Photo-alignment materials

Abstract

The present invention relates to photoalignment compounds of formula (I), to a process for the preparation of said compounds, to photoalignment compositions obtainable by this process, and to the use of said compositions as alignment layers for liquid crystals and in the construction of unstructured and structured optical elements and multilayer systems, especially liquid crystal displays.

Description

[Technical field]

[0001] The present invention relates to a photoalignment compound of formula (I), a process for the preparation of said compound, a photoalignment composition obtained by said process, and the use of said composition as an alignment layer for liquid crystals and in the construction of unstructured and structured optical elements and multilayer systems, especially liquid crystal displays. There is an increasing demand for the development of new photoalignment materials for optical and electro-optical applications. Recently, there has been an increasing demand for green technology, both for consumers and for large-scale manufacturing processes. In particular, the display industry has a continuous need to increase production efficiency by reducing the power consumption and duration of the various processing steps. On the other hand, consumers prefer to watch larger and higher definition televisions, which generally consume high energy. One way to reduce energy consumption is to reduce the brightness required by the backlight. Y. Yamada, Q. Tang, M. Koechlin and Y. Yamaoto in Late-News Paper, SID 2017 DIGEST, pages 708 to 711 state that effective use of the backlight requires high transmittance.

[0002] In the present invention, a new photoalignment material has been found that leads to economical manufacturing processes and low energy consumption LCDs without compromising the required technical properties. As a result, in the present invention, a photoalignment material having the formula (I): [ka] [In the formula, M 1 , M 2 and M. 3 are, independently of one another, monocyclic rings of 5 or 6 atoms; two adjacent monocyclic rings of 5 or 6 atoms, bicyclic ring systems of 8, 9 or 10 atoms, tricyclic ring systems of 13 or 14 atoms, as well as mono-, bi- and tricyclic rings, which are unsubstituted or di-(C1-C20 linear or branched, substituted or unsubstituted C-C alkyl)amino, C-C alkyloxy, nitro, cyano and / or chlorine or fluorine; and one or more C-, CH-, CH2- groups may be independently replaced by a linking group; 20 represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic or non-aromatic diamine group selected from mono-, bi-, or tricyclic rings linked by an alkanediyl; D 1 , D 2 and D. 3 represent, independently of one another, an unsubstituted or substituted aliphatic, alicyclic or carbocyclic or heterocyclic aromatic group substituted with at least two carboxylic acid groups, or activated carboxyl groups, or anhydride groups; m 1 , m 2 or m 3 are independent of each other, 0 <m 1 <1, 0≦m 2 ≦0.7 and 0≦m 3 <1; preferably, 0 <m 1 <1, 0≦m 2 ≦0.5 and 0≦m 3 represents the mole fraction of comonomer that is <1, S 1 and S 2 represent, independently of each other, a spacer unit, E 1 and E 2 are each independently an aromatic group, an oxygen atom, a sulfur atom, -NH-, -N(C1-C6 alkyl)-, -CR 4 R 5 where R 4 and R 5 are each independently hydrogen or a cyclic, linear or branched, substituted or unsubstituted C1-C 30 alkyl, in which one or more C-, CH-, CH2- groups may be replaced, independently of one another, by a linking group, with the proviso that R 4 and R 5is not hydrogen; A represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic group, preferably A is unsubstituted or substituted phenylene, naphthalene, biphenylene or triphenylene, more preferably A is unsubstituted or substituted phenylene; Z 1 , Z 2 , Z 3 and Z 4 represent, independently of one another, a bridging group, said bridging group being preferably selected from -(CO)-, -(CO)O-, -O(CO)-, -O(CO)O-, -O-, -(CO)NH- or a single bond, Q 1 and Q 2 are, independently of one another, a single bond or a linear or branched, substituted or unsubstituted C1-C 20 alkanediyl, which is unsubstituted or di-(C 20 alkyl)amino, C1-C6 alkyloxy, nitro, cyano and / or chlorine or fluorine; and one or more C-, CH-, CH2- groups therein may be independently replaced by a linking group; R 2 is hydrogen or a linear or branched C1-C 20 alkyl, wherein the alkyl is unsubstituted or di-(C 20 and one or more C-, CH-, CH2- groups may be independently replaced by a linking group, preferably R 2 represents hydrogen, methyl or trifluoromethyl; R 1 and R 3 are each independently hydrogen or C c H α F β where c is an integer from 0 to 20, and α and β are each an integer from 0 to 2c+1, where α+β=2c+1; T 1 , T 2 , T 3 , T 4 and T 5 are, independently of one another, hydrogen, halogen, hydroxyl, nitro, cyano or carboxy groups, and / or cyclic, linear or branched C-C 30 represents alkyl, said alkyl being unsubstituted or mono- or polysubstituted with halogen, acryloyloxy, alkylacryloyloxy, alkoxy, alkylcarbonyloxy, alkyloxycarbonyloxy, alkyloxocarbonyloxy, vinyl, vinyloxy and / or allyloxy groups, in which the alkyl residue preferably has 1 to 20 carbon atoms, more preferably has 1 to 10 carbon atoms; preferred substituents of the alkyl residue are hydrogen, methyl, trifluoromethyl, fluorine and / or chlorine, in which one or more, preferably non-adjacent C-, CH-, CH2- groups may be replaced, independently of one another, by a linking group; preferably the linking group is selected from -O-, -(CO)-, -(CO)O- and -O(CO)-; more preferably T 1 , T 2 , T 3 , T 4 and T 5 represents hydrogen, methyl, trifluoromethyl or an alkyl residue, in which one or more, preferably non-adjacent C-, CH-, CH2- groups may be replaced, independently of one another, by a linking group; preferably, the linking group is selected from -O-, -(CO)-, -(CO)O- and / or -O(CO)-; n 1 is 0, 1 or 2, preferably 0 or 1, more preferably 1; n 3 , n 4 , n 5 , n 6 and n 7 are each independently 0, 1, 2 or 3; preferably, n 3 , n 4 , n 5 , n 6 and n7 represents 0 or 1; more preferably, n 4 , n 5 , n 6 and n 7 is 0, and n 3 is 0 or 1; w 3 represents 0, 1, 2, 3 or 4; preferably represents 0, 1 or 2; w 1 and w 2 are each independently 0, 1, 2, 3 or 4, However, w 1 Or w 2 If is 2, 3, or 4, then each S 1 and S 2 , E 1 and E 2 , Z 1 , Z 2 , Z 3 and Z 4 , Q 1 and Q 2 , R 2 , R 1 and R 3 , T 1 , T 2 , T 3 , T 4 and T 5 , n 1 , n 3 , n 4 , n 5 , n 6 and n 7 may be the same or different, preferably they are the same. Preferably, a photo-aligned copolymer, Preferably, preferably w 1 Or w 2 Or w 3 When is >1, the side chain is a group M 1 , M 2 or / and M 3 or These are the group M 1 , M 2 or / and M3 are connected to different atomic positions in These are the group M 1 , M 2 or / and M 3 or / and Compounds of formula (I) have now been found in which these may be linked at further intervals.

[0003] In the context of the present invention, m 2 If is 0, then M 2 has no side chain, m 3 If is 0, then M 3 It is understood that there are no side chains.

[0004] The term "linking group" as used in the context of the present invention preferably means Single bond, -O-, -CO, -(CO)-, -O(CO)-, [ka] , -NR 1’ -, -NR 1’ -CO-, -CO-NR 1’ -, -NR 1’ -(CO)O-, -O(CO)-NR 1’ -, -NR 1’ -CO-NR 1’ -, -CH=CH-, -C≡C-, -O-CO-O-, and -Si(CH3)2-O-Si(CH3)2-, where: R 1 represents a hydrogen atom or C1-C6 alkyl; However, the oxygen atoms of the linking groups are not directly linked to each other.

[0005] The term "spacer unit" as used in the context of the present invention preferably refers to a single bond, a cyclic, linear or branched, substituted or unsubstituted C-C 20Alkanediyl, in which the C-, CH-, CH2- groups may be replaced independently of one another by non-aromatic, aromatic unsubstituted or substituted carbocyclic or heterocyclic groups connected via linking and / or bridging groups as described above.

[0006] More preferably, the spacer unit is a cyclic, linear or branched, substituted or unsubstituted C-C 20 Alkanediyl, in which one or more, preferably non-adjacent C-, CH-, CH2- groups may be replaced independently of one another by a non-aromatic, aromatic unsubstituted or substituted carbocyclic or heterocyclic group connected via a linking group and / or a bridging group.

[0007] A bridging group, as used in the context of the present invention, is -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-, -CHO-, -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, linear or branched, substituted or unsubstituted C1-C 20 alkanediyl, in which one or more C-, CH-, CH2 groups may be replaced, independently of one another, by a linking group as defined above.

[0008] Preferably, the bridging group is selected from -O-, -(CO)O-, -O(CO)-, or a single bond.

[0009] Alkyl, alkyloxy, alkylcarbonyloxy, acryloyloxyalkoxy, acryloyloxyalkyl, acryloyloxyalkene, alkyloxycarbonyloxy, alkylacryloyloxy, methacryloyloxyalkoxy, methacryloyloxyalkyl, methacryloyloxyalkene, alkylmethacryloyloxy, alkylmethacryloyloxy, alkylvinyl, alkylvinyloxy and alkylaryloxy as well as alkanediyl, when used in the context of the present invention, mean their alkyl residues; respectively, their alkanediyl residues; cyclic, linear or branched, substituted or unsubstituted alkyl, respectively, alkanediyl, in which one or more, preferably non-adjacent, C-, CH-, CH2- groups may be replaced by a linking group.

[0010] Further, the alkyl residue can be, for example, C1-C 40 Alkyl, especially C1-C 30 Alkyl, preferably C-C 20 Alkyl, more preferably C-C 16 Alkyl, most preferably C-C 10 Alkyl, most preferably C1-C6 alkyl. Thus, alkanediyl is, for example, C1-C 40 - , in particular, C1-C 30 -, preferably C1-C 20 -, more preferably C1-C 16 -, most preferably C1-C 10 -, and most preferably C1-C6 alkanediyl.

[0011] In the context of the present invention, the definition given below for alkyl is applicable to alkanediyl as well as to the oxyethers of alkyl derivatives, such as acryloyloxyalkanediyl, acryloyloxyalkoxy, such as, preferably, methacryloyloxyalkoxy.

[0012] C1-C6 alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl or hexyl. 10 Alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl.

[0013] C1-C 16 Alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl.

[0014] C1-C 20 Alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nondecyl, eicosyl.

[0015] Aliphatic groups are, for example, saturated or unsaturated 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-valent alkyl, alkanediyl, alkyloxy, alkylcarbonyloxy, acryloyloxy, alkylacryl, alkylmethacryl, alkyl(ene)acryl(ene), alkyl(ene)methacryl(ene), alkyloxycarbonyloxy, alkyloxycarbonyloxy, methacryloyloxy, alkylvinyl, alkylvinyloxy, or alkylaryloxy, which may contain one or more heteroatoms and / or bridging groups.

[0016] The alicyclic group is a non-aromatic group or unit.Preferably, the alicyclic group is a non-aromatic carbocyclic or heterocyclic group, such as a ring system having 3 to 30 carbon atoms, such as cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cyclohexadiene, bicyclohexylene, decalin, tetrahydrofuran, dioxane, pyrrolidine, piperidine or a steroid skeleton such as cholesterol.

[0017] The term "aromatic" group, as used in the context of the present invention, refers to unsubstituted or substituted carbocyclic and heterocyclic groups, preferably including 5, 6, 10 to 14 ring atoms according to the Hückel rule (for the ring: its π-electron count corresponds to 4n+2, n being a natural integer, e.g. 0, 1, 2, 3, etc.), e.g. furan, phenylene, pyridine, pyrimidine, naphthalene, which may form ring assemblies, such as biphenylene or triphenylene, uninterrupted or interrupted by at least one single heteroatom and / or at least one single bridging group; or fused polycyclic systems, such as phenanthrene, tetralin. Preferably, the aromatic group is a phenylene, naphthalene, biphenylene or triphenylene group. More preferred aromatic groups are phenylene, naphthalene, and biphenylene groups.

[0018] The carbocyclic or heterocyclic aromatic or non-aromatic group, preferably the carbocyclic or heterocyclic aromatic or non-aromatic diamine group, preferably comprises 3, 4, 5, 6, 10 or 14 ring atoms and is, for example, a furan, pyrazole, imidazole, oxazole, thiazole and thiazine, pyridine, piperidine, triazine, pyrimidine, quinoline, isoquinoline, indole, purine, benzimidazole, naphthalene, phenanthrene, biphenylene or tetralin unit, preferably naphthalene, phenanthrene, biphenylene or phenylene, more preferably naphthalene, biphenylene or phenylene, most preferably phenylene.

[0019] The carbocyclic or heterocyclic aromatic or non-aromatic groups, preferably the carbocyclic or heterocyclic aromatic or non-aromatic diamine groups, are, for example, unsubstituted or mono- or polysubstituted. Preferred substituents are at least one halogen, hydroxyl, polar group, alkyl, carboxylic acid, acyl group, such as acid chloride, ester group, carbonate, such as tert-butyl carbonate; anhydride; trifluoroalkyl, acryloyloxy, alkylacryloyloxy, alkoxy, alkylcarbonyloxy, alkyloxycarbonyloxy, alkyloxocarbonyloxy, methacryloyloxy, vinyl, vinyloxy and / or allyloxy groups, in which the alkyl residue preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Preferred polar groups are nitro, cyano or carboxy groups, and / or cyclic, linear or branched C1-C 30 Alkyl, said alkyl being unsubstituted, mono- or polysubstituted. 30 Preferred substituents of alkyl are methyl, fluorine and / or chlorine, in which one or more, preferably non-adjacent C-, CH-, CH2- groups may be replaced independently of one another by a linking group, preferably selected from -O-, -CO-, -(CO)O- and / or -O(CO)-.

[0020] Monocyclic rings of 5 or 6 atoms are, for example, unsubstituted or substituted furan, phenylene, pyridine, pyrimidine, preferably phenylene, pyridine, pyrimidine.

[0021] Bicyclic ring systems of 8, 9 or 10 atoms are, for example, unsubstituted or substituted naphthalene, biphenylene, benzimidazole or tetralin.

[0022] A tricyclic ring system of 13 or 14 atoms is, for example, unsubstituted or substituted phenanthrene.

[0023] The term "phenylene" as used in the context of the present invention preferably denotes an unsubstituted or substituted 1,2-, 1,3- or 1,4-phenylene group, which is optionally substituted. The phenylene group is preferably either a 1,3-phenylene group or a 1,4-phenylene group. The 1,4-phenylene group is especially preferred.

[0024] The term "halogen" means a chloro, fluoro, bromo or iodo substituent, preferably a chloro or fluoro substituent, more preferably fluoro.

[0025] The term "polar group", as used in the context of the present invention, primarily means groups such as nitro, cyano, or carboxy groups.

[0026] The term "heteroatom" when used in the context of the present invention primarily means oxygen, sulfur and nitrogen, preferably oxygen and nitrogen, in the latter case preferably in the form oxygen or --NH--.

[0027] The phrase "optionally substituted", when used in the context of the present invention, means primarily substituted by lower alkyl, e.g. C1-C6 alkyl, lower alkoxy, e.g. C1-C6 alkoxy, trifluoro-C1-C6 alkyl, hydroxy, halogen, preferably fluoro, or by a polar group as defined above.

[0028] The term "diamine group" should be understood to refer to a chemical structure having at least two amino groups, i.e., potentially having three or more amino groups, which are preferably capable of reacting with, for example, two carboxylic acid groups, or activated carboxyl groups, or anhydride groups; as outlined in more detail below.

[0029] The term "dinitro" or "dinitro compound" should be understood to refer to a chemical structure having at least two nitro groups, i.e., potentially having three or more nitro groups, where the dinitro group is a precursor compound to a "diamino compound." Dinitro compounds are conventionally converted to diamino compounds by reduction methods known in the art.

[0030] It is reiterated that for linear or branched alkyl, alkane group, alkoxy, alkylcarbonyloxy, acryloyloxyalkoxy, acryloyloxyalkyl, acryloyloxyalkene, alkyloxycarbonyloxy, alkylacryloyloxy, methacryloyloxyalkoxy, methacryloyloxyalkyl, methacryloyloxyalkene, alkylmethacryloyloxy, alkylmethacryloyloxy, alkylvinyl, alkylvinyloxy, alkylaryloxy and alkanediyl groups, some or several C-, CH-, CH2- groups can be replaced, for example, by heteroatoms, but also by other groups, preferably bridging groups.In such cases, it is generally preferred that such substituents are not directly linked to each other.Alternatively, it is preferred that heteroatoms, especially oxygen atoms, are not directly linked to each other.

