Patent Application
20180320072
The present invention relates to compositions comprising a polymer comprising a monomer of formula (I) or of formula (IV) and an additive selected from the group consisting of acid generators, base generators, acids or bases.
Polymer comprising a monomer of formula (I) are already known in the art and are used as photo-alignable materials for optical and electro-optical applications. These photo-alignable materials are coated on substrates, dried by heating and subsequently irradiated with UV light. Subsequently, the photo-alignable materials may be subjected to thermal treatment. A method for preparing liquid crystal cells is by assembling two coated substrates and pouring the liquid crystal on the coated substrates. After assembly the liquid crystal cell is annealed by heat. It is also possible to subject the cell to a thermal treatment before pouring with the liquid crystal. In some applications, the annealing temperature is above 90° C., in other applications above 100° C., in still other above 110° C., in other applications above 120° C. or 130° C.
Liquid crystal cells that have been annealed at higher temperature, i.e. above 100° C. may lose their electro-optical properties. Therefore there is the need to develop compositions comprising photo-alignable materials that show good electro-optical properties after thermal treatment.
It is therefore an aim of the present invention of providing a composition which allows the stabilization of the photo-alignable material at high temperatures, preferably above 100° C.
It is a first object of the present invention to provide a composition comprising a photo-alignable material and an additive selected from the group consisting of acid generators, base generators, acids and bases.
It is a second object of the present invention to provide a composition comprising at least one photo-alignable material, a polymer which is different from the first one and an additive selected from the group consisting of acid generators, base generators, acids or bases.
It is a third object of the present invention to provide an orientation layer comprising said composition, preferably further comprising a polymerisable liquid crystal.
It is a fourth object of the present invention to provide a method for preparing the orientation layer comprising said composition and to orientation layers obtained by such method.
In its fifth embodiment the invention relates to the use of said orientation layer to align liquid crystal, or for the alignment of liquid crystals comprising polymerizable liquid crystals, or polymerizable liquid crystals, or for the alignment of liquid crystals which are sandwiched between a pair of said orientation layers.
It is an sixth object of the present invention to provide a method for manufacturing a liquid crystal display comprising said composition or said orientation layer.
It is a seventh object of the present invention to provide optical or electro-optical unstructured or structured elements comprising said composition or said orientation layer.
In a first embodiment the invention relates to compositions comprising a photo-alignable material and an additive, selected from the group consisting of acid generators, base generators, acids or bases.
Preferably, the photo-alignable materials according to the invention incorporate photo-alignable moieties, which are capable of developing a preferred direction upon exposure to aligning light and thus inducing an alignment capability for liquid crystals. Photo-alignable moieties preferably have anisotropic absorption properties and preferably exhibit absorption within the wavelength range from 230 to 500 nm.
Preferably the photo-alignable moieties have carbon-carbon, carbon-nitrogen, or nitrogen-nitrogen double bonds.
For example, photo-alignable moieties are substituted or un-substituted azo dyes, anthraquinone, coumarin, mericyanine, methane, 2-phenylazothiazole, 2-phenylazobenzthiazole, stilbene, cyanostilbene, chalcone, cinnamate, stilbazolium, 1,4-bis(2-phenylethylenyl)benzene, 4,4′-bis(arylazo)stilbenes, perylene, 4,8-diamino-1,5-naphthoquinone dyes, diaryl ketones, having a ketone moiety or ketone derivative in conjugation with two aromatic rings, such as for example substituted benzophenones, benzophenone imines, phenylhydrazones, and semicarbazones.
Preparation of the anisotropically absorbing materials listed above are well known as shown, e.g. by Hoffman et al., U.S. Pat. No. 4,565,424, Jones et al., in U.S. Pat. No. 4,401,369, Cole, Jr. et al., in U.S. Pat. No. 4,122,027, Etzbach et al., in U.S. Pat. No. 4,667,020, and Shannon et al., in U.S. Pat. No. 5,389,285.
Preferably, the photo-alignable moieties comprise arylazo, poly(arylazo), stilbene, cyanostillbene, diaryl ketone derivatives and cinnamates, more preferred, the photo-alignable moieties comprise a cinnamate.
A photo-alignment material may have the form of a monomer, oligomer or polymer.
The photo-alignable moieties can be covalently bonded within the main chain or within a side chain of a polymer or oligomer or they may be part of a monomer.
Polymers denotes for example to polyacrylate, polymethacrylate, polyimide, polyamic acids, polymaleinimide, poly-2-chloroacrylate, poly-2-phenylacrylate; unsubstituted or with C1-C6alkyl substituted poylacrylamide, polymethacyrlamide, poly-2-chloroacrylamide, poly-2-phenylacrylamide, polyvinylether, polyvinylester, polystyrene-derivatives, polysiloxane, staright-chain or branched alkyl esters of polyacrylic or polymethacrylic acids; polyphenoxyalkylacrylates, polyphenoxyalkylmethacrylates, polyphenylalkylmathacrylates, with alkyl residues of 1-20 carbon atoms; polyacrylnitril, polymethacrylnitril, polystyrene, poly-4-methylstyrene or mixtures thereof. Further, preferred photo-alignable monomers or oligomers or polymers are described in U.S. Pat. No. 5,539,074, U.S. Pat. No. 6,201,087, U.S. Pat. No. 6,107,427, U.S. Pat. No. 6,335,409 and U.S. Pat. No. 6,632,909.
In a preferred embodiment the invention relates to compositions comprising a photo-alignable material comprising or deriving from a monomer of formula (I)
The wording “polymerizable group” as used in the context of the present invention refers to a functional group that can be subjected to polymerization (optionally with other comonomers) to yield an oligomer, dendrimer, polymer or copolymer. The obtained oligomer, dendrimer, polymer or copolymer can either be linear, branched or crosslinked. For a person skilled in the art it will be obvious which functional groups are intended for any specific polymer. Thus for example in case of “imid monomer” as the indicated polymerizable group it is obvious to a person skilled in the art that the actual monomer units for polymerization to yield a polyimid are e.g. diamines and dianhydrides. Similarly regarding “urethane monomer” the actual monomer units are diols and diisocyanates.
In the context of the present invention, the term “a functional group” means that there can be more than one functional group, as for example 2 functional groups or 3 functional groups or 4 functional groups. So for example the compound of formula (I) can have 1, 2, 3 or 4 functional groups in the PG.
PG is preferably selected from unsubstituted or substituted acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate, optionally N-lower alkyl substituted acrylamide, methacrylamide, 2-chloroacrylamide, 2-phenylacrylamide, vinyl, allyl, vinyl ether and ester, allyl ether and ester, carbonic acid ester, acetal, urea, maleinimide, norbornene, norbornene derivatives, epoxy, styrene and styrene derivatives, for example alpha-methylstyrene, p-methylstyrene, p-tert-butyl styrene, p-chlorostyrene, siloxane, silane, diamine, imide monomers, amic acid monomers and their esters, amidimide monomers, maleic acid and maleic acid derivatives, for example, di-n-butyl maleate, dimethyl maleate, diethyl maleate, etc, fumaric acid and fumaric acid derivatives, for example, di-n-butyl fumarate, di-(2-ethylhexyl) fumarate, etc, urethanes or their corresponding homo- and co-polymers.
More preferably the polymerizable group PG is selected from acrylate, methacrylate, vinyl ether and ester, epoxy, styrene derivatives, siloxane, silane, maleinimide, diamine, norbornene, norbornene derivatives, imide monomers, amic acid monomers and their corresponding homo and copolymers, or an unsubstituted or substituted, aliphatic, aromatic and/or alicyclic diamine group.
More preferably PG represents an unsubstituted or substituted, aliphatic, aromatic and/or alicyclic diamine group, siloxane, maleinimide, especially 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 or a siloxane.
Even more preferably PG is a siloxane compound.
The spacers G and S2 independently from each other represent a single bond or a spacer unit, which could be a cyclic, straight-chain or branched, substituted or unsubstituted C1-C24 alkylen, especially C1-C12 alkylen, especially C1-C8 alkylen, more especially C1-C6 alkylen, most especially C1-C4 alkylen; in which one or more, preferably non-adjacent, —C—, —CH—, —CH2— group may be unreplaced or at least once replaced by a linking group.
More preferably spacers G and S2 independently from each other represent C1-C24 alkylen, in which one or more, preferably non-adjacent, —C—, —CH—, —CH2— group may be unreplaced or at least once replaced by a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group connected via bridging groups.
Substituents of the non-aromatic, aromatic, alicyclic group or phenylene, cylohexylen or the carbocyclic or heterocyclic group in G and S2 are preferably, at least one halogen, such as chloro or fluoro or trifluoromethyl, and/or C1-C6alkoxy, preferably methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and/or oxygen.
Preferably, the non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group connected via bridging groups of G and S2 each independently from each other are represented by formula (II):
—(Z2a)a4—(Z1—C1)a1—(Z2—C2)a2—(Z1a)a3— (II)
More preferably, the non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group of S2 is represented by formula (II) and wherein:
—(Z2a)a
More preferably G is a single bond, a unsubstituted or unsubstituted non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group or —(CH2)n1—, —(CH2)n1—O—(CH2)n1—, (CH2)n1—O(OC)—(CH2)n1—, (CH2)n1—(OC)O—(CH2)n1—, (CH2)n1—NH—(CH2)n1—, (CH2)n1—NH(OC)—(CH2)n1—, —(CH2)n1—(OC)NH—(CH2)n1—, (CH2)n1—S—(CH2)n1—, (CH2)n1—S(SC)—(CH2)n1—, (CH2)n1—(SC)NH—(CH2)n1—, (CH2)n1—NH(CS)—(CH2)n1—, (CH2)n1—(SC)S—(CH2)n1—, (CH2)n1—NHCONH—(CH2)n1—, (CH2)n1—NHCSNH—(CH2)n1—, (CH2)n1—O(CO)O—(CH2)n1—, —(CH2)n1—OCONH—(CH2)n1—, —(CH2)n1—NHOCO—(CH2)n1—.
Most preferably G is a single bond, phenylene, substituted or unsubstituted cyclohexylen or —(CH2)n1—, —(CH2)n1—O(OC)—(CH2)n1—, —(CH2)n1—NH(CO)O—(CH2)n1—, preferably —(CH2)1, —(CH2)2—, —(CH2)5—, —(CH2)8—, —O(OC)—(CH2)6—, —O(OC)—(CH2)8—, —(CH2)3—NH(CO)O—(CH2)3—,
wherein n1 is independently from each other is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and preferably 0, 1, 2, 3, 4, 5, 6, and more preferably 0, 1, 2, 3, 4 and most preferably 0, 1 or 2.
