Composition for forming liquid crystal alignment film

Abstract

The composition for forming a liquid crystal alignment film includes a photoalignable polymer material having a side chain containing a photoalignable group for forming a liquid crystal alignment film, and a solvent mixture. The solvent mixture includes (i) at least one of N-alkylpyrrolidone and lactone in a total amount of 45 to 70 wt %, (ii) diethylene glycol dialkyl ether in an amount of 5 to 15 wt %, and (iii) ethylene glycol monoalkyl ether in an amount added to bring the solvent mixture to 100 wt %. The composition has a solids content of 3.0 to 6.0 wt %. The composition can improve coating properties while also allowing for thicker film thickness near the boundaries of printed films without compromising film uniformity.

Description

[Technical Field]

[0001] The present invention relates to compositions for forming liquid crystal alignment films, methods for forming liquid crystal alignment films, liquid crystal alignment films, and structured or unstructured optical and electro-optical elements and devices comprising liquid crystal alignment films.

[0002] A liquid crystal device provides a display by controlling the alignment direction of liquid crystal molecules contained in the liquid crystal layer by applying a voltage to electrodes arranged on the liquid crystal layer side of the substrate. A liquid crystal display device usually includes a liquid crystal alignment film for controlling the alignment direction of the liquid crystal molecules, and this alignment film is arranged on the liquid crystal layer side of the substrate.

[0003] Resins such as polyamic acid, polyimide, polyamide, polysiloxane, polymaleimide, and polyacrylate have been used as materials for the alignment films that constitute such liquid crystal display devices. For example, alignment films containing polyimide have been found to exhibit excellent physical properties, such as heat resistance, compatibility with liquid crystals, and mechanical strength.

[0004] Methods for printing alignment films include spin coating, roll coating, flexographic printing and inkjet printing. Inkjet printing is suitable for printing films on large substrates with high throughput.

[0005] However, inkjet printing is limited by the narrow optimal range of ink physical properties. For example, the optimal range for surface tension is 28–40 mN / m, the optimal range for viscosity is 5–12 mPa·s, and the optimal range for solvent boiling point is approximately 180–210°C. Although numerous solvents and their combinations are available, optimizing the ink components and their ratios so that the ink can meet various, sometimes conflicting, requirements is no easy task.

[0006] Defects in the alignment layer coating process can manifest themselves as defects in the display panel's visual quality when the alignment film is molded into a panel. These defects are called "mura" (the Japanese word for "blemish"). Mura refers to large patterns of uneven brightness across the display. Conventional inkjet printers used in inkjet printing have multiple heads arranged perpendicular to the printing direction. If the ink dries before leveling, stripes of irregular film thickness can occur, resulting in display unevenness. Therefore, to improve the ink's leveling behavior, conventionally, low-surface-tension, low-boiling-point solvents, such as alcohols, ketones, or esters, are added to the ink, thereby improving the ink's wetting and spreading properties.

[0007] Although ink wetting and spreading improves the film uniformity of the alignment layer, excessive spreading can lead to a type of defect called "frame unevenness," which is associated with a decrease in alignment effectiveness near the borders of the printed film. This phenomenon is caused by a decrease in the alignment film thickness near the edges of the printed film, which in turn leads to ink spreading beyond the printed area.

[0008] Therefore, there is a need to further improve the coating properties of the ink, particularly the spreading properties, in order to increase the film thickness near the boundary of the printed film without deteriorating the film uniformity.

[0009] JP 2006017982 describes a liquid crystal aligning agent for inkjet coating, which comprises a polymer having at least one of an amic acid repeating unit and an imidized repeating unit thereof, and N-methylpyrrolidone.

[0010] A liquid crystal aligning agent is described in CN No. 102031122. Comparative Example 2 illustrates a solvent composition containing NMP, butyl cellosolve, γ-butyrolactone and diethylene glycol ethyl methyl ether.

[0011] EP 2375278 describes a composition for forming a liquid crystal alignment film, which contains materials for forming a liquid crystal alignment film: 4,6-dimethyl-2-heptanone; diisobutyl ketone, and at least one of γ-butyrolactone and N-methyl-2-pyrrolidone.

