WO2016156079A1 - Photoalignment composition - Google Patents

Photoalignment composition Download PDF

Info

Publication number
WO2016156079A1
WO2016156079A1 PCT/EP2016/056090 EP2016056090W WO2016156079A1 WO 2016156079 A1 WO2016156079 A1 WO 2016156079A1 EP 2016056090 W EP2016056090 W EP 2016056090W WO 2016156079 A1 WO2016156079 A1 WO 2016156079A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxy
benzoyl
phenyl
prop
enoyl
Prior art date
Application number
PCT/EP2016/056090
Other languages
French (fr)
Inventor
Jean-François ECKERT
Thierry Becret
Masato Hoshino
Qian Tang
Original Assignee
Rolic Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rolic Ag filed Critical Rolic Ag
Priority to JP2017551247A priority Critical patent/JP6821594B2/en
Priority to CN201680019215.5A priority patent/CN107438653B/en
Priority to US15/562,277 priority patent/US10557085B2/en
Priority to KR1020177031685A priority patent/KR102629649B1/en
Publication of WO2016156079A1 publication Critical patent/WO2016156079A1/en

Links

Classifications

    • 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
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K2019/525—Solvents
    • 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
    • C09K2019/528—Surfactants

Definitions

  • the invention relates to a photoalignment composition
  • a photoalignment composition comprising at least a single photoalignment polymer, preferably a homo- or a copolymer having at least one photoreactive group; and at least a single solvent of formula (I)
  • R and R' are independently from each other straigt-chain or branched alkyl chain, with the proviso that at least one alkyl chain is branched.
  • the present invention relates to the use of this composition for coating or printing, especially for printing, more especially for inkjet or offset printing processes, and most especially for an offset printing process.
  • the present invention relates to the use of the photoalignment composition for the preparation of liquid crystal aligning layers and in the construction of unstructured and structured optical elements and multi-layer systems, especially liquid crystal displays, LCDs.
  • photoalignment materials are applied by two main techniques, the coating and printing.
  • Coating methods are for example spin coating, air doctor coating, blade coating, knife coating, reverse-roll coating, transfer roll coating, gravure roll coating, kiss roll coating, cast coating, spray coating, slot-orifice coating, calendar coating, electrodepositing coating, dip coating or die coating.
  • Printing methods are for example relief printing such as flexographic printing, intaglio printing such as direct gravure printing or offset gravure printing, lithographic printing such as offset printing, or stencil printing such as screen printing.
  • the printed image is transferred to the substrate either directly or indirectly.
  • direct printing the image is transferred directly from the image carrier to the substrate, examples of direct printing are gravure, flexography, screen printing and letterpress printing processes.
  • indirect, or offset, printing the image is first transferred from the image carrier to the blanket cylinder and then to the substrate.
  • Lithography currently the dominant printing technology, is an indirect (offset) process.
  • Image carriers can generally be classified as one of four types: relief, planographic, intaglio, or screen.
  • relief printing the image or printing area is raised above the no image areas. Of the five major printing processes, those relying on relief printing are letterpress and flexography.
  • planographic printing the image and no image areas are on the same plane. The image and no image areas are defined by differing physiochemical properties.
  • Lithography is a planographic process.
  • intaglio process the nonprinting area is at a common surface level with the substrate while the printing area, consisting of minute etched or engraved wells of differing depth and/or size, is recessed.
  • Gravure is an intaglio process.
  • the screen process also known as porous printing
  • the image is transferred to the substrate by pushing ink through a porous mesh which carries the pictorial or typographic image.
  • Inkjet printing represents a further established and strongly growing industrial image deposition process which is also called printing despite its quite different character (e.g. its lack of an image carrier) in comparison to the above described conventional printing processes.
  • Inkjet printers may operate either in continuous or drop-on-demand (DOD) mode.
  • DOD drop-on-demand
  • continuous-mode the fluid is pumped through a nozzle to form a liquid jet.
  • Uniformly spaced and sized droplets are obtained by imposing a periodic perturbation, leading to surface-tension driven jet break-up. This requires the fluid to have certain conductivity.
  • Drop-on-demand is the method of choice for many industrial applications such as electronics and displays. This is mainly because of its smaller drop size, higher accuracy and no need to use dopants to make the fluid more conductive.
  • An acoustic pulse ejects fluid droplets from a reservoir through a nozzle.
  • the pulse can be generated either thermally (Bubble-jet) or piezo-electrically (piezo- jet). Piezo-electric DOD is generally more suited to a variety of solvents.
  • the most critical part of inkjet printing technology is probably the fluid and its physical properties.
  • the fluid parameters should be on one hand optimised to get reliable droplet formation during printing with specific printer (such as viscosity and surface tension).
  • the fluid should be also optimised in order to get good wetting properties, with specific substrates, and homogeneous films.
  • the liquid crystal aligning layers can be directly printed in a predetermined pattern without requiring any etching process.
  • the flexographic process can be a substantially continuous process which uses a series of rollers to transfer a quantity of alignment material as a predetermined pattern onto the desired surface of substrate (typically glass).
  • the flexographic apparatus can be configured to
  • the apparatus employs a special resin plate with a series of holding cells configured in a predetermined pattern to hold a quantity of alignment material processing solution.
  • the resin plate is rotated and subsequently brought into direct contact with the glass panel surface to release the solution and transfer the predetermined pattern to form the liquid crystal aligning layers onto the surface.
  • the glass panel is then heated to pre-cure the liquid crystal aligning layers.
  • the alignment material solution is dropped and maintained on a so-called anilox roll.
  • the anilox roll is preferably plated with chrome, or chrome and nickel (the alignment material solution contacting surface). Cells having a pyramid shape are formed in the anilox roll to a depth of approximately 20 ⁇ so that the alignment material can be retained in the cells.
  • a doctor roll is rotated together with the anilox roll to help assure that the alignment material solution is evenly applyied on the surface of the anilox roll.
  • a resin plate is attached to an underlying plate typically comprising copper.
  • the resin plate is formed from a polybutadiene resin, e.g., an Asahi Kasei photosensitive resin ("APR").
  • APR Asahi Kasei photosensitive resin
  • the resin plate will be described subsequently herein as an "APR plate”.
  • the APR plate includes an exterior surface of predetermined patterns.
  • the patterns include a plurality of cells as intaglios so that the alignment material solution can be accommodated in the cells.
  • the depth of the cells is preferably in the range of approximately 15 to 20 ⁇ .
  • the flexographic printers for liquid crystal aligning layer application use an intaglio instead of a relief process.
  • the alignment material solution is dispensed onto the anilox roll.
  • the anilox roll and the doctor roll rotate and contact on an outer circumference portion.
  • the contact pressure provided by the doctor roll helps the alignment material solution in the anilox roll (i.e., in the cells) to be uniformly distributed and to bring a certain quantity of the solution to fill the cell of the anilox roll.
  • the APR plate then contacts the anilox roll and the alignment material solution is supplied or delivered to the APR plate.
  • the amount of the alignment material solution transferred to the APR plate is determined by the contact force that the doctor roll exerts against the anilox roll (or the reverse).
  • the alignment material solution is then held in the APR plate cells.
  • the LCD panel or glass is fixed to the print table.
  • the table advances and the glass is moved forward at the same time that the copper plate holding the APR plate rotates.
  • the APR plate thus directly contacts the glass substrate and the alignment material solution is applied to the glass from the cells of the patterns in the APR plate. As a result, an orientation layer is formed on the glass substrate.
  • the present invention relates to a photoalignment composition
  • a photoalignment composition comprising
  • At least a single photoalignment polymer preferably a homo- or a copolymer having at least one photoreactive group
  • R and R' are independently from each other a straigt-chain alkyl; preferably a straigt-chain a branched d-C 6 alkyl chain ; more preferably a branched CrC 6 alkyl chain, most preferably a branched C 3 -,C4-,C5-,C 6 alkyl chain, especially most preferably a branched C 4 alkyl chain; with the proviso that at least one alkyl chain is branched.
  • polymer has the meaning of e.g. homopolymer, copolymer, graft polymer, block polymer, hyper branched polymer or oligomer; preferably has the meaning of polymer or copolymer;
  • polymer of the present invention comprises a backbone, which is not particularly limited, and is represented for example by polyamic acid, partially imidised polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polysiloxane, polymaleinimide, polyacrylate, polyvinyl, cellulose derivative, polyacetal, polyurea, polyurethane, polystyrene derivative, poly(styrene-phenyl- maleimide)-derivative and poly(meth)acrylate, cyclo olefin polymer or a mixture thereof.
  • backbone which is not particularly limited, and is represented for example by polyamic acid, partially imidised polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polysiloxane, polymaleinimide, polyacrylate, polyvinyl, cellulose derivative, polyacetal, polyurea, polyurethane, polystyrene derivative, poly(styrene-phenyl- maleimide
  • polymer is a polyamic acid, partially imidised polyamic acid, polyimide, polyamic acid ester, polysiloxane derivative or mixtures thereof; polyamic acid, partially imidised polyamic acid, polyimide and mixtures thereof are most preferred and especially most prefered is polyamic acid.
  • coating has the meaning of e.g. coating techniques like for example spin-coating, meniscus-coating, wire-coating, slot-coating, printing, such as offset-printing, flexo- printing, gravur-printing, especially of inkjet or offset printing;
  • photoalignment polymer has the meaning of an organic polymer, copolymer or oligomer comprising photoreactive groups, which are able to undergo photoreaction after radiation with aligning light.
  • aligning light has the meaning of light of wavelengths, which can initiate
  • aligning light is at least partially linearly polarized, elliptically polarized, such as for example circularly polarized, or nonpolarized, most preferably circiulary polarized, or non-polarized light exposed obliquely, or at least partially linearly polarized light.
  • aligning light denotes substantially polarised light, especially linearly polarised light; or aligning light denotes non-polarised light, which is applied by an oblique irradiation.
  • aligning group exhibiting a property of controlling alignment of liquid crystal molecules without photo-irradiation has the meaning of an organic group which is able to align liquid crsytals, preferably homeotropically or planarly align liquid crystals.
  • aligning groups are an unsubstituted or substituted steroidal skeleton such as a cholesterol group, which is uninterrupted or interrupted by at least a single heteroatom and/or at least a single bridging group, preferably, a cholesterol group is cholesteryl, cholestanyl, cholestan; or an aligning group is an unsubstituted or substituted organic chemical structure, which is, for example, 3 to 4 rings selected from any one of 1 ,4-cyclohexylene and 1 ,4-phenylene, which are linearly coupled e.g.
  • organic chemical structure is preferably composed of three or four pieces of 1 ,4-cyclohexylene, three or four pieces of 1 ,4-phenylene or is composed of both 1 ,4-cyclohexylene and 1 ,4- phenylene wherein the number of total piece thereof are 3 or 4 pieces;
  • substituents are for example straight chain or branched CrC 30 alkyl.
  • photo reactive group has the meaning of an organic group which is able to undergo a reaction after irradiation with light.
  • a photoreactive group is able to make electrocyclic reactions, radical reactions, photoisomerization and Norrish reactions, and is e.g. dimerizable, decompositable, isomerizable, polymerizable and/or cross-linkable group;
  • the photoreactive group is a cinnamate-, coumarine-, quinoline-, azo-, stilbene-, cyanostilbene-, chalcone-, diphenylacetylene, benzylidene- phthalimidine, benzylideneacetophenone, phenylenediacryloyl, stilbazole and/or azo-group; most preferred are cinnamate-, coumarine-, quinoline-, cyanostilbene-, and/or chalcone-groups; especially most preferred are cinnamate- or cyanostilbene groups, and more especially cinnamate groups are preferred.
  • straigt-chain alkyl has the meaning of example straigt-chain Ci-C 40 alkyl, especially straigt-chain CrC 3 oalkyl, preferably straigt-chain Ci-C 24 alkyl, more preferably straigt-chain d-C ⁇ alkyl, most preferably straigt-chain d-Ci 0 alkyl and especially most preferably straigt-chain CrC 6 alkyl, very especially most preferably methyl, ethyl, propyl, butyl, pentyl or hexyl;
  • straigt-chain CrCi 0 alkyl is for example methyl, ethyl, propyl, butyl, pentyl, hexyl, hepty, octyl, nonyl, decyl or undecyl;
  • straigt-chain CrCi 6 alkyl is for example methyl, ethyl, propyl, butyl, pentyl, hexyl, hepty, octyl, nonyl, decyl or undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl.
  • branched alkyl chain has the meaning of example branched C 3 -C 40 alkyl, especially branched C 3 -C 3 oalkyl, preferably branched C 3 -C 20 alkyl, more preferably branched C 3 -Ci 6 alkyl, most preferably branched C 3 -Ci 0 alkyl and especially most preferably branched C 3 -C 6 alkyl, which is branched C 3 -C 4 -C 5 -C 6 alkyl, very especially most preferably C 3 -C 6 alkyl isopropyl, sec-butyl, tert.-butyl, isopentyl, dimethyl propyl, or 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,2- dimethylbutane.
  • Branched C 3 -Ci 0 alkyl is for example isopropyl, sec-butyl, tert.-butyl, isopentyl, dimethyl propyl, or 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,2- dimethylbutane isoheptyl, isooctyl, isononyl, isodecyl.
  • Branched C 3 -Ci 6 alkyl is for example isopropyl, sec-butyl, tert.-butyl, isopentyl, dimethyl propyl, or 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,2- dimethylbutane, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl or isohexadecyl.
  • Branched C 3 -C 20 alkyl is for example isopropyl, sec-butyl, tert.-butyl, isopentyl, dimethyl propyl, or 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,2- dimethylbutane, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, isonondecyl, isoeicosyl.
  • Branched C 3 -C 30 alkyl is for example example isopropyl, sec-butyl, tert.-butyl, isopentyl, dimethyl propyl, or 2-methylpentane, 3-methylpentane, 2,3- dimethylbutane, 2,2-dimethylbutane, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, isonondecyl, isoeicosyl, isoheneicosyl, isotricosyl, isotetracosy, isopentacosyl, isohexacosdy, isoheptacosyl, isooctacosyl,
  • Branched C 3 -C 40 alkyl is for example isopropyl, sec-butyl, tert.-butyl, isopentyl, dimethyl propyl, or 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,2- dimethylbutane, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, isonondecyl, isoeicosyl, isoheneicosyl, isotricosyl, isotetracosy, isopentacosyl, isohexacosdy, isoheptacosyl, isooctacosyl, is
  • alkylen if used as single term has the meaning of (C-
  • R 3 is CrC 24 alkylen is preferably at least one CrC 6 alkyl, more preferably methyl, ethyl, propyl.
  • - CrC 6 alkylen is for example methylene, ethylene, propylene, isopropylene, sec- butylene, ter.-butylene, pentylene, isopentylene, hexylene, isohexylene.
  • Ci-C 30 alkyl is preferably Ci-C 30 alkyl, more preferably CrCi 6 alkyl, most preferably C Cealkyl and especially most preferrerd CrC 6 alkyl, which is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl.
  • Ci-C 30 alkyl has the meaning of straigt-chain CrC 30 alkyl and branched C 3 -C 30 alkyl as described above within the all preferences given.
  • alicyclic group has the meaning of an unsubstituted or substituted steroidal skeleton such as a cholesterol group, which is uninterrupted or interrupted by at least a single heteroatom and/or at least a single bridging group, preferably, a cholesterol group is cholesteryl, cholestanyl, cholestan; or "alicyclic group” has the meaning of an organic chemical structure, which is, for example, cyclohexylene, especially 1 ,4-cyclohexylene .
  • linkinig group has meaning of -0-, -CO, -CO-O-, -O-CO-, , -NR 1 -,
  • R 1 represents a hydrogen atom or d-C 6 alkyl
  • the present invention relates a photoalignment composition comprising at least a single photoalignment polymer, which is preferably a homopolymer, comprising at least one photoreactive group.
  • the present invention relates a photoalignment composition comprising at least a single photoalignment polymer, which comprises at least two monomers, wherein at least a first monomer comprises a photoreactive group;
  • the at least second monomer comprises a further photoreactive group, which is identical or different to the first monomer; or the at least second monomer does not comprise a a photreactive group and preferably comprises an aligning group exhibiting a property of controlling alignment of liquid crystal molecules without photo- irradiation within the meaning and preferences as described above.
  • the present invention relates a photoalignment composition
  • a photoalignment composition comprising at least a single photoalignment polymer, comprising at least one monomer having a photoreactive group and one monomer having an aligning group exhibiting a property of controlling alignment of liquid crystal molecules without photo-irradiation.
  • the present invention relates a photoalignment
  • composition comprising at least a single photoalignment polymer, comprising at least two monomers having a photoreactive group, which is identical to the first monomer.
  • the present invention relates a photoalignment composition, comprising c ) a further polymer not having a photoreactive group, which comprises a backbone which is a polyamic acid, a partially imidised polyamic acid, a polyimide, a polyamic acid ester or a polysiloxane.
  • a photoalignment composition with the meaning and preferences as given above which comprises a further polymer not having a photoreactive group and, which preferably has the same backbone as the
  • the backbone is a polyamic acid, partially imidised polyamic acid, polyimide, polyamic acid ester, polysiloxane, polysiloxane derivative or mixtures thereof; more preferably the backbone is polyamic acid, partially imidised polyamic acid, polyimide and mixtures thereof; most preferably the backbone is polyamic acid; especially most preferably the backbone is more preferably the backbone is a polyamic acid, polyimide or a mixture thereof.
  • the present invention relates to a photoalignment composition, wherein the photoalignment polymer comprises a photoreactive group, which is preferably a dimerizable, isomerizable, decompositable, polymerizable and/or cross-linkable group; more preferably the photoreactive group is
  • cinnamate-, coumarine-, quinoline-, cyanostilbene-, and/or chalcone-groups are most preferred.
  • the present invention relates to a photoalignment composition, comprising
  • R and R' are independently from each other a straigt-chain alkyl; preferably a straigt-chain a branched d-C 6 alkyl chain; preferably a branched CrC 6 alkyl, more preferably a branched C 3 - or C 4 alkyl , with the proviso that at least one alkyl chain is branched;
  • photoalignment polymer has a photoreactive group, which is
  • photoalignment compounds which are herewith incorporated by reference: photoalignment materials as described in USRe36625, US6201087 , US6107427, US6335409, US5965761 , US6277502, US6649230, US6833421 ,
  • photoalignment polymer comprises at least a diamine (I) or at least two diamines, and a tetracarboxylic acid anhydride
  • A represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic group selected from a monocyclic ring of five or six atoms, two adjacent monocyclic rings of five or six atoms, a bicyclic ring system of eight, nine or ten atoms, or a tricyclic ring system of thirteen or fourteen atoms;
  • F is fluorine
  • X1 is an integer from 1 to 15, preferably an integer from 1 to 10; more preferably 1 , 2, 3, 4, 5, 6, 7, 8 or 9 and most preferred 3, 4, 5 or 7;
  • B represents a straight-chain or branched d-Ci 6 alkyl group, which is in addition to its fluorine substituent(s) unsubstituted or substituted by
  • D represents an unsubstituted or substituted, aliphatic, aromatic and/or alicyclic diamine group having from 1 to 40 carbon atoms; preferably D represents an unsubstituted or substituted, aliphatic, aromatic and/or alicyclic diamine group having from 1 to 40 carbon atoms, wherein the diamine group comprises an aliphatic group, which may comprise one or more heteroatom and/or bridging group;
  • E represents an aromatic group, an oxygen atom, a sulphur atom, -NH-,
  • R 2 and R 3 are independently from each other hydrogen or a cyclic, straight-chain or branched, substituted or unsubstituted CrC 24 alkyl, wherein one or more -CH2- group(s) may be independently from each other replaced by a linking group, and with the proviso that at least one of R 2 and R 3 is not hydrogen;
  • S 1 , S 2 each independently from each other represents a spacer unit
  • X, Y each independently from each other represents hydrogen, fluorine, chlorine, cyano, unsubstituted or with fluorine substituted d-C ⁇ alkyl, in which one or more -CH2- groups may be replaced by a linking group;
  • n, n1 each independently from each other represents 1 , 2, 3 or 4, preferably n1 is 1 and n is 1 or 2;
  • compound (I) has several side-chains [ wherein side-chain has the meaning of structures (I) without the group D], which are linked to residue D at one atomic position within group D, e.g. two or three side chains linked to one single carbon atom within group D, or they can be linked to group D at different atomic positions within group D, e.g. at adjacent atomic positions within group D, or/and they can linked spaced further apart.
  • photoalignment composition which comprises
  • diamine (I) and tetracarboxylic acid dianhydride as basic building blocks, and more preferably wherein the polymer is selected from a polyamic acid, polyamic ester, polyimide or a mixture thereof, and most preferably wherein the polymer is a polyamic acid;
  • a further polymer which is a polymer comprising a diamine (I) tetracarboxylic acid dianhydride as basic building blocks, and more preferably wherein the polymer is selected from a polyamic acid, polyamic ester, polyimide or a mixture thereof, and most preferably wherein the polymer is a polyamic acid;
  • R and R' are independently from each other a straigt-chain alkyl; preferably a straigt-chain a branched CrC 6 alkyl chain; more preferably a branched CrC 6 alkyl chain, most preferably a branched C 3 -,C4- ,C5-,C 6 alkyl chain, especially most preferably a branched C 4 alkyl chain; with the proviso that at least one alkyl chain is branched.
  • polyimide has the meaning of partially or full imidisated polyamic acid or polyamic ester.
  • the term “imidisation” has in the context of the present invention the meaning of partially or complete imidisation.
  • the linking group is selected from -0-, -CO, -CO-0-, -0-CO-, , -NR 1 -,
  • R 1 represents a hydrogen atom or d-C 6 alkyl
  • the spacer unit is a single bond, a cyclic, straight-chain or branched, substituted or unsubstituted CrC 24 alkylen, wherein one or more -CH2- group may independently from each other be replaced by a linking group as described above and/or an non- aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group connected via bridging groups.
  • diamine (I) wherein
  • D is preferably selected from formula (III):
  • R5, R6 each independently from each other represents a hydrogen atom or
  • Sp 1 , Sp 2 each independently from each other represents an unsubstituted or substituted straight-chain or branched CrC 20 alkylene, in which one or more -CH2-group may independently from each other be replaced by a linking group, and
  • k 1 , k 2 each independently is an integer having a value of 0 or 1 ;
  • X 1 , X 2 each independently represents a linking spacer
  • t 1 , t 2 each independently is an integer having a value of 0 or 1 ;
  • C3, C 4 each independently represents a non-aromatic, aromatic, substituted or
  • Z 4 represents a substituted or unsubstituted straight-chain or branched
  • CrC 20 alkylene group in which one or more -CH 2 - group may independently from each other be replaced by a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group; and/or a heteroatom and/or by a bridging group; and
  • a3, a4 are independently integers from 0 to 3, such that a3 + a_ ⁇ ⁇ 4; and wherein D is at least once linked to at least one group S 1 in formula (I) via group Sp 1 and/or group Sp 2 ; and/or linked via at least one non-aromatic, aromatic, substituted or unsubstituted carbocyclic or heterocyclic group of and/or group of C 4 , and/or linked via at least one side chain T of group C 4 and/or group of C3; and/or linked via group Z 4 ; and at least one of k 1 , k 2 , a ⁇ and a 4 is not equal to zero; and wherein
  • linking group and bridging group are as defined above.
  • the side chain, T represents a substituted or unsubstituted straight-chain or branched CrC 20 alkylene group, in which one or more -CH 2 - group(s) may independently from each other be replaced by a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, or a heteroatom and/or by a bridging group, which is at least once linked to at least once group S 1 in formula (I) as described above;
  • C3, C 4 independently from each other are selected from a compound of group G 2 , wherein G 2 is:
  • R5, R6 each independently from each other represents a hydrogen atom or d-C 6 alkyl
  • T represents a substituted or unsubstituted straight-chain or branched
  • CrC 20 alkylene group in which one or more -CH 2 - group may independently from each other be replaced by a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, or a heteroatom and/or by a bridging group;
  • n is an integer from 0 to 2;
  • ui is an integer from 0 to 4, with the proviso that m + ui is ⁇ 4;
  • U2 is an integer from 0 to 3; with the proviso that m + U2 is ⁇ 3; and is an integer from 0 to 2; with the proviso that m + 113 is ⁇ 2.
  • D is a selected the group of the following compounds:
  • T, T 1 ; T 2 and T 3 are independently from each other a substituted or unsubstituted
  • q is an integer of 1 or 2;
  • q1 , q2 and q3 are independently from each other an integer from 0 to 2;
  • n is an integer of 1 or 2;
  • nl , m2 and m3 are independently from each other an integer from 0 to 2;
  • U3 ; U3' and 113" are independently from each other an integer from 0 to 2;
  • R5, R6 each independently from each other represents a hydrogen atom or C
  • Z 4 represents a substituted or unsubstituted straight-chain or branched
  • CrC 20 alkylene group in which one or more -CH 2 - group may independently from each other be replaced by a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group; and/or a heteroatom and/or by a bridging group; and wherein D is at least once linked to at least one group S 1 in formula (I), as described in claim 1 , via a single bond "— "; or via a side chain T, T 1 ; T 2 or T 3 ; or via group Z4;
  • u3 + q1 and/or u3' + q2 or/and u3 + ml , or/and u3' + m2, or/and u3" + q3, or/and u3" + m3 is ⁇ 4;
  • S 1 , S 2 each independently from each other represents a single bond or a cyclic, straight-chain or branched, substituted or unsubstituted Ci-C 24 alkylen, in which one or more -CH2- group may independently from each other be replaced by a linking group, and/or a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group of formula (IV): -(Z 1 -C 1 ) a1 -(Z 2 -C 2 ) a2 -(Z 1a ) a3 - (IV) wherein:
  • C 1 , C 2 each independently represents a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group
  • Z 1 , Z 2 , Z 1 a each independently represents a bridging group
  • ai . 3 ⁇ 4 . 33 each independently represents an integer from 0 to 3, ai + a2 + a3 ⁇ 6, wherein the bridging groups Z 1 , Z 1 a and Z 2 are as above.
  • A, B, xi , n, n1 , D, E, S 2 ,S 1 , X and Y have the above given meanings as in claim 1 and
  • R5, R6 and Z 4 have the same meanings as given above;
  • U3 is an integer from 0 to 2;
  • F is fluorine
  • X1 is an integer from 1 to 9
  • B represents a straight-chain or branched d-C 8 alkyl group, which is unsubstituted or in addition to its fluorine substituent(s) substituted by
  • R 1 represents a hydrogen atom or CrC 6 alkyl
  • photoalignment polymers are polymers composed of aat least one diamine of:
  • the diamine compounds are prepared according to methods known in the art or according to a process comprising contacting a compound of formula (XIV)
  • reaction between compounds (XIV) and (XVI) can be conducted in many known ways (see J. March, Advanced Organic Chemistry, second edition, pages 363 and 365).
  • a method for the preparation of a photoalignment polymer of the present invention is applied through polycondensation reaction of a diamine (I) with one or more tetracarboxylic acid anhydrides, preferably of the general formula (V) as given below, optionally in the presence of one or more additional other diamines.
  • the tetracarboxylic acid anhydride is of formula (V)
  • (V) represents a tetravalent organic radical.
  • the tetravalent organic radical T is preferably derived from an aliphatic, alicyclic or aromatic tetracarboxylic acid dianhydride.
  • aliphatic or alicyclic tetracarboxylic acid dianhydrides are:
  • aromatic tetracarboxylic acid dianhydrides are: pyromellitic acid dianhydride,
  • tetracarboxylic acid dianhydrides used to form the tetravalent organic radical T are selected from:
  • the polymer, copolymer or oligomer, especially the polyamic acid, polyamic acid ester and polyimide and mixtures thereof may be prepared in line with known methods, such as those described in Plast. Eng. 36 (1996), (Polyimides, fundamentals and applications), Marcel Dekker, Inc.
  • the amidisation, poly-condensation reaction for the preparation of the polyamic acids is carried out in solution in a polar aprotic organic solvent, such as ⁇ -butyrolactone, ⁇ , ⁇ -dimethylacetamide, 2-butoxyethanol (BC), N-methylpyrrolidone or ⁇ , ⁇ -dimethylformamide.
  • a polar aprotic organic solvent such as ⁇ -butyrolactone, ⁇ , ⁇ -dimethylacetamide, 2-butoxyethanol (BC), N-methylpyrrolidone or ⁇ , ⁇ -dimethylformamide.
  • a polar aprotic organic solvent such as ⁇ -butyrolactone, ⁇ , ⁇ -dimethylacetamide, 2-butoxyethanol (BC), N-methylpyrrolidone or ⁇ , ⁇ -dimethylformamide.
  • the reaction is carried out at temperatures of less than 100 °C.
  • the imidisation, cyclisation of the polyamic acids to form the polyimides can be carried out by heating, i.e. by condensation with removal of water or by other imidisation reactions using appropriate reagents.
  • Partially imidisation is achieved for example, if the imidisation is carried out purely thermally, the imidisation of the polyamic acids may not always be complete, i.e. the resulting polyimides may still contain proportions of polyamic acid.
  • Complete imidisation reactions are carried out at temperatures between 60 and 250 °C, preferably at temperatures of less than 200 °C.
  • additional reagents that facilitate the removal of water are added to the reaction mixture.
  • Such reagents are, for example, mixtures consisting of acid anhydrides, such as acetic acid anhydride, propionic acid anhydride, phthalic acid anhydride, trifluoroacetic acid anhydride or tertiary amines, such as triethylamine, trimethylamine, tributylamine, pyridine,
  • the amount of aforementioned additional reagents that facilitate the removal of water is preferably at least four equivalents of acid anhydride and two equivalents of amine per equivalent of polyamic acid to be condensed.
  • the imidization degree of each polymer used in the liquid crystal alignment agent of the invention can be arbitrarily adjusted by controlling the catalyst amount, reaction time and reaction temperature employed in production of the polymer.
  • "imidization degree" of polymer refers to a proportion (expressed in %) of the number of recurring units of polymer forming an imide ring or an isoimide ring to the number of total recurring units of polymer.
  • the imidization degree of a polyamic acid not subjected to dehydration and ring closure is 0%.
  • the imidization degree of each polymer is determined by dissolving the polymer in deuterated dimethyl sulfoxide, subjecting the resulting solution to H-NMR
  • a 1 Peak area based on protons of NH groups (in the vicinity of 10ppm)
  • a 2 Peak area based of one proton of acrylate double bond (in the vicinity of 6.5 ppm).
  • B Proportion of the number of acrylate protons to one proton of NH group in the polymer precursor
  • the imidization degree is usually in the range of 1 to 99%, preferably 5 to 50%, more preferably 10 to 40%.
  • the cyclisation may be conducted subsequent to the poly-condensation with thermal removal of water under formation of a polyimide.
  • a further preferred embodiment of the invention relates to photoalignment polymers comprising a photoreactive group, which is coumarine- and quinoline-groups as for example described in US 6,201 ,087 B1 , and are incorporated by reference herewith. More preferred are those of US 6,201 ,087, claims 1 -14, more preferred are those enumerated in examples 1 -10 in col. 10, line 6 - col. 31 , line 54;
  • a further preferred embodiment of the invention relates to photoalignment polymers comprising cyanostilbene-groups photoreactive groups, which are for example described in US7959990.
  • photoalignment polymers comprising at least one monomer or at least two monomers of the general formula (I)