More preferably, S2 is a single bond, straight-chain or branched, substituted or unsubstituted C1-C8 alkylen, more especially C1-C6 alkylen, most especially C1-C4 alkylen within the above-given preferences; in which one or more, preferably non-adjacent, —C—, —CH—, —CH2— group may be unreplaced or at least once replaced
with the proviso that oxygen atoms of linking groups are not directly linked to each other.
If is further encompassed by the present invention that if S2 comprises an aromatic group, then the bondings to the remaining of the molecule can occur at any carbon atom of the aromatic ring.
The term “linking group”, as used in the context of the present invention is preferably selected from an unsubstituted or substituted alicyclic group, preferably cyclohexylen, or an unsubstituted or substituted aromatic group, single bond, heteroatom cationic carbohydrogen group such as —(C+)—, —O—, —CO, -arylen-, —CO—O—, —O—CO—,
CN, —NR1—, —NR1—CO—, —CO—NR1—, —NR1—CO—O—, —O—CO—NR1—, —NR1—CO—NR1—, —CH═CH—, —C≡C—, —O—CO—O—, and —Si(CH3)2—O—Si(CH3)2—, and wherein:
R1 represents a hydrogen atom or C1-C6alkyl;
with the proviso that oxygen atoms of linking groups are not directly linked to each other.
Substituents of the substituted alicyclic or aromatic group of the linking groups my be one or more and, are preferably halogene, such as fluor, chloro, bromo, iodo, and preferably fluoro and/chloro and more preferably fluor; or C1-C6alkoxy, such as preferably methoxy, or triflouromethyl.
In a further embodiment of the invention E preferably represents a substituted or unsubstituted phenylene, a single bond, —O—, —COO—, —OOC—, —NHCO—, —CONH—, —CONR2—, —NR2CO, —SCS, —CO—, most preferred E is —O—, —COO—, —OOC— or substituted or unsubstituted phenylene.
In a preferred embodiment W is a with A substituted phenyl ring, wherein A represents one or more halogens, H or one or more substituted or unsubstituted C1-C24 alkyls, one or more substituted or unsubstituted C1-C24 alkenyls, one or more substituted or unsubstituted C1-C24 alkynyls, or one or more carboxylic acid, wherein one or more, —C—, —CH—, —CH2—, group may independently from each other be replaced by a heteroatom.
More preferred T is a single bond, a straight-chain C1-C16 alkyl, wherein at least one —C—, —CH—, —CH2— or —CH3 group is independently from each other be unreplaced or replaced by at least one heteroatom, preferably the —C—, —CH—, —CH2— group is unreplaced or replaced by at least one heteroatom, wherein the heteroatom can be —O— or —S—; and/or by a primary, secondary, tertiary or quaternary nitrogen, such as an ammonium cation, more preferably replaced by a secondary, or tertiary amine; and/or replaced by a linking group, more preferably such linking group is a halogene, such as fluoro, chloro, bromo, iodo, and more preferably fluoro and/or chloro, and most preferably fluoro; and/or a linking group, which is preferably an unsubstituted or substituted alicyclic or aromatic group, —CH═CH—, —C≡C—, single bond, heteroatom, —O—, —CO, —CO—O—CN,
CN, —NR1— and wherein:
In a preferred embodiment of the invention E preferably represents a substituted or unsubstituted phenylene, a single bond, —O—, —COO—, —OOC—, —NHCO—, —CONH—, —CONR2—, —NR2CO, —SCS, —CO—, most preferred E is —O—, —COO—, —OOC— or substituted or unsubstituted phenylene.
In the context of the present invention the wording “end group” is selected from the group consisting of:
Preferred is in the context of the present invention the wording “end group” represents for example preferably
More preferred aromatic groups are benzyl, phenyl and biphenyl; More preferred are chloro or fluoro, trifluoromethyl, ether, such as C1-C6 alkoxy, di-(C1-C16 alkyl)amino, nitrile, pyridyl, unsubstituted or substituted straight-chain or branched alkynyl, which is preferably -Ξ-, -Ξ—CH3, acetyl; unsubstituted or substituted carbocyclic or heterocyclic aromatic group or alicyclic group, incorporating preferably five, six, ten or 14 ring atoms, e.g. furan, benzyl or phenyl, pyridinyl, pyridinium cation, pyrimidinyl, pyrimidinium cation, naphthyl, which may form ring assemblies, such as biphenylyl or triphenyl, which are uninterrupted or interrupted by at least a single heteroatom and/or at least a single bridging group; or fused polycyclic systems, such as phenanthryl, tetralinyl. Preferably aromatic group are benzyl, phenyl, biphenyl or triphenyl. More preferred aromatic groups are benzyl, phenyl and biphenyl; Most preferred is chloro or fluoro, trifluoromethyl, ether, such as C1-C6 alkoxy, di-(C1-C16 alkyl)amino, nitrile, pyridyl, unsubstituted or substituted straight-chain or branched alkynyl, which is preferably -Ξ-, -Ξ—CH3, acetyl; unsubstituted or substituted benzyl, phenyl or biphenyl; and especially preferred is nitrile.
A bridging group as used in the context of the present invention is preferably selected from —CH(OH)—, —CO—, —CH2(CO)—, —SO—, —CH2(SO)—, —SO2—, —CH2(SO2)—, —COO—, —OCO—, —COCF2—, —CF2CO, —S—CO—, —CO—S—, —SOO—, —OSO—, —SOS—, —O—CO—O—, —CH2—CH2—, —OCH2—, —CH2O—, —CH═CH—, —C≡C—, —(C1-C6alkyl)1-6C═CH—COO—, —CH═CH—COO—, —OCO—CH═CH—, —OCO—CH═C(C1-C6alkyl)1-6CH—, —CH═N—, —C(CH3)═N—, —N═N—, heteroatom, cationic carbohydrogen group such as —(C+)-, or a single bond; or a cyclic, straight-chain or branched, substituted or unsubstituted C1-C24alkylen, wherein one or more —C—, —CH—, —CH2— groups may independently from each other be unreplaced or replaced by a linking group as described above.
In the context of the present invention alkyl has the meaning of unsubstituted or substituted alkyl, wherein substituted alkyl has also the meaning alkylen.
Alkyl, alkyloxy, alkoxy, alkylcarbonyloxy, acryloyloxyalkoxy, acryloyloxyalkyl, acryloyloxyalken, alkyloxycarbonyloxy, alkylacryloyloxy, methacryloyloxyalkoxy, methacryloyloxyalkyl, methacryloyloxyalken, alkylmethacryloyloxy, alkylmethacryloyloxy, alkylvinyl, alkylvinyloxy and alkylallyloxy and alkylene, as used in the context of the present invention denote with their alkyl residue, respectively their alkylene residue, a cyclic, straight-chain or branched, substituted or unsubstituted alkyl, respectively alkylene, in which one or more, preferably non-adjacent, —C—, —CH—, or —CH2— group may be unreplaced or replaced by a linking group, preferably replaced by —O—, NH, —COO, OCO.
Further, in the context of the present invention “alkyl” is branched or straight chain, unsubstituted or substituted alkyl, preferably C1-C40 alkyl, especially C1-C30 alkyl, preferably C1-C20 alkyl, more preferably C1-C16 alkyl, most preferably C1-C10 alkyl and especially most preferably C1-C6 alkyl. Accordingly alkylen is for example C1-C40 alkylen, especially C1-C30 alkylen, preferably C1-C20 alkylen, more preferably C1-C16 alkylen, most preferably C1-C10alkylen and especially most preferably C1-C6 alkylen.
In the context of the present invention the definitions for alkyl given below, are applicable to alkylene in analogy.
C1-C6 alkyl is for example methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl or hexyl.
C1-C10 alkyl is for example methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl.
C1-C16 alkyl is for example methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl.
C1-C20 alkyl is for example methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nondecyl, eicosyl.
C1-C24 alkyl is for example methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nondecyl, eicosyl.
C1-C30 alkyl is for example methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nondecyl, eicosyl, heneicosyl, tricosyl, tetracosy, pentacosyl, hexacosdy, heptacosyl, octacosyl, nonacosy or triacontyl.
C1-C40 alkyl is for example methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nondecyl, eicosyl, heneicosyl, tricosyl, tetracosy, pentacosyl, hexacosdy, heptacosyl, octacosyl, nonacosy, triacontyl or tetracontyl.
C1-C6 alkoxy is for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec.-butoxy, tert.-butoxy, pentoxy or hexoxy.
C1-C20 acryloyloxyalkylene, preferably C1-C10 acryloyloxyalkylene, C1-C6 acryloyloxyalkylene is for example acryloyloxymethylen, acryloyloxyethylene, acryloyloxypropylene, acryloyloxyisopropylene, acryloyloxybutylene, acryloyloxy-sec.-butylene, acryloyloxypentylene, acryloyloxyhexylene, acryloyloxyheptylene, acryloyloxyoctylene, acryloyloxynonylene, acryloyloxydecylene, acryloyloxyundecylene, acryloyloxydodecane, acryloyloxytridecylene, acryloyloxytetradecylene, acryloyloxypentyldecane, acryloyloxyhexadecylene, acryloyloxyheptadecylene, acryloyloxyoctadecylene, acryloyloxynondecylene, acryloyloxyeicosylene.
C1-C20 methacryloyloxyalkylene, preferably C1-C10 methacryloyloxyalkylene,
C1-C6 methacryloyloxyalkylene is for example methacryloyloxymethylen, methacryloyloxyethylene, methacryloyloxypropylene, methacryloyloxyisopropylene, methacryloyloxybutylene, methacryloyloxy-sec.-butylene, methacryloyloxypentylene, methacryloyloxyhexylene, methacryloyloxyheptylene, methacryloyloxyoctylene, methacryloyloxynonylene, methacryloyloxydecylene, methacryloyloxyundecylene, methacryloyloxydodecane, methacryloyloxytridecylene, methacryloyloxytetradecylene, methacryloyloxypentyldecane, methacryloyloxyhexadecylene, methacryloyloxyheptadecylene, methacryloyloxyoctadecylene, methacryloyloxynondecylene, methacryloyloxyeicosylene.
C1-C20 acryloyloxyalkoxy, preferably C1-C10 acryloyloxyalkoxy,
C1-C6 acryloyloxyalkoxy is for example acryloyloxymethoxy, acryloyloxyethoxy, acryloyloxypropoxy, acryloyloxyisopropoxy, acryloyloxybutoxy, acryloyloxy-sec.-butoxy, acryloyloxypentoxy, acryloyloxyhexoxy, acryloyloxyheptoxy, acryloyloxyoctoxy, acryloyloxynonoxy, acryloyloxydecoxy, acryloyloxyundecoxy, acryloyloxydodecanoxy, acryloyloxytridecyloxy.
