Patent Application
20250180952
The present invention relates to a photoaligning compound of formula (I), to a process for the preparation of this compound, to a photoaligning composition, obtained by this process, to the use of said compositions as orienting layer for liquid crystals and in the construction of unstructured and structured optical elements and multi-layer systems, especially liquid crystal displays. There is an ever-growing demand to develop new photo-aligning materials for optical and electro-optical applications. Nowadays there is an increasing demand for green technology for the consumer and in large scale manufacturing processes. Especially, in display industries there is a constant need to increase the production efficiency by reduction of power consumption and time durations during different process steps. The consumer on the other hand prefers to watch large size higher definition televisions, which consume generally high energy. One way to decrease energy consuming is to decrease the intensity needed by the backlight. It is described by Y. Yamada, Q. Tang, M. Koechlin and Y. Yamaoto in Late-News Paper, SID 2017 DIGEST, pages 708 to 711, that an efficient use of backlight requires high transmittance.
In the present invention new photoaligning material was found which gives access to an economic manufacturing process and low energy consuming LCDs without decreasing the required technical properties. Accordingly, in the present invention a compound of formula (I), preferably a photoaligning copolymer, was found:
It is understood in the context of the present invention that if m2 is 0, there is also no side chain at M2, and if m3 is 0, there is also no side chain at M3.
The term “linking group”, as used in the context of the present invention is preferably be selected from a single bond, —O—, —CO, —(CO)—, —O(CO)—,
The term “spacer unit” as used in the context of the present invention, is preferably a single bond, a cyclic, straight-chain or branched, substituted or unsubstituted C1-C20alkanediyl nt, C—, CH—, CH2— group may independently from each other be replaced by a linking group as described above and/or a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group connected via bridging groups.
More preferably, the spacer unit is a cyclic, straight-chain or branched, substituted or unsubstituted C1-C20alkanediyl, wherein one or more, preferably non-adjacent, C—, CH—, CH2— group may independently from each other be replaced by a linking group and/or a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group connected via bridging groups.
A bridging group as used in the context of the present invention is selected from —CH(OH)—, —CO—, —CH2(CO)—, —SO—, —CH2(SO)—, —SO2—, —CH2(SO2)—, —O—, —(CO)O—, —O(CO)—, —O(CO)O—, —COCF2—, —CF2CO, —S—CO—, —CO—S—, —SOO—, —OSO—, —SOS—, —CH2—CH2—, —OCH2—, —CH2O—, —CH═CH—, —C≡C—, —CH═CH—(CO)O—, —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-C20alkanediyl, wherein one or more C—, CH—, CH2 groups may independently from each other be replaced by a linking group as described above.
Preferably, a briding group is selected from —O—, —(CO)O—, —O(CO)—, or a single bond.
Alkyl, alkyloxy, alkylcarbonyloxy, acryloyloxyalkoxy, acryloyloxyalkyl, acryloyloxyalken, alkyloxycarbonyloxy, alkylacryloyloxy, methacryloyloxyalkoxy, methacryloyloxyalkyl, methacryloyloxyalken, alkylmethacryloyloxy, alkylmethacryloyloxy, alkylvinyl, alkylvinyloxy and alkylallyloxy and alkanediyl, as used in the context of the present invention denote with their alkyl residue; respectively their alkanediyl residue; a cyclic, straight-chain or branched, substituted or unsubstituted alkyl, respectively alkanediyl in which one or more, preferably non-adjacent, C—, CH—, CH2— group may be replaced by a linking group.
Further, the alkyl residue is for example C1-C40alkyl, especially C1-C30alkyl, preferably C1-C20alkyl, more preferably C1-C16alkyl, most preferably C1-C10alkyl and especially most preferably C1-C6alkyl. Accordingly, alkanediyl is for example C1-C40-, especially C1-C30-, preferably C1-C20-, more preferably C1-C16-, most preferably C1-C10- and especially most preferably C1-C6alkanediyl.
In the context of the present invention the definitions for alkyl given below, are applicable in analogy to alkanediyl, to oxy ether of alkyl derivatives such as acryloyloxyalkanediyl, acryloyloxyalkoxy, such as preferably methacryloyloxyalkoxy.
C1-C6alkyl is for example methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl or hexyl. C1-C10alkyl is for example methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl.
C1-C16alkyl 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-C20alkyl 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.
An aliphatic group is for example a saturated or unsaturated, mono-, bi-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca-valent alkyl, alkanediyl, 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 a non-aromatic group or unit. 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, bicylcohexylene, decaline, tetrahydrofuran, dioxane, pyrrolidine, piperidine or a steroidal skeleton such as cholesterol.
The term “aromatic” group, follows Hückel's rule (for rings: when the number of its π electrons equals 4n+2, wherein n is an integer natural number, e.g. 0, 1, 2, 3, etc) as used in the context of the present invention, and preferably denotes unsubstituted or substituted carbocyclic and heterocyclic groups, incorporating five, six, ten ot 14 ring atoms, e.g. furan, phenylene, pyridine, pyrimidine, naphthalene, 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 phenylene, naphthalene, biphenylene or triphenylene groups. More preferred aromatic groups are phenylene, naphthalene, and biphenylene groups.
A carbocyclic or heterocyclic aromatic or non-aromatic group, preferably carbocyclic or heterocyclic aromatic or non-aromatic diamine group, incorporates preferably, three, four, five, six, ten or 14 ring atoms, as for example furan, pyrazol, imidazole, oxazole, thiazole und thiazine, pyridine, piperidine, triazine, pyrimidine, chinolin, isochinoline, indol, purine, benzimidazole, naphthalene, phenanthrene, biphenylene or tetraline units, preferably naphthalene, phenanthrene, biphenylene or phenylene, more preferably naphthalene, biphenylene or phenylene, and most preferably phenylene. The carbocyclic or heterocyclic aromatic or non-aromatic group, preferably carbocyclic or heterocyclic aromatic or non-aromatic diamine group, is for example unsubstituted or mono- or poly-substituted. Preferred substitutents are at least one halogen, hydroxyl, a polar group, alkyl, a carboxylic acid, an acyl group, such as acid chloride, ester groups, carbonates, such as tert-butyl carbonates; an anhydride; trifluoroalkyl, acryloyloxy, alkylacryloyloxy, alkoxy, 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, cyano or a carboxy group, and/or a cyclic, straight-chain or branched C1-C30alkyl, which is unsubstituted, mono- or poly-substituted. Preferred substitutents of C1-C30alkyl 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—, —(CO)O— and/or —O(CO)—.
A monocyclic ring of five or six atoms is for example unsubstituted or substituted furan, phenylene, pyridine, pyrimidine, preferably phenylene, pyridine, pyrimidine.