[0031] Preferably, M 1 , M 2 and M. 3 are each independently of one another represented by the formula (III): H(R 6’ )N-(Sp 1 ) k1 -(X 1 ) t1 -(Z 5 -C 3 ) a3 -(Z 6 -C 4 ) a4 -(X 2 ) t2 -(Sp 2 ) k2 -N(R 6 )H (III) [In formula: R 6 , R 6’ each independently of the other represents hydrogen or C1-C6 alkyl; preferably, they represent hydrogen, Sp 1 , Sp 2 are each independently a single bond, an unsubstituted or substituted linear or branched C1-C 20 alkanediyl, in which one or more C-, CH-, CH2- groups may be replaced independently of one another by a linking group, k 1 , k 2 are each independently an integer having a value of 0 or 1; X 1 , X 2 each independently represents a linking spacer or a single bond preferably selected from -O-, -S-, -NH-, N(CH3)-, -CH(OH)-, -CO-, -CH2(CO)-, -SO-, -CH2(SO)-, -SO2-, -CH2(SO2)-, -(CO)O-, -O(CO)-, -O(CO)-O-, -S-CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -CH2-CH2-, -OCH2-, -CHO-, -CH=CH- or -C≡C-; preferably, they are single bonds; t 1 , t 2 are each independently an integer having a value of 0 or 1; C 3 , C 4 each independently represents a non-aromatic, aromatic, substituted or unsubstituted carbocyclic or heterocyclic group, which may have a side chain T; Preferably, C 3 , C 4 is a substituted or unsubstituted phenylene, biphenylene or benzimidazole, where the substituents are methyl or trifluoromethyl; Z 5 represents a bridging group; preferably represents a single bond, Z 6is a single bond or a substituted or unsubstituted linear or branched C1-C 20 an alkanediyl group, in which one or more C-, CH-, CH2- groups are independently by non-aromatic, aromatic unsubstituted or substituted carbocyclic or heterocyclic groups; and / or by a heteroatom, preferably oxygen; and / or By the bridging groups as described above may be replaced; preferably, Z 6 is Z 5 or unsubstituted or substituted linear or branched C1-C 14 represents an alkanediyl group, in which one or more, preferably non-adjacent C-, CH-, CH2- groups may be replaced by an oxygen atom and / or one or more carbon-carbon single bonds are replaced by a carbon-carbon double bond or a carbon-carbon triple bond; preferably Z 6 is oxygen or a single bond. is selected from Preferably, M in formula (I) 1 and M. 3 independently of one another, at least one group S 1 At least once in the group Sp 1 and / or Sp 2 and / or C 3 and / or group C 4 and / or via at least one non-aromatic, aromatic, substituted or unsubstituted carbocyclic or heterocyclic group of the group C 4 and / or group C 3 and / or a group Z 6 are connected via;k 1 , k 2 , a 3 and a 4 at least one of is not equal to zero; where the linking and bridging groups are as described above; M in formula (I)2 has at least one group R 2 At least once in the group Sp 1 and / or Sp 2 and / or C 3 and / or group C 4 and / or via at least one non-aromatic, aromatic, substituted or unsubstituted carbocyclic or heterocyclic group of the group C 4 and / or group C 3 and / or a group Z 6 are connected via;k 1 , k 2 , a 3 and a 4 is not equal to zero; where the linking and bridging groups are as described above.

[0032] The term "side chain" T refers to a substituted or unsubstituted straight or branched C1-C 20 represents an alkanediyl group, in which one or more C-, CH-, CH2- groups may be replaced, independently of one another, by a non-aromatic, aromatic unsubstituted or substituted carbocyclic or heterocyclic group, or by a heteroatom and / or by a bridging group, and the "side chain" represents at least one group S in formula (I). 1 or S 2 is concatenated at least once to

[0033] More preferably, M 1 , M 2 and M. 3 are independent of each other, C 3 , C 4 independently of each other, the group G 2 wherein the group G 2 but, [ka] wherein [ka] But, C 3 and C 4 means a connecting bond between adjacent groups of a compound of formula (III) as defined above; L is C1-C6 alkyl, especially -CH3; C1-C6 alkyl fluoro, especially -CF3; -COCH3, -OCH3, nitro, cyano, halogen, CH2=CH-, CH2=C(CH3)-, CH2=CH-(CO)O-, CH2=CH-O-, -NR 6’ R 6 , CH2=C(CH3)-(CO)O-, CH2=C(CH3)-O-, where: R 6’ , R 6 each independently represents a hydrogen atom or a C1-C6 alkyl; T is a substituted or unsubstituted linear or branched C1-C 20 represents an alkanediyl group, in which one or more CH2- groups may be replaced, independently of one another, by a non-aromatic, aromatic unsubstituted or substituted carbocyclic or heterocyclic group, or by a heteroatom and / or by a bridging group; m is an integer of 0 to 2; preferably 1 or 0; more preferably 0; Z 6 is a single bond or a substituted or unsubstituted linear or branched C1-C 20 represents an alkanediyl group, in which one or more C-, CH-, CH2- groups may be replaced, independently of one another, by a non-aromatic, aromatic unsubstituted or substituted carbocyclic or heterocyclic group; and / or by a heteroatom and / or by a bridging group as described above; preferably Z 6 unsubstituted or substituted linear or branched C1-C 14 represents an alkanediyl group, in which one or more, preferably non-adjacent C-, CH-, CH2- groups may be replaced by an oxygen atom and / or one or more carbon-carbon single bonds are replaced by a carbon-carbon double bond or a carbon-carbon triple bond; preferably Z6 is oxygen or a single bond; u1 is an integer from 0 to 4, provided that m+u1 is ≦4; and u2 is an integer from 0 to 3; provided that m+u2 is ≦3; and u3 is an integer from 0 to 2; provided that m+u3 is ≦2; is selected from formula (III):

[0034] Even more preferred is M 1 , M 2 and M. 3 are more preferably selected, independently of one another, from the following structural group: substituted or unsubstituted o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, biphenyldiamine, 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline, aminophenylene-Z 6 -phenyleneamino (wherein Z 6 represents Z in the compound of formula (III) 6with the same meanings and preferences as given above for , in particular 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, tetrabromomethylenedianiline, 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)alkylenes, and, The following amino compounds are considered as derivatives that do not carry two amino groups but have at least one additional amino group: aniline, 4-amino-2,3,5,6-tetrafluorobenzoic acid, 4-amino-3,5-diiodobenzoic acid, 4-amino-3-methylbenzoic acid, 4-amino-2-chlorobenzoic acid, 4-aminosalicylic acid, 4-aminobenzoic acid, 4-aminophthalic acid, 1-(4-aminophenyl)ethanol, 4-aminobenzyl alcohol, 4-amino-3-methoxybenzoic acid, 4-aminophenyl ethyl carbinol, 4-amino-3-nitrobenzoic acid, 4-amino-3,5-dinitrobenzoic acid, 4-amino-3,5-dichlorobenzoic acid, 4-amino-3-hydroxybenzoic acid, 4-aminobenzyl alcohol hydrochloride, 4-aminobenzoic acid hydrochloride, pararosaniline base, 4-amino-5-chloro-2-methoxybenzoic acid, 4-(hexafluoro-2-hydroxyisopropyl)aniline, piperazine-p-aminobenzoate, 4-amino-3,5-dibromobenzoic acid, isonicotinic acid hydrazide p-Amino-salicylate, 4-amino-3,5-diiodosalicylic acid, 4-amino-2-methoxybenzoic acid, 2-[2-(4-aminophenyl)-2-hydroxy-1-(hydroxymethyl)ethyl]isoindoline-1,3-dione, 4-amino-2-nitrobenzoic acid, ethyl 2-(4-aminophenyl)-3,3,3-trifluoro-2-hydroxypropanoate, ethyl 2-(4-amino-3-methylphenyl)-3,3,3-trifluoro-2-hydroxypropanoate, ethyl 2-(4-amino-3-methoxyphenyl)-3,3,3-trifluoro-2-hydroxypropanoate, 4-aminonaphthalene-1,8-dicarboxylic acid, 4-amino-3-chloro-5-methylbenzoic acid, 4-amino-2,6-dimethylbenzoic acid, 4-amino-3-fluorobenzoic acid, 4-amino-5-bromo-2-methoxybenzenecarboxylic acid, 3,3'-tolidine-5-sulfonic acid, or derivatives thereof, but again, any recited compound not bearing two amino groups shall be considered a derivative having at least one additional amino group.

[0035] Diamine group M 1, M 2 and M. 3 are commercially available or accessible by known methods. The second amino group is accessible, for example, by a substitution reaction.

[0036] Most preferably, M 1 , M 2 and M. 3 are independently selected from the following group of compounds: [ka] [In formula: L is C1-C6 alkyl, especially -CH3, C1-C6 alkylfluoro, especially -CF3; -COCH3, -OCH3, nitro, cyano, halogen, especially fluoro, CH2=CH-, CH2=C(CH3)-, CH2=CH-(CO)O-, CH2=CH-O-, -NR 5 R 6 , CH2=C(CH3)-(CO)O- or CH2=C(CH3)-O-, preferably L is -CH3 or -CF3; T is a substituted or unsubstituted linear or branched C1-C6 alkanediyl group, in which one or more C-, CH-, -CH2- groups may be replaced, independently of one another, by heteroatoms and / or by bridging groups; preferably, T is a branched C1-C6 alkanediyl, more preferably a branched C3, C4, C5, C6-alkanediyl group, m is an integer of 0, 1 or 2; u1 is an integer from 0 to 3, provided that m+u1 is ≦3; R 6’ , R 6 each independently represents a hydrogen atom or a C1-C6 alkyl; preferably hydrogen; Z 6 is an unsubstituted or substituted straight or branched C1-C 14represents an alkanediyl group, in which one or more, preferably non-adjacent C-, CH-, CH2- groups may be replaced by an oxygen atom and / or one or more carbon-carbon single bonds are replaced by a carbon-carbon double bond or a carbon-carbon triple bond; preferably Z 6 is oxygen or a single bond. And here M 1 and M. 3 are, independently of one another, at least one group S in formula (I) 1 to a single bond [ka] or through the side chain T; or through the group Z 6 is connected at least once via (w 1 Or w 2 is > 1); and here M 2 is at least one group R in formula (I) 2 to a single bond [ka] or through the side chain T; or through the group Z 6 is connected at least once via (w 3 is > 1).

[0037] D in formula (I) 1 , D 2 and D. 3 are preferably, independently of one another, at least two carboxylic acid groups; or at least two activated carboxyl groups, preferably two acyl groups, more preferably an acid chloride, an ester group or a carbonate (wherein the carbonate is preferably tert-butyl carbonate); or Di-, tri- or tetraanhydride groups, preferably dianhydride groups, most preferably tetracarboxylic dianhydrides represents an unsubstituted or substituted aliphatic, alicyclic or carbocyclic or heterocyclic aromatic group substituted with

[0038] D 1 , D 2 and D. 3 The tetracarboxylic dianhydrides of the formula (V): [ka] [In formula: T represents a tetravalent organic radical. It is a tetracarboxylic dianhydride represented by the formula:

[0039] The tetravalent organic radical T is preferably derived from an aliphatic, alicyclic or aromatic tetracarboxylic dianhydride.

[0040] Preferred examples of aliphatic or alicyclic tetracarboxylic dianhydrides are: 1,2,3,4-Cyclobutanetetracarboxylic dianhydride;3-(Carboxymethyl)-1,2,4-cyclopentane-tricarboxylic 1,4:2,3-dianhydride;1,1,4,4-Butanetetracarboxylic dianhydride;Ethylene maleic dianhydride;1,2,3,4-Cyclobutanetetracarboxylic dianhydride;1,2,3,4-Cyclopentanetetracarboxylic dianhydride;2,3,5-Tricarboxycyclopentylacetic dianhydride;3,5,6-Tricarboxynorbornylacetic dianhydride;2,3,4,5-Tetrahydrofurantetracarboxylic dianhydride;rel-[1S,5R,6R]-3 -Oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione);4-(2,5-dioxotetrahydrofuran-3-yl)-tetrahydronaphthalene-1,2-dicarboxylic dianhydride;5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride;Bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride;Bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride;1,8-Dimethylbicyclo[2.2.2]Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride;Pyromellitic dianhydride;3,3',4,4'-Benzophenonetetracarboxylic dianhydride;4,4'-Oxydiphthalic dianhydride;3,3',4,4'-Diphenylsulfonetetracarboxylic dianhydride;1,4,5,8-Naphthalenetetracarboxylic dianhydride, 2,3,6,7-Naphthalenetetracarboxylic dianhydride;3,3',4,4'-Dimethyldiphenylsilanetetracarboxylic dianhydride;3,3',4,4'-Tetraphenylsilanetetracarboxylic dianhydride;1,2,3,4-Furanetetracarboxylic dianhydride;4,4'-Bis(3,4-dicarboxyphenoxy)diphenylsulfonate sulfide dianhydride;4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride;4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride;3,3',4,4'-biphenyltetracarboxylic dianhydride;ethylene glycol bis(trimellitic) dianhydride;4,4'-(1,4-phenylene)bis(phthalic) dianhydride;4,4'-(1,3-phenylene)-bis(phthalic) dianhydride;4,4'-(hexafluoroisopropylidene)diphthalic dianhydride;4,4'-oxydi(1,4-phenylene)bis(phthalic) dianhydride, and 4,4'-methylenedi(1,4-phenylene)bis(phthalic) dianhydride.

[0041] Preferred examples of aromatic tetracarboxylic dianhydrides are: Pyromellitic dianhydride;3,3',4,4'-Benzophenonetetracarboxylic dianhydride;4,4'-Oxydiphthalic dianhydride;3,3',4,4'-Diphenylsulfonetetracarboxylic dianhydride;1,4,5,8-Naphthalenetetracarboxylic dianhydride;2,3,6,7-Naphthalenetetracarboxylic dianhydride;3,3',4,4'-Dimethyldiphenylsilanetetracarboxylic dianhydride;3,3',4,4'-Tetraphenylsilanetetracarboxylic dianhydride;1,2,3,4-Furanetetracarboxylic dianhydride;4,4'-Bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride;4,4'-Bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride Bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride;4,4'-Bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride;3,3',4,4'-Biphenyl-tetracarboxylic dianhydride;Ethylene glycol bis(trimellitic) dianhydride;4,4'-(1,4-phenylene)bis(phthalic) dianhydride;4,4'-(1,3-phenylene)bis(phthalic) dianhydride;4,4'-(hexafluoroisopropylidene)diphthalic dianhydride;4,4'-oxydi(1,4-phenylene)bis(phthalic) dianhydride;4,4'-methylenedi(1,4-phenylene)bis(phthalic) dianhydride.

[0042] More preferably, the tetracarboxylic dianhydride used to form the tetravalent organic radical T is selected from: 1,2,3,4-Cyclobutanetetracarboxylic dianhydride; 3-(carboxymethyl)-1,2,4-cyclopentanetricarboxylic 1,4:2,3-dianhydride; 1,2,3,4-Cyclobutanetetracarboxylic dianhydride; 1,2,3,4-Cyclopentanetetracarboxylic dianhydride; 2,3,5-Tricarboxycyclopentylacetic dianhydride; 5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride; 4-(2,5-dioxotetrahydrofuran-3-yl)-tetrahydronaphthalene-1,2-dicarboxylic dianhydride; 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride, and bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride.

[0043] In the context of the present invention, preferably S in formula (I) 1 and S 2 each independently represents a single bond or a spacer unit, the spacer unit being a cyclic, linear or branched, substituted or unsubstituted C-C 20 alkanediyl, in which one or more, preferably non-adjacent C-, CH-, CH2- groups are a linking group and / or a group of formula (IV): -(Z 1 -C 1 ) a1 -(Z 2 -C 2 ) a2 -(Z 1a ) a3 - (IV) [In formula: C 1 , C 2 are each independently preferably a bridging group Z 1 and Z 2 and / or Z 1a represents a non-aromatic, aromatic, optionally substituted carbocyclic or heterocyclic group connected to each other via 1 and C 2 is the bridging group Z 1 and Z 2and / or Z 1a are connected at opposite positions via 1 and / or S. 2 has a long molecular axis, Z 1 , Z 2 , Z 1a represents each independently a bridging group or a single bond preferably selected from -CH(OH)-, -CH2-, -O-, -CO-, -CH2(CO)-, -SO-, -CH2(SO)-, -SO2-, -CH2(SO2)-, -(CO)O-, -O(CO)-, -(CO)CF2-, -CF2CO-, -S-CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -CH2-CH2-, -OCH2-, -CHO-, -CH=CH-, -C≡C-, -CH=CH-(CO)O-, -O(CO)-CH=CH-, -CH=N-, -C(CH3)=N-, -O-CO-O-, -N=N-; a1, a2, and a3 each independently represent an integer of 0 to 3 such that a1+a2+a3≦6; preferably, a3 is 0 and a1+a2≦4. The ring may be replaced by a non-aromatic, aromatic unsubstituted or substituted carbocyclic or heterocyclic group represented by the formula:

[0044] More preferred S 1 and S 2 are each independently a linear or branched C1-C 20 alkylene, in which one or more C-, CH-, CH2- groups may be independently replaced by a linking group or / and a group represented by formula (IV): C 1 , C 2 is the group G 1 wherein the group G 1 is: [ka] [In formula: [ka] is C 1 and C 2 and the connecting bond between adjacent groups in formula (IV); L is -CH3, -OCH3, -COCH3, nitro, cyano, halogen, CH2=CH-, CH2=C(CH3)-, CH2=CH-(CO)O-, CH2=CH-O-, CH2=C(CH3)-(CO)O-, or CH2=C(CH3)-O-; u1 is an integer from 0 to 4; and u2 is an integer from 0 to 3; and u3 is an integer between 0 and 2. Z 1 , Z 2 , Z 1a each independently represent -O-, -CO-, -COO-, -OCO-, -COCF2-, -CF2CO-, -CH2-CH2-, -OCH2-, -CHO-, -CH=CH-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, or a single bond; with the proviso that the heteroatoms are not directly linked to each other; a1, a2, and a3 each independently represent an integer of 0 to 3 such that a1+a2+a3≦6; preferably, a3 is 0 and a1+a2≦4.