  • a and B each independently are a ring system of 5 to 40 atoms, wherein each ring system includes at least one unsaturation directly connected via electron conjugation ( ⁇ - ⁇ bonding) to the double bond shown in formula (IV),
  • S 1 is a single covalent bond or a spacer unit
  • n 1 , 2 or 3;
  • G is a hydrogen atom, optionally substituted alkyl, or a polymerizable group
  • ring system A is 1 ,4-phenylene, which is unsubstituted or substituted with halogen, cyano and/or nitro
  • ring system B is 1 ,4-phenylene, which is unsubstituted or substituted with halogen, cyano and/or nitro, or pyrimidine-
  • X is different from -CN and -COO-alkyl having from 1 to 12 carbon atoms.
  • the present invention relates to a photoalignment composition within the meaning and preferences as described above and below comprising
  • the present invention relates to a photoalignment composition within the meaning and preferences as described above comprising
  • a further polymer not having a photoreactive group which is a polyamic acid, polyimide or a mixture thereof, which comprises at least one diamine (DX) and at least one tetracarboxylic acid dianhydride.
  • the amount of the photoalignment polymer is 0.5% - 50% by weight of the sum of weights of the photoalignment polymer and the polymer not having a photoreactive group, preferably 1 % to 25% by weight and most preferably 1 % to 20% by weight, and especially most preferably 1 % to 15% by weight, and more especially most preferably 1 % to 10% by weight.
  • diamine (DX) has the meaning of an organic diamine.
  • Diamine (DX) may be commercially available or is accessible by known methods.
  • the second amino group is accessible for example by substitution reaction.
  • the diamine (DX) is selected from the group of the following compounds:
  • T, Ti , T 2 and T3 are independently from each other hydrogen, a substituted or unsubstituted straight-chain or branched C-
  • U3, U3' and U3" are indepently from each other an integer from 0 to 2 ;
  • R5, R6 each independently from each other represents a hydrogen atom or C
  • Z 4 represents a substituted or unsubstituted straight-chain or branched Ci-C 20 alkylene group, in which one or more -CH 2 - group may independently from each other be replaced by a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group; and/or a heteroatom and/or by a bridging group; preferably Z 4 is unsubstituted or substituted straight-chain or branched C-
  • X 4 , X 5 > X 6 , X 7 , X 8 , X 9 , X 0 and X 1 1 are independently from each other a bridging group or a single bond; preferably wherein X ?
  • X 8 , X 9 and X 0 or X are independently from each other a single bond, -O-alkoxy-, such as -O-methylen-, methylen-O-; C-
  • X 1 0 is -SO-, -S0 2 -, -0-, -N(CH 3 )-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, 1 ,1 '-cyclohexyl,
  • X 9 and X are identical and are methylene, ethylen, propylene, butylen, pentylen, hexylen, a single bond or -0-;
  • n is an integer from 0 to 3, preferably, 0 or 1 ;
  • n is 0 than X 9 and X are identical and are methylene, ethylene, propylene, butylene, pentylene, hexylene, a single bond -0-; -S-, -C(CH 3 )2-, -C(CF 3 )2-; and
  • X 5 is a bridging group or a single bond, and X 7 is CH2, O, NH;
  • R 9 , R 10 , R 11 are hydrogen or C-
  • X 7 is CH 2 , O, NH
  • R and R 2 is hydrogen, or C-
  • X 5 and X 6 are independently from each other a single bond or Ci -Csrjalkyl, preferably Ci -C 6 alkyl, -COO- and -CONH-; -COO(Ci -C 6 alkylene)-, -CONH(Cr Cealkylene)-.
  • DX diamine
  • X 6 is a bridging group or a single bond, and is preferably for example -0-, -S- or substituted or unsubstituted, branced or straight-chain C-
  • n is an integer from 1 to 6
  • n i are an integer from 0 to 6
  • R 5 and R 6 are each independently from each other represents a hydrogen atom or
  • R , R 2 , R 3 and R 4 are indepently from each other hydrogen, or C-
  • DX especially more preferred diamine (DX) is selected from compounds as given below:
  • n is independently from each other 0 or 1 and
  • Ci-C 24 alkyl is preferably at least one CrC 6 alkyl, more preferably methyl, ethyl, propyl;
  • R 9 , R 0 are indepentenly from each other hydrogen or C-
  • X 4 and X 17 are indepentenly from each other a bridging group or a single bond, and is preferably for example -0-, -S- or substituted or unsubstituted, branched or straight- chain Ci -C 6 alkylen, -0(CH 2 CH 2 0) n -; -0-(Ci -Ci 2 alkyl) n -0-, -S-(Ci -Ci 2 alkyl) n -S-, triazine, 1 ,3,5-triazinane-2,4,6-trione, 1 ,1 '-cyclohexylene, NR 5 ((C-
  • n is an integer from 1 to 6
  • n i are an integer from 0 to 6
  • R 5 and R 6 are each independently from each other represents a hydrogen atom or Ci-C 6 alkyl
  • 4,4'-diaminodiphenyl 4,4'-diaminodiphenyl-3,3'-dimethoxy, 4,4'-diaminodiphenyl-3,3'- dimethyl, 4,4'-diaminodiphenyl-3,3'-dihydroxy, 4,4'-diamino-diphenylmethane, 4,4'- diaminodi-phenylsulfide, 4,4'-diamino-diphenylsulfone, 4,4'-diaminodiphenylcarbonyl, 4,4'-diaminodiphenyl oxomethylene, 4,4'-diaminodiphenyl-bis(trifluoromethyl)- methylene,
  • DX diamines
  • n is 0 or 1
  • X 9 and X 0 or X have the above given meanings and preferences
  • diamine (DX) are those as enclosed by reference are diamines as described in EP-A-1 ,818,354 on page 10, lines 48 to 58 and on page 1 1 , lines 1 to 19.
  • X 6 has the meaning and preferences as given above, and is preferably for examplea single bomd, -0-, -S- or substituted or unsubstituted C-
  • n is an integer from 1 to 6
  • n i are an integer from 0 to 6
  • R , R 2 , R 3 and R 4 have indepently from each other the same meanings and preferences as given above, preferably X 6 is a single bond, -0-, -CH 2 -.
  • X 6 , R and R 2 are independently from each other have the same meaning as given above, and R and R 2 are preferably hydrogen, C-
  • the present invention also refers to a
  • photoalignment composition within the given description and preferences, which in addition comprises d) at least one further solvent.
  • the solvent or solvent mixture used in the present application may be any solvent that can dissolve the composition according to the invention.
  • the at least one further solvent is a polar solvent or a nonpolar solvent.
  • the solvents which are particularly preferred are those leading to a good coatability or printability of the photo- alignment composition to the substrate such as glass.
  • Non-polar solvents have low dielectric constants and are not miscible with water, such as for example hexane, benzene, toluene, diethyl ether, chloroform, ethyl acetate, dichloromethane, chlorobenzene.
  • Preferred polar solvent is an aprotic or protic polar solvent.
  • Polar aprotic solvents are solvents that share ion dissolving power with protic solvents but lack an acidic hydrogen. These solvents generally have high dielectric constants and high polarity. Examples are 1 ,4-dioxane, tetrahydrofuran (THF), acetone, acetonitrile (MeCN), N, N-dimethylformamide (DMF), ⁇ , ⁇ -dimethylacetamide , dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N- vinylpyrrolidone, tetramethylurea, hexamethylphosphoric acid triamide, gamma.- butyrolactone (BL), N-methylmorpholine, acetonitrile, ethylcarbitol acetate, ethylene glycol, propylene glycol diacetate, dipropylene glycol, chlorobenzene, tetrahydro
  • aprotic solvent is N-methylpyrrolidone (NMP), N- ethylpyrrolidone (NEP), diethylene glycol diethyl ether, ethylethoxy propionate or gamma.-butyrolactone (BL) or mixtures thereof.
  • NMP N-methylpyrrolidone
  • NMP N- methylpyrrolidone
  • Polar protic solvents are solvents, which contain dissociable H+, such as hydrogen fluoride, are called a protic solvent. The molecules of such solvents can donate an H+ (proton). Conversely, aprotic solvents cannot donate hydrogen bonds.
  • protic solvents are to display hydrogen bonding, to have an acidic hydrogen (although they may be very weak acids), to be able to stabilize ions (cations by unshared free electron pairs, anions by hydrogen bonding).
  • Examples are acetic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol, formic acid, 2- butoxyethanol (BC), ethylcarbitol, butylcarbitol, ethylene glycol, propylene glycol monoacetate, dipropylene glycol monomethyl ether and water.
  • Preferred polar protic solvent is 2-butoxyethanol (BC).
  • Preferred further solvents are gamma.-butyrolactone (BL), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), 2-butoxyethanol (BC), diethylene glycol diethyl ether, ethylethoxy propionate, N-vinylpyrrolidone, ⁇ , ⁇ -dimethylacetamide, N,N- dimethylformamide, ethylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol, propylene glycol monoacetate, propylene glycol diacetate, dipropylene glycol, and dipropylene glycol monomethyl ether, chlorobenzene, tetrahydrofuran, N- methylpyrrolidone (NMP), butylcellosolve, cyclopentanone (CP), methylethylketone (MEK), ethyl
  • More preferred solvents are gamma.-butyrolactone (BL), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N-vinylpyrrolidone, ⁇ , ⁇ -dimethylacetamide, N,N-dimethyl- formamide, ethylcellosolve, methylethylketone (MEK), diethylene glycol diethyl ether, ethylethoxy propionate, cyclohexanone (CHN), 2-butoxyethanol, (BC) butylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol, propylene glycol monoacetate, propylene glycol diacetate, dipropylene glycol, and dipropylene glycol monomethyl ether, chlorobenzene, tetrahydrofuran, and mixtures thereof.
  • BL gamma.-
  • MEK methylethylketone
  • CHN cyclohexanone
  • BL butyrolactone
  • NMP N-methylpyrrolidone
  • diethylene glycol diethyl ether diethylene glycol diethyl ether
  • ethylethoxy propionate N-ethylpyrrolidone
  • BC 2- butoxyethanol
  • butyrolactone (BL), N-methylpyrrolidone (NMP), N- ethylpyrrolidone (NEP), diethylene glycol diethyl ether, ethylethoxy propionate , dimethylformamide and/or 2-butoxyethanol (BC) and more esepcially N- methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), dimethylformamide and/or 2- butoxyethanol (BC) and mixtures thereof.
  • NMP N-methylpyrrolidone
  • NEP N-ethylpyrrolidone
  • BC 2- butoxyethanol
  • a further embodiment of the present invention relates to a photoalignment composition within the meanings and preferences as given above comprising in addition at least one aprotic polar solvent, preferably two aprotic polar solvents, more preferably at least one solvent is selected from is N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP) and most preferably two aprotic solvents which are N-methylpyrrolidone (NMP) and 2-butoxyethanol (BC) or N-ethylpyrrolidone (NEP) and 2-butoxyethanol (BC).
  • NMP N-methylpyrrolidone
  • NEP N-ethylpyrrolidone
  • BC 2-butoxyethanol
  • BC N-ethylpyrrolidone
  • BC N-butoxyethanol
  • a more preferred embodiment of the present invention relates to a method for the manufacturing of uniform and defect free liquid crystal aligning layers by applying onto a substrate a photoalignment composition of the present invention within the meaning and preferences as described above, preferably having a viscosity in the range of 1 to 100 mPa.s, more preferably in the range of 1 to 50 mPa.s and even more preferably in the range from 10 to 40 mPa.s for Offset printing and 4 to 15 mPa.s for Inkjet priting, and most preferably in the range of 15 to 40 mPa.s for Offset printing;and 4 to 10 mPa.s for Inkjet printing, which comprises in addition at least one solvent, which is selected from the group of solvents as following:
  • butyrolactone (BL), N-methylpyrrolidone (NMP), N-Ethylpyrrolidone (NEP),
  • the amount of solvent (I) and optionally further solvents in the composition of the present invention is in the range of 99-70% by weight, preferably 99-80% by weight and more preferably 99 to 90% by weight.
  • the sum of all weight ratios of all components including solvents of the photoalignment composition of the present invention is 100%.
  • the photoalignment composition of the present invention may further comprise surfactants.
  • Surfactants are chemicals that have a tendency to adsorb physically at a surface or interface, thereby altering the energy relationship at the interface. Thereby surfactants change the surface tension.
  • Suitable surfactants are wetting-, or levelling-, blocking-, scratch-, slip-, mar- or abrasion-restistant-; deaerating-, defoaming-, hydrophobing-, dispersing-,
  • wetting-, dispersing-, levelling-, blocking- scratch-restistant-agents are more preferred.
  • surfactants wetting-, dispersing-, levelling- agents are especially most preferred.
  • wetting- and levelling agents are especially most preferred.
  • the surfactants with the above cited properties are well known in the art.
  • the surfactants are non-polymeric or polymeric; reactive or non-reactive, saturated or unsaturated; non-ionic, amphotheric; anionic or cationic compounds.
  • reactive has the meaning of crosslinkable, polymerisable or dimerisable.
  • Preferred surfactants are polymeric and crosslinkable, polymerisable or dimerisable.
  • Amphoteric are for example alkyl ampho(di)acetates, amido betaines or
  • alky I betaines are for example alkyl dimethylamines, alkyl amidopropylamines, alkyl imidazoline derivatives, quaternised amine ethoxylates, quaternary ammonium compounds;
  • sufactants which are polymers are homo- or copolymers (block, statistic, grafted, branched) or un reactive or reactive, such as crosslinkable, polymerisable or dimerisable surfactants. Most preferred are reactive, such as crosslinkable surfactants.
  • non-polymeric surfactants are organic sulphonate derivatives, such as alkyl phenol ether sulphates, alpha olefin sulphonates, aromatic hydrocarbon sulphonic acids, salts and blends, naphthalene sulphonates, condensed naphthalene
  • sulphonates fatty alcohol sulphates, di-alkyl sulpho-succinates, mono-alkyl sulphosuccinates, alkyl sulphosuccinamates, di-alkyl sulphosuccinates, lecithine derivates such as sojalecithine; tenside derivates, such as cationic, anionic or amphoteric tensides especially fatty acid ester derivatives; carbonic acid ester or ether derivates, such as hydroxyfunctional carbonic acid ester or ether derivates, alkyl ether phosphates, alkyl ether carboxylic acids and salts, alkyl ether sulphates; alkyl phosphates, alkyl benzene sulphonic acids and salts, alkyl phenol ether phosphates, alkyl phenol ether sulphates, aromatic hydrocarbon sulphonic acids, salts and blends.
  • Preferred non-polymeric surfactants are carbonic acid ester or ether derivates, especially, Disperbyk®-108.
  • polymeric surfactants are for example organic polymers, such as amide polymers, imide polymers, polyurethane, silicon/siloxane polymers, fluoro polymers or acrylate polymers, polyether polycarbonic acid structure (also containing organo- modified polysiloxane or an amine derivative), or non-ionic dispersing polymers.
  • Organic polymer surfactants are for example hydrocarbon surfactants, such as solvent blend of high-boiling aromatics, ketones and esters, or fame (Fatty Acid Modified Emulsifiers).
  • Fame is based upon fatty acid chemistry, having polar heads based on tertiary amines, such as for example fatty acid modified polyester, aliphatic polyether with acidic groups, solution of fatty acid modified, polyester in water.
  • tertiary amines such as for example fatty acid modified polyester, aliphatic polyether with acidic groups, solution of fatty acid modified, polyester in water.
  • Silicon/siloxane polymers are for example reactive or non-reactive polysiloxane, such as
  • silicone acrylate Fluoro polymers are for example
  • Non-ionic dispersing polymers are for example amine oxides
  • Preferred polymeric surfactants are non-ionic polymeric surfactants, especially silicone or siloxane polymers and most preferred is silicone acrylate, especially, Tego®Rad 2500.
  • a further preferred embodiment of the present invention concerns compositions of 2 or more than 2 surfactants.
  • Typical suppliers for surfactants having wetting and levelling properties are for example ADD APT, Air Products, Akzo-Nobel, Akzo-Nobel Cellulosic Specialities, BASF, Borchers, BYK Chemie, Ciba Specialty Chemicals, Cognis, Condea Servo, Degussa-Goldschmidt, Dexter Chemical, Dow Chemical, Dow Corning, DuPont, Elementis, GE Silicones, International Speciality Product, Rhodia, Tego, Tiarco Chemical, Troy, UCB Chemical, Ultra Additive, Worlee, 3M, Additek, C. P. Hall, Cytec, Efka Additives, Hercules, Liaoyang Huaxing Chemical, Polyvel, R. T. Vanderbilt, Sovereign Chemical, Stepan, Tiarco Chemical, Sachtleben, Rhodia, Raschig, Potters Ballotini.
  • Tego® Colorol Tego® Dispers
  • Tego® Lipotin Tego® Twin
  • Tego® Wet Rewopol®
  • Tego® Surten Tego®Rad, Tego®Glide
  • Tegomer® Tego®Flow
  • Tego®Flow such as Tego®Flow 300, Tego® Colorol E, Tego® Colorol F , Tego® Colorol Standard
  • Tego® Dispers 655 Tego® Dispers 660 C , Tego® Dispers 661 C, Tego® Dispers 662 C ,Tego® Dispers 680 UV , Tego® Dispers 681 UV, Tego® Lipotin A , Tego® Lipotin BL, Tego® Lipotin DB, Tego® Lipotin SB, Tego® Twin 4000 , Tego® Wet 250 , Tego® Wet 260 , Tego® Wet 265, Tego® Wet 270 , Tego® Wet 280
  • Rewoquat® W 75 Rewoteric® AM CAS , Tego® Surten W 1 1 1 , Tego® Surten W 125 , Tego® Surten W 130 , Tego® Surten W 133 , Tego® Surten W 5840 , Tego® Surten W 5878, Tego®Rad 2100, Tego®Rad 2200 N, Tego®Rad 2250, Tego®Rad 2300, Tego®Rad 2500, Tego®Rad 2600, Tego®Rad 2700, Tego®Glide 130,
  • Tego®Glide 406 Tego®Glide 410, Tego®Glide 41 1 , Tego®Glide 415, Tego®Glide 420, Tego®Glide 432, Tego®Glide 435, Tego®Glide 440, Tego®Glide 450,
  • Tego®Glide 482 Tego®Glide A 1 15, Tego®Glide B 1484, Tego®Glide ZG 400, Tego®Flow 300, Tegomer® CSi 2342, Tegomer® D 3403, Tegomer® E-si.
  • Tegomer® ESi 2330 Tegomer® HSi 231 1 , Tegomer® VSi 2250.
  • Efka available EFKA 3033 , EFKA 3034, EFKA 3232 , EFKA 3277, EFKA 3299, EFKA 3883, EFKA 6903, EFKA 6906, EFKA 3522 , EFKA 5010 , EFKA 5044 , EFKA 5054 , EFKA 5055 , EFKA 5063, EFKA , EFKA 5066 , EFKA , EFKA 5207, EFKA 5244 , Efka® 3500, Efka® 3600 , Efka® 3650 , Efka® 4590 , EFKA® 5065 , EFKA® 5070, Efka® 6225, Efka® 6230 , Efka® , Efka® 731 1 , Efka® 7315, Efka® 7316 , Efka® 7340 , Efka® 7361 , Efka® 7375 , Efka® 7381
  • Byk® additives such as Byk® 307, Byk® 333, Byk® 9075, Byk® 9076, Byk® 9077, Byk® 935, Byk® 961 , Byk® A 560, Byk® W 909, BYKOPLAST® 1000 , Disperplast 101 1 , Byk® S 706, Byk® W 909, Aquacer® 840, Byk® -077, Byk® -085, Byk® -315, Byk® -320, Byk® -321 , Byk® -322, Byk® -323 , Byk® -325 , Byk® - 336 , Byk® -340 , Byk® -345 , Byk® -346 , Byk® -347 , Byk® -348 , Byk® -352 , Byk® -353, Byk® -354 , Byk® -355 , Byk® -356, Byk® additives such as By
  • surfactants are Tego®Flow 300, Tego®Rad 2600, Tegomer® E-si, Tego®Rad 2700, EFKA-3883, EFKA 6903, EFKA 6906, EFKA 3299, Tego®Rad 2500 a polydimethylsiloxane and Disperbyk® -108 a hydroxyl functionalized carbonic ester with pigment affine groups.
  • Especially most preferred surfactants are Tego®Flow 300, Tego®Rad 2500 and Disperbyk® -108.
  • substrate describes a base material on which a process is conducted which produces one or more layers or films on a part of or on the complete surface of the base material.
  • the substrate can consist of any type of solid material as e.g. glass, metals, polymer films or composite materials. Not necessarily, but in most cases substrates are applied in the shape of slabs, either individually cut pieces or in case of flexible base materials also rolled up into a cylinder shape.
  • the present invention relates to the photoalignment composition within the meanings and preferences as given above and in addition comprising a surfactant in the solvent in the range of between 1 and 99%, preferred between 1 and 20%, more preferred between 1 and 10% by weight.
  • the amount of the surfactants in the composition is determined according to the wished performances in respect of mechanical and thermal stability, and of optical and electro-optical performances.
  • a further preferred embodiment the present invention relates to a method, wherein the addition level of the surfactant on the liquid crystal photoalignment material is below 20%, preferably between 0.01 and 10%, more preferably between 0.1 and 5% by weight and most preferably between 0.1 and 1 % per weight.
  • the present invention relates to a photoalignment composition
  • a photoalignment composition comprising in addition a surfactant, wherein the latter does not have any negative impact on the Voltage Holding Ratio (VHR), Residual DC (RDC) or AC Memory (ACM).
  • VHR Voltage Holding Ratio
  • RDC Residual DC
  • ACM AC Memory
  • VHR, ACM and RDC are commonly known values in the technical field of liquid crystal displays and will be described as following:
  • VHR voltage holding ratio
  • RDC ResidualDirectCurrent
  • the external DC-voltage for which the flicker is eliminated or minimized by compensation of the internal residual DC-voltage is taken to be equivalent to the internal residual DC-voltage.
  • non-ionic surfactants not having any negative impact on Voltage Holding Ratio (VHR), Residual DC (RDC) or AC Memory (ACM) are non-ionic surfactants.
  • VHR Voltage Holding Ratio
  • RDC Residual DC
  • ACM AC Memory
  • a further preferred embodiment of the present invention relates to a method for the preparation of liquid crystal aligning layers, comprising applying a photoalignment composition as described above with all described preferences to a substrate by printing or coating.
  • the composition is applied onto a substrate optionally coated with an electrode [for example a glass plate coated with indium-tin oxide (ITO)] so that homogeneous layers of 0.05 to 100 ⁇ thickness are produced.
  • ITO indium-tin oxide
  • a further preferred embodiment of the present invention relates to a method as described above and all described preferences of the method, for the preparation of uniform and defect free liquid crystal aligning layers having a thickness of ⁇ 300 nm, preferably ⁇ 250 nm, more preferably from ⁇ 200 nm; and preferably, wherein the liquid crystal photoalignment material is a polymer comprising diamine (I) and tetracarboxylic acid anhydride as described above, and with all preferences described above.
  • Coating methods are for example spin coating, air doctor coating, blade coating, knife coating, reverse-roll coating, transfer roll coating, gravure roll coating, kiss roll coating, cast coating, spray coating, spin-coating, meniscus-coating, wire-coating, slot-orifice coating, calendar coating, electro-deposition coating, dip coating or die coating.
  • Printing methods are for example ink-jet-printing, direct-printing, relief printing such as flexographic printing, intaglio printing such as direct gravure printing or offset gravure printing, lithographic printing such as offset printing, or stencil printing such as screen printing, flexographic-printing or planographic-printing.
  • indirect printing such as offset printing
  • planographic printing such as lithography; relief printing, intaglio printing and ink-jet printing, and
  • a further more preferred embodiment of the present invention relates to a method as described above and all described preferences of the method, comprising a composition which is applied to a substrate by printing, preferably by indirect printing, such as offset printing;
  • planographic printing such as lithography; relief printing, intaglio printing;
  • flexographic printing more preferably by ink-jet printing.
  • the liquid crystal photoalignment material with aligning light.
  • the regions, which should be aligned are irradiated, for example, with a high-pressure mercury vapour lamp, a xenon lamp or a pulsed UV laser, using a polarizer and optionally a mask for creating images of structures. Further, it is possible to vary the direction of orientation and the tilt angle within the liquid crystal aligning layer by controlling the polarization plane and/or the irradiance direction of the irradiation of the aligning light. It is understood that by selectively irradiating specific regions of the liquid crystal aligning layer very specific regions of the layer can be aligned. In this way, layers with a defined tilt angle can be provided. The induced orientation and tilt angle are retained in the liquid crystal aligning layer by the process, especially by the process of crosslinking.
  • the treatment with aligning light may be conducted in a single step or in several separate steps. In a preferred embodiment of the invention the treatment with aligning light is conducted in a single step.
  • the incidence direction of the aligning light may be normal to the substrate or at any oblique angle.
  • the aligning light is exposed from oblique angles. Further preferred methods of the invention relate to
  • the present invention relates to the use of a liquid crystal aligning layer comprising a photoalignment composition as described in the present invention within the given meanings and all preferences, and as prepared according to a method of, the present invention for aligning liquid crystals.
  • a further embodiment of the present invention relates to a liquid crystal aligning layer obtainable by a method to the present invention.
  • the invention relates to a liquid crystal aligning layer comprising a photoalignment composition according to the present invention in a cross-linked and/or isomerized form.
  • a further preferred embodiment of the present invention relates to a liquid crystal aligning layer having a thickness of ⁇ 300 nm, preferably ⁇ 250 nm, more preferably ⁇ 200 nm.
  • the liquid crystal aligning layer can be used in the manufacture of unstructured or structured optical-or electro-optical elements, preferably in the production of hybrid layer elements.
  • transparent support such as glass or plastic substrates, optionally coated with indium tin oxide (ITO) are used.
  • ITO indium tin oxide
  • the direction of orientation and the tilt angle within the liquid crystal aligning layer by controlling the direction of the irradiation of the aligning light. It is understood that by selectively irradiating specific regions of the polymer or oligomer layer very specific regions of the layer can be aligned. In this way, layers with a defined tilt angle can be provided. The induced orientation and tilt angle are retained in the liquid crystal aligning layer by the process, especially by the process of cross- linking.
  • the present invention relates to a method, wherein imidisation is carried out prior or after the application of the polymer, copolymer or oligomer to a support.
  • liquid crystal aligning layer of the present invention can also be used in form of a polymer gel, a polymer network, a polymer film, etc..
  • the liquid crystal aligning layer can be used in the manufacture of unstructured or structured optical-or electro-optical elements, preferably in the production of hybrid layer elements.
  • the present invention relates to a method for the preparation of a liquid crystal aligning layer, wherein the photoalignment composition according to the present invention is applied to a support, and subsequent evaporation of the solvent, and wherein, after any imidisation step which may be necessary, the polymer or oligomer or polymer mixture or oligomer mixture treated with aligning light, and preferably isomerized and/or cross-linked by irradiation with aligning light.
  • a preferred method of the present invention relates to a method, wherein the direction of orientation and the tilt angle within the liquid crystal aligning layer is varied by controlling the direction of the irradiation with aligning light, and/or wherein by selectively irradiating specific regions of the polymer layer or oligomer layer specific regions of the layer are aligned.
  • the liquid crystal aligning layer are suitably prepared from a solution of the polymer or oligomer material.
  • the polymer or oligomer solution is applied to a support optionally coated with an electrode [for example a glass plate coated with indium-tin oxide (ITO)].
  • ITO indium-tin oxide
  • different coating techniques like spin-coating, meniscus-coating, wire-coating, slot-coating, offset-printing, flexo-printing, gravur-printing may be used.
  • the regions to be oriented are irradiated, for example, with a high-pressure mercury vapour lamp, a xenon lamp or a pulsed UV laser, using a polarizer and optionally a mask for creating images of structures.
  • the present invention relates to the use of a liquid crystal aligning layer according to the present invention, preferably in cross-linked form, as an orientation layer for liquid crystals. Further, the present invention relates to preferably the use of a liquid crystal aligning layer for the induction of vertical or planar alignment of adjacent liquid crystalline layers, in particular for operating a cell in MVA mode.
  • the irradiation time is dependent upon the output of the individual lamps and can vary from a few seconds to several hours.
  • the photo-reaction can also be carried out, however, by irradiation of the homogeneous layer using filters that, for example, allow only the radiation suitable for the cross- linking reaction to pass through.
  • liquid crystal aligning layer of the invention may be used in the production of optical or electro-optical devices having at least one orientation layer as well as unstructured and structured optical elements and multi-layer systems.
  • the present invention relates to the use of a liquid crystal aligning layer for the orientation of liquid crystals.
  • Preferred is the use for the induction of vertical alignment of adjacent liquid crystalline layers.
  • a further embodiment of the invention relates to an optical or electro-optical device comprising a photoalignment layer according to the present invention, preferably in a cross-linked form.
  • the electro-optical devices may comprise more than one layer, preferably there are two layers.
  • the layer or each of the layers may contain one or more regions of different spatial orientation.
  • a further embodiment of the present invention relates to optical and electro-optical unstructured or structured constructional elements, preferably liquid crystal display cells, multi-layer and hybrid layer elements, comprising at least one liquid crystal aligning layer as described above. Further, the present invention relates to preferably the use of a liquid crystal aligning layer for the induction of vertical alignment of adjacent liquid crystalline layers, in particular for operating a cell in MVA mode. Preferred is the use of the liquid crystal aligning layer for the induction of vertical alignment or planar alignment of adjacent liquid crystalline layers.
  • a further preferred embodiment of the invention relates to an optical or electro-optical device comprising one or more liquid crystal aligning layers.
  • the electro-optical devices may comprise more than one layer.
  • the layer or each of the layers may contain one or more regions of different spatial orientation.
  • the present invention concerns an optical and electro-optical unstructured or structured constructional elements, preferably liquid crystal display cells, multi-layer and hybrid layer elements, comprising at least one liquid crystal aligning layer, such as a polymer layer, copolymer or oligomer layer according to the present invention.
  • An optical component, system or device creates, manipulates, or measures electromagnetic radiation.
  • An electro-optical component, system or device operates by modification of the optical properties of a material by an electric field. Thus it concerns the interaction between the electromagnetic (optical) and the electrical (electronic) states of materials.
  • the optical or electro-optical component can be used for (but are not limited to) a waveguide, a security or brand protection element, a bar code, an optical grating, a filter, a retarder, a compensation film, a reflectively polarizing film, an absorptive polarizing film, an anisotropically scattering film compensator and retardation film, a twisted retarder film, a cholesteric liquid crystal film, a guest-host liquid crystal film, a monomer corrugated film, a smectic liquid crystal film, a polarizer, a piezoelectric cell, a thin film exhibiting non-linear optical properties, a decorative optical element, a brightness enhancement film, a component for wavelength-band-selective compensation, a component for multi-domain compensation, a component of multiview liquid crystal displays, an achromatic retarder, a polarization state correction / adjustment film, a component of optical or electro-optical sensors, a component of brightness enhancement film, a
  • IBIB Isobutyl isobutyrate (cas: 97-85-8)
  • Polymer formed was characterized through its intrinsec viscosity and NMR data. In NMR, some representative signals could be seen. The integration is given as relative values.
  • Polyamic acid 2 is obtained in the form of a white powder with an inherent viscosity [ ⁇ ] of 0.33dL/g.
  • Polyamic acid 3 is obtained in the form of a white powder with an inherent viscosity [ ⁇ ] of 0.37dL/g.
  • Polyamic acid 4 is obtained in the form of a white powder with an inherent viscosity [ ⁇ ] of 0.56dL/g.
  • Formulation 3 1 1 .65 g of a 30% solution of Polyamic acid 2 in NMP are added to 157.52 g of a 20% solution of Polyamic acid 4 in NMP. 144.85 g of NMP and 139.6 g of BC and 46.52 g of IBIB are added. The mixture is stirred during 30 minutes and filtrated on 0.2 ⁇ PTFE- filter to give Formulation 3.
  • Offset Printing is processed on a Nakan E-400 MIZ with the following parameters:
  • coated substrates are dried on a hot plate at 80 'C for 1 .5 minutes followed by 40 minutes at 200 °C.
  • Substrates used for testing are:
  • the coating quality is controlled and summarized in the following table, with surface aspect quality being noted from 1 to 4 respectively equivalent to "very good, no defect”, “light mura, few defects", “mura, defects” and “mura, defects overall the surface”;
  • levelling being noted from 1 to 4 respectively equivalent to " very good”, “good”, “poor” and very poor, whereby bad levelling also means de-wetting where some uncoated area can be observed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Liquid Crystal (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a photoalignment composition comprising at least a single photoalignment polymer, preferably a homo- or a copolymer having at least one photoreactive group; and at least a single solvent of formula (I) (R-CO-O-R'), wherein R and R' are independently from each other straigt-chain or branched alkyl chain, with the proviso that at least one alkyl chain is branched. Further, the present invention relates to the use of this composition for coating or printing, especially for printing, more especially for inkjet or offset printing processes, and most especially for an offset printing process. In addition, the present invention relates to the use of the photoalignment composition for the preparation of orientation layers for liquid crystals and in the construction of unstructured and structured optical elements and multi-layer systems, especially liquid crystal displays, LCDs.

