US20150008373A1 - Reactive mesogen formulation with conductive additive - Google Patents

Reactive mesogen formulation with conductive additive Download PDF

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US20150008373A1
US20150008373A1 US14/377,579 US201314377579A US2015008373A1 US 20150008373 A1 US20150008373 A1 US 20150008373A1 US 201314377579 A US201314377579 A US 201314377579A US 2015008373 A1 US2015008373 A1 US 2015008373A1
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atoms
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alkyl
polymerisable
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Graham Smith
Owain Llyr Parri
Vicki Cook
Georg Bernatz
David Wilkes
Jonathan Henry Wilson
Mark James
Philip Edward May
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Merck Patent GmbH
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3804—Polymers with mesogenic groups in the main chain
    • C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
    • 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
    • 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
    • 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
    • C09K19/58—Dopants or charge transfer agents
    • C09K19/582—Electrically active dopants, e.g. charge transfer agents
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • 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
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    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K2019/523—Organic solid particles
    • 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
    • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
    • C09K2219/03—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used in the form of films, e.g. films after polymerisation of LC precursor

Definitions

  • the invention relates to a reactive mesogen (RM) formulation comprising a conductive additive, to a polymer film obtained thereof, and the use of the RM formulation and polymer film in optical or electrooptical components or devices, like optical retardation films for liquid crystal displays (LCDs).
  • RM reactive mesogen
  • RMs and mixtures of RMs can be used to make optical films, like compensation, retardation or polarisation films, e.g. for use as components of optical or electrooptical devices like LC displays, through the process of in-situ polymerisation.
  • the optical properties of the films can be controlled by various factors, such as mixture formulation or substrate properties.
  • the films are usually prepared by coating a solution of an RM or of an RM mixture on a substrate, removing the solvent, aligning the RMs into the desired orientation, and polymerising the coated and aligned RMs in situ by exposure to heat or actinic radiation, for example to UV radiation, and optionally removing the polymerised film from the substrate.
  • coating of a substrate with a solution containing RMs can lead to a build up of static charge if the solution is not conducting. This can lead to an electrostatic discharge by arcing, and, if the solvent is flammable, result in a fire or explosion. This hazard can be reduced by engineering solutions such as the use of tinsel and electrostatic neutralization bars.
  • the rapid pumping of a non-conductive flammable fluid to a coating head can also lead to electrostatic discharge.
  • a typical manufacturing method for such polymerised RM film products is roll to roll processing of a plastic substrate, in which coating of a reactive mesogen solution is an integral step.
  • a reactive mesogen solution is an integral step.
  • This invention has the aim of providing improved RM formulations and methods which enable the preparation of polymer films with reduced, or even without, build up of static charge, in order to avoid drawbacks and risks like electrostatic discharge by arcing, uneven coatings and optical defects like mura, while retaining the advantageous RM and film properties such as good coatability, good alignment and high durability.
  • Other aims of the invention are immediately evident to the expert from the following description.
  • the inventors of the present invention found that these aims can be achieved by adding certain conductive additives to the RM formulation. Thereby the static build up when coating the mixture on a substrate is reduced, whilst other properties such as good coatability, alignment and durability are retained.
  • WO 2003/083523 discloses that polar additives can be added to liquid crystal (LC) mixtures, however their role is to induce electro-hydrodynamic instability in a bistable LC mode. The additives are therefore not polymerisable.
  • WO 2008/110342 also describes the use of highly polar additives to enhance the properties of an RM formulation, but in this case, the additives are magnetic or paramagnetic particles. Also the formulations described in WO 2008/110342 are designed for inkjet printing rather than solution coating.
  • WO 2008/110316 discloses the use of similar polar pigments in RM formulations that can be processed to prepare polarisation selective scattering devices for security devices.
  • WO 2008/110317 describes the preparation of inkjettable RM formulations, but wherein the polar additives are pigmented or polymer additives.
  • US 2011/0240927 describes a formulation that contains a direactive RM and a polar additive, and can be processed to make a transparent conducting layer as an alternative to the ITO electrodes that ate commonly used as electrodes for LC display (LCD) manufacture.
  • the amount of RM is limited to 20% and the formulation does not give a film that acts as a birefringent retardation film.
  • the additives are PEDOT/PSS (poly-3,4-ethylenedioxy-thiophene/polystyrene sulphonate), which are not soluble in the solvents commonly used for RM formulations.
  • PEDOT/PSS poly-3,4-ethylenedioxy-thiophene/polystyrene sulphonate
  • the invention relates to a formulation comprising >50% of one or more polymerisable mesogenic compounds, and further comprising one or more conductive additives, which are preferably selected from reactive organic compounds and/or ionic organic compounds.
  • the invention further relates to a polymer film comprising or consisting of a polymerised RM formulation as described above and below.
  • the invention further relates to a polymer film obtained by polymerising a layer of an RM formulation as described above and below, preferably wherein the RMs are aligned, and preferably at a temperature where the RM formulation exhibits a liquid crystal phase.
  • the invention further relates to the use of an RM formulation or polymer film as described above and below in polymer films, preferably for use as optical films, antistatic protection sheets or electromagnetic interference protection sheets.
  • the invention further relates to the use of an RM formulation or polymer film as described above and below in optical, electrooptical or electronic components or devices.
  • the invention further relates to an optical, electrooptical or electronic device or a component thereof, comprising an RM formulation or polymer film as described above and below.
  • Said components include, without limitation, optical retardation films, polarizers, compensators, beam splitters, reflective films, alignment layers, colour filters, antistatic protection sheets, or electromagnetic interference protection sheets, polarization controlled lenses for autostereoscopic 3D displays, and IR reflection films for window applications.
  • Said devices include, without limitation, electrooptical displays, especially liquid crystal displays, autostereoscopic 3D displays, organic light emitting diodes (OLEDs), optical data storage devices, and window applications.
