aligning agent made of a polyimide solution. It is produced by applying and forming a film. When the liquid crystal is aligned in parallel or inclined with respect to the substrate surface, a surface stretching process is further performed by rubbing after film formation.
- a vertical alignment (VA) method when the liquid crystal is aligned perpendicularly to the substrate (referred to as a vertical alignment (VA) method), a long chain alkyl, a cyclic group, or a combination of a cyclic group and an alkyl group (see, for example, Patent Document 1), a steroid skeleton ( For example, a liquid crystal alignment film in which a hydrophobic group is introduced into a side chain of polyimide such as Patent Document 2) is used.
- a voltage is applied between the substrates to incline the liquid crystal molecules in a direction parallel to the substrate, the liquid crystal molecules need to be inclined from the substrate normal direction toward one direction in the substrate surface. .
- a method of providing a protrusion on the substrate a method of providing a slit in the display electrode, or a liquid crystal molecule is slightly tilted from the normal direction of the substrate toward one direction in the substrate surface by rubbing ( Pretilt method, and also pre-tilt the liquid crystal by adding a photopolymerizable compound to the liquid crystal composition in advance and using it with a vertical alignment film such as polyimide and irradiating ultraviolet rays while applying voltage to the liquid crystal cell
- a vertical alignment film such as polyimide and irradiating ultraviolet rays while applying voltage to the liquid crystal cell
- a highly polar solvent such as N-methyl-2-pyrrolidone (also referred to as NMP) is used because the solvent solubility of these polyimide polymers is low. in use.
- NMP N-methyl-2-pyrrolidone
- These highly polar solvents have high boiling points.
- NMP has a boiling point of 200 ° C. or higher. Therefore, in order to produce a liquid crystal alignment film using a liquid crystal alignment treatment agent using NMP as a solvent, in order to eliminate NMP remaining in the liquid crystal alignment film, at a high temperature of about 200 ° C. near the boiling point of NMP. Need to be fired.
- An object of this invention is to provide the liquid crystal display element which has the said characteristic. That is, an object of the present invention is to provide a liquid crystal display element that can be fired at a low temperature when forming a liquid crystal alignment film capable of imparting alignment regulating ability and pretilt angle expression by a photo-alignment method.
- it aims at providing the vertical liquid crystal aligning film used for the said liquid crystal display element, and the liquid crystal aligning agent which can provide this vertical liquid crystal aligning film.
- ⁇ 1> (a) a site having an isocyanate group and / or a blocked isocyanate group, (b) a site having at least one functional group selected from an amino group and a hydroxyl group in the molecule, and (c) A liquid crystal aligning agent containing a polymer having a photo-alignable photoreactive group.
- the present invention it is possible to provide a liquid crystal aligning agent capable of forming a liquid crystal alignment film capable of imparting alignment regulating ability and pretilt angle expression by low temperature baking by a photo-alignment method. Further, the liquid crystal display device manufactured by the method of the present invention has high stability of the pretilt angle of the liquid crystal, and the display characteristics are not impaired even when continuously driven for a long time.
- the liquid crystal aligning agent of the present invention comprises (a) a site having an isocyanate group and / or a blocked isocyanate group, and (b) at least one selected from an amino group and a hydroxyl group in the molecule. It contains a polymer having a functional group-containing moiety and (c) a moiety having a photo-alignable photoreactive group (hereinafter also referred to as “specific polymer”).
- specific polymer a polymer having a functional group-containing moiety
- the three “sites” can all be side chains in the polymer, they can also be referred to as “side chains” as necessary.
- Sa, Sb, and Sc each represent an independent spacer unit, and each of the left binders of Sa, Sb, and Sc is bound to the main chain of the specific polymer, optionally via a spacer,
- a divalent organic group Ia has an isocyanate group or a blocked isocyanate group,
- Ib is a monovalent organic group having a photoalignable photoreactive group,
- Ic represents a monovalent organic group having at least one functional group selected from an amino group and a hydroxyl group.
- Ma, Mb, Mc, Md, Me, and Mf are the same as those defined in the formula (1m), formula (3m), and formula (4m) described later.
- x, y, and z are not particularly limited.
- x, y, and z can independently take values of 0.1 or more and 0.8 or less.
- Formula (I) means that each side chain exists in the ratio of x, y, z, Comprising: In a polymer, it means the block copolymer in which each side chain was blocked. It is not a thing.
- the specific polymer contained in the liquid crystal aligning agent of the present invention is sensitive to light and causes a crosslinking reaction or an isomerization reaction.
- part which has photo-orientation property is not specifically limited, What has a cinnamic acid structure is desirable.
- the specific polymer is cured by causing a cross-linking reaction between the polymers by the reaction of an isocyanate group with an amino group or a hydroxyl group. In this case, even if exposed to external stress such as heat, the realized vertical alignment control ability can be stably maintained for a long period of time.
- the specific polymer contained in the liquid crystal aligning agent has a site having an isocyanate group and / or a blocked isocyanate group.
- the specific polymer has an isocyanate group and / or a blocked isocyanate group in the side chain.
- the site having an isocyanate group and / or a blocked isocyanate group is preferably the following formula (1).
- the part is preferably derived from a monomer represented by the following formula (1m).
- Sa represents a spacer unit, and the left connector of Sa indicates that it is bonded to the main chain of the specific polymer, optionally via a spacer, Ia is an isocyanate group or a blocked isocyanate group.
- Ma represents the first polymerizable group.
- (meth) acrylate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, norbornene, radical polymerizable group of (meth) acrylamide and its derivatives, and siloxane are used.
- (Meth) acrylate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide and acrylamide are preferred.
- p is an integer of 1 to 3, preferably 1 or 2.
- Mb is a single bond, a divalent heterocycle, a trivalent heterocycle, a tetravalent heterocycle, a substituted or unsubstituted linear or branched alkyl having 1 to 10 carbon atoms Group, divalent aromatic group, trivalent aromatic group, tetravalent aromatic group, divalent alicyclic group, trivalent alicyclic group, tetravalent alicyclic group, bivalent A fused cyclic group, a trivalent fused cyclic group or a tetravalent fused cyclic group, each group being unsubstituted or having one or more hydrogen atoms as fluorine, chlorine, cyano, methyl or methoxy It may be substituted by a group.
- Sa is derived from the following formula (2).
- the left bond of W 1 represents the bond to Mb
- the right bond of W 3 represents the bond to Ia W 1 , W 2 and W 3 each independently represent a single bond, a divalent heterocyclic ring, — (CH 2 ) n— (wherein n represents 1 to 20), —OCH 2 —, — CH 2 O—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF—, —CF 2 O—, —OCF 2 —, —CF 2 CF 2 — or —C ⁇ C— is represented.
- one or more of the non-adjacent CH 2 groups in these substituents are independently —O—, —CO—, —CO—O—, —O—CO—, —Si (CH 3 ) 2 —. O—Si (CH 3 ) 2 —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —OCO—NR—, —NR—CO—NR—, —CH ⁇ CH—, —C ⁇ C— or —O—CO—O— (wherein R independently represents hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms) It can, A 1 and A 2 are each independently a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group, and each group has no It may be substituted or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom
- the “blocked isocyanate group” in Ia of the above formula (1) or formula (1m) is an isocyanate group in which an isocyanate group (—NCO) is blocked with an appropriate protecting group (BL). (II).
- the blocked isocyanate group is removed by thermal dissociation of the protective group (block part) by heating and baking at the time of forming the liquid crystal alignment film, thereby generating a reactive isocyanate group.
- the generated isocyanate group undergoes a crosslinking reaction with other side chains of the polymer constituting the liquid crystal alignment film.
- this isocyanate group reacts with the compound which has 2 or more of 1 or more types of functional groups chosen from the group which consists of an amino group and a hydroxyl group in a molecule
- BL represents an isocyanate protecting group
- the site having a blocked isocyanate group in the present invention is not particularly limited in terms of its type and structure.
- the blocked isocyanate group can be obtained, for example, by allowing a suitable blocking agent to act on a compound having an isocyanate group in the molecule.
- blocking agents include alcohols such as methanol, ethanol, isopropanol, n-butanol, 1-methoxy-2-propanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, and cyclohexanol.
- alcohols such as methanol, ethanol, isopropanol, n-butanol, 1-methoxy-2-propanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, and cyclohexanol.
- Phenols such as phenol, o-nitrophenol, p-chlorophenol, o-, m- or p-cresol; lactams such as ⁇ -caprolactam; acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone Oximes such as oxime and benzophenone oxime; pyrazoles such as pyrazole, 3,5-dimethylpyrazole and 3-methylpyrazole; thiols such as dodecanethiol and benzenethiol S; carboxylic acid esters such as diethyl malonate, and the like. Ethanol, isopropanol, 1-methoxy-2-propanol, 3,5-dimethylpyrazole, ⁇ -caprolactam, and methyl ethyl ketone oxime are preferable.
- BL-1 to Bl-7 are shown as preferred specific structures of BL, but are not limited thereto. Note that the broken-line connector indicates the bonding site with the carbon of formula (I).
- Ia examples include, but are not limited to, the following Ia-1 to Ia-8.
- a broken line represents a bond to Sa in the above formula (1)
- R 6 represents a linear or branched alkyl group having 1 to 10 carbon atoms (however, one or more of non-adjacent CH 2 groups are independent). And may be replaced by an oxygen atom).
- the isocyanate group when further using a crosslinkable compound as described later, when an isocyanate group that is not blocked is contained as a component of the specific polymer, the isocyanate group is selected from the group consisting of an amino group and a hydroxyl group in the molecule. Since it exhibits excellent reactivity with a compound having two or more kinds of functional groups of at least species, a crosslinking reaction can be efficiently carried out even at low temperature firing.
- the reaction temperature between the isocyanate group and the amino group or hydroxyl group is preferably 50 ° C. to 200 ° C., more preferably 80 ° C. to 200 ° C., more preferably 80 ° C. to 180 ° C.
- the isocyanate group is excellent in reactivity with an amino group or a hydroxyl group, particularly an amino group, and the crosslinking reaction may proceed even at a low temperature, which may deteriorate the storage stability of the liquid crystal aligning agent. Therefore, when storing a liquid crystal aligning agent for a long period, the blocked isocyanate group may be used.
- Blocked isocyanate sites are those in which the block portion undergoes thermal dissociation and the crosslinking reaction proceeds via isocyanate groups in a high temperature state such as the temperature of heating and baking at the time of forming the liquid crystal alignment film.
- a state where the liquid crystal aligning agent is stored at a low temperature eg, ⁇ 20 ° C. to 40 ° C.
- crosslinking by isocyanate groups does not proceed.
- the side chain having a blocked isocyanate group has a temperature at which the thermal dissociation of the block portion is considerably higher than that during storage of the liquid crystal aligning agent, for example, at 50 ° C. to 230 ° C. Some are preferred, and those with 60-150 ° C. are more preferred.
- the site having an isocyanate group and / or a blocked isocyanate group in the present invention is preferably derived from the monomer represented by the above formula (1m).
- the monomer represented by the formula (1m) include, but are not limited to, the following.
- the polymer having a blocked isocyanate group in the side chain contained in the liquid crystal aligning agent of the present invention is obtained by producing a polymer using various polymer raw materials containing the blocked isocyanate group. be able to.
- a (meth) acrylic polymer is used as a polymer, by polymerizing a (meth) acrylic polymer using a compound having an isocyanate group blocked by a monomer having a (meth) acrylic group as a raw material. Can be obtained.
- part which has the isocyanate group and / or blocked isocyanate group contained in the polymer of this invention may be used individually by 1 type, and may be used in combination of 2 or more types.
- the introduction amount of the site having an isocyanate group and / or a blocked isocyanate group is preferably 5 to 90 mol% of the specific polymer (component (A)), more preferably 10 to 90 mol%, More preferably, it is 20 to 80 mol%.
- the specific polymer contained in the liquid crystal aligning agent of the present invention has a site having a photoalignable photoreactive group (hereinafter also referred to as a photoreactive side chain).
- the structure of the site having photo-alignment property is not particularly limited, but a structure having a cinnamic acid structure is desirable. In this case, even if exposed to external stress such as heat, the realized vertical alignment control ability can be stably maintained for a long period of time. In addition, since the sensitivity to light is high, the ability to control alignment can be exhibited even when irradiated with polarized UV light with a low exposure amount.
- the site having a photoalignable photoreactive group is preferably represented by the following formula (3).
- the site is preferably derived from a monomer represented by the following formula (3m).
- Ib is a monovalent organic group having a photoalignable photoreactive group.
- Sb represents a spacer unit, and the connector on the left of Sb indicates that it is bonded to the main chain of the specific polymer, optionally via a spacer.
- Sb is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, a divalent aromatic group, or a divalent alicyclic group.
- Mc represents a second polymerizable group.
- (Meth) acrylate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide and acrylamide are preferred.
- Md is a single bond, divalent heterocycle, trivalent heterocycle, tetravalent heterocycle, substituted or unsubstituted linear or branched alkyl having 1 to 10 carbon atoms.
- divalent aromatic group divalent aromatic group, trivalent aromatic group, tetravalent aromatic ring, divalent alicyclic group, trivalent alicyclic group, tetravalent alicyclic group, bivalent A fused cyclic group, a trivalent fused cyclic group or a tetravalent fused cyclic group, each group being unsubstituted or one or more hydrogen atoms being a fluorine atom, a chlorine atom, a cyano group, or a methyl group Alternatively, it may be substituted with a methoxy group.
- Sb is preferably a group represented by the above formula (2) independently of Sa.
- Sb represents formula (2), in the formula, definition of each group of formula (2) that Sa can represent in formula (1) described above, except that the left bond of W 1 represents a bond to Md Is the same.