A bicyclic ring system of eight, nine or ten atoms is for example unsubstituted or substituted naphthalene, biphenylene, benzimidazole or tetraline.
A tricyclic ring system of thirteen or fourteen atoms is for example unsubstituted or substituted phenanthrene.
The term “phenylene”, as used in the context of the present invention, preferably denotes a unsubstituted or substituted 1,2-, 1,3- or 1,4-phenylene group, which is optionally substituted. 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, more preferably fluoro.
The term “polar group”, as used in the context of the present invention primarily denotes a group like a nitro, cyano, or a carboxy group.
The term “heteroatom”, as used in the context of the present invention primarily denotes oxygen, sulphur, and nitrogen, preferably oxygen and nitrogen, in the latter case preferably in the form of oxygen or —NH—.
The wording “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, trifluoro-C1-C6alkyl, hydroxy, halogen, preferably fluoro, or by a polar group as defined above.
The term “diamine group” 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. The at least two amino groups are preferably able to react with e.g., two carboxylic acid groups, or activated carboxylic groups, or anhydride groups; as outlined in more detail below.
The term “dinitro” or “dinitro compound” is to be understood as designating a chemical structure which has at least two nitro groups, i.e., which may also have 3 or more nitro groups, and wherein the dinitro group is a precursor compound of the “diamino compound”. The dinitro compound is conventionally converted to the diamino compound by reduction methods known in the art.
With respect to straight chain or branched alkyl, alkane group alkoxy, alkylcarbonyloxy, acryloyloxyalkoxy, acryloyloxyalkyl, acryloyloxyalkene, alkyloxycarbonyloxy, alkylacryloyloxy, methacryloyloxyalkoxy, methacryloyloxyalkyl, methacryloyloxyalkene, alkylmethacryloyloxy, alkylmethacryloyloxy, alkylvinyl, alkylvinyloxy, alkylallyloxy and alkanediyl groups it is repeatedly pointed out that some or several of the C—, CH—, CH2— group 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.
Preferably, M1, M2 and M3 are independently from each other selected from formula (III):
H(R6′)N-(Sp1)k1-(X1)t1—(Z5—C3)a3—(Z6—C4)a4—(X2)t2-(Sp2)k2-N(R6)H (III)
The wording “side chain”, T, represents a substituted or unsubstituted straight-chain or branched C1-C20alkanediyl group(s), in which one or more C—, CH—, CH2— group may independently from each other be replaced by a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, or a heteroatom and/or by a bridging group, which is at least once linked to at least one group S1 or S2 in formula (I).
More preferably, M1, M2 and M3 are independently from each other selected from formula (III), wherein:
Further more preferred M1, M2 and M3 are independently from each other more preferably selected from the following group of structures: substituted or unsubstituted o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, biphenyldiamine, 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline, aminophenylen-Z6-phenylenamino, wherein Z6 has the same meaning and preferences as given above for Z6 in compound of formula (III), and is especially oxygen; naphthylenediamine, benzidine, diaminofluorene, 3,4-diaminobenzoic acid, 3,4-diaminobenzyl alcohol dihydrochloride, 2,4-diaminobenzoic acid, L-(+)-threo-2-amino-1-(4-aminophenyl)-1,3-propanediol, p-aminobenzoic acid, [3,5-3h]-4-amino-2-methoxybenzoic acid, L-(+)-threo-2-(N,N-dimethylamino)-1-(4-aminophenyl)-1,3-propanediol, 2,7-diaminofluorene, 4,4′-diaminooctafluorobiphenyl, 3,3′-diaminobenzidine, 2,7-diamino-9-fluorenone, 3,5,3′,5′-tetrabromo-biphenyl-4,4′-diamine, 2,2′-dichloro[1,1′-biphenyl]-4,4′-diamine, 3,9-diamino-1,11-dimethyl-5,7-dihydro-dibenzo(a,c)cyclohepten-6-one, dibenzo(1,2)dithiine-3,8-diamine, 3,3′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 4-(4-amino-2-methyl-phenyl)-3-methyl-aniline, 2-(trifluoromethyl)benzene-1,3-diamine, 2-methylbenzene-1,3-diamine, 5-methylbenzene-1,3-diamine, 5-(trifluoromethyl)benzene-1,3-diamine, 4-(4-aminophenoxy)aniline, 2-(4-aminophenyl)-1H-benzimidazol-5-amine, 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline, 4,4-bis-(3-amino-4-hydroxyphenyl)-valeric acid, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, tetrabromo methylenedianiline, 2,7-diamino-9-fluorenone, 2,2-bis(3-aminophenyl)hexafluoropropane, bis-(3-amino-4-chloro-phenyl)-methanone, bis-(3-amino-4-dimethylamino-phenyl)-methanone, 3-[3-amino-5-(trifluoromethyl)benzyl]-5-(trifluoromethyl)aniline, 1,5-diaminonaphthalene, benzidine-3,3′-dicarboxylic acid, 4,4′-diamino-1,1′-binaphthyl, 4,4′-diaminodiphenyl-3,3′-diglycolic acid, dihydroethidium, o-dianisidine, 2,2′-dichloro-5,5′-dimethoxybenzidine, 3-methoxybenzidine, 3,3′-dichlorobenzidine (diphenyl-d6), 2,2′-bis(trifluoromethyl)benzidine, 3,3′-bis(trifluoromethyl)benzidine, 3,3′-dichlorobenzidine-d6, tetramethylbenzidine, di-(aminophenyl)alkylen and
The tetracarboxylic acid dianhydride of D1, D2 and D3 is independently from each other a tetracarboxylic acid dianhydride of formula (V)
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:
Preferred examples of aromatic tetracarboxylic acid dianhydrides are:
More preferably the tetracarboxylic acid dianhydrides used to form the tetravalent organic radical T are selected from:
In the context of the present invention preferred is
—(Z1—C1)a1—(Z2—C2)a2—(Z1a)a3— (IV)
More preferred S1 and S2 each independently from each other represents a straight-chain or branched C1-C20alkylen, wherein one or more C—, CH—, CH2— group may independently be replaced by a linking group or/and a group represented by the formula (IV), wherein:
Most preferred S1 and S2 each independently from each other represents a single bond or a spacer unit such as a straight-chain or branched C1-C14alkanediyl wherein one or more, preferably non adjacent, C—, CH—, CH2— group may independently be replaced by a linking group and/or a group represented by formula (IV), wherein:
Especially most preferred S1 and S2 each independently from each other represent a straight-chain C1-C12alkanediyl, preferably C1-C6alkanediyl, and more preferably methylene, ethylene, propylene, butylene, oentylene, hexylene; wherein one or more C—, CH—, CH2— group(s) may be replaced by —O—, —O(CO)—, —(CO)O—, preferably wherein C—, CH—, CH2— group(s) are not replaced.