Description

Photoalignment composition
The invention relates to a photoalignment composition comprising at least a single photoalignment polymer, preferably a homo- or a copolymer having at least one photoreactive group; and at least a single solvent of formula (I)
(R-CO-O-R'),
wherein R and R' are independently from each other straigt-chain or branched alkyl chain, with the proviso that at least one alkyl chain is branched.
Further, the present invention relates to the use of this composition for coating or printing, especially for printing, more especially for inkjet or offset printing processes, and most especially for an offset printing process. In addition, the present invention relates to the use of the photoalignment composition for the preparation of liquid crystal aligning layers and in the construction of unstructured and structured optical elements and multi-layer systems, especially liquid crystal displays, LCDs.
In general photoalignment materials are applied by two main techniques, the coating and printing.
Coating methods are for example spin coating, air doctor coating, blade coating, knife coating, reverse-roll coating, transfer roll coating, gravure roll coating, kiss roll coating, cast coating, spray coating, slot-orifice coating, calendar coating, electrodepositing coating, dip coating or die coating.
Printing methods are for example relief printing such as flexographic printing, intaglio printing such as direct gravure printing or offset gravure printing, lithographic printing such as offset printing, or stencil printing such as screen printing.
In general, there are five major printing processes which are distinguished by the method of image transfer and by the general type of image carrier employed.
Depending upon the process, the printed image is transferred to the substrate either directly or indirectly. In direct printing the image is transferred directly from the image carrier to the substrate, examples of direct printing are gravure, flexography, screen printing and letterpress printing processes. In indirect, or offset, printing, the image is first transferred from the image carrier to the blanket cylinder and then to the substrate. Lithography, currently the dominant printing technology, is an indirect (offset) process.
Image carriers (or plates) can generally be classified as one of four types: relief, planographic, intaglio, or screen. In relief printing, the image or printing area is raised above the no image areas. Of the five major printing processes, those relying on relief printing are letterpress and flexography. In planographic printing, the image and no image areas are on the same plane. The image and no image areas are defined by differing physiochemical properties. Lithography is a planographic process. In the intaglio process, the nonprinting area is at a common surface level with the substrate while the printing area, consisting of minute etched or engraved wells of differing depth and/or size, is recessed. Gravure is an intaglio process. In the screen process (also known as porous printing), the image is transferred to the substrate by pushing ink through a porous mesh which carries the pictorial or typographic image.
Inkjet printing represents a further established and strongly growing industrial image deposition process which is also called printing despite its quite different character (e.g. its lack of an image carrier) in comparison to the above described conventional printing processes. Inkjet printers may operate either in continuous or drop-on-demand (DOD) mode. In continuous-mode, the fluid is pumped through a nozzle to form a liquid jet. Uniformly spaced and sized droplets are obtained by imposing a periodic perturbation, leading to surface-tension driven jet break-up. This requires the fluid to have certain conductivity. Drop-on-demand is the method of choice for many industrial applications such as electronics and displays. This is mainly because of its smaller drop size, higher accuracy and no need to use dopants to make the fluid more conductive. An acoustic pulse ejects fluid droplets from a reservoir through a nozzle. The pulse can be generated either thermally (Bubble-jet) or piezo-electrically (piezo- jet). Piezo-electric DOD is generally more suited to a variety of solvents. The most critical part of inkjet printing technology is probably the fluid and its physical properties. The fluid parameters should be on one hand optimised to get reliable droplet formation during printing with specific printer (such as viscosity and surface tension). The fluid should be also optimised in order to get good wetting properties, with specific substrates, and homogeneous films.
Flexographic technology is successfully used to apply liquid crystal aligning layers in the LCD industry. According to the flexographic technology, the liquid crystal aligning layers can be directly printed in a predetermined pattern without requiring any etching process. Generally described, the flexographic process can be a substantially continuous process which uses a series of rollers to transfer a quantity of alignment material as a predetermined pattern onto the desired surface of substrate (typically glass). Stated differently, the flexographic apparatus can be configured to
automatically convey a plurality of glass panels sequentially through the process. The apparatus employs a special resin plate with a series of holding cells configured in a predetermined pattern to hold a quantity of alignment material processing solution. The resin plate is rotated and subsequently brought into direct contact with the glass panel surface to release the solution and transfer the predetermined pattern to form the liquid crystal aligning layers onto the surface. The glass panel is then heated to pre-cure the liquid crystal aligning layers.
In more detail the fabrication of a liquid crystal aligning layer by means of flexographic printing is described in the following. The alignment material solution is dropped and maintained on a so-called anilox roll. The anilox roll is preferably plated with chrome, or chrome and nickel (the alignment material solution contacting surface). Cells having a pyramid shape are formed in the anilox roll to a depth of approximately 20 μηι so that the alignment material can be retained in the cells.
A doctor roll is rotated together with the anilox roll to help assure that the alignment material solution is evenly applyied on the surface of the anilox roll. A resin plate is attached to an underlying plate typically comprising copper. In a preferred
embodiment, the resin plate is formed from a polybutadiene resin, e.g., an Asahi Kasei photosensitive resin ("APR"). For ease of description, the resin plate will be described subsequently herein as an "APR plate".
The APR plate includes an exterior surface of predetermined patterns. The patterns include a plurality of cells as intaglios so that the alignment material solution can be accommodated in the cells. The depth of the cells is preferably in the range of approximately 15 to 20 μηι. Thus, in contrast to the above general description the flexographic printers for liquid crystal aligning layer application use an intaglio instead of a relief process. The alignment material solution is dispensed onto the anilox roll. The anilox roll and the doctor roll rotate and contact on an outer circumference portion. The contact pressure provided by the doctor roll helps the alignment material solution in the anilox roll (i.e., in the cells) to be uniformly distributed and to bring a certain quantity of the solution to fill the cell of the anilox roll. The APR plate then contacts the anilox roll and the alignment material solution is supplied or delivered to the APR plate. Typically, the amount of the alignment material solution transferred to the APR plate is determined by the contact force that the doctor roll exerts against the anilox roll (or the reverse). The alignment material solution is then held in the APR plate cells.
The LCD panel or glass is fixed to the print table. The table advances and the glass is moved forward at the same time that the copper plate holding the APR plate rotates. The APR plate thus directly contacts the glass substrate and the alignment material solution is applied to the glass from the cells of the patterns in the APR plate. As a result, an orientation layer is formed on the glass substrate.
There is an enormous demand of photoalignment compositions since these materials give access to very efficient and economic large scale manufacturing processes. However, their applicability, such as their printabilty is often not satisfying with the high industrial standards. Here are high quality standards required, such as even wetting properties; a desired thickness of the applyied layer, homogenty over the whole surface of the layer is required.
Therefore, is a constant need for photoalignment materials allowing good coatability or printability for the fabrication of thin liquid crystal aligning layers which fulfil the requirement of uniform defect free surfaces.
In the present invention the above-cited new photoalignment compositions were found which give access to improved printing processes.
Thus, the present invention relates to a photoalignment composition comprising
a) at least a single photoalignment polymer, preferably a homo- or a copolymer having at least one photoreactive group;
and c ) preferably a further polymer not having a photoreactive group, and b) at least a single solvent of formula (I)
(R-CO-O-R'),
wherein R and R' are independently from each other a straigt-chain alkyl; preferably a straigt-chain a branched d-C6alkyl chain ; more preferably a branched CrC6alkyl chain, most preferably a branched C3-,C4-,C5-,C6alkyl chain, especially most preferably a branched C4alkyl chain; with the proviso that at least one alkyl chain is branched.
Preferred is a photoalignment composition of the present invention, wherein R and R' are simoultaneaously a branched alkyl chain.
In the context of the present invention the below given wordings have the given meanings and preferences as given below:
- "polymer" has the meaning of e.g. homopolymer, copolymer, graft polymer, block polymer, hyper branched polymer or oligomer; preferably has the meaning of polymer or copolymer;
preferred "polymer" of the present invention comprises a backbone, which is not particularly limited, and is represented for example by polyamic acid, partially imidised polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polysiloxane, polymaleinimide, polyacrylate, polyvinyl, cellulose derivative, polyacetal, polyurea, polyurethane, polystyrene derivative, poly(styrene-phenyl- maleimide)-derivative and poly(meth)acrylate, cyclo olefin polymer or a mixture thereof. More preferred "polymer" is a polyamic acid, partially imidised polyamic acid, polyimide, polyamic acid ester, polysiloxane derivative or mixtures thereof; polyamic acid, partially imidised polyamic acid, polyimide and mixtures thereof are most preferred and especially most prefered is polyamic acid.
- "coating" has the meaning of e.g. coating techniques like for example spin-coating, meniscus-coating, wire-coating, slot-coating, printing, such as offset-printing, flexo- printing, gravur-printing, especially of inkjet or offset printing;
- "photoalignment polymer" has the meaning of an organic polymer, copolymer or oligomer comprising photoreactive groups, which are able to undergo photoreaction after radiation with aligning light.
- "aligning light" has the meaning of light of wavelengths, which can initiate
photoalignment. Preferably, the wavelengths are in the UV-A, UVB and/or UV/C- range, or in the visible range. It depends on the photoalignment compound, which wavelengths are appropriate. Preferably, the photo-reactive groups are sensitive to visible and/or UV light. More preferably, aligning light is at least partially linearly polarized, elliptically polarized, such as for example circularly polarized, or nonpolarized, most preferably circiulary polarized, or non-polarized light exposed obliquely, or at least partially linearly polarized light. Especially, most preferred aligning light denotes substantially polarised light, especially linearly polarised light; or aligning light denotes non-polarised light, which is applied by an oblique irradiation.
"aligning group exhibiting a property of controlling alignment of liquid crystal molecules without photo-irradiation" has the meaning of an organic group which is able to align liquid crsytals, preferably homeotropically or planarly align liquid crystals.
Examples of such aligning groups are an unsubstituted or substituted steroidal skeleton such as a cholesterol group, which is uninterrupted or interrupted by at least a single heteroatom and/or at least a single bridging group, preferably, a cholesterol group is cholesteryl, cholestanyl, cholestan; or an aligning group is an unsubstituted or substituted organic chemical structure, which is, for example, 3 to 4 rings selected from any one of 1 ,4-cyclohexylene and 1 ,4-phenylene, which are linearly coupled e.g. directly or throuogh 1 ,2-ethylene, and which organic chemical structure is preferably composed of three or four pieces of 1 ,4-cyclohexylene, three or four pieces of 1 ,4-phenylene or is composed of both 1 ,4-cyclohexylene and 1 ,4- phenylene wherein the number of total piece thereof are 3 or 4 pieces;
substituents are for example straight chain or branched CrC30 alkyl.
"photo reactive group", has the meaning of an organic group which is able to undergo a reaction after irradiation with light. For examplea photoreactive group is able to make electrocyclic reactions, radical reactions, photoisomerization and Norrish reactions, and is e.g. dimerizable, decompositable, isomerizable, polymerizable and/or cross-linkable group;
more preferably the photoreactive group is a cinnamate-, coumarine-, quinoline-, azo-, stilbene-, cyanostilbene-, chalcone-, diphenylacetylene, benzylidene- phthalimidine, benzylideneacetophenone, phenylenediacryloyl, stilbazole and/or azo-group; most preferred are cinnamate-, coumarine-, quinoline-, cyanostilbene-, and/or chalcone-groups; especially most preferred are cinnamate- or cyanostilbene groups, and more especially cinnamate groups are preferred. "straigt-chain alkyl" has the meaning of example straigt-chain Ci-C40alkyl, especially straigt-chain CrC3oalkyl, preferably straigt-chain Ci-C24alkyl, more preferably straigt-chain d-C^alkyl, most preferably straigt-chain d-Ci0alkyl and especially most preferably straigt-chain CrC6alkyl, very especially most preferably methyl, ethyl, propyl, butyl, pentyl or hexyl;
straigt-chain CrCi0alkyl is for example methyl, ethyl, propyl, butyl, pentyl, hexyl, hepty, octyl, nonyl, decyl or undecyl;
straigt-chain CrCi6alkyl is for example methyl, ethyl, propyl, butyl, pentyl, hexyl, hepty, octyl, nonyl, decyl or undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl.
"branched alkyl chain" has the meaning of example branched C3-C40alkyl, especially branched C3-C3oalkyl, preferably branched C3-C20alkyl, more preferably branched C3-Ci6alkyl, most preferably branched C3-Ci0alkyl and especially most preferably branched C3-C6alkyl, which is branched C3-C4-C5-C6alkyl, very especially most preferably C3-C6alkyl isopropyl, sec-butyl, tert.-butyl, isopentyl, dimethyl propyl, or 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,2- dimethylbutane.
Branched C3-Ci0alkyl is for example isopropyl, sec-butyl, tert.-butyl, isopentyl, dimethyl propyl, or 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,2- dimethylbutane isoheptyl, isooctyl, isononyl, isodecyl.
Branched C3-Ci6alkyl is for example isopropyl, sec-butyl, tert.-butyl, isopentyl, dimethyl propyl, or 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,2- dimethylbutane, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl or isohexadecyl.
Branched C3-C20alkyl is for example isopropyl, sec-butyl, tert.-butyl, isopentyl, dimethyl propyl, or 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,2- dimethylbutane, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, isonondecyl, isoeicosyl.
Branched C3-C30alkyl is for example example isopropyl, sec-butyl, tert.-butyl, isopentyl, dimethyl propyl, or 2-methylpentane, 3-methylpentane, 2,3- dimethylbutane, 2,2-dimethylbutane, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, isonondecyl, isoeicosyl, isoheneicosyl, isotricosyl, isotetracosy, isopentacosyl, isohexacosdy, isoheptacosyl, isooctacosyl, isononacosy or isotriacontyl.
Branched C3-C40alkyl is for example isopropyl, sec-butyl, tert.-butyl, isopentyl, dimethyl propyl, or 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,2- dimethylbutane, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, isonondecyl, isoeicosyl, isoheneicosyl, isotricosyl, isotetracosy, isopentacosyl, isohexacosdy, isoheptacosyl, isooctacosyl, isononacosy or isotriacontyl or tetracontyl.
- "alkylen" if used as single term has the meaning of (C-| -C-| 2)alkylene, preferably d- C6alkylen, which is branched, straight-chain, substituted, unsubstituted,
uninterrupted or interrupted by a linking group, and an alicyclic group, such as cyclohexylen or a C17-C40 alicyclic group, or -Si(R3)2- or -0-Si(R3)2-, wherein R3 is CrC24alkylen is preferably at least one CrC6alkyl, more preferably methyl, ethyl, propyl.
- CrC6alkylen is for example methylene, ethylene, propylene, isopropylene, sec- butylene, ter.-butylene, pentylene, isopentylene, hexylene, isohexylene.
- Ci-C30alkyl is preferably Ci-C30alkyl, more preferably CrCi6alkyl, most preferably C Cealkyl and especially most preferrerd CrC6alkyl, which is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl. Ci-C30alkyl has the meaning of straigt-chain CrC30alkyl and branched C3-C30alkyl as described above within the all preferences given.
- "alicyclic group" has the meaning of an unsubstituted or substituted steroidal skeleton such as a cholesterol group, which is uninterrupted or interrupted by at least a single heteroatom and/or at least a single bridging group, preferably, a cholesterol group is cholesteryl, cholestanyl, cholestan; or "alicyclic group" has the meaning of an organic chemical structure, which is, for example, cyclohexylene, especially 1 ,4-cyclohexylene .
- "bridging group" has meaning of -0-, -CH(OH)-, -CO-, -CH2(CO)-, -SO-, -CH2(SO)-, -S02-, -CH2(S02)-, -COO-, -OCO-, -COCF2-, -CF2CO , -S-CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -0-CO-O, -CH2-CH2-, -OCH2-, -CH20-, -CH=CH-, -C≡C-,
-CH=CH-COO-, -OCO-CH=CH-, -CH=N-, -C(CH3)=N-, -N=N- or a single bond; or a cyclic, straight-chain or branched, substituted or unsubstituted CrC24alkylen, wherein one or more C-atom, -CH- and/or -CH2- group may independently from each other be replaced independently from each other by a linking group.
- "linkinig group" has meaning of -0-, -CO, -CO-O-, -O-CO-, , -NR1 -,
-NR1 -CO-, -CO-NR1 -, -NR1 -CO-0-, -O-CO-NR1 -, -NR1 -CO-NR1 -, -CH=CH-,
-C≡C-, -O-CO-O-, or -Si(CH3)2-0-Si(CH3)2-, or a single bond and wherein:
R1 represents a hydrogen atom or d-C6alkyl;
with the proviso that oxygen atoms of linking groups are not directly linked to each other.
Preferably, the present invention relates a photoalignment composition comprising at least a single photoalignment polymer, which is preferably a homopolymer, comprising at least one photoreactive group. In addition preferably, the present invention relates a photoalignment composition comprising at least a single photoalignment polymer, which comprises at least two monomers, wherein at least a first monomer comprises a photoreactive group;
preferably the at least second monomer comprises a further photoreactive group, which is identical or different to the first monomer; or the at least second monomer does not comprise a a photreactive group and preferably comprises an aligning group exhibiting a property of controlling alignment of liquid crystal molecules without photo- irradiation within the meaning and preferences as described above.
Further more preferably, the present invention relates a photoalignment composition comprising at least a single photoalignment polymer, comprising at least one monomer having a photoreactive group and one monomer having an aligning group exhibiting a property of controlling alignment of liquid crystal molecules without photo-irradiation.
In addition more preferably, the present invention relates a photoalignment
composition comprising at least a single photoalignment polymer, comprising at least two monomers having a photoreactive group, which is identical to the first monomer. Further, more preferably, the present invention relates a photoalignment composition, comprising c ) a further polymer not having a photoreactive group, which comprises a backbone which is a polyamic acid, a partially imidised polyamic acid, a polyimide, a polyamic acid ester or a polysiloxane.
In addition, further more preferred is a photoalignment composition with the meaning and preferences as given above which comprises a further polymer not having a photoreactive group and, which preferably has the same backbone as the
photoalignment polymer; preferably the backbone is a polyamic acid, partially imidised polyamic acid, polyimide, polyamic acid ester, polysiloxane, polysiloxane derivative or mixtures thereof; more preferably the backbone is polyamic acid, partially imidised polyamic acid, polyimide and mixtures thereof; most preferably the backbone is polyamic acid; especially most preferably the backbone is more preferably the backbone is a polyamic acid, polyimide or a mixture thereof.
Preferably the present invention relates to a photoalignment composition, wherein the photoalignment polymer comprises a photoreactive group, which is preferably a dimerizable, isomerizable, decompositable, polymerizable and/or cross-linkable group; more preferably the photoreactive group is
a cinnamate-, coumarine-, quinoline-, azo-, stilbene-, cyanostilbene-, chalcone-, diphenylacetylene, benzylidenephtalimidine, benzylideneacetophenone,
phenylenediacryloyl, stilbazole and/or azo-group;
most preferred are cinnamate-, coumarine-, quinoline-, cyanostilbene-, and/or chalcone-groups;
especially most preferred are cinnamate- or cyanostilbene groups, and
more especially cinnamate groups are preferred.
More preferably the present invention relates to a photoalignment composition, comprising
a) at least a single photoalignment polymer having a photoreactive group, c ) and preferably a further polymer having preferably the same backbone as the photoalignment polymer,
b) at least a single solvent of formula (I)
(R-CO-O-R'), wherein R and R' are independently from each other a straigt-chain alkyl; preferably a straigt-chain a branched d-C6alkyl chain; preferably a branched CrC6alkyl, more preferably a branched C3- or C4alkyl , with the proviso that at least one alkyl chain is branched;
wherein the photoalignment polymer has a photoreactive group, which is
a cinnamate-, coumarine-, quinoline-, azo-, stilbene- and/or cyanostilbene-group; especially photoalignment compounds which are herewith incorporated by reference: photoalignment materials as described in USRe36625, US6201087 , US6107427, US6335409, US5965761 , US6277502, US6649230, US6833421 ,
US6831 148,US7514514 US7750185, US7994273, US8436132, US76871 18,
US6340506 , US7959990, US8173749, US201 1 -0065859-A1 , US-2010-0048849-A1 , US2010-0266814 A1 , US 2012-0316317 A1 , US 2013-0035446 A1 , US 2014-0162076 A1 , US 2014-0192305 A1 , US2014-0249244 A1 , US2014-0342086 A1 ,
US20140162076A1
Preferred is a photoalignment polymer as herewith incorporatated by reference:
- USRe36,625, claims 1 -8, more preferred are those enumerated in examples 1 -6 in col. 7, line 58 - col. 33, line 8;
- US6107427, claims, more preferred are those enumerated in examples 1 -9;
- US5965761 , claims 1 -7, more preferred are those enumerated in examples
1 -6 in col. 9, line 9 - col. 17, line 9;
- US 6277502, claims 1 -4, more preferred are those enumerated in examples 1 -5 in col. 8, line 55- col. 16, line 37;
- US 6632909, claims 1 -6, more preferred are those enumerated in examples 1 -7 in col. 9, line 50 - col. 89, line 24;
- US 6649230, claims, more preferred are those enumerated in examples
1 -4;
- US6833421 , claims, more preferred are those enumerated in examples
1 -9;
- US76871 18, claims, more preferred are those enumerated in examplesl -18; further preferred are those of US817374, US8329823, and US8557922, wherein the photoalignment polymer comprises at least a diamine (I) or at least two diamines, and a tetracarboxylic acid anhydride
Figure imgf000013_0001
(I)
wherein.
A represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic group selected from a monocyclic ring of five or six atoms, two adjacent monocyclic rings of five or six atoms, a bicyclic ring system of eight, nine or ten atoms, or a tricyclic ring system of thirteen or fourteen atoms;
and
wherein the following compound residue of formula (I), the compound residue (la)
Figure imgf000013_0002
represents a straight-chain or branched d-defluoralkyl group, wherein
F is fluorine, and
X1 is an integer from 1 to 15, preferably an integer from 1 to 10; more preferably 1 , 2, 3, 4, 5, 6, 7, 8 or 9 and most preferred 3, 4, 5 or 7;
B represents a straight-chain or branched d-Ci6alkyl group, which is in addition to its fluorine substituent(s) unsubstituted or substituted by
di-(Ci-Ci6alkyl)amino, CrC6alkyloxy, nitro, cyano and/or chlorine; and wherein one or more -CH2- group may independently from each other be replaced by a linking group;