  • electrooptical displays especially liquid crystal displays, autostereoscopic 3D displays, organic light emitting diodes (OLEDs), optical data storage devices, and window applications.
  • OLEDs organic light emitting diodes
  • FIG. 1 shows the retardation versus viewing angle for polymer films prepared in accordance with example 2.
  • FIG. 2 shows the retardation versus viewing angle for polymer films prepared in accordance with example 3.
  • FIGS. 3 , 4 and 5 show the retardation durability (retardation drop vs. temperature) for polymer films prepared in accordance with example 4.
  • liquid crystal means a compound that under suitable conditions of temperature, pressure and concentration can exist as a mesophase or in particular as a LC phase.
  • Non-amphiphilic mesogenic compounds comprise for example one or more calamitic, banana-shaped or discotic mesogenic groups.
  • calamitic means a rod- or board/lath-shaped compound or group.
  • banana-shaped means a bent group in which two, usually calamitic, mesogenic groups are linked through a semi-rigid group in such a way as not to be collinear.
  • discotic means a disc- or sheet-shaped compound or group.
  • mesogenic group means a group with the ability to induce liquid crystal (LC) phase behaviour.
  • Mesogenic groups especially those of the non-amphiphilic type, are usually either calamitic or discotic.
  • the compounds comprising mesogenic groups do not necessarily have to exhibit an LC phase themselves. It is also possible that they show LC phase behaviour only in mixtures with other compounds, or when the mesogenic compounds or the mixtures thereof are polymerised.
  • liquid crystal is used hereinafter for both mesogenic and LC materials.
  • a calamitic mesogenic compound is usually comprising a calamitic, i.e. rod- or lath-shaped, mesogenic group consisting of one or more aromatic or alicyclic groups connected to each other directly or via linkage groups, optionally comprising terminal groups attached to the short ends of the rod, and optionally comprising one or more lateral groups attached to the long sides of the rod, wherein these terminal and lateral groups are usually selected e.g. from carbyl or hydrocarbyl groups, polar groups like halogen, nitro, hydroxy, etc., or polymerisable groups.
  • a discotic mesogenic compound is usually comprising a discotic, i.e. relatively flat disc- or sheet-shaped mesogenic group consisting for example of one or more condensed aromatic or alicyclic groups, like for example triphenylene, and optionally comprising one or more terminal groups that are attached to the mesogenic group and are selected from the terminal and lateral groups mentioned above.
  • RM reactive mesogen
  • Polymerisable compounds with one polymerisable group are also referred to as “monoreactive” compounds, compounds with two polymerisable groups as “direactive” compounds, and compounds with more than two polymerisable groups as “multireactive” compounds.
  • Compounds without a polymerisable group are also referred to as “non-reactive” compounds.
  • ionic liquid refers to organic salts that usually have melting points below 373 K.
  • Review articles on ionic liquids are, for example, R. Sheldon “Catalytic reactions in ionic liquids”, Chem. Commun., 2001, 2399-2407; M. J. Earle, K. R. Seddon “Ionic liquids. Green solvent for the future”, Pure Appl. Chem., 72 (2000), 1391-1398; P. Wasserscheid, W. Keim “Ionische bysstechniken—neueterrorism für die fürmaschinesmetallkatalyse” [Ionic Liquids—Novel Solutions for Transition-Metal Catalysis], Angew. Chem., 112 (2000), 3926-3945; T.
  • PIL polymerisable ionic liquid
  • spacer or “spacer group”, also referred to as “Sp” below, is known to the person skilled in the art and is described in the literature, see, for example, Pure Appl. Chem. 73(5), 888 (2001) and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368. Unless stated otherwise, the term “spacer” or “spacer group” above and below denotes a flexible organic group, which in a polymerisable mesogenic compound (“RM”) connects the mesogenic group and the polymerisable group(s).
  • RM polymerisable mesogenic compound
  • film includes rigid or flexible, self-supporting or free-standing films with mechanical stability, as well as coatings or layers on a supporting substrate or between two substrates.
  • Thin film means a film having a thickness in the nanometer or micrometer range, preferably at least 10 nm, very preferably at least 100 nm, and preferably not more than 100 ⁇ m, very preferably not more than 10 ⁇ m.
  • carbyl group means any monovalent or multivalent organic radical moiety which comprises at least one carbon atom either without any non-carbon atoms (like for example —C ⁇ C—), or optionally combined with at least one non-carbon atom such as N, O, S, P, Si, Se, As, Te or Ge (for example carbonyl etc.).
  • hydrocarbyl group denotes a carbyl group that does additionally contain one or more H atoms and optionally contains one or more hetero atoms like for example N, O, S, P, Si, Se, As, Te or Ge.
  • a carbyl or hydrocarbyl group comprising a chain of 3 or more C atoms may also be linear, branched and/or cyclic, including spiro and/or fused rings.
  • the conductive additives allow for an increase in conductivity.
  • the increase of conductivity of the RM formulation enables the preparation of polymer films with reduced, or even without, build up of static charge during the film forming process, and thereby avoids hazards like spontaneous and undesired electrostatic discharge by arcing.
  • it reduces or avoids uneven coatings and optical defects like mura, while retaining the advantageous RM and film properties such as good coatability, good alignment and high durability.
  • the conductive additives are ionic organic compounds, or organic salts, of the formula C + A ⁇ , wherein C + is an organic cation and A ⁇ is an anion, for example selected from quaternary ammonium salts, phosphonium salts, imidazolium salts or other N-heterocyclic salts.
  • Ionic liquid molecules provide soft, bulky ions that have the ability to dissociate in low dielectric constant liquids.
  • the anion has a van der Waals volume of at least 80 A 3 .
  • the conductive additives are selected from organic compounds that are both ionic and reactive, i.e. ionic organic compounds comprising one or more polymerisable functional groups, or polymerisable ionic liquids (PIL).