[0045] Most preferred S 1 and S 2 are each independently a single bond or a linear or branched C1-C 14 represents a spacer unit such as an alkanediyl, in which one or more, preferably non-adjacent, C-, CH-, CH2- groups may be independently replaced by a linking group and / or a group represented by formula (IV), in which C 1 , C 2 each independently represents a 1,4-phenylene, 2-methoxy-1,4-phenylene, 1,4-cyclohexylene, or 4,4'-biphenylene group; Z 1 , Z 2 , Z 1aeach independently represents -(CO)O-, -O(CO)-, -CH-CH-, -OCH-, -CHO-, -CH=CH-, -C≡C-, -CH=CH-(CO)O-, -O(CO)-CH=CH-, or a single bond; a1, a2, and a3 are independently 0 or 1, and preferably a3 is 0.

[0046] Among the most preferred is S 1 and S 2 are each independently a linear C1-C 12 Alkanediyl, preferably C1-C6 alkanediyl, more preferably methylene, ethylene, propylene, butylene, pentylene, hexylene; one or more C-, CH-, CH2- groups therein may be replaced by -O-, -O(CO)-, -(CO)O-, preferably the C-, CH-, CH2- groups are not replaced.

[0047] In the context of the present invention, preferably E 1 and E 2 are each independently a phenylene, an oxygen atom or a -N(H)- group; 1 and E 2 are, independently of each other, oxygen or a -N(H)- group; the most preferred E 1 and E 2 is oxygen.

[0048] In the context of the present invention, preferably Z in formula (I) 1 and Z 3 represent, independently of each other, a bridging group selected from -(CO)O- or -O(CO)-; more preferably -O(CO)-; Z in formula (I) 2 and Z 4 represent, independently of each other, -O- or a single bond; more preferably, Z 2 is a single bond, and Z 4 is -O-;

[0049] Q in formula (I) 1 and Q 2 are preferably, independently of one another, a single bond, a linear or branched C-C 12 alkanediyl, preferably C1-C8 alkanediyl, in which one or more, preferably non-adjacent C-, CH-, CH2- groups are independently -O-, -CO, -(CO)O-, -O(CO)-, -NR 1’ -, -NR 1’ -(CO)-, -(CO)-NR 1’ -, -NR 1’ -(CO)O-, -O(CO)-NR 1’ -, -NR 1’ -(CO)-NR 1’ -, -CH=CH-, -C≡C-, -O-CO-O-, and -Si(CH3)2-O-Si(CH3)2-, aromatic and alicyclic groups; preferably -O-, -CO, -(CO)O-, -O(CO)-, -NR 1’ -, -NR 1’ -CO-, -CO-NR 1’ - or -CH=CH-, more preferably a single bond or a group selected from -O-, -CO-, -(CO)O-, -O(CO)-, and -CH=CH-; R 1’ represents a hydrogen atom or a C1-C6 alkyl; However, the oxygen atoms are not directly linked to each other.

[0050] Furthermore, in the context of the present invention, R in formula (I) 1 represents hydrogen, C1-C6 alkyl, where C1-C6 alkyl is more preferably methyl or ethyl; or R 1is preferably selected from -CF2H, -CF3, -CF2CF3, -CF2CHF2, -(CF2)2CF3, -(CF2)2CHF2, -(CF2)3CHF2, -(CF2)3CF3, -CF(CF3)2 and -CF2(CHF)CF3, more preferably -CF2H and -CF3, most preferably -CF3; 16 is a fluoroalkyl group; R in formula (I) 2 preferably represents hydrogen or a linear or branched C1-C6 alkyl, said alkyl being unsubstituted or di-(C1-C 20 alkyl)amino, C1-C6 alkyloxy, nitro, cyano and / or chlorine or fluorine; and one or more C-, CH-, CH2- groups therein may be independently replaced by a linking group; Preferably, R 2 is hydrogen, a linear or branched C1-C6 alkyl, more preferably methyl or ethyl, most preferably methyl; or a linear or branched C1-C6 alkyl, preferably selected from -CF2H, -CF3, -CF2CF3, -CF2CHF2, -(CF2)2CF3, -(CF2)2CHF2, -(CF2)3CHF2, -(CF2)3CF3, -CF(CF3)2 and -CF2(CHF)CF3, more preferably -CF2H and -CF3, most preferably -CF3; 16 R in formula (I) represents a fluoroalkyl group; 3 is preferably hydrogen or a linear or branched C1-C alkyl group, preferably selected from -CF2H, -CF3, -CF2CF3, -CF2CHF2, -(CF2)2CF3, -(CF2)2CHF2, -(CF2)3CHF2, -(CF2)3CF3, -CF(CF3)2 and -CF2(CHF)CF3, more preferably selected from -CF2H and -CF3. 16 represents a fluoroalkyl group; T in formula (I) 1 , T 2 , T 3 , T 4 and T 5preferably, independently of one another, hydrogen, fluorine and / or chlorine; substituted or unsubstituted branched or linear C1-C6 alkyl, more preferably C1-C6 alkyl, furthermore methyl, ethyl or trifluoromethyl; More preferably, T 3 represents hydrogen or fluorine, T 1 , T 2 , T 4 and T 5 represents hydrogen; n in formula (I) 3 , n 4 , n 5 , n 6 and n 7 preferably, independently of each other, represent 0 or 1; more preferably, n 4 , n 5 , n 6 and n 7 is 0, and n 3 is either 0 or 1, n in formula (I) 1 preferably represents 0 or 1, more preferably 1; In formula (I), w 1 and w 2 preferably, independently of each other, represent 1 or 2, preferably 1; In formula (I), w 3 preferably represents 0, 1 or 2.

[0051] A further preferred embodiment of the invention is 4 -Q 2 -R 3 but, Trifluoromethyl;2,2,2-Trifluoroethyl;Difluoromethyl;Pentafluoroethyl;2,2-Tetrafluoroethyl;3,2-Tetrafluoroethyl;3,3,3-Trifluoropropyl;2,2,3,3-Tetrafluoropropyl;2,2,3,3,3-Pentafluoropropyl;Hexafluoropropyl;Heptafluoropropyl;4,4,4-Trifluorobutyl;Tetrafluorobutyl;3,3,4,4,4-Pentafluorobutyl;Hexafluorobutyl;2,2,3,3,4,4,4-Heptafluorobutyl;5,5,5-Trifluoropentyl;Tetrafluoropentyl;4,4,5,5,5-Pentafluoropentyl;Hexafluoropentyl;3,3,4,4,5,5,5 -Heptafluoropentyl;6,6,6-trifluorohexyl;tetrafluorohexyl;5,5,6,6,6-pentafluorohexyl;hexafluorohexyl;4,4,5,5,6,6,6-heptafluorohexyl;nonafluorohexyl;1-trifluoro-1,2,2,2-tetrafluoroethoxy, 2-trifluoro-2,3,3,3-tetrafluoropropoxy, 3-trifluoro-3,4,4,4-tetrafluorobutoxy, 4-trifluoro-4,5,5,5-tetrafluoropentoxy, 5-trifluoro-5,6,6,6-tetrafluorohexoxy, 6-trifluoro-6,7,7,7-tetrafluoroheptoxy, 7-trifluoro-7,8,8,8-tetrafluorononoxy; Fluoroalkoxy derivatives, e.g. Trifluoromethoxy;2,2,2-Trifluoroethoxy;Difluoromethoxy;Pentafluoroethoxy;1,1,2,2-Tetrafluoroethoxy;2,2,2,1-Tetrafluoroethoxy;3,3,3-Trifluoropropoxy;2,2,3,3-Tetrafluoropropoxy;2,2,3,3,3-Pentafluoropropoxy;Hexafluoropropoxyl;Heptafluoropropoxy;4,4,4-Trifluorobutoxy;Tetrafluorobutoxy;3,3,4,4,4-Pentafluorobutoxy;2,2,3,3,4,4-Hexa Fluorobutoxy;2,2,3,3,4,4,4-Heptafluorobutoxy;5,5,5-Trifluoropentoxy;Tetrafluoropentoxy;4,4,5,5,5-Pentafluoropentoxy;Hexafluoropentoxy;3,3,4,4,5,5,5-Heptafluoropentoxy;6,6,6-Trifluorohexoxy;Tetrafluorohexoxy;5,5,6,6,6-Pentafluorohexoxy;Hexafluorohexoxy;4,4,5,5,6,6,6-Heptafluorohexoxy;Nonafluorohexoxy;Trifluoromethyleneca Carbamate;2,2,2-Trifluoroethylene carbamate;Difluoromethylene carbamate;Pentafluoroethylene carbamate;2,2-Tetrafluoroethylene carbamate;3,2-Tetrafluoroethylene carbamate;3,3,3-Trifluoropropylene carbamate;2,2,3,3-Tetrafluoropropylene carbamate;2,2,3,3,3-Pentafluoropropylene carbamate;Hexafluoropropylene carbamate;Heptafluoropropylene carbamate;4,4,4-Trifluorobutylene carbamate tetrafluorobutylene carbamate;3,3,4,4,4-pentafluorobutylene carbamate;hexafluorobutylene carbamate;2,2,3,3,4,4,4-heptafluorobutylene carbamate;5,5,5-trifluoropentylene carbamate;tetrafluoropentylene carbamate;4,4,5,5,5-pentafluoropentylene carbamate;hexafluoropentylene carbamate;3,3,4,4,5,5,5-heptafluoropentylene carbamate;6,6,6-trifluorohexylene carbamate;Tetrafluorohexylene carbamate;5,5,6,6,6-pentafluorohexylene carbamate;hexafluorohexylene carbamate;4,4,5,5,6,6,6-heptafluorohexylene carbamate;nonafluorohexylene carbamate; Fluoroalkyloyloxy derivatives, e.g. Trifluoromethyloxy;2,2,2-trifluoroethyloxy;pentafluoroethyloxy;1,1,2,2-tetrafluoroethyloxy;2,2,2,1-tetrafluoroethyloxy;3,3,3-trifluoropropyloxy;tetrafluoropropyloxy;2,2,3,3,3-pentafluoropropyloxy;hexafluoropropyloxy;1,1,2,2,3,3,3-heptafluoropropyloxy;4,4,4-trifluorobutyroyloxy;tetrafluorobutyroyloxy;3,3,4,4,4-pentafluorobutyroyloxy ;Hexafluorobutyroyloxy;2,2,3,3,4,4,4-Heptafluorobutyroyloxy;5,5,5-Trifluoropentyroyloxy;Tetrafluoropentyroyloxy;4,4,5,5,5-Pentafluoropentyroyloxy;Hexafluoropentyroyloxy;3,3,4,4,5,5,5-Heptafluoropentyroyloxy;6,6,6-Trifluorohexyroyloxy;Tetrafluorohexyroyloxy;5,5,6,6,6-Pentafluorohexyroyloxy;Hexafluorohexyroyloxy;4,4,5,5,6,6,6-Heptafluorohexyroyloxy; Trifluoroacetyl;Nonafluorohexyloxy;4,4,4-Trifluorobut-2-enyl;5,5,5-Trifluoropent-1-enyl;6,6,6-Trifluorohex-1-enyl;7,7,7-Trifluorohept-1-enyl;Trifluoroacetylaminomethoxy;Trifluoroacetylaminoethoxy;Trifluoroacetylaminopropoxy;Trifluoroacetylaminobutoxy;2-Fluoroethyl;3-Fluoropropyl;4-Fluorobutyl;5-Fluoropentyl;6-Fluorohexyl;2-Fluoroethoxy oxy;3-fluoropropoxy;4-fluorobutoxy;5-fluoropentoxy;6-fluorohexyloxy;4-fluorobut-1-enyl;5-fluoropent-1-enyl;6-fluorohex-1-enyl;7-fluorohept-1-enyl;4,4,4-trifluoro-3-(trifluoromethyl)butoxy;4,5,5-trifluoropent-4-enoxy;4,5,5-trifluoropent-4-enoyloxy;5,6,6-trifluorohex-5-enoxy or 5,6,6-trifluoropent-5-enoyloxy; Particular preference is given to compounds of formula (I) as defined above which are fluoroalkoxy, preferably trifluoro- and pentafluoroalkoxy derivatives, particularly preferred are 4,4,4-trifluorobutoxy and 5,5,5-trifluoropentoxy, especially 4,4,4-trifluorobutoxy.

[0052] Preferably, the present invention relates to a method for producing a pharmaceutical composition comprising the steps of: M 1 , M 2 and M. 3 are each independently of one another represented by the formula (III): H(R 6’ )N-(Sp 1 ) k1 -(X 1 ) t1 -(Z 5 -C 3 ) a3 -(Z 6 -C 4 ) a4 -(X 2 ) t2-(Sp 2 ) k2 -N(R 6 )H (III) [In formula: k 1 , k 2 is either 0 or 1, t 1 , t 2 is 0, R 6’ , R 6 are identical and represent a hydrogen atom, a methyl, ethyl or isopropyl group; C 3 , C 4 are each independently a group G as described above. 2 A compound selected from the group consisting of: Z 5 represents a group selected from -CH(OH)-, -CH(CH3)-, -C(CH3)2-, -CO-, -(CO)O-, -O(CO)-, -COCF2-, -CF2CO- or a single bond; Z 6 is Z 5 or a substituted or unsubstituted linear or branched C1-C 20 alkanediyl, in which one or more, preferably non-adjacent C-, CH-, CH2- groups may be replaced independently of one another by cyclohexylene, phenylene, aromatic or non-aromatic N-heterocycles; or by heteroatoms and / or by oxygen atoms; and / or one or more carbon-carbon single bonds are replaced by carbon-carbon double or carbon-carbon triple bonds, preferably Z 6 is oxygen or a single bond; a 3 , a 4 are each independently 3 +a 4 represents an integer between 0 and 2, with ≦3; Sp 1 , Sp 2 , X 1 , X 2 have the same meaning as above] an optionally substituted aliphatic, alicyclic, aromatic or non-aromatic diamine group having 1 to 40 carbon atoms selected from; D 1 , D 2 and D. 3 But independently of each other, at least two carboxylic acid groups; or at least two activated carboxyl groups, preferably two acyl groups; more preferably an acid chloride, an ester group or a carbonate, where the carbonate is preferably tert-butyl carbonate; or Di-, tri- or tetraanhydride groups, preferably dianhydride groups represents an unsubstituted or substituted aliphatic, alicyclic or carbocyclic or heterocyclic aromatic group, substituted by m 1 , m 2 or m 3 are independent of each other, 0 <m 1 <1, 0≦m 2 ≦0.7 and 0≦m 3 < 1, preferably 0 <m 1 <1, 0≦m 2 ≦0.5 and 0≦m 3 represents the mole fraction of comonomer that is <1, S 1 and S 2 are, independently of one another, a single bond or a cyclic, linear or branched, substituted or unsubstituted C1-C 20 alkanediyl, in which one or more C-, CH-, CH2- groups may be replaced, independently of one another, by a linking group as defined above; E 1 and E 2 represent, independently of one another, phenylene, an oxygen atom or an -N(H)- group; preferably an oxygen atom, Z 1 , Z 2 , Z 3 and Z 4 are independently selected from -CO-, -(CO)O-, -O(CO)-, -O- or a single bond; Q1 and Q 2 are each independently a single bond or a linear or branched C1-C 12 alkanediyl, preferably C1-C8 alkanediyl, in which one or more, preferably non-adjacent C-, CH-, CH2- groups are independently -O-, -CO, -(CO)O-, -O(CO)-, -NR 1’ -, -NR 1’ -CO-, -CO-NR 1’ - or -CH=CH-, more preferably a single bond or a group selected from -O-, -CO-, -(CO)O-, -O(CO)-, and -CH=CH-; R 1’ represents a hydrogen atom or a C1-C6 alkyl; provided that the oxygen atoms are not directly linked to each other; R 2 represents hydrogen or a linear or branched C1-C6 alkyl, said alkyl being unsubstituted or di-(C1-C 20 and one or more C-, CH-, CH2- groups may be independently replaced by a linking group, preferably R 2 represents hydrogen, methyl or trifluoromethyl; R 3 is selected from -CF2H or -CF3, -CF2CF3, -CF2CHF2, -(CF2)2CF3, -(CF2)2CHF2, -(CF2)3CHF2, -(CF2)3CF3, -CF(CF3)2 and -CF2(CHF)CF3, preferably selected from -CF2H and -CF3, more preferably -CF3; 16 represents a fluoroalkyl group, R 1 represents hydrogen or -CF3, preferably hydrogen; T in formula (I) 1 , T 2 , T 3, T 4 and T 5 represent, independently of one another, hydrogen, fluorine and / or chlorine; substituted or unsubstituted branched or linear C1-C6 alkyl, more preferably C1-C6 alkyl, and furthermore methyl, ethyl or trifluoromethyl; More preferably, T 3 represents hydrogen or fluorine, and T 1 , T 2 , T 4 and T 5 represents hydrogen; n 1 , n 2 are each independently 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably n 1 is 0 or 1, and n 2 is 0, 1 or 2; n in formula (I) 3 , n 4 , n 5 , n 6 and n 7 are each independently 0 or 1; more preferably, n 4 , n 5 , n 6 and n 7 is 0, and n 3 is 0 or 1, n in formula (I) 1 represents 0 or 1, more preferably 1; In formula (I), w 3 represents 0, 1 or 2; In formula (I), w 1 and w 2 preferably, independently of each other, represent 1 or 2, preferably 1; However, w 1 and / or w 2 If is 2, 3, or 4, then each T 1 , T 2 , T 3 , T 4 and T 5 , R 1 and R 3 , Q 1 and Q 2 , Z 1 , Z2 , Z 3 and Z 4 , E 1 and E 2 , S 1 , S 2 , n 1 , n 3 , n 4 , n 5 , n 6 and n 7 relates to compounds of formula (I) with the proviso that may be the same or different.