- the photo-alignment photoreactive group means a group that undergoes photoisomerization or photodimerization reaction by the stimulation of ultraviolet rays, and is represented by, for example, the following formulas (III) -1 to (III) -4:
- the present invention is not limited thereto.
- the “monovalent organic group having a photoalignable photoreactive group” that can be represented by Ib means a monovalent organic group having a group of the above formulas (III) -1 to (III) -4 Means.
- the “monovalent organic group” means an organic group that includes any structure of the above formulas (III) -1 to (III) -4 in the structure and can be bonded to Sb.
- a structure of the following formula (3m) -1 having a group represented by the above (III) -1 Although it can mention, it is not limited to this.
- Z is an oxygen atom or a sulfur atom.
- Xa and Xb are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 3 carbon atoms.
- R 1 is a single bond, an oxygen atom, —COO— or —OCO—, preferably a single bond, —COO— or —OCO—.
- R 2 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group.
- R 3 is a single bond, an oxygen atom, —COO— or —OCO—.
- R 4 is a monovalent organic group having 3 to 40 carbon atoms including a linear or branched alkyl group having 1 to 40 carbon atoms or an alicyclic group.
- R 5 is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, preferably a methyl group, a methoxy group or a fluorine atom.
- a is an integer of 0 to 3
- b is an integer of 0 to 4.
- the linear or branched alkylene group having 1 to 10 carbon atoms of Sb is preferably a linear or branched alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, an n-propylene group, An n-butylene group, a t-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group and an n-octylene group are preferred.
- Examples of the divalent aromatic group of Sb include 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 2,3,5,6-tetrafluoro And 1,4-phenylene group.
- Examples of the divalent alicyclic group of Sb include trans 1,4-cyclohexylene, trans-trans-1,4-bicyclohexylene, and the like.
- Examples of the divalent heterocyclic group of Sb include 1,4-pyridylene group, 2,5-pyridylene group, 1,4-furylene group, 1,4-piperazine group, 1,4-piperidine group and the like. Can do.
- Examples of the divalent fused cyclic group of Sb include a naphthylene group.
- Sb is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.
- Examples of the divalent aromatic group for R 2 include 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 2,3,5,6-tetra A fluoro-1,4-phenylene group can be exemplified.
- Examples of the divalent alicyclic group for R 2 include trans 1,4-cyclohexylene, trans-trans-1,4-bicyclohexylene, and the like.
- Examples of the divalent heterocyclic group for R 2 include 1,4-pyridylene group, 2,5-pyridylene group, 1,4-furylene group, 1,4-piperazine group, 1,4-piperidine group, and the like. be able to.
- Examples of the divalent fused cyclic group for R 2 include a naphthylene group.
- R 2 is preferably a 1,4-phenylene group, trans 1,4-cyclohexylene, or trans-trans-1,4-bicyclohexylene.
- Examples of the linear or branched alkyl group having 1 to 40 carbon atoms of R 4 include, for example, a linear or branched alkyl group having 1 to 20 carbon atoms, wherein some or all of the hydrogen atoms of the alkyl group are fluorine. It is preferable that it may be substituted by an atom.
- alkyl groups include, for example, methyl, ethyl, n-propyl, n-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n -Nonyl group, n-decyl group, n-lauryl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n -Nonadecyl group, n-eicosyl group, 4,4,4-trifluorobutyl group, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-heptafluoro Hexyl group, 3,
- Examples of the monovalent organic group having 3 to 40 carbon atoms including the alicyclic group of R 4 include a cholestenyl group, a cholestanyl group, an adamantyl group, the following formula (A-1) or (A-2) (wherein R 7 includes a group represented by a hydrogen atom, a fluorine atom, or an alkyl group which may be substituted with a fluorine atom having 1 to 20 carbon atoms.
- the site having photo-alignment property is preferably derived from the monomer represented by the above formula (3m) or (3m) -1 as described above.
- Examples of the monomer represented by the formula (3m) or (3m) -1 include, but are not limited to, the following.
- One type of photoreactive site contained in the polymer of the present invention may be used alone, or two or more types may be used in combination.
- the photoreactive site is contained in an amount of 10% to 80%, preferably 20% to 60%, based on at least one polymer. There exists a possibility that the liquid crystal orientation of the liquid crystal aligning film formed may fall that content of a photoreactive side chain is less than the minimum of the said range.
- the introduction amount of the site having photo-alignment is too small, a sufficient pretilt angle may not be obtained. If the introduction amount is too large, the introduction amount of the site having an isocyanate group and / or a blocked isocyanate group may be obtained.
- the cross-linking reaction with the site having at least one functional group selected from the group consisting of an amino group and a hydroxyl group in the molecule and the cross-linking compound added if not necessary does not proceed sufficiently, and a sufficient pretilt is achieved. Corners may not be obtained.
- the specific polymer contained in the liquid crystal aligning agent of the present invention has a site having at least one functional group selected from an amino group and a hydroxyl group in the molecule, that is, from an amino group and a hydroxyl group in the molecule. It has at least one selected functional group in the side chain. This site can undergo a cross-linking reaction with an isocyanate group which the specific polymer of the present invention has or an isocyanate group which is generated by detaching the block site.
- the site having at least one functional group selected from an amino group and a hydroxyl group in the molecule is preferably represented by the following formula (4).
- the site is preferably derived from a monomer represented by the following formula (4m).
- Ic is a monovalent organic group having at least one functional group selected from an amino group and a hydroxyl group in the molecule.
- Sc represents a spacer unit, and the left connector of Sc indicates that it is bonded to the main chain of the specific polymer, optionally via a spacer.
- Sc is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, a divalent aromatic group, or a divalent alicyclic group.
- Me represents a third polymerizable group.
- (Meth) acrylate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide and acrylamide are preferred.
- Mf is a single bond, divalent heterocycle, trivalent heterocycle, tetravalent heterocycle, substituted or unsubstituted linear or branched alkyl having 1 to 10 carbon atoms.
- divalent aromatic group divalent aromatic group, trivalent aromatic group, tetravalent aromatic ring, divalent alicyclic group, trivalent alicyclic group, tetravalent alicyclic group, bivalent A fused cyclic group, a trivalent fused cyclic group or a tetravalent fused cyclic group, each group being unsubstituted or one or more hydrogen atoms being a fluorine atom, a chlorine atom, a cyano group, or a methyl group Alternatively, it may be substituted with a methoxy group.
- Sc is preferably a group represented by the above formula (2) independently of Sa.
- Sc represents Formula (2)
- the polymer having at least one functional group selected from an amino group and a hydroxyl group in the molecule contained in the liquid crystal aligning agent of the present invention can be obtained by using various polymer raw materials containing an amino group and a hydroxyl group. It can be obtained by producing a coalescence.
- a (meth) acrylic polymer is used as a polymer, by polymerizing a (meth) acrylic polymer using a compound having an isocyanate group blocked by a monomer having a (meth) acrylic group as a raw material. Can be obtained.
- the site having at least one functional group selected from an amino group and a hydroxyl group in the molecule may be derived from the monomer represented by the above formula (4m) as described above.
- Preferred examples of the monomer represented by the formula (4m) include, but are not limited to, the following.
- numerator contained in the polymer of this invention may be used individually by 1 type, and may be used combining 2 or more types of site
- the site having at least one functional group selected from an amino group and a hydroxyl group in the molecule is 10% to 80%, preferably 20% to 60%, based on at least one polymer. Contained.
- the specific polymer contained in the liquid crystal aligning agent of the present invention includes (a) a monomer having an isocyanate group and / or a blocked isocyanate group, and (b) a monomer having a photoalignable photoreactive group. And (c) polymerizing a monomer having at least one functional group selected from an amino group and a hydroxyl group in the molecule. Moreover, it can copolymerize with another monomer in the range which does not impair the orientation and other characteristics. Examples of other monomers include industrially available monomers capable of radical polymerization reaction.
- monomers include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound.
- unsaturated carboxylic acid examples include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
- acrylate compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert- Butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2 -Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate And, like 8-ethyl-8-tricyclodecyl acrylate.
- methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl.
- (Meth) acrylate compounds having a cyclic ether group such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, and (3-ethyl-3-oxetanyl) methyl (meth) acrylate are also used. be able to.
- Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
- Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.
- Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
- the method for producing the specific polymer in the present invention is not particularly limited, and a general-purpose method handled industrially can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a photo-alignment monomer, a vinyl group of a monomer having an isocyanate group and / or a blocked isocyanate group. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.
- RAFT reversible addition-cleavage chain transfer
- the radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher.
- radical thermal polymerization initiators include ketone peroxides (such as methyl ethyl ketone peroxide and cyclohexanone peroxide), diacyl peroxides (such as acetyl peroxide and benzoyl peroxide), and hydroperoxides (peracid).
- the radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation.
- examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-Methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy -2-Phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [
- the radical polymerization method is not particularly limited, and an emulsion polymerization method, suspension polymerization method, dispersion polymerization method, precipitation polymerization method, bulk polymerization method, solution polymerization method and the like can be used.
- the organic solvent used for the polymerization reaction of the polymer having a portion having an isocyanate group and / or a blocked isocyanate group and a portion having photo-alignment property is not particularly limited as long as the produced polymer can be dissolved. . Specific examples are given below.
- organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the polymer
- the polymerization temperature at the time of radical polymerization can be selected from any temperature of 30 ° C. to 150 ° C., but is preferably in the range of 50 ° C. to 100 ° C.
- the reaction can be performed at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass.
- the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
- the molecular weight of the obtained polymer is decreased when the ratio of the radical polymerization initiator is large relative to the monomer, and the molecular weight of the obtained polymer is increased when the ratio is small, the ratio of the radical initiator is
- the content is preferably 0.1 mol% to 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added during the polymerization.
- the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced.
- the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
- the molecular weight of the polymer of the present invention is the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method when considering the strength of the obtained coating film, the workability during coating film formation, and the uniformity of the coating film. 2000 to 1000000 is preferable, and 5000 to 100,000 is more preferable.
- the liquid crystal aligning agent (namely, polymer composition) used for this invention is prepared as a coating liquid so that it may become suitable for formation of a liquid crystal aligning film. That is, the liquid crystal aligning agent of the present invention is preferably prepared as a solution in which a resin component for forming a resin film is dissolved in an organic solvent.
- the resin component is the specific polymer (component (A)) already described.
- the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 15% by mass, and particularly preferably 2% by mass to 10% by mass.
- the content of the resin component is 1% by mass to 20%. % By mass is preferable, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
- the resin component described above includes all the above-described isocyanate groups and / or blocked isocyanate groups, a portion having photo-orientation, an amino group in the molecule, and A polymer having a site having at least one functional group selected from the group consisting of hydroxyl groups may be used, but other polymers may be mixed with each other as long as the photo-alignment ability and the crosslinking reactivity are not impaired. It may be. In that case, the content of the other polymer in the resin component is 0.5 to 90% by mass, preferably 1 to 80% by mass.
- Such other polymers are made of, for example, poly (meth) acrylate, polyamic acid, polyimide, and the like, and have a portion having an isocyanate group and / or a blocked isocyanate group and a portion having a photo-alignment property.
- examples include polymers that are not molecules.
- Organic solvent used for the liquid crystal aligning agent of this invention will not be specifically limited if it is an organic solvent in which a resin component is dissolved. Specific examples are given below.
- the liquid crystal aligning agent of this invention may contain other components other than the said characteristic polymer component.
- Such other components include crosslinkable compounds (crosslinking agents), solvents and compounds that improve film thickness uniformity and surface smoothness when a liquid crystal alignment agent is applied, and adhesion between the liquid crystal alignment film and the substrate. Examples thereof include compounds that improve the properties, but are not limited thereto.
- the liquid crystal aligning film may be a dielectric or conductive material, or a liquid crystal for the purpose of changing electrical properties such as dielectric constant or conductivity of the liquid crystal aligning film
- a crosslinkable compound may be added for the purpose of increasing the hardness and density of the alignment film.
- the crosslinkable compound that can be added to the liquid crystal aligning agent of the present invention is preferably a compound having two or more functional groups selected from the group consisting of an amino group and a hydroxyl group (“(B) component” in the molecule. ”).
- all of the two or more functional groups may be the same kind (one kind) of amino group or hydroxyl group, or may be two or more kinds of amino group or hydroxyl group.
- An amino group and a hydroxyl group may be mixed.
- (B) component of this invention may be a polymer which has a repeating unit, as long as it has 2 or more of 1 or more types of functional groups chosen from the group which consists of an amino group and a hydroxyl group in a molecule
- the polymer having a repeating unit may have two or more functional groups selected from the group consisting of an amino group and a hydroxyl group at the terminal.
- the polymer corresponds to the component (B) of the present invention as long as the polymer has two or more functional groups.
- 2-hydroxyethyl methacrylate HEMA
- HEMA 2-hydroxyethyl methacrylate
- the component (B) of the present invention may be a polymer having a repeating unit derived from a monomer having two or more functional groups (the functional group is an amino group and / or a hydroxyl group). Good.
- the component (B) undergoes a crosslinking reaction with the polymer which is the component (A) described above, particularly the isocyanate group in the component (A) (including the isocyanate group in which the blocking group is eliminated from the blocked isocyanate group). be able to.
- a crosslinking reaction with the polymer which is the component (A) described above, particularly the isocyanate group in the component (A) (including the isocyanate group in which the blocking group is eliminated from the blocked isocyanate group).
- the component (B) when the component (B) is a polymer having a repeating unit as described above and the number average molecular weight is 2000 or less, or a compound having no repeating unit,
- the component (B) may be contained in an amount of 1 to 80% by mass, preferably 1 to 50% by mass, more preferably 2 to 30% by mass with respect to 100% by mass of the component (A).