D represents an unsubstituted or substituted, aliphatic, aromatic and/or alicyclic diamine group having from 1 to 40 carbon atoms; preferably D represents an unsubstituted or substituted, aliphatic, aromatic and/or alicyclic diamine group having from 1 to 40 carbon atoms, wherein the diamine group comprises an aliphatic group, which may comprise one or more heteroatom and/or bridging group;
and/or an aromatic group;
and/or an alicyclic group;
E represents an aromatic group, an oxygen atom, a sulphur atom, -NH-,
-N(C C6alkyl)-, -CR2R3,
wherein R2 and R3 are independently from each other hydrogen or a cyclic, straight-chain or branched, substituted or unsubstituted CrC24alkyl, wherein one or more -CH2- group(s) may be independently from each other replaced by a linking group, and with the proviso that at least one of R2 and R3 is not hydrogen;
S1 , S2 each independently from each other represents a spacer unit;
X, Y each independently from each other represents hydrogen, fluorine, chlorine, cyano, unsubstituted or with fluorine substituted d-C^alkyl, in which one or more -CH2- groups may be replaced by a linking group;
n, n1 each independently from each other represents 1 , 2, 3 or 4, preferably n1 is 1 and n is 1 or 2;
with the proviso that if n is 2, 3, or 4, each A, B, x1 ; E, S1 , S2, X, Y are identical or different; and if n1 is 2, 3 or 4 each B, xi is identical or different;
preferably,
wherein, if n > 1 , compound (I) has several side-chains [ wherein side-chain has the meaning of structures (I) without the group D], which are linked to residue D at one atomic position within group D, e.g. two or three side chains linked to one single carbon atom within group D, or they can be linked to group D at different atomic positions within group D, e.g. at adjacent atomic positions within group D, or/and they can linked spaced further apart.
In addition, most preferred is a photoalignment composition which comprises
a) at least a single photoalignment polymer, which is a polymer comprising a
diamine (I) and tetracarboxylic acid dianhydride as basic building blocks, and more preferably wherein the polymer is selected from a polyamic acid, polyamic ester, polyimide or a mixture thereof, and most preferably wherein the polymer is a polyamic acid;
c ) and preferably a further polymer, which is a polymer comprising a diamine (I) tetracarboxylic acid dianhydride as basic building blocks, and more preferably wherein the polymer is selected from a polyamic acid, polyamic ester, polyimide or a mixture thereof, and most preferably wherein the polymer is a polyamic acid;
b) at least a single solvent of formula (I)
(R-CO-O-R'),
wherein R and R' are independently from each other a straigt-chain alkyl; preferably a straigt-chain a branched CrC6alkyl chain; more preferably a branched CrC6alkyl chain, most preferably a branched C3-,C4- ,C5-,C6alkyl chain, especially most preferably a branched C4alkyl chain; with the proviso that at least one alkyl chain is branched. In the context of the present invention the term "polyimide" has the meaning of partially or full imidisated polyamic acid or polyamic ester. In analogy, the term "imidisation" has in the context of the present invention the meaning of partially or complete imidisation.
Further more preferred is diamine (I), wherein
-N
the linking group is selected from -0-, -CO, -CO-0-, -0-CO-, , -NR1 -,
-NR1 -CO-, -CO-NR1 -, -NR1 -CO-0-, -0-CO-NR1 -, -NR1 -CO-NR1 -, -CH=CH-, -C≡C-, -0-C0-0-, and -Si(CH3)2-0-Si(CH3)2-, and wherein:
R1 represents a hydrogen atom or d-C6alkyl;
with the proviso that oxygen atoms of linking groups are not directly linked to each other.
Further more preferred is diamine (I), wherein
the spacer unit is a single bond, a cyclic, straight-chain or branched, substituted or unsubstituted CrC24alkylen, wherein one or more -CH2- group may independently from each other be replaced by a linking group as described above and/or an non- aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group connected via bridging groups. Further more preferred is the diamine (I), wherein
the bridging group is selected from -CH(OH)-, -CO-, -CH2(CO)-, -SO-, -CH2(SO)-, -S02-, -CH2(S02)-, -COO-, -OCO-, -COCF2-, -CF2CO , -S-CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -0-CO-O, -CH2-CH2-, -OCH2-, -CH20-, -CH=CH-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, -CH=N-, -C(CH3)=N-, -N=N- or a single bond; or a cyclic, straight- chain or branched, substituted or unsubstituted CrC24alkylen, wherein one or more -CH2- group may independently from each other be replaced independently from each other by a linking group as described above.
Further more preferred is the diamine (I), wherein
D is preferably selected from formula (III):
H(R5)N-(Sp1)k1-(X1)t1-(Z3-C3)a3-(Z4-C4)a4-(XV(Sp2)k2- N(R6)H (III) wherein:
R5, R6 each independently from each other represents a hydrogen atom or
C C6alkyl;
Sp1 , Sp2 each independently from each other represents an unsubstituted or substituted straight-chain or branched CrC20alkylene, in which one or more -CH2-group may independently from each other be replaced by a linking group, and
k1 , k2 each independently is an integer having a value of 0 or 1 ; and
X1 , X2 each independently represents a linking spacer, and
t1 , t2 each independently is an integer having a value of 0 or 1 ; and
C3, C4 each independently represents a non-aromatic, aromatic, substituted or
unsubstituted carbocyclic or heterocyclic group, which may have a side chain
T, and
7? represents a bridging group; and
Z4 represents a substituted or unsubstituted straight-chain or branched
CrC20alkylene group, in which one or more -CH2- group may independently from each other be replaced by a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group; and/or a heteroatom and/or by a bridging group; and
a3, a4 are independently integers from 0 to 3, such that a3 + a_} < 4; and wherein D is at least once linked to at least one group S1 in formula (I) via group Sp1 and/or group Sp2; and/or linked via at least one non-aromatic, aromatic, substituted or unsubstituted carbocyclic or heterocyclic group of and/or group of C4, and/or linked via at least one side chain T of group C4 and/or group of C3; and/or linked via group Z4; and at least one of k1 , k2, a^ and a4 is not equal to zero; and wherein
linking group and bridging group are as defined above.
Further more preferred is the diamine (I), wherein
the side chain, T, represents a substituted or unsubstituted straight-chain or branched CrC20alkylene group, in which one or more -CH2- group(s) may independently from each other be replaced by a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, or a heteroatom and/or by a bridging group, which is at least once linked to at least once group S1 in formula (I) as described above;
Further more preferred is the photoalignment polymer of US817374, US8329823, and US8557922, composed of at least one diamine compound (I) or at least two different diamine of formula (I), wherein
C3, C4 independently from each other are selected from a compound of group G2, wherein G2 is:
Figure imgf000017_0001
Figure imgf000018_0001
wherein:
" " denotes the connecting bonds of and C4 to the adjacent groups of
compound of formula (III) as described above; and
L is -CH3, -COCH3, -OCH3, nitro, cyano, halogen, CH2=CH-, CH2=C(CH3)-,
CH2=CH-(CO)0-, CH2=CH-0-, -NR5R6 , CH2=C(CH3)-(CO)0-, CH2=C(CH3)- 0-,
wherein:
R5, R6 each independently from each other represents a hydrogen atom or d-C6alkyl;
T represents a substituted or unsubstituted straight-chain or branched
CrC20alkylene group, in which one or more -CH2- group may independently from each other be replaced by a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, or a heteroatom and/or by a bridging group;
m is an integer from 0 to 2;
ui is an integer from 0 to 4, with the proviso that m + ui is <4; and
U2 is an integer from 0 to 3; with the proviso that m + U2 is <3; and is an integer from 0 to 2; with the proviso that m + 113 is <2.
Further more preferred is diamine (I), wherein
D is a selected the group of the following compounds:
Figure imgf000019_0001
wherein
L, l_i , l_2 and L3 are independently from each other -CH3, -COCH3, -OCH3, nitro, cyano, halogen, CH2=CH-, CH2=C(CH3)-, CH2=CH-(CO)0-, CH2=CH-0-, -NR5R6 , CH2=C(CH3)-(CO)0- or CH2=C(CH3)-0-,
T, T1 ; T2 and T3 are independently from each other a substituted or unsubstituted
straight-chain or branched CrC20alkylene group, in which one or more -CH2- group(s) may independently from each other be replaced by a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, and/or a heteroatom and/or by a bridging group; "— " is a single bond,
q is an integer of 1 or 2; and
q1 , q2 and q3 are independently from each other an integer from 0 to 2;
m is an integer of 1 or 2;
ml , m2 and m3 are independently from each other an integer from 0 to 2;
U3; U3' and 113" are independently from each other an integer from 0 to 2;
R5, R6 each independently from each other represents a hydrogen atom or C
C6alkyl and;
Z4 represents a substituted or unsubstituted straight-chain or branched
CrC20alkylene group, in which one or more -CH2- group may independently from each other be replaced by a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group; and/or a heteroatom and/or by a bridging group; and wherein D is at least once linked to at least one group S1 in formula (I), as described in claim 1 , via a single bond "— "; or via a side chain T, T1 ; T2 or T3; or via group Z4;
with the proviso that
u3 + q, or u3 + m is < 4;
u3 + q1 and/or u3' + q2 or/and u3 + ml , or/and u3' + m2, or/and u3" + q3, or/and u3" + m3 is < 4;
q1 + q2, and ml + m2; and q1 + q2 + q3, and ml + m2 + m3 is > 1 ;
Further more preferred is the diamine compound (I), wherein
the following compound residue of formula (la)
Figure imgf000020_0001
represents a straight-chain or branched CrCi6fluoralkyl group with terminal units selected from -CF2H and -CF3.
Further more preferred is the diamine compound (I), wherein
S1 , S2 each independently from each other represents a single bond or a cyclic, straight-chain or branched, substituted or unsubstituted Ci-C24alkylen, in which one or more -CH2- group may independently from each other be replaced by a linking group, and/or a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group of formula (IV): -(Z1-C1)a1-(Z2-C2) a2-(Z1a)a3- (IV) wherein:
C1 , C2 each independently represents a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, and
Z1 , Z2, Z1 a each independently represents a bridging group, and ai . ¾ . 33 each independently represents an integer from 0 to 3, ai + a2 + a3 < 6, wherein the bridging groups Z1 , Z1 a and Z2 are as above.
Most preferred is the photoalignment polymer of US817374, US8329823, and
US8557922, disclosed in examples 1 to 20;
especially most preferred are photoalignment polymer_composed from tetracarboxylic acid anhydride and at least one diamine compound of formulae (VI), (VII), (VIII), (IX), (X), (XI), (XIa) or (Xlb) or at least two diamine compound of formulae (VI), (VII), (VIII), (IX), (X), (XI), (XIa) or (Xlb)
Figure imgf000021_0001
Figure imgf000022_0001
- 21 -
Figure imgf000023_0001
Figure imgf000024_0001
(Xlb)
wherein
A, B, xi , n, n1 , D, E, S2,S1 , X and Y have the above given meanings as in claim 1 and
R5, R6 and Z4 have the same meanings as given above;
L is -CHg, -OCH3, -COCH3, nitro, cyano, halogen, CH2=CH-, CH2=C(CH3)-,
CH2=CH-(CO)0-, CH2=CH-0-, CH2=C(CH3)-(CO)0-, or CH2=C(CH3)-0-,
U3 is an integer from 0 to 2;
and preferably from
diamine of formula (XII)
Figure imgf000024_0002
and U2 have the same meanings and more preferably from
at least one diamine compound or at least two diamine compounds selected from the chemical formulas given below:
Figure imgf000025_0001
wherein S ' has the above given meaning as in claim and
wherein the following compound residue B represents a straight-chain or branched CrC8fluoralkyl group, wherein
F is fluorine, and
X1 is an integer from 1 to 9,
B represents a straight-chain or branched d-C8alkyl group, which is unsubstituted or in addition to its fluorine substituent(s) substituted by
di-(Ci-Ci6alkyl)amino, CrC6alkyloxy, nitro, cyano and/or chlorine; and wherein one or more -CH2- group may independently be replaced by a linking group selected from -0-, -CO-, -CO-0-, -0-CO-, -NR1 -, -NR1 -CO-, -CO-NR1 - and -CH=CH-, wherein:
R1 represents a hydrogen atom or CrC6alkyl;
with the proviso that oxygen atoms are not directly linked to each other;
and wherein the CrC8fluoralkyl group has terminal units selected
from -CF2H, -CF3.
Most especially preferred photoalignment polymers are polymers composed of aat least one diamine of:
6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5 diaminobenzoate
6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5 diaminobenzoate
2- {[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5- diaminobenzoate
3- {[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5- diaminobenzoate
4- {[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5- diaminobenzoate
5- {[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5- diaminobenzoate 7- {[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl 3,5- diaminobenzoate
8- {[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5- diaminobenzoate
1 1 -{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]} undecyl 3,5- diaminobenzoate
2- {[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5- diaminobenzoate
3- {[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5- diaminobenzoate
4- {[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5- diaminobenzoate
5- {[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5- diaminobenzoate
6-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyll 3,5- diaminobenzoate
7- {[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl 3,5- diaminobenzoate
8- {[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5- diaminobenzoate
2- {[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5- diaminobenzoate
3- {[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5- diaminobenzoate
4-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5- diaminobenzoate
5- {[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5- diaminobenzoate
6- {[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyll 3,5- diaminobenzoate
8-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5- diaminobenzoate
1 1 -{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyll 3,5- diaminobenzoate 2-[2-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate
2{2-[2-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate
2,2-dimethyl-3-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}propyl 3,5-diaminobenzoate
2- {[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate
3- {[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate
4- {[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate.
6-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate
7-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl 3,5-diaminobenzoate
8-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate
1 1 -{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]} undecyl 3,5-diaminobenzoate
2-[2-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate
2{2-[2-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate
2,2-dimethyl-3-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}propyl 3,5-diaminobenzoate
2- {[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5- diaminobenzoate
3- {[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate
4- {[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5- diaminobenzoate
5- {[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5-diaminobenzoate 7- {[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl 3,5-diaminobenzoate
8- {[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5- diaminobenzoate
1 1 -{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]} undecyl 3,5-diaminobenzoate
2-[2-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate
2{2-[2-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate
2,2-dimethyl-3-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}propyl 3,5-diaminobenzoate
2-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate
3-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate
4- {[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate
5- {[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5-diaminobenzoate
6- {[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate
8-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate
1 1 -{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]} undecyl 3,5-diaminobenzoate
2-[2-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate
2{2-[2-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate
2,2-dimethyl-3-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}propyl 3,5-diaminobenzoate
2-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate 3- {[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl 3,5-diaminobenzoate
4- {[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate
5-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl 3,5-diaminobenzoate
7- {[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl 3,5-diaminobenzoate
8- {[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate
1 1 -{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]} undecyl 3,5-diaminobenzoate
2- [2-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate
2{2-[2-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate
2,2-dimethyl-3-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}propyl 3,5-diaminobenzoate
3- {[((2E)-3-{4-[(3-methoxy 4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}propyl 3,5-diaminobenzoate
8-{[((2E)-3-{4-[(3-methoxy 4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}octyl 3,5-diaminobenzoate
1 1 -{[((2E)-3-{4-[(3-methoxy 4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]} undecyl 3,5-diaminobenzoate
6-{[((2E)-3-{4-[(3-methoxy 4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}hexyll 3,5-diaminobenzoate
8-{[((2E)-3-{4-[(3-methoxy 4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}octyl 3,5-diaminobenzoate
1 1 -{[((2E)-3-{4-[(3-methoxy 4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]} undecyl 3,5-diaminobenzoate
4- {[((2E)-3-{4-[(3-methoxy 4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}butyl 3,5-diaminobenzoate
6-{[((2E)-3-{4-[(3-methoxy 4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}hexyl3,5-diaminobenzoate 4-{[((2E)-3-{4-[(3-methoxy 4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}butyl 3,5-diaminobenzoate
6-{[((2E)-3-{4-[(3-methoxy 4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}hexyl 3,5-diaminobenzoate
2-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}ethyl 3,5-diaminobenzoate
3- {[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}propyl 3,5-diaminobenzoate
4- {[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}butyl 3,5-diaminobenzoate
6- {[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}hexyl 3,5-diaminobenzoate
7- {[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}heptyl 3,5-diaminobenzoate
8-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}octyl 3,5-diaminobenzoate
1 1 -{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]} undecyl 3,5-diaminobenzoate
2-[2-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}ethoxy]ethyl 3,5-diaminobenzoate
2{2-[2-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}ethoxy]ethoxy}ethyl 3,5-diaminobenzoate
2,2-Dimethyl-3-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-
2- enoyl)oxy]}propyl 3,5-diaminobenzoate
2-{[((2E)-3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl 3,5-diaminobenzoate
3- {[((2E)-3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}propyl 3,5-diaminobenzoate
4- {[((2E)-3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl 3,5-diaminobenzoate
5- {[((2E)-3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}pentyl 3,5-diaminobenzoate
6- {[((2E)-3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}hexyll 3,5-diaminobenzoate 7- {[((2E)-3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}heptyl 3,5-diaminobenzoate
8- {[((2E)-3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl 3,5-diaminobenzoate
1 1 -{[((2E)-3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}undecyl 3,5-diaminobenzoate
6-{[((2E)-3-{4-[(4-{[(4,4,4-trifluorobutoxy)carbonyl]amino}benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}hexyll 3,5-diaminobenzoate
6-{[((2E)-3-{4-[(4-{[(4,4,5,5,5-pentafluoropentoxy)carbonyl]amino}benzoyl)oxy] phenyl}prop-2-enoyl)oxy]}hexyl 3,5-diaminobenzoate
6-{[((2E)-3-{4-[(4-({[(4,4,5,5,6,6,6-heptafluorohexyloxy)carbonyl]amino})benzoyl)oxy] phenyl}prop-2-enoyl)oxy]}hexyll 3,5-diaminobenzoate
3,5-Diaminobenzyl (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy] phenyljacrylate 3,5-Diaminobenzyl (2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate
3,5-Diaminobenzyl (2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate
3,5-Diaminobenzyl (2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate 3,5-Diaminobenzyl (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy] phenyljacrylate
3,5-Diaminobenzyl (2E) 3-{4-[(4-(3, 3,4,4, 5,5, 6,6, 6-nonafluorohexyloxy)benzoyl)oxy] phenyljacrylate
3,5-Diaminobenzyl (2E) 3-{4-[(4-(2,2,3,3,3-pentafluoropropyloxy)benzoyl)oxy] phenyljacrylate
3,5-Diaminobenzyl (2E) 3-{4-[(4-(2,2,3,4,4,4-hexafluorobutoxy)benzoyl)oxy] phenyljacrylate
3,5-Diaminobenzyl (2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] phenyljacrylate 3,5-Diaminobenzyl (2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoropropoxy)benzoyl)oxy]
phenyljacrylate
3,5-Diaminobenzyl (2E) 3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy] phenyljacrylate
3,5-Diaminobenzyl (2E) 3-{4-[(4-(4,5,5,5-tetrafluoro-4- (trifluoromethyl)pentyloxy)benzoyl)oxy] phenyljacrylate
3,5-Diaminobenzyl (2E) 3-{4-{ [(4-(4,4,5,5,6,6,6-heptafluorohexyloyl)oxy)benzoyl oxyjphenyljacrylate 3,5-Diaminobenzyl (2E) 3-{4-[(4-[ (4,4,4-trifluorobutoxy)carbonyl]amino)benzoyl)oxy] phenyljacrylate
3,5-Diaminobenzyl (2E) 3-{4-[(4-[ (4,4,4-trifluoropentyloxy)carbonyl]amino)
benzoyl]oxy} phenyljacrylate
3,5-Diaminobenzyl (2E) 3-{4-[4-(4,4,5,5,5,-pentafluoropentyloyloxy)benzoyl oxy]phenyl}acrylate
3,5-Diaminobenzyl (2E) 3-{4-[4-(4,4,5,5,6,6,6-heptafluorohexyloyloxy)benzoyl oxy]phenyl}acrylate
3,5-Diaminobenzyl (2E) 3-{4-[(3-fluoro-4-(4,4,4- trifluorobutoxy)benzoyl)oxy]phenyl}acrylate
2,5-Diaminobenzyl (2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate
2,5-Diaminobenzyl (2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate 2,5-Diaminobenzyl (2E) 3-{4-[(4-(5,5,5-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 2,5-Diaminobenzyl (2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate 2,5-Diaminobenzyl (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy] phenyljacrylate
2,5-Diaminobenzyl (2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] phenyljacrylate 2,5-Diaminobenzyl (2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoropropoxy)benzoyl)oxy]
phenyljacrylate
2,5-Diaminobenzyl (2E) 3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy] phenyljacrylate
2,5-Diaminobenzyl (2E) 3-{4-{ [(4-(4,4,5,5,6,6,6-heptafluorohexyloyl)oxy)benzoyl oxyjphenyljacrylate
2,5-Diaminobenzyl (2E) 3-{4-[(4-[ (4,4,4-trifluorobutoxy)carbonyl]amino)benzoyl)oxy] phenyljacrylate
2,5-Diaminobenzyl (2E) 3-{4-[(4-[ (4,4,4-trifluoropentyloxy)carbonyl]amino)
benzoyljoxyj phenyljacrylate
2,5-Diaminobenzyl (2E) 3-{4-[4-(4,4,5,5,5,-pentafluoropentyloyloxy)benzoyl oxyjphenyljacrylate
2,5-Diaminobenzyl (2E) 3-{4-[4-(4,4,5,5,6,6,6-heptafluorohexyloyloxy)benzoyl oxy]phenyl}acrylate2,5-Diaminobenzyl (2E) 3-{4-[(2-fluoro-4-(4,4,4- trifluorobutoxy)benzoyl)oxy]phenyl}acrylate
2,4-Diaminobenzyl (2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate
2,4-Diaminobenzyl (2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenylJacrylate 2,4-Diaminobenzyl (2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate 2,4-Diaminobenzyl (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy] phenyljacrylate 2,4-Diaminobenzyl (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy] phenyljacrylate
2,4-Diaminobenzyl (2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] phenyljacrylate 2,4-Diaminobenzyl (2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoropropoxy)benzoyl)oxy]
phenyljacrylate
2,4-Diaminobenzyl (2E) 3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy] phenyljacrylate
2,4-Diaminobenzyl (2E) 3-{4-{ [(4-(4,4,5,5,6,6,6-heptafluorohexyloyl)oxy)benzoyl oxyjphenyljacrylate
2,4-Diaminobenzyl (2E) 3-{4-[(4-[ (4,4,4-trifluorobutoxy)carbonyl]amino)benzoyl)oxy] phenyljacrylate
2,4-Diaminobenzyl (2E) 3-{4-[(4-[ (4,4,4-trifluoropentyloxy)carbonyl]amino)
benzoyljoxyj phenyljacrylate
2,4-Diaminobenzyl (2E) 3-{4-[4-(4,4,5,5,5,-pentafluoropentyloyloxy)benzoyl oxyjphenyljacrylate
2,4-Diaminobenzyl (2E) 3-{4-[4-(4,4,5,5,6,6,6-heptafluorohexyloyloxy)benzoyl oxyjphenyljacrylate