[0053] A further preferred embodiment of the present invention comprises n 1 represents 1, and n 3 represents 1, and T 1 represents halogen, preferably fluoro, or n 1 represents 1, and n 3 represents 0, or n 1 represents 0, and n 3 represents 1, and T 1 represents halogen, preferably fluoro, Concerning compounds of formula (I):

[0054] 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 diamines (L), more preferably the diamines (L) are diamines M 1 , M 2 and / or M 3 , especially within the meanings and preferences given above as described for those of formula (III).

[0055] Even more preferred diamines (L) have 1 to 40 carbon atoms and preferably represent unsubstituted or substituted aliphatic, aromatic or cycloaliphatic diamine radicals made up or selected from the following structural group: p-phenylenediamine, m-phenylenediamine, benzidine, 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, phenoxybenzene, or L is a diamine group selected from the compounds given below and monodiamine compounds (substituted with a second diamine as given below): Aniline, phenoxybenzene, 4-amino-2,3,5,6-tetrafluorobenzoic acid, 4-amino-3,5-diiodobenzoic acid, 3,4-diaminobenzoic acid, 4-amino-3-methylbenzoic acid, 4-amino-2-chlorobenzoic acid, 4-aminosalicylic acid, 4-aminobenzoic acid, 4-aminophthalic acid, 1-(4-aminophenyl)-ethanol, 4-aminobenzyl alcohol, 4-amino-3-methoxybenzoic acid, 4-aminophenylethyl carbinol, 4-amino-3-nitrobenzoic acid, 4-amino-3,5-dinitrobenzoic acid, 4-amino-3,5-dichlorobenzoic acid, 4-amino-3-hydroxybenzoic acid, 4-aminobenzyl alcohol hydrochloride, 4-aminobenzoic acid hydrochloride, pararosaniline base, 4-amino-5-chloro-2-methoxybenzoic acid, 4-( Hexafluoro-2-hydroxyisopropyl)aniline, piperazine-p-aminobenzoate, 4-amino-3,5-dibromobenzoic acid, isonicotinic acid hydrazide, p-aminosalicylate, 4-amino-3,5-diiodosalicylic acid, 4-amino-2-methoxybenzoic acid, 2-[2-(4-aminophenyl)-2-hydroxy-1-(hydroxymethyl)ethyl]-isoindoline-1,3-dione, 4-amino-2-nitrobenzoic acid, 2,4-diaminobenzoic acid, p-aminobenzoic acid, [3,5-3h]-4-amino-2-methoxybenzoic acid, L-(+)-threo-2-amino-1-(4-aminophenyl)-1,3-propanediol, L-(+)-threo-2-(N,N-dimethylamino)-1-(4-aminophenyl)-1,3-propanediol, ethyl 2-(4-aminophenyl)-3,3,3-trifluoro-2-hydroxypropanoate, ethyl 2-(4-amino-3-methylphenyl)-3,3,3-trifluoro-2-hydroxypropanoate, ethyl 2-(4-amino-3-methoxyphenyl)-3,3,3-trifluoro-2-hydroxypropanoate, 3,4-diaminobenzyl alcohol dihydrochloride, 4-aminonaphthalene-1,8-dicarboxylic acid, 4-amino-3-chloro-5-methylbenzoic acid, 4-amino-2,6-dimethylbenzoic acid, 4-amino-3-fluorobenzoic acid, 4-amino-5-bromo-2-methoxybenzenecarboxylic acid, 2,7-diaminofluorene, 4,4'-Diaminooctafluorobiphenyl, 3,3'-diaminobenzidine, 3,3',5,5'-tetramethylbenzidine, 3,3'-dimethoxybenzidine, o-tolidine, 3,3'-dinitrobenzidine, 2-nitrobenzidine, 3,3'-dihydroxybenzidine, o-tolidine sulfone, benzidine, 3,3'-dichlorobenzidine, 2,2',5,5'-tetrachlorobenzidine, benzidine-3,3'-dicarboxylic acid, 4,4'-diamino-1,1'-binaphthyl, 4,4'-diamino Nodiphenyl-3,3'-diglycolic acid, dihydroethidium, o-dianisidine, 2,2'-dichloro-5,5'-dimethoxybenzidine, 3-methoxybenzidine, 3,3'-dichlorobenzidine (diphenyl-d6), 2,7-diamino-9-fluorenone, 3,5,3',5'-tetrabromo-biphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)benzidine, 2,2'-dichloro[1,1'-biphenyl]-4,4'-diamine, 3,9-diamino-1,11-diamine 5,7-dihydro-dibenzo(a,c)cyclohepten-6-one, 3,3'-bis(trifluoromethyl)benzidine, dibenzo(1,2)dithiine-3,8-diamine, 3,3'-tolidine-5-sulfonic acid, 3,3'-dichlorobenzidine-d6, tetramethylbenzidine, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4-bis-(3-amino-4-hydroxyphenyl)-valeric acid, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro 2,2-bis(3-amino-4-methylphenyl)-hexafluoropropane, tetrabromomethylenedianiline, 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, or derivatives thereof, provided that, again, any recited compound not bearing two amino groups shall be considered a derivative having at least one additional amino group.

[0056] The following (L) diamines are preferred: p-Phenylenediamine, m-Phenylenediamine, benzidine, 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, phenoxybenzene, unsubstituted or substituted with methyl or trifluoromethyl.

[0057] The following (L) diamines are more preferred: Ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, 1,7-heptylenediamine, 1,8-octylenediamine, 1,9-nonylenediamine, 1,10-decylenediamine, 1,11-undecylenediamine, 1,12-dodecylenediamine, α,α'-diamino-m-xylene, α,α'-diamino-p-xylene, (5-amino-2,2,4-trimethylcyclopentyl)methylamine, 1,2-diaminocyclohexane, 4,4'-diaminodicyclohexane xylmethane, 1,3-bis(methylamino)cyclohexane, 4,9-dioxadodecane-1,12-diamine, 3,5-diaminobenzoic acid methyl ester, 3,5-diaminobenzoic acid hexyl ester, 3,5-diaminobenzoic acid dodecyl ester, 3,5-diaminobenzoic acid isopropyl ester, 4,4'-methylenedianiline, 4,4'-ethylenedianiline, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3',5,5'-tetramethylbenzidine, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl phenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diamino-2,2'-dimethylbibenzyl, bis[4-(4-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 2,7-diaminofluorene, 9,9-bis(4-amino phenyl)fluorene, 4,4'-methylenebis(2-chloroaniline), 4,4'-bis(4-aminophenoxy)biphenyl, 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-(1,4-phenyleneisopropylidene)bisaniline, 4,4'-(1,3-phenyleneisopropylidene)bisaniline, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[3-amino-4-methylphenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, and 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-2,3,5,6,2',3',5',6'-octafluorobiphenyl; and the diamines (L) disclosed in US 6,340,506, WO 00 / 59966 and WO 01 / 53384, all of which are expressly incorporated herein by reference;

[0058] The diamine compounds (L) according to the present invention can be prepared using methods known to those skilled in the art.

[0059] More preferred are the (L) diamines, which are commercially available and are listed below: polymer: Poly(3,3',4,4'-benzophenonetetracarboxylic dianhydride-co-4,4'-oxydianiline / 1,3-phenylenediamine), amic acid solution Poly(3,3',4,4'-benzophenonetetracarboxylic dianhydride-co-4,4'-oxydianiline / 1,3-phenylenediamine), amic acid solution Poly(pyromellitic dianhydride-co-4,4'-oxydianiline), amic acid solution Aromatic Diamines 2,7-Diaminofluorene, 1,5-Diaminoanthraquinone, 2,6-Diaminoanthraquinone, Pararosaniline hydrochloride, 3,6-Acridinediamine, 4,4'-Diaminooctafluorobiphenyl, 2,2'-Dithiodianiline, 3,3',5,5'-Tetramethylbenzidine, 3,3'-Diaminodiphenylsulfone, 4,4'-Diamino-2,2'-Dimethylbibenzyl, 4,4'-Diaminodiphenyl ether, 4,4'-Dithiodianiline, 4,4'-Diaminodiphenylsulfone, 4,4'- Diaminodiphenylmethane, 4,4'-ethylenedianiline, 3,3'-dimethoxybenzidine, 2,2'-dithiobis(1-naphthylamine), 3,7-diamino-2-methoxyfluorene, 3,6-diamino-10-methylacridinium chloride, propidium iodide, o-dianisidine dihydrochloride, 2,7-diaminofluorene dihydrochloride, pararosaniline acetate, 3,6-diamino-10-methylacridinium chloride hydrochloride, proflavine dihydrochloride, o-tolidine dihydrochloride, 3,3',5,5'-tetramethylphenylamine Methylbenzidine dihydrochloride, 3,3'-diaminobenzidine tetrahydrochloride, 4,4'-diaminostilbene dihydrochloride, 4,4'-diaminodiphenylamine sulfate, proflavin hemisulfate, 2,2'-ethylenedianiline diphosphate, 1,5-diamino-4,8-dihydroxyanthraquinone, o-tolidine, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)-phenyl]hexafluoro Propane, 4,4'-diamino-1,1'-dianthramide, 3,3'-dinitrobenzidine, 4,4'-diamino-5,5'-dimethyl-2,2'-biphenyl disulfonic acid, 4,4'-diaminostilbene-2,2'-disulfonic acid, 3-amino-4-hydroxyphenyl sulfone, 4,4-bis-(3-amino-4-hydroxyphenyl)-valeric acid, 2,2'-diamino-4,4'-difluorobibenzyl, 2-amino-4-chlorophenyl disulfide, 3,3'-(decamethylenedioxy)dianiline, 3,3'-(Pentamethylenedioxy)dianiline, 4-(p-aminoanilino)-3-sulfoaniline, 4-[3-(4-aminophenoxy)propoxy]aniline, 2-nitrobenzidine, benzidine-3-sulfonic acid, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminobenzanilide, n,n'-bis(3-aminophenylsulfonyl)-ethylenediamine, 2,2'-biphenyldiamine, 3,4'-diaminodiphenyl ether, proflavin hemisulfate, phenosafranine, 4,4'-diamino benzophenone, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)-hexafluoropropane, 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)benzene, 1,3-Bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 9,9-bis(4-aminophenyl)fluorene, o-tolidine sulfone, benzidine, 3,3'-dichlorobenzidine dihydrochloride, benzidine dihydrochloride, 3,6-thioxanthene diamine-10,10-dioxide, 4,4'-diamino-2,2'-biphenyl disulfonic acid, 4,4'-azodianiline, 2,5-bis-(4-aminophenyl)-(1,3,4)oxadiazole, 3,3'-dimethylnaphthidine, benzidine sulfate, 1 ,3-Bis(3-aminophenoxy)benzene, 3,3'-dichlorobenzidine, 2,2',5,5'-tetrachlorobenzidine, 4,4'-diamino-1,1'-binaphthyl, diamine bordeaux, benzoflavin, chrysaniline, 2,2'-thiobis(5-aminobenzenesulfonic acid), 4,4'-methylene-bis(2-chloroaniline), tetrabromomethylenedianiline, 4,4'-diamino-3,3'-dinitrodiphenyl ether, benzidine pyrophosphate, 3,6-diaminothioxanthene-10-dioxide dihydrochloride, 4,4''-diamin Amino-p-terphenyl, 1,8-diamino-4,5-dihydroxyanthraquinone, bis(p-aminophenoxy)-dimethylsilane, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4'-methylenedi-2,6-xylidine, 2-aminobenzaldehyde-ethylene-diimine, 3-methylbenzidine dihydrochloride, 3,3'-diethylbenzidine dihydrochloride, 3,6-diaminoacridine hydrochloride, 4,4'-diamino-5,5'-dimethyl-2,2'-biphenyl disulfonic acid disodium salt, 4,4'-methylenebis(3-chloro-2,6 -diethylaniline), 4,4'-methylene-bis-(2,6-diethylaniline), 4,4'-methylenebis-(2,6-diisopropylaniline), toluylenediamine, 3,8-diamino-6-phenylphenanthridine, thionine perchlorate, dihydroethidium, thionine, 4,4-diaminobenzenesulfonylanilide, o-dianisidine hydrochloride, 2,2'-dichloro-5,5'-dimethoxy-benzidine, 3-methoxybenzidine, 2,2'-(hexamethylenedioxy)dianiline, 2,2'-(pentamethylenedioxy)dianiline, 2,2'-(Ethylenedioxy)dianiline, 4-[4-(4-aminophenoxy)butoxy]aniline, 2,2'-diamino-4'-methoxy-4-methylbenzanilide, 5,5'-dimethyl-2,2'-dinitrobenzidine, n,n'-bis(2-aminophenyl)-1,3-propanediamine, 3,4'-diaminochalcone, 2,3',4,5',6-pentaphenyl-3,4'-biphenyldiamine, 2-([1-(4-(1-[(2-aminophenyl)thio]-2-nitroethyl)phenyl)-2-nitroethyl]thio)aniline, 2-( (2-[(2-aminophenyl)thio]ethyl)thio)aniline, 2-((4-[(2-aminophenyl)thio]but-2-enyl)thio)aniline, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminobibenzyl, trimethylene bis(4-aminobenzoate), fluorescein amine, benzidine mixture, 3-nitro-4,4'-methylenedianiline, 4,4-diamino-2,2'-dichlorodiphenyl disulfide, 1,6-diaminopyrene, 1,8-diaminopyrene, 3,6-diaminocarbazole, 4,4' (5')-Diamino[2,4]-dibenzo-18-crown-6 dihydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid disodium salt, (r)-(+)-2,2'-diamino-1,1'-binaphthyl, proflavine hemisulfate dihydrate, 3,6-diaminoacridine hemisulfate hemihydrate, dimidium bromide monohydrate, o-tolidine dihydrochloride hydrate, 3,3',5,5'-tetramethylbenzidine dihydrochloride hydrate, 3,3'-diaminobenzidine tetrahydrochloride dihydrate, 3,6-[bis(4-amino-3-(sodium sulfonate) n,n'-bis(4-aminophenyl)-1,3-bis(aminomethyl)benzene dihydrochloride, 4',4''(5'')-Diaminodibenzo-15-crown-5, 2,2'-bis(trifluoromethyl)benzidine, bis(4-amino-2,3-dichlorophenyl)methane, alpha,alpha'-bis(4-aminophenyl)-1,4-diisopropylbenzene, 2,2-bis(3-aminophenyl)hexafluoropropane, 3,10-diamino-6,13-dichlorobenzo[5,6][1,4]oxazino[2,3-b]phenoxazine-4,11-disulfo, n1-(2-amino-4-methylphenyl)-2-aminobenzamide , n1-(2-amino-4-chlorophenyl)-2-aminobenzamide, 2,2'-dichloro[1,1'-biphenyl]-4,4'-diamine, 4,4'(5')-diaminodibenzo-15-crown-5 dihydrochloride, bis-(4-amino-3-nitro-phenyl)-methanone, bis-(3-amino-4-chloro-phenyl)-methanone, bis-(3-amino-4-dimethylamino-phenyl)-methanone, n,n'-bis-(4-amino-2-chloro-phenyl)-isophthalamide, n,n'-bis-(4-amino-2-chloro-phenyl)-isophthalamide (z)-terephthalamide, 3,9-diamino-1,11-dimethyl-5,7-dihydro-dibenzo(a,c)cyclohepten-6-one, 2-aminobenzaldehyde, n-[(z)-(2-aminophenyl)methylidene]hydrazone, 3,3'-bis(trifluoromethyl)-benzidine-dicarboxydine dihydrochloride, 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 1,4-phenylenebis[[4-(4-aminophenoxy)phenyl]methanone], 2-((5-[(2-aminophenyl)thio]-3,4-dinitrile 1-(2-aminobenzoyl)-2-aminobenzene-1-carbohydrazide, 2-[4-(5-amino-1h-benzimidazol-2-yl)phenyl]-1h-benzimidazol-5-amine, 4-[4-(4-aminophenoxy)-2,3,5,6-tetrafluorophenoxy]aniline, 3,3'-dinitro-4,4'-diaminodiphenylsulfone, 3,3',4,4'-tetraamino-diphenylsulfone, 4-[1-(4-aminophenyl)-1-methylethyl]aniline, 3,3-Diaminodiphenylurea, bis(4-aminophenyl)acetylene, dibenzo(1,2)dithiine-3,8-diamine, ethidium homodimer-2, 4.4'-bis-(2-aminobenzenesulfonyl)bis-phenol ester, neopentyl glycol bis(4-aminophenyl)ether, 2,2'-oxydianiline, 4,4'-diaminodiphenylamine-2,2-disulfonic acid, 4,4-diaminodiphenylurea, 3,3'-tolidine-5-sulfonic acid, n1-(3-[(2-aminobenzoyl)amino]propyl)- 2-Aminobenzamide, 2-((6-[(2-aminophenyl)sulfanyl]-5-nitro-2-pyridyl)sulfanyl)aniline, 2-((6-amino-1,3-benzothiazol-2-yl)dithio)-1,3-benzothiazol-6-ylamine, tetramethylbenzidine, 2-([6-[(2-aminophenyl)sulfanyl]-3,5-di(trifluoromethyl)-2-pyridyl]sulfanyl)anile, 3,6-diaminothioxanthene-10-dioxide dihydrochloride, m-tolidine dihydrochloride hydrate, 2-amino No-n-[2-amino-4-(trifluoromethyl)phenyl]-5-methylbenzamide, 2-([2-[(2-aminophenyl)thio]-6-nitro-4-(trifluoromethyl)phenyl]thio)aniline, 2-[(3-([(2-aminophenyl)thio]methyl)-2,4,6-trimethylbenzyl)thio]aniline, 3-[3-amino-5-(trifluoromethyl)benzyl]-5-(trifluoromethyl)aniline, 2-((5-[(2-aminophenyl)thio]-4-chloro-2-nitrophenyl)thio)aniline, 4-(1- (4-aminophenyl)-2-[4-(dimethylamino)phenyl]vinyl)aniline, 1,5-bis(4-aminophenoxy)pentane, 2,3'-dichlorobenzidine dihydrochloride, 3,3'-diamino-4,4'-dichlorodiphenylsulfone, 3-(bis-(4-amino-phenyl)-methyl)-2,3-dihydro-isoindol-1-one, 4,4-diaminodiphenyl-2-sulfonic acid, 4,4'-diaminodiphenylene-cyclohexane, 4,5'-diamino(1,1')bianthracenyl-9,10,9',10'-tetraone.