C1-C20 methacryloyloxyalkoxy, preferably C1-C10 methacryloyloxyalkoxy, C1-C6 methacryloyloxyalkoxy is for example methacryloyloxymethoxy, methacryloyloxyethoxy, methacryloyloxypropoxy, methacryloyloxyisopropoxy, methacryloyloxybutoxy, methacryloyloxy-sec.-butoxy, methacryloyloxypentoxy, methacryloyloxyhexoxy, methacryloyloxyheptoxy, methacryloyloxyoctoxy, methacryloyloxynonoxy, methacryloyloxydecoxy, methacryloyloxyundecoxy, methacryloyloxydodecanoxy, methacryloyloxytridecyloxy.
An aliphatic group is for example a saturated or unsaturated, mono-, bi-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca-valent alkyl, alkylene, alkyloxy, alkylcarbonyloxy, acryloyloxy, alkylacryl, alkylmethacryl, alkyl(en)acryl(en), alkyl(en)methacryl(en), alkyloxycarbonyloxy, alkyloxycarbonyloxy methacryloyloxy, alkylvinyl, alkylvinyloxy or alkylallyloxy, which may comprise one or more heteroatom and/or bridging group.
An alicyclic group is preferably a non-aromatic group or unit and may be substituted or unsubstituted. Preferably an alicyclic group is a non-aromatic carbocyclic or heterocyclic group and represents for example ring systems, with 3 to 30 carbon atoms, as for example cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cyclohexadiene, decaline, tetrahydrofuran, dioxane, pyrrolidine, piperidine or a steroidal skeleton such as cholesterol. Preferred alicyclic group is cyclohexene. Substituents of an alicyclic group are halogene, preferably fluor or/and chloro, C1-C6 alkoxy, preferably methoxy or triflourmethyl.
The term “aromatic”, as used in the context of the present invention, preferably denotes unsubstituted or substituted carbocyclic and heterocyclic groups, incorporating five, six, ten ot 14 ring atoms, e.g. furan, benzene or phenylene, pyridine, pyrimidine, naphthalenen, which may form ring assemblies, such as biphenylene or triphenylen, which are uninterrupted or interrupted by at least a single heteroatom and/or at least a single bridging group; or fused polycyclic systems, such as phenanthrene, tetraline.
Preferably aromatic group are benzene, phenylene, biphenylene or triphenylen. More preferred aromatic group is benzene, phenylene and biphenylene. Especially preferred substituents of an aromatic group or of a carbocyclic and heterocyclic groups are halogene, preferably fluor or/and chloro, C1-C6 alkoxy, preferably methoxy or triflourmethyl.
A carbocyclic or heterocyclic aromatic group or alicyclic group incorporates preferably three, four, five, six, ten or 14 ring atoms, as for example aziridin, epoxy, cyclopropyl, furan, pyrollidin, oxazolin, imidazol, benzene, pyridine, triazine, pyrimidine, naphthalene, phenanthrene, biphenylene or tetraline units, preferably naphthalene, phenanthrene, biphenylene or phenylene, more preferably naphthalene, biphenylene or phenylene, and most preferably phenylene.
Especially preferred substituents of carbocyclic and heterocyclic aromatic groups are halogene, preferably fluor or/and chloro, C1-C6alkoxy, preferably methoxy or triflourmethyl.
The unsubstituted or substituted carbocyclic or heterocyclic aromatic or alicyclic group is for example unsubstituted or mono- or poly-substituted. Preferred substitutents of carbocyclic or heterocyclic aromatic groups are at least one triflourmethyl, halogen, such as fluor, chloro, bromo, iodo, especially fluor or/and cloro, and more especially fluor; hydroxyl, a polar group, acryloyloxy, alkylacryloyloxy, alkoxy, especially methoxy, ethoxy, propoxy; alkylcarbonyloxy, alkyloxycarbonyloxy, alkyloxocarbonyloxy, methacryloyloxy, vinyl, vinyloxy and/or allyloxy group, wherein the alkyl residue has preferably from 1 to 20 carbon atoms, and more preferably having from 1 to 10 carbon atoms. Preferred polar groups are nitro, nitrile or a carboxy group, and/or a cyclic, straight-chain or branched C1-C30 alkyl, which is unsubstituted, mono- or poly-substituted. Preferred substitutents of C1-C30 alkyl are methyl, fluorine and/or chlorine, wherein one or more, preferably non-adjacent, —C—, —CH—, —CH2— group may independently of each other be replaced by a linking group. Preferably, the linking group is selected from —O—, —CO—, —COO— and/or —OCO—.
A monocyclic ring of five or six atoms is for example furan, benzene, preferably phenylene, pyridine, pyrimidine, pyridine cation, pyrimidine cation.
A bicyclic ring system of eight, nine or ten atoms is for example naphthalene, biphenylene or tetraline.
A tricyclic ring system of thirteen or fourteen atoms is for example phenanthrene.
The term “phenylene”, as used in the context of the present invention, preferably denotes a 1,2-, 1,3- or 1,4-phenylene group, which is optionally substituted. Especially preferred substituents of phenylene are halogene, preferably fluor or/and chloro, C1-C6alkoxy, preferably methoxy or triflourmethyl. It is preferred that the phenylene group is either a 1,3- or a 1,4-phenylene group. 1,4-phenylene groups are especially preferred.
The term “halogen” denotes a chloro, fluoro, bromo or iodo substituent, preferably a chloro or fluoro substituent, and more preferably fluoro.
The term “heteroatom”, as used in the context of the present invention is a neutral, anionic or cationic heteroatom and primarily denotes oxygen, sulphur and nitrogen, halogene, such as fluoro, chloro, bromo, iodo, and more preferably fluoro and/or chloro, and most preferably fluoro; preferably halogene, oxygen and nitrogen, in the latter case primary amine, secondary amine, tertiary amine or quartarnary ammonium cation, preferably in the form of —NH—.
The term “optionally substituted” as used in the context of the present invention primarily means substituted by lower alkyl, such as C1-C6alkyl, lower alkoxy, such as C1-C6alkoxy, hydroxy, halogen or by a polar group as defined above.
With respect to straight chain or branched alkyl, alkylene, alkoxy, alkylcarbonyloxy, acryloyloxyalkoxy, acryloyloxyalkyl, acryloyloxyalkene, alkyloxycarbonyloxy, alkylacryloyloxy, methacryloyloxyalkoxy, methacryloyloxyalkyl, methacryloyloxyalkene, alkylmethacryloyloxy, alkylmethacryloyloxy, alkylvinyl, alkylvinyloxy, alkylallyloxy and alkylene groups it is repeatedly pointed out that some or several of the —C—, —CH—, —CH2— groups may be replaced e.g. by heteroatoms, but also by other groups, preferably bridging groups. In such cases it is generally preferred that such replacement groups are not directly linked to each other. It is alternatively preferred that heteroatoms, and in particular oxygen atoms are not directly linked to each other.
More preferred in the context of the first embodiment of the inventions are compositions comprising a photoalignable material polymers comprising or deriving from the siloxane monomer of formula (IV)
wherein,
Ra represents OH, Cl, substituted or unsubstituted alkoxyl group having 1 to 20 carbons, alkyl group having 1 to 20 carbons, or aryl group having 1 to 20 carbons;
S1 represents a single bond or a straight-chain or branched, substituted or unsubstituted C1-C24 alkylen, especially C1-C12 alkylen, more especially C1-C8 alkylen, more especially C1-C6 alkylen, most especially C1-C4 alkylen, most especially C1-C2 alkylen in which one or more —C—. —CH—, CH2— groups may be replaced by a linking group;
z is an integer from 0 to 15, preferably from 1 to 10, more preferably from 1 to 8, more preferably from 1 to 5, even more preferably from 1 to 3, most preferred n is 1;
Z1 represents a single bond, or substituted or unsubstituted aliphatic or alicyclic group of C3 to C12, more preferably C3 to C10, even more preferably C5 to C8, most preferably C5 to C6.
n0 is an integer from 0 to 4, preferably from 0 to 2; even more preferably from 1 to 2;
n1 is an integer from 0 to 15, preferably from 1 to 10, more preferably from 1 to 8, more preferably from 1 to 5, most preferably from 1 to 3, most preferred n is 1;
n2 is an integer from 1 to 15, preferably from 1 to 10, more preferably from 1 to 8, more preferably from 1 to 5, most preferably from 1 to 3, most preferred n is 1;
x0 is an integer from 1 to 2;
X, Y each independently from each other represents H, F, Cl, ON, with the proviso that at least one is H;
S2 represents a cyclic, aromatic, straight-chain or branched, substituted or unsubstituted C1-C24 alkylen, especially C1-C12 alkylen, more especially C1-C8 alkylen, more especially C1-C6 alkylen, most especially C1-C4 alkylen, most especially C1-C2 alkylen in which one or more —C—, —CH—, —CH2— groups may be replaced by a linking group;
E represents a single bond, an aromatic group, O, S, NH, C(C1-C6 alkyl), NR4, OC, OOC, OCONH, OCONR4, SCS, SC, wherein R4 is cyclic, straight chain or branched, substituted or unsubstituted C1-C24 alkyl wherein one or more —C—, —CH—, —CH2— group(s) may be independently from each other be replaced by a linking group;
A represents halogen, H or substituted or unsubstituted C1-C24 alkyl, a substituted or unsubstituted C1-C24 alkenyl, a substituted or unsubstituted C1-C24 alkynyl, or a carboxylic acid, wherein one or more, —C—, —CH—, —CH2—, group may independently from each other be replaced by a heteroatom; preferably A is halogen, H, or a C1-C24 alkoxy or a carboxylic acid; most preferably A is H, F, methoxy or a carboxylic acid;
R0 represents OH, Cl, a linear or branched, substituted or unsubstituted alkoxyl group having 1 to 20 carbons, in which a —C—, —CH—, —CH2— could be replaced by unsubstituted or substituted C6-C20 aryl group;
Z2 represents a chemical group having a delocalisation of its electronical density and/or inducing a delocalisation of the electronical density of its neighboring atom; and
T represents an unsubstituted or substituted, straight-chain C1-C16 alkyl;
and an additive selected from the group consisting of acid generators, base generators, acids and bases.
More preferred in the context of the first embodiment of the inventions are compositions comprising a photoalignable material polymers comprising or deriving from the siloxane monomer of formula (IV):
Wherein
Ra, z, n0, n1, n2, x0, S2, A, R1, T are as described above; and
Z1 represents a substituted or unsubstituted C5-C6 aliphatic or alicyclic group;
S1 represents a substituted or unsubstituted C1-C24 straight chain alkyl;
E represents O, or S or NH;
X, Y are H; and
Z2 is CN.
and an additive selected from the group consisting of acid generators, base generators, acids and bases.