In the context of the present invention preferably,
In the context of the present invention preferably,
Further, in the context of the present invention preferably,
A further preferred embodiment of the present invention relates to a compound of formula (I) as described above, wherein the terminal residue —Z4-Q2-R3 is:
Preferred, the present invention relates to a compound of formula (I),
H(R6′)N-(Sp1)k1-(X1)t1—(Z5—C3)a3—(Z6—C4)a4—(X2)t2-(Sp2)k2-N(R6)H (III)
Further one preferred embodiment of the present invention relates to a compound of formula (I), wherein n1 represent 1, and wherein n3 represents 1 and T1 represents halogen, preferably fluoro, or
A further embodiment of the present invention is a composition comprising at least one compound of formula (I) and preferably at least one or two diamine (L), more preferably the diamine (L) is within the above given meanings and preferences as described for diamines M1, M2 and/or M3, especially those of formula (III).
Further more preferred the diamine (L) represents unsubstituted or substituted aliphatic, aromatic or alicyclic diamine group having from 1 to 40 carbon atoms and preferably made from or selected from the following group of structures:
The diamine compounds (L) according to the present invention may be prepared using methods that are known to a person skilled in the art.
(L) diamine is further preferred, which is commercially available and listed below:
From the class of commercially available diamines (L) preferred are the below listed ones:
From the class of commercially available diamines (L) more preferred are the below listed ones:
Preferred is a composition comprising at least one compound of formula (I), within the meaning and preferences as described above,
A further embodiment of the present invention is a composition comprising at least one compound of formula (I), or a composition as described above, within the meaning and preferences as described above, and an additive.
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
Additional additives are photo-sensitizers, photo-radical generators, cationic photo-initiators.
Suitable photo-active additives include 2,2-dimethoxyphenylethanone, a mixture of diphenylmethanone and N,N-dimethylbenzenamine or ethyl 4-(dimethylamino)-benzoate, xanthone, thioxanthone, Irgacure® 184, 369, 500, 651 and 907 (Ciba), Michler's ketone, triaryl sulfonium salt and the like.
Further, preferably, the present invention relates to a composition, especially a blend, comprising
Further preferably, the present invention relates to a composition, especially a blend, comprising
In the context of the present invention the compound of formula (I) is a polymer, especially a copolymer or oligomer. Preferred the compound of formula (I) is a polyamic acid, polyamic ester, polyimide or a mixture thereof. Preferred compound of formula (I) is polyamic acid. If compound of formula (I) is a mixture, this mixture is preferably of polyamic acid and polyamic ester and/or polyimide. More preferred is a mixture of polyamic acid and polyimide.
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 polymer, copolymer or oligomer, especially the polyamic acid, polyamic acid ester and polyimide and mixtures thereof may be prepared in line with known methods, such as those described in Plast. Eng. 36 (1996), (Polyimides, fundamentals and applications), Marcel Dekker, Inc.
For example, the amidisation, poly-condensation reaction for the preparation of the polyamic acids is carried out in solution in a polar aprotic organic solvent, such as γ-butyrolactone, N,N-dimethylacetamide, N-methylpyrrolidone or N,N-dimethyl-formamide. In most cases equimolar amounts of the anhydride and the diamine are used, i.e., one amino group per anhydride group. If it is desired to stabilize the molecular weight of the polymer, copolymer or oligomer, it is possible for that purpose to either add an excess or a less-than-stoichiometric amount of one of the two components or to add a mono-functional compound in the form of a dicarboxylic acid monoanhydride or in the form of a monoamine. Examples of such mono-functional compounds are maleic acid anhydride, phthalic acid anhydride, aniline, and the like. Preferably the reaction is carried out at temperatures of less than 100° C.
The imidisation, cyclisation of the polyamic acids to form the polyimides can be carried out by heating, i.e., by condensation with removal of water or by other imidisation reactions using appropriate reagents.
Partially imidisation is achieved for example, if the imidisation is carried out purely thermally, the imidisation of the polyamic acids may not always be complete, i.e., the resulting polyimides may still contain proportions of polyamic acid.
Complete imidisation reactions are carried out at temperatures between 6° and 250° C., preferably at temperatures of less than 200° C.
In order to achieve imidisation at lower temperatures additional reagents that facilitate the removal of water are added to the reaction mixture. Such reagents are, for example, mixtures consisting of acid anhydrides, such as acetic acid anhydride, propionic acid anhydride, phthalic acid anhydride, trifluoroacetic acid anhydride or tertiary amines, such as triethylamine, trimethylamine, tributylamine, pyridine, N,N-dimethylaniline, lutidine, collidine etc. The amount of aforementioned additional reagents that facilitate the removal of water is preferably at least four equivalents of acid anhydride and two equivalents of amine per equivalent of polyamic acid to be condensed.
The imidization degree of each polymer used in the liquid crystal alignment agent of the invention can be arbitrarily adjusted by controlling the catalyst amount, reaction time and reaction temperature employed in production of the polymer. In the present description, “imidization degree” of polymer refers to a proportion (expressed in %) of the number of recurring units of polymer forming an imide ring or an isoimide ring to the number of total recurring units of polymer. In the present description, the imidization degree of a polyamic acid not subjected to dehydration and ring closure is 0%. The imidization degree of each polymer is determined by dissolving the polymer in deuterated dimethyl sulfoxide, subjecting the resulting solution to 1H-NMR measurement at a room temperature using tetramethylsilane as a standard substance, and calculating from the following formula.
Imidization degree (%)=1−(A1/A2×B)×100
The imidization degree is usually in the range of 1 to 99%, preferably 5 to 50%, more preferably 10 to 40%.
The present invention relates to a process for the preparation of a compound (I) comprising polymerisation of at least one of each a diamine M1, M2 and M3, withing the meanings and preferences as given above, with at least one D1, D2 and D3, withing the meanings and preferences as given above.
Preferably the polymerisation for the preparation of a compound (I) comprises
In a more preferred embodiment of the invention, the polymersiation of the diamine comprises the amidsation of at least one M1, M2 and M3, withing the meanings and preferences as given above, with tetracarboxylic acid anhydride (V), and/or the imidisation, preferably by elevated temperature, and wherein the amidisation and/or imidisation is optionally conducted
Preferably, the further polymer, copolymer or oligomer comprises as basic building block a diamine (L) and a tetracarboxylic acid anhydride, preferably a tetracarboxylic acid anhydride of formula (V).