[0060] Alicyclic diamine 4,4'-Methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine).

[0061] Aliphatic Diamines 1,8-diamino-p-menthane, 4,4'-methylenebis(cyclohexylamine), d-cystine, l-cystine dimethyl ester dihydrochloride, neamine, bis(2-aminopropyl)amine, l-cystine dibenzyl ester ditosylate, 1,4-diaminocyclohexane, dl-2-aminopropionic anhydride, l-cystine (di-b-naphthylamide) hydrochloride, l-cystine-bis-p-nitroanilide dihydrobromide, l-cystine diethyl ester dihydrochloride, trans-1,4-cyclohexane di Amines, 4,4'-methylenebis(2-methylcyclohexylamine), l-leucine thiol oxide dihydrochloride, 1,3-diaminoadamantane dihydrochloride, l-leucine thiol disulfide dihydrochloride, l-cystine disodium salt monohydrate, l-homocystine methyl ester hydrochloride, 1,3-adamantanediamine, tetracyclo-[8.2.1.1(8,11).0(2,7)-]tetradeca-2,4,6-triene-10,11-diamine, tricyclo[3.3.1.0(3,7)]nonane-3,7-diamine.

[0062] From the class of commercially available diamines (L), the following are preferred: Alicyclic diamine 4,4'-Methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine). Aliphatic Diamines 4,4'-methylenebis(cyclohexylamine), 1,4-diaminocyclohexane, trans-1,4-cyclohexanediamine, 4,4'-methylenebis(2-methylcyclohexylamine), 1,3-adamantanediamine. Aromatic Diamines 2,7-diaminofluorene, 2,6-diaminoanthraquinone, 4,4'-diaminooctafluorobiphenyl, 4,4'-diaminodiphenyl ether, 4,4'-dithiodianiline, 4,4'-diaminodiphenylmethane, 4,4'-ethylenedianiline, 3,3'-dimethoxybenzidine, o-tolidine, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 4-[3-(4-aminophenoxy)phenyl]hexafluoropropane, 4,4'-Diaminodiphenyl sulfide, 4,4'-Diaminobenzophenone, 2,2-Bis(4-aminophenyl)hexafluoropropane, 4,4'-Bis(4-aminophenoxy)biphenyl, 2,2-Bis[4-(4-aminophenoxy)phenyl]propane, 1,4-Bis(4-aminophenoxy)benzene, 1,3-Bis(4-aminophenoxy)benzene, Bis[4-(4-aminophenoxy)phenyl]sulfone, 9,9-Bis(4-aminophenyl)fluorene, Benzidine, 4,4'-Azodianiline Phosphorus, 1,3-bis(3-aminophenoxy)benzene, 4,4'-diamino-1,1'-binaphthyl, 4,4''-diamino-p-terphenyl, bis(p-aminophenoxy)dimethylsilane, 4-[4-(4-aminophenoxy)butoxy]aniline, 3,4'-diaminochalcone, trimethylene bis(4-aminobenzoate), 3,4'-diaminobiphenyl, 2,7-diamino-9-fluorenone, 4',4''(5'')-diaminodibenzo-15-crown-5, 2,2'-bis(trifluoromethyl)benzidine, alpha, alpha α'-Bis(4-aminophenyl)-1,4-diisopropylbenzene, 3,3'-bis(trifluoromethyl)benzidine, 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 1,4-phenylenebis-[[4-(4-aminophenoxy)phenyl]methanone], 4-[4-(4-aminophenoxy)-2,3,5,6-tetrafluorophenoxy]aniline, 4-[1-(4-aminophenyl)-1-methylethyl]aniline, neopentyl glycol bis(4-aminophenyl)ether, 4,4-diaminodiphenyl, 1,5-Bis(4-aminophenoxy)pentane.

[0063] From the class of commercially available diamines (L), the following are more preferred: Aromatic Diamines 2,7-diaminofluorene, 4,4'-diaminooctafluorobiphenyl, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-ethylenedianiline, 3,3'-diaminobenzophenone, 4-[3-(4-aminophenoxy)propoxy]aniline, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-amino nophenoxy)benzene, 9,9-bis(4-aminophenyl)fluorene, benzidine, bis(p-aminophenoxy)-dimethylsilane, 4-[4-(4-aminophenoxy)butoxy]aniline, 3,4'-diaminochalcone, trimethylene bis(4-aminobenzoate), 3,4'-diaminobiphenyl, 2,7-diamino-9-fluorenone, 4',4''(5'')-diaminodibenzo-15-crown-5, 4-[4-(4-aminophenoxy)-2,3,5,6-tetrafluorophenoxy]aniline, 4-[1-(4-aminophenyl)-1-methylethyl]aniline, 1,5-bis(4-aminophenoxy)pentane. Aliphatic Diamines 4,4'-Methylenebis(cyclohexylamine), 1,4-diaminocyclohexane. Alicyclic diamine 4,4'-Methylenebis(cyclohexylamine).

[0064] Preference is given to at least one compound of formula (I) within the meanings and preferences as mentioned above, p-Phenylenediamine, m-Phenylenediamine, Benzidine, 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, phenoxybenzene diamine (L) A composition comprising:

[0065] A further embodiment of the present invention is a composition comprising at least one compound of formula (I) within the meanings and preferences as defined above or a composition as defined above and an additive.

[0066] Additives such as silane-containing compounds and epoxy-containing crosslinkers may be added.

[0067] Suitable silane-containing additives are described in Plast. Eng. 36 (1996), (Polyimides, fundamentals and applications), Marcel Dekker, Inc.

[0068] Suitable epoxy-containing crosslinking additives include 4,4'-methylene-bis-(N,N-diglycidylaniline), trimethylolpropane triglycidyl ether, benzene-1,2,4,5-tetracarboxylic acid 1,2,4,5-N,N'-diglycidyldiimide, polyethylene glycol diglycidyl ether, N,N-diglycidyl-cyclohexylamine, and the like.

[0069] The additional additives are photosensitizers, photoradical generators, and cationic photoinitiators.

[0070] Suitable photoactive additives include 2,2-dimethoxyphenylethanone, mixtures of diphenyl-methanone with N,N-dimethylbenzenamine or 4-(dimethylamino)-ethylbenzoate, xanthones, thioxanthones, Irgacure® 184, 369, 500, 651 and 907 (Ciba), Michler's ketone, triarylsulfonium salts, and the like.

[0071] Further preferably, the present invention relates to a polymer, copolymer or oligomer according to the definitions and preferences of the present invention, comprising at least one compound (I), or Polymers, copolymers or oligomers according to the definitions and preferences of the invention obtainable by the process of the invention, and / or further polymers, copolymers or oligomers comprising a diamine (L) as one basic building block, or further polymers, copolymers or oligomers different from polyamic acids, polyamic acid esters or polyimides, more preferably further polymers, copolymers or oligomers selected from the group of polyacrylates, polystyrenes, polyesters, polyurethanes, polyethylenes, polypropylenes, polyvinyl chlorides, polytetrafluoroethylenes, polycarbonates, polyterephthalates and dendrimers. The present invention relates to a composition, particularly a formulation, comprising:

[0072] More preferably, the present invention provides a method for producing Compound (I), or Compound (I) obtainable by the process of the invention, an additive, preferably a silane-containing compound; and / or further polymers, copolymers or oligomers which comprise as one basic building block a further diamine different from the diamine (I), preferably at least one diamine (L). and / or further polymers, copolymers or oligomers different from polyamic acids, polyamic acid esters or polyimides, more preferably selected from the group of polymers comprising polyacrylates, polymethacrylates, polyacrylamides, polymethacrylamides, polyvinyl ethers and polyvinyl esters, polyallyl ethers and esters, polystyrenes, polysiloxanes, polyimides, polyamic acids and their esters, polyamideimides, polymaleic acids, polyfumaric acids, polyurethanes and derivatives thereof, and / or photoactive polymers, oligomers and / or monomers; and / or a crosslinking agent, preferably an epoxy-containing crosslinking agent, most preferably a crosslinking agent selected from the group: 4,4'-methylene-bis-(N,N-diglycidylaniline), trimethylolpropane triglycidyl ether, benzene-1,2,4,5-tetracarboxylic acid 1,2,4,5-N,N'-diglycidyldiimide, polyethylene glycol diglycidyl ether, N,N-diglycidyl-cyclohexylamine The present invention relates to a composition, particularly a formulation, comprising:

[0073] In the context of the present invention, the compound of formula (I) is a polymer, in particular a copolymer or oligomer. The preferred compound of formula (I) is a polyamic acid, a polyamic acid ester, a polyimide or a mixture thereof. The preferred compound of formula (I) is a polyamic acid. When the compound of formula (I) is a mixture, this mixture is preferably a mixture of a polyamic acid with a polyamic acid ester and / or a polyimide. More preferred is a mixture of a polyamic acid with a polyimide.

[0074] In the context of the present invention, the term "polyimide" has the meaning of a partially or fully imidized polyamic acid or polyamic acid ester. Similarly, the term "imidized" has the meaning of partially or fully imidized in the context of the present invention.

[0075] The polymers, copolymers or oligomers, especially polyamic acids, polyamic acid esters and polyimides, and mixtures thereof, can be prepared according to known methods, for example, those described in Plast. Eng. 36 (1996), (Polyimides, fundamen-tals and applications), Marcel Dekker, Inc.

[0076] For example, the amidation, polycondensation reaction for the preparation of polyamic acids is carried out in a solution of a polar aprotic organic solvent, such as γ-butyrolactone, N,N-dimethylacetamide, N-methylpyrrolidone or N,N-dimethyl-formamide. Often equimolar amounts of anhydride and 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 add one of the two components in excess or less than the stoichiometric amount, or to add a monofunctional compound in the form of a dicarboxylic monoanhydride or in the form of a monoamine. Examples of such monofunctional compounds are maleic anhydride, phthalic anhydride, aniline, etc. Preferably, the reaction is carried out at a temperature below 100° C.

[0077] Imidization, cyclization of the polyamic acid to form the polyimide can be carried out by heating, ie, by condensation with removal of water, or by other imidization reactions using appropriate reagents.

[0078] Partial imidization is achieved, for example, when imidization is carried out solely by heat; imidization of the polyamic acid is not necessarily complete, i.e., the resulting polyimide may still contain a proportion of polyamic acid.

[0079] The complete imidization reaction is carried out at a temperature between 60 and 250°C, preferably at a temperature below 200°C.

[0080] In order to achieve imidization at low temperatures, an additional reagent that facilitates the removal of water is added to the reaction mixture. Such a reagent is, for example, a mixture of acid anhydrides, such as acetic anhydride, propionic anhydride, phthalic anhydride, trifluoroacetic anhydride, or tertiary amines, such as triethylamine, trimethylamine, tributylamine, pyridine, N,N-dimethyl-aniline, lutidine, collidine, etc. The amount of the aforementioned additional reagent that facilitates the removal of water is preferably at least 4 equivalents of acid anhydride and 2 equivalents of amine per equivalent of polyamic acid to be condensed.

[0081] The imidization degree of each polymer used in the liquid crystal alignment agent of the present invention can be adjusted arbitrarily by controlling the amount of catalyst used in the production of the polymer, the reaction time and the reaction temperature. In the description of the present invention, the "imidization degree" of a polymer refers to the ratio (expressed as %) of the number of repeating units of the polymer that form an imide ring or an isoimide ring to the total number of repeating units of the polymer. In the description of the present invention, the imidization degree of a polyamic acid that is not subjected to dehydration and ring closure is 0%. The imidization degree of each polymer was measured by dissolving the polymer in deuterated dimethyl sulfoxide and measuring the resulting solution at room temperature using tetramethylsilane as a standard substance. 1 It is determined by subjecting the mixture to H-NMR measurement and calculating from the following formula: Imidization degree (%) = 1-(A 1 / A 2 ×B)×100 A 1 : Peak area based on NH group protons (around 10 ppm) A 2 : Peak area based on one proton of acrylate double bond (around 6.5 ppm) B: Ratio of the number of acrylate protons to one proton of the NH group in the polymer precursor.

[0082] The degree of imidization is usually in the range of 1 to 99%, preferably 5 to 50%, and more preferably 10 to 40%.

[0083] The present invention relates to each diamine M within the meaning and preferences as given above. 1 , M 2 and M. 3 and at least one D within the meaning and preference as given above. 1 , D 2 and D. 3 The present invention relates to a process for the preparation of compound (I), comprising the polymerization of

[0084] Preferably, the polymerization for the preparation of compound (I) is a) At least one D, within the meaning and preference as given above 1 , D 2 and D. 3 By each M 1 , M 2 and M. 3 amidation of at least one of the following to a polyamic acid or polyamic acid ester; and / or b) imidization of the resulting polyamic acid or ester to a polyimide, or c) Imidization of compound (I) into polyimide Includes.

[0085] In a more preferred embodiment of the present invention, the polymerization of diamines is carried out by the addition of at least one M 1 , M 2 and M. 3 with a tetracarboxylic anhydride (V) and / or imidization, preferably by increasing the temperature, the amidation and / or imidization optionally comprising in the presence of additives as given above, and / or - M in formula (I) 1 , M 2 and M. 3 Further M within the meaning and preferences as given above, which are different from those of 1 in the presence of, preferably at least one diamine (L), and / or in the presence of a further polymer, copolymer or oligomer comprising a diamine (L) as one basic building block, or a further polymer, copolymer or oligomer different from the polyamic acids, polyamic acid esters or polyimides, more preferably selected from the group of polymers comprising polyacrylates, polymethacrylates, polyacrylamides, polymethacrylamides, polyvinyl ethers and polyvinyl esters, polyaryl ethers and esters, polystyrenes, polysiloxanes, polyimides, polyamic acids and their esters, polyamideimides, polymaleic acids, polyfumaric acids, polyurethanes and derivatives thereof.

[0086] Preferably, the further polymer, copolymer or oligomer comprises as basic building blocks a diamine (L) and a tetracarboxylic acid anhydride, preferably a tetracarboxylic acid anhydride of formula (V).

[0087] The polymers, copolymers or oligomers containing diamine (L) as a basic building block are prepared in the same manner as the polymers, copolymers or oligomers of the invention containing compound (I).

[0088] The imidization is carried out after or during the amidation. Generally, the imidization is carried out after the amidation.

[0089] Partial imidization of the polyamic acid or polyamic acid ester is preferred.

[0090] If the polymer is prepared solely by imidization, compound (I) is contacted with an imidization compound having at least two polymerizable functional groups, such as, for example, carbonyl or halogen groups.

[0091] A further embodiment of the present invention relates to compounds (I) or compositions within the meanings and preferences as described above, obtainable according to the process and preferred processes of the present invention.