  • ionic organic compounds comprising one or more polymerisable functional groups
  • PIL polymerisable ionic liquids
  • a polymerisable ionic compound or PIL is used, where the cation is modified with a polymerisable group to incorporate soft, bulky ions into the polymer formed by the RM formulation. This is then copolymerised with the RMs contained in the RM formulation to form a polymer film.
  • the conductive additives are selected from reactive organic compounds comprising one or more polar groups which increases the conductivity of the RM formulation, and further comprising one or more polymerisable functional groups which can co-polymerise with the RMs forming a polymer network.
  • the additive for example by selection of the type of ionic components or polymerisable functional group, it can be achieved that the processing and properties of the RM formulation and of the final polymerised film, are unchanged or only slightly changed, compared to an RM formulation without a conductive additive.
  • the ionic organic compounds preferably contain an organic cation, very preferably selected from the group consisting of ammonium, phosphonium, sulfonium, uronium, thiouronium, guanidinium, and heterocyclic cations such as imidazolium, pyridinium, pyrrolidinium, triazolium, morpholinium or piperidinium cation.
  • organic cation very preferably selected from the group consisting of ammonium, phosphonium, sulfonium, uronium, thiouronium, guanidinium, and heterocyclic cations such as imidazolium, pyridinium, pyrrolidinium, triazolium, morpholinium or piperidinium cation.
  • Preferred heterocyclic cations are selected from the group consisting of
  • the cation C + is an alkyl substituted ammonium, pyridinium, pyrrolidinium or imidazolium group, very preferably a tetraalkylammonium, tetraalkylphosphonium, N-alkylpyridinium, N,N-dialkylpyrrolidinium, 1,3-dialkylimidazolium or trialkylsulfonium cation.
  • the cation C + is selected from the group consisting of tetraalkyl ammonium, tetraaryl ammonium, or mixed tetra alkyl-aryl ammonium, wherein the alkyl or aryl groups may be identical or different from each other, furthermore heterocyclic ammonium, protonated alkyl or aryl ammonium or other nitrogen based ions such as dilauryl ammonium.
  • Preferred examples include, without limitation, tetraalkylammonium, 1-alkyl-3-methylimidazolium, 1-alkyl-2,3-dimethylimidazolium, N-alkyl-3-methyl-pyridinium, N-alkyl-3-hydroxypropyl-pyridinium, N-alkyl-3-hydroxymethyl-pyridinium, N-alkyl-4-dimethylamino-pyridinium, N-methyl-N-alkyl-pyrrolidinium, wherein “alkyl” denotes an alkyl group having 1, 2, 3, 4, 5 or 6 C atoms.
  • the anion is preferably an inorganic anion, very preferably a halide, borate, imide, phosphate, sulfonate, sulfate, succinate, naphthenate or carboxylate anion.
  • the anion is selected from the group consisting of halides, hydrogensulfate, alkylsulfates, fluoroalkyl-phosphates, hexafluorophosphate, bis(trifluoromethylsulfonyl)imide, formate, trifluoroacetate, tetrafluoroborate, oxalatoborate, tetracyanoborate, dicyanamide, tricyanomethide, thiocyanate, methanesulfonate, triflate (trifluoromethane-sulfonate), nonaflate (nonafluorobutane-sulfonate), tosylate (toluene-sulfonate) and hydrogensulfate.
  • halides hydrogensulfate
  • alkylsulfates fluoroalkyl-phosphates
  • hexafluorophosphate bis(trifluoromethylsulfonyl)imide
  • formate trifluor
  • the anion is selected from the group consisting of Cl ⁇ , Br ⁇ , I ⁇ , [HSO 4 ] ⁇ , [CH 3 SO 4 ] ⁇ , [C 2 H 5 SO 4 ] ⁇ , [C 4 H 9 SO 4 ] ⁇ , [C 6 H 13 SO 4 ] ⁇ , [C 8 H 17 SO 4 ] ⁇ , [C 5 H 11 O 2 SO 4 ] ⁇ , [(C 2 F 5 ) 3 PF 3 ] ⁇ , [PF 6 ] ⁇ , [N(SO 2 CF 3 ) 2 ] ⁇ , [HCOO] ⁇ , [CF 3 COO] ⁇ , [BF 4 ] ⁇ , [B(C 2 O 4 ) 2 ] ⁇ , [B(CN) 4 ] ⁇ , [N(CN) 2 ] ⁇ , [C(CN) 3 ] ⁇ , [SCN] ⁇ , [CH 3 SO 3 ]
  • Suitable and preferred anions of this group include, without limitation, tetracyanoborate (TCB), tetraphenylborate (TPB), tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (TFPB), bis(trifluoromethylsulfonyl)imide (NTF), tris(pentafluoroethyl)trifluorophosphate (FAP), bis[bis(pentafluoroethyl)phosphinyl]imide (FPI), nonafluorobutane sulfonate (nonaflate) (NFS), (bis(2-2-ethyl hexyl) sulfosuccinate (AOT), pentafluoroethyl-dicyano-fluoro borate, methoxy-tricyano borate, ethoxy-tricyano borate and 2,2,2-trifluoroethoxy-tricyano borate.
  • TBC
  • Preferred fluoroalkyl phosphate anions include [PF 3 (C 2 F 5 ) 3 ] ⁇ , [PF 3 (C 4 F 9 ) 3 ] ⁇ , [PF 3 (C 3 F 7 ) 3 ] ⁇ , [PF 4 (C 2 F 5 ) 2 ] ⁇ , [PF 5 (C 2 F 5 )] ⁇ ,
  • Preferred fluoroalkyl-fluoro borate anions include [B(CF 3 ) 4 ] ⁇ , B(C 2 F 5 ) 4 ] ⁇ , [BF 3 (CF 3 )] ⁇ , [BF 3 (C 2 F 5 )] ⁇ , [BF 3 (i-C 3 F 7 )] ⁇ , [BF 2 (CF 3 ) 2 ) 2 ] ⁇ , [BF 2 (C 2 F 5 ) 2 ] ⁇ , [BF 2 (CF 3 ) 2 ] ⁇ , [BF(C 2 F 5 ) 3 ] ⁇ , [BF(CF 3 ) 3 ] ⁇ oder [BF(CF 3 )(C 2 F 5 ) 2 ] ⁇ .