- the component (A): component (B) should have a mass ratio of 100: 1 to 100: 80, preferably 100: 1 to 100: 50, more preferably 100: 2 to 100: 30. .
- the component (B) is a polymer having a repeating unit and the number average molecular weight is 2000 or more
- the component (B) is based on 100% by mass of the component (A) described above. 5 to 1000% by mass, preferably 5 to 900% by mass, more preferably 10 to 800% by mass.
- the component (A): component (B) should have a mass ratio of 100: 5 to 100: 1000, preferably 100: 5 to 100: 900, more preferably 100: 10 to 100: 800. .
- the compound of the (B) component of this invention is represented by following formula (5).
- T represents an amino group or a hydroxyl group
- Y represents an m-valent organic group
- m is an integer of 2 or more.
- m is 2 or more, but a larger number of m is preferable because a crosslinking reaction with a specific polymer easily proceeds.
- a general diamine compound, triamine compound, tetraamine compound or polyamine compound can be used as the compound having two or more amino groups in the molecule.
- Y when m is 2 include, but are not limited to, the following formulas (Y-1) to (Y-120).
- Y is a long-chain alkyl group (for example, an alkyl group having 10 or more carbon atoms), an aromatic ring, an aliphatic ring, a steroid skeleton, or these It is preferable that the raw material is a diamine compound having a combined structure.
- Y As such Y, (Y-83), (Y-84), (Y-85), (Y-86), (Y -87), (Y-88), (Y-89), (Y-90), (Y-91), (Y-92), (Y-93), (Y-94), (Y-95 ), (Y-96), (Y-97), (Y-98), (Y-99), (Y-100), (Y-101), (Y-102), (Y-103), Examples include (Y-104), (Y-105), (Y-106), (Y-107), or (Y-108), but are not limited thereto.
- a photoreactive site is also introduced into the specific polymer, and (Y-17), (Y-18), (Y-111), (Y-112), (Y-113), (Y-114), (Y-115), (Y-116), (Y-117), (Y-118), (Y-119) can also be used.
- Y when m is 3 or more include trivalent or more organic groups represented by the following formula, and the above-mentioned (Y-1) to (Y— 120) from which hydrogen atoms are eliminated, but is not limited thereto.
- Me is a methyl group.
- a general diol compound, triol compound, tetraol compound, polyol compound, or a polymer having a plurality of hydroxyl groups in the molecule can be used.
- m is 2 include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9.
- Y is (Y-1) to (Y- 120) and the like, but is not limited thereto.
- Y 1 , Y 2 and Y 3 each independently represent an aromatic ring. Any hydrogen atom of the aromatic ring may be substituted with a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a vinyl group.
- Z 1 is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms which may be bonded to form a cyclic structure by a single bond or all or a part thereof, and any hydrogen atom is substituted with a fluorine atom. Or —NH—, —N (CH 3 ) —, or a group represented by the formula (9).
- X 1 is a 1-valent organic group containing an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group.
- l is an integer of 2 to 6
- d 1 is an integer of 2 to 4
- d 2 and d 3 are each independently an integer of 1 to 3
- e and f are each independently an integer of 1 to 3
- K 1 and K 2 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted alkenyl group having 2 to 4 carbon atoms, or An alkynyl group having 2 to 4 carbon atoms which may have a substituent.
- at least one of K 1 and K 2 represents a hydrocarbon group substituted with a hydroxy group.
- L in the formula (8) is preferably 2 to 4 from the viewpoint of solubility.
- P 1 and P 2 are each independently an alkylene group having 1 to 5 carbon atoms, and Q 1 represents an aromatic ring. Since the —CH 2 —OH group in formula (6) and formula (7) is directly bonded to the aromatic ring, Y 1 , Y 2 and Y 3 are each independently an aromatic ring.
- aromatic ring examples include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, Pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thioline ring, Examples include phenanthroline ring, indole ring, quinoxaline ring,
- more preferable aromatic rings include benzene ring, naphthalene ring, fluorene ring, anthracene ring, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, isoquinoline ring, carbazole ring, pyridazine ring, pyrazine. Ring, benzimidazole ring, benzimidazole ring, indole ring, quinoxaline ring, acridine ring and the like.
- a benzene ring More preferred are a benzene ring, a naphthalene ring, a pyridine ring and a carbazole ring, and most preferred are a benzene ring and a pyridine ring.
- the hydrogen atoms of these aromatic rings may be substituted with a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a vinyl group.
- d 2 and d 3 are more preferably integers of 1 or 2.
- E and f are more preferably 1 or 2.
- Z 1 in the formula (7) is a divalent saturated hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms that may be bonded to all or part of it to form a cyclic structure. Any hydrogen atom that it has may be substituted with a fluorine atom.
- Z 1 include an alkylene group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, a combination of an alkylene group and an alicyclic hydrocarbon group, and 1 to 1 carbon atom.
- a group in which any hydrogen atom of the above-described group is substituted with a fluorine atom is exemplified.
- Q 1 in the formula (8) is an aromatic ring, and specific examples thereof include a benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, pyrrole ring, Imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring Benzimidazole ring, benzimidazole ring, thioline ring, phenanthroline ring, indo
- more preferable aromatic rings include benzene ring, naphthalene ring, fluorene ring, anthracene ring, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, isoquinoline ring, carbazole ring, pyridazine ring, pyrazine. Ring, benzimidazole ring, benzimidazole ring, indole ring, quinoxaline ring, acridine ring and the like. More preferably, a benzene ring, a naphthalene ring, a pyridine ring, a carbazole ring, a fluorene ring, etc. are mentioned.
- K 1 and K 2 are preferably a structure represented by the following formula (10) from the viewpoint of reactivity, and a structure represented by the following formula (11) More preferably.
- K 3 to K 6 are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group.
- Specific examples of the specific compound used in the present invention include compounds [P1] to [P37], but are not limited thereto.
- the specific compound as the component (B) is [P9], [P11], [P12], [P15], [P18], [P21], [P22], [P27], [P29] to [P37].
- compounds represented by [P9], [P11], [P12], [P15], and [P29] are more preferable.
- Solvent that improves film thickness uniformity and surface smoothness includes the following.
- These poor solvents may be used alone or in combination of two or more.
- it is preferably 5% by mass to 80% by mass of the total solvent, more preferably so as not to significantly reduce the solubility of the entire solvent contained in the liquid crystal aligning agent. It is 20% by mass to 60% by mass.
- the solvent contains a hydroxyl group. If so, the above solvent is preferably a solvent having no hydroxyl group because it may react with the isocyanate in the polymer to impair the crosslinking reactivity of the polymer.
- Examples of the compound that improves film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
- Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Company), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) It is done.
- the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the polymer composition. Part by mass.
- Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds.
- the following epoxy group-containing compound additives are added to the liquid crystal for the purpose of preventing deterioration of electrical characteristics due to the backlight when the liquid crystal display element is constructed. You may make it contain in an orientation agent.
- Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′,-tetraglycidyl-4, 4 ′ Although such diaminodip
- the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent. More preferably, it is 1 to 20 parts by mass. If the amount used is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
- a photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.
- photosensitizers aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarins, carbonylbiscoumarins, aromatic 2-hydroxyketones, and amino-substituted Aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl- ⁇ -naphthothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- ( ⁇ -naphthoylmethylene)
- aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.
- the liquid crystal aligning agent of the present invention may be applied to a substrate and baked, and then subjected to an alignment treatment by rubbing treatment, light irradiation, or the like, or may be used as a liquid crystal alignment film without an alignment treatment in some vertical alignment applications. it can.
- the application method of the liquid crystal aligning agent of the present invention is not particularly limited, but a method performed by screen printing, flexographic printing, offset printing, ink jet, or the like is common.
- a method using a coating liquid there are a dip, a roll coater, a slit coater, a spin coater, etc., and these may be used according to the purpose.
- the solvent can be evaporated by a heating means such as a hot plate to form a coating film.
- Firing after applying the liquid crystal aligning agent can be performed at an arbitrary temperature of 50 to 300 ° C., preferably 80 ° C. to 250 ° C., more preferably 80 ° C. to 230 ° C.
- This baking can be performed with a hot plate, a hot-air circulating furnace, an infrared furnace, or the like.
- the liquid crystal alignment film for vertical alignment is difficult to obtain a uniform alignment state by rubbing treatment, it is preferably used without rubbing when used as a liquid crystal aligning agent for vertical alignment.
- the photo-alignment treatment is performed by irradiating the coating film formed on the substrate with linearly polarized ultraviolet rays having a wavelength of 200 nm to 450 nm using a linearly polarized ultraviolet exposure apparatus.
- a more preferable wavelength of the linearly polarized ultraviolet light is 250 nm to 400 nm.
- the liquid crystal cell of the present invention can be produced by an ordinary method, and the production method is not particularly limited.
- a sealing agent is applied to a glass substrate having a liquid crystal alignment film formed on at least one substrate, spacers are dispersed so that a certain gap can be maintained, and then the two substrates are bonded and sealed.
- An agent is cured to produce an empty cell, and then a liquid crystal is injected from a liquid crystal injection port under vacuum, and the injection port is sealed to prepare a liquid crystal cell; or a liquid crystal is formed on a substrate in which spacers are dispersed.
- a method of manufacturing a liquid crystal cell by dropping and then bonding two substrates together can be used.
- fluorine-based liquid crystal or cyano-type liquid crystal having positive or negative dielectric anisotropy can be used depending on the application.
- the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention can give a large pretilt angle to the liquid crystal and can be used as a liquid crystal alignment film for vertical alignment.
- a monomer capable of forming a site having an isocyanate group and / or a blocked isocyanate group and a monomer capable of forming a site having at least one functional group selected from an amino group and a hydroxyl group in the molecule is also shown below.
- MOI-BM 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate
- MOI-BP 2-[(3,5-dimethylpyrazoyl) carbonylamino] ethyl methacrylate
- FT-NMR Fourier transform type superconducting nuclear magnetic resonance apparatus
- INOVA-400 manufactured by Varian 400 MHz.
- Solvent deuterated chloroform (CDCl 3 ) or deuterated N, N-dimethyl sulfoxide ([D 6 ] -DMSO).
- Standard substance Tetramethylsilane (TMS).
- the reaction solution was filtered to remove insoluble matters, and the filtrate was poured into pure water (3.8 L) and neutralized with 12N-HCl aqueous solution. After neutralization, ethyl acetate (2.5 L) was poured and extracted. To the extracted organic layer, anhydrous magnesium sulfate was added, dehydrated and dried, and anhydrous magnesium sulfate was filtered. The obtained filtrate was evaporated using a rotary evaporator, and the crude product was repulped with cold methanol (180 g) to obtain 144.0 g of [MA-1-1] (white solid) (yield) 82%).
- the reaction solution was filtered to remove insoluble matters, and the filtrate was poured into pure water (3.8 L) and neutralized with 12N-HCl aqueous solution. After neutralization, ethyl acetate (2.5 L) was poured and extracted. To the extracted organic layer, anhydrous magnesium sulfate was added, dehydrated and dried, and anhydrous magnesium sulfate was filtered. The solvent of the obtained filtrate was distilled off with a rotary evaporator, and the crude product was repulped with cold methanol (190 g) to obtain 137.0 g of [MA-2-1] (white solid) (yield) 79%).
- the reaction solution was filtered to remove insoluble matters, and the filtrate was poured into pure water (3.8 L) and neutralized with 12N-HCl aqueous solution. After neutralization, ethyl acetate (2.5 L) was poured and extracted. To the extracted organic layer, anhydrous magnesium sulfate was added, dehydrated and dried, and anhydrous magnesium sulfate was filtered. The obtained filtrate was evaporated with a rotary evaporator, and the crude product was repulped with cold methanol (180 g) to obtain 151.6 g of [MA-3-1] (white solid) (yield) 89%).
- the molecular weight of the polymer in the synthesis example was measured as follows using a normal temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. and a column (KD-803, KD-805) manufactured by Shodex.
- GPC gel permeation chromatography
- Example 11 HEMA (19.5 g, 150.0 mmol) was dissolved in PGME (83.2 g), and after deaeration with a diaphragm pump, AIBN (1.25 g, 7.5 mmol) was added and deaeration was performed again. . Thereafter, the mixture was reacted at 80 ° C. for 12 hours to obtain a polymer solution of methacrylate. CHN (166.0 g) and PGME (76.1 g) were added to this polymer solution, diluted to 6% by mass, and stirred at room temperature for 5 hours to obtain a polymer solution (O). The number average molecular weight of this polymer was 4,800, and the weight average molecular weight was 5,700. Next, the liquid crystal aligning agent (P) obtained by adding the liquid crystal aligning agent (B) (7.0 g) obtained in Example 2 to the polymer solution (O) (3.0 g) obtained above and stirring. Got.
- This polymer had a number average molecular weight of 39000 and a weight average molecular weight of 112,000.
- TM-BIP 40 mg (corresponding to 10% by weight of the solid content of the solution) was added as a crosslinking agent to 10.0 g of the liquid crystal aligning agent (J) and stirred for 3 hours to obtain a liquid crystal aligning agent (J1).
- Example 13 3AMPDA (40 mg) (corresponding to 10% by weight of the solid content of the solution) was added as a crosslinking agent to 10.0 g of the liquid crystal aligning agent (J) obtained in Example 12, and the liquid crystal aligning agent (J2) was stirred for 3 hours.
- This polymer had a number average molecular weight of 44,000 and a weight average molecular weight of 115,000.
- TM-BIP 40 mg (corresponding to 10% by weight of the solid content of the solution) was added as a crosslinking agent to 10.0 g of the liquid crystal aligning agent (K) and stirred for 3 hours to obtain a liquid crystal aligning agent (K1).