2,4-Diaminobenzyl (2E) 3-{4-[(3-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl)oxy] phenyljacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy] phenyljacrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate 2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenylJ acrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenylJ acrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenylJ acrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy] phenyljacrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] phenyljacrylate 2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy} phenyljacrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(3-methoxy-4- trifluoromethoxybenzoyl)oxy]phenyl}acrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(3-methoxy 4-(2,2,2- trifluoroethoxy)benzoyl)oxy]phenyl} acrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(3-methoxy 4-(4,4,4- trifluorobutoxy)benzoyl)oxy]phenyl} acrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(3-methoxy 4-(5,5,5- trifluoropentyloxy)benzoyl)oxy]phenyl} acrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(3-methoxy 4-(4,4,5,5,5- pentafluoropentoxy)benzoyl)oxy] phenyljacrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(3-methoxy 4-(1 , 1 ,2,2- tetrafluoroethoxy)benzoyl)oxy] phenyljacrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(3-methoxy 4-(4,4,4- trifluorobutanoyl)oxy)benzoyl]oxyJ phenyljacrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3- methoxyphenyljacrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3- methoxyphenylj acrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3- methoxyphenylj acrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3- methoxyphenylj acrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]-3- methoxyphenyljacrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] -3-methoxyphenylJacrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}-3- methoxyphenyljacrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4- trifluoromethoxyphenoxy)carbonyl]phenyl}acrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(2,2,2- trifluoroethoxy)phenoxy)carbonyl]phenyl} acrylate 2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,4- trifluorobutoxy)phenoxy)carbonyl]phenyl} acrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(5,5,5- trifluoropentyloxy)p enoxy)carbonyl]phenyl} acrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,5!5,5- pentafluoropentoxy)phenoxy)carbonyl] phenyljacrylate
2-(3,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)phenoxy)carbonyl] phenyljacrylate
2-(2,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate 2-(2,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenylJ acrylate
2-(2,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenylJ acrylate
2-(2,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenylJ acrylate
2-(2,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy] phenyljacrylate
2-(2,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] phenyljacrylate
2-(2,5-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy] phenyljacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate 2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenylJ acrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenylJ acrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenylJ acrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(2,2,3,3,3-pentafluoropropyloxy) benzoyl)oxy] phenyljacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(2,2,3,4,4,4-hexafluorobutoxy)benzoyl)oxy] phenyljacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(3,3,4,4,5,5,6,6,6-nonafluorohexyloxy) benzoyl)oxy] phenyljacrylate 2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] phenyljacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoropropoxy)benzoyl)oxy] phenyljacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,5,5,6,6,6- heptafluorohexyloxy)benzoyl)oxy] phenyljacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(5,5,6,6,6-pentafluorohexyl)benzoyl)oxy] phenyljacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxyJ phenyljacrylate
[4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1 -enyl]phenyl] 4-(4,4,4- trifluorobutoxy)benzoate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(3-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl) oxyjphenylj acrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy] phenyljacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(3,4-di(4,4,4-trifluorobutoxy)benzoyl) oxyjphenylj acrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy
carbonyl)phenoxy)carbonyl] phenyljacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-[ (4,4,4-trifluorobutoxy)carbonyl]amino) benzoyljoxyj phenyljacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-[ (4,4,5,5,5- pentafluoropentoxy)carbonyl]amino) benzoyljoxyj phenyljacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(3-methoxy-4- trifluoromethoxybenzoyl)oxy]phenyl}acrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(3-methoxy 4-(2,2,2- trifluoroethoxy)benzoyl)oxy]phenyl} acrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(3-methoxy 4-(4,4,4- trifluorobutoxy)benzoyl)oxy]phenyl} acrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(3-methoxy 4-(5,5,5- trifluoropentyloxy)benzoyl)oxy]phenyl} acrylate 2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(3-methoxy 4-(4,4,5,5,5- pentafluoropentoxy)benzoyl)oxy] phenyljacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(3-methoxy 4-(1 , 1 ,2,2- tetrafluoroethoxy)benzoyl)oxy] phenyljacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(3-methoxy 4-(4,4,4- trifluorobutanoyl)oxy)benzoyl]oxyJ phenyljacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3-methoxy phenyl} acrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3- methoxyphenylj acrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]-3- methoxyphenyljacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] -3-methoxyphenylJacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}-3- methoxyphenyljacrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,4- trifluorobutoxy)phenoxy)carbonyl]phenyl} acrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(5,5,5- trifluoropentyloxy)phenoxy)carbonyl]phenyl} acrylate
2-(2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(4,4,5,5,5- pentafluoropentoxy)phenoxy)carbonyl] phenyljacrylate
2- (2,4-Diaminophenyl)ethyl (2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)phenoxy)carbonyl] phenyljacrylate
3-(3,5-Diaminophenyl)propyl (2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenylJ acrylate
3- (3,5-Diaminophenyl)propyl (2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenylJ acrylate
3-(3,5-Diaminophenyl)propyl (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenylJ acrylate
3-(3,5-Diaminophenyl)propyl (2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenylJ acrylate
3-(3,5-Diaminophenyl)propyl (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy] phenyljacrylate 3-(3,5-Diaminophenyl)propyl (2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] phenyljacrylate
3-(3,5-Diaminophenyl)propyl (2E) 3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy} phenyljacrylate 3-(2,4-Diaminophenyl)propyl (2E) 3-{4-[(4-(4,4,4- trifluorobutoxy)benzoyl)oxy]phenyl} acrylate
3-(2,4-Diaminophenyl)propyl (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy] phenyljacrylate
3-(2,4-Diaminophenyl)propyl (2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] phenyljacrylate
3-(2,4-Diaminophenyl)propyl (2E) 3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxyJ phenyljacrylate
6-(2,4-Diaminophenyl)hexyl (2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenylJ acrylate
6-(2,4-Diaminophenyl)hexyl (2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy] phenyljacrylate
6-(2,4-Diaminophenyl)hexyl (2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] phenyljacrylate
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E)-3-{4-[(4-(4,4,4- trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2- enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenylJ prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenylJ prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-(5,5,5- trifluoropentyloxy)benzoyl)oxy]phenyl} prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy] phenyl}prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] phenyl}prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxyJ phenyl}prop-2-enoyl] propanediol 2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy-4- trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(2,2,2- trifluoroethoxy)benzoyl)oxy]phenyl} prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(4,4,4- trifluorobutoxy)benzoyl)oxy]phenyl} prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(5,5,5- trifluoropentyloxy)benzoyl)oxy]phenyl} prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(4,4,5,5,5- pentafluoropentoxy)benzoyl)oxy] phenyl}prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(1 ,1 ,2,2- tetrafluoroethoxy)benzoyl)oxy] phenyl}prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(4,4,4- trifluorobutanoyl)oxy)benzoyl]oxy} phenyl}prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3- methoxyphenyl}prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3- methoxyphenyl} prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3- methoxy phenyl} prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3- methoxyphenyl} prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]- 3-methoxyphenyl}prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] -3-methoxyphenyl}prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}-3- methoxyphenyl}prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4- trifluoromethoxyphenoxy)carbonyl]phenyl}prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-(2,2,2- trifluoroethoxy)phenoxy)carbonyl]phenyl} prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,4- trifluorobutoxy)phenoxy)carbonyl]phenyl} prop-2-enoyl] propanediol 2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-(5,5,5- trifluoropentyloxy)phenoxy)carbonyl]phenyl} prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,5,5,5- pentafluoropentoxy)phenoxy)carbonyl] phenyl}prop-2-enoyl] propanediol
2,2-bis(4-aminobenzyl)-1 ,3 di[(2E) 3-{4-[(4-(1 ,1 ,2,2- tetrafluoroethoxy)phenoxy)carbonyl] phenyl}prop-2-enoyl] propanediol
6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5- Diamino-4-[6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2- enoyl)oxy]}hexyloxy]benzoate
2,2'-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl 4,4'-Diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]methyl 4,4'- diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl} prop-2-enoyl]methyl 4, 4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl} prop-2-enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl} prop-2-enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] phenyl}prop-2-enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy} phenyl]prop-2-enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(3-methoxy 4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl} prop-2- enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(3-methoxy 4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl} prop-2- enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(3-methoxy 4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl} prop-2- enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(3-methoxy 4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy] phenyl}prop-2-enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl 2,2'-bis[(2E) 3-{4-[(3-methoxy 4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] phenyl}prop-2- enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(3-methoxy 4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy} phenyl]prop- 2-enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3-methoxyphenyl} prop-2- enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3-methoxy phenyl} prop-2- enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl} prop-2- enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]-3- methoxyphenyl}prop-2-enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy]
-3-methoxyphenyl}prop-2-enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}-3-methoxyphenyl]prop-2- enoyl] methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(4-trifluoromethoxyphenoxy)carbonyl]phenyl}prop-2-enoyl]methyl 4, 4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)phenoxy)carbonyl]phenyl} prop-2- enoyl]methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)phenoxy)carbonyl]phenyl} prop-2- enoyl]methyl 4,4'-diamino 1 ,1 '-biphenyl
[4-[(E)-3-[[5-amino-2-[4-amino-2-[[(E)-3-[4-[4-(4,4,4- trifluorobutoxy)benzoyl]oxyphenyl]prop-2- enoyl]oxymethyl]phenyl]phenyl]methoxy]-3-oxo-prop-1 -enyl]phenyl] 4-(4,4,4- trifluorobutoxy)benzoate
2,2'-bis[(2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl} prop-2-enoyl methyl 4,4'-diamino 1 ,1 '-biphenyl
2,2'-bis[(2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)phenoxy)carbonyl] phenyl}prop-2- enoyl]methyl 4,4'-diamino 1 ,1 '-biphenyl 2,2'-bis[(2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)phenoxy)carbonyl] phenyl}prop-2- enoyl]methyl 4,4'-diamino 1 ,1 '-biphenyl
2-(2,4-Diaminophenyl)- 1 ,3 di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)
benzoyl)oxy]phenyl}prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)- 1 ,3 di[(2E)-3-{4-[(4-(4 ,4,4-trifluorobutoxy)
benzoyl)oxy]phenyl}prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2- enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl} prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl} prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl} prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy] phenyl}prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] phenyl}prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy} phenyl}prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy-4- trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(2,2,2- trifluoroethoxy)benzoyl)oxy]phenyl} prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(4,4,4- trifluorobutoxy)benzoyl)oxy]phenyl} prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(5,5,5- trifluoropentyloxy)benzoyl)oxy]phenyl} prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(4,4,5,5,5- pentafluoropentoxy)benzoyl)oxy] phenyl}prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(1 ,1 ,2,2- tetrafluoroethoxy)benzoyl)oxy] phenyl}prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(4,4,4- trifluorobutanoyl)oxy)benzoyl]oxy} phenyl}prop-2-enoyl] propanediol 2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3- methoxyphenyl}prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3- methoxyphenyl} prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3- methoxy phenyl} prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3- methoxyphenyl} prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]- 3-methoxyphenyl}prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] -3-methoxyphenyl}prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}-3- methoxyphenyl}prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4- trifluoromethoxyphenoxy)carbonyl]phenyl}prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(2,2,2- trifluoroethoxy)phenoxy)carbonyl]phenyl} prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,4- trifluorobutoxy)phenoxy)carbonyl]phenyl} prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(5,5,5- trifluoropentyloxy)phenoxy)carbonyl]phenyl} prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,5!5,5- pentafluoropentoxy)phenoxy)carbonyl] phenyl}prop-2-enoyl] propanediol
2-(2,4-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)phenoxy)carbonyl] phenyl}prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2- enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl} prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl} prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl} prop-2-enoyl] propanediol 2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy] phenyl}prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] phenyl}prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy} phenyl}prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy-4- trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(2,2,2- trifluoroethoxy)benzoyl)oxy]phenyl} prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(4,4,4- trifluorobutoxy)benzoyl)oxy]phenyl} prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(5,5,5- trifluoropentyloxy)benzoyl)oxy]phenyl} prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(4,4,5,5,5- pentafluoropentoxy)benzoyl)oxy] phenyl}prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(1 ,1 ,2,2- tetrafluoroethoxy)benzoyl)oxy] phenyl}prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(3-methoxy 4-(4,4,4- trifluorobutanoyl)oxy)benzoyl]oxy} phenyl}prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3- methoxyphenyl}prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3- methoxyphenyl} prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3- methoxy phenyl} prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3- methoxyphenyl} prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]- 3-methoxyphenyl}prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)benzoyl)oxy] -3-methoxyphenyl}prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}-3- methoxyphenyl}prop-2-enoyl] propanediol 2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4- trifluoromethoxyphenoxy)carbonyl]phenyl}prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(2,2,2- trifluoroethoxy)phenoxy)carbonyl]phenyl} prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,4- trifluorobutoxy)phenoxy)carbonyl]phenyl} prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(5,5,5- trifluoropentyloxy)phenoxy)carbonyl]phenyl} prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(4,4,5>5>5- pentafluoropentoxy)phenoxy)carbonyl] phenyl}prop-2-enoyl] propanediol
2-(3,5-Diaminophenyl)-1 ,3 di[(2E) 3-{4-[(4-(1 ,1 ,2,2-tetrafluoroethoxy)phenoxy)carbonyl] phenyl}prop-2-enoyl] propanediol.
The diamine compounds are prepared according to methods known in the art or according to a process comprising contacting a compound of formula (XIV)
Figure imgf000046_0001
preferably
Figure imgf000046_0002
with a dinitro compound of formula (XVI)
Figure imgf000046_0003
Figure imgf000047_0001
in the corresponding diamino compound of formula (XII)
Figure imgf000047_0002
wherein
F, Xi , rii , n, B, D, , X, Y, Z1 , L, u-| , U2 and S have the same meanings and preferences as given above, and wherein D1 has the same meaning and preferences as D as given above, with the proviso that the two amino groups of D are replaced by two nitro groups.
The reaction between compounds (XIV) and (XVI) can be conducted in many known ways (see J. March, Advanced Organic Chemistry, second edition, pages 363 and 365). In general a method for the preparation of a photoalignment polymer of the present invention is applied through polycondensation reaction of a diamine (I) with one or more tetracarboxylic acid anhydrides, preferably of the general formula (V) as given below, optionally in the presence of one or more additional other diamines. Preferably, the tetracarboxylic acid anhydride is of formula (V)
Figure imgf000048_0001
(V) represents a tetravalent organic radical.
The tetravalent organic radical T is preferably derived from an aliphatic, alicyclic or aromatic tetracarboxylic acid dianhydride.
Preferred examples of aliphatic or alicyclic tetracarboxylic acid dianhydrides are:
1 ,1 ,4,4-butanetetracarboxylic acid dianhydride,
ethylenemaleic acid dianhydride,
1 ,2,3,4-cyclobutanetetracarboxylic acid dianhydride,
1 .2.3.4- cyclopentanetetracarboxylic acid dianhydride,
2.3.5- tricarboxycyclopentylacetic acid dianhydride,
3.5.6- tricarboxynorbornylacetic acid dianhydride,
2.3.4.5- tetrahydrofurantetracarboxylic acid dianhydride,
rel-[1 S,5R,6R]-3-oxabicyclo[3.2.1 ]octane-2,4-dione-6-spiro-3'- (tetrahydrofuran2',5'-dione),
4- (2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1 ,2-dicarboxylicacid dianhydride,
5- (2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1 ,2-dicarboxylic- acid dianhydride,
bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride,
bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid dianhydride,
1 ,8-dimethylbicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, pyromellitic acid dianhydride,
3,3',4,4'-benzophenonetetracarboxylic acid dianhydride,
4,4'-oxydiphthalic acid dianhydride,
3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1 ,4,5,8-naphthalenetetracarboxylic acid dianhydride,
2,3,6,7-naphthalenetetracarboxylic acid dianhydride,
3,3',4,4'-dimethyldiphenylsilanetetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic acid dianhydride, 1 ,2,3,4-furantetracarboxylic acid dianhydride,
4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride,
ethylene glycol bis(trimellitic acid) dianhydride,
4,4'-(1 ,4-phenylene)bis(phthalic acid) dianhydride,
4,4'-(1 ,3-phenylene)bis(phthalic acid) dianhydride,
4,4'-(hexafluoroisopropylidene)diphthalic acid dianhydride, 4,4'-oxydi(1 ,4-phenylene)bis(phthalic acid) dianhydride, and 4,4'-methylenedi(1 ,4-phenylene)bis(phthalic acid) dianhydride.
Preferred examples of aromatic tetracarboxylic acid dianhydrides are: pyromellitic acid dianhydride,
3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride,
3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1 ,4,5,8-naphthalenetetracarboxylic acid dianhydride,
2,3,6,7-naphthalenetetracarboxylic acid dianhydride,
3,3',4,4'-dimethyldiphenylsilanetetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic acid dianhydride, 1 ,2,3,4-furantetracarboxylic acid dianhydride,
4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride,
ethylene glycol bis(trimellitic acid) dianhydride,
4,4'-(1 ,4-phenylene)bis(phthalic acid) dianhydride,
4,4'-(1 ,3-phenylene)bis(phthalic acid) dianhydride,
4,4'-(hexafluoroisopropylidene)diphthalic acid dianhydride, 4,4'-oxydi(1 ,4-phenylene)bis(phthalic acid) dianhydride,
4,4'-methylenedi(1 ,4-phenylene)bis(phthalic acid) dianhydride,
and the like. More preferably the tetracarboxylic acid dianhydrides used to form the tetravalent organic radical T are selected from:
1 ,2,3,4-cyclobutanetetracarboxylic acid dianhydride,
1 ,2,3,4-cyclopentanetetracarboxylic acid dianhydride,
2,3,5-tricarboxycyclopentylacetic acid dianhydride,
5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1 ,2- dicarboxylic acid dianhydride,
4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1 ,2- dicarboxylic acid dianhydride,
4,4'-(hexafluoroisopropylidene)diphthalic acid dianhydride and
bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride.
The polymer, copolymer or oligomer, especially the polyamic acid, polyamic acid ester and polyimide and mixtures thereof may be prepared in line with known methods, such as those described in Plast. Eng. 36 (1996), (Polyimides, fundamentals and applications), Marcel Dekker, Inc.
For example, the amidisation, poly-condensation reaction for the preparation of the polyamic acids is carried out in solution in a polar aprotic organic solvent, such as γ-butyrolactone, Ν,Ν-dimethylacetamide, 2-butoxyethanol (BC), N-methylpyrrolidone or Ν,Ν-dimethylformamide. In most cases equimolar amounts of the anhydride and the diamine are used, i.e. one amino group per anhydride group. If it is desired to stabilize the molecular weight of the polymer, copolymer or oligomer, it is possible for that purpose to either add an excess or a less-than-stoichiometric amount of one of the two components or to add a mono-functional compound in the form of a dicarboxylic acid monoanhydride or in the form of a monoamine. Examples of such mono-functional compounds are maleic acid anhydride, phthalic acid anhydride, aniline and the like. Preferably the reaction is carried out at temperatures of less than 100 °C. The imidisation, cyclisation of the polyamic acids to form the polyimides can be carried out by heating, i.e. by condensation with removal of water or by other imidisation reactions using appropriate reagents.
Partially imidisation is achieved for example, if the imidisation is carried out purely thermally, the imidisation of the polyamic acids may not always be complete, i.e. the resulting polyimides may still contain proportions of polyamic acid.
Complete imidisation reactions are carried out at temperatures between 60 and 250 °C, preferably at temperatures of less than 200 °C. In order to achieve imidisation at lower temperatures additional reagents that facilitate the removal of water are added to the reaction mixture. Such reagents are, for example, mixtures consisting of acid anhydrides, such as acetic acid anhydride, propionic acid anhydride, phthalic acid anhydride, trifluoroacetic acid anhydride or tertiary amines, such as triethylamine, trimethylamine, tributylamine, pyridine,
Ν,Ν-dimethylaniline, lutidine, collidine etc. The amount of aforementioned additional reagents that facilitate the removal of water is preferably at least four equivalents of acid anhydride and two equivalents of amine per equivalent of polyamic acid to be condensed.
The imidization degree of each polymer used in the liquid crystal alignment agent of the invention can be arbitrarily adjusted by controlling the catalyst amount, reaction time and reaction temperature employed in production of the polymer. In the present description, "imidization degree" of polymer refers to a proportion (expressed in %) of the number of recurring units of polymer forming an imide ring or an isoimide ring to the number of total recurring units of polymer. In the present description, the imidization degree of a polyamic acid not subjected to dehydration and ring closure is 0%. The imidization degree of each polymer is determined by dissolving the polymer in deuterated dimethyl sulfoxide, subjecting the resulting solution to H-NMR
measurement at a room temperature using tetramethylsilane as a standard substance, and calculating from the following formula.
Imidization degree (%) = 1 -(A7A2 X B)X100
A1 : Peak area based on protons of NH groups (in the vicinity of 10ppm)
A2: Peak area based of one proton of acrylate double bond (in the vicinity of 6.5 ppm). B: Proportion of the number of acrylate protons to one proton of NH group in the polymer precursor The imidization degree is usually in the range of 1 to 99%, preferably 5 to 50%, more preferably 10 to 40%.