This polymer, copolymer or oligomer comprising as basic building block a diamine (L) is prepared in analogy to the polymer, copolymer or oligomer of the invention comprising compound (I).
The imidisation is conducted after or during amidisation. In general, the imidisation is conducted after amidisation.
Preferred is the partially imidisation of polyamic acid or polyamic ester.
If the polymer is prepared only by imidisation, compound (I) will be contacted with an imidisation compound, with at least two polymerisable functional groups, such as for example, carbonyl groups or halogen groups.
A further embodiment of the present invention relates to a compound (I), or a composition, within the meaning and preferences as described above, obtainable according to the processes and preferred processes of the invention.
The polymers 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, good surface wetting, a high voltage holding ratio, a specific anchoring energy, etc.
Polymer or oligomer layers may readily be prepared from the polymers or oligomers of the present invention and a further embodiment of the invention relates to a polymer or oligomer layer comprising a polymer or oligomer according to the present invention, which is preferably prepared by treatment with aligning light. Preferably, the invention relates to a polymer or oligomer layer comprising a polymer or oligomer according to the present invention in a cross-linked and/or isomerized form.
The polymer or oligomer layer is preferably prepared by applying one or more polymers or oligomers according to the invention to a support and, after imidisation or without imidisation, treating, preferably cross-linking and/or isomerising, the polymer or oligomer or polymer mixture or oligomer mixture by irradiation with aligning light.
In the context of the present invention, aligning light is light of wavelengths, which can initiate photoalignment. Preferably, the wavelengths are in the UV-A, UV-B 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.
For generating tilt angles, preferably the aligning light is exposed from oblique angles. 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.
In a more preferred embodiment of the invention the polymer, copolymer or oligomer is treated with polarised light, especially linearly polarised light, or by oblique radiation with non-polarised light.
In general, transparent support such as glass or plastic substrates, optionally coated with indium tin oxide (ITO) are used.
Further, it is possible to vary the direction of orientation and the tilt angle within the polymer or oligomer layer by controlling the direction of the irradiation of the aligning light. It is understood that by selectively irradiating specific regions of the polymer or oligomer layer very specific regions of the layer can be aligned. In this way, layers with a defined tilt angle can be provided. The induced orientation and tilt angle are retained in the polymer or oligomer layer by the process, especially by the process of cross-linking.
Further, the present invention relates to a method for the preparation of a compound, preferably a polymer, copolymer or oligomer according to the invention, wherein in a polycondensation reaction at least one of each M1, M2 and M3 diamine is reacted with one or more D1, D2 and D3, as described above withing the meaning and preferences given there; preferably with D1, D2 and D3 are tetracarboxylic acid dianhydrides of the general formula (V), optionally in the presence of one or more additional other diamines.
Further, the present invention preferably relates to a method, wherein a poly-condensation reaction for the preparation of the polyamic acids is carried out in solution in a polar aprotic organic solvent, preferably selected from y-butyrolactone N,N-dimethylacetamide, N-methylpyrrolidone or N,N-dimethylformamide
Preferably, the present invention relates to a method, wherein subsequent to the poly-condensation cyclisation with removal of water is carried out thermally under formation of a polyimide.
More preferably, the present invention relates to a method, wherein imidisation is carried out prior or after the application of the polymer, copolymer or oligomer to a support.
A further preferred embodiment of the present invention relates to a preferred methods of the invention relate to
A further embodiment of the present invention relates to a polymer, copolymer or oligomer layer, in particular orientation layer, comprising at least one polymer, copolymer or oligomer according to the present invention.
It is understood that the polymer or oligomer layers of the present invention (in form of a polymer gel, a polymer network, a polymer film, etc.) can also be used as orientation layers for liquid crystals. A further preferred embodiment of the invention relates to an orientation layer comprising one or more polymers or oligomers according to the invention, 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 addition, the present invention relates to a method for the preparation of a polymer layer or oligomer layer, wherein one or more polymers, copolymers or oligomers according to the present invention is applied to a support, preferably from a solution of the polymer or oligomer material and subsequent evaporation of the solvent, and wherein, after any imidisation step which may be necessary, the polymer or oligomer or polymer mixture or oligomer mixture treated with aligning light, and preferably isomerized and/or cross-linked by irradiation with aligning light.
A preferred method of the present invention relates to a method, wherein the direction of orientation and the tilt angle within the 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 orientation layers are suitably prepared from a solution of the polymer or oligomer material. The polymer or oligomer solution is applied to a support optionally coated with an electrode [for example a glass plate coated with indium-tin oxide (ITO)] so that homogeneous layers of 0.05 to 50 μm thickness are produced. In this process different coating techniques like spin-coating, inkjet, meniscus-coating, wire-coating, slot-coating, offset-printing, flexo-printing, gravur-printing may be used. Then, or optionally after a prior imidisation step, the regions to be oriented are irradiated, for example, with a high-pressure mercury vapour lamp, a xenon lamp or a pulsed UV laser, using a polarizer and optionally a mask for creating images of structures.
Further, the present invention relates to the use of a polymer layer, copolymer or oligomer layer according to the present invention, preferably in cross-linked form, as an orientation layer for liquid crystals.
Further, the present invention relates to preferably the use of a polymer layer, copolymer or oligomer layer for the induction of vertical alignment of adjacent liquid crystalline layers, in particular for operating a cell in VA mode.
The irradiation time is dependent upon the output of the individual lamps and can vary from a few seconds to several hours. The photo-reaction (dimerisation, 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 polymer or oligomer 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 present invention relates to the use of a polymer layer, copolymer, or oligomer layer as an orientation layer for liquid crystals.
Preferred is the use for the induction of vertical alignment of adjacent liquid crystalline layers.
A further embodiment of the invention relates to an optical or electro-optical device comprising one or more polymers or oligomers according to the present invention in cross-linked form. The electro-optical devices may comprise more than one layer. The layer, or each of the layers may contain one or more regions of different spatial orientation.
Preferably, the present invention relates to 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.
More preferably, the present invention relates to an orientation layer, comprising at least one polymer layer, copolymer or oligomer layer according to the present invention.
The advantages of the present invention could not be foreseen by a skilled person. It has surprisingly been found that low pre-tilt angles and/or low ACM values are assible by the compounds of present invention.