- Example 15 3AMPDA (40 mg) (corresponding to 10% by weight of the solid content of the solution) was added as a crosslinking agent to 10.0 g of the liquid crystal aligning agent (K) obtained in Example 14, and the liquid crystal aligning agent (K2) was stirred for 3 hours.
- the polymer composition corresponding to this example is shown below.
- the liquid crystal aligning agent (A) obtained in Example 1 was spin-coated on the ITO surface of a glass substrate with a transparent electrode made of an ITO film, dried on a hot plate at 50 ° C. for 120 seconds, and then on a hot plate at 140 ° C. Baking was performed for 20 minutes to form a liquid crystal alignment film having a thickness of 100 nm.
- a 313 nm linearly polarized ultraviolet ray having an irradiation intensity of 4.3 mW / cm 2 is irradiated onto the coating surface through a polarizing plate by 50 mJ / cm 2 from an angle inclined by 40 ° from the normal direction of the substrate, and a substrate with a liquid crystal alignment film Got.
- the incoming linearly polarized UV light was prepared by passing a 313 nm bandpass filter through the ultraviolet light of a high pressure mercury lamp and then passing it through a 313 nm polarizing plate.
- Example 2 For Examples 2 to 15 and Comparative Examples 1 to 2, the same operations as in Example 1 were performed to evaluate the pretilt angle and liquid crystal orientation of the liquid crystal cell. Also, some examples were evaluated when the baking temperature and the polarized UV exposure amount were changed.
- a good pretilt angle could be obtained even when firing at a low temperature of 140 ° C. or lower.
- a combination of a side chain having a photoreactive group and a side chain having at least one functional group selected from an amino group and a hydroxyl group in the molecule, or a photoreactive group Only a combination of the side chain and the side chain having an isocyanate group and / or a blocked isocyanate group could not provide a good pretilt angle and liquid crystal orientation. It was considered that the anisotropy imparted to the side chain by the photoreaction disappeared due to the curing of the sealing agent and the heating during the isotropic phase treatment.
- the liquid crystal aligning agent of this invention can form the liquid crystal aligning film which improved various characteristics comparatively freely, it can be widely used in the liquid crystal display element which responds to various requirements.
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nonlinear Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Mathematical Physics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Liquid Crystal (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
現在、工業的に使用されている主な液晶配向膜は、ポリイミド前駆体であるポリアミド酸(ポリアミック酸ともいわれる)、ポリアミック酸エステルや、ポリイミドの溶液からなるポリイミド系の液晶配向剤を、基板に塗布し成膜することで作製される。
また、基板面に対して液晶を平行配向又は傾斜配向させる場合は、成膜した後、更にラビングによる表面延伸処理が行われている。
すなわち、本発明の目的は、光配向法によって、配向規制能およびプレチルト角発現性を付与できる液晶配向膜を成膜する際の焼成を低温で行うことができる液晶表示素子を提供することを目的とする。
加えて、上記液晶表示素子に用いる垂直液晶配向膜およびこの垂直液晶配向膜を提供することのできる液晶配向剤を提供することを目的とする。
<1> (a)イソシアネート基及び/又はブロック化されたイソシアネート基を有する部位と、(b)分子内にアミノ基及びヒドロキシル基から選ばれる少なくとも1種の官能基を有する部位と、(c)光配向性の光反応性基を有する部位とを有する重合体を含有する液晶配向剤。
また、本発明の方法によって製造された液晶表示素子は液晶のプレチルト角の安定性が高く、長時間連続駆動しても表示特性が損なわれることがない。
前記の特定重合体は、下記の式(I)のように概念的に示すことができる。
Sa、Sb、及びScは、それぞれ独立したスペーサー単位を表し、Sa、Sb、及びScの左の結合子はそれぞれ、特定重合体の主鎖に、任意にスペーサーを介して結合することを示し、2価の有機基であり、
Iaは、イソシアネート基又はブロックイソシアネート基あり、
Ibは、光配向性の光反応性基を有する1価の有機基であり、
Icは、アミノ基及びヒドロキシル基から選ばれる少なくとも1種の官能基を有する1価の有機基を表す。
なお、式(I)は、各側鎖ごとがx、y、zの割合で存在することを意味するものであって、重合体において、各側鎖がブロック化したブロック共重合体を意味するものではない。
本発明において、液晶配向剤中に含有される特定重合体は、イソシアネート基及び/又はブロック化されたイソシアネート基を有する部位を有することを特徴とする。換言すると、特定重合体は、イソシアネート基及び/又はブロック化されたイソシアネート基を側鎖に有することを特徴とする。
Saはスペーサー単位を表し、Saの左の結合子は特定重合体の主鎖に、任意にスペーサーを介して結合することを示し、
Iaはイソシアネート基又はブロック化されたイソシアネート基である。
W1の左の結合はMbへの結合を表し、
W3の右の結合はIaへの結合を表し、
W1、W2及びW3は、それぞれ独立して、単結合、二価の複素環、-(CH2)n-(式中、nは1~20を表す)、-OCH2-、-CH2O-、―COO-、-OCO-、-CH=CH-、-CF=CF-、-CF2O-、-OCF2-、-CF2CF2-又は-C≡C-を表すが、これらの置換基において非隣接のCH2基の一つ以上は独立して、-O-、-CO-、-CO-O-、-O-CO-、-Si(CH3)2-O-Si(CH3)2―、-NR-、-NR-CO-、-CO-NR-、-NR-CO-O-、-OCO-NR-、-NR-CO-NR-、-CH=CH-、-C≡C-又は-O-CO-O-(式中、Rは独立して水素又は炭素原子数1から5の直鎖又は分岐鎖のアルキル基を表す)で置換することができ、
A1及びA2は、それぞれ独立して、2価の芳香族基、2価の脂環式基、2価の複素環式基または2価の縮合環式基であり、それぞれの基は無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、シアノ基、メチル基又はメトキシ基によって置換されていても良い。
ブロック剤として、例えば、メタノール、エタノール、イソプロパノール、n-ブタノール、1-メトキシ-2-プロパノール、2-エトキシヘキサノール、2-N,N-ジメチルアミノエタノール、2-エトキシエタノール、シクロヘキサノール等のアルコール類;フェノール、o-ニトロフェノール、p-クロロフェノール、o-、m-又はp-クレゾール等のフェノール類;ε-カプロラクタム等のラクタム類;アセトンオキシム、メチルエチルケトンオキシム、メチルイソブチルケトンオキシム、シクロヘキサノンオキシム、アセトフェノンオキシム、ベンゾフェノンオキシム等のオキシム類;ピラゾール、3,5-ジメチルピラゾール、3-メチルピラゾールなどのピラゾール類;ドデカンチオール、ベンゼンチオール等のチオール類;マロン酸ジエチル等のカルボン酸エステル類;などが挙げられる。好ましくは、エタノール、イソプロパノール、1-メトキシ-2-プロパノール、3,5-ジメチルピラゾール、γ-カプロラクタム、メチルエチルケトンオキシムであるのがよい。
本発明の液晶配向剤中に含有される特定重合体は、光配向性の光反応性基を有する部位(以下、光反応性の側鎖ともいう)を有する。
また、該部位は、下記式(3m)のモノマー由来であるのがよい。
Sbは、スペーサー単位を表し、Sbの左の結合子は特定重合体の主鎖に、任意にスペーサーを介して結合することを示す。
Sbは炭素数1~10の直鎖又は分岐鎖のアルキレン基、2価の芳香族基又は2価の脂環式基であるのがよい。
また、式(3m)中、Mcは第2の重合性基を表す。該第2の重合性基として、上述の第1の重合性基と同様に、(メタ)アクリレート、フマレート、マレエート、α-メチレン-γ-ブチロラクトン、スチレン、ビニル、マレイミド、ノルボルネン、(メタ)アクリルアミド及びその誘導体のラジカル重合性基、及びシロキサンを挙げることができる。好ましくは(メタ)アクリレート、α-メチレン-γ-ブチロラクトン、スチレン、ビニル、マレイミド、アクリルアミドであるのがよい。
式(3m)中、Mdは、単結合、2価の複素環、3価の複素環、4価の複素環、置換、又は非置換の直鎖または分岐鎖である炭素数1~10のアルキル基、2価の芳香族基、3価の芳香族基、4価の芳香族環、2価の脂環式基、3価の脂環式基、4価の脂環式基、2価の縮合環式基、3価縮合環式基または4価の縮合環式基、であり、それぞれの基は無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、シアノ基、メチル基又はメトキシ基によって置換されていても良い。
また、Zは酸素原子、または硫黄原子である。
Xa及びXbは、それぞれ独立して水素原子、フッ素原子、塩素原子、シアノ基又は炭素数1~3のアルキル基である。
R1は単結合、酸素原子、-COO-または-OCO-、好ましくは単結合、-COO-又は-OCO-である。
R2は2価の芳香族基、2価の脂環式基、2価の複素環式基または2価の縮合環式基である。
R3は単結合、酸素原子、-COO-または-OCO-である。
R4は炭素数1~40の直鎖又は分岐鎖のアルキル基または脂環式基を含む炭素数3~40の1価の有機基である。
R5は炭素数1~3のアルキル基、炭素数1~3のアルコキシ基、フッ素原子またはシアノ基、好ましくはメチル基、メトキシ基又はフッ素原子である。
aは0~3の整数であり、bは0~4の整数である。
Sbの2価の芳香族基として、例えば1,4-フェニレン基、2-フルオロ-1,4-フェニレン基、3-フルオロ-1,4-フェニレン基、2,3,5,6-テトラフルオロ-1,4-フェニレン基等を挙げることができる。
Sbの2価の脂環式基として、例えばトランス1,4-シクロヘキシレン、トランス-トランス-1,4-ビシクロヘキシレン等を挙げることができる。
Sbの2価の複素環式基として、例えば1,4-ピリジレン基、2,5-ピリジレン基、1,4-フラニレン基、1,4-ピペラジン基、1,4-ピペリジン基等を挙げることができる。
Sbの2価の縮合環式基として、例えばナフチレン基等を挙げることができる。
Sbは、炭素数1~8のアルキレン基であることが好ましく、より好ましくは炭素数1~6のアルキレン基であり、さらに好ましくは炭素数1~4のアルキレン基であるのがよい。
R2の2価の脂環式基として、例えばトランス1,4-シクロヘキシレン、トランス-トランス-1,4-ビシクロヘキシレン等を挙げることができる。
R2の2価の複素環式基として、例えば1,4-ピリジレン基、2,5-ピリジレン基、1,4-フラニレン基、1,4-ピペラジン基、1,4-ピペリジン基等を挙げることができる。
R2の2価の縮合環式基として、例えばナフチレン基等を挙げることができる。
R2は、1,4-フェニレン基、トランス1,4-シクロヘキシレン、トランス-トランス-1,4-ビシクロヘキシレンであるのがよい。
また、光反応性の部位は、少なくとも1種の重合体に対して、10%~80%、好ましくは20%~60%の割合で含有される。
光反応性の側鎖の含有量が前記範囲の下限未満の過少量であると、形成される液晶配向膜の液晶配向性が低下する懸念がある。
本発明の液晶配向剤中に含有される特定重合体は、分子内にアミノ基及びヒドロキシル基から選ばれる少なくとも1種の官能基を有する部位を有する、すなわち、分子内にアミノ基及びヒドロキシル基から選ばれる少なくとも1種の官能基を側鎖に有する。
この部位は、本発明の特定重合体が有するイソシアネート基もしくはブロック部位が外れ発生したイソシアネート基と架橋反応が可能である。
Scは、スペーサー単位を表し、Scの左の結合子は特定重合体の主鎖に、任意にスペーサーを介して結合することを示す。
Scは炭素数1~10の直鎖又は分岐鎖のアルキレン基、2価の芳香族基又は2価の脂環式基であるのがよい。
また、式(4m)中、Meは第3の重合性基を表す。該第3の重合性基として、上述の第1の重合性基と同様に、(メタ)アクリレート、フマレート、マレエート、α-メチレン-γ-ブチロラクトン、スチレン、ビニル、マレイミド、ノルボルネン、(メタ)アクリルアミド及びその誘導体のラジカル重合性基、及びシロキサンを挙げることができる。好ましくは(メタ)アクリレート、α-メチレン-γ-ブチロラクトン、スチレン、ビニル、マレイミド、アクリルアミドであるのがよい。