The cyclisation may be conducted subsequent to the poly-condensation with thermal removal of water under formation of a polyimide.
A further preferred embodiment of the invention relates to photoalignment polymers comprising a photoreactive group, which is coumarine- and quinoline-groups as for example described in US 6,201 ,087 B1 , and are incorporated by reference herewith. More preferred are those of US 6,201 ,087, claims 1 -14, more preferred are those enumerated in examples 1 -10 in col. 10, line 6 - col. 31 , line 54;
A further preferred embodiment of the invention relates to photoalignment polymers comprising cyanostilbene-groups photoreactive groups, which are for example described in US7959990.
More preferred are photoalignment polymers comprising at least one monomer or at least two monomers of the general formula (I)
Figure imgf000052_0001
wherein
A and B each independently are a ring system of 5 to 40 atoms, wherein each ring system includes at least one unsaturation directly connected via electron conjugation (π-π bonding) to the double bond shown in formula (IV),
wherein the ring system may be unsubstituted or mono- or poly-substituted by a halogen atom, a hydroxyl group and/or a polar group like nitro, nitrile or a carboxy group, and/or a cyclic, straight-chain or branched alkyl residue having from 1 to 30 carbon atoms, which is unsubstituted, mono- or poly-substituted by methyl, fluorine and/or chlorine, wherein one or more, preferably non-adjacent -CH2- groups independently may be replaced by a group selected from -0-, -CO- -CO-O-, -O-CO-, -NR1 -, -NR1 -CO-, -CO-NR1 -, -NR1 -CO-0-, -O-CO-NR1 -, -NR1 -CO-NR1 -, -CH=CH-, -C≡C-, -0-CO-O- and -Si(CH3)2-0-Si(CH3)2-, an aromatic or an alicyclic group, wherein R1 is a hydrogen atom or lower alkyl; and/or an acryloyloxy, alkoxy, alkylcarbonyloxy, alkyloxocarbonyloxy, methacryloyloxy, vinyl, allyl, vinyloxy and/or allyloxy group, having from 1 to 20 carbon atoms, preferably having from 1 to 10 carbon atoms,
S1 is a single covalent bond or a spacer unit;
n is 1 , 2 or 3;
X and Y represent groups of which one is a hydrogen atom and the other is an electron withdrawing group, which preferably is selected from the groups -COR2, -COOR2, -COSR2,-CO-NR2, -SOR2, -SOCF3, -SO2CF2COR2, -SOOR2, -C≡S, -NO2, -CF3, -CN, wherein R2 is a hydrogen atom or a straight-chain or branched alkyl or alkylene group, having from 1 to 16 carbon atoms, wherein one or more, preferably non-adjacent -CH2- groups independently may be replaced by a group, selected from -0-, -CO-, -CO-O-, -O-CO-, -C=C-, -C≡C- , or by an optionally substituted alkyl, or by a polymerizable group,
G is a hydrogen atom, optionally substituted alkyl, or a polymerizable group,
with the proviso, that when Y is -CN and A is unsubstituted phenylene, then B may not be phenylene para-substituted by -CN, -N02 or -COOH; and
with the proviso that if ring system A is 1 ,4-phenylene, which is unsubstituted or substituted with halogen, cyano and/or nitro, and ring system B is 1 ,4-phenylene, which is unsubstituted or substituted with halogen, cyano and/or nitro, or pyrimidine-
2.5- diyl, pyridine-2,5-diyl, 2,5-thiophenylenediyl, 2,5-furanylene, 1 ,4-naphthylene or
2.6- naphthylene, then X is different from -CN and -COO-alkyl having from 1 to 12 carbon atoms.
A further preferred embodiment of the invention relates to photoalignment materials comprising
- chalcone-groups as described in J. Photopolym. Sci. Technol., 1 1 , 187 (1998), diphenylacetylene groups as described in Chem. Mat., 1 1 , 1293 (1999),
- benzylidenephtalimidine as described in Macromol. Chem. Phys., 199, 375 (1998),
- phenylenediacryloyl groups as described in Japan. J. Appl. Phys., 1 , 37, 2620 (1998),
- stilbazole derivatives groups as described in J. Photopolym. Sci. Technol., 12, 279 (1999), - azo derivatives groups as described in Chemical Reviews, 100, 1847 (2000)), which are incorporated with reference herewith.
Especially most preferably the present invention relates to a photoalignment composition within the meaning and preferences as described above and below comprising
a) at least a single photoalignment polymer having a photoreactive group, which is a polyamic acid, polyimide or a mixture thereof, and which is preferably a poylamic acid, comprising at least one diamine (I) or at least two diamines (I) and at least one tetracarboxylic acid dianhydride.
Further especially most preferably the present invention relates to a photoalignment composition within the meaning and preferences as described above comprising
c ) a further polymer not having a photoreactive group, which is a polyamic acid, polyimide or a mixture thereof, which comprises at least one diamine (DX) and at least one tetracarboxylic acid dianhydride.
In general the amount of the photoalignment polymer is 0.5% - 50% by weight of the sum of weights of the photoalignment polymer and the polymer not having a photoreactive group, preferably 1 % to 25% by weight and most preferably 1 % to 20% by weight, and especially most preferably 1 % to 15% by weight, and more especially most preferably 1 % to 10% by weight.
In the context of the present invention the diamine (DX) has the meaning of an organic diamine. Diamine (DX) may be commercially available or is accessible by known methods. The second amino group is accessible for example by substitution reaction. Prefereably, the diamine (DX) is selected from the group of the following compounds:
Figure imgf000055_0001
wherein
L, l_i , L2 and L3 are independently from each other hydrogen, -CH3, -COCH3, -OCH3, nitro, nitrile, halogen, CH2=CH-, CH2=C(CH3)-, CH2=CH-(CO)0-, CH2=CH-0-, - NR5R6 , CH2=C(CH3)-(CO)0- or CH2=C(CH3)-0-,
T, Ti , T2 and T3 are independently from each other hydrogen, a substituted or unsubstituted straight-chain or branched C-| -C24alkylene group, in which one or more C-atom, CH- or CH2-, group may independently from each other be replaced by a non- aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, and/or a heteroatom and/or by a linking group;
U3, U3' and U3" are indepently from each other an integer from 0 to 2 ;
R5, R6 each independently from each other represents a hydrogen atom or C
C6alkyl and;
Z4 represents a substituted or unsubstituted straight-chain or branched Ci-C20alkylene group, in which one or more -CH2- group may independently from each other be replaced by a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group; and/or a heteroatom and/or by a bridging group; preferably Z4 is unsubstituted or substituted straight-chain or branched C-| -C-| 2alkylene group, C-| - Cealkylene in which one or more, preferably non-adjacent, - C-atom, CH- or CH2-, group may be replaced by an oxygen or nitrogen atom; more preferred Z4 is methylen, ethylen, propylen, 2,2-dimethyl-propylen, butylen, pentylen, hexylen, (-0-C
C6alkylen)2methylen or (-(CO)0-CrC6alkylen) 2methylen or the mono- or bi-radicals thereof;
and
Figure imgf000056_0001
wherein X4, X5> X6, X7, X8, X9, X 0 and X1 1 are independently from each other a bridging group or a single bond; preferably wherein X? and X8, X9 and X 0 or X are independently from each other a single bond, -O-alkoxy-, such as -O-methylen-, methylen-O-; C-| -C-| 2alkylen such as methylene, ethylen, propylene, butylen, pentylen or hexylen, substituted or unsubstituted 1 ,1 '-cyclohexylene, -SO-, -S-, -SO2-, -0-, - N(R25)-, -C(CH3)2-, -C(CF3)2-, 1 ,1 '-cyclohexyl, substituted or unsubstituted 4-(Ci -C3o alkyl)-cyclohexyl, substituted or unsubstituted 3,4"-bis[4'-(C-| -C-3oalkyl)-1 ,1 'bi- (cyclohexyl) -4-yl] , 1 ,1 '-bi(cyclohexyl)-4-yl, wherein R25 is hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl;
preferably X1 0 is -SO-, -S02-, -0-, -N(CH3 )-, -C(CH3)2-, -C(CF3)2-, 1 ,1 '-cyclohexyl,
4-(Ci -C30 alkyl)-cyclohexyl, 3,4"-bis[4'-(Ci -C30 alkyl)--1 ,1 '-bi(cyclohexyl)-4-yl] or
1 ,1 '-bi(cyclohexyl)-4-yl, and wherein X9 and X are identical and are methylene, ethylen, propylene, butylen, pentylen, hexylen, a single bond or -0-;
wherein n is an integer from 0 to 3, preferably, 0 or 1 ; and
if n is 0 than X9 and X are identical and are methylene, ethylene, propylene, butylene, pentylene, hexylene, a single bond -0-; -S-, -C(CH3)2-, -C(CF3)2-; and
Figure imgf000057_0001
wherein X5 is a bridging group or a single bond, and X 7 is CH2, O, NH;
and (XV)
Figure imgf000058_0001
wherein
R9, R10, R11 are hydrogen or C-|-C-3oalkyl, and preferably R9 and R10 are hydrogen methyl and R11 is hydrogen, or Ci-C3oalkyl, and preferably methyl, or 2- methylheptane and n is 0, if y is 1 and y is 0 if n is 1 , and y1 is a single or a double bond, and X 8 is carbonyl or a single bond or NH,
wherein X 7 is CH2, O, NH;
and
Figure imgf000058_0002
more preferred are
Figure imgf000059_0001
wherein R and R 2 is hydrogen, or C-| -C3oalkyl, and preferably methyl,
X 5 and X 6 are independently from each other a single bond or Ci -Csrjalkyl, preferably Ci -C6 alkyl, -COO- and -CONH-; -COO(Ci -C6alkylene)-, -CONH(Cr Cealkylene)-.
More preferred is diamine (DX) as given below:
of formula (IX-1 )
Figure imgf000059_0002
(XI-1 )
wherein X6 is a bridging group or a single bond, and is preferably for example -0-, -S- or substituted or unsubstituted, branced or straight-chain C-| -C6alkylen,
-0(CH2CH20)n-; -0-(Ci -Ci 2alkyl)n-0-, -S-(Ci -Ci 2alkyl)n-S-, triazine, 1 ,3,5-triazinane- 2,4,6-trione, 1 ,1 '-cyclohexylene, NR5((C-| -C6alkyl)nNR6), -(piperidine)ni -(C-| -C6alkyl)n- (piperidine)n,
wherein n is an integer from 1 to 6, and ni are an integer from 0 to 6, wherein
R5 and R6 are each independently from each other represents a hydrogen atom or
C C6alkyl;
R , R 2, R 3 and R 4 are indepently from each other hydrogen, or C-| -C3oalkyl, and preferably methyl; and X6 is a single bond, -0-, or -CH2-;
especially more preferred diamine (DX) is selected from compounds as given below:
Figure imgf000060_0001
Figure imgf000060_0002
Figure imgf000060_0003
wherein n is independently from each other 0 or 1 and
R3 is Ci-C24alkyl is preferably at least one CrC6alkyl, more preferably methyl, ethyl, propyl;
R9, R 0 are indepentenly from each other hydrogen or C-| -C3oalkyl, and preferably R9 and R 0 are indepentenly from each other hydrogen or methyl R and R 2 are indepently from each other hydrogen, or C-| -C3oalkyl, and preferably methyl;
X 4 and X17 are indepentenly from each other a bridging group or a single bond, and is preferably for example -0-, -S- or substituted or unsubstituted, branched or straight- chain Ci -C6alkylen, -0(CH2CH20)n-; -0-(Ci -Ci 2alkyl)n-0-, -S-(Ci -Ci 2alkyl)n-S-, triazine, 1 ,3,5-triazinane-2,4,6-trione, 1 ,1 '-cyclohexylene, NR5((C-| -C6alkyl)nNR6), - (piperidine)ni -(Ci -C6alkyl)n-(piperidine)n,
wherein n is an integer from 1 to 6, and ni are an integer from 0 to 6, wherein
R5 and R6 are each independently from each other represents a hydrogen atom or Ci-C6alkyl;
and
further more preferred are diamine (DX)
4,4'-diaminodiphenyl, 4,4'-diaminodiphenyl-3,3'-dimethoxy, 4,4'-diaminodiphenyl-3,3'- dimethyl, 4,4'-diaminodiphenyl-3,3'-dihydroxy, 4,4'-diamino-diphenylmethane, 4,4'- diaminodi-phenylsulfide, 4,4'-diamino-diphenylsulfone, 4,4'-diaminodiphenylcarbonyl, 4,4'-diaminodiphenyl oxomethylene, 4,4'-diaminodiphenyl-bis(trifluoromethyl)- methylene,
,4'-diaminodiphenyl-bis(trifluoromethyl)methylene-3,3'-dimethoxy or 4,4'- diaminodiphenyl-bis(trifluoromethyl)methylene-3,3'-dihydroxy, 4,4'-diaminodiphenyl ether, 4,4'-(p-pheny-leneiso-propylidene)bisaniline, 2,2-bis[4-(4-aminophenoxy)phenyl]- hexafluoro-propane,
2,2'-bis[4-4-amino-2-trifluoro-methyl-phenoxy-)phenyl)hexafluoropropane,4,4'-diamino- 2,2'-bis/trifluoromethyl)-biphenyl, 4,4'-bis[4-amino-2-trifluoromethyl)phenoxy]- octafluorobiphenyl;
and
further selected from diamines (DX) as given below :
Figure imgf000061_0001
Figure imgf000062_0001
wherein n is 0 or 1 , and wherein X9 and X 0 or X have the above given meanings and preferences; and
Figure imgf000063_0001
and further, 1 -cholesteryl-oxy-2,4-diamino-benzene, 1 -cholestanyloxy-2,4- diaminobenzene, cholesteryloxy(3,5-diamino-benzoyl), cholestan-yloxy(3,5- diaminobenzoyl); and
Further, diamine (DX) are those as enclosed by reference are diamines as described in EP-A-1 ,818,354 on page 10, lines 48 to 58 and on page 1 1 , lines 1 to 19.
Most preferred is the diamine (DX) of formula (IX-1 )
Figure imgf000063_0002
(XI-1 )
wherein X6 has the meaning and preferences as given above, and is preferably for examplea single bomd, -0-, -S- or substituted or unsubstituted C-| -C6alkylen, -O- (CH2CH20)n-; -0-(Ci -Ci 2alkyl)n-0-, -S-(Ci -Ci 2alkyl)n-S-, triazine, 1 ,3,5-triazinane- 2,4,6-trione, 1 ,1 '-cyclohexylene, NR5((C-| -C6alkyl)nNR6), -(piperidine)ni -(C-| -C6alkyl)n- (piperidine)n,
wherein n is an integer from 1 to 6, and ni are an integer from 0 to 6, wherein R , R 2, R 3 and R 4 have indepently from each other the same meanings and preferences as given above, preferably X6 is a single bond, -0-, -CH2-.
Further most preferred diamine (DX) is:
Figure imgf000064_0001
wherein X6 , R and R 2 are independently from each other have the same meaning as given above, and R and R 2 are preferably hydrogen, C-| -C6alkyl, preferably C-| - alkyl or hydroxyl, and X6 is preferably single bond, -0-, -CH2-.
It may be advantageful for the envisaged application method to adapt the composition by adding further solvents. Hence, the present invention also refers to a
photoalignment composition within the given description and preferences, which in addition comprises d) at least one further solvent.
In the context of the present invention the wording "further solvents" has the meaning and preferences as given below:
The solvent or solvent mixture used in the present application may be any solvent that can dissolve the composition according to the invention. Preferably the at least one further solvent is a polar solvent or a nonpolar solvent. The solvents which are particularly preferred are those leading to a good coatability or printability of the photo- alignment composition to the substrate such as glass.
Non-polar solvents have low dielectric constants and are not miscible with water, such as for example hexane, benzene, toluene, diethyl ether, chloroform, ethyl acetate, dichloromethane, chlorobenzene. Preferred polar solvent is an aprotic or protic polar solvent.
Polar aprotic solvents are solvents that share ion dissolving power with protic solvents but lack an acidic hydrogen. These solvents generally have high dielectric constants and high polarity. Examples are 1 ,4-dioxane, tetrahydrofuran (THF), acetone, acetonitrile (MeCN), N, N-dimethylformamide (DMF), Ν,Ν-dimethylacetamide , dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N- vinylpyrrolidone, tetramethylurea, hexamethylphosphoric acid triamide, gamma.- butyrolactone (BL), N-methylmorpholine, acetonitrile, ethylcarbitol acetate, ethylene glycol, propylene glycol diacetate, dipropylene glycol, chlorobenzene, tetrahydrofuran, cyclopentanone (CP), methylethylketone (MEK), ethyl acetate (EA), anisole (AN), ethylethoxy propionate, cyclohexanone (CHN), methyl isobutyl ketone (MIBK), 1 - methoxy-2-propanol acetate (MPA), Diethylene glycol diethyl ether, dichloromethane, and mixtures thereof. Preferred aprotic solvent is N-methylpyrrolidone (NMP), N- ethylpyrrolidone (NEP), diethylene glycol diethyl ether, ethylethoxy propionate or gamma.-butyrolactone (BL) or mixtures thereof. Especially preferred is N- methylpyrrolidone (NMP). Polar protic solvents are solvents, which contain dissociable H+, such as hydrogen fluoride, are called a protic solvent. The molecules of such solvents can donate an H+ (proton). Conversely, aprotic solvents cannot donate hydrogen bonds. Common characteristics of protic solvents are to display hydrogen bonding, to have an acidic hydrogen (although they may be very weak acids), to be able to stabilize ions (cations by unshared free electron pairs, anions by hydrogen bonding). Examples are acetic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol, formic acid, 2- butoxyethanol (BC), ethylcarbitol, butylcarbitol, ethylene glycol, propylene glycol monoacetate, dipropylene glycol monomethyl ether and water. Preferred polar protic solvent is 2-butoxyethanol (BC).
Preferred further solvents are gamma.-butyrolactone (BL), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), 2-butoxyethanol (BC), diethylene glycol diethyl ether, ethylethoxy propionate, N-vinylpyrrolidone, Ν,Ν-dimethylacetamide, N,N- dimethylformamide, ethylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol, propylene glycol monoacetate, propylene glycol diacetate, dipropylene glycol, and dipropylene glycol monomethyl ether, chlorobenzene, tetrahydrofuran, N- methylpyrrolidone (NMP), butylcellosolve, cyclopentanone (CP), methylethylketone (MEK), ethyl acetate (EA), anisole (AN), cyclohexanone (CHN), methyl isobutyl ketone (MIBK), 1 -methoxy-2-propanol acetate (MPA), Ν,Ν-dimethylformamide (DMF), dichloromethane, gamma-butyrolactone (BL), and mixtures thereof.
More preferred solvents are gamma.-butyrolactone (BL), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N-vinylpyrrolidone, Ν,Ν-dimethylacetamide, N,N-dimethyl- formamide, ethylcellosolve, methylethylketone (MEK), diethylene glycol diethyl ether, ethylethoxy propionate, cyclohexanone (CHN), 2-butoxyethanol, (BC) butylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol, propylene glycol monoacetate, propylene glycol diacetate, dipropylene glycol, and dipropylene glycol monomethyl ether, chlorobenzene, tetrahydrofuran, and mixtures thereof.
Most preferred further solvents are methylethylketone (MEK), cyclohexanone (CHN), butyrolactone (BL), N-methylpyrrolidone (NMP), diethylene glycol diethyl ether, ethylethoxy propionate, N-ethylpyrrolidone (NEP), dimethylformamide and 2- butoxyethanol (BC) and mixtures thereof.
Especially most preferred are butyrolactone (BL), N-methylpyrrolidone (NMP), N- ethylpyrrolidone (NEP), diethylene glycol diethyl ether, ethylethoxy propionate , dimethylformamide and/or 2-butoxyethanol (BC) and more esepcially N- methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), dimethylformamide and/or 2- butoxyethanol (BC) and mixtures thereof.
A further embodiment of the present invention relates to a photoalignment composition within the meanings and preferences as given above comprising in addition at least one aprotic polar solvent, preferably two aprotic polar solvents, more preferably at least one solvent is selected from is N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP) and most preferably two aprotic solvents which are N-methylpyrrolidone (NMP) and 2-butoxyethanol (BC) or N-ethylpyrrolidone (NEP) and 2-butoxyethanol (BC). A more preferred embodiment of the present invention relates to a method for the manufacturing of uniform and defect free liquid crystal aligning layers by applying onto a substrate a photoalignment composition of the present invention within the meaning and preferences as described above, preferably having a viscosity in the range of 1 to 100 mPa.s, more preferably in the range of 1 to 50 mPa.s and even more preferably in the range from 10 to 40 mPa.s for Offset printing and 4 to 15 mPa.s for Inkjet priting, and most preferably in the range of 15 to 40 mPa.s for Offset printing;and 4 to 10 mPa.s for Inkjet printing, which comprises in addition at least one solvent, which is selected from the group of solvents as following:
butyrolactone (BL), N-methylpyrrolidone (NMP), N-Ethylpyrrolidone (NEP),
dimethylformamide and 2-butoxyethanol (BC)
wherein the amount of solvent (I) and optionally further solvents in the composition of the present invention is in the range of 99-70% by weight, preferably 99-80% by weight and more preferably 99 to 90% by weight.
The sum of all weight ratios of all components including solvents of the photoalignment composition of the present invention is 100%.
In the present invention the photoalignment composition of the present invention may further comprise surfactants.
Surfactants are chemicals that have a tendency to adsorb physically at a surface or interface, thereby altering the energy relationship at the interface. Thereby surfactants change the surface tension.
Suitable surfactants are wetting-, or levelling-, blocking-, scratch-, slip-, mar- or abrasion-restistant-; deaerating-, defoaming-, hydrophobing-, dispersing-,
rheology controlling- agents; and
preferred are wetting-, levelling-, blocking- scratch-, slip-, mar- or abrasion-restistant-; dispersing- and rheology controlling- agents; and
more preferred are wetting-, dispersing-, levelling-, blocking- scratch-restistant-agents; and
most preferred are surfactants wetting-, dispersing-, levelling- agents. Especially most preferred are wetting- and levelling agents.
The surfactants with the above cited properties are well known in the art. Preferably, the surfactants are non-polymeric or polymeric; reactive or non-reactive, saturated or unsaturated; non-ionic, amphotheric; anionic or cationic compounds. In the context of the present invention reactive has the meaning of crosslinkable, polymerisable or dimerisable.
Preferred surfactants are polymeric and crosslinkable, polymerisable or dimerisable. Amphoteric are for example alkyl ampho(di)acetates, amido betaines or
alky I betaines. Cationic surfactants are for example alkyl dimethylamines, alkyl amidopropylamines, alkyl imidazoline derivatives, quaternised amine ethoxylates, quaternary ammonium compounds;
More preferably the sufactants which are polymers are homo- or copolymers (block, statistic, grafted, branched) or un reactive or reactive, such as crosslinkable, polymerisable or dimerisable surfactants. Most preferred are reactive, such as crosslinkable surfactants.
Examples of non-polymeric surfactants are organic sulphonate derivatives, such as alkyl phenol ether sulphates, alpha olefin sulphonates, aromatic hydrocarbon sulphonic acids, salts and blends, naphthalene sulphonates, condensed naphthalene
sulphonates, fatty alcohol sulphates, di-alkyl sulpho-succinates, mono-alkyl sulphosuccinates, alkyl sulphosuccinamates, di-alkyl sulphosuccinates, lecithine derivates such as sojalecithine; tenside derivates, such as cationic, anionic or amphoteric tensides especially fatty acid ester derivatives; carbonic acid ester or ether derivates, such as hydroxyfunctional carbonic acid ester or ether derivates, alkyl ether phosphates, alkyl ether carboxylic acids and salts, alkyl ether sulphates; alkyl phosphates, alkyl benzene sulphonic acids and salts, alkyl phenol ether phosphates, alkyl phenol ether sulphates, aromatic hydrocarbon sulphonic acids, salts and blends.
Preferred non-polymeric surfactants are carbonic acid ester or ether derivates, especially, Disperbyk®-108.
Examples of polymeric surfactants are for example organic polymers, such as amide polymers, imide polymers, polyurethane, silicon/siloxane polymers, fluoro polymers or acrylate polymers, polyether polycarbonic acid structure (also containing organo- modified polysiloxane or an amine derivative), or non-ionic dispersing polymers. Organic polymer surfactants are for example hydrocarbon surfactants, such as solvent blend of high-boiling aromatics, ketones and esters, or fame (Fatty Acid Modified Emulsifiers).
Fame is based upon fatty acid chemistry, having polar heads based on tertiary amines, such as for example fatty acid modified polyester, aliphatic polyether with acidic groups, solution of fatty acid modified, polyester in water.
Silicon/siloxane polymers are for example reactive or non-reactive polysiloxane, such as
organically modified polysiloxane
organically modified polysiloxane
fluorocarbon modified polysiloxane
solvent-free modified polysiloxane
modified polysiloxane emulsion
polysiloxane
polysiloxane copolymer
polyether siloxane copolymer
isocyanate-terminated polysiloxane
polysiloxane modified with unsaturated terminal groups
polysiloxane modified polyisocyanates
emulsion of polyether siloxane copolymer
polysiloxane based products containing fumed silica
silicone acrylate Fluoro polymers are for example
fluorocarbon modified polymer
fluorocarbon modified polyacrylate
fluorosilicone
polymeric fluorocarbon compound
Acrylate polymers are for example
acrylic polymer
ammonium polyacrylate
sodium polyacrylate ammonium polyacrylate copolymer sodium polyacrylate copolymer;
Non-ionic dispersing polymers are for example amine oxides
alkyl polysaccharides
block copolymers
castor oil ethoxylates
ceto-oleyl alcohol ethoxylates
ceto-stearyl alcohol ethoxylates
decyl alcohol ethoxylates
dinonyl phenol ethoxylates
dodecyl phenol ethoxylates
end-capped ethoxylates
ether amine derivatives
ethoxylated alkanolamides
ethylene glycol esters
fatty acid alkanolamides
fatty alcohol alkoxylates
lauryl alcohol ethoxylates
mono-branched alcohol ethoxylates natural alcohol ethoxylates
monyl phenol ethoxylates
octyl phenol ethoxylates
oleyl amine ethoxylates
random copolymer alkoxylates
sorbitan ester ethoxylates
stearic acid ethoxylates
stearyl amine ethoxylates
synthetic alcohol ethoxylates
tall oil fatty acid ethoxylates
tallow amine ethoxylates
trid tridecanol ethoxylates Preferred polymeric surfactants are non-ionic polymeric surfactants, especially silicone or siloxane polymers and most preferred is silicone acrylate, especially, Tego®Rad 2500. A further preferred embodiment of the present invention concerns compositions of 2 or more than 2 surfactants.