[0012] The present inventors have discovered that the above objectives can be achieved by selecting a particular solvent mixture useful for ink jet printing.

[0013] Therefore, the present invention provides a composition for forming a liquid crystal alignment film, comprising: - a photoalignable polymer material having a side chain containing a photoalignable group for forming a liquid crystal alignment film; a solvent mixture containing, relative to the weight of the solvent mixture, (i) at least one of N-alkylpyrrolidone and lactone in a total amount of 45 to 70% by weight, (ii) diethylene glycol dialkyl ether in an amount of 5 to 15% by weight, and (iii) ethylene glycol monoalkyl ether in an amount sufficient to add up to 100% by weight of the solvent mixture; The composition has a solids content of 3.0 to 6.0% by weight.

[0014] The solvent mixture comprises (i) at least one of an N-alkylpyrrolidone and a lactone; (ii) an ethylene glycol monoalkyl ether; and (iii) a diethylene glycol dialkyl ether.

[0015] In the N-alkylpyrrolidone, the alkyl moiety may be linear or branched. Suitable N-alkylpyrrolidones include N-(C1-C8-alkyl)pyrrolidones, in particular N-(C1-C4-alkyl)pyrrolidones, such as N-methylpyrrolidone, N-ethylpyrrolidone, and N-propylpyrrolidone. A particularly preferred N-alkylpyrrolidone is N-methyl-2-pyrrolidone.

[0016] Suitable lactones include α-lactones such as α-acetolactone, β-lactones such as β-propiolactone, γ-lactones such as γ-butyrolactone, and δ-lactones such as δ-valerolactone. β-lactone, γ-lactone, and δ-valerolactone are preferred, especially γ-lactone and δ-valerolactone. A particularly preferred lactone is γ-butyrolactone.

[0017] In the ethylene glycol monoalkyl ether, the alkyl moiety may be linear or branched. Suitable ethylene glycol monoalkyl ethers (glycol ethers) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, and ethylene glycol monobutyl ether. A particularly preferred ethylene glycol monoalkyl ether is ethylene glycol monobutyl ether.

[0018] In the diethylene glycol dialkyl ether, the alkyl moiety may be linear or branched. Suitable diethylene glycol dialkyl ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether. A particularly preferred diethylene glycol dialkyl ether is diethylene glycol diethyl ether.

[0019] In a preferred embodiment, the solvent mixture comprises both an N-alkylpyrrolidone and a lactone. Preferably, the solvent mixture comprises 20-40 wt% N-alkylpyrrolidone and 20-40 wt% lactone, based on the weight of the solvent mixture, with the proviso that the sum of the amounts of N-alkylpyrrolidone and lactone is 45-70 wt%.

[0020] In a more preferred embodiment, the solvent mixture comprises (i) at least one of N-alkylpyrrolidone and lactone in a total amount of 55 to 65 wt % based on the weight of the solvent mixture, (ii) diethylene glycol dialkyl ether in an amount of 7 to 13 wt % based on the weight of the solvent mixture, and (iii) ethylene glycol monoalkyl ether in an amount sufficient to bring the solvent mixture to 100 wt %. Preferably, the solvent mixture comprises 25 to 35 wt % N-alkylpyrrolidone and 25 to 35 wt % lactone based on the weight of the solvent mixture, with the proviso that the total amount of N-alkylpyrrolidone and lactone is 55 to 65 wt % based on the weight of the solvent mixture.

[0021] In one embodiment, the N-alkylpyrrolidone is N-methylpyrrolidone, the lactone is γ-butyrolactone, the ethylene glycol monoalkyl ether is ethylene glycol monobutyl ether, and the diethylene glycol dialkyl ether is diethylene glycol diethyl ether.

[0022] The composition has a solids content of 3.0 to 6.0 wt %, preferably 3.5 to 5.5 wt %, more preferably 3.5 to 5.0 wt %, and most preferably 3.7 to 4.7 wt %, including the photoalignable polymeric material and the additional polymeric material.