In another preferred embodiment, the first aspect of the invention relates to composition comprising a photoalignable material comprising or deriving from the siloxane monomer of formula (IV):
wherein
Ra, z, n0, n1, n2, x0, S2, R1, T are as described above; and
A represents H, one or more halogens, one or more methoxy groups or one or more carboxylic groups;
Z1 represents a substituted or unsubstituted C5-C6 alicyclic group;
S1 represents a substituted or unsubstituted C1-C24 straight chain alkyl;
E represents O, or S or NH;
X, Y are H; and
Z2 is CN;
and an additive selected from the group consisting of acid generators, base generators, acids and bases.
In another preferred embodiment, the first aspect of the invention relates a composition comprising a photoalignable material comprising or deriving from a siloxane monomer of formula (IV):
Wherein
Ra, z, n0, n1, n2, x0, S2, R1, T are as described above; and
A represents H, one or more halogens, one or more methoxy groups or one or more carboxylic groups;
Z1 represents a substituted or unsubstituted C5-C6 alicyclic group;
S1 represents a substituted or unsubstituted C1-C24 straight chain alkyl;
E represents O;
X, Y are H; and
Z2 is CN;
and an additive selected from the group consisting of acid generators, base generators, acids and bases.
In a further preferred embodiment the first aspect of the invention relates to a composition comprising a photo-alignable material comprising or deriving from a monomer of formula (IV):
Wherein:
Ra, z, n0, n1, n2, x0, S2, R1, Z2, B are as described above; and
A represents H, one or more halogens, one or more methoxy groups or one or more carboxylic groups;
Z1 is a substituted or unsubstituted cyclohexanol group or a substituted or unsubstituted cyclohexanether group;
S1 is ethyl group;
E is O;
X, Y are H; and
Z2 is CN;
and an additive selected from the group consisting of acid generators, base generators, acids and bases.
The additive is selected from the group consisting of acid generators, base generators, acids and bases.
Examples of acid generators in the context of the present invention are onium salt acid generators and onium salt photo-initiators. Exemplary onium salt photo-initiators include diaryl iodonium salts, triaryl sulfonium salts, monoaryl dialkyl sulfonium salts, triaryl selenonium salts, tetraaryl phosphonium salts, aryl diazonium salts, triazine photo-acid generators, sulfonate photo-acid generators and disulfone photo-acid generators.
Examples of diaryl iodonium salts include but are not limited to diphenyliodonium salt, di-p-tolyliodonium salt, bis(4-dodecylphenyl)iodonium salt, bis(4-methoxyphenyl)iodonium salt, (4-octyloxyphenyl)phenyliodonium salt, bis(4-decyloxy)phenyliodonium salt, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium salt, 4-isopropylphenyl(p-tolyl)iodonium salt, 4-isobutylphenyl(p-tolyl)iodonium salt, 4-methylphenyl)[4 (2-methylpropyl)phenyl]-, hexafluorophosphate(1-) (Irgacure 250 from BASF), 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate diphenyliodonium tetrafluoroborate; di(4-methylphenyl)iodonium tetrafluoroborate; phenyl-4-methylphenyliodonium tetrafluoroborate; Bis(4-tert-butylphenyl)iodonium Hexafluorophosphate, Diphenyliodonium Trifluoromethanesulfonate, 4-Isopropyl-4′-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, bis(4-fluorophenyl)iodonium triflate, (2-Bromophenyl)(2,4,6-trimethylphenyl)iodonium triflate, [3-(Trifluoromethyl)phenyl](2,4,6-trimethylphenyl)iodonium, Phenyl[3-(trifluoromethyl)phenyl]iodonium triflate, (4-Nitrophenyl)(2,4,6-trimethylphenyl)iodonium triflate, (4-Nitrophenyl)(2,4,6-trimethylphenyl)iodonium triflate, di(4-heptylphenyl)iodonium tetrafluoroborate; di(3-nitrophenyl)iodonium hexafluorophosphate; di(4-chlorophenyl)iodonium hexafluorophosphate; di(naphthyl)iodonium tetrafluoroborate; di(4-trifluoromethylphenyl)iodonium tetrafluoroborate; diphenyliodonium hexafluorophosphate; di(4-methylphenyl)iodonium hexafluorophosphate; diphenyliodonium hexafluoroarsenate; di(4-phenoxyphenyl)iodonium tetrafluoroborate; phenyl-2-thienyliodonium hexafluorophosphate; 3,5-dimethylpyrazolyl-4-phenyliodonium hexafluorophosphate; diphenyliodonium hexafluoroantimonate; di(2,4-dichlorophenyl)iodonium hexafluorophosphate; di(4-bromophenyl)iodonium hexafluorophosphate; di(4-methoxyphenyl)iodonium hexafluorophosphate; di(3-carboxyphenyl)iodonium hexafluorophosphate; di(3-methoxycarbonylphenyl)iodonium hexafluorophosphate; di(3-methoxysulfonylphenyl)iodonium hexafluorophosphate; di(4-acetamidophenyl)iodonium hexafluorophosphate; di(2-benzothienyl)iodonium hexafluorophosphate; bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate, and diphenyliodonium hexafluoroantimonate.
Examples of sulfonium compounds include but are not limited to triphenylsulfonium trifluoromethanesulfonate, tri(4-methylphenyl)sulfonium trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 1-(2-naphtholylmethyl)thoranium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, tri-p-tolylsulfonium salt, 4-(phenylthio)phenyldiphenylsulfonium salt, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium salt, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthran-2-yldi-p-tolylsulfonium salt, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium salt, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium salt, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium salt, diphenylphenacylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium salt, 4-hydroxyphenylmethylphenacylsulfonium salt, phenyl[4-(4-biphenylthio)phenyl]-4-biphenylsulfonium salt, phenyl[4-(4-biphenylthio)phenyl]-3-biphenylsulfonium salt, [4-(4-acetophenylthio)phenyl]diphenylsulfonium salt, octadecylmethylphenacylsulfonium salt, 4-(phenylthio)phenyldiphenylsulfonium salt, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfoniumsalt, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium salt, phenyl[4-(4-biphenylthio)phenyl]-4-biphenylsulfonium salt, phenyl[4-(4-biphenylthio)phenyl]-3-biphenylsulfonium salt, and diphenyl[4-(p-terphenylthio)phenyl]diphenylsulfonium salt, triphenylsulfonium tetrafluoroborate, methyldiphenylsulfonium tetrafluoroborate, dimethylphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenylnaphthylsulfonium hexafluoroarsenate, tritolysulfonium hexafluorophosphate, anisyldiphenylsulfonium hexafluoroantimonate, 4-butoxyphenyldiphenylsulfonium tetrafluoroborate, 9-[4-(2-Hydroxyethoxy)phenyl]thianthrenium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, tri(4-phenoxyphenyl)sulfonium hexafluorophosphate, di(4-ethoxyphenyl)methylsulfonium hexafluoroarsenate, 4-acetonylphenyldiphenylsulfonium tetrafluoroborate, 4-thiomethoxyphenyldiphenylsulfonium hexafluorophosphate, di(methoxysulfonylphenyl)methylsulfonium hexafluoroantimonate, di(nitrophenyl)phenylsulfonium hexafluoroantimonate, di(carbomethoxyphenyl)methylsulfonium hexafluorophosphate, 4-acetamidophenyldiphenylsulfonium tetrafluoroborate, dimethylnaphthylsulfonium hexafluorophosphate, trifluoromethyldiphenylsulfonium tetrafluoroborate, p-(phenylthiophenyl)diphenylsulfonium hexafluoroantimonate Examples of diazonium compounds include but are not limited to diazonium salts, 2-chloro-4-(dimethylamino)-5-methoxybenzenediazonium, 4-n-phenyl-amino-2-methoxy-phenyl diazonium sulfate, 4-n-phenyl-amino-2-methoxy-phenyl diazonium p-ethyl phenyl sulfates, 4-n-phenylamino-2-methoxy-phenyl diazonium 2-naphthylsulfate, 4-n-phenyl-amino-2-methoxy-phenyl diazonium phenyl sulfates, 2,5-diethoxy-4-n-4′-methoxyphenyl carbonyl phenyl diazonium-3-carboxy-4-hydroxy-phenyl sulfates, 2-methoxy-4-n-phenyl diazonium-3-carboxy-4-hydroxy-phenyl sulfates, 4-Nitrobenzenediazonium Tetrafluoroborate.
Examples of triazine compounds include but are not limited to trichloromethyl-S-triazine compound as 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(2,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(2-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(Furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Examples of sulfonate compounds include but are not limited to -benzoyl-1-phenylmethyl p-toluenesulfonate, 2-benzoyl-2-hydroxy-2-phenylethyl p-toluenesulfonate, 1,2,3-benzene-triyl-tris(methanesulfonate), 2-dinitrobenzyl p-toluenesulfonate, or 4-nitrobenzyl p-toluenesulfonate, 2-Phenyl-2-(p-toluenesulfonyloxy)acetophenone.
Base generators include for example carbamate type, an α-aminoketone, a quaternary ammonium type as quaternary ammonium tetraphenyl borates salt, an o-acyloxime type as O-phenylacetyl 2-acetonaphthone oxime, sulfone amide, nifedipines, aromatic sulfonamides. Examples of base generators are 2-(9-Oxoxanthen-2-yl)propionic Acid 1,5,7-Triazabicyclo[4.4.0]dec-5-ene Salt, Acetophenone O-Benzoyloxime, 2-nitrobenzylcarbamate, nitrobenzylcyclohexylcarbamate, 3,5-dimethoxybenzylcyclohexylcarbamate, 1,2-Bis(4-methoxyphenyl)-2-oxoethyl Cyclohexylcarbamate, 3-nitrophenylcyclohexylcarbamate, benzylcyclohexylcarbamate, [[(2-nitrobenzyl)oxy]carbonyl]octylamine, [[(2-nitrobenzyl)oxy]carbonyl]cyclohexylamine, [[(2-nitrobenzyl)oxy]carbonyl]piperazine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2,6-dinitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, N-[[(2-nitrophenyl)-1-methylmethoxy]carbonyl]cyclohexylamine, N-[[(2-nitrophenyl)-1-methylmethoxy]carbonyl]-octadecylamine, bis[[(α-methyl-2-nitrobenzyl)oxy]carbonyl]hexane, 1,6-diamine, N-[[(2,6-dinitrophenyl)-1-methylmethoxy]carbonyl]cyclohexylamine, N-[[(2-nitrophenyl)-1-(2′-nitrophenyl)methoxy]carbonyl]cyclohexyl amine, N-substituted 4-(o-nitrophenyl)dihydroxypyridines, N-(2-nitrobenzyloxycarbonyl)piperidine, 1,3-bis(N-(2-nitrobenzyloxycarbonyl)-4-piperidyl]propane, N,N′-bis(2-nitrobenzyloxycarbonyl)dihexylamine, and O-benzylcarbonyl-N-(1-phenylethylidene)hydroxylamine, N-[[(2,6-dinitrophenyl)-1-(2′,6′-dinitrophenyl)methoxy]carbonyl]cyclohexylamine, N-cyclohexyl-4-methylphenylsulfonamide, N-cyclohexyl-2-naphthylsulfonamide, o-phenylacetyl-2-acetonaphthonoxim, and N-methylnifedipine, but are not limited thereto.