Typical suppliers for surfactants having wetting and levelling properties are for example ADD APT, Air Products, Akzo-Nobel, Akzo-Nobel Cellulosic Specialities, BASF, Borchers, BYK Chemie, Ciba Specialty Chemicals, Cognis, Condea Servo, Degussa-Goldschmidt, Dexter Chemical, Dow Chemical, Dow Corning, DuPont, Elementis, GE Silicones, International Speciality Product, Rhodia, Tego, Tiarco Chemical, Troy, UCB Chemical, Ultra Additive, Worlee, 3M, Additek, C. P. Hall, Cytec, Efka Additives, Hercules, Liaoyang Huaxing Chemical, Polyvel, R. T. Vanderbilt, Sovereign Chemical, Stepan, Tiarco Chemical, Sachtleben, Rhodia, Raschig, Potters Ballotini.
Example of surfactants having wetting and levelling properties are:
- by Tego/Degussa available: Tego® Colorol, Tego® Dispers, Tego® Lipotin, Tego® Twin, Tego® Wet , Rewopol®, Tego® Surten , Tego®Rad, Tego®Glide, Tegomer®, Tego®Flow such as Tego®Flow 300, Tego® Colorol E, Tego® Colorol F , Tego® Colorol Standard , Tego® Dispers 655 , Tego® Dispers 660 C , Tego® Dispers 661 C, Tego® Dispers 662 C ,Tego® Dispers 680 UV , Tego® Dispers 681 UV, Tego® Lipotin A , Tego® Lipotin BL, Tego® Lipotin DB, Tego® Lipotin SB, Tego® Twin 4000 , Tego® Wet 250 , Tego® Wet 260 , Tego® Wet 265, Tego® Wet 270 , Tego® Wet 280 , Tego® Wet 500 , Tego® Wet 505 , Tego® Wet 510 , Tego® Wet 590 , Tego® Wet 591 , Tego® Wet KL 245, Rewopol® B 2003, Rewopol® M 365 , Rewopol® SB DO 70 , Rewopol® SB DO , Rewopol® SB DO 75 PG , Rewopol® SB FA 50 ,
Rewoquat® W 75 , Rewoteric® AM CAS , Tego® Surten W 1 1 1 , Tego® Surten W 125 , Tego® Surten W 130 , Tego® Surten W 133 , Tego® Surten W 5840 , Tego® Surten W 5878, Tego®Rad 2100, Tego®Rad 2200 N, Tego®Rad 2250, Tego®Rad 2300, Tego®Rad 2500, Tego®Rad 2600, Tego®Rad 2700, Tego®Glide 130,
Tego®Glide 406, Tego®Glide 410, Tego®Glide 41 1 , Tego®Glide 415, Tego®Glide 420, Tego®Glide 432, Tego®Glide 435, Tego®Glide 440, Tego®Glide 450,
Tego®Glide 482, Tego®Glide A 1 15, Tego®Glide B 1484, Tego®Glide ZG 400, Tego®Flow 300, Tegomer® CSi 2342, Tegomer® D 3403, Tegomer® E-si. Tegomer® ESi 2330, Tegomer® HSi 231 1 , Tegomer® VSi 2250.
- by Efka available: EFKA 3033 , EFKA 3034, EFKA 3232 , EFKA 3277, EFKA 3299, EFKA 3883, EFKA 6903, EFKA 6906, EFKA 3522 , EFKA 5010 , EFKA 5044 , EFKA 5054 , EFKA 5055 , EFKA 5063, EFKA , EFKA 5066 , EFKA , EFKA 5207, EFKA 5244 , Efka® 3500, Efka® 3600 , Efka® 3650 , Efka® 4590 , EFKA® 5065 , EFKA® 5070, Efka® 6225, Efka® 6230 , Efka® , Efka® 731 1 , Efka® 7315, Efka® 7316 , Efka® 7340 , Efka® 7361 , Efka® 7375 , Efka® 7381 , Efka® 7390 , Efka® 7500 , Efka® 7544 , Efka® 7554, Efka® 7564
- by BYK available: Byk® additives such as Byk® 307, Byk® 333, Byk® 9075, Byk® 9076, Byk® 9077, Byk® 935, Byk® 961 , Byk® A 560, Byk® W 909, BYKOPLAST® 1000 , Disperplast 101 1 , Byk® S 706, Byk® W 909, Aquacer® 840, Byk® -077, Byk® -085, Byk® -315, Byk® -320, Byk® -321 , Byk® -322, Byk® -323 , Byk® -325 , Byk® - 336 , Byk® -340 , Byk® -345 , Byk® -346 , Byk® -347 , Byk® -348 , Byk® -352 , Byk® -353, Byk® -354 , Byk® -355 , Byk® -356, Byk® -357 , Byk® -358 N , Byk® - 359, Byk® -360 P , Byk® -361 N , Byk® -363 P , Byk® -364 P , Byk® -365 P , Byk® - 366 P , Byk® -368 P , Byk® -370 , Byk® -371 , Byk® -373 , Byk® -375 , Byk® -380 N , Byk® -381 , Byk® -390 , Byk® -392 , Byk® -P 104 S , Byk® -S 706 , Byk® -Silclean 3700 , Byk® -UV 3500 , Byk® -UV 3510 , Byk® -UV 3530 , Byketol® -OK , Byketol® - Special , Byketol® -WS , Minerpol® 221 , Disperbyk® -108.
Most preferred surfactants are Tego®Flow 300, Tego®Rad 2600, Tegomer® E-si, Tego®Rad 2700, EFKA-3883, EFKA 6903, EFKA 6906, EFKA 3299, Tego®Rad 2500 a polydimethylsiloxane and Disperbyk® -108 a hydroxyl functionalized carbonic ester with pigment affine groups. Especially most preferred surfactants are Tego®Flow 300, Tego®Rad 2500 and Disperbyk® -108. Within the scope of the invention the term substrate describes a base material on which a process is conducted which produces one or more layers or films on a part of or on the complete surface of the base material. The substrate can consist of any type of solid material as e.g. glass, metals, polymer films or composite materials. Not necessarily, but in most cases substrates are applied in the shape of slabs, either individually cut pieces or in case of flexible base materials also rolled up into a cylinder shape. In a further preferred embodiment the present invention relates to the photoalignment composition within the meanings and preferences as given above and in addition comprising a surfactant in the solvent in the range of between 1 and 99%, preferred between 1 and 20%, more preferred between 1 and 10% by weight. The amount of the surfactants in the composition is determined according to the wished performances in respect of mechanical and thermal stability, and of optical and electro-optical performances.
A further preferred embodiment the present invention relates to a method, wherein the addition level of the surfactant on the liquid crystal photoalignment material is below 20%, preferably between 0.01 and 10%, more preferably between 0.1 and 5% by weight and most preferably between 0.1 and 1 % per weight.
Preferably, the present invention relates to a photoalignment composition comprising in addition a surfactant, wherein the latter does not have any negative impact on the Voltage Holding Ratio (VHR), Residual DC (RDC) or AC Memory (ACM).
VHR, ACM and RDC are commonly known values in the technical field of liquid crystal displays and will be described as following:
VHR:
In the case of liquid crystal displays of thin-film transistor type a certain amount of charge is applied over the course of a very short period of time to the electrodes of a pixel and must not subsequently drain away by means of the resistance of the liquid crystal. The ability to hold that charge and thus to hold the voltage drop over the liquid crystal is quantified by what is known as the "voltage holding ratio" (VHR). It is the ratio of the RMS-voltage (root mean square voltage) at a pixel within one frame period and the initial value of the voltage applied. ACM (AlternativeCurrentMemorv): An AC (AlternativeCurrent) voltage of 7 Volts (1 kHz) is applied to the cell for 700 hours. The pre-tilt angle of the cell is measured before and after the application of the AC stress. The ACM performance is expressed in terms of a pretilt angle difference, ΔΘ.
RDC (ResidualDirectCurrent) : An adjustable DC (DirectCurrent)-component of V=2VDC is added to the symmetric square wave signal of V=2.8V(30Hz), the fluctuations of light transmitted by the test cell can be eliminated or at least minimized by adequate selection of the external DC component. The external DC-voltage for which the flicker is eliminated or minimized by compensation of the internal residual DC-voltage is taken to be equivalent to the internal residual DC-voltage.
Preferred are non-ionic surfactants not having any negative impact on Voltage Holding Ratio (VHR), Residual DC (RDC) or AC Memory (ACM) are non-ionic surfactants.
A further preferred embodiment of the present invention relates to a method for the preparation of liquid crystal aligning layers, comprising applying a photoalignment composition as described above with all described preferences to a substrate by printing or coating.
In general, the composition is applied onto a substrate optionally coated with an electrode [for example a glass plate coated with indium-tin oxide (ITO)] so that homogeneous layers of 0.05 to 100 μηι thickness are produced. A further preferred embodiment of the present invention relates to a method as described above and all described preferences of the method, for the preparation of uniform and defect free liquid crystal aligning layers having a thickness of <300 nm, preferably <250 nm, more preferably from <200 nm; and preferably, wherein the liquid crystal photoalignment material is a polymer comprising diamine (I) and tetracarboxylic acid anhydride as described above, and with all preferences described above.
Coating methods are for example spin coating, air doctor coating, blade coating, knife coating, reverse-roll coating, transfer roll coating, gravure roll coating, kiss roll coating, cast coating, spray coating, spin-coating, meniscus-coating, wire-coating, slot-orifice coating, calendar coating, electro-deposition coating, dip coating or die coating.
Printing methods are for example ink-jet-printing, direct-printing, relief printing such as flexographic printing, intaglio printing such as direct gravure printing or offset gravure printing, lithographic printing such as offset printing, or stencil printing such as screen printing, flexographic-printing or planographic-printing.
Preferred is the direct printing such as for example gravure, flexography; screen printing and letterpress printing processes;
further preferred are the indirect printing, such as offset printing; and
planographic printing, such as lithography; relief printing, intaglio printing and ink-jet printing, and
flexographic printing.
A detailed description of the single printing processes is common knowledge and partially given above.
A further more preferred embodiment of the present invention relates to a method as described above and all described preferences of the method, comprising a composition which is applied to a substrate by printing, preferably by indirect printing, such as offset printing;
planographic printing, such as lithography; relief printing, intaglio printing;
ink-jet printing or
flexographic printing; more preferably by ink-jet printing.
A further preferred embodiment of the present invention relates to a method as described above and all preferences described for these methods and which in addition comprises
treating, preferably aligning, more preferably cross-linking and/or isomerising, the liquid crystal photoalignment material with aligning light. The regions, which should be aligned, are irradiated, for example, with a high-pressure mercury vapour lamp, a xenon lamp or a pulsed UV laser, using a polarizer and optionally a mask for creating images of structures. Further, it is possible to vary the direction of orientation and the tilt angle within the liquid crystal aligning layer by controlling the polarization plane and/or the irradiance direction of the irradiation of the aligning light. It is understood that by selectively irradiating specific regions of the liquid crystal aligning layer very specific regions of the layer can be aligned. In this way, layers with a defined tilt angle can be provided. The induced orientation and tilt angle are retained in the liquid crystal aligning layer by the process, especially by the process of crosslinking.
The treatment with aligning light may be conducted in a single step or in several separate steps. In a preferred embodiment of the invention the treatment with aligning light is conducted in a single step.
The incidence direction of the aligning light may be normal to the substrate or at any oblique angle. For generating tilt angles, preferably the aligning light is exposed from oblique angles. Further preferred methods of the invention relate to
- a method for the preparation of liquid crystal aligning layer, which are vertically aligned;
- a method for the preparation of multi-domain vertical alignment of a liquid crystal aligning layer;
- a method for the preparation of a liquid crystal aligning layer with tilted optical axis.
Further, the present invention relates to the use of a liquid crystal aligning layer comprising a photoalignment composition as described in the present invention within the given meanings and all preferences, and as prepared according to a method of, the present invention for aligning liquid crystals.
A further embodiment of the present invention relates to a liquid crystal aligning layer obtainable by a method to the present invention. Prefereably, the invention relates to a liquid crystal aligning layer comprising a photoalignment composition according to the present invention in a cross-linked and/or isomerized form. A further preferred embodiment of the present invention relates to a liquid crystal aligning layer having a thickness of <300 nm, preferably <250 nm, more preferably <200 nm.
The liquid crystal aligning layer can be used in the manufacture of unstructured or structured optical-or electro-optical elements, preferably in the production of hybrid layer elements.
In general, transparent support such as glass or plastic substrates, optionally coated with indium tin oxide (ITO) are used.
Further, it is possible to vary the direction of orientation and the tilt angle within the liquid crystal aligning layer by controlling the direction of the irradiation of the aligning light. It is understood that by selectively irradiating specific regions of the polymer or oligomer layer very specific regions of the layer can be aligned. In this way, layers with a defined tilt angle can be provided. The induced orientation and tilt angle are retained in the liquid crystal aligning layer by the process, especially by the process of cross- linking.
More preferably, the present invention relates to a method, wherein imidisation is carried out prior or after the application of the polymer, copolymer or oligomer to a support.
Further preferred methods of the invention relates to
- a method for the preparation of a liquid crystal aligning layer, which are vertically aligned;
- a method for the preparation of multi-domain vertical alignment of a liquid crystal aligning layer;
- a method for the preparation of a liquid crystal aligning layer with tilted optical axis. It is understood that the liquid crystal aligning layer of the present invention can also be used in form of a polymer gel, a polymer network, a polymer film, etc.. The liquid crystal aligning layer can be used in the manufacture of unstructured or structured optical-or electro-optical elements, preferably in the production of hybrid layer elements.
In addition, the present invention relates to a method for the preparation of a liquid crystal aligning layer, wherein the photoalignment composition according to the present invention is applied to a support, and subsequent evaporation of the solvent, and wherein, after any imidisation step which may be necessary, the polymer or oligomer or polymer mixture or oligomer mixture treated with aligning light, and preferably isomerized and/or cross-linked by irradiation with aligning light. A preferred method of the present invention relates to a method, wherein the direction of orientation and the tilt angle within the liquid crystal aligning layer is varied by controlling the direction of the irradiation with aligning light, and/or wherein by selectively irradiating specific regions of the polymer layer or oligomer layer specific regions of the layer are aligned.
The liquid crystal aligning layer are suitably prepared from a solution of the polymer or oligomer material. The polymer or oligomer solution is applied to a support optionally coated with an electrode [for example a glass plate coated with indium-tin oxide (ITO)]. In this process different coating techniques like spin-coating, meniscus-coating, wire-coating, slot-coating, offset-printing, flexo-printing, gravur-printing may be used. Then, or optionally after a prior imidisation step, the regions to be oriented are irradiated, for example, with a high-pressure mercury vapour lamp, a xenon lamp or a pulsed UV laser, using a polarizer and optionally a mask for creating images of structures.
Further, the present invention relates to the use of a liquid crystal aligning layer according to the present invention, preferably in cross-linked form, as an orientation layer for liquid crystals. Further, the present invention relates to preferably the use of a liquid crystal aligning layer for the induction of vertical or planar alignment of adjacent liquid crystalline layers, in particular for operating a cell in MVA mode.
The irradiation time is dependent upon the output of the individual lamps and can vary from a few seconds to several hours. The photo-reaction (dimerisation, polymersiation, cross-linking) can also be carried out, however, by irradiation of the homogeneous layer using filters that, for example, allow only the radiation suitable for the cross- linking reaction to pass through.
It is understood that the liquid crystal aligning layer of the invention may be used in the production of optical or electro-optical devices having at least one orientation layer as well as unstructured and structured optical elements and multi-layer systems.
The present invention relates to the use of a liquid crystal aligning layer for the orientation of liquid crystals.
Preferred is the use for the induction of vertical alignment of adjacent liquid crystalline layers.
A further embodiment of the invention relates to an optical or electro-optical device comprising a photoalignment layer according to the present invention, preferably in a cross-linked form. The electro-optical devices may comprise more than one layer, preferably there are two layers. The layer or each of the layers may contain one or more regions of different spatial orientation.
A further embodiment of the present invention relates to optical and electro-optical unstructured or structured constructional elements, preferably liquid crystal display cells, multi-layer and hybrid layer elements, comprising at least one liquid crystal aligning layer as described above. Further, the present invention relates to preferably the use of a liquid crystal aligning layer for the induction of vertical alignment of adjacent liquid crystalline layers, in particular for operating a cell in MVA mode. Preferred is the use of the liquid crystal aligning layer for the induction of vertical alignment or planar alignment of adjacent liquid crystalline layers.
A further preferred embodiment of the invention relates to an optical or electro-optical device comprising one or more liquid crystal aligning layers. The electro-optical devices may comprise more than one layer. The layer or each of the layers may contain one or more regions of different spatial orientation.
Further preferred is the use of the liquid crystal aligning layer for optical and electro- optical elements. More preferably, the present invention concerns an optical and electro-optical unstructured or structured constructional elements, preferably liquid crystal display cells, multi-layer and hybrid layer elements, comprising at least one liquid crystal aligning layer, such as a polymer layer, copolymer or oligomer layer according to the present invention.
An optical component, system or device creates, manipulates, or measures electromagnetic radiation.
An electro-optical component, system or device operates by modification of the optical properties of a material by an electric field. Thus it concerns the interaction between the electromagnetic (optical) and the electrical (electronic) states of materials.
The optical or electro-optical component, can be used for (but are not limited to) a waveguide, a security or brand protection element, a bar code, an optical grating, a filter, a retarder, a compensation film, a reflectively polarizing film, an absorptive polarizing film, an anisotropically scattering film compensator and retardation film, a twisted retarder film, a cholesteric liquid crystal film, a guest-host liquid crystal film, a monomer corrugated film, a smectic liquid crystal film, a polarizer, a piezoelectric cell, a thin film exhibiting non-linear optical properties, a decorative optical element, a brightness enhancement film, a component for wavelength-band-selective compensation, a component for multi-domain compensation, a component of multiview liquid crystal displays, an achromatic retarder, a polarization state correction / adjustment film, a component of optical or electro-optical sensors, a component of brightness enhancement film, a component for light-based telecommunication devices, a patterned G/H-polarizer with an anisotropic absorber, a patterned reflective circular polarizer, a patterned reflective linear polarizer, a patterned MC (monomer corrugated film).
Preferred are security elements, compensator and retardation films.
The advantages of the present invention could not be foreseen by a skilled person. It has surprisingly been found, that high coating quality can be accessed using the photoalignment compositions of the present invention. Also very astonishing the fabrication of thin liquid crystal aligning layers which fulfil the requirement of uniformed defect free films are accessible with the photoalignment compositions of the present invention .
Examples
Abbreviation of solvents:
NMP: 1 -Methyl-2-pyrrolidone (cas: 872-50-4)
BC: 2-Butoxyethanol (Butyl cellosolve) (cas: 1 1 -76-2)
IBIB: Isobutyl isobutyrate (cas: 97-85-8)
Polymer formed was characterized through its intrinsec viscosity and NMR data. In NMR, some representative signals could be seen. The integration is given as relative values.
Synthesis of polymers
Polyamic acid 1
0.820g (3.66 mmol) of 2,3,5-tricarboxycyclopentylacetic-1 ,2:3,4-dianhydride is added to a solution of 3.649 g (3.66 mmol) of [4-[(E)-3-[[5-amino-2-[4-amino-2-[[(E)-3-[4-[4- (4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2- enoyl]oxymethyl]phenyl]phenyl]methoxy]-3-oxo-prop-1 -enyl]phenyl] 4-(4,4,4- trifluorobutoxy)benzoate in 6.6ml_ of NMP. Stirring is then carried out at 0°C for 2 hours. The mixture is subsequently allowed to react for 21 hours at room temperature. The polymer mixture is diluted with 18ml_ of THF, precipitated into 800ml_ of deionised water to yield, after drying at room temperature under vacuum, Polyamic acid 1 in the form of a white powder with an inherent viscosity [η] of 0.50dL/g.
NMR H NMR /DMSO d6 300MHz
δ= 12.43 (s, 2H), 10.23 (m 2H), 8.03 (m, 2H), 7.86-7.58 (m, 10H), 7.27-7.06 (m, 10H), 6.57 (m, 2H), 4.91 (s, 4H), 4.10 (t, 4H), 3.43-2.49 (m, 8H), 2.42 (m, 4H), 1 .92 (m, 4H). Polyamic acid 2
Analogous to the synthesis of Polyamic acid 1 and using, as diamines, 4-{(1 £)-3-[2- (2,4-diaminophenyl)ethoxy]-3-oxoprop-1 -enyl}phenyl 4-(4,4,4-trifluorobutoxy)benzoate and [4-[(E)-3-[[5-amino-2-[4-amino-2-[[(E)-3-[4-[4-(4,4,4- trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoyl]oxymethyl]phenyl]phenyl]methoxy]-3- oxo-prop-1 -enyl]phenyl] 4-(4,4,4-trifluorobutoxy)benzoate in a molar ratio of 7/3,
Polyamic acid 2 is obtained in the form of a white powder with an inherent viscosity [η] of 0.33dL/g.
NMR H NMR /DMSO d6 300MHz δ= 12.42 (s, 2.8H), 10.21 -9.40 (m 2.8H), 8.17 (m, 4.2H), 8.06-7.75 (m, 10.2H), 7.31 - 7.09 (m, 10.3H), 6.63 (m, 2H), 4.90 (s, 1 .8H), 4.25 -4.1 1 (m 6.4H), 3.43-2.49 (m, 6.9H), 2.27 (m, 6.9H), 1 .95 (m, 6.0H).
Polyamic acid 3
Analogous to the synthesis of Polyamic acid 1 and using 4-(4-aminophenoxy) aniline and 1 ,2,3,4-cyclobutane tetracarboxylic dianhydride, Polyamic acid 3 is obtained in the form of a white powder with an inherent viscosity [η] of 0.37dL/g.
NMR H NMR /DMSO de 300MHz
δ= 12.40 (br, 2H), 10.15 (s 2H), 7.59 (d, 4H), 6.96 (d, 4H), 3.87-3.53 (m, 4H)
Polyamic acid 4
Analogous to the synthesis of Polyamic acid 1 and using, as diamine , 4-(4-amino-2- methyl-phenyl)-3-methyl-aniline, Polyamic acid 4 is obtained in the form of a white powder with an inherent viscosity [η] of 0.56dL/g.
NMR H NMR /DMSO d6 300MHz
δ= 12.30 (br, 2H), 10.07 (m, 2H), 7.57 (m, 2H), 7.43 (m, 2H), 6.97 (m, 2H), 3.52-2.54 (m, 8H), 1 .97 (s, 6H)
Preparation of formulations
Formulation 1
7.0835 g of a 30% solution of Polyamic acid 1 in NMP are added to 201 .875 g of a 20% solution of Polyamic acid 3 in NMP. 108.042 g of NMP and 183.02 g of BC are added. The mixture is stirred during 30 minutes and filtrated on 0.2 μηι PTFE-filter to give Formulation 1 .
Formulation 2
7.0836 g of a 30% solution of Polyamic acid 1 in NMP are added to 201 .872 g of a 20% solution of Polyamic acid 3 in NMP. 108.043 g of NMP, 137.25 g of BC and
45.75 g of IBIB are added. The mixture is stirred during 30 minutes and filtrated on 0.2 μηι PTFE-filter to give Formulation 2.
Formulation 3 1 1 .65 g of a 30% solution of Polyamic acid 2 in NMP are added to 157.52 g of a 20% solution of Polyamic acid 4 in NMP. 144.85 g of NMP and 139.6 g of BC and 46.52 g of IBIB are added. The mixture is stirred during 30 minutes and filtrated on 0.2 μηι PTFE- filter to give Formulation 3.
Figure imgf000084_0001
Application examples
Offset Printing is processed on a Nakan E-400 MIZ with the following parameters:
- coating speed of 20 m/min (conditionl ), or 25 m/min (condition2)
- Anilox roll speed of 20 m/min (conditionl ), or 25 m/min (condition2)
- Anilox NIP of 5-8 mm
- Table NIP of 10-15 mm
- Anilox-Scrubber pressure of 0.48Mpa.
The coated substrates are dried on a hot plate at 80 'C for 1 .5 minutes followed by 40 minutes at 200 °C.
Substrates used for testing (conditions l and conditions 2) are:
- Asahi glass PD200 with a thickness of 0.3 mm
- ITO coated Asahi glass (sputter deposition Si02 200 nm /ITO 20 nm)
- Color filter (CF)
The coating quality is controlled and summarized in the following table, with surface aspect quality being noted from 1 to 4 respectively equivalent to "very good, no defect", "light mura, few defects", "mura, defects" and "mura, defects overall the surface";
levelling being noted from 1 to 4 respectively equivalent to " very good", "good", "poor" and very poor, whereby bad levelling also means de-wetting where some uncoated area can be observed. Table :
Figure imgf000085_0001
Example of "defect overall the surface": in Fig. 1 of coated formulation 1 on CF, microscopic defects can observed overall the coated surface.
Example of "good coating aspect with very good levelling": in Fig. 1 of coated formulation 2 on CF.