A polymer backbone which can be referred as polymer main chain is a polyimide or polyamic acid material. Polyamic acids (PAA) are precursor materials of polyimides (PI). This procedure follows the general procedure written in text books “Polyimides: Fundamentals and Application” where it involves reacting a dianhydride and a diamine in an aprotic solvent as a first stage to generate the Polyamic acid (PAA) intermediate polymer. PAA can be subsequently cyclized to the corresponding Polyimide (PI). Polyamic acids (PAA) were synthesized by “solution polycondensation” of diamines or mixture of diamines with dianhydrides or a mixture of dianhydrides and PAA were readily soluble in polar organic solvents (e.g. N-methylpyrrolidinone). The polymer composition is in accordance with the monomers (diamines, dianhydrides) structures with respect of their molar contribution and possible isomers. The polymer formation is characterized by an increase of the viscosity of the reaction mixture. An inherent viscosity >0.1 dL/g attests the formation of the polymer main chain.
4.897 g (24.970 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 5.000 g (24.970 mmol) of 4-(4-aminophenoxy) aniline in 39.59 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid PX1 is obtained as 20 wt % NMP-solution with an inherent viscosity [η] of 0.37 dL/g.
4.622 g (23.570 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 5.000 g (23.570 mmol) of 4-(4-amino-2-methyl-phenyl)-3-methyl-aniline in 38.49 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid PX2 is obtained as 20 wt % NMP-solution with an inherent viscosity [η] of 0.50 dL/g.
2.750 g (12.267 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone is added to a solution of 2.500 g (11.776 mmol) of 4-(4-amino-2-methyl-phenyl)-3-methyl-aniline and, 0.110 g (0.491 mmol) of 2-(4-aminophenyl)-1H-benzimidazol-5-amine in 21.44 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid PX3 is obtained as 20 wt % NMP-solution with an inherent viscosity [η] of 0.57 dL/g.
5.598 g (24.970 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone is added to a solution of 5.000 g (24.970 mmol) of 4-(4-aminophenoxy) aniline in 42.39 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid PX4 is obtained as 20 wt % NMP-solution with an inherent viscosity [η] of 0.44 dL/g.
5.284 g (23.570 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone is added to a solution of 5.000 g (23.570 mmol) of 4-(4-amino-2-methyl-phenyl)-3-methyl-aniline in 41.14 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid PX5 is obtained as 20 wt % NMP-solution with an inherent viscosity [η] of 0.62 dL/g.
19.5 g (164.1 mmol) of thionylchloride are added by portion in 30 min to a suspension of 37.0 g (149.1 mmol) of 4-(4,4,4-trifluorobutoxy)benzoic acid in 100 mL of toluene and 0.8 mL of DMF at 70° C. After 2 hours at 75° C. the excess of thionyl chloride is distilled off under pressure. The reaction mixture is subsequently cooled down to room temperature and 18.9 g (155.1 mmol) of 4-hydroxybenzaldehyde, 0.91 g (7.5 mmol) of 4-Dimethylaminopyridine and 52.0 g (657.4 mmol) of pyridine are added. After 2 hours of agitation at room temperature, 26.53 g (254.9 mmol) of malonic acid and 7.3 g (102.6 mmol) of pyrrolidine are added and the reaction mixture is heated up to 80° C. After 4 h at 80° C., the reaction mixture is cooled down to 40° C., 150 mL of MeOH are added and the reaction mixture is cooled down to 0° C. After 1 h at 0° C., the precipitated is filtered off, washed with 100 mL of cold methanol and dry under vacuum at 40° C. to give 53.0 g (90%) of (E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoic acid as a white powder.
1H NMR (300 MHz) in DMSO-D6: 12.40 (b, 1H), 8.08 (d, 2H), 7.79 (d, 2H), 7.63 (d, 1H), 7.32 (d, 2H), 7.14 (d, 2H), 6.54 (d, 1H), 4.17 (t, 2H), 2.45 (m, 2H), 1.98 (m, 2H).
2.50 g (11.8 mmol) of 2-(2,4-dinitrophenyl)ethanol, 4.65 g (11.8 mmol) of (E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoic acid, 144 mg (1.2 mmol) of 4-Dimethylaminopyridine are dissolved in 30 ml of dichloromethane. 2.48 g (13.0 mmol) of N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDC hydrochloride) are added at 0° C. The solution is stirred for 1 h at 0° C. and allowed to stir at room temperature overnight. After 22 hours at room temperature the reaction mixture is partitioned between dichloromethane and water. The organic phase is washed repeatedly with water, dried over sodium sulphate, filtered, and concentrated by rotary evaporation. Chromatography of the residue on silica gel using toluene:ethyl acetate 95:5 as eluant and crystallization form ethylacetate:hexane mixture to yield 5.21 g (75%) of [4-[(E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate as colorless crystals.
1H NMR (300 MHz) in DMSO-D6: 8.74 (d, 1H), 8.51 (dd, 1H), 8.09 (dd, 2H), 7.93 (d, 1H), 7.80 (d, 2H), 7.65 (d, 1H), 7.34 (d, 2H), 7.14 (d, 2H), 6.55 (d, 1H), 4.47 (t, 2H), 4.17 (t, 2H), 2.45 (m, 2H), 2.00 (m, 2H).
4.93 g (8.38 mmol) of ([4-[(E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate are dissolved in a mixture of 54 ml of N,N-dimethylformamide and 6 ml water. 13.9 g (51.4 mmol) ferric chloride hexahydrate are added. 5.60 g (85.7 mmol) Zinc powder are added portion wise within 60 min. The mixture is allowed to react for 2 hours. The reaction mixture is then partitioned between ethyl acetate and water and filtered. The organic phase is washed repeatedly with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. Filtration of the residue on silica gel using toluene:ethyl acetate (1:3) as eluant and crystallization form ethylacetate:hexane mixture to yield 3.20 g (72%) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate as orange powder.
1H NMR (300 MHz) in DMSO-D6: 8.10 (d, 2H), 7.83 (d, 2H), 7.70 (d, 1H), 7.34 (d, 2H), 7.15 (d, 2H), 6.64 (m, 1H+1H), 5.90 (m, 1H), 5.80 (m, 1H), 4.66 (m, 2H), 4.58 (m, 2H) 4.18 (m, 2H+2H), 2.70 (t, 2H), 2.47 (m, 2H), 2.01 (m, 2H).