式(4m)中、Mfは、単結合、2価の複素環、3価の複素環、4価の複素環、置換、又は非置換の直鎖または分岐鎖である炭素数1~10のアルキル基、2価の芳香族基、3価の芳香族基、4価の芳香族環、2価の脂環式基、3価の脂環式基、4価の脂環式基、2価の縮合環式基、3価縮合環式基または4価の縮合環式基、であり、それぞれの基は無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、シアノ基、メチル基又はメトキシ基によって置換されていても良い。
本発明の液晶配向剤に含有される特定重合体は、上記の(a)イソシアネート基及び/又はブロック化されたイソシアネート基を有するモノマーと、(b)光配向性の光反応性基を有するモノマーと、(c)分子内にアミノ基及びヒドロキシル基から選ばれる少なくとも1種の官能基を有するモノマーとを重合することによって得られる。また、配向性やその他の特性を損なわない範囲でその他のモノマーと共重合することができる。その他のモノマーとしては、例えば工業的に入手できるラジカル重合反応可能なモノマーが挙げられる。
グリシジル(メタ)アクリレート、(3-メチル-3-オキセタニル)メチル(メタ)アクリレート、および(3-エチル-3-オキセタニル)メチル(メタ)アクリレートなどの環状エーテル基を有する(メタ)アクリレート化合物も用いることができる。
スチレン化合物としては、例えば、スチレン、メチルスチレン、クロロスチレン、ブロモスチレン等が挙げられる。
マレイミド化合物としては、例えば、マレイミド、N-メチルマレイミド、N-フェニルマレイミド、及びN-シクロヘキシルマレイミド等が挙げられる。
チルエステル、パーオキシ 2-エチルシクロヘキサン酸-tert-アミルエステル等)、過硫酸塩類(過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等)、アゾ系化合物(アゾビスイソブチロニトリル、および2,2′-ジ(2-ヒドロキシエチル)アゾビスイソブチロニトリル等)が挙げられる。このようなラジカル熱重合開始剤は、1種を単独で使用することもできるし、あるいは2種以上を組み合わせて使用することもできる。
-2-モルホリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン-1、4-ジメチルアミノ安息香酸エチル、4-ジメチルアミノ安息香酸イソアミル、4,4’-ジ(t-ブチルペルオキシカルボニル)ベンゾフェノン、3,4,4’-トリ(t-ブチルペルオキシカルボニル)ベンゾフェノン、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド、2-(4’-メトキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(3’,4’-ジメトキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(2’,4’-ジメトキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(2’-メトキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4’-ペンチルオキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、4-[p-N,N-ジ(エトキシカルボニルメチル)]-2,6-ジ(トリクロロメチル)-s-トリアジン、1,3-ビス(トリクロロメチル)-5-(2’-クロロフェニル)-s-トリアジン、1,3-ビス(トリクロロメチル)-5-(4’-メトキシフェニル)-s-トリアジン、2-(p-ジメチルアミノスチリル)ベンズオキサゾール、2-(p-ジメチルアミノスチリル)ベンズチアゾール、2-メルカプトベンゾチアゾール、3,3’-カルボニルビス(7-ジエチルアミノクマリン)、2-(o-クロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾール、2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラキス(4-エトキシカルボニルフェニル)-1,2’-ビイミダゾール、2,2’-ビス(2,4-ジクロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾール、2,2’ビス(2,4-ジブロモフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾール、2,2’-ビス(2,4,6-トリクロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ビイミダゾール、3-(2-メチル-2-ジメチルアミノプロピオニル)カルバゾール、3,6-ビス(2-メチル-2-モルホリノプロピオニル)-9-n-ドデシルカルバゾール、1-ヒドロキシシクロヘキシルフェニルケトン、ビス(5-2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)-フェニル)チタニウム、3,3’,4,4’-テトラ(t-ブチルペルオキシカルボニル)ベンゾフェノン、3,3’,4,4’-テトラ(t-ヘキシルペルオキシカルボニル) ベンゾフェノン、3,3’-ジ(メトキシカルボニル)-4,4’-ジ(t-ブチルペルオキシカルボニル)ベンゾフェノン、3,4’-ジ(メトキシカルボニル)-4,3’-ジ(t-ブチルペルオキシカルボニル)ベンゾフェノン、4,4’-ジ(メトキシカルボニル)-3,3’-ジ(t-ブチルペルオキシカルボニル)ベンゾフェノン、2-(3-メチル-3H-ベンゾチアゾール-2-イリデン)-1-ナフタレン-2-イル-エタノン、又は2-(3-メチル-1,3-ベンゾチアゾール-2(3H)-イリデン)-1-(2-ベンゾイル)エタノン等を挙げることができる。これらの化合物は単独で使用してもよく、2つ以上を混合して使用することもできる。
上述の反応により得られた、イソシアネート基及び/又はブロック化されたイソシアネート基を有する部位と、光配向性を有する部位を有する高分子の反応溶液から、生成した高分子を回収する場合には、反応溶液を貧溶媒に投入して、それら重合体を沈殿させれば良い。沈殿に用いる貧溶媒としては、メタノール、アセトン、ヘキサン、ヘプタン、ブチルセルソルブ、ヘプタン、エタノール、トルエン、ベンゼン、ジエチルエーテル、メチルエチルエーテル、水等を挙げることができる。貧溶媒に投入して沈殿させた重合体は、濾過して回収した後、常圧あるいは減圧下で、常温あるいは加熱して乾燥することができる。また、沈殿回収した重合体を、有機溶媒に再溶解させ、再沈殿回収する操作を2回~10回繰り返すと、重合体中の不純物を少なくすることができる。この際の貧溶媒として、例えば、アルコール類、ケトン類、炭化水素等が挙げられ、これらの中から選ばれる3種類以上の貧溶媒を用いると、より一層精製の効率が上がるので好ましい。
本発明に用いられる液晶配向剤(すなわち、重合体組成物)は、液晶配向膜の形成に好適となるように塗布液として調製されることが好ましい。すなわち、本発明の液晶配向剤は、樹脂被膜を形成するための樹脂成分が有機溶媒に溶解した溶液として調製されることが好ましい。ここで、その樹脂成分とは、既に説明した特定重合体((A)成分)である。その際、樹脂成分の含有量は、1質量%~20質量%が好ましく、より好ましくは2質量%~15質量%、特に好ましくは2質量%~10質量%である。
またここで、樹脂成分として、既に説明した特定重合体((A)成分)に加えて、架橋性化合物((B)成分))を含む場合、樹脂成分の含有量は、1質量%~20 質量%が好ましく、より好ましくは3質量%~15質量%、特に好ましくは3質量%~10質量%である。
本発明の液晶配向剤に用いる有機溶媒は、樹脂成分を溶解させる有機溶媒であれば特に限定されない。その具体例を以下に挙げる。
本発明の液晶配向剤は、上記特性重合体成分以外の他の成分を含有してもよい。
このような他の成分としては、架橋性化合物(架橋剤)や、液晶配向剤を塗布した際の、膜厚均一性や表面平滑性を向上させる溶媒や化合物、液晶配向膜と基板との密着性を向上させる化合物等を挙げることができるが、これに限定されない。
本発明の液晶配向剤は、本発明の効果が損なわれない範囲であれば、液晶配向膜の誘電率や導電性などの電気特性を変化させる目的で、誘電体や導電物質、さらには、液晶配向膜にした際の膜の硬度や緻密度を高める目的で、架橋性化合物を添加してもよい。
本発明の(B)成分は、分子内にアミノ基及びヒドロキシル基からなる群から選ばれる1種以上の官能基を2つ以上有すれば、繰り返し単位を有する重合体であってもよい。
例えば、繰り返し単位を有する重合体は、その末端に、アミノ基及びヒドロキシル基からなる群から選ばれる1種以上の官能基を2つ以上有していてもよい。
また、例えば、該重合体は、1つの官能基を有するモノマー由来の重合体であっても、該重合体が官能基を2つ以上有するものであれば、本発明の(B)成分に該当する。より具体的には、メタクリル酸2-ヒドロキシエチル(HEMA)は、ヒドロキシル基を1つのみ有する化合物であり、本発明の(B)成分には該当しないが、該HEMAを重合させて得られる重合体は、ヒドロキシル基を2つ以上有するため、本発明の(B)成分に該当する。
さらに、例えば、本発明の(B)成分は、2つ以上の官能基(該官能基はアミノ基及び/又はヒドロキシル基である)を有するモノマー由来の、繰り返し単位を有する重合体であってもよい。
本発明の液晶配向剤において、(B)成分が、上述したような、繰り返し単位を有する重合体であってその数平均分子量が2000以下である場合、又は繰り返し単位を有しない化合物である場合、該(B)成分は、上述の(A)成分100質量%に対して、1~80質量%、好ましくは1~50質量%、より好ましくは2~30質量%含有するのがよい。換言すると、(A)成分:(B)成分は、質量比で100:1~100:80、好ましくは100:1~100:50、より好ましくは100:2~100:30であるのがよい。
また、(B)成分が、繰り返し単位を有する重合体であってその数平均分子量が2000以上の重合体である場合、該(B)成分は、上述の(A)成分100質量%に対して、5~1000質量%、好ましくは5~900質量%、より好ましくは10~800質量%含有するのがよい。換言すると、(A)成分:(B)成分は、質量比で100:5~100:1000、好ましくは100:5~100:900、より好ましくは100:10~100:800であるのがよい。
式中、Tはアミノ基またはヒドロキシル基を表し、Yはm価の有機基を表し、mは2以上の整数である。
上記式において、mは2以上であるが、mの数が多い方が特定重合体との架橋反応が進行しやすいため好ましい。
mが2の場合のYの具体的例として、下記式(Y-1)~(Y-120)などを挙げることができるがこれらに限定されない。
なかでも、液晶のプレチルト角を高くするための液晶配向膜とする場合、Yは、長鎖アルキル基(例えば炭素数10以上のアルキル基)、芳香族環、脂肪族環、ステロイド骨格、又はこれらを組み合わせた構造を有するジアミン化合物を原料とする構造であることが好ましい
このようなYとして、(Y-83)、(Y-84)、(Y-85)、(Y-86)、(Y-87)、(Y-88)、(Y-89)、(Y-90)、(Y-91)、(Y-92)、(Y-93)、(Y-94)、(Y-95)、(Y-96)、(Y-97)、(Y-98)、(Y-99)、(Y-100)、(Y-101)、(Y-102)、(Y-103)、(Y-104)、(Y-105)、(Y-106)、(Y-107)、又は(Y-108)などが挙げられるが、これに限定されるものではない。
また、特定重合体にも光反応性部位が導入されているが、それと共に光反応性を付与した(Y-17)、(Y-18)、(Y-111)、(Y-112)、(Y-113)、(Y-114) 、(Y-115)、(Y-116)、(Y-117)、(Y-118)、(Y-119)なども用いることができる。
mが2の場合の具体的例としては、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、1,7-ヘプタンジオール、1,8-オクタンジオール,1,9-ノナンジオール、1,10-デカンジオール、1,11-ドデカンジール、下記式(6)~(8)で表される2価以上の有機基や、Yが(Y-1)~(Y-120)である構造などが挙げられるが、これらに限定されない。
Z1は、単結合、全部又は一部が結合して環状構造を形成してもよい炭素原子数1~10の2価の飽和炭化水素基であり任意の水素原子はフッ素原子で置換されていてもよい、-NH-、-N(CH3)-、式(9)で表される基である。
X1は炭素数1~20の脂肪族炭化水素基、又は芳香族炭化水素基を含むl価の有機基である。
lは2~6の整数であり、d1は2~4の整数であり、d2及びd3はそれぞれ独立に1~3の整数であり、e及びfはそれぞれ独立に1~3の整数である。
K1及びK2は、それぞれ独立して、水素原子、置換基を有してもよい炭素数1~4のアルキル基、置換基を有してもよい炭素数2~4のアルケニル基、又は置換基を有してもよい炭素数2~4のアルキニル基である。また、K1及びK2のうち少なくとも1つは、ヒドロキシ基で置換された炭化水素基を表す。式(8)中のlは、溶解性の観点から、2~4が好ましい。
式(6)及び式(7)の-CH2-OH基は芳香環に直接結合しているので、Y1、Y2、及びY3は、それぞれ独立に芳香環である。
なお、これら芳香環の水素原子は、水酸基、炭素原子数1~3のアルキル基、ハロゲン原子、炭素原子数1~3のアルコキシ基又はビニル基で置換されていてもよい。
式(7)におけるZ1は、その全部又は一部が結合して環状構造を形成してもよい炭素原子数1~10、好ましくは、1~5の2価の飽和炭化水素基の場合、その有する任意の水素原子がフッ素原子で置換されていてもよい。
Z1の例として、炭素原子数1~10のアルキレン基、炭素原子数3~10の脂環式炭化水素基、アルキレン基と脂環式炭化水素基とが組み合わされ、且つ炭素原子数1~10の基が挙げられる。加えて、前記した基の任意の水素原子がフッ素原子で置換された基が挙げられる。
式(8)中、K3~K6は、それぞれ独立して、水素原子、炭化水素基、又はヒドロキシ基で置換された炭化水素基である。
上記(B)成分である特定化合物は、[P9]、[P11]、[P12]、[P15]、[P18]、[P21]、[P22]、[P27]、[P29]~[P37]で表される化合物が好ましく、なかでも、[P9]、[P11]、[P12]、[P15]、[P29]で表される化合物がより好ましい。
膜厚の均一性や表面平滑性を向上させる 溶媒(貧溶媒)の具体例としては、次のものが挙げられる。
膜厚の均一性や表面平滑性を向上させる 化合物としては、フッ素系界面活性剤、シリコーン系界面活性剤およびノ二オン系界面活性剤等が挙げられる。
液晶配向膜と基板との密着性を向上させる化合物の具体例としては、次に示す官能性シラン含有化合物などが挙げられる。
例えば、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、2-アミノプロピルトリメトキシシラン、2-アミノプロピルトリエトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン、3-ウレイドプロピルトリメトキシシラン、3-ウレイドプロピルトリエトキシシラン、N-エトキシカルボニル-3-アミノプロピルトリメトキシシラン、N-エトキシカルボニル-3-アミノプロピルトリエトキシシラン、N-トリエトキシシリルプロピルトリエチレントリアミン、N-トリメトキシシリルプロピルトリエチレントリアミン、10-トリメトキシシリル-1,4,7-トリアザデカン、10-トリエトキシシリル-1,4,7-トリアザデカン、9-トリメトキシシリル-3,6-ジアザノニルアセテート、9-トリエトキシシリル-3,6-ジアザノニルアセテート、N-ベンジル-3-アミノプロピルトリメトキシシラン、N-ベンジル-3-アミノプロピルトリエトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシラン、N-フェニル-3-アミノプロピルトリエトキシシラン、N-ビス(オキシエチレン)-3-アミノプロピルトリメトキシシラン、N-ビス(オキシエチレン)-3-アミノプロピルトリエトキシシラン等が挙げられる。