Base generators include aminoketone having a group C6H5CH2OCONH—, as for example -Methyl-1 [4-(methylthio)phenyl]-2-morpholinopropan-1-one or alkylaminocetophenone
Example of acids in the context of the present invention include Bronsted acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, hydrofluoric acid, formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, oxalic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, maleic acid, oleic acid, methylmalonic acid, p-aminobenzoic acid, methanesulfonic acid, para-toluenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, acetic acid and trifluoroacetic acid; and Lewis acids such as aluminum trichloride, boron trifluoride, titanium tetrarchloride, iron (III) chloride, zinc chloride, tin chloride, trialkylaluminum, zinc octanoate, tin octanoate, dibutyltin dilaurate, aluminum (III) acetylacetonate and dibutyltin dimethoxide. It is also possible to combine the Bronsted and the Lewis acids.
Examples of the bases in the context of the present invention include metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium dydroxide, alyl metals such al butyllithium, metal alkoxide ausch as sodium methoxide and potassium methoxide, metal silanolates ausch as sodium silanolate, potassium silanolate and lithium silanotale, primary, secondary and tertiary amines such as trimethylamine, ethylene diamine, diethylene triamine, 1,8-diazabicyclo[5.4.0]undec-7-ene and 1,4-diazabicyclo[2.2.2]octane, and phosphines such as tryphenyl phospine, tri(4-methoxyphenyl)phosphine and tributyl phosphine.
The composition according to the present invention may contain also other additives. The additive is selected from the group consisting of: nucleating agents, clarifying agents, antistatics, antioxidants, slip agents, silica, talc, stabilizers, UV stabilizers, lubricants, coupling agents, antimicrobial agents, crosslinking agents, surfactants, photo-active agents, photo-sensitizers, photo generators, in particular cationic photo-generators. Additives such as silane-containing compounds and epoxy-containing crosslinking agents may be added. Suitable silane-containing additives are described in Plast. Eng. 36 (1996), (Polyimides, fundamentals and applications), Marcel Dekker, Inc. Suitable epoxy-containing cross-linking additives include 4,4′-methylene-bis-(N,N-diglycidylaniline), trimethylolpropane triglycidyl ether, benzene-1,2,4,5-tetracarboxylic acid 1,2,4,5-N,N′-diglycidyldiimide, polyethylene glycol diglycidyl ether, N,N-diglycidylcyclohexylamine and the like. Other suitable additives include 2,2-dimethoxyphenylethanone, a mixture of diphenylmethanone and N,N-dimethylbenzenamine or ethyl 4-(dimethylamino)benzoate, 1-Hydroxy-cyclohexyl-phenyl-ketone, 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, Irgacure® 500 (1:1 mixture by weight of 1-Hydroxy-cyclohexyl-phenyl-ketone and benzophenone), 2,2-Dimethoxy-1,2-diphenylethan-1-one or Michler's ketone.
The compositions according to definition and preferences of the invention, optionally further comprise an organic solvent. Example of organic solvents are chlorobenzene, pyrrolidone solvents, preferably, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone; imidazolidinone, dimethylsulfoxide, dimethylformamide, toluene, chloroform, organic ester, such as acetyl acetic ester or butyl acetic ester, pentyl acetic ester, hexyl acetic ester; further Y-butyrolactone, methyl cellosolve, butyl cellosolve, butyl carbitol, tetrahydrofuran, ditehylene glycol diethylether, dipentylether dipropylene glycol dimethylether, diisobutyl ketone momoethylene glycol dimethyl ether, etc. These solvents can be used alone or in mixtures thereof.
In the context of the present invention, a copolymer is defined as a polymer comprising at least two different types of monomers, wherein the first monomer is a compound of formula (I) and the at least second monomer is different from the first one.
In a preferred embodiment of the invention the copolymer comprising a first monomer of formula (I) and a second monomer as described in WO2014/191292, which is incorporated here by reference, which comprises a cyanostilbene group.
In a second embodiment the invention relates to compositions comprising a photo-alignable material and an additive as described above and a second polymer which is different from the first one.
The second polymer of the second embodiment of the present invention is a polymer selected from the group consisting of: polyamic acids, polyamic esters, polyimides, polymerizable liquid crystals, polymerized liquid crystals (LCP), polysiloxanes, polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polyvinylether, polyvinylester, polyallylether, polyallylester, polystyrene, polyamidimide, polymaleic acid, polyfumaric acid, polyurethane and derivatives thereof, polystyrol, polyester, polyurethane, polyethylene, polypropylen, polyvinylchloride, polytetrafluoroethylen, polycarbonate, polysilane, polymaleinimide, polynorbornene, polyterephthalate, polycyanostilbenes and dendrimere.
More preferred is polyamic acid or polyimide. Most preferred is polyamic acid.
More preferably the polymerizable liquid crystal or the polymerized liquid crystal contains a polar group.
More preferably the second polymer is selected from the group consisting of polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polyvinylether, polyvinylester, polyallylether, polyallylester, polystyrene, polysiloxane, polyamidimide, polymaleic acid, polyfumaric acid, polyurethane and derivatives thereof, polystyrol, polyester, polyurethane, polyethylene, poylpopylen, polyvinylchloride, polytetrafluoroethylen, polycabonate, polysilane, polymaleinimide, polynorbornene, polyterephthalate and dendrimere.
The term “diamine” or “diamine compound” is to be understood as designating a chemical structure which has at least two amino groups, i.e. which may also have 3 or more amino groups.
If the second polymer is a diamine, the diamine represents an optionally substituted aliphatic, aromatic or alicyclic diamino group having from 1 to 40 carbon atoms and preferably made from or selected from the following group of structures: aniline, p-phenylenediamine, m-phenylenediamine, benzidine, diaminofluorene, or their derivatives, with the proviso that compounds listed which do not carry two amino groups are taken as derivatives with at least one additional amino group, and more preferably made from or selected from the following commercially available amino compounds (example of suppliers: Aldrich, ABCR, ACROS, Fluka) which can also be used as comonomers:
Preferred examples of additional other diamines are:
as well as diamines disclosed in U.S. Pat. No. 6,340,506, WO 00/59966 and WO 01/53384, all of which are explicitely incorporated herein by reference;
The diamine compounds according to the present invention may be prepared using methods that are known to a person skilled in the art.
In addition, preferred diamines are the commercially available ones listed below:
Polymers:
Alicyclic Diamines
Aliphatic Diamines
From the class of commercially available diamines preferred are the below listed ones:
Alicyclic Diamines
Aliphatic diamines
From the class of commercially available diamines (L) more preferred are the below listed ones:
Aromatic Diamines
Preferably, the further polymer, homo- or copolymer or oligomer comprises at least a diamine as one of the basic building block, and a tetracarboxylic acid anhydride, preferably a tetracarboxylic acid anhydride of formula (II).
Preferably, the substituted or unsubstituted, preferably substituted within polar group or unsubstituted, tetracarboxylic acid anhydride is of formula (II)
wherein:
T represents a tetravalent organic radical.
The tetravalent organic radical T is preferably derived from an aliphatic, alicyclic or aromatic tetracarboxylic acid dianhydride.
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-cyclopentanetetracarboxyli c acid dianhydride; 2,3,5-tricarboxycyclopentylacetic acid dianhydride (with the term “2,3,5-tricarboxycyclopentylacetic acid dianhydride” all isomers of this compound are incorporated especially the exo and/or endo body), 2,3,5-tricarboxycyclopentylacetic-1,2:3,4-dianhydride is accessible for example by processes as described in JP59-190945, JP60-13740 and JP58-109479, respectively DE 1078120 and JP58-109479, or GB 872,355, and JP04458299, which processes are herewith incorporated by reference; tetrahydro-4,8-methanofuro[3,4-d]oxepine-1,3,5,7-tetrone, 3-(carboxymethyl)-1,2,4-cyclopentanetricarboxylic acid 1,4:2,3-dianhydride, hexahydrofuro[3′,4′:4,5]cyclopenta[1,2-c]pyran-1,3,4,6-tetrone, 3,5,6-tricarboxy-norbornylacetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic acid dianhydride,rel-[1S,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-dicarboxy-licacid dianhydride, 5-(2,5-dioxotetrahydro-furan-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic-acid dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetra-carboxylic 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, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylicacid dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylicacid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylicacid dianhydride, 1,2,3-trimethyl-1,2,3,4-cyclobutanetetracarboxylicacid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylicacid dianhydride, 1-methyl-1,2,3,4-cyclobutanetetracarboxylicacid 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 di-anhydride, 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-tert-butyl-6-(2,5-dioxotetrahydro-3-furanyl)-2-benzofuran-1,3-dione, 5-(2,5-dioxotetrahydro-3-furanyl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydro-3-furanyl)-5-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydro-3-furanyl)-6-methylhexahydro-2-benzofuran-1,3-dione, 5-(2,5-dioxotetrahydro-3-furanyl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione, 6-(2,5-dioxotetrahydro-3-furanyl)-4-methylhexahydro-2-benzofuran-1,3-dione, 9-isopropyloctahydro-4,8-ethenofuro[3′,4′:3,4]cyclobuta[1,2-f][2]benzofuran-1,3,5,7-tetrone, 1,2,5,6-cyclooctanetetracarboxylic acid dianhydride, octahydro-4,8-ethenofuro[3′,4′:3,4]cyclobuta[1,2-f][2]benzofuran-1,3,5,7-tetrone, octahydrofuro[3′,4′:3,4]cyclobuta[1,2-t][2]benzofuran-1,3,5,7-tetrone, tetrahydro-3,3′-bifuran-2,2′,5,5′-tetrone, 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,
4-tert-butyl-6-(2,5-dioxotetrahydro-3-furanyl)-2-benzofuran-1,3-dione,
and the like.