[0092] The polymers or oligomers according to the present invention, in the form of a polymer or oligomer layer, may be used alone or in combination with other polymers, oligomers, monomers, photoactive polymers, photoactive oligomers and / or photoactive monomers, depending on the application to which the polymer or oligomer layer is applied. It is therefore understood that by varying the composition of the polymer or oligomer layer, it is possible to control certain desired properties, such as induced pretilt angle, good surface wettability, high voltage holding ratio, specific anchoring energy, etc.

[0093] Polymer or oligomer layers can be easily prepared from the polymers or oligomers of the present invention, and a further embodiment of the present invention relates to a polymer or oligomer layer comprising a polymer or oligomer according to the present invention, preferably prepared by treatment with aligning light.Preferably, the present invention relates to a polymer or oligomer layer comprising a polymer or oligomer according to the present invention in crosslinked and / or isomerized form.

[0094] The polymer or oligomer layer is preferably prepared by applying one or more polymers or oligomers according to the invention to a support and treating, preferably crosslinking and / or isomerizing, the polymer or oligomer or polymer mixture or oligomer mixture by irradiation with aligning light, with or without imidization.

[0095] In the context of the present invention, aligning light is light of a wavelength that can initiate photoalignment. Preferably, the wavelength is in the UV-A, UV-B and / or UV-C range, or in the visible range. Which wavelength is appropriate depends on the photoalignment compound. Preferably, the photoreactive group is sensitive to visible light and / or UV light. A further embodiment of the present invention relates to the generation of aligning light by laser light.

[0096] The immediate direction of the aligning light can be perpendicular to the substrate or at any oblique angle.

[0097] To generate a tilt angle, the aligning light is preferably exposed from an oblique angle.

[0098] More preferably, the aligning light is at least partially linearly polarized, elliptically polarized (e.g., circularly polarized, etc.), or unpolarized light; most preferably, at least partially circularly polarized or partially linearly polarized, or unpolarized light exposed obliquely. In particular, the most preferred aligning light refers to substantially polarized light, especially linearly polarized light; or, the aligning light refers to unpolarized light applied by oblique illumination.

[0099] In a more preferred embodiment of the invention the polymer, copolymer or oligomer is treated with polarized light, in particular linearly polarized light, or by oblique irradiation with unpolarized light.

[0100] Generally, a transparent support is used, such as a glass or plastic substrate, optionally coated with indium tin oxide (ITO).

[0101] Furthermore, by controlling the direction of irradiation of the aligning light, it is possible to change the direction of alignment and tilt angle in the polymer or oligomer layer. It is understood that by selectively irradiating certain areas of the polymer or oligomer layer, very limited areas of the layer can be oriented. In this way, a layer with a defined tilt angle can be provided. The induced alignment and tilt angle are retained in the polymer or oligomer layer by processes, especially crosslinking processes.

[0102] The present invention furthermore relates to a process for the preparation of the compounds according to the invention, preferably polymers, copolymers or oligomers, in which, in a polycondensation reaction, each M 1 , M 2and M. 3 At least one of the diamines and one or more D 1 , D 2 and D. 3 (Preferably, D 1 , D 2 and D. 3 is a tetracarboxylic dianhydride of general formula (V) optionally in the presence of one or more additional other diamines.

[0103] Furthermore, the present invention preferably relates to a process, wherein the polycondensation reaction for the preparation of the polyamic acid is preferably carried out in a solution of a polar aprotic organic solvent selected from γ-butyrolactone, N,N-dimethylacetamide, N-methylpyrrolidone or N,N-dimethyl-formamide.

[0104] Preferably, the present invention relates to a process in which polycondensation followed by cyclization with removal of water is carried out under heat to form a polyimide.

[0105] More preferably, the present invention relates to a process, wherein the imidization is carried out before or after applying the polymer, copolymer or oligomer to a support.

[0106] A further preferred embodiment of the present invention comprises - a method for the preparation of vertically oriented polymer or oligomer layers; - a method for the preparation of a multi-domain vertically oriented polymer or oligomer layer; - Method for the preparation of a polymer or oligomer layer with a tilted optical axis The present invention relates to a preferred method for

[0107] A further embodiment of the present invention relates to a polymer, copolymer or oligomer layer, in particular an alignment layer, comprising at least one polymer, copolymer or oligomer according to the present invention.

[0108] It is understood that the polymer or oligomer layer of the present invention (in the form of a polymer gel, polymer network, polymer film, etc.) can also be used as an alignment layer for liquid crystals. A further preferred embodiment of the present invention relates to an alignment layer comprising one or more polymers or oligomers according to the present invention, preferably in crosslinked form. Such an alignment layer can be used in the manufacture of unstructured or structured optical or electro-optical elements, preferably in the production of hybrid layer elements.

[0109] In addition, the present invention relates to a method for the preparation of a polymeric or oligomeric layer, in which one or more polymers, copolymers or oligomers according to the invention are applied to a support, preferably from a solution of the polymeric or oligomeric material, followed by evaporation of the solvent and, if necessary, after an optional imidization step, the polymer or oligomer or polymer mixture or oligomeric mixture is treated with aligning light, preferably isomerized and / or crosslinked by irradiation with aligning light.

[0110] Preferred methods of the present invention relate to changing the direction of alignment and tilt angle in a polymer or oligomer layer by controlling the direction of irradiation with aligning light and / or orienting specific regions of the polymer or oligomer layer by selectively irradiating specific regions of the layer.

[0111] The alignment layer is suitably prepared from a solution of polymer or oligomer material. The polymer or oligomer solution is applied to a support, optionally coated with electrodes, such as a glass plate coated with indium tin oxide (ITO), so as to produce a homogeneous layer with a thickness of 0.05 to 50 μm. In this process, various coating techniques may be used, such as spin coating, inkjet, meniscus coating, wire coating, slot coating, offset printing, flexographic printing, gravure printing. Then, or optionally after a preceding imidization step, the areas to be aligned are irradiated, for example with a high pressure mercury lamp, a xenon lamp or a pulsed UV laser, using a polarizer and optionally a mask to create an image of the structure.

[0112] Furthermore, the present invention relates to the use of a polymer, copolymer or oligomer layer according to the invention, preferably in crosslinked form, as an alignment layer for liquid crystals.

[0113] Furthermore, the present invention preferably relates to the use of a polymer, copolymer or oligomer layer for inducing vertical alignment of an adjacent liquid crystal layer, in particular for operating the cell in VA mode.

[0114] The irradiation time depends on the power of the individual lamps and can vary from a few seconds to a few hours. However, the photoreaction (dimerization, polymerization, crosslinking) can also be carried out by irradiation of the homogeneous layer, for example using a filter that passes only radiation suitable for the crosslinking reaction.

[0115] It will be appreciated that the polymer or oligomer layers of the present invention may be used in the production of unstructured and structured optical elements and multilayer systems, as well as optical or electro-optical devices having at least one alignment layer.

[0116] The present invention relates to the use of a polymer, copolymer or oligomer layer as an alignment layer for liquid crystals.

[0117] Preferred is its use for inducing homeotropic alignment of an adjacent liquid crystal layer.

[0118] A further embodiment of the present invention relates to an optical or electro-optical device comprising one or more polymers or oligomers according to the present invention in crosslinked form. The electro-optical device may comprise more than one layer. The layer, or each of the layers, may contain one or more regions of different spatial arrangement.

[0119] Preferably, the invention relates to optical and electro-optical unstructured or structured components, preferably liquid crystal display cells, multi-layer and hybrid layer elements, which comprise at least one polymer, copolymer or oligomer layer according to the invention.

[0120] More preferably, the present invention relates to an alignment layer comprising at least one polymer, copolymer or oligomer layer according to the present invention.

[0121] The advantages of the present invention could not have been foreseen by one skilled in the art.

[0122] Surprisingly, it has been found that low pretilt angles and / or low ACM values ​​are achievable with the compounds of the present invention.

[0123] Working Example General Procedure for Forming Polyamic Acid The polymer backbone, which can be referred to as the polymer backbone, is a polyimide or polyamic acid material. Polyamic acid (PAA) is a precursor material to polyimides (PI). The procedure follows the general procedure described in the textbook "Polyimides: Fundamentals and Applications," which involves, as a first step, the reaction of a dianhydride with a diamine in an aprotic solvent to produce a polyamic acid (PAA) intermediate polymer. The PAA can then be cyclized to the corresponding polyimide (PI).

[0124] Polyamic acids (PAA) were synthesized by "solution polycondensation" of a diamine or mixture of diamines with a dianhydride or mixture of dianhydrides, PAA being readily soluble in polar organic solvents (e.g., N-methylpyrrolidinone). The polymer composition follows the monomer (diamine, dianhydride) structure with respect to their molar contributions and possible isomers. Polymer formation is characterized by an increase in the viscosity of the reaction mixture. An intrinsic viscosity >0.1 dL / g confirms the formation of a polymer backbone.

[0125] Definitions used in the examples: 1H NMR: 1 H nuclear magnetic resonance spectroscopy DMSO-d6: Deuterated dimethyl sulfoxide 300MHz: 300 megahertz m: multiplet, d: doublet, dd: doublet-doublet, t: triplet, s: singlet, b: broad NMP: N-methyl-2-pyrrolidone DMF: N,N-dimethylformamide MeOH: Methanol GBL: gamma-butyrolactone IBIB: Isobutyl isobutyrate DEE: Diethylene glycol diethyl ether wt%: weight percent PTFE: Polytetrafluoroethylene 4,9-Dioxatricyclo[5.3.0.0 2,6 ]Decane-3,5,8,10-tetrahydrofuran refers to 1,2,3,4-cyclobutanetetracarboxylic dianhydride, which is CAS [4415-87-6], 4-(4-aminophenoxy)aniline refers to CAS[101-80-4]. 4,10-Dioxatricyclo[6.3.1.0 2,7]Dodecane-3,5,9,11-tetrone refers to 3-(carboxymethyl)-1,2,4-cyclopentanetricarboxylic acid 1,4:2,3-dianhydride, which is CAS [6053-46-9]; 4-(4-amino-2-methyl-phenyl)-3-methyl-aniline refers to CAS[84-67-3] 2-(4-aminophenyl)-1H-benzimidazol-5-amine refers to 5-amino-2-(4-aminophenyl)benzimidazole, which is CAS [7621-86-5]; 2-Methylbenzene-1,3-diamine refers to CAS[823-40-5]. 5-(trifluoromethyl)benzene-1,3-diamine refers to CAS[368-53-6]. 4-[4-Amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline refers to CAS[341-58-2].

[0126] Example 1: Preparation of polyamic acid PX1 4,9-Dioxatricyclo[5.3.0.0 2,6 4.897 g (24.970 mmol) of decane-3,5,8,10-tetrone are 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 then allowed to react at room temperature for 72 hours. Polyamic acid PX1 is obtained as a 20 wt% NMP solution with an intrinsic viscosity [η] of 0.37 dL / g.

[0127] Example 2: Preparation of polyamic acid PX2 4,9-Dioxatricyclo[5.3.0.0 2,64.622 g (23.570 mmol) of decane-3,5,8,10-tetrone are 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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid PX2 is obtained as a 20 wt% NMP solution with an intrinsic viscosity [η] of 0.50 dL / g.

[0128] Example 3: Preparation of polyamic acid PX3 4,10-Dioxatricyclo[6.3.1.0 2,7 2.750 g (12.267 mmol) of ]dodecane-3,5,9,11-tetrone are 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 then allowed to react at room temperature for 72 hours. Polyamic acid PX3 is obtained as a 20 wt% NMP solution with an intrinsic viscosity [η] of 0.57 dL / g.

[0129] Example 4: Preparation of polyamic acid PX4 4,10-Dioxatricyclo[6.3.1.0 2,7 5.598 g (24.970 mmol) of ]dodecane-3,5,9,11-tetrone are 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 then allowed to react at room temperature for 72 hours. Polyamic acid PX4 is obtained as a 20 wt% NMP solution with an intrinsic viscosity [η] of 0.44 dL / g.

[0130] Example 5: Preparation of polyamic acid PX5 4,10-Dioxatricyclo[6.3.1.0 2,75.284 g (23.570 mmol) of ]dodecane-3,5,9,11-tetrone are 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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid PX5 is obtained as a 20 wt% NMP solution with an intrinsic viscosity [η] of 0.62 dL / g.

[0131] Example 7a: Preparation of (E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoic acid 19.5 g (164.1 mmol) of thionyl chloride are added in portions over 30 minutes 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, excess thionyl chloride is distilled off under pressure. The reaction mixture is then cooled 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 stirring for 2 hours 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 to 80 ° C. After 4 h at 80° C., the reaction mixture is cooled to 40° C., 150 mL of MeOH is added, and the reaction mixture is cooled to 0° C. After 1 h at 0° C., the precipitate is filtered off, washed with 100 mL of cold methanol, and dried 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. 1 H 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)

[0132] Example 7b: Preparation of [4-[(E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate 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, and 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 overnight at room temperature. After 22 h at room temperature, the reaction mixture is partitioned between dichloromethane and water. The organic phase is repeatedly washed with water, dried over sodium sulfate, filtered and concentrated by rotary evaporation. Chromatography of the residue on silica gel using toluene:ethyl acetate 95:5 as eluent followed by crystallization from an ethyl acetate:hexane mixture gives 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. 1 H 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)

[0133] Example 7c: Preparation of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate 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 is dissolved in a mixture of 54 ml of N,N-dimethylformamide and 6 ml of water. 13.9 g (51.4 mmol) of iron chloride hexahydrate is added. 5.60 g (85.7 mmol) of zinc powder is added in small portions within 60 min. The mixture is allowed to react for 2 h. The reaction mixture is then diluted with ethyl acetate and cooled to 50° C. Partition with chill and water and filter. Wash the organic phase repeatedly with water, dry with sodium sulfate, filter and concentrate by rotary evaporation. Filtration of the residue onto silica gel using toluene:ethyl acetate (1:3) as eluent and crystallization from an ethyl acetate:hexane mixture gives 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 an orange powder. 1 H 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)

[0134] Example 8a: Preparation of (E)-3-[4-[4-(4-pentylcyclohexyl)cyclohexanecarbonyl]oxyphenyl]prop-2-enoic acid 11.63 g (97.74 mmol) of thionyl chloride are added in portions over 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 h, at 75 ° C, excess thionyl chloride is distilled off under pressure. The reaction mixture is then cooled 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 stirring for 2 h 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 to 80 ° C. After 4 h at 80° C., the reaction mixture is cooled to 40° C., 150 mL of MeOH is added, and the reaction mixture is cooled to 0° C. After 1 h at 0° C., the precipitate is filtered off, washed with 100 mL of cold methanol, and dried under vacuum at 40° C. to give 31.54 g (83%) of (E)-3-[4-[4-(4-pentylcyclohexyl)cyclohexanecarbonyl]oxyphenyl]prop-2-enoic acid as a white powder. 1 H 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)

[0135] Example 8b: Preparation of [4-[(E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate 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, and 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 overnight at room temperature. After 22 h at room temperature, the reaction mixture is partitioned between dichloromethane and water. The organic phase is repeatedly washed with water, dried over sodium sulfate, filtered and concentrated by rotary evaporation. Chromatography of the residue on silica gel using toluene:ethyl acetate 95:5 as eluent followed by crystallization from an ethyl acetate:hexane mixture gives 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. 1 H 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)

[0136] Example 8c: Preparation of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate 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 of water. 13.9 g (51.4 mmol) of iron chloride hexahydrate are added. 5.60 g (85.7 mmol) of zinc powder are added in portions within 60 minutes. 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 repeatedly washed with water, dried over sodium sulfate, filtered and concentrated by rotary evaporation. Filtration of the residue over silica gel using toluene:ethyl acetate (1:3) as eluent and crystallization from an ethyl acetate:hexane mixture gives 3.06 g (65%) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate as a yellow-orange powder. 1 H 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)

[0137] Example 9: Preparation of polyamic acid P1 4,10-Dioxatricyclo[6.3.1.0 2,70.672 g (3.00 mmol) of ]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 for 2 hours at 0°C. The mixture is then allowed to react at room temperature for 72 hours. Polyamic acid P1 is obtained as a 30 wt % NMP solution having an intrinsic viscosity [η] of 0.36 dL / g.

[0138] Example 10: Preparation of polyamic acid P2 4,10-Dioxatricyclo[6.3.1.0 2,7 0.672 g (3.00 mmol) of ]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 for 2 hours at 0 ° C. The mixture is then allowed to react at room temperature for 72 hours. Polyamic acid P2 is obtained as a 30 wt % NMP solution having an intrinsic viscosity [η] of 0.38 dL / g.

[0139] Example 11: Preparation of polyamic acid P3 4,10-Dioxatricyclo[6.3.1.0 2,70.672 g (3.00 mmol) of ]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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid P3 is obtained as a 30 wt % NMP solution having an intrinsic viscosity [η] of 0.47 dL / g.

[0140] Example 12: Preparation of polyamic acid P4 4,9-Dioxatricyclo[5.3.0.0 2,6 0.588 g (3.00 mmol) of 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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid P4 is obtained as a 30 wt % NMP solution having an intrinsic viscosity [η] of 0.90 dL / g.

[0141] Example 13: Preparation of polyamic acid P5 4,9-Dioxatricyclo[5.3.0.0 2,60.588 g (3.00 mmol) of 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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid P5 is obtained as a 30 wt % NMP solution with an intrinsic viscosity [η] of 0.30 dL / g.