さらに、基板と液晶配向膜の密着性の向上に加え、液晶表示素子を構成した時のバックライトによる電気特性の低下等を防ぐ目的で、以下のようなエポキシ基含有化合物の添加剤を、液晶配向剤中に含有させても良い。
具体的なエポキシ基含有化合物としては、 エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、グリセリンジグリシジルエーテル、2,2-ジブロモネオペンチルグリコールジグリシジルエーテル、1,3,5,6-テトラグリシジル-2,4-ヘキサンジオール、N,N,N’,N’,-テトラグリシジル-m-キシレンジアミン、1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、N,N,N’,N’,-テトラグリシジル-4、4’-ジアミノジフェニルメタンなどが 例示されるが、これに限定されない。
光増感剤としては、芳香族ニトロ 化合物、クマリン(7-ジエチルアミノ-4-メチルクマリン、7-ヒドロキシ4-メチルクマリン)、ケトクマリン、カルボニルビスクマリン、芳香族2-ヒドロキシ ケトン、およびアミノ置換された、芳香族2-ヒドロキシケトン(2-ヒドロキシベンゾフェノン、モノ-もしくはジ-p-(ジメチルアミノ)-2-ヒドロキシベンゾフェノン)、アセトフェノン、アントラキノン、キサントン、チオキサントン、ベンズアントロン、チアゾリン(2-ベンゾイルメチレン-3-メチル-β-ナフトチアゾリン、2-(β-ナフトイルメチレン)-3-メチルベンゾチアゾリン、2-(α-ナフトイルメチレン)-3-メチルベンゾチアゾリン、2-(4-ビフェノイルメチレン)-3-メチルベンゾチアゾリン、2-(β-ナフトイルメチレン)-3-メチル
-β-ナフトチアゾリン、2-(4-ビフェノイルメチレン)-3-メチル-β-ナフトチアゾリン、2-(p-フルオロベンゾイルメチレン)-3-メチル-β-ナフトチアゾリン)、オキサゾリン(2-ベンゾイルメチレン-3-メチル-β-ナフトオキサゾリン、2-(β-ナフトイルメチレン)-3-メチルベンゾオキサゾリン、2-(α-ナフトイルメチレン)-3-メチルベンゾオキサゾリン、2-(4-ビフェノイルメチレン)-3-メチルベンゾオキサゾリン、2-(β-ナフトイルメチレン)-3-メチル-β-ナフトオキサゾリン、2-(4-ビフェノイルメチレン)-3-メチル-β-ナフトオキサゾリン、2-(p-フルオロベンゾイルメチレン)-3-メチル-β-ナフトオキサゾリン)、ベンゾチアゾール、ニトロアニリン(m-もしくはp-ニトロアニリン、2,4,6-トリニトロアニリン)またはニトロアセナフテン(5-ニトロアセナフテン)、(2-[(m-ヒドロキシ-p-メトキシ)スチリル]ベンゾチアゾール、ベンゾインアルキルエーテル、N-アルキル化フタロン、アセトフェノンケタール(2,2-ジメトキシフェニルエタノン)、ナフタレン、アントラセン(2- ナフタレンメタノール、2-ナフタレンカルボン酸、9-アントラセンメタノール、および9-アントラセンカルボン酸)、ベンゾピラン、アゾインドリジン、メチルクマリン等がある。
本発明の液晶配向剤は、基板上に塗布、焼成した後、ラビング処理や光照射などで配向処理をして、又は一部の垂直配向用途などでは配向処理無しで液晶配向膜とすることができる。 本発明の液晶配向剤の塗布方法は特に限定されないが、スクリーン印刷、フレキソ印刷、オフセット印刷、インクジェットなどによって行う方法が一般的である。その他、塗布液を用いる方法としては、ディップ、ロールコーター、スリットコーター、スピンコーターなどがあり、目的に応じてこれらを用いてもよい。これらの方法により基板上に塗布した後、ホットプレートなどの加熱手段により溶媒を蒸発させて、塗膜を形成させることができる。
MOI-BM: 2-(0-[1’-メチルプロピリデンアミノ]カルボキシアミノ)エチルメタクリレート(昭和電工社製 カレンズMOI-BM)
MOI-BP: 2-[(3,5-ジメチルピラゾイル)カルボニルアミノ]エチルメタクリレート(昭和電工社製 カレンズMOI-BP)
NMP:N-メチル-2-ピロリドン
BCS:ブチルセロソルブ
CHN:シクロヘキサノン
PGME:プロピレングリコールモノメチルエーテル
AIBN:2,2’-アゾビスイソブチロニトリル
装置:フーリエ変換型超伝導核磁気共鳴装置(FT-NMR)「INOVA-400」(Varian製)400MHz。
溶媒:重水素化クロロホルム(CDCl3)又は重水素化N,N-ジメチルスルホキシド([D6]-DMSO)。
標準物質:テトラメチルシラン(TMS)。
[MA-1]の合成:
2L四つ口フラスコに、[MA-1-1](144.0g、441mmol)、ギ酸(1000g)を加えて、50℃に加熱しながら攪拌した。反応終了後、反応液を純水(3.0L)に注ぎ、沈殿物を濾過した。得られた粗物を酢酸エチル(200g)にてリパルプ洗浄することで、[MA-1-2](白色固体)を111.1g得た(収率92%)。目的物の1H-NMRの結果を以下に示す。この結果から、得られた固体が、目的の[MA-1-2]であることを確認した。
1H NMR (400 MHz, [D6]-DMSO):δ12.34 (s,1H), 7.53-7.60 (m,3H), 7.25-7.27 (d,2H), 6.44-6.48 (d,1H), 2.45-2.51 (t,1H), 1.76-1.83 (t,4H), 1.28-1.48 (m,5H), 1.15-1.21 (m,2H), 0.97-1.07 (m,2H), 0.87-0.89 (t,3H)
1H NMR (400 MHz, [D6]-DMSO):δ7.62-7.66 (m,3H), 7.25-7.27 (d,2H), 6.58-6.62 (d,1H), 6.05 (s,1H), 5.70 (s,1H), 4.37-4.42 (m,4H), 2.44-2.48 (t,1H), 1.88 (s,3H), 1.76-1.82 (t,4H), 1.24-1.47 (m,5H), 1.15-1.21 (m,2H), 0.96-1.06 (m,2H), 0.85-0.89 (t,3H)
[MA-2]の合成:
2L四つ口フラスコに、[MA-2-1](137.0g、384mmol)、ギ酸(1000g)を加えて、50℃に加熱しながら攪拌した。反応終了後、反応液を純水(3.0L)に注ぎ、沈殿物を濾過した。得られた粗物を酢酸エチル(200g)にてリパルプ洗浄することで、[MA-2-2](白色固体)を111.8g得た(収率96%)。目的物の1H-NMRの結果を以下に示す。この結果から、得られた固体が、目的の[MA-2-2]であることを確認した。
1H NMR (400 MHz, [D6]-DMSO):δ12.34 (s,1H), 7.53-7.60 (m,3H), 7.25-7.27 (d,2H), 6.44-6.48 (d,1H), 2.45-2.51 (t,1H), 1.77-1.83 (t,4H), 1.38-1.48 (m,2H), 1.17-1.34 (m,9H), 0.97-1.07 (m,2H), 0.87-0.89 (t,3H)
1H NMR (400 MHz, [D6]-DMSO):δ7.62-7.66 (m,3H), 7.25-7.27 (d,2H), 6.58-6.62 (d,1H), 6.04 (s,1H), 5.70 (s,1H), 4.36-4.42 (m,4H), 2.48-2.52 (t,1H), 1.88 (s,3H), 1.76-1.83 (t,4H), 1.36-1.44 (m,2H), 1.18-1.31 (m,9H), 1.00-1.03 (m,2H), 0.85-0.88 (t,3H)
[MA-3]の合成:
2L四つ口フラスコに、[MA-3-1](151.6g、394mmol)、ギ酸(1061g)を加えて、50℃に加熱しながら攪拌した。反応終了後、反応液を純水(3.0L)に注ぎ、沈殿物を濾過した。得られた粗物を酢酸エチル(500g)にてリパルプ洗浄することで、[MA-3-2](白色固体)を121.7g得た(収率94%)。目的物の1H-NMRの結果を以下に示す。この結果から、得られた固体が、目的の[MA-3-2]であることを確認した。
1H NMR (400 MHz, [D6]-DMSO):δ12.34 (s,1H), 7.53-7.59 (m,3H), 7.25-7.27 (d,2H), 6.44-6.48 (d,1H), 2.44-2.51 (t,1H), 1.77-1.82 (t,4H), 1.37-1.48 (m,2H), 1.17-1.28 (m,13H), 0.97-1.07 (m,2H), 0.86-0.88 (t,3H)
1H NMR (400 MHz, [D6]-DMSO):δ7.61-7.66 (m,3H), 7.24-7.26 (d,2H), 6.57-6.61 (d,1H), 6.04 (s,1H), 5.69 (s,1H), 4.36-4.42 (m,4H), 2.43-2.52 (t,1H), 1.88 (s,3H), 1.76-1.82 (t,4H), 1.36-1.46 (m,2H), 1.15-1.29 (m,13H), 0.95-1.05 (m,2H), 0.84-0.87 (t,3H)
[MA-4]の合成:
1H NMR (400 MHz, [D6]-DMSO):δ12.36 (s,1H), 7.52-7.59 (m,3H), 7.25-7.27 (d,2H), 6.44-6.48 (d,1H), 2.44-2.50 (t,1H), 1.79-1.82 (m,4H), 1.61-1.70 (m,5H), 1.40-1.42 (d,2H), 1.14-1.20 (m,7H), 0.97-1.02 (m,2H)
1H NMR (400 MHz, [D6]-DMSO):δ7.62-7.66 (m,3H), 7.25-7.27 (d,2H), 6.58-6.62 (d,1H), 6.04 (s,1H), 5.70 (s,1H), 4.38-4.41 (m,4H), 2.43-2.51 (t,1H), 1.88 (s,3H), 1.79-1.82 (m,4H), 1.60-1.69 (m,5H), 1.39-1.42 (d,2H), 1.13-1.20 (m,7H), 0.96-1.02 (m,2H)
[MA-5]の合成:
500mL四つ口フラスコに、[MA-5-1](42.2g、139mmol)、ギ酸(300g)を加えて、50℃に加熱しながら攪拌した。反応終了後、反応液を純水(1.5L)に注ぎ、沈殿物を濾過した。得られた粗物をアセトニトリル(80g)にてリパルプ洗浄することで、[MA-5-2](白色固体)を31.9g得た(収率92%)。
500mL四つ口フラスコに、[MA-5-3](43.6g、97mmol)、ギ酸(300g)を加えて、50℃に加熱しながら攪拌した。反応終了後、反応液を純水(1.5L)に注ぎ、沈殿物を濾過した。得られた粗物をアセトニトリル(500g)にてリパルプ洗浄することで、[MA-5-4](白色固体)を36.6g得た(収率96%)。目的物の1H-NMRの結果を以下に示す。この結果から、得られた固体が、目的の[MA-5-4]であることを確認した。
1H NMR (400 MHz, [D6]-DMSO):δ12.46 (s,1H), 8.08-8.10 (d,2H), 7.78-7.81 (d,2H), 7.61-7.65 (d,1H), 7.31-7.34 (d,2H), 7.13-7.16 (d,2H), 6.53-6.57 (d,1H), 4.16-4.19 (t,2H), 2.40-2.47 (m,2H), 1.95-2.02 (m,2H)
1H NMR (400 MHz, [D6]-DMSO):δ8.07-8.11 (d,2H), 7.84-7.86 (d,2H), 7.70-7.74 (d,1H), 7.32-7.34 (d,2H), 7.13-7.16 (d,2H), 6.68-6.72 (d,1H), 6.05 (s,1H), 5.71 (s,1H), 4.37-4.44 (m,4H), 4.16-4.19 (t,2H), 2.42-2.49 (m,2H), 1.95-2.02 (m,2H), 1.88 (s,3H)
[MA-8]の合成:
1H NMR (400 MHz, [D6]-DMSO):δ7.61-7.66 (m,3H), 7.26-7.28 (d,2H), 6.55-6.60 (d,1H), 4.85-4.88 (t,1H), 4.14-4.16 (t,2H), 3.62-3.65 (q,2H), 2.46-2.51 (t,1H), 1.77-1.83 (t,4H), 1.38-1.49 (m,2H), 1.17-1.30 (m,9H), 0.97-1.07 (m,2H), 0.85-0.89 (t,3H)
1H NMR (400 MHz, [D6]-DMSO):δ7.93-7.95 (d,2H), 7.60-7.63 (m,5H), 7.23-7.25 (d,2H), 6.78-6.85 (q,1H), 6.59-6.63 (d,1H) , 5.98-6.02 (d,1H), 5.42-5.45 (d,1H), 4.51-4.55 (m,4H), 2.43-2.52 (t,1H), 1.75-1.80 (t,4H), 1.36-1.45 (m,2H), 1.16-1.30 (m,9H), 0.95-1.04 (t,2H), 0.84-0.88 (t,3H)
合成例におけるポリマーの分子量はセンシュー科学社製 常温ゲル浸透クロマトグラフィー(GPC)装置(SSC-7200)、Shodex社製カラム(KD-803、KD-805)を用い以下のようにして測定した。
カラム温度:50℃
溶離液:N,N’-ジメチルホルムアミド(添加剤として、臭化リチウム-水和物(LiBr・H2O)が30mmol/L、リン酸・無水結晶(o-リン酸)が30mmol/L、テトラヒドロフラン(THF)が10ml/L)
流速:1.0ml/分
検量線作成用標準サンプル:東ソー社製 TSK 標準ポリエチレンオキサイド(分子量約9000,000、150,000、100,000、30,000)、及び、ポリマーラボラトリー社製 ポリエチレングリコール(分子量 約12,000、4,000、1,000)。
MOI-BP(3.02g、12.0mmol)、MA-1(4.61g、12.0mmol)、HEMA(2.08g、16.0mmol)をCHN(40.2g)中に溶解し、ダイアフラムポンプで脱気を行なった後、AIBNを(0.33g、2.0mmol)を加え再び脱気を行なった。この後55℃で15時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液にCHN(75.3g)、PGME(125.5g)を加え4質量%に希釈し、室温で5時間攪拌することにより液晶配向剤(A)を得た。このポリマーの数平均分子量は45000、重量平均分子量は129000であった。
MOI-BP(3.02g、12.0mmol)、MA-2(4.95g、12.0mmol)、HEMA(2.08g、16.0mmol)をCHN(41.5g)中に溶解し、ダイアフラムポンプで脱気を行なった後、AIBNを(0.33g、2.0mmol)を加え再び脱気を行なった。この後55℃で15時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液にCHN(78.3g)、PGME(129.7g)を加え4質量%に希釈し、室温で5時間攪拌することにより液晶配向剤(B)を得た。このポリマーの数平均分子量は39000、重量平均分子量は112000であった。