Claims

Claims:
1 . A photoalignment composition comprising
a) at least a single photoalignment polymer, preferably a homo- or a copolymer having at least one photoreactive group;
and preferably a further polymer not having a photoreactive group, and b) at least a single solvent of formula (I)
(R-CO-O-R'),
wherein R and R' are independently from each other a straigt-chain alkyl, or branched alkyl chain; with the proviso that at least one alkyl chain is branched.
2. A photoalignment composition according to claim 1 , comprising
c) a further polymer not having a photoreactive group.
3. A photoalignment composition according to any of the preceding claims, comprising and
a) at least a single solvent of formula (I)
(R-CO-O-R'),
wherein R and R' are independently from each other a straigt-chain d-C6alkyl or a branched CrC6alkyl chain; with the proviso that at least one alkyl chain is branched.
4. A photoalignment composition according to any of the preceding claims, comprising at least a single solvent of formula (I)
(R-CO-O-R'),
wherein R and R' are simoultaneaously a branched alkyl chain.
5. A photoalignment composition according to any of the preceding claims, comprising wherein the photoreactive group is a dimerizable, isomerizable, polymerizable and/or cross-linkable group; and preferably the photoreactive group is a cinnamate-, coumarine-, quinoline-, azo-, stilbene-, cyanostilbene-, chalcone-,
diphenylacetylene, benzylidene-phthalimidine, benzylideneacetophenone, phenylenediacryloyl, stilbazole and/or azo-group.
6. A photoalignment composition according to any of the preceding claims, comprising at least a single photoalignment polymer, comprising at least two monomers, wherein at least monomer comprises a photoreactive group.
7. A photoalignment composition according to any of the preceding claims,
comprising at least a single photoalignment polymer, comprising at least two monomers having a photoreactive group.
8. A photoalignment composition according to any of the preceding claims, comprising a further polymer not having a photoreactive group, which comprises a backbone which is a polyamic acid, a partially imidised polyamic acid, a polyimide, a polyamic acid ester or a polysiloxane.
9. A photoalignment composition according to any of the preceding claims,
comprising a further polymer not having a photoreactive group, which has the same backbone as the photoalignment polymer.
10. A photoalignment composition according to any of the preceding claims, comprising at least a single photoalignment polymer in an amount of 0.5% - 50% by weight of the sum of weights of the photoalignment polymer and the polymer not having a photoreactive group.
1 1 . A photoalignment composition according to any of the preceding claims, comprising d) at least one further, which is a polar solvent, which is aprotic or protic polar solvent.
12. A photoalignment composition according to any of the preceding claims, comprising d) at least one aprotic polar solvent, preferably two aprotic polar solvents, more preferably at least one solvent is selected from is N- methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP) and most preferably two aprotic solvents which are N-methylpyrrolidone (NMP) and 2-butoxyethanol (BC) or N-ethylpyrrolidone (NEP) and 2-butoxyethanol (BC).
13. A photoalignment composition according to any of the preceding claims, comprising solvent (I) and optionally further solvents in a total amount of 99-70% by weight in relation to the total weight of the composition.
14. A photoalignment composition according to any of the preceding claims, comprising in addition at least one surfactant.
15. A method for the preparation of liquid crystal aligning layers comprising applying a photoalignment composition as described in any of the preceding claims to a substrate by printing or coating.
16. A liquid crystal aligning layer comprising a photoalignment composition as described in any of the preceding claims 1 to 14, or a prepared according to a method as described in claim 15.
17. Use of the liquid crystal aligning layer according to claim 17 layer for optical and electro-optical elements.
18. Optical and electro-optical elements comprising a liquid crystal aligning layer according to claim 16.
PCT/EP2016/056090 2015-03-31 2016-03-21 Photoalignment composition WO2016156079A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2017551247A JP6821594B2 (en) 2015-03-31 2016-03-21 Optical alignment composition
CN201680019215.5A CN107438653B (en) 2015-03-31 2016-03-21 Photoalignment composition
US15/562,277 US10557085B2 (en) 2015-03-31 2016-03-21 Photoalignment composition
KR1020177031685A KR102629649B1 (en) 2015-03-31 2016-03-21 Photoalignment composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15161811 2015-03-31
EP15161811.3 2015-03-31

Publications (1)

Publication Number Publication Date
WO2016156079A1 true WO2016156079A1 (en) 2016-10-06

Family

ID=52780467

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2016/056090 WO2016156079A1 (en) 2015-03-31 2016-03-21 Photoalignment composition

Country Status (6)

Country Link
US (1) US10557085B2 (en)
JP (1) JP6821594B2 (en)
KR (1) KR102629649B1 (en)
CN (2) CN107438653B (en)
TW (1) TWI727943B (en)
WO (1) WO2016156079A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018158254A3 (en) * 2017-03-03 2018-11-15 Rolic Technologies AG New photoalignment composition for the stabilization of the pre-tilt angle in liquid crystal layers

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6945052B2 (en) * 2018-02-15 2021-10-06 富士フイルム株式会社 Binder composition, binder layer, optical laminate and image display device

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1818354A2 (en) 2006-01-30 2007-08-15 JSR Corporation Liquid crystal aligning agent, alignment film and liquid crystal display device
EP1975687A1 (en) * 2007-03-29 2008-10-01 Rolic AG Method of uniform and defect free liquid crystal aligning layers
US20100197186A1 (en) * 2009-02-03 2010-08-05 Samsung Electronics Co., Ltd. Photoalignment material and method of manufacturing display substrate using the same
WO2013017467A1 (en) * 2011-08-02 2013-02-07 Rolic Ag Photoaligning material
EP2557119A1 (en) * 2010-04-08 2013-02-13 Nissan Chemical Industries, Ltd. Composition forming heat-cured film having photo-alignment properties
WO2013026691A1 (en) * 2011-08-25 2013-02-28 Rolic Ag Photoreactive compounds
WO2013050122A1 (en) * 2011-10-03 2013-04-11 Rolic Ag Photoaligning materials

Family Cites Families (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE59408097D1 (en) 1993-02-17 1999-05-20 Rolic Ag Orientation layer for liquid crystals
US6201087B1 (en) 1994-09-29 2001-03-13 Rolic Ag Coumarin and quinolinone derivatives for the production of orienting layers for liquid crystals
US6107427A (en) 1995-09-15 2000-08-22 Rolic Ag Cross-linkable, photoactive polymer materials
DE59707681D1 (en) 1996-10-28 2002-08-14 Rolic Ag Zug Crosslinkable, photoactive silane derivatives
DE59807348D1 (en) 1997-02-05 2003-04-10 Rolic Ag Zug Photocrosslinkable silane derivatives
DE59814236D1 (en) 1997-02-24 2008-07-17 Rolic Ag Photocrosslinkable polymers
CN1211418C (en) 1997-09-25 2005-07-20 罗列克股份公司 Photocrosslinkable polyimides
GB9907801D0 (en) 1999-04-06 1999-06-02 Rolic Ag Photoactive polymers
EP1070731A1 (en) 1999-07-23 2001-01-24 Rolic AG Compound
ATE278731T1 (en) 2000-01-24 2004-10-15 Rolic Ag PHOTOACTIVE POLYIMIDES, POLYAMIDE ACIDS OR ESTERS WITH PENDANT, PHOTO-CROSS-LINKABLE GROUPS
EP1219651A1 (en) * 2000-12-29 2002-07-03 Rolic AG Photoactive copolymer
EP1386910A1 (en) 2002-07-30 2004-02-04 Rolic AG Photoactive materials
CN101040028B (en) 2004-10-13 2012-03-28 罗利克有限公司 Photocrosslinkable materials
EP1764405A1 (en) 2005-09-20 2007-03-21 Rolic AG Functionalized photoreactive compounds
EP2305632A1 (en) 2005-12-23 2011-04-06 Rolic AG Photocrosslinkable materials
KR101397267B1 (en) * 2006-06-02 2014-05-20 제이에스알 가부시끼가이샤 Liquid crystal aligning agent and liquid crystal display device
JP5201330B2 (en) * 2007-02-23 2013-06-05 Ｊｓｒ株式会社 Liquid crystal aligning agent and liquid crystal display element for forming horizontal alignment film
JP5088561B2 (en) * 2007-02-23 2012-12-05 Ｊｓｒ株式会社 Liquid crystal alignment agent
WO2008135131A1 (en) 2007-05-02 2008-11-13 Rolic Ag Thermally stable alignment materials
KR101469572B1 (en) 2007-05-25 2014-12-05 롤리크 아게 Photocrosslinkable materials comprising alicyclic group
KR100882586B1 (en) * 2007-10-10 2009-02-13 제일모직주식회사 Photoalignment agent of liquid crystal, photoalignment film of liquid crystal including the same, and liquid crystal display including the same
CN101903494B (en) 2007-12-21 2016-03-02 罗利克有限公司 Photoalignment composition
EP2222740B1 (en) * 2007-12-21 2017-10-11 Rolic AG Functionalized photoreactive compounds
JP5532195B2 (en) * 2008-06-10 2014-06-25 Ｊｓｒ株式会社 Liquid crystal aligning agent and liquid crystal display element
TWI591096B (en) 2010-02-12 2017-07-11 羅利克股份公司 Photoaligning material with lateral substitution
US9097938B2 (en) 2010-04-23 2015-08-04 Rolic Ag Photoaligning material
JP5790156B2 (en) * 2010-07-15 2015-10-07 Jsr株式会社 Liquid crystal aligning agent for retardation film, liquid crystal aligning film for retardation film, retardation film and method for producing the same
EP2763957A1 (en) 2011-10-03 2014-08-13 Rolic AG Photoaligning materials
JP6146100B2 (en) * 2012-06-21 2017-06-14 Jsr株式会社 Liquid crystal aligning agent, liquid crystal aligning film, retardation film, liquid crystal display element and method for producing retardation film
KR102159410B1 (en) * 2013-03-14 2020-09-23 제이엔씨 주식회사 Liquid crystal aligning agents and liquid crystal display devices

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1818354A2 (en) 2006-01-30 2007-08-15 JSR Corporation Liquid crystal aligning agent, alignment film and liquid crystal display device
EP1975687A1 (en) * 2007-03-29 2008-10-01 Rolic AG Method of uniform and defect free liquid crystal aligning layers
US20100197186A1 (en) * 2009-02-03 2010-08-05 Samsung Electronics Co., Ltd. Photoalignment material and method of manufacturing display substrate using the same
EP2557119A1 (en) * 2010-04-08 2013-02-13 Nissan Chemical Industries, Ltd. Composition forming heat-cured film having photo-alignment properties
WO2013017467A1 (en) * 2011-08-02 2013-02-07 Rolic Ag Photoaligning material
WO2013026691A1 (en) * 2011-08-25 2013-02-28 Rolic Ag Photoreactive compounds
WO2013050122A1 (en) * 2011-10-03 2013-04-11 Rolic Ag Photoaligning materials

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
"Plast. Eng.", vol. 36, 1996, MARCEL DEKKER, INC
CHEM. MAT., vol. 11, 1999, pages 1293
CHEMICAL REVIEWS, vol. 100, 2000, pages 1847
J. APPL. PHYS., vol. 1, no. 37, 1998, pages 2620
J. PHOTOPOLYM. SCI. TECHNOL., vol. 11, 1998, pages 187
J. PHOTOPOLYM. SCI. TECHNOL., vol. 12, no. 279, 1999
MACROMOL. CHEM. PHYS., vol. 199, 1998, pages 375

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018158254A3 (en) * 2017-03-03 2018-11-15 Rolic Technologies AG New photoalignment composition for the stabilization of the pre-tilt angle in liquid crystal layers
CN110392725A (en) * 2017-03-03 2019-10-29 罗利克技术有限公司 Novel smooth orientation composition for pre-tilt angle in stabilizing solution crystal layer
KR20190126082A (en) * 2017-03-03 2019-11-08 롤릭 테크놀로지스 아게 Novel Photoalignment Composition for Stabilization of Pre-Tilt Angle in Liquid Crystal Layer
US11561440B2 (en) 2017-03-03 2023-01-24 Rolic Technologies AG Photoalignment composition for the stabilization of the pre-tilt angle in liquid crystal layers
KR102533309B1 (en) 2017-03-03 2023-05-16 롤릭 테크놀로지스 아게 Novel photo-alignment composition for stabilization of pre-tilt angle in liquid crystal layer
CN110392725B (en) * 2017-03-03 2023-12-01 罗利克技术有限公司 Photoalignment composition for stabilizing pretilt angle in liquid crystal layer

Also Published As

Publication number Publication date
KR20170132869A (en) 2017-12-04
JP2018516382A (en) 2018-06-21
JP6821594B2 (en) 2021-01-27
KR102629649B1 (en) 2024-01-29
TWI727943B (en) 2021-05-21
US10557085B2 (en) 2020-02-11
CN107438653A (en) 2017-12-05
CN113652167A (en) 2021-11-16
US20180079961A1 (en) 2018-03-22
CN107438653B (en) 2022-01-07
TW201638248A (en) 2016-11-01

Similar Documents

Publication Publication Date Title
KR100913605B1 (en) Photoalignment agent of liquid crystal, photoalignment film of liquid crystal including the same, and liquid crystal display including the same
KR100882586B1 (en) Photoalignment agent of liquid crystal, photoalignment film of liquid crystal including the same, and liquid crystal display including the same
CN106029836B (en) Liquid crystal alignment composition, liquid crystal alignment film and liquid crystal display element
KR101625539B1 (en) Liquid crystal aligning agent, liquid crystal display device and related compounds
KR101877826B1 (en) Producing method of liquid crystal aligning agent
KR102225386B1 (en) Liquid crystal aligning agent, liquid crystal aligning film and its manufacturing method, liquid crystal element, and polymer
JP2007183564A (en) Liquid crystal alignment agent
EP1975687A1 (en) Method of uniform and defect free liquid crystal aligning layers
KR100782436B1 (en) Alignment Agent of Liquid Crystal
JP7318787B2 (en) Liquid crystal aligning agent
KR20160123991A (en) Liquid crystal aligning agent, liquid crystal alignment film and manufacturing method therefor, and liquid crystal device
CN103173228A (en) Liquid crystal photoalignment agent, liquid crystal photoalignment film using the same, and liquid crystal display device including the liquid crystal photoalignment film
US10557085B2 (en) Photoalignment composition
KR101474794B1 (en) Liquid crystal alignment agent, liquid crystal alignment film manufactured using same, and liquid crystal display device including the liquid crystal alignment film
KR20130070230A (en) Liquid crystal alignment agent, liquid crystal alignment film using the same, and liquid crystal display device including the liquid crystal alignment film
KR101443754B1 (en) Liquid crystal alignment agent, liquid crystal alignment film using the same, and liquid crystal display device including the liquid crystal alignment film
KR100827336B1 (en) Diamine Compound having Functional Side Chain for LC Alignment Layer and LC Alignment Material
TWI666232B (en) Liquid crystal alignment agent and production method thereof, liquid crystal alignment film and production method thereof, and liquid crystal display element
CN113544184B (en) Composition for film formation, cured film, liquid crystal alignment film, and retardation film
KR20110068519A (en) Liquid crystal photo-alignment agent, liquid crystal photo-alignment film manufactured using the same, and liquid crystal display device including thereof
KR20220076312A (en) Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal device, and polymer
CN114540044A (en) Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal element
CN114058382A (en) Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal element
KR20120073820A (en) Liquid crystal alignment agent, liquid crystal alignment film manufactured using the same, and liquid crystal display device including the liquid crystal alignment film

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: 16713782

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 15562277

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2017551247

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: 20177031685

Country of ref document: KR

Kind code of ref document: A

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205 DATED 26.01.2018

122 Ep: pct application non-entry in european phase

Ref document number: 16713782

Country of ref document: EP

Kind code of ref document: A1