11.63 g (97.74 mmol) of thionylchloride are added by portion in 30 min to a suspension of 24.92 g (88.86 mmol) of 4-(4-pentylcyclohexyl)cyclohexanecarboxylic acid in 75 mL of toluene and 0.06 mL of DMF at 75° C. After 2 hours at 75° C. the excess of thionyl chloride is distilled off under pressure. The reaction mixture is subsequently cooled down to room temperature and 11.29 g (92.41 mmol) of 4-hydroxybenzaldehyde, 0.54 g (4.44 mmol) of 4-Dimethylaminopyridine and 30.5 g (385.64 mmol) of pyridine are added. After 2 hours of agitation at room temperature, 15.81 g (151.95 mmol) of malonic acid and 3.22 g (45.32 mmol) of pyrrolidine are added and the reaction mixture is heated up to 80° C. After 4 h at 80° C., the reaction mixture is cooled down to 40° C., 150 mL of MeOH are added and the reaction mixture is cooled down to 0° C. After 1 h at 0° C., the precipitated is filtered off, washed with 100 mL of cold methanol and dry under vacuum at 40° C. to give to give 31.54 g (83%) of (E)-3-[4-[4-(4-pentylcyclohexyl)cyclohexanecarbonyl]oxyphenyl]prop-2-enoic acid as a white powder.
1H NMR (300 MHz) in DMSO-D6: 12.37 (b, 1H), 7.73 (d, 2H), 7.59 (d, 1H), 7.14 (d, 2H), 6.50 (d, 1H), 2.08 (m, 2H), 1.73 (m, 6H), 1.5-0.7 (m, 20H), 0.85 (t, 3H).
2.50 g (11.8 mmol) of 2-(2,4-dinitrophenyl)ethanol, 5.03 g (11.8 mmol) of (E)-3-[4-[4-(4-pentylcyclohexyl)cyclohexanecarbonyl]oxyphenyl]prop-2-enoic acid, 144 mg (1.2 mmol) of 4-Dimethylaminopyridine are dissolved in 30 ml of dichloromethane. 2.48 g (13.0 mmol) of N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDC hydrochloride) are added at 0° C. The solution is stirred for 1 h at 0° C. and allowed to stir at room temperature overnight. After 22 hours at room temperature the reaction mixture is partitioned between dichloromethane and water. The organic phase is washed repeatedly with water, dried over sodium sulphate, filtered, and concentrated by rotary evaporation. Chromatography of the residue on silica gel using toluene:ethyl acetate 95:5 as eluant and crystallization form ethylacetate:hexane mixture to yield 5.49 g (75%) of [4-[(E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate as colorless crystals.
1H NMR (300 MHz) in DMSO-D6: 8.74 (d, 1H), 8.51 (dd, 1H), 7.92 (d, 1H), 7.75 (d, 2H), 7.61 (d, 1H), 7.16 (d, 2H), 6.52 (d, 1H), 4.46 (t, 2H), 3.38 (t, 2H), 2.1 (m, 2H), 1.7 (m, 6H), 1.5-0.7 (m, 20H), 0.85 (t, 3H).
5.20 g (8.38 mmol) of [4-[(E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate are dissolved in a mixture of 54 ml of N,N-dimethylformamide and 6 ml water. 13.9 g (51.4 mmol) ferric chloride hexahydrate are added. 5.60 g (85.7 mmol) Zinc powder are added portion wise within 60 min. The mixture is allowed to react for 2 hours. The reaction mixture is then partitioned between ethyl acetate and water and filtered. The organic phase is washed repeatedly with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. Filtration of the residue on silica gel using toluene:ethyl acetate (1:3) as eluant and crystallization form ethylacetate:hexane mixture to yield 3.06 g (65%) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate as yellow-orange powder.
1H NMR (300 MHz) in DMSO-D6: 7.76 (d, 2H), 7.65 (d, 1H), 7.14 (m, 2H), 6.59 (m, 1H+1H), 5.89 (m, 1H), 5.80 (m, 1H), 4.64 (s, 2H), 4.57 (s, 2H), 4.17 (t, 2H), 3.38 (t, 2H), 2.1 (m, 2H), 1.7 (m, 6H), 1.5-0.7 (m, 20H), 0.85 (t, 3H).
0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone is added to a solution of 0.951 g (1.80 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.073 g (0.60 mmol) of 2-methylbenzene-1,3-diamine in 4.741 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P1 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.36 dL/g.
0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone is added to a solution of 0.634 g (1.20 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.673 g (1.20 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.073 g (0.60 mmol) of 2-methylbenzene-1,3-diamine in 4.790 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P2 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.38 dL/g.
0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.348 g (2.55 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, and 0.252 g (0.45 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, in 5.302 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P3 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.47 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 1.110 g (2.10 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.037 g (0.30 mmol) of 2-methylbenzene-1,3-diamine in 4.833 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P4 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.90 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 0.539 g (1.02 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.555 g (0.99 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.120 g (0.99 mmol) of 2-methylbenzene-1,3-diamine in 4.208 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P5 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.30 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 0.951 g (1.80 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.120 g (0.60 mmol) of 4-(4-aminophenoxy) aniline in 4.658 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P6 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.32 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 0.951 g (1.80 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.106 g (0.60 mmol) of 5-(trifluoromethyl)benzene-1,3-diamine in 4.624 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P7 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.27 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 1.110 g (2.10 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.096 g (0.30 mmol) of 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline in 4.972 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P8 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.33 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 1.110 g (2.10 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.252 g (0.45 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.055 g (0.45 mmol) of 2-methylbenzene-1,3-diamine in 4.680 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P9 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.60 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 0.951 g (1.80 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.073 g (0.60 mmol) of 2-methylbenzene-1,3-diamine in 4.549 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P10 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.38 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 0.872 g (1.65 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.092 g (0.75 mmol) of 2-methylbenzene-1,3-diamine in 4.406 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P11 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.58 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 0.951 g (1.80 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.192 g (0.60 mmol) of 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline in 4.826 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P12 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.32 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 1.031 g (1.95 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.252 g (0.45 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.192 g (0.60 mmol) of 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline in 4.815 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P13 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.45 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 0.793 g (1.50 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.288 g (0.90 mmol) of 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline in 4.680 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P14 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.87 dL/g.
To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P1 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 1.
To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P1 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 2.
To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P2 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 3.
To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P2 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 4.
To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P3 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 5.
To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P3 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 6.
To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P4 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 8.
To a solution of 1.700 g of Polyamic acid PX5 and 0.200 g of Polyamic acid P4 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 3.
To a solution of 1.910 g of Polyamic acid PX2 and 0.225 g of Polyamic acid P4 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 9.
To a solution of 1.700 g of Polyamic acid PX4 and 0.200 g of Polyamic acid P4 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 10.
To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P5 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 11.
To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P6 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 12.
To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P7 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 13.
To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P7 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 14.
To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P8 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 15.
To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P8 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 16.
To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P9 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 17.
To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P9 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 18.
To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P10 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 19.
To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P10 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 20.
To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P11 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 21.
To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P11 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 22.
To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P12 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 23.
To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P12 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 24.
To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P13 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 25.
To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P14 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 26.