  • Preferred examples of ionic organic compounds are for example tetra-n-butyl ammonium chloride, tetraoctyl ammonium bromide, benzyl tridecylammonium benzene sulfate, diphenyl didodecyl ammonium hexafluorophosphate, N-Methyl-N-trioctyl-ammonium bis(trifluoromethylsulfonyl)imide, or mixtures thereof.
  • the reactive ionic organic compounds, or polymerisable ionic liquids, of the second preferred embodiment, hereinafter also referred to as “polymerisable ionic compounds”, are preferably selected of formula 1:
  • P 1 is a polymerisable group
  • Sp is a spacer group or a single bond
  • C + is a cation
  • a ⁇ is an anion
  • Preferred compounds of formula 1 are selected of formula 1a-c:
  • Preferred compounds of formula 1a-c are selected of formula 1a1-1c:
  • P 1 , R a , R b , R c and A ⁇ are as defined in formula 1 and 1a-1c, and t is an integer from 1 to 12.
  • P 1 is preferably an acrylate or methacrylate group.
  • R a , R b and R c preferably denote straight-chain or branched alkyl with 1 to 12 C atoms, very preferably methyl or ethyl.
  • a ⁇ is preferably an anion selected from the group of preferred or very preferred anions as defined above.
  • R a , R b and R c preferably are selected from the group consisting of
  • R a , R b and R c denote straight-chain or branched alkyl having 4-20 C atoms, preferably 4-10 C atoms.
  • Preferred polymerisable cations P 1 -Sp-C + are selected from the group consisting of:
  • Very preferred polymerisable cations include, without limitation, N-[2-(methacryloyloxy)ethyl]-N,N,N-trimethylammonium (MOTMA) and N-[2-(methacryloyloxy)ethyl]-N,N,N-trihexylammonium (MOTHA).
  • MOTMA N-[2-(methacryloyloxy)ethyl]-N,N,N-trimethylammonium
  • MOTHA N-[2-(methacryloyloxy)ethyl]-N,N,N-trihexylammonium
  • Suitable and preferred polymerisable ionic compounds include, without limitation, the compounds listed in Table 1.
  • polymerisable ionic compounds comprising as cation N-[2-(methacryloyloxy)ethyl]-N,N,N-trimethylammonium (MOTMA), N-[2-(methacryloyloxy)propyl]-N,N,N-trimethylammonium, N-[2-(acryloyloxy)ethyl]-N,N,N-trimethylammonium (AOTMA), N-[2-(methacryloyloxy)ethyl]-N,N,N-trihexylammonium (MOTHA), N-[2-(methacryloyloxy)propyl]-N,N,N-trihexylammonium or N-[2-(acryloyloxy)ethyl]-N,N,N-trihexylammonium (AOTHA) and as anion tetraphenylborate, tetrakis(3,5-bis(trifluoromethyl)
  • the reactive organic compounds of the third preferred embodiment preferably contain one or more polymerisable functional groups, and one or more polar groups that increase the conductivity of the RM formulation.
  • P 1 is preferably an acrylate or methacrylate group.
  • Sp is preferably alkylene with 1 to 12 C atoms.
  • Preferred compounds of formula 2 are those of formula 2a and 2b:
  • P 1 is preferably an acrylate or methacrylate group.
  • R a and b1 are as defined in formula 2.
  • a1 is preferably 2, 3, 4, 5 or 6.
  • Preferred compounds of formula 2a and 2b are those of the following formulae:
  • P 1 and R a are as defined in formula 2a, P 1 is preferably an acrylate or methacrylate group, R a is preferably OH or COOH, and z is an integer from 2 to 12, preferably 2, 3, 4, 5 or 6.
  • Suitable and preferred compounds of formula 2a and 2b include, without limitation, the following compounds:
  • P 1 is as defined in formula 2a, and is preferably an acrylate or methacrylate group.
  • Scheme 1 shows by way of example of MOTMA the synthesis of polymerisable ionic compounds of the invention by ion exchange, which can be carried out under conditions known to the person skilled in the art.
  • NTF, FAP, NFS, TCB or MOTMA are commercially available or can be synthesised by known methods, for example salts containing tetracyanoborate anions in accordance with the disclosure of WO 2004/072089.
  • Fluoroalkylborate anions and processes for their preparation are described in EP 1205480 and EP 1229038.
  • the invention furthermore relates to the novel ionic organic compounds or polymerisable ionic compounds as shown above and below.
  • the RM formulation comprises one or more polymerisable mesogenic compounds having only one polymerisable functional group (monoreactive), and one or more polymerisable mesogenic compounds having two or more polymerisable functional groups (di- or multireactive).
  • the di- or multireactive RMs are preferably selected of formula I
  • P 1 and P 2 independently of each other denote a polymerisable group
  • Sp 1 and Sp 2 independently of each other are a spacer group or a single bond
  • MG is a rod-shaped mesogenic group, which is preferably selected of formula II
  • Preferred groups A 1 and A 2 include, without limitation, furan, pyrrol, thiophene, oxazole, thiazole, thiadiazole, imidazole, phenylene, cyclohexylene, bicyclooctylene, cyclohexenylene, pyridine, pyrimidine, pyrazine, azulene, indane, fluorene, naphthalene, tetrahydronaphthalene, anthracene, phenanthrene and dithienothiophene, all of which are unsubstituted or substituted by 1, 2, 3 or 4 groups L as defined above.