[0142] Example 14: Preparation of polyamic acid P6 4,9-Dioxatricyclo[5.3.0.0 2,6 0.588 g (3.00 mmol) of 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 then allowed to react at room temperature for 72 hours. Polyamic acid P6 is obtained as a 30 wt % NMP solution with an intrinsic viscosity [η] of 0.32 dL / g.

[0143] Example 15: Preparation of polyamic acid P7 4,9-Dioxatricyclo[5.3.0.0 2,60.588 g (3.00 mmol) of 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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid P7 is obtained as a 30 wt % NMP solution with an intrinsic viscosity [η] of 0.27 dL / g.

[0144] Example 16: Preparation of polyamic acid P8 4,9-Dioxatricyclo[5.3.0.0 2,6 0.588 g (3.00 mmol) of ]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 for 2 hours at 0° C. The mixture is then reacted for 72 hours at room temperature. Polyamic acid P8 is obtained as a 30 wt % NMP solution with an intrinsic viscosity [η] of 0.33 dL / g.

[0145] Example 17: Preparation of polyamic acid P9 4,9-Dioxatricyclo[5.3.0.0 2,60.588 g (3.00 mmol) of 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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid P9 is obtained as a 30 wt % NMP solution with an intrinsic viscosity [η] of 0.60 dL / g.

[0146] Example 18: Preparation of polyamic acid P10 4,9-Dioxatricyclo[5.3.0.0 2,6 0.588 g (3.00 mmol) of 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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid P10 is obtained as a 30 wt % NMP solution with an intrinsic viscosity [η] of 0.38 dL / g.

[0147] Example 19: Preparation of polyamic acid P11 4,9-Dioxatricyclo[5.3.0.0 2,60.588 g (3.00 mmol) of 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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid P11 is obtained as a 30 wt % NMP solution with an intrinsic viscosity [η] of 0.58 dL / g.

[0148] Example 20: Preparation of polyamic acid P12 4,9-Dioxatricyclo[5.3.0.0 2,6 0.588 g (3.00 mmol) of ]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 for 2 hours at 0° C. The mixture is then reacted for 72 hours at room temperature. Polyamic acid P12 is obtained as a 30 wt % NMP solution with an intrinsic viscosity [η] of 0.32 dL / g.

[0149] Example 21: Preparation of polyamic acid P13 4,9-Dioxatricyclo[5.3.0.0 2,60.588 g (3.00 mmol) of ]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 for 2 hours at 0° C. The mixture is then reacted for 72 hours at room temperature. Polyamic acid P13 is obtained as a 30 wt % NMP solution with an intrinsic viscosity [η] of 0.45 dL / g.

[0150] Example 22: Preparation of polyamic acid P14 4,9-Dioxatricyclo[5.3.0.0 2,6 0.588 g (3.00 mmol) of ]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 for 2 hours at 0° C. The mixture is then reacted for 72 hours at room temperature. Polyamic acid P14 is obtained as a 30 wt % NMP solution with an intrinsic viscosity [η] of 0.87 dL / g.

[0151] Example 23: Preparation of Formulation 1 To a solution of 1.700 g of polyamic acid PX3 and 0.200 g of polyamic acid P1, 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give Formulation 1.

[0152] Example 24: Preparation of Formulation 2 To a solution of 1.910 g of polyamic acid PX1 and 0.225 g of polyamic acid P1, 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 2.

[0153] Example 25: Preparation of Formulation 3 To a solution of 1.700 g of polyamic acid PX3 and 0.200 g of polyamic acid P2, 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 3.

[0154] Example 26: Preparation of Formulation 4 To a solution of 1.910 g of polyamic acid PX1 and 0.225 g of polyamic acid P2, 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 4.

[0155] Example 27: Preparation of Formulation 5 To a solution of 1.700 g of polyamic acid PX3 and 0.200 g of polyamic acid P3, 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 5.

[0156] Example 28: Preparation of Formulation 6 To a solution of 1.910 g of polyamic acid PX1 and 0.225 g of polyamic acid P3, 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 6.

[0157] Example 29: Preparation of Formulation 7 To a solution of 1.700 g of polyamic acid PX3 and 0.200 g of polyamic acid P4, 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 8.

[0158] Example 30: Preparation of Formulation 8 To a solution of 1.700 g of polyamic acid PX5 and 0.200 g of polyamic acid P4, 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 3.

[0159] Example 31: Preparation of Formulation 9 To a solution of 1.910 g of polyamic acid PX2 and 0.225 g of polyamic acid P4, 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 9.

[0160] Example 32: Preparation of Formulation 10 To a solution of 1.700 g of polyamic acid PX4 and 0.200 g of polyamic acid P4, 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 10.

[0161] Example 33: Preparation of Formulation 11 To a solution of 1.910 g of polyamic acid PX1 and 0.225 g of polyamic acid P5, 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 11.

[0162] Example 34: Preparation of Formulation 12 To a solution of 1.910 g of polyamic acid PX1 and 0.225 g of polyamic acid P6, 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 12.

[0163] Example 35: Preparation of Formulation 13 To a solution of 1.700 g of polyamic acid PX3 and 0.200 g of polyamic acid P7, 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 13.

[0164] Example 36: Preparation of Formulation 14 To a solution of 1.910 g of polyamic acid PX1 and 0.225 g of polyamic acid P7, 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 14.

[0165] Example 37: Preparation of Formulation 15 To a solution of 1.700 g of polyamic acid PX3 and 0.200 g of polyamic acid P8, 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 15.

[0166] Example 38: Preparation of Formulation 16 To a solution of 1.910 g of polyamic acid PX1 and 0.225 g of polyamic acid P8, 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 16.

[0167] Example 39: Preparation of Formulation 17 To a solution of 1.700 g of polyamic acid PX3 and 0.200 g of polyamic acid P9, 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 17.

[0168] Example 40: Preparation of Formulation 18 To a solution of 1.910 g of polyamic acid PX1 and 0.225 g of polyamic acid P9, 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 18.

[0169] Example 41: Preparation of Formulation 19 To a solution of 1.700 g of polyamic acid PX3 and 0.200 g of polyamic acid P10, 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 19.

[0170] Example 42: Preparation of Formulation 20 To a solution of 1.910 g of polyamic acid PX1 and 0.225 g of polyamic acid P10, 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 20.

[0171] Example 43: Preparation of Formulation 21 To a solution of 1.700 g of polyamic acid PX3 and 0.200 g of polyamic acid P11, 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 21.

[0172] Example 44: Preparation of Formulation 22 To a solution of 1.910 g of polyamic acid PX1 and 0.225 g of polyamic acid P11, 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 22.

[0173] Example 45: Preparation of Formulation 23 To a solution of 1.700 g of polyamic acid PX3 and 0.200 g of polyamic acid P12, 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 23.

[0174] Example 46: Preparation of Formulation 24 To a solution of 1.910 g of polyamic acid PX1 and 0.225 g of polyamic acid P12, 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 24.

[0175] Example 47: Preparation of Formulation 25 To a solution of 1.910 g of polyamic acid PX1 and 0.225 g of polyamic acid P13, 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 25.

[0176] Example 48: Preparation of Formulation 26 To a solution of 1.910 g of polyamic acid PX1 and 0.225 g of polyamic acid P14, 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 26.

[0177] Application Examples Pretilt angle measurements used in the examples: To measure the pretilt angle, a rotating analyzer is used as described in Michio Kitamura, Shunsuke Kobayashi and Katsumi Mori; Journal of the SID14 / 5, 2006; p509-p514.

[0178] Example 1 Formulation 1 is spin-coated onto two ITO-coated glass substrates at a spin speed of about 2000 rpm for 30 seconds. After spin-coating, the substrates are subjected to a baking procedure consisting of a pre-bake at 80°C for 90 seconds and a post-bake at 200°C for 40 minutes. The substrates are then exposed to linearly polarized light at an incidence angle of 40° relative to the normal to the substrate plane (22 mJ.cm -2 -LPUVB). The polarization plane is parallel to the long side of the substrate. The two substrates are used to assemble a cell such that the exposed polymer layers face each other inside the cell. The substrates are adjusted relative to each other so that the induced alignment directions are parallel to each other. The cell is capillary filled with liquid crystal MLC-6610 (Merck KGA-Δε<0). Finally, the filled cell is further subjected to thermal annealing at 130°C for 10 min, thereby completing the cell processing. The liquid crystal in the cell showed a well-defined and uniform vertical alignment before and after the thermal annealing of the cell. A pretilt angle of 87.88° is measured.

[0179] Example 2 The cell is prepared as in Example 1, except that it is coated with Formulation 2. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 88.01° is measured.

[0180] Example 3 The cell is prepared as in Example 1, except that it is coated with Formulation 3. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 88.18° is measured.

[0181] Example 4 The cell is prepared as in Example 1, except that it is coated with Formulation 4. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 88.29° is measured.

[0182] Example 5 The cell is prepared as in Example 1, except that it is coated with Formulation 5. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 88.22° is measured.

[0183] Example 6 The cell is prepared as in Example 1, except that it is coated with Formulation 6. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 88.25° is measured.

[0184] Example 7 The cell is prepared as in Example 1, except that it is coated with Formulation 7. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 87.03° is measured.

[0185] Example 8 The cell is prepared as in Example 1, except that it is coated with Formulation 8. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 87.16° is measured.

[0186] Example 9 The cell is prepared as in Example 1, except that it is coated with Formulation 9. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 87.13° is measured.

[0187] Example 10 The cell is prepared as in Example 1, except that it is coated with Formulation 10. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 87.26° is measured.

[0188] Example 11 The cell is prepared as in Example 1, except that it is coated with Formulation 11. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 87.23° is measured.

[0189] Example 12 The cell is prepared as in Example 1, except that it is coated with Formulation 12. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 87.32° is measured.

[0190] Example 13 The cell is prepared as in Example 1, except that it is coated with Formulation 13. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 87.05° is measured.

[0191] Example 14 The cell is prepared as in Example 1, except that it is coated with Formulation 14. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 87.23° is measured.

[0192] Example 15 The cell is prepared as in Example 1, except that it is coated with Formulation 15. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 87.09° is measured.

[0193] Example 16 The cell is prepared as in Example 1, except that it is coated with Formulation 16. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 87.23° is measured.

[0194] Example 17 The cell is prepared as in Example 1, except that it is coated with Formulation 17. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 86.72° is measured.

[0195] Example 18 The cell is prepared as in Example 1, except that it is coated with Formulation 18. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 86.91° is measured.

[0196] Example 19 The cell is prepared as in Example 1, except that it is coated with Formulation 19. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 86.69° is measured.

[0197] Example 20 The cell is prepared as in Example 1, except that it is coated with Formulation 20. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 86.94° is measured.

[0198] Example 21 The cell is prepared as in Example 1, except that it is coated with Formulation 21. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 86.62° is measured.

[0199] Example 22 The cell is prepared as in Example 1, except that it is coated with Formulation 22. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 86.90° is measured.

[0200] Example 23 The cell is prepared as in Example 1, except that it is coated with Formulation 23. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 86.74° is measured.

[0201] Example 24 The cell is prepared as in Example 1, except that it is coated with Formulation 24. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 87.02° is measured.

[0202] Example 25 The cell is prepared as in Example 1, except that it is coated with Formulation 25. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 86.55° is measured.

[0203] Example 26 The cell is prepared as in Example 1, except that it is coated with Formulation 26. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A pretilt angle of 86.37° is measured.

[0204] Example 27 The voltage holding ratio (VHR) of the cells is measured at 60°C using an LCM-1 instrument (Tokyo, Japan). The VHR was measured using short and long frame periods (T). With the short frame period, a voltage surge 64 μs voltage drop V (at T=16.67 ms) is then measured with V0 (V at t=0) = 1 V over a period of T=16.67 ms. Then, at room temperature, the voltage holding ratio is measured, which is given by integrating the measurement curve between V0 and V weighted by the area for 100% VHR. The table below shows the measured VHR for all test cells. The results show a VHR ≥ 99% for all test cells.

[0205] [Table 1]

[0206] Example 28: Determination of AC Memory (ACM) An AC voltage with a frequency of 60 Hz and an amplitude of 7.5 V is applied to the cells made in Examples 1-25. After 48 hours of stress, the cells are shorted and the change in pretilt angle is measured after 60 minutes of relaxation. The difference in the pretilt measurement before and after the stress-relaxation cycle gives the AC memory (ACM°). ACM° is excellent below -0.015°, very good between -0.016° and -0.030°, good between -0.031° and -0.045°, fair between -0.046° and -0.060° and poor for values ​​higher than -0.061°.

[0207] [Table 2]

[0208] Example 2 Example 49: Preparation of polyamic acid P15 4,10-Dioxatricyclo[6.3.1.0 2,70.672 g (3.00 mmol) of ]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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid P15 is obtained as a 30 wt % solution in NMP with an intrinsic viscosity [η] of 0.47 dL / g.

[0209] Example 50: Preparation of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-pentyl cyclohexanecarboxylate [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-pentylcyclohexanecarboxylate is prepared according to the three steps described in Examples 8a, 8b and 8c, but starting from 4-pentylcyclohexanecarboxylic acid instead of 4-(4-pentylcyclohexyl)cyclohexanecarboxylic acid. 1 H 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)

[0210] Example 51: Preparation of polyamic acid P16 4,10-Dioxatricyclo[6.3.1.0 2,70.672 g (3.00 mmol) of ]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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid P16 is obtained as a 30 wt% NMP solution with an intrinsic viscosity [η] of 0.63 dL / g.

[0211] Example 52: Preparation of polyamic acid P17 4,10-Dioxatricyclo[6.3.1.0 2,7 0.672 g (3.00 mmol) of ]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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid P17 is obtained as a 30 wt% NMP solution with an intrinsic viscosity [η] of 0.34 dL / g.

[0212] Example 53: Preparation of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]-2-methoxy-phenyl] 4-(4-pentylcyclohexyl)cyclohexanecarboxylate [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]-2-methoxy-phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate is prepared according to the three steps described in Examples 8a, 8b and 8c, but starting from 4-hydroxy-3-methoxy-benzaldehyde instead of 4-hydroxybenzaldehyde. 1 H 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)

[0213] Example 54: Preparation of polyamic acid P18 4,9-Dioxatricyclo[5.3.0.0 2,6 0.588 g (3.00 mmol) of 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 for 2 hours at 0° C. The mixture is then allowed to react at room temperature for 72 hours. Polyamic acid P18 is obtained as a 30 wt % NMP solution with an intrinsic viscosity [η] of 0.84 dL / g.

[0214] Example 55: Preparation of polyamic acid P19 4,9-Dioxatricyclo[5.3.0.02,6 0.588 g (3.00 mmol) of 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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid P19 is obtained as a 30 wt % NMP solution with an intrinsic viscosity [η] of 0.42 dL / g.

[0215] Example 56: Preparation of polyamic acid P20 4,9-Dioxatricyclo[5.3.0.0 2,6 0.588 g (3.00 mmol) of decane-3,5,8,10-tetrone is added to a solution of 110.0 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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid P20 is obtained as a 30 wt % NMP solution with an intrinsic viscosity [η] of 0.61 dL / g.

[0216] Example 57: Preparation of polyamic acid P21 4,10-Dioxatricyclo[6.3.1.0 2,70.672 g (3.00 mmol) of ]dodecane-3,5,9,11-tetrone is added to a solution of 0.673 g (1.2 mmol) of [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 then allowed to react at room temperature for 72 hours. Polyamic acid P21 is obtained as a 30 wt% NMP solution with an intrinsic viscosity [η] of 0.53 dL / g.

[0217] Example 58: Preparation of polyamic acid P22 4,10-Dioxatricyclo[6.3.1.0 2,7 0.672 g (3.00 mmol) of ]dodecane-3,5,9,11-tetrone is added to a solution of 1.178 g (2.1 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate and 0.288 g (0.9 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 then allowed to react at room temperature for 72 hours. Polyamic acid P22 is obtained as a 30 wt% NMP solution with an intrinsic viscosity [η] of 0.53 dL / g.

[0218] Example 59: Preparation of polyamic acid P23 4,9-Dioxatricyclo[5.3.0.0 2,60.588 g (3.00 mmol) of ]decane-3,5,8,10-tetrone is added to a solution of 0.841 g (1.5 mmol) of [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 then allowed to react at room temperature for 72 hours. Polyamic acid P23 is obtained as a 30 wt% NMP solution with an intrinsic viscosity [η] of 0.52 dL / g.

[0219] Example 60: Preparation of polyamic acid P24 4,9-Dioxatricyclo[5.3.0.0 2,6 0.588 g (3.00 mmol) of ]decane-3,5,8,10-tetrone is added to a solution of 0.757 g (1.35 mmol) of [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 then allowed to react at room temperature for 72 hours. Polyamic acid P24 is obtained as a 30 wt% NMP solution with an intrinsic viscosity [η] of 0.55 dL / g.

[0220] Example 61: Preparation of polyamic acid P25 4,9-Dioxatricyclo[5.3.0.0 2,60.588 g (3.00 mmol) of ]decane-3,5,8,10-tetrone is added to a solution of 0.757 g (1.35 mmol) of [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 then allowed to react at room temperature for 72 hours. Polyamic acid P25 is obtained as a 30 wt% NMP solution with an intrinsic viscosity [η] of 0.65 dL / g.