More preferably the tetracarboxylic acid dianhydrides used to form the tetravalent organic radical T are selected from:
In the context of the present invention the term “polyimide” has the meaning of partially or complete 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.
The second embodiment of the present invention relates more particularly to a composition wherein the second polymer is 100% imidised, or has an imidisation degree in the range of 1 to 99%, preferably 5 to 50%, more preferably 10 to 40% by weight.
In the context of the second embodiment of the present invention, the composition may comprise a siloxane oligomer, polymer or copolymer as described above, a second polymer which is different from the first one and at least one additional polymer which is different from the first and from the second polymer of the composition.
The third object of the present invention is to provide an orientation layer comprising said composition. More preferably the orientation layer further comprises a polymerisable liquid crystal.
It is understood that the orientation layers of the present invention (in form of a polymer gel, a polymer network, a polymer film, etc.) can be used as orientation layers for liquid crystals. A further preferred embodiment of the invention relates to an orientation layer comprising the composition according to the invention, wherein the polymers comprising the monomer of formula (I) or (IV) are preferably in a cross-linked form. Such orientation layers can be used in the manufacture of unstructured or structured optical- or electro-optical elements, preferably in the production of hybrid layer elements.
In the context of the present invention the wording “polymer or oligomer layer” has the meaning of “polymer layer, copolymer layer, homopolymer layer or oligomer layer”.
In the context of the present invention the wording “orientation layer” has the same meaning as “orientation film”.
In the context of the present invention polymer or oligomer layers are preferably orientation layers.
The polymers, homo- or copolymers or oligomers according to the invention may be used in form of polymer layers or oligomer layers alone or in combination with other polymers, oligomers, monomers, photo-active polymers, photo-active oligomers and/or photo-active monomers, depending upon the application to which the polymer or oligomer layer is to be added. Therefore it is understood that by varying the composition of the polymer or oligomer layer it is possible to control specific and desired properties, such as an induced pre-tilt angle, or surpressing of tilt, good alignment quality, contrast ratio, good surface wetting, a high voltage holding ratio, a specific anchoring energy, image sticking etc.
The orientation layers are suitably prepared from a composition according to the present invention. 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)] so that homogeneous layers of 0.05 to 50 m thickness are produced. 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.
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, polymerisation, 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 orientation layers 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 fourth object of the present invention is to provide a method for the preparation of the orientation layer by exposure composition with aligning light.
The polymer comprising a monomer of formula (I) or (IV) as described above, has at least a photo-reactive group in a side chain. Preferably, the photo-reactive group of the side chains reacts by exposure to aligning light.
In the context of the present invention the term photo-reactive groups have the meaning of groups, which are able to react by interaction with light, preferably aligning light.
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.
In the context of the present invention photo-reactive group has preferably the meaning of a dimerizable, isomerizable, polymerizable and/or cross-linkable group.
In the context of the present invention, aligning light, preferably polarized light is 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. A further embodiment of the invention concerns the generating of aligning light by laser light.
The instant direction of the aligning light may be normal to the substrate or at any oblique angle.
More preferably, aligning light is at least partially linearly polarized, elliptically polarized, such as for example circulary polarized, or non-polarized; most preferably at least circulary or partially linearly polarized light, or non-polarized light exposed obliquely.
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.
A more preferred embodiment of the invention relates to a method for the preparation of the orientation layer by exposuring the composition comprising a polymer comprising a monomer of fomula (I) or (IV) and an additive selected from the group consisting of acid generators, base generators, acids and bases with polarised light, especially linearly polarised light, or by oblique radiation with non-polarised light.
Further preferred polymers comprising a monomer of formula (I) or (IV),
Polymer or oligomer layers may readily be prepared from composition of the present invention and a further embodiment of the invention relates to an orientation layer comprising said composition and which is preferably prepared by treatment with aligning light.
The polymer or oligomer layer is preferably prepared by applying one or more compositions according to the invention to a support and subsequent evaporation of the solvent and/or of the additives, and, after imidisation or without imidisation, irradiating the polymer or oligomer or polymer mixture or oligomer mixture with aligning light. Aligning light has the above given meaning and preferences.
The term “support” as used in the context of the present invention is preferably transparent or not-transparent, preferably glass or plastic substrates, polymer films, such as polyethyleneterephthalat (PET), tri-acetyl cellulose (TAC), polypropylen, optionally coated with indium tin oxide (ITO), however not limited to them.
In general a composition comprising the siloxane polymers, copolymers or oligomers of the invention is applied by general coating and printing methods known in the art, such as spin-coating, meniscus-coating, wire-coating, slot-coating, offset-printing, flexo-printing, gravure-printing, ink jet printing may be used. 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, ink jet 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.
A further preferred embodiment of the present invention relates to orientation layers which are unstructured or structured.
In addition the present invention relates to a process for the preparation of structured polymer layers, copolymer layers or oligomer layers comprising varying the direction of orientation and/or the tilt angle within the polymer or oligomer layer. This varying of the direction of orientation and/or the tilt angle can for example be conducted 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 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 reaction to pass through.
Further preferred is a process for the preparation of a polymer layer, copolymer layer or oligomer layer; for the preparation of planar multi-domain planar alignment of a polymer layer or oligomer layer; and/or for the preparation of a polymer layer, copolymer or oligomer layer having a tilt angle within the given meaning and preferences of the invention.
A further preferred embodiment of the invention relates to an orientation layer comprising one or more compositions according to the invention.
In the context of the present invention orientation layer has the same meaning and preferences as alignment layer, polymer, homo- or copolymer or oligomer layer and is preferably a photo alignment layer.
In the context of the invention relates to an orientation layer according to the invention for the planar alignment of liquid crystals or for the vertical alignment of liquid crystals.
In a preferred embodiment of the present invention, the orientation layer is used for the planar alignment of liquid crystals. In an even more preferred embodiment according to the invention, the orientation layer comprising the compound of formula (IV) is used for the planar alignemtn of liquid crystals.
In the context of the present invention the wording “planar alignment of liquid crystals” means that the liquid crystals have tilt angle.
The term tilt angle as used in the context of the present invention is the angle between the liquid crystal director and the surface of the alignment layer. The liquid crystal director shall mean the average direction of the long axes of the liquid crystal molecules. In the context of the present invention, planar alignment shall mean that the tilt angle is less than 30°, preferably 0 to 30°, vertical alignment shall mean that the tilt angle is around 90°, preferably between 85° to 90°.
In preferred embodiments the tilt angle of the liquid crystals, induced by the photo-alignment layer is less than 10°, preferably 0 to 10°. In more preferred embodiments the tilt angle is less than 5°, preferably 0 to 5°, and in most preferred embodiments the tilt angle is less than 1°, preferably 0 to 1°, even more preferably from 0° to 0.5°. Preferred are tilt angles of less than 0.2° or 0.1°.
A preferred method of the present invention concerns a method, wherein the direction of orientation and the tilt angle within the polymer layer or oligomer 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 fifth embodiment of the present invention relates to the use of said orientation layer, for the alignment, especially the planar alignment, of
Example of LCsP are described in US2012/114907 A1, which is herewith incorporated by reference.
Further, the present invention relates preferably to the use of an orientation layer according to the invention for the induction of planar alignment of adjacent liquid crystalline layers, in particular for operating a cell wherein planar orientation is provided, such in IPS, such as IPS modes like S-IPS (Super IPS), AS-IPS (Advanced super IPS), E-IPS (Enhanced IPS), H-IPS (Horizontal IPS), UH-IPS, S-IPS II, e-IPS, p-IPS (performance IPS), PLS technology (plane to line switching), PS-IPS (polymer stabilized IPS), Field induced photoreactive alignment IPS FFS (fringe field switching), TN (twisted nematic), STN (supertwisted nematic).
Liquid crystal compositions of the present invention comprise a polymerizable monomer, or a polymer or oligomer, which is the polymerized form of said poylmerizable monomer. The polymerizable monomer or the polymer or oligomer, is bifunctional and/or has a rigid core (e.g. benzene). Further preferred is a polymerizable monomer, or a polymer or oligomer, which have one or more ring or condensed ring structures and functional groups bonded directly to the ring or condensed ring structure.
More preferred liquid crystals have a monomer of formula (V)
P1—S1-A1-(Z1-A2)n-S2—P2 (V)
wherein
P1 and P2 are functional groups and are independently selected from acrylate, methacrylate, halogenacrylate, such as fluoroacrylate, chloroacrylate; oxetanyl, maleinimidyl, allyl, allyloxy, vinyl, vinyloxy and epoxy groups.
S1 and S2 of formula (V) are independently from each other a single bond or a spacer unit, which is preferably a straight-chain or branched, substituted or unsubstituted C1-C24alkylen, in which one or more, preferably non-adjacent, C-atom, CH— or CH2—, group may be replaced by a linking group within the above given meaning and preferences, and, preferably replaced by is a single bond, —O—, —O(CO), —S—, —(CO)O— or
NR2—, and wherein the substituent is preferably at least one C1-C6alkyl, preferably methyl.
A1 and A2 of formula (V) are ring structures and independently selected from unsubstituted or substituted carbocyclic or heterocyclic aromatic or alicyclic group with the meaning and preferences given in the present invention, especially preferred are 1,4-phenylene naphthalene-2,6-diyl, terphenyl, quarterphenyl, phenanthrene groups, Z, of formula (V) is selected from —O—, —CO—, —CH(OH)—, —CH2(CO)—, —OCH2—, —CH2O—, —O—CH2—O—, —COO—, —OCO—, —(CO)—(CO)—, —OCF2—, —CF2O—, —CF2—, —CON(C1-C16alkyl)-, —(C1-C16alkyl)NCO—, —CONH—, —NHCO—, —HNOCO—, —OCONH—, —NHCONH—, —OCOO—, —CO—S—, —S—CO—, —CSS, —SOO—, —OSO—, —SOS—, —SO—, —CH2(SO)—, —SO2—, —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 C1-C24alkylen, wherein one or more C-atom, CH- or CH2-group may independently from each other be replaced by a linking group;
preferably, Z, of formula (V) is —O—, —CO—, —COO—, —OCO—, —OCOO—, —OCF2—, —CF2O—, —CON(CH3)—, —(CH3)NCO—, —CONH—, —NHCO—, —CO—S—, —S—CO—, —CSS, —SOO—, —OSO—, —CSS—, —SOO—, —OSO—, —CH2(SO2)—, —CH2—CH2—, —OCH2—, —CH2O—, —CH═CH—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, or a single bond;
more preferably Z, of formula (V) is —COO—, —OCO—, —OCOO—, —OCF2—, —CF2O—, —CON(CH3)—, —(CH3)NCO—, —CONH—, —NHCO—, —CO—S—, —S—CO—, —CS—S—, —SOO—, —OSO,
especially
—COO—, —OCO—, —OCF2—, —CF2O—, —CON(CH3)—, —(CH3)NCO—, —CONH—, —NHCO— or a single bond,
most preferred Z1 is a single bond, —COO— or —OCO—; and
n of formula (V) is an integer of 1, 2, or 3.