  • Particular preferred groups A 1 and A 2 are selected from 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, thiophene-2,5-diyl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydro-naphthalene-2,6-diyl, indane-2,5-diyl, bicyclooctylene or 1,4-cyclohexylene wherein one or two non-adjacent CH 2 groups are optionally replaced by O and/or S, wherein these groups are unsubstituted or substituted by 1, 2, 3 or 4 groups L as defined above.
  • Preferred RMs of formula I are selected of formula Ia
  • the concentration of di- or multireactive RMs, preferably those of formula I and its subformulae, in the RM formulation is preferably from 30% to 99.9%, very preferably from 50 to 80%.
  • the monoreactive RMs are preferably selected from formula III:
  • RMs of formula II are selected from the following formulae.
  • the concentration of the monoreactive RMs in the RM formulation is preferably from 1 to 90%, very preferably from 10 to 70%.
  • the polymer film according to the present invention is preferably prepared by providing the RM formulation onto a substrate, aligning the RMs in the formulation into planar alignment (i.e. with the long molecular axes of the RMs and LC molecules aligned parallel to the substrate), and polymerising the RM formulation in its LC phase at a selected temperature, for example by exposure to heat or actinic radiation, preferably by photopolymerisation, very preferably by UV-photopolymerisation, to fix the alignment of the LC molecules.
  • Polymerisation of the RM formulation is preferably carried out in the presence of an initiator absorbing at the wavelength of the actinic radiation.
  • the RM formulation additionally contains one or more polymerisation initiators.
  • a photoinitiator when polymerising by means of UV light, a photoinitiator can be used that decomposes under UV irradiation to produce free radicals or ions that start the polymerisation reaction.
  • a radical photoinitiator is used for polymerising acrylate or methacrylate groups.
  • a cationic photoinitiator is used for polymerising vinyl, epoxide or oxetane groups preferably a cationic photoinitiator is used.
  • a thermal polymerisation initiator that decomposes when heated to produce free radicals or ions that start the polymerisation.
  • Typical radical photoinitiators are for example the commercially available Irgacure® or Darocure® (Ciba AG). for example Irgacure 651, Irgacure 907 or Irgacure 369.
  • a typical cationic photoinitiator is for example UVI 6974 (Union Carbide).
  • the concentration of the polymerisation initiator in the RM formulation is preferably from 0.01 to 5%, very preferably from 0.1 to 3.
  • the RM formulation additionally contains one or more surfactants.
  • the surfactants are selected such that they to promote planar surface alignment of the LC molecules when preparing the polymer film. Suitable surfactants are described for example in J. Cognard, Mol. Cryst. Liq. Cryst., Supplement 1, 1-77 (1981).
  • non-ionic surfactants preferably polymerisable or unpolymerisable fluorocarbon surfactants, like for example Fluorad® FC-171 (from 3M Co.) or Zonyl FSN® (from DuPont), or Fluorad® FX-13 or FX-14 (from 3M Co.).
  • the concentration of the surfactants in the RM formulation is preferably from 0.1 to 5%, very preferably from 0.1 to 1%.
  • the RM formulation comprises:
  • the RM formulation invention comprises:
  • the RM formulation may also comprise one or more monoreactive polymerisable non-mesogenic compounds, preferably in an amount of 0 to 30%, very preferably 0 to 15%.
  • monoreactive polymerisable non-mesogenic compounds preferably in an amount of 0 to 30%, very preferably 0 to 15%.
  • Typical examples are alkylacrylates or alkylmethacrylates.
  • the RM formulation may also comprise one or more di- or multireactive polymerisable non-mesogenic compounds, preferably in an amount of 0 to 30%, very preferably 0 to 15%, alternatively or in addition to the di- or multireactive polymerisable mesogenic compounds.
  • di- or multireactive polymerisable non-mesogenic compounds preferably in an amount of 0 to 30%, very preferably 0 to 15%, alternatively or in addition to the di- or multireactive polymerisable mesogenic compounds.
  • Typical examples of direactive non-mesogenic compounds are alkyldiacrylates or alkyldimethacrylates with alkyl groups of 1 to 20 C atoms.
  • Typical examples of multireactive non-mesogenic compounds are trimethylpropanetrimethacrylate or pentaerythritoltetraacrylate.
  • the RM formulation may also comprise a polymeric binder or one or more monomers capable of forming a polymeric binder, and/or one or more dispersion auxiliaries. Suitable binders and dispersion auxiliaries are disclosed for example in WO 96/02597. Preferably, however, the RM formulation does not contain a binder or dispersion auxiliary.
  • the RM formulation can additionally comprise one or more additives like for example catalysts, sensitizers, stabilizers, inhibitors, chain-transfer agents, co-reacting monomers, surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, degassing or defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colourants, dyes, pigments or nanoparticles.
  • additives like for example catalysts, sensitizers, stabilizers, inhibitors, chain-transfer agents, co-reacting monomers, surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, degassing or defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colourants, dyes, pigments or nanoparticles.
  • the RM formulation preferably exhibits a nematic LC phase, very preferably a nematic at room temperature, or a smectic phase and a nematic phase.
  • the RM formulation further comprises one or more organic solvents.
  • the solvents are preferably selected from ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone or cyclohexanone; acetates such as methyl, ethyl or butyl acetate or methyl acetoacetate; alcohols such as methanol, ethanol or isopropyl alcohol; aromatic solvents such as toluene or xylene; alicyclic hydrocarbons such as cyclopentane or cyclohexane; halogenated hydrocarbons such as di- or trichloromethane; glycols or their esters such as PGMEA (propyl glycol monomethyl ether acetate), ⁇ -butyrolactone.
  • ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone
  • the total concentration of all solids, including the RMs, in the solvent(s) is preferably from 10 to 60%.
  • L is preferably selected from F, Cl, CN, NO 2 or straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonlyoxy or alkoxycarbonyloxy with 1 to 12 C atoms, wherein the alkyl groups are optionally perfluorinated, or P-Sp-.