MOI-BP(3.02g、12.0mmol)、MA-3(5.29g、12.0mmol)、HEMA(2.08g、16.0mmol)をCHN(42.9g)中に溶解し、ダイアフラムポンプで脱気を行なった後、AIBNを(0.33g、2.0mmol)を加え再び脱気を行なった。この後55℃で15時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液にCHN(80.3g)、PGME(133.9g)を加え4質量%に希釈し、室温で5時間攪拌することにより液晶配向剤(C)を得た。このポリマーの数平均分子量は44000、重量平均分子量は115000であった。
MOI-BP(2.01g、8.0mmol)、MA-4(8.49g、20.0mmol)、HEMA(1.56g、12.0mmol)をCHN(49.6g)中に溶解し、ダイアフラムポンプで脱気を行なった後、AIBNを(0.33g、2.0mmol)を加え再び脱気を行なった。この後55℃で15時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液にCHN(92.9g)、PGME(154.9g)を加え4質量%に希釈し、室温で5時間攪拌することにより液晶配向剤(D)を得た。このポリマーの数平均分子量は31000、重量平均分子量は87000であった。
MOI-BP(2.01g、8.0mmol)、MA-5(10.13g、20.0mmol)、HEMA(1.56g、12.0mmol)をCHN(56.1g)中に溶解し、ダイアフラムポンプで脱気を行なった後、AIBNを(0.33g、2.0mmol)を加え再び脱気を行なった。この後55℃で15時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液にCHN(105.2g)、PGME(175.4g)を加え4質量%に希釈し、室温で5時間攪拌することにより液晶配向剤(E)を得た。このポリマーの数平均分子量は36000、重量平均分子量は101000であった。
MOI-BM(2.91g、12.0mmol)、MA-2(4.95g、12.0mmol)、HEMA(2.08g、16.0mmol)をCHN(41.0g)中に溶解し、ダイアフラムポンプで脱気を行なった後、AIBNを(0.33g、2.0mmol)を加え再び脱気を行なった。この後55℃で15時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液にCHN(77.0g)、PGME(128.4g)を加え4質量%に希釈し、室温で5時間攪拌することにより液晶配向剤(F)を得た。このポリマーの数平均分子量は48000、重量平均分子量は132000であった。
MOI-BP(3.02g、12.0mmol)、MA-2(4.95g、12.0mmol)、HEMA(2.08g、16.0mmol)をNMP(41.5g)中に溶解し、ダイアフラムポンプで脱気を行なった後、AIBNを(0.33g、2.0mmol)を加え再び脱気を行なった。この後55℃で15時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液にNMP(51.9g)、BCS(69.2g)を加え6質量%に希釈し、室温で5時間攪拌することにより液晶配向剤(G)を得た。このポリマーの数平均分子量は18000、重量平均分子量は80000であった。
MOI-BP(3.52g、14.0mmol)、MA-2(4.13g、10.0mmol)、HEMA(1.82g、14.0mmol)、MA-6(0.51g、2.0mmol)をCHN(41.2g)中に溶解し、ダイアフラムポンプで脱気を行なった後、AIBNを(0.33g、2.0mmol)を加え再び脱気を行なった。この後55℃で15時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液にCHN(37.8g)、PGME(82.4g)を加え6質量%に希釈し、室温で5時間攪拌することにより液晶配向剤(L)を得た。このポリマーの数平均分子量は38000、重量平均分子量は126000であった。
MOI-BP(3.52g、14.0mmol)、MA-2(4.13g、10.0mmol)、HEMA(1.82g、14.0mmol)、MA-7(0.68g、2.0mmol)をCHN(41.9g)中に溶解し、ダイアフラムポンプで脱気を行なった後、AIBNを(0.33g、2.0mmol)を加え再び脱気を行なった。この後55℃で15時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液にCHN(38.4g)、PGME(83.8g)を加え6質量%に希釈し、室温で5時間攪拌することにより液晶配向剤(M)を得た。このポリマーの数平均分子量は41000、重量平均分子量は141000であった。
MOI-BP(4.02g、16.0mmol)、MA-8(3.80g、8.0mmol)、HEMA(2.08g、16.0mmol)をCHN(40.9g)中に溶解し、ダイアフラムポンプで脱気を行なった後、AIBNを(0.33g、2.0mmol)を加え再び脱気を行なった。この後55℃で15時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液にCHN(37.5g)、PGME(81.8g)を加え6質量%に希釈し、室温で5時間攪拌することにより液晶配向剤(N)を得た。このポリマーの数平均分子量は27000、重量平均分子量は81000であった。
HEMA(19.5g、150.0mmol)をPGME(83.2g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(1.25g、7.5mmol)を加え再び脱気を行った。この後80℃で12時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液にCHN(166.0g)、PGME(76.1g)を加え6質量%に希釈し、室温で5時間攪拌することによりポリマー溶液(O)を得た。このポリマーの数平均分子量は4800、重量平均分子量は5700であった。
次に、上記で得られたポリマー溶液(O)(3.0g)に、実施例2で得られた液晶配向剤(B)(7.0g)を加え攪拌することにより液晶配向剤(P)を得た。
MOI-BP(7.04g、28.0mmol)、MA-2(4.95g、12.0mmol)をCHN(41.5g)中に溶解し、ダイアフラムポンプで脱気を行なった後、AIBNを(0.33g、2.0mmol)を加え再び脱気を行なった。この後55℃で15時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液にCHN(92.4g)、PGME(153.9g)を加え4質量%に希釈し、室温で5時間攪拌することにより液晶配向剤(H)を得た。このポリマーの数平均分子量は41000、重量平均分子量は125000であった。
HEMA(3.64g、28.0mmol)、MA-2(4.95g、12.0mmol)をCHN(35.7g)中に溶解し、ダイアフラムポンプで脱気を行なった後、AIBNを(0.33g、2.0mmol)を加え再び脱気を行なった。この後55℃で15時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液にCHN(66.9g)、PGME(111.5g)を加え4質量%に希釈し、室温で5時間攪拌することにより液晶配向剤(I)を得た。このポリマーの数平均分子量は31000、重量平均分子量は87000であった。
MOI-BP(3.02g、12.0mmol)、MA-2(4.95g、12.0mmol)、HEMA(2.08g、16.0mmol)をCHN(41.5g)中に溶解し、ダイアフラムポンプで脱気を行なった後、AIBNを(0.33g、2.0mmol)を加え再び脱気を行なった。この後55℃で15時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液にCHN(78.3g)、PGME(129.7g)を加え4質量%に希釈し、室温で5時間攪拌することにより液晶配向剤(J)を得た。このポリマーの数平均分子量は39000、重量平均分子量は112000であった。
上記液晶配向剤(J)10.0gに対してTM-BIP(40mg)(溶液の固形分の10重量%相当)を架橋剤として添加し3時間撹拌し液晶配向剤(J1)を得た。
実施例12で得られた液晶配向剤(J)10.0gに対して3AMPDA(40mg)(溶液の固形分の10重量%相当)を架橋剤として添加し3時間撹拌し液晶配向剤(J2)を得た。
MOI-BP(3.02g、12.0mmol)、MA-3(5.29g、12.0mmol)、HEMA(2.08g、16.0mmol)をCHN(42.9g)中に溶解し、ダイアフラムポンプで脱気を行なった後、AIBNを(0.33g、2.0mmol)を加え再び脱気を行なった。この後55℃で15時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液にCHN(80.3g)、PGME(133.9g)を加え4質量%に希釈し、室温で5時間攪拌することにより液晶配向剤(K)を得た。このポリマーの数平均分子量は44000、重量平均分子量は115000であった。
上記液晶配向剤(K)10.0gに対してTM-BIP(40mg)(溶液の固形分の10重量%相当)を架橋剤として添加し3時間撹拌し液晶配向剤(K1)を得た。
実施例14で得られた液晶配向剤(K)10.0gに対して3AMPDA(40mg)(溶液の固形分の10重量%相当)を架橋剤として添加し3時間撹拌し液晶配向剤(K2)を得た。
実施例1で得られた液晶配向剤(A)を、ITO膜からなる透明電極付きガラス基板のITO面にスピンコートし、50℃のホットプレートで120秒間乾燥した後、140℃のホットプレートで20分間焼成を行い、膜厚100nmの液晶配向膜を形成した。次いで、塗膜面に偏光板を介して、照射強度4.3mW/cm2の313nmの直線偏光紫外線を基板法線方向から40°傾斜した角度から50mJ/cm2照射し、液晶配向膜付き基板を得た。入直線偏光UVは高圧水銀ランプの紫外光に313nmのバンドパスフィルターを通した後、313nmの偏光板を通すことで調製した。
液晶セルのプレチルト角の測定はAxo Metrix社製の「AxoScan」を用いてミューラーマトリックス法により測定した。結果を表1にまとめる。
液晶セル作製後、120℃で1時間等方相処理を行った後に偏光顕微鏡にてセル観察を行い、光抜けやドメイン発生などの配向不良が無い場合や液晶セルに電圧印可した際に均一な液晶の駆動が得られる場合を配向性良好とした。
一方、比較例にあるように、光反応性基を有する側鎖と分子内にアミノ基及びヒドロキシル基から選ばれる少なくとも1種の官能基を有する側鎖との組み合わせや、光反応性基を有する側鎖とイソシアネート基及び/又はブロック化されたイソシアネート基を有する側鎖との組み合わせのみでは良好なプレチルト角および液晶配向性を得ることができなかった。
これらは、光反応によって側鎖に付与された異方性が、シール剤の硬化や等方相処理時の加熱によって消失してしまったと考えられた。
Claims (18)
- (a) イソシアネート基及び/又はブロック化されたイソシアネート基を有する部位と、
(b) 分子内にアミノ基及びヒドロキシル基から選ばれる少なくとも1種の官能基を有する部位と、
(c) 光配向性の光反応性基を有する部位
とを有する重合体を含有する、液晶配向剤。 - 前記(a)イソシアネート基及び/又はブロック化されたイソシアネート基を有する部位が、下記式(1m)で表されるモノマー由来である、請求項1又は2に記載の液晶配向剤。
[式中、
Maは、第1の重合性基を表し、
Mbは、単結合、2価の複素環、3価の複素環、4価の複素環、置換又は非置換の直鎖または分岐鎖である炭素数1~10のアルキル基、2価の芳香族基、3価の芳香族基、4価の芳香族環、2価の脂環式基、3価の脂環式基、4価の脂環式基、2価の縮合環式基、3価縮合環式基または4価の縮合環式基であり、それぞれの基は無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、シアノ基、メチル基又はメトキシ基によって置換されていてもよく、
Saは、スペーサー単位を表し、
Iaは、イソシアネート基又はブロック化されたイソシアネート基であり、
pは1から3の整数である]。 - 前記式(1)及び/又は式(1m)におけるSaが、下記式(2)で表される、請求項2又は3に記載の液晶配向剤。
[式中、
W1の左の結合はMbへの結合を表し、
W3の右の結合はIaへの結合を表し、
W1、W2及びW3は、それぞれ独立して、単結合、二価の複素環、-(CH2)n-(式中、nは1~20を表す)、-OCH2-、-CH2O-、―COO-、-OCO-、-CH=CH-、-CF=CF-、-CF2O-、-OCF2-、-CF2CF2-又は-C≡C-を表すが、これらの置換基において非隣接のCH2基の一つ以上は独立して、-O-、-CO-、-CO-O-、-O-CO-、-Si(CH3)2-O-Si(CH3)2―、-NR-、-NR-CO-、-CO-NR-、-NR-CO-O-、-OCO-NR-、-NR-CO-NR-、-CH=CH-、-C≡C-又は-O-CO-O-(式中、Rは独立して水素又は炭素原子数1から5の直鎖又は分岐鎖のアルキル基を表す)で置換することができ、
A1及びA2は、それぞれ独立して、2価の芳香族基、2価の脂環式基、2価の複素環式基または2価の縮合環式基であり、それぞれの基は無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、シアノ基、メチル基又はメトキシ基によって置換されていても良い)]。 - 前記(b)光配向性の光反応性基を有する部位が、下記式(3m)で表されるモノマー由来である請求項1~6のいずれか一項に記載の液晶配向剤。
[式中、
Mcは、第2の重合性基を表し、
Mdは、単結合、2価の複素環、3価の複素環、4価の複素環、置換又は非置換の直鎖または分岐鎖である炭素数1~10のアルキル基、2価の芳香族基、3価の芳香族基、4価の芳香族環、2価の脂環式基、3価の脂環式基、4価の脂環式基、2価の縮合環式基、3価縮合環式基または4価の縮合環式基であり、それぞれの基は無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、シアノ基、メチル基又はメトキシ基によって置換されていてもよく、
Sbは、スペーサー単位を表し、
Ibは、光配向性の光反応性基を有する1価の有機基であり、
qは1から3の整数である]。 - 前記式(3)及び/又は式(3m)におけるSbが下記式(2)で表される、請求項6又は7に記載の液晶配向剤。
[式中、
W1の左の結合はMdへの結合を表し、
W3の右の結合はIaへの結合を表し、
W1、W2及びW3は、それぞれ独立して、単結合、二価の複素環、-(CH2)n-(式中、nは1~20を表す)、-OCH2-、-CH2O-、―COO-、-OCO-、-CH=CH-、-CF=CF-、-CF2O-、-OCF2-、-CF2CF2-又は-C≡C-を表すが、これらの置換基において非隣接のCH2基の一つ以上は独立して、-O-、-CO-、-CO-O-、-O-CO-、-Si(CH3)2-O-Si(CH3)2―、-NR-、-NR-CO-、-CO-NR-、-NR-CO-O-、-OCO-NR-、-NR-CO-NR-、-CH=CH-、-C≡C-又は-O-CO-O-(式中、Rは独立して水素又は炭素原子数1から5の直鎖又は分岐鎖のアルキル基を表す)で置換することができ、
A1及びA2は、それぞれ独立して、2価の芳香族基、2価の脂環式基、2価の複素環式基または2価の縮合環式基であり、それぞれの基は無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、シアノ基、メチル基又はメトキシ基によって置換されていても良い)]。 - 前記式(3m)で表されるモノマーが、下記式(3m)-1で表されるモノマーである請求項7~9のいずれか1項に記載の液晶配向剤。
[式中、
Mc、Md及びqは、上記と同じ定義を有し、