In formula (II), P1 and P2 are preferably acrylate or methacrylate groups, S1 and S2 are a single bond Z1 is preferably a single bond, and n is preferably 0 or 1.
Most preferred is a compound represented by any one of the formulae (VI), (VII) or (VIII)
wherein P1 and P2 are independently from each other an acrylate, methacrylate, oxetane, maleinimide, allyl, allyloxy, vinyl, vinylamide, vinyloxy and epoxy group, epoxy derivatives, butoxy and butoxy derivatives,
B is a single bond, —CO—C(C1-C6alkoxy)2-, —COO—, —OCO—,
Y1, Y2, Y3, Y4, Y5, Y6 are independently from each other hydrogen, a straight-chain or branched C1-C16alkyl group, which is unsubstituted or substituted by fluorine, di-(C1-C16alkyl)amino, C1-C15alkyloxy, nitro, nitrile and/or chlorine; and wherein one or more C-atom, CH— or CH2— group may independently from each other be replaced by a linking group; halogen or nitrile; preferred substituents are C1-C6alkyl group, especially methyl or ethyl, C1-C6alkoxy group, especially methoxy or ethoxy, chlorine, fluorine, or nitrile, more preferably methoxy, chlorine, fluorine, or CN and most preferably methoxy, chlorine or fluorine; further, if the aromatic group is substituted, then it is preferably substituted once or twice;
S1, S2, are independently from each other a single bond or a spacer unit, as described above.
In formula (V), P1 and P2 are preferably acrylate or methacrylate groups, S1 and S2 are a single bond Z1 is preferably a single bond, and n is preferably 0 or 1.
In formulae (V) and (VII) a substituent group for the benzene ring is present at the o-position, m-position, or p-position. In formula (VI), a substituent group for the naphthalene ring is present at the o-position, m-position, p-position, ana-position, E (epi)-position, kata-position, pen-position, pros-position, amphi-position, or 2,7-position. The substituent group for the benzene ring is preferablypresent at the p-position among the above positions. The substituent group for the naphthalene ring is preferably present at the amphi-position among the above positions.
Preferred are:
In general the liquid crystals compositions or liquid crystal layers are not particularly limited, provided that they contain the mono- or/and multi-polymerizable monomer described above. The liquid crystals compositions or liquid crystal layers can thus be made of any of various liquid crystal materials that have been known publicly. The liquid crystals compositions or liquid crystal layers may be made of a liquid crystal material identical to or different from that for display use.
The oligomer, which is the polymerized form of the polymerizable monomer1 is in general not limited to any molecular weight. Preferably the molecular weight is in the range of 200 to 5000 Dalton, more preferably in the range of 500 to 2000 Dalton and most preferred in the range of 500 to 1000 Dalton.
In the sixth embodiment the present invention relates to a method for manufacturing a liquid crystal display.
In the context of the present invention the term “display” has the same meaning as the term “panel”.
The method for producing the liquid crystal display panel may involve using a polymerization initiator, such as methyl ethyl ketone peroxide and a benzoyl ether-based compound.
Preferably, the present invention relates to a method for manufacturing a liquid crystal display comprising applying at least a single LCP onto a siloxane polymer, copolymer or oligomer layer according to the first or second embodiment, or preferably on the orientation layer according to the third or fourth embodiment of the present invention, and polymerizing said LCP.
In general the polymerization of the LCP is conducted by irraditation or at elevated temperature.
The LCP may be applied onto the orientation layer in any amount, so the amount is not particularly limited. The amount may be set as appropriate in accordance with, for example, respective thicknesses of the LCP polymer films formed by polymerization of the monomeric LCP.
Further the present invention relates to a method for manufacturing a liquid crystal display comprising bringing into contact a liquid crystal composition comprising a polymerizable liquid crystal monomer according to the present invention, or a polymer or oligomer, which is the polymerized form of said poylmerizable liquid crystal monomer; with at least a single orientation layer according to the present invention, preferably two orientation layers facing each other; and polymerising said polymerizable liquid crystal monomer.
Generally the polymerization methods are not limited so far as they have no adverse effects on the manufactured device. Preferably the polymerization is conducted by irradiation, especially UV radiation, or by heat.
More specifically the process for the preparation of liquid crystal displays, preferably LCDs comprising planar alignment of liquid crystals, more especially LCDs comprising the IPS mode, comprising an orientation layer according to the present invention and electrodes, comprises performing an exposure, preferably a first exposure, of the material with the polarised light, wherein the exposure induces an orientation direction of the liquid crystals perpendicular to polarised light, or/and wherein an exposure, preferably a first exposure, induces an orientation direction of the liquid crystals and polarised light direction make an angle higher than 70°, or/andwherein an exposure, preferably a first exposure, with polarized light is conducted with an angle >70° between the electrode and the polarized light direction.
The seventh object of the present invention relates to optical or electro-optical unstructured of structured elements comprising the composition according to the present invention or the orientation layer of the third embodiment.
In the optical or electro-optical device according to the present invention the compound comprising the monomer of formula (I) or (IV) may be in cross-linked form. The electro-optical devices may comprise more than one orientation layer. The layer or each of the layers may contain one or more regions of different spatial orientation.
In a preferred embodiment the element is a liquid crystal display cell.
In the context of the present invention elements, device, cell, structure all refer to objects comprising polymerized or polymerizable liquid crystal to be oriented with the linear, branched or crosslinked siloxane polymer, copolymer or oligomer according to the present invention.
Preferably, the present invention further relates to unstructured or structured elements optical or electrooptical devices, especially a LCD, comprising a pair of substrates facing each other; wherein the substrates is provided with a pair of orientation layers according to the present invention and
The present invention also relates to the use of such orientation layers for the alignment, preferably planar alignment, of liquid crystals, preferably in the manufacture of unstructured or structured optical- or electro-optical elements, preferably in the production of hybrid layer elements. Preferably, these optical or electro-optical devices have at least one orientation layer as well as unstructured and structured optical elements and multi-layer systems. The layer or each of the layers may contain one or more regions of different spatial orientation.
Polarised light direction shall mean the intersection line of the alignment layer surface and the plane of polarization of the polarised light during the exposure. If the polarised light is elliptically polarized, the plane of polarization shall mean the plane defined by the incident direction of the light and by the major axis of the polarization ellipse.
The term polarised light direction is used in the context of the present invention not only to describe a direction for the duration of the exposure process, but also after exposure to refer to the direction of the polarised light on the alignment layer as it was applied during exposure.
The electrodes are preferably in the form of parallel stripes, zig-zag or comb-like electrodes.
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 polymer layer, copolymer or oligomer layer according to the present invention.
The present invention the wording optical or electro-optical elements has preferably the meaning of multilayer systems, or devices for the preparation of a display 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 G/H-polarizer with an anisotropic absorber, a reflective circular polarizer, a reflective linear polarizer, a MC (monomer corrugated film), twisted nematic (TN) liquid crystal displays, hybrid aligned nematic (HAN) liquid crystal displays, electrically controlled birefringence (ECB) liquid crystal displays, supertwisted nematic (STN) liquid crystal displays, optically compensated birefringence (OCB) liquid crystal displays, pi-cell liquid crystal displays, PLS technology (plane to line switching), PS-IPS (polymer stabilized IPS), in-plane switching (IPS) liquid crystal displays, such as IPS modes like S-IPS (Super IPS), AS-IPS (Advanced super IPS), E-IPS (Enhanced IPS), H-IPS (Horizontal IPS), UH-IPS, S-IPS II, e-IPS, p-IPS (performance IPS); Field induced photoreactive alignment IPS, fringe field switching (FFS) liquid crystal displays; (FPA) field-induced photo-reactive alignment; hybrid FPA; VA-IPS mode liquid crystal displays, or displays using blue phase liquid crystals; all above display types are applied in either transmissive or reflective or transflective mode.
More preferred optical or electro-optical elements are PLS technology (plane to line switching), PS-IPS (polymer stabilized IPS), in-plane switching (IPS) liquid crystal displays, such as IPS modes like S-IPS (Super IPS), AS-IPS (Advanced super IPS), E-IPS (Enhanced IPS), H-IPS (Horizontal IPS), UH-IPS, S-IPS II, e-IPS, p-IPS (performance IPS); Field induced photoreactive alignment IPS, fringe field switching (FFS) liquid crystal displays; (FPA) field-induced photo-reactive alignment; hybrid FPA; VA-IPS mode liquid crystal displays, or displays using blue phase liquid crystals; all above display types are applied in either transmissive or reflective or transflective mode.
The advantages of the present invention could not be foreseen by a skilled person.
It has surprisingly been found, that the compositions of the present invention, upon irradiation with polarized light, orient polymerized or polymerizable liquid crystals and are stable at high annealing temperatures. Further, said compositions show good and homogenous planar orientation quality. The further examples will demonstrate that the compositions of the present invention have good or very good image sticking properties, contrast ratios, and voltage holding ratios.
The further examples are a non-limiting selection of examples which will further explain the invention.
NMP: N-methyl-2-pyrrolidone
BC: Butyl cellusolve
THF: tetrahydrofuran
RT: room temperature, usually in the range of 18 CC to 28° C.
wt %: weight percent
MLC7067: is a mixture of liquid crystal available from Merck KGA with a Dielectric anisotropy of 10.3, an optical anisotropy of 0.1025 and a rotational viscosity of 81 m·Pa·s.
The polymers used in the examples are
The different additives are supplied for example by Aldrich, TCI, Acros, BASF, Momentive.
The composition comprising a polymer obtained from the formula I and an additive described in this invention allows stabilization of the electro-optical properties. In the following examples, the stabilization of the alignment quality (contrast ratio) via the use of this composition is shown.
A 5.5 wt % solution of polymer P1 is prepared by mixing the solid P1 in NMP and stirring thoroughly until the solid is dissolved. To this solution 3 wt % of 4-Isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate (Irgacure 250 from BASF) are added. Other diaryl iodonium salts can be used instead of Irgacure 250. Then a second solvent, butyl cellusolve (BC) is added and the whole composition is stirred thoroughly to obtain the final solution. The solvent ratio between NMP and butyl cellulose is 1:1.