  • L is selected from F, Cl, CN, NO 2 , CH 3 , C 2 Hs, C(CH 3 ) 3 , CH(CH 3 ) 2 , CH 2 CH(CH 3 )C 2 H 5 , OCH 3 , OC 2 Hs, COCH 3 , COC 2 H 5 , COOCH 3 , COOC 2 H 5 , CF 3 , OCF 3 , OCHF 2 , OC 2 F 5 or P-Sp-, in particular F, Cl, CN, CH 3 , C 2 Hs, C(CH 3 ) 3 , CH(CH 3 ) 2 , OCH 3 , COCH 3 or OCF 3 , most preferably F, Cl, CH 3 , C(CH 3 ) 3 , OCH 3 or COCH 3 , or P-Sp-.
  • an alkyl or alkoxy radical i.e. where the terminal CH 2 group is replaced by —O—
  • An alkyl group wherein one or more CH 2 groups are replaced by —CH ⁇ CH— can be straight-chain or branched. It is preferably straight-chain, has 2 to 10 C atoms and accordingly is preferably vinyl, prop-1-, or prop-2-enyl, but-1-, 2- or but-3-enyl, pent-1-, 2-, 3- or pent-4-enyl, hex-1-, 2-, 3-, 4- or hex-5-enyl, hept-1-, 2-, 3-, 4-, 5- or hept-6-enyl, oct-1-, 2-, 3-, 4-, 5-, 6- or oct-7-enyl, non-1-, 2-, 3-, 4-, 5-, 6-, 7- or non-8-enyl, dec-1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or dec-9-enyl.
  • alkenyl groups are C 2 -C 7 -1E-alkenyl, C 4 -C 7 -3E-alkenyl, C 5 -C 7 -4-alkenyl, C 6 -C 7 -5-alkenyl and C 7 -6-alkenyl, in particular C 2 -C 7 -1E-alkenyl, C 4 -C 7 -3E-alkenyl and C5-C 7 -4-alkenyl.
  • alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 C atoms are generally preferred.
  • these radicals are preferably neighboured. Accordingly these radicals together form a carbonyloxy group —CO—O— or an oxycarbonyl group —O—CO—.
  • this group is straight-chain and has 2 to 6 C atoms.
  • An alkyl group wherein two or more CH 2 groups are replaced by —O— and/or —COO— can be straight-chain or branched. It is preferably straight-chain and has 3 to 12 C atoms. Accordingly it is preferably bis-carboxy-methyl, 2,2-bis-carboxy-ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy-butyl, 5,5-bis-carboxy-pentyl, 6,6-bis-carboxy-hexyl, 7,7-bis-carboxy-heptyl, 8,8-bis-carboxy-octyl, 9,9-bis-carboxy-nonyl, 10,10-bis-carboxy-decyl, bis-(methoxycarbonyl)-methyl, 2,2-bis-(methoxycarbonyl)-ethyl, 3,3-bis-(methoxycarbonyl)-propyl, 4,4-bis-(methoxycarbonyl
  • An alkyl or alkenyl group that is monosubstituted by CN or CF 3 is preferably straight-chain.
  • the substitution by CN or CF 3 can be in any desired position.
  • An alkyl or alkenyl group that is at least monosubstituted by halogen is preferably straight-chain.
  • Halogen is preferably F or Cl, in case of multiple substitution preferably F.
  • the resulting groups include also perfluorinated groups.
  • the F or Cl substituent can be in any desired position, but is preferably in ⁇ -position.
  • Examples for especially preferred straight-chain groups with a terminal F substituent are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl and 7-fluoroheptyl. Other positions of F are, however, not excluded.
  • R 00 and R 000 are preferably selected from H, straight-chain or branched alkyl with 1 to 12 C atoms.
  • CY 1 ⁇ CY 2 — is preferably —CH ⁇ CH—, —CF ⁇ CF— or —CH ⁇ C(CN)—.
  • Halogen is F, Cl, Br or I, preferably F or Cl.
  • R, R 0 , R 1 and R 2 can be an achiral or a chiral group.
  • the polymerisable groups P 1 , P 2 and P 0 denote a group that is capable of participating in a polymerisation reaction, like radical or ionic chain polymerisation, polyaddition or polycondensation, or capable of being grafted, for example by condensation or addition, to a polymer backbone in a polymer analogous reaction.
  • polymerisable groups for chain polymerisation reactions like radical, cationic or anionic polymerisation.
  • Suitable and preferred polymerisable groups P 1 , P 2 and P 0 include, without limitation, CH 2 ⁇ CW 1 —COO—, CH 2 ⁇ CW 1 —CO—,
  • Very preferred polymerisable groups P 1 , P 2 and P 0 are selected from CH 2 ⁇ CW 1 —COO—, CH 2 ⁇ CW 1 —CO—,
  • P 1 , P 2 and P 0 are selected from CH 2 ⁇ CH—COO—, CH 2 ⁇ C(CH 3 )—COO—, CH 2 ⁇ CF—COO—, (CH 2 ⁇ CH) 2 CH—OCO—, (CH 2 ⁇ CH) 2 CH—O—,
  • Polymerisation can be carried out according to methods that are known to the ordinary expert and described in the literature, for example in D. J. Broer; G. Challa; G. N. Mol, Macromol. Chem., 1991, 192, 59.
  • the spacer groups Sp, Sp 1 and Sp 2 are preferably selected of formula Sp′-X′, such that e.g. P-Sp- is P-Sp′-X′—, wherein
  • X′ is preferably —O—, —S—CO—, —COO—, —OCO—, —O—COO—, —CO—NR 0 —, —NR 0 —CO—, —NR 0 —CO—NR 0 — or a single bond.