Sbは、炭素数1~10のアルキレン基または2価の芳香族基であり、
Zは、酸素原子または硫黄原子であり、
Xa及びXbは、それぞれ独立して水素原子、フッ素原子、塩素原子、シアノ基又は炭素数1~3のアルキル基であり、
R1は、単結合、酸素原子、-COO-または-OCO-であり、
R2は、2価の芳香族基、2価の脂環式基、2価の複素環式基または2価の縮合環式基であり、
R3は、単結合、酸素原子、-COO-または-OCO-であり、
R4は、炭素数1~20のアルキル基または脂環式基を含む炭素数3~20の1価の有機基であり、
R5は、フッ素原子またはシアノ基であり、
aは0~3の整数であり、bは0~4の整数である]。 - 前記(c)分子内にアミノ基及びヒドロキシル基から選ばれる少なくとも1種の官能基を有する部位が、下記式(4m)で表されるモノマー由来である請求項1~11のいずれか一項に記載の液晶配向剤。
[式中、
Meは、第3の重合性基を表し、
Mfは、単結合、2価の複素環、3価の複素環、4価の複素環、置換又は非置換の直鎖または分岐鎖である炭素数1~10のアルキル基、2価の芳香族基、3価の芳香族基、4価の芳香族環、2価の脂環式基、3価の脂環式基、4価の脂環式基、2価の縮合環式基、3価縮合環式基または4価の縮合環式基であり、それぞれの基は無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、シアノ基、メチル基又はメトキシ基によって置換されていてもよく、
Scは、スペーサー単位を表し、
Icは、分子内にアミノ基及びヒドロキシル基から選ばれる少なくとも1種の官能基を有する1価の有機基であり、
rは1から3の整数である]。 - 前記式(4)及び/又は式(4m)におけるSbが下記式(2)で表される、請求項11又は12に記載の液晶配向剤。
[式中、
W1の左の結合はMfへの結合を表し、
W3の右の結合はIaへの結合を表し、
W1、W2及びW3は、それぞれ独立して、単結合、二価の複素環、-(CH2)n-(式中、nは1~20を表す)、-OCH2-、-CH2O-、―COO-、-OCO-、-CH=CH-、-CF=CF-、-CF2O-、-OCF2-、-CF2CF2-又は-C≡C-を表すが、これらの置換基において非隣接のCH2基の一つ以上は独立して、-O-、-CO-、-CO-O-、-O-CO-、-Si(CH3)2-O-Si(CH3)2―、-NR-、-NR-CO-、-CO-NR-、-NR-CO-O-、-OCO-NR-、-NR-CO-NR-、-CH=CH-、-C≡C-又は-O-CO-O-(式中、Rは独立して水素又は炭素原子数1から5の直鎖又は分岐鎖のアルキル基を表す)で置換することができ、
A1及びA2は、それぞれ独立して、2価の芳香族基、2価の脂環式基、2価の複素環式基または2価の縮合環式基であり、それぞれの基は無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、シアノ基、メチル基又はメトキシ基によって置換されていても良い)]。 - 前記第1、第2及び第3の重合性基が、各々独立に、(メタ)アクリレート、フマレート、マレエート、α-メチレン-γ-ブチロラクトン、スチレン、ビニル、マレイミド、ノルボルネン、(メタ)アクリルアミド及びその誘導体のラジカル重合性基、及びシロキサンからなる群から選ばれる少なくとも1種の基である、請求項2~13のいずれか一項に記載の液晶配向剤。
- 架橋性化合物として、分子内にアミノ基及びヒドロキシル基からなる群から選ばれる1種以上の官能基を2つ以上有する化合物をさらに含有する、請求項1~14のいずれか一項に記載の液晶配向剤。
- 請求項1~16のいずれか一項に記載の液晶配向剤から得られる、液晶配向膜。
- 請求項17に記載の液晶配向膜を具備する、液晶表示素子。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020187021567A KR20180094104A (ko) | 2015-12-28 | 2016-12-27 | 액정 배향제, 액정 배향막, 및 액정 표시 소자 |
JP2017559203A JP6877698B2 (ja) | 2015-12-28 | 2016-12-27 | 液晶配向剤、液晶配向膜、及び液晶表示素子 |
CN201680082798.6A CN108700779B (zh) | 2015-12-28 | 2016-12-27 | 液晶取向剂、液晶取向膜、及液晶表示元件 |
US16/066,472 US10921650B2 (en) | 2015-12-28 | 2016-12-27 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015256573 | 2015-12-28 | ||
JP2015-256573 | 2015-12-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017115791A1 true WO2017115791A1 (ja) | 2017-07-06 |
Family
ID=59225767
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/088869 WO2017115791A1 (ja) | 2015-12-28 | 2016-12-27 | 液晶配向剤、液晶配向膜、及び液晶表示素子 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10921650B2 (ja) |
JP (1) | JP6877698B2 (ja) |
KR (1) | KR20180094104A (ja) |
CN (1) | CN108700779B (ja) |
TW (1) | TWI764880B (ja) |
WO (1) | WO2017115791A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112639595A (zh) * | 2018-08-30 | 2021-04-09 | 日产化学株式会社 | 液晶取向剂、液晶取向膜和液晶表示元件 |
JP2021073522A (ja) * | 2015-12-28 | 2021-05-13 | 日産化学株式会社 | イソシアネート基及び/又はブロック化されたイソシアネート基を有する部位及び光反応性を有する部位を有する重合体と架橋剤を含有する液晶配向剤、液晶配向膜、及び液晶表示素子 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI774891B (zh) * | 2017-12-22 | 2022-08-21 | 日商迪愛生股份有限公司 | 液晶組成物及液晶顯示元件 |
CN110803990B (zh) * | 2018-08-04 | 2023-08-08 | 石家庄诚志永华显示材料有限公司 | 化合物、液晶组合物、液晶显示元件及液晶显示器 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005187618A (ja) * | 2003-12-25 | 2005-07-14 | Asahi Glass Co Ltd | 液晶組成物、該液晶組成物を用いた高分子液晶の製造方法 |
JP2013513017A (ja) * | 2009-12-08 | 2013-04-18 | トランジションズ オプティカル, インコーポレイテッド | 向上した接着性を有する光配向材料 |
KR20130073024A (ko) * | 2013-04-25 | 2013-07-02 | 동우 화인켐 주식회사 | 접착력 강화제 및 이를 포함하는 배향막 형성용 조성물 |
JP2014012823A (ja) * | 2012-06-06 | 2014-01-23 | Jnc Corp | 光配向性基を有する高分子組成物、該高分子組成物から作製される液晶配向膜及び該液晶配向膜から作製される位相差板を備えた光デバイス |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4995267A (ja) | 1973-01-17 | 1974-09-10 | ||
JP2857779B2 (ja) | 1988-12-19 | 1999-02-17 | セイコーエプソン株式会社 | 液晶配向膜用組成物および液晶装置 |
US5276132A (en) | 1991-03-11 | 1994-01-04 | Japan Synthetic Rubber Co., Ltd. | Liquid crystal aligning agent and aligning agent-applied liquid crystal display device |
JP2893671B2 (ja) | 1991-03-11 | 1999-05-24 | ジェイエスアール株式会社 | 液晶配向剤 |
JP4504626B2 (ja) | 2003-03-31 | 2010-07-14 | シャープ株式会社 | 液晶表示装置及びその製造方法 |
US8310636B2 (en) | 2007-03-26 | 2012-11-13 | Sharp Kabushiki Kaisha | Liquid crystal display device and polymer for aligning film material |
CN110256630B (zh) * | 2014-02-28 | 2021-09-28 | 日产化学工业株式会社 | 相位差材形成用树脂组合物、取向材及相位差材 |
-
2016
- 2016-12-27 TW TW105143398A patent/TWI764880B/zh active
- 2016-12-27 KR KR1020187021567A patent/KR20180094104A/ko not_active Application Discontinuation
- 2016-12-27 WO PCT/JP2016/088869 patent/WO2017115791A1/ja active Application Filing
- 2016-12-27 CN CN201680082798.6A patent/CN108700779B/zh active Active
- 2016-12-27 US US16/066,472 patent/US10921650B2/en active Active
- 2016-12-27 JP JP2017559203A patent/JP6877698B2/ja active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005187618A (ja) * | 2003-12-25 | 2005-07-14 | Asahi Glass Co Ltd | 液晶組成物、該液晶組成物を用いた高分子液晶の製造方法 |
JP2013513017A (ja) * | 2009-12-08 | 2013-04-18 | トランジションズ オプティカル, インコーポレイテッド | 向上した接着性を有する光配向材料 |
JP2014012823A (ja) * | 2012-06-06 | 2014-01-23 | Jnc Corp | 光配向性基を有する高分子組成物、該高分子組成物から作製される液晶配向膜及び該液晶配向膜から作製される位相差板を備えた光デバイス |
KR20130073024A (ko) * | 2013-04-25 | 2013-07-02 | 동우 화인켐 주식회사 | 접착력 강화제 및 이를 포함하는 배향막 형성용 조성물 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021073522A (ja) * | 2015-12-28 | 2021-05-13 | 日産化学株式会社 | イソシアネート基及び/又はブロック化されたイソシアネート基を有する部位及び光反応性を有する部位を有する重合体と架橋剤を含有する液晶配向剤、液晶配向膜、及び液晶表示素子 |
JP7055281B2 (ja) | 2015-12-28 | 2022-04-18 | 日産化学株式会社 | イソシアネート基及び/又はブロック化されたイソシアネート基を有する部位及び光反応性を有する部位を有する重合体と架橋剤を含有する液晶配向剤、液晶配向膜、及び液晶表示素子 |
CN112639595A (zh) * | 2018-08-30 | 2021-04-09 | 日产化学株式会社 | 液晶取向剂、液晶取向膜和液晶表示元件 |
Also Published As
Publication number | Publication date |
---|---|
US20190018289A1 (en) | 2019-01-17 |
KR20180094104A (ko) | 2018-08-22 |
CN108700779B (zh) | 2022-06-10 |
JPWO2017115791A1 (ja) | 2018-10-25 |
TWI764880B (zh) | 2022-05-21 |
CN108700779A (zh) | 2018-10-23 |
US10921650B2 (en) | 2021-02-16 |
TW201736424A (zh) | 2017-10-16 |
JP6877698B2 (ja) | 2021-05-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7055281B2 (ja) | イソシアネート基及び/又はブロック化されたイソシアネート基を有する部位及び光反応性を有する部位を有する重合体と架橋剤を含有する液晶配向剤、液晶配向膜、及び液晶表示素子 | |
KR102113892B1 (ko) | 횡전계 구동형 액정 표시 소자용 액정 배향막을 갖는 기판의 제조 방법 | |
JP2020042288A (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
KR102674352B1 (ko) | 액정 배향제, 액정 배향막 및 액정 표시 소자 | |
WO2017199986A1 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
JP6823458B2 (ja) | 横電界駆動型液晶表示素子用液晶配向膜製造用組成物、該組成物を用いた液晶配向膜及びその製造方法、並びに液晶配向膜を有する液晶表示素子及びその製造方法 | |
JP6877698B2 (ja) | 液晶配向剤、液晶配向膜、及び液晶表示素子 | |
JP2024037839A (ja) | 液晶配向剤、液晶配向膜、液晶表示素子及び新規モノマー | |
KR102573453B1 (ko) | 액정 배향제, 액정 배향막, 및 액정 표시 소자 | |
WO2017069133A1 (ja) | 液晶配向剤、液晶配向膜および液晶表示素子 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16881765 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017559203 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20187021567 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020187021567 Country of ref document: KR |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 16881765 Country of ref document: EP Kind code of ref document: A1 |