Measurement of the pretilt angle as used in the examples: To measure the pretilt angle a rotating analyzer is used, as described by Michio Kitamura, Shunsuke Kobayashi and Katsumi Mori; Journal of the SID14/5, 2006; p509-p514.”
Formulation 1 is spin-coated onto two ITO coated glass substrates at a spin speed of c.a. 2000 rpm for 30 seconds. After spin-coating, the substrates are subjected to a baking procedure consisting of pre-baking for 90 seconds at 80° C. and post-baking for 40 minutes at 200° C. Then, the substrates are exposed to linearly polarized light at an incidence angle of 40° relative to the normal of the substrate surface (22 mJ·cm2-PLUMBOL). The plane of polarization is parallel to the substrate's longest edges. The cells are assembled with the 2 substrates, the exposed polymer layers facing 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 cells are capillary filled with liquid crystal MLC-6610 (Merck KGA-Δε<0). Finally, the filled cells are further subjected to a thermal annealing at 130° C. for 10 minutes, thereby completing the cell process. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.88° is measured.
A cell is prepared as in Example 1, except that formulation 2 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 88.01° is measured.
A cell is prepared as in Example 1, except that formulation 3 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 88.18° is measured.
A cell is prepared as in Example 1, except that formulation 4 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 88.29° is measured.
A cell is prepared as in Example 1, except that formulation 5 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 88.22° is measured.
A cell is prepared as in Example 1, except that formulation 6 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 88.25° is measured.
A cell is prepared as in Example 1, except that formulation 7 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.03° is measured.
A cell is prepared as in Example 1, except that formulation 8 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.16° is measured.
A cell is prepared as in Example 1, except that formulation 9 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.13° is measured.
A cell is prepared as in Example 1, except that formulation 10 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.26° is measured.
A cell is prepared as in Example 1, except that formulation 11 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.23° is measured.
A cell is prepared as in Example 1, except that formulation 12 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.32° is measured.
A cell is prepared as in Example 1, except that formulation 13 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.05° is measured.
A cell is prepared as in Example 1, except that formulation 14 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.23° is measured.
A cell is prepared as in Example 1, except that formulation 15 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.09° is measured.
A cell is prepared as in Example 1, except that formulation 16 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.23° is measured.
A cell is prepared as in Example 1, except that formulation 17 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.72° is measured.
A cell is prepared as in Example 1, except that formulation 18 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.91° is measured.
A cell is prepared as in Example 1, except that formulation 19 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.69° is measured.
A cell is prepared as in Example 1, except that formulation 20 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.94° is measured.
A cell is prepared as in Example 1, except that formulation 21 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.62° is measured.
A cell is prepared as in Example 1, except that formulation 22 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.90° is measured.
A cell is prepared as in Example 1, except that formulation 23 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.74° is measured.
A cell is prepared as in Example 1, except that formulation 24 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.02° is measured.
A cell is prepared as in Example 1, except that formulation 25 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.55° is measured.
A cell is prepared as in Example 1, except that formulation 26 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.37° is measured.
Voltage holding ratio (VHR) of the cells is measured at 60° C. using LCM-1 instrument from Toyo, Japan. The VHR was measured using a short and a long frame period (T). In the short one, the voltage decay V (at T=16.67 ms) of a voltage surge of 64 μs with V0(V at t=0)=1V is then measured over a period of T=16.67 ms. The voltage holding ratio is then determined, at room temperature, given by integration of the measurement curve between V0 and V weighted by the area in the case of 100% VHR. The table below shows VHR measured for all tested cells. The results show VHR >99% for all tested cells.
An AC-voltage of 60 Hz frequency and 7.5 V amplitude is applied to cells prepared examples 1 to 25. After 48 hours of stress, the cells are short-circuited, and the change of the pre-tilt angle is measured after 60 min of relaxation. The difference in pretilt measurement between before and after the stress-relaxation cycle gives AC-Memory (ACM°). If ACM° is excellent below −0.015°, very good between −0.016° and −0.030°, good between −0.031° and −0.045°, medium between −0.046° and −0.060° and bad for value higher than −0.061°.
0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.268 g (2.40 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, and 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-4 pentylcyclohexyl)cyclohexanecarboxylate, in 5.311 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P15 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.47 dL/g.
[4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-pentylcyclohexanecarboxylate is prepared following the three steps described in example 8a, 8b and 8c but starting from 4-pentylcyclohexanecarboxylic acid instead 4-(4-pentylcyclohexyl)cyclohexanecarboxylic acid
1H NMR (300 MHz) in DMSO-D6: 7.77 (d, 2H), 7.65 (d, 1H), 7.15 (d, 2H), 6.60 (m, 1H+1H), 5.89 (d, 1H), 5.79 (dd, 1H), 4.64 (s, 2H), 4.58 (s, 2H), 4.17 (t, 2H), 3.38 (t, 2H), 2.68 (t, 2H), 2.50 (m, 1H), 2.06 (m, 2H), 1.65 (m, 2H), 1.6-0.8 (m, 13H), 0.86 (t, 3H).
0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.268 g (2.40 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, and 0.287 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-pentylcyclohexanecarboxylate, in 5.196 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P16 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.63 dL/g.
0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.189 g (2.25 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, and 0.359 g (0.75 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-pentylcyclohexanecarboxylate, in 5.180 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P17 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.34 dL/g.
[4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]-2-methoxy-phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate is prepared following the 3 steps described in example 8a, 8b and 8c but starting from 4-hydroxy-3-methoxy-benzaldehyde instead 4-hydroxybenzaldehyde
1H NMR (300 MHz) in DMSO-D6: 7.63 (d, 1H), 7.50 (d, 1H), 7.27 (m, 1H), 7.08 (m, 1H), 6.66 (m, 1H), 6.62 (m, 1H), 5.90 (m, 1H), 5.78 (m, 1H), 4.62 (m, 4H), 4.18 (t, 2H), 3.80 (s, 3H), 2.68 (m, 2H), 2.5 (m, 2H), 2.1 (m, 2H), 1.7 (m, 6H), 1.5-0.7 (m, 16H), 0.85 (t, 3H).
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 1.268 g (2.4 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, and 0.354 g (0.6 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]-2-methoxy-phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, in 5.156 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P18 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.84 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 0.951 g (1.8 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.354 g (0.6 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]-2-methoxy-phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.073 g (0.6 mmol) of 2-methylbenzene-1,3-diamine in 4.587 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P19 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.42 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 1110.0 g (2.1 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.355 g (0.6 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]-2-methoxy-phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.037 g (0.3 mmol) of 2-methylbenzene-1,3-diamine in 4.876 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P20 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.61 dL/g.