  • Typical groups Sp′ are, for example, —(CH 2 ) p1 —, —(CH 2 CH 2 O) q1 —CH 2 CH 2 —, —CH 2 CH 2 —S—CH 2 CH 2 — or —CH 2 CH 2 —NH—CH 2 CH 2 — or —(SiR 0 R 00 —O) p1 —, with p1 being an integer from 2 to 12, q1 being an integer from 1 to 3 and R 0 and R 00 having the meanings given above.
  • Preferred groups Sp′ are ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxy-butylene, ethylene-thioethylene, ethylene-N-methyl-iminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene for example.
  • the polymerisable groups P 1 and the spacer groups Sp 1 can be identical or different.
  • the reactive compounds comprise one or more terminal groups R 0,1,2 or substituents L that are substituted by two or more polymerisable groups P or P-Sp- (multifunctional polymerisable groups).
  • Suitable multifunctional polymerisable groups of this type are disclosed for example in U.S. Pat. No. 7,060,200 B1 oder US 2006/0172090 A1.
  • Very preferred are compounds comprising one or more multifunctional polymerisable groups selected from the following formulae:
  • the preparation of polymer films according to this invention can be carried out by methods that are known to the skilled person and described in the literature, for example in D. J. Broer; G. Challa; G. N. Mol, Macromol. Chem., 1991, 192, 59.
  • the RM formulation is coated or otherwise applied onto a substrate where it aligns into uniform orientation, preferably planar alignment (i.e. with the long molecular axes of the calamitic RMs or LC molecules aligned parallel to the substrate), and polymerised in situ in its LC phase at a selected temperature for example by exposure to heat or actinic radiation, preferably by photo-polymerisation, very preferably by UV-photopolymerisation, to fix the alignment of the LC molecules.
  • uniform alignment can promoted by additional means like shearing or annealing the LC material, surface treatment of the substrate, or adding surfactants to the LC material.
  • substrate for example glass or quartz sheets or plastic films can be used. It is also possible to put a second substrate on top of the coated material prior to and/or during and/or after polymerisation.
  • the substrates can be removed after polymerisation or not.
  • at least one substrate has to be transmissive for the actinic radiation used for the polymerisation.
  • Isotropic or birefringent substrates can be used. In case the substrate is not removed from the polymerised film after polymerisation, preferably isotropic substrates are used.
  • Suitable and preferred plastic substrates are for example films of polyester such as polyethyleneterephthalate (PET) or polyethylene-naphthalate (PEN), polyvinylalcohol (PVA), polycarbonate (PC) or triacetylcellulose (TAC), very preferably PET or TAC films.
  • PET films are commercially available for example from DuPont Teijin Films under the trade name Melinex®.
  • the RMs and the other solid additives are dissolved in a solvent.
  • the solution is then coated or printed onto the substrate, for example by spin-coating or printing or other known techniques, and the solvent is evaporated off before polymerisation. In many cases it is suitable to heat the coated solution in order to facilitate the evaporation of the solvent.
  • the RM formulaion can be applied onto the substrate by conventional coating techniques like spin-coating or blade coating. It can also be applied to the substrate by conventional printing techniques which are known to the expert, like for example screen printing, offset printing, reel-to-reel printing, letter press printing, gravure printing, rotogravure printing, flexographic printing, intaglio printing, pad printing, heat-seal printing, inkjet printing or printing by means of a stamp or printing plate.
  • the RM formulation should preferably exhibit planar alignment. This can be achieved for example by rubbing treatment of the substrate, by shearing the material during or after coating, by annealing the material before polymerisation, by application of an alignment layer, by applying a magnetic or electric field to the coated material, or by the addition of surface-active compounds to the formulation.
  • Reviews of alignment techniques are given for example by I. Sage in “Thermotropic Liquid Crystals”, edited by G. W. Gray, John Wiley & Sons, 1987, pages 75-77; and by T. Uchida and H. Seki in “Liquid Crystals—Applications and Uses Vol. 3”, edited by B. Bahadur, World Scientific Publishing, Singapore 1992, pages 1-63.
  • a review of alignment materials and techniques is given by J. Cognard, Mol. Cryst. Liq. Cryst. 78, Supplement 1 (1981), pages 1-77.
  • Suitable alignment layers are known in the art, like for example rubbed polyimide or alignment layers prepared by photoalignment as described in U.S. Pat. No. 5,602,661, U.S. Pat. No. 5,389,698 or U.S. Pat. No. 6,717,644.
  • Polymerisation is achieved for example by exposing the polymerisable material to heat or actinic radiation.
  • Actinic radiation means irradiation with light, like UV light, IR light or visible light, irradiation with X-rays or gamma rays or irradiation with high energy particles, such as ions or electrons.
  • Preferably polymerisation is carried out by UV irradiation.
  • a source for actinic radiation for example a single UV lamp or a set of UV lamps can be used. When using a high lamp power the curing time can be reduced.
  • Another possible source for actinic radiation is a laser, like for example a UV, IR or visible laser.
  • the curing time depends, inter alia, on the reactivity of the RM formulation, the thickness of the coated layer, the type of polymerisation initiator and the power of the UV lamp.
  • the curing time is preferably ⁇ 5 minutes, very preferably ⁇ 3 minutes, most preferably ⁇ 1 minute. For mass production short curing times of ⁇ 30 seconds are preferred.
  • the polymerisation process is not limited to one curing step. It is also possible to carry out polymerisation by two or more steps, in which the film is exposed to two or more lamps of the same type, or two or more different lamps in sequence.
  • the curing temperature of different curing steps might be the same or different.
  • the lamp power and dose from different lamps might also be the same or different.
  • the process steps may also include a heat step between exposure to different lamps, as described for example in JP 2005-345982 A and JP 2005-265896 A.
  • polymerisation is carried out in air, but polymerising in an inert gas atmosphere like nitrogen or argon is also possible.
  • the thickness of a polymer film according to the present invention is preferably from 0.2 to 10 microns, very preferably from 0.3 to 5 microns, most preferably from 0.5 to 3 microns.