The above polymer solution is spin-coated onto two ITO coated glass substrates at a spin speed of 1700 rpm for 30 seconds. After spin coating the substrates are subjected to baking procedure consisting of pre-baking for 90 seconds at 130° C. and post-baking for 40 minutes at a temperature of 200° C. The resulting layer thickness is around 80 nm. The substrates with the coated polymer layer on top are exposed to linearly polarized UV light (LPUV) at an incidence angle of 0° relative to the normal of the substrate surface. The plane of polarization is within the plane spanned by the substrate normal and the propagation direction of the light. The applied exposure dose is 100 mJ/cm2. After LPUV exposure, a cell is assembled with the 2 substrates, the exposed polymer layers facing to the inside of the cell. The substrates are adjusted relative to each other such that the induced alignment directions are parallel to each other. The cell is capillary filled with liquid crystal MLC7067 (Merck KGA), which has a positive dielectric anisotropy. After that, the cell is optionally annealed at about 130° C. for 30 minutes and cooled down to room temperature. Alignment quality of the liquid crystal in the cell is checked by placing the cell between two crossed polarizers and adjusted to obtain dark state. The alignment quality is defined to be good if the dark state shows no defects and the liquid crystal is well oriented. The alignment quality is defined to be medium if the dark state has light leakage because of slight inhomogeneous orientation of liquid crystal in some areas of the cell. The alignment quality is defined to be worse, if liquid crystal is not oriented with absence of dark state.
The liquid crystal in the cell showed well defined and homogeneous planar orientation before and after thermal annealing of the cell.
A 5.5 wt % solution of polymer P1 is prepared by mixing the solid P1 in NMP and stirring thoroughly until the solid is dissolved. Then a second solvent, butyl cellusolve (BC) is added and the whole composition is stirred thoroughly to obtain the final solution. The solvent ratio between NMP and butyl cellulose is 1:1.
The above polymer solution is spin-coated onto two ITO coated glass substrates at a spin speed of 1700 rpm for 30 seconds. After spin coating the substrates are subjected to baking procedure consisting of pre-baking for 90 seconds at 130° C. and post-baking for 40 minutes at a temperature of 200° C. The resulting layer thickness is around 80 nm. The substrates with the coated polymer layer on top are exposed to linearly polarized UV light (LPUV) at an incidence angle of 0° relative to the normal of the substrate surface. The plane of polarization is within the plane spanned by the substrate normal and the propagation direction of the light. The applied exposure dose is 100 mJ/cm2. After LPUV exposure, a cell is assembled with the 2 substrates, the exposed polymer layers facing to the inside of the cell. The substrates are adjusted relative to each other such that the induced alignment directions are parallel to each other. The cell is capillary filled with liquid crystal MLC7067 (Merck KGA), which has a positive dielectric anisotropy. After that, the cell is optionally annealed at about 130° C. for 30 minutes and cooled down to room temperature. The liquid crystal in the cell showed very bad planar orientation before and after thermal annealing of the cell.
The alignment quality of the cells from example 1 and comparative example 1 are quantified by the measurement of the contrast ratio (CR). The contrast of an unbiased IPS cell is determined with a polarizing microscope equipped with a photo-multiplier to measure the transmitted light power. As a light source a LED backlight from ELDIM is used. The measurement area in the focal plane (sample) of the microscope objective is about 1 mm2. Without sample the polarizers from the microscope are brought to the perpendicular position where the detector signal displays a minimum value. The cell is then fixed on a rotatable sample folder under the microscope objective. For determination of the contrast two measurements are performed. For the first measurement, the cell is rotated until the detector displays a minimum value V0. In this position, the alignment direction of the cell is parallel to the polarizer and V0 is defined as the dark state. Then, for the second measurement the cell is rotated by 90°until the detector displays a maximum value Vmax defined as the bright state. The contrast of the sample is the determined as the ratio bright state to dark state (CR=Vmax/V0). If the value is below 500, the contrast is defined as −, if the value is above 1000 the contrast is defined as ++.
A cell is prepared as in example 1, except that the solution to be coated comprised the polymer P1 and 2% of 4-Isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate (Irgacure 250 from BASF). The liquid crystal in the cell showed well defined and homogeneous planar orientation before and after thermal annealing of the cell. A tilt angle below 0.1° is measured using the rotating analyzer method.
A cell is prepared as in example 1, except that the solution to be coated comprised the polymer P1 and 3% of 2-Methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one (Irgacure 907). The liquid crystal in the cell showed well defined and homogeneous planar orientation before and after thermal annealing of the cell. A tilt angle below 0.1° is measured using the rotating analyzer method.
A cell is prepared as in example 1, except that the solution to be coated comprised the polymer P1 and 3% of tris(4-(4-acetylphenylthio)phenyl)sulfonium tetrakis(pentafluorophenyl)borate. The liquid crystal in the cell showed well defined and homogeneous planar orientation before and after thermal annealing of the cell. A tilt angle below 0.1° is measured using the rotating analyzer method.
A cell is prepared as in example 1, except that the solution to be coated comprised the polymer P1 and 1% of dodecylbenzenesulfonic acid The liquid crystal in the cell showed well defined and homogeneous planar orientation before and after thermal annealing of the cell. A tilt angle below 0.1° is measured using the rotating analyzer method.
The Contrast ratio measurement with the method described in example 2 is performed for the cells obtained in example 3, example 4, example 5 and example 6.
A cell is prepared as in example 1, except that a 5.5 wt % solution is prepared by mixing the polysiloxane P1 and a polyamic acid PAA-1 in ratio of 10:90 per weight % in NMP to form a blend composition. The mixture is stirred thoroughly until the solid is dissolved and then 4 wt % of 4-Isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate (Irgacure 250 from BASF) are added. Then a second solvent, butyl cellusolve (BC) is added and the whole composition is stirred thoroughly to obtain the final solution. The solvent ratio between NMP and butyl cellulose is 1:1.
The spin speed used is 2500 rpm for 30 seconds to obtain a thickness layer of about 100 nm. The liquid crystal in the cell showed well defined and homogeneous planar orientation before and after thermal annealing of the cell.
A cell is prepared as in example 1, except that the solution to be coated comprised the polysiloxane P1 and the polyamic acid PAA-1 in ratio of 10:90 per weight % and 2% of 4-Isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate (Irgacure 250 from BASF) The liquid crystal in the cell showed well defined and homogeneous planar orientation before and after thermal annealing of the cell.
A cell is prepared as in example 1, except that the solution to be coated comprised the polysiloxane P1 and the polyamic acid PAA-1 in ratio of 10:90 per weight % and 4% of UV9390C from Momentive The liquid crystal in the cell showed well defined and homogeneous planar orientation before and after thermal annealing of the cell.
A cell is prepared as in example 1, except that the solution to be coated comprised the polysiloxane P1 and the polyamic acid PAA-1 in ratio of 10:90 per weight % and 5% of 4-Isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate (Irgacure 250 from BASF). The liquid crystal in the cell showed well defined and homogeneous planar orientation before and after thermal annealing of the cell.
A cell is prepared as in example 1, except that a 5.5 wt % solution is prepared by mixing the polysiloxane P1 and a polyamic acid PAA-1 in ratio of 10:90 per weight % in NMP to form a blend composition. The mixture was stirred thoroughly till the solid is dissolved. Then a second solvent butyl cellusolve (BC) is added and the whole composition is stirred thoroughly to obtain final solution. The solvent ratio between NMP and butyl cellulose is 1:1.
The spin speed used is 2500 rpm for 30 seconds to obtain a thickness layer of 100 nm. The liquid crystal in the cell showed defined and homogeneous planar orientation before and after thermal annealing of the cell.
The contrast ratio measurement is performed as described in example 2 for the cell obtained in example 8, example 9, example 10, example 11, example 12 and comparative example 14 with the proviso that if the value is below 3000 the contrast is defined as—and if the value is above 3000 the contrast is defined as ++.
This example shows that for compositions according to the present invention have better contrast ratios after thermal treatment compared to state of the art compositions.
A cell is prepared as in example 1, except that the solution to be coated comprises the polymer P2 and 2% of 4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate (Irgacure 250 from BASF). The liquid crystal in the cell showed well defined and homogeneous planar orientation before and after thermal annealing of the cell.
A cell is prepared as in Comparative example 1, except that the solution to be coated comprises the polymer P2. The liquid crystal in the cell showed bad planar orientation before and after thermal annealing of the cell.
The Contrast ratio measurement is performed with the method described in example 2 for the cell obtained in example 15 and in comparative example 15.
A cell is prepared as in example 1, except that the solution to be coated comprises the polymer P3 and 2% of 4-Isobutylphenyl-4′-methyl iodonium hexafluorophosphate (Irgacure 250 from BASF). The liquid crystal in the cell showed well defined and homogeneous planar orientation before and after thermal annealing of the cell.
A cell is prepared as in Comparative example 1, except that the solution to be coated comprises the polymer P3. The liquid crystal in the cell showed bad planar orientation before and after thermal annealing of the cell.
The Contrast ratio measurement is performed with the method described in example 2 for the cell obtained in example 17 and in comparative example 17.
A cell is prepared as in example 1, except that the solution to be coated comprises the polymer P4 and 5% of 4-Isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate (Irgacure 250 from BASF). The liquid crystal in the cell showed well defined and homogeneous planar orientation before and after thermal annealing of the cell.
A cell is prepared as in Comparative example 1, except that the solution to be coated comprises the polymer P4. The liquid crystal in the cell showed bad planar orientation before and after thermal annealing of the cell.
The Contrast ratio measurement is performed with the method described in example 2 for the cell obtained in example 19 and in comparative example 19
A cell is prepared as in example 1, except that the solution to be coated comprised the polymer P5 and 5% of 4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate (Irgacure 250 from BASF). The liquid crystal in the cell showed well defined and homogeneous planar orientation before and after thermal annealing of the cell.
A cell is prepared as in Comparative example 1, except that the solution to be coated comprised the polymer P5. The liquid crystal in the cell showed bad planar orientation before and after thermal annealing of the cell.
The Contrast ratio measurement is performed with the method described in example 2 for the cell obtained in example 21 and in comparative example 21.
A cell is prepared as in example 1, except that the solution to be coated comprises the polymer P6 and 5% of 4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate (Irgacure 250 from BASF). The liquid crystal in the cell showed well defined and homogeneous planar orientation before and after thermal annealing of the cell.
A cell is prepared as in Comparative example 1, except that the solution to be coated comprises the polymer P6. The liquid crystal in the cell showed bad planar orientation before and after thermal annealing of the cell.
The Contrast ratio measurement is performed with the method described in example 2 for the cell obtained in example 22 and in comparative example 22.
| Number | Date | Country | Kind |
|---|---|---|---|
| 15194025.1 | Nov 2015 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2016/076930 | 11/8/2016 | WO | 00 |