0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone is added to a solution of 0.673 g (1.2 mmol) [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.576 g (1.8 mmol) of 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline, in 4.482 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P21 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.53 dL/g.
0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.178 g (2.1 mmol) [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.288 g (0.9 mmol) of 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline, in 4.989 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P22 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.53 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 0.841 g (1.5 mmol) [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.480 g (1.5 mmol) of 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline, in 4.454 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P23 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.52 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 0.757 g (1.35 mmol) [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.350 g (1.65 mmol) of 4-(4-amino-2-methyl-phenyl)-3-methyl-aniline, in 3.955 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P24 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.55 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 0.757 g (1.35 mmol) [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.330 g (1.65 mmol) of 4-(4-aminophenoxy)aniline, in 3.908 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P25 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.65 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 1.346 g (2.4 mmol) [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.192 g (0.6 mmol) of 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline, in 4.961 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P26 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.72 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 1.110 g (2.1 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.287 g (0.6 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-pentylcyclohexanecarboxylate, and 0.037 g (0.3 mmol) of 2-methylbenzene-1,3-diamine in 4.208 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P27 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.61 dL/g.
[4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-ethylcyclohexyl)cyclohexanecarboxylate is prepared following the three steps described in example 8a, 8b and 8c but starting from 4-(4-ethylcyclohexyl)cyclohexanecarboxylic acid instead 4-(4-pentylcyclohexyl)cyclohexanecarboxylic acid
1H NMR (300 MHz) in THF-D8: 7.62 (m, 1+2H), 7.11 (d, 2H), 6.64 (d, 1H), 6.49 (d, 1H), 5.88 (m, 1H+1H), 4.27 (s broad, 4H), 4.21 (t, 2H), 2.73 (t, 2H), 2.46 (m, 2H), 2.14 (m, 2H), 1.79 (m, 4H), 1.50 (m, 2H), 1.4-0.9 (m, 12H), 0.88 (t, 3H).
0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.348 g (2.55 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, and 0.233 g (0.45 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-ethylcyclohexyl)cyclohexanecarboxylate, in 5.257 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P28 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.30 dL/g.
[4-(4-pentylcyclohexyl)cyclohexyl]4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]benzoate is prepared following the 2 steps described in examples 8b and 8c but starting from E)-3-[4-[4-(4-pentylcyclohexyl)cyclohexoxy]carbonylphenyl]prop-2-enoic acid instead (E)-3-[4-[4-(4-pentylcyclohexyl)cyclohexanecarbonyl]oxyphenyl]prop-2-enoic acid
1H NMR (300 MHz) in THF-D8: 8.01 (d, 2H), 7.71 (m, 2H+1H), 6.64 (m, 1H+1H), 5.88 (m, 1H+1H), 4.85 (m, 1H), 4.26 (t, 2H), 4.20 (s broad, 4H), 2.74 (t, 2H), 2.12 (m, 2H), 1.7 (m, 6H), 1.9-0.8 (m, 22H), 0.85 (t, 3H).
0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.348 g (2.55 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, and 0.252 g (0.45 mmol) of [4-(4-pentylcyclohexyl)cyclohexyl]4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]benzoate, in 5.301 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P29 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.31 dL/g.
0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.682 g (3.00 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, in 5.495 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P30 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.29 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 1.682 g (3.00 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, in 5.296 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P31 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.30 dL/g.
0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.436 g (3.00 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-pentylcyclohexanecarboxylate, in 4.919 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P32 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.29 dL/g.
0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone is added to a solution of 1.586 g (3.00 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, in 5.073 g of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P33 is obtained as 30 wt % NMP-solution with an inherent viscosity [η] of 0.54 dL/g.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P15 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 27.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P16 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 28.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P17 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 29.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P18 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 30.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P19 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 31.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P20 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 32.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P21 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 33.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P22 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 34.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P23 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 35.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P24 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 36.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P25 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 37.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P26 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 38.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P27 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 39.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P28 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 40.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P29 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 41.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P30 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 42.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P31 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 43.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P32 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 44.
To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P33 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 μm PTFE-filter to give Formulation 45.
Formulation 27 is spin-coated onto two ITO coated glass substrates at a spin speed of c.a. 2000 rpm for 30 seconds. After spin-coating, the substrates are subjected to a baking procedure consisting of pre-baking for 90 seconds at 80° C. and post-baking for 40 minutes at 200° C. Then, the substrates are exposed to linearly polarized light at an incidence angle of 40° relative to the normal of the substrate surface (22 mJ·cm2-LPUVB). The plane of polarization is parallel to the substrate's longest edges. The cells are assembled with the 2 substrates, the exposed polymer layers facing 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 cells are capillary filled with liquid crystal MLC-6610 (Merck KGA-Δε<0). Finally, the filled cells are further subjected to a thermal annealing at 130° C. for 10 minutes, thereby completing the cell process. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.27 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 28 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.04 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 29 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.17 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 30 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.14 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 31 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.21 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 32 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.16 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 33 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 87.97 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 34 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 87.17 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 35 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 87.01 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 36 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 87.23 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 37 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 87.38 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 38 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 87.04 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 39 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 86.67 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 40 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.64 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 41 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.18 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 42 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.27 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 43 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 87.89 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 44 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.29 is measured using the rotating analyser method from Shintech.
A cell is prepared as in Example 29, except that formulation 45 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 86.66 is measured using the rotating analyser method from Shintech.
Voltage holding ratio (VHR) of the cells is measured at 60° C. using LCM-1 instrument from Toyo, Japan. The VHR was measured using a short and a long frame period (T). In the short one, the voltage decay V (at T=16.67 ms) of a voltage surge of 64 μs with V0(V at t=0)=1V is then measured over a period of T=16.67 ms. The voltage holding ratio is then determined, at room temperature, given by integration of the measurement curve between V0 and V weighted by the area in the case of 100% VHR. The table below shows VHR measured for all tested cells. The results show VHR >99% for all tested cells except the comparative examples 44, 45 and 46 which led to poor electrical property.
An AC-voltage of 60 Hz frequency and 7.5 V amplitude is applied to cells prepared examples 1 to 25. After 48 hours of stress, the cells are short-circuited, and the change of the pre-tilt angle is measured after 60 min of relaxation. The difference in pretilt measurement between before and after the stress-relaxation cycle gives AC-Memory (ACM°). If ACM° is excellent below −0.015°, very good between −0.016° and −0.030°, good between −0.031° and −0.045°, medium between −0.046° and −0.060° and bad for value higher than −0.061°.
| Number | Date | Country | Kind |
|---|---|---|---|
| 22162400.0 | Mar 2022 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2023/055888 | 3/8/2023 | WO |