  • the polymer films and materials of the present invention can be used in optical, electrooptical or electronic devices ort components thereof.
  • they can be used in optical retardation films, polarizers, compensators, beam splitters, reflective films, alignment layers, colour filters, antistatic protection sheets, or electromagnetic interference protection sheets, polarization controlled lenses for autostereoscopic 3D displays, and IR reflection films for window applications.
  • the polymer films, materials and components can be used in devices is selected from electrooptical displays, especially liquid crystal displays (LCDs), autostereoscopic 3D displays, organic light emitting diodes (OLEDs), optical data storage devices, and window applications.
  • electrooptical displays especially liquid crystal displays (LCDs), autostereoscopic 3D displays, organic light emitting diodes (OLEDs), optical data storage devices, and window applications.
  • the polymer films and materials of the present invention can be used outside the switchable LC cell of an LCD or between the substrates, usually glass substrates, forming the switchable LC cell and containing the switchable LC medium (incell application).
  • the polymer film and materials of the present invention can be used in conventional LC displays, for example displays with vertical alignment like the DAP (deformation of aligned phases), ECB (electrically controlled birefringence), CSH (colour super homeotropic), VA (vertically aligned), VAN or VAC (vertically aligned nematic or cholesteric), MVA (multi-domain vertically aligned), PVA (patterned vertically aligned) or PSVA (polymer stabilised vertically aligned) mode; displays with bend or hybrid alignment like the OCB (optically compensated bend cell or optically compensated birefringence), R—OCB (reflective OCB), HAN (hybrid aligned nematic) or pi-cell ( ⁇ -cell) mode; displays with twisted alignment like the TN (twisted nematic), HTN (highly twisted nematic), STN (super twisted nematic), AMD-TN (active matrix driven TN) mode; displays of the IPS (in plane
  • the polymer films of the present invention can be used for various types of optical films, like twisted optical retarders, reflective polarisers and brightness enhancement films.
  • the invention also relates to an RM formulation as described above and below, which has increased electrical conductivity and decreased electrical resistivity, preferably a resistivity ⁇ 1E06 ⁇ m, very preferably ⁇ 7E05 ⁇ m and a conductivity ⁇ 1E-06 S/m, very preferably ⁇ 1.2E68 S/m.
  • the invention also relates to a polymer film with reduced (electrical) sheet resistance, which comprises or consists of a polymerised RM formulation as described above and below, or is obtained by polymerising a layer of an RM formulation as described above and below, preferably wherein the RMs are aligned, and preferably at a temperature where the RM formulation exhibits a liquid crystal phase.
  • One preferred embodiment relates to polymer films having a sheet resistance ⁇ 10,000 ⁇ /sq. Such films are especially suitable for example as antistatic protection sheets. Another preferred embodiment relates to polymer films having a sheet resistance ⁇ 50 ⁇ /sq, very preferably ⁇ 5 ⁇ /sq. Such films are suitable for example as electromagnetic interference protection sheets.
  • the sheet resistance can be measured by the four point probe method or Van der Pauw method, which is described in the literature.
  • the thickness of a polymer film with reduced sheet resistance is preferably from 0.2 to 5, very preferably from 0.5 to 3 microns.
  • the percentages of components of a polymerisable formulation as given above and below refer to the total amount of solids in the formulation without any solvents.
  • optical, electrooptical properties and physical parameters like birefringence, permittivity, electrical conductivity, electrical resistivity and sheet resistance, refer to a temperature of 20° C.
  • the RM formulation RMS1 is prepared as follows:
  • MOTMA-NTF 5039-78-1
  • MOTMA- C CA3 6891-44-7
  • MOTMA- MS CA4 H 2 O
  • Isopropyl- alcolhol CA6
  • MOTMA-NTF was preared as described in Scheme 1 above.
  • the conductive additives are to the RM formulation either alone or in combination with each other, for example, by combining additive CA2 with additive CA4, or combining additive CA3 with additive CA4.
  • Additive CA1 is added in concentrations of 0.1, 0.5 and 1% to the formulation RMS1.
  • the individual formulations with and without additive CA1 are coated on rubbed polyimide glass by spin coating (3000 rpm, 30 sec). This is followed by an annealing step (at 50° C. for 60 sec) to remove the solvent.
  • the coatings are cooled to room temperature and then exposed to UV light from a high pressure mercury lamp (1200 mJ/cm 2 ), forming a polymerised film.
  • Optical properties of the film are measured by ellipsometry, with a rotating sample stage providing retardation values at angles of incidence from ⁇ 40 to 40 degrees.
  • the results are shown in FIG. 1 for the films prepared from RMS1 containing 0%, 0.1%, 0.5% and 1% of CA1. No effect of the additive on the optical properties of the films is observed. All films show the same retardation value and off-axis performance for each concentration of CA1.
  • Polymerised RM films are prepared from RMS 1 without and with varying concentrations of additive CA2 as described above in Example 2, and their retardation values are measured by ellipsometry. The results are shown in FIG. 2 . No effect of the additive on the processing or optical properties of the film is observed.
  • RM film samples are prepared from RMS 1 without or with additive CA1, CA2 or CA3 in concentrations of 0.1%, 0.5% and 1%, respectively, by the method as described above.
  • the film samples are then placed in a temperature chamber at 120° C. and their retardation is measured periodically by ellipsometry.
  • the effect of the temperature treatment on the retardation of the films is shown in FIGS. 3 , 4 and 5 for additive CA1, CA2 and CA3, respectively. It can be seen that the retardation drop due to exposure to high temperature is identical, within experimental error, for film samples with concentrations of the additive between 0-1%. The same trend was observed for each of additive CA1, CA2 and CA3.

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US20170283699A1 (en) 2017-10-05
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EP2812413B1 (en) 2016-03-16
JP2015513567A (ja) 2015-05-14
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KR20140129093A (ko) 2014-11-06

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