[0221] Example 62 Preparation of polyamic acid P26 4,9-Dioxatricyclo[5.3.0.0 2,6 0.588 g (3.00 mmol) of ]decane-3,5,8,10-tetrone is added to a solution of 1.346 g (2.4 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate and 0.192 g (0.6 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 then allowed to react at room temperature for 72 hours. Polyamic acid P26 is obtained as a 30 wt% NMP solution with an intrinsic viscosity [η] of 0.72 dL / g.

[0222] Example 63: Preparation of polyamic acid P27 4,9-Dioxatricyclo[5.3.0.0 2,60.588 g (3.00 mmol) of 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 for 2 hours at 0° C. The mixture is then allowed to react at room temperature for 72 hours. Polyamic acid P27 is obtained as a 30 wt % NMP solution with an intrinsic viscosity [η] of 0.61 dL / g.

[0223] Example 64: Preparation of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-ethylcyclohexyl)cyclohexanecarboxylate [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-ethylcyclohexyl)cyclohexanecarboxylate is prepared according to the three steps described in Examples 8a, 8b and 8c, but starting from 4-(4-ethylcyclohexyl)cyclohexanecarboxylic acid instead of 4-(4-pentylcyclohexyl)cyclohexanecarboxylic acid. 1 H 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)

[0224] Example 65: Preparation of polyamic acid P28 4,10-Dioxatricyclo[6.3.1.0 2,70.672 g (3.00 mmol) of ]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 for 2 hours at 0° C. The mixture is then allowed to react at room temperature for 72 hours. Polyamic acid P28 is obtained as a 30 wt % NMP solution with an intrinsic viscosity [η] of 0.30 dL / g.

[0225] Example 66: Preparation of [4-(4-pentylcyclohexyl)cyclohexyl]4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]benzoate [4-(4-pentylcyclohexyl)cyclohexyl]4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]benzoate is prepared following the two steps described in Examples 8b and 8c, but starting from (E)-3-[4-[4-(4-pentylcyclohexyl)cyclohexoxy]carbonylphenyl]prop-2-enoic acid instead of (E)-3-[4-[4-(4-pentylcyclohexyl)cyclohexanecarbonyl]oxyphenyl]prop-2-enoic acid. 1 H 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)

[0226] Example 67: Preparation of polyamic acid P29 4,10-Dioxatricyclo[6.3.1.0 2,70.672 g (3.00 mmol) of ]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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid P29 is obtained as a 30 wt % solution in NMP with an intrinsic viscosity [η] of 0.31 dL / g.

[0227] Example 68: Preparation of polyamic acid P30 4,10-Dioxatricyclo[6.3.1.0 2,7 0.672 g (3.00 mmol) of ]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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid P30 is obtained as a 30 wt% NMP solution with an intrinsic viscosity [η] of 0.29 dL / g.

[0228] Example 69: Preparation of polyamic acid P31 4,9-Dioxatricyclo[5.3.0.0 2,60.588 g (3.00 mmol) of ]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 then allowed to react at room temperature for 72 hours. Polyamic acid P31 is obtained as a 30 wt% NMP solution with an intrinsic viscosity [η] of 0.30 dL / g.

[0229] Example 70: Preparation of polyamic acid P32 4,10-Dioxatricyclo[6.3.1.0 2,7 0.672 g (3.00 mmol) of ]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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid P32 is obtained as a 30 wt% NMP solution with an intrinsic viscosity [η] of 0.29 dL / g.

[0230] Example 71: Preparation of polyamic acid P33 4,9-Dioxatricyclo[5.3.0.0 2,6 0.588 g (3.00 mmol) of ]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 for 2 hours at 0° C. The mixture is then allowed to react for 72 hours at room temperature. Polyamic acid P33 is obtained as a 30 wt% NMP solution with an intrinsic viscosity [η] of 0.54 dL / g.

[0231] Example 72: Preparation of Formulation 27 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P15, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 27.

[0232] Example 73: Preparation of Formulation 28 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P16, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 28.

[0233] Example 74: Preparation of Formulation 29 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P17, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 29.

[0234] Example 75: Preparation of Formulation 30 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P18, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 30.

[0235] Example 76: Preparation of Formulation 31 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P19, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 31.

[0236] Example 77: Preparation of Formulation 32 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P20, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 32.

[0237] Example 78: Preparation of Formulation 33 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P21, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 33.

[0238] Example 79: Preparation of Formulation 34 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P22, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 34.

[0239] Example 80: Preparation of Formulation 35 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P23, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 35.

[0240] Example 81: Preparation of Formulation 36 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P24, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 36.

[0241] Example 82: Preparation of Formulation 37 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P25, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 37.

[0242] Example 83: Preparation of Formulation 38 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P26, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give Formulation 38.

[0243] Example 84: Preparation of Formulation 39 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P27, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 39.

[0244] Example 85: Preparation of Formulation 40 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P28, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 40.

[0245] Example 86: Preparation of Formulation 41 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P29, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 41.

[0246] Example 87: Preparation of Formulation 42 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P30, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 42.

[0247] Example 88: Preparation of Formulation 43 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P31, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 43.

[0248] Example 89: Preparation of Formulation 44 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P32, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 44.

[0249] Example 90: Preparation of Formulation 45 To a solution of 2.125 g of polyamic acid PX1 and 0.250 g of polyamic acid P33, 2.875 g of NMP and 4.751 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 μm PTFE filter to give formulation 45.

[0250] Application example part 2 Example 29 Formulation 27 is spin-coated onto two ITO-coated glass substrates at a spin speed of about 2000 rpm for 30 seconds. After spin-coating, the substrates are subjected to a baking procedure consisting of a pre-bake at 80°C for 90 seconds and a post-bake at 200°C for 40 minutes. The substrates are then exposed to linearly polarized light at an incidence angle of 40° relative to the normal to the substrate plane (22 mJ.cm -2 -LPUVB). The polarization plane is parallel to the long side of the substrate. The two substrates are used to assemble a cell such that the exposed polymer layers face each other inside the cell. The substrates are adjusted relative to each other so that the induced alignment directions are parallel to each other. The cell is capillary filled with liquid crystal MLC-6610 (Merck KGA-Δε<0). Finally, the filled cell is further subjected to thermal annealing at 130° C. for 10 min, thereby completing the cell processing. The liquid crystal in the cell exhibits a well-defined and uniform vertical alignment before and after the thermal annealing of the cell. A tilt angle of 88.27 is measured using the Shintech rotating analyzer method.

[0251] Example 30 The cell is prepared as in Example 29, except that it is coated with Formulation 28. The liquid crystal in the cell shows a well-defined and uniform vertical alignment before and after thermal annealing of the cell. Using the Shintech rotating analyzer method, a tilt angle of 88.04 is measured.

[0252] Example 31 The cell is prepared as in Example 29, except that it is coated with Formulation 29. The liquid crystal in the cell shows a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A tilt angle of 88.17 is measured using the Shintech rotating analyzer method.

[0253] Example 32 The cell is prepared as in Example 29, except that it is coated with Formulation 30. The liquid crystal in the cell shows a well-defined and uniform vertical alignment before and after thermal annealing of the cell. Using the Shintech rotating analyzer method, a tilt angle of 88.14 is measured.

[0254] Example 33 The cell is prepared as in Example 29, except that it is coated with Formulation 31. The liquid crystal in the cell shows a well-defined and uniform vertical alignment before and after thermal annealing of the cell. Using the Shintech rotating analyzer method, a tilt angle of 88.21 is measured.

[0255] Example 34 The cell is prepared as in Example 29, except that it is coated with Formulation 32. The liquid crystal in the cell shows a well-defined and uniform vertical alignment before and after thermal annealing of the cell. Using the Shintech rotating analyzer method, a tilt angle of 88.16 is measured.

[0256] Example 35 The cell is prepared as in Example 29, except that it is coated with Formulation 33. The liquid crystal in the cell shows a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A tilt angle of 87.97 is measured using the Shintech rotating analyzer method.

[0257] Example 36 The cell is prepared as in Example 29, except that it is coated with Formulation 34. The liquid crystal in the cell shows a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A tilt angle of 87.17 is measured using the Shintech rotating analyzer method.

[0258] Example 37 The cell is prepared as in Example 29, except that it is coated with Formulation 35. The liquid crystal in the cell shows a well-defined uniform vertical alignment before and after thermal annealing of the cell. Using the Shintech rotating analyzer method, a tilt angle of 87.01 is measured.

[0259] Example 38 The cell is prepared as in Example 29, except that it is coated with Formulation 36. The liquid crystal in the cell shows a well-defined and uniform vertical alignment before and after thermal annealing of the cell. Using the Shintech rotating analyzer method, a tilt angle of 87.23 is measured.

[0260] Example 39 The cell is prepared as in Example 29, except that it is coated with Formulation 37. The liquid crystal in the cell shows a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A tilt angle of 87.38 is measured using the Shintech rotating analyzer method.

[0261] Example 40 The cell is prepared as in Example 29, except that it is coated with Formulation 38. The liquid crystal in the cell shows a well-defined uniform vertical alignment before and after thermal annealing of the cell. Using the Shintech rotating analyzer method, a tilt angle of 87.04 is measured.

[0262] Example 41 The cell is prepared as in Example 29, except that it is coated with Formulation 39. The liquid crystal in the cell shows a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A tilt angle of 86.67 is measured using the Shintech rotating analyzer method.

[0263] Example 42 The cell is prepared as in Example 29, except that it is coated with Formulation 40. The liquid crystal in the cell shows a well-defined and uniform vertical alignment before and after thermal annealing of the cell. Using the Shintech rotating analyzer method, a tilt angle of 88.64 is measured.

[0264] Example 43 The cell is prepared as in Example 29, except that it is coated with Formulation 41. The liquid crystal in the cell shows a well-defined and uniform vertical alignment before and after thermal annealing of the cell. Using the Shintech rotating analyzer method, a tilt angle of 88.18 is measured.

[0265] Comparative Example 44 The cell is prepared as in Example 29, except that it is coated with Formulation 42. The liquid crystal in the cell shows a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A tilt angle of 88.27 is measured using the Shintech rotating analyzer method.

[0266] Comparative Example 45 The cell is prepared as in Example 29, except that it is coated with Formulation 43. The liquid crystal in the cell shows a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A tilt angle of 87.89 is measured using the Shintech rotating analyzer method.

[0267] Comparative Example 46 The cell is prepared as in Example 29, except that it is coated with Formulation 44. The liquid crystal in the cell shows a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A tilt angle of 88.29 is measured using the Shintech rotating analyzer method.

[0268] Comparative Example 47 The cell is prepared as in Example 29, except that it is coated with Formulation 45. The liquid crystal in the cell shows a well-defined and uniform vertical alignment before and after thermal annealing of the cell. A tilt angle of 86.66 is measured using the Shintech rotating analyzer method.

[0269] Example 48 The voltage holding ratio (VHR) of the cells is measured at 60° C. using an LCM-1 instrument (Tokyo, Japan). The VHR was measured using short and long frame periods (T). With the short frame period, a voltage surge 64 μs voltage drop V (at T=16.67 ms) is then measured with V0 (V at t=0)=1 V over a period of T=16.67 ms. Then, at room temperature, the voltage holding ratio is measured, which is given by integrating the measurement curve between V0 and V weighted by the area for 100% VHR. The table below shows the VHR measured for all test cells. The results show a VHR≧99% for all test cells except for comparative examples 44, 45 and 46, which resulted in poor electrical properties.

[0270] [Table 3]

[0271] Example 49: Determination of AC Memory (ACM) An AC voltage with a frequency of 60 Hz and an amplitude of 7.5 V is applied to the cells made in Examples 1-25. After 48 hours of stress, the cells are shorted and the change in pretilt angle is measured after 60 minutes of relaxation. The difference in the pretilt measurement before and after the stress-relaxation cycle gives the AC memory (ACM°). ACM° is excellent below -0.015°, very good between -0.016° and -0.030°, good between -0.031° and -0.045°, fair between -0.046° and -0.060° and poor for values ​​higher than -0.061°.

[0272] [Table 4]

Claims

1. Formula (I) 【Chemistry 11】 [In the formula, M １ , M ２ and M ３ are, independently of one another, monocyclic rings of 5 or 6 atoms; two adjacent monocyclic rings of 5 or 6 atoms, bicyclic ring systems of 8, 9 or 10 atoms, tricyclic ring systems of 13 or 14 atoms, as well as mono-, bi- and tricyclic rings, which are unsubstituted or di-(C １ -C ２０ alkyl)amino, C １ -C ６ substituted by alkyloxy, nitro, cyano and / or chlorine or fluorine; and ２ - groups may be independently replaced by a linking group, linear or branched, substituted or unsubstituted C １ -C ２０ represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic or non-aromatic diamine group selected from mono-, bi-, or tricyclic rings linked by alkanediyl; D １ , D ２ and D ３ represent, independently of one another, an unsubstituted or substituted aliphatic, alicyclic or carbocyclic or heterocyclic aromatic group substituted with at least two carboxylic acid groups, or activated carboxyl groups, or anhydride groups; m １ , m ２ or m ３ are independent of each other, 0<m １ <1, 0≦m ２ ≦0.7 and 0≦m ３ represents the mole fraction of comonomer that is <1; S １ and S ２ represent, independently of each other, spacer units, E １ and E ２ are each independently an aromatic group, an oxygen atom, a sulfur atom, -NH-, -N(C １ -C ６ alkyl)-, -CR ４ R ５ where R ４ and R ５ are each independently hydrogen or a cyclic, linear or branched, substituted or unsubstituted C １ -C ３０ alkyl, wherein one or more of C—, CH—, CH ２ - groups may be replaced independently of each other by a linking group, provided that R ４ and R ５ is not hydrogen; A represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic group; Z １ , Z ２ , Z ３ and Z ４ represent, independently of one another, a bridging group, Q １ and Q ２ are each independently a single bond or a linear or branched, substituted or unsubstituted C １ -C ２０ represents an alkanediyl, wherein the alkanediyl is unsubstituted or di-(C １ -C ２０ alkyl)amino, C １ -C ６ substituted by alkyloxy, nitro, cyano and / or chlorine or fluorine; and ２ - groups may be independently replaced by linking groups; R ２ is hydrogen or a straight or branched C １ -C ２０ alkyl, wherein the alkyl is unsubstituted or di-(C １ -C ２０ alkyl)amino, C １ -C ６ substituted by alkyloxy, nitro, cyano and / or chlorine or fluorine; and ２ - groups may be independently replaced by linking groups; R １ and R ３ are each independently hydrogen or C ｃ H α F β where c is an integer from 0 to 20, and α and β are each an integer from 0 to 2c+1, where α+β=2c+1; T １ , T ２ , T ３ , T ４ and T ５ are, independently of one another, hydrogen, halogen, hydroxyl, nitro, cyano or carboxy groups, and / or cyclic, linear or branched C １ -C ３０ represents alkyl, which is unsubstituted or mono- or polysubstituted with halogen, acryloyloxy, alkylacryloyloxy, alkoxy, alkylcarbonyloxy, alkyloxycarbonyloxy, alkyloxocarbonyloxy, vinyl, vinyloxy and / or allyloxy groups; n １ is 0, 1 or 2, n ３ , n ４ , n ５ , n ６ and n ７ are, independently of one another, 0, 1, 2 or 3; w ３ represents 0, 1, 2, 3 or 4; w １ and w ２ are each independently 1, 2, 3 or 4, However, w １ Or w ２ If is 2, 3, or 4, then each S １ and S ２ , E １ and E ２ , Z １ , Z ２ , Z ３ and Z ４ , Q １ and Q ２ , R ２ , R １ and R ３ , T １ , T ２ , T ３ , T ４ and T ５ , n １ , n ３ , n ４ , n ５ , n ６ and n ７ may be the same or different] A compound represented by the formula:

2. 2. The compound of claim 1, wherein A is a substituted or unsubstituted phenylene, naphthalene, biphenylene, or triphenylene ring.

3. m １ , m ２ or m ３ are independent of each other, 0<m １ <1, 0≦m ２ ≦0.5 and 0≦m ３ 2. The compound of claim 1, wherein the molar fraction of comonomer is <1.

4. R ２ is hydrogen, linear or branched C １ -C ６ alkyl; or straight or branched C １ -C １６ The compound of claim 1 , which represents a fluoroalkyl group.

5. A composition comprising at least one compound of formula (I) as defined in claim 1.

6. At least one diamine M １ , M ２ or M ３ and at least one D, which independently represent an unsubstituted or substituted aliphatic, alicyclic or carbocyclic or heterocyclic aromatic group substituted with at least two carboxylic acid groups, or activated carboxyl groups, or anhydride groups. １ , D ２ and D ３ 2. A process for the preparation of compound (I) as defined in claim 1, comprising polymerizing

7. A polymeric, copolymeric or oligomeric layer comprising a compound of formula (I) as defined in claim 1.

8. Use of a compound according to any one of claims 1 to 4 or a composition according to claim 5 in the manufacture of an optical or electro-optical device.

9. An optical or electro-optical device comprising a compound according to any one of claims 1 to 4, a composition according to claim 5 or a layer of a polymer, copolymer or oligomer according to claim 7.

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