[0023] Photoalignable polymeric materials are photoactive polymeric compounds that contain photoalignable groups. It is understood that the composition may contain more than one photoalignable polymeric material.

[0024] Suitable photoalignable polymeric materials are well known in the field of liquid crystal alignment materials.Such materials are used to prepare liquid crystal alignment films for manufacturing optical and electro-optical devices, and are disclosed in, for example, the following publications: O. Yaroshuk, Y. Renikov, J. Mater.Chem., 2012, 22, 286-300 and the references cited therein; US Pat. No. 5,389,698, US Pat. No. 5,838,407, US Pat. No. 5,602,661, US Pat. No. 6,160,597, US Pat. No. 6,369,869, US Pat. No. 6,717,644, US Pat. No. 6,215,539, US Pat. No. 6,300,991 and US Pat. No. 6,608,661.

[0025] When irradiated with alignment light, especially polarized light, the photoalignable groups undergo photoreactions, such as photocrosslinking, dimerization, cis / trans isomerization, rearrangement, and decomposition. As a result, anisotropy is induced in the photoalignment layer. Liquid crystals contained in a layer formed on the alignment film can be aligned under the influence of such a photoinduced alignment film.

[0026] The photoalignable polymeric material containing a photoalignable group is a polymer, including a copolymer, having a side chain containing at least one photoalignable group, and preferably the side chain contains one or more aromatic or alicyclic groups in addition to the photoalignable group.

[0027] In one embodiment, the photo-alignment group is selected from cinnamates and chalcones; coumarins and quinolones; stilbenes and cyanostilbenes; azo groups; chromones and chromenes; mono- and di-acetylene groups, such as diphenylacetylene groups; benzylidenephthalimide groups, benzylideneacetophenone groups, and / or phenylenediacryloyl groups. The photo-alignment group is optionally substituted. The photo-alignment material may contain one or more photo-alignment groups.

[0028] Preferably, the photo-orientable group is selected from cinnamates and chalcones; coumarins; stilbenes and azo groups. In a particularly preferred embodiment, the photo-orientable group is a cinnamate.

[0029] Suitable photo-alignable groups are represented by the following formulas (I) to (VI). As will be described later, the photo-alignable group is connected at one end thereof (in the general formula, an asterisk) via a single bond, a linking group, or a spacer group. * The far end has a monovalent residue attached to the polymer backbone.

[0030] [ka]

[0031] The term "subst." means any substituent described below.

[0032] Formula (I) represents a cinnamate group as an example of an α,β-unsaturated carbonyl group, where X is -O-; -S- or -NR a - and R a is hydrogen or C1-C6-alkyl.

[0033] Formula (II) represents a chalcone group.

[0034] Formula (III) represents an azo group.

[0035] Formula (IV) represents a stilbene group, where Y is hydrogen, nitrile (cyano, CN) or another electron-withdrawing group.

[0036] Formula (V) represents a coumarin group.

[0037] Formula (VI) represents an α,β-unsaturated nitrile group.

[0038] The photoalignable group may be linked to the polymer backbone via a single bond, a linking group such as an ester group, a thioester group, an ether group, a carbonate group, an amide group, or a sulfide group, or via a spacer group. Preferably, the photoalignable group is linked to the polymer backbone via a spacer group. The term "spacer group" refers to an optionally substituted aromatic or heteroaromatic group having 6 to 40 carbon atoms, or preferably a cyclic, linear, or branched, optionally substituted C1-C 24 -alkylene group, in which one or more non-adjacent -CH2- groups are each independently -O-, -CO-, -CO-O-, -O-CO, -NR b -, -NR b -CO-, -CO-NR b -, -NR b -CO-O-, -O-CO-NR b -, -NR b -CO-NR b may be replaced by a group selected from -, -CH=CH-, -C≡C-, -O-CO-O- and -(CH3)2Si-O-Si(CH3)2-, wherein R b represents a hydrogen atom or a C1-C6 alkyl group.

[0039] The photoalignable group is optionally substituted. Suitable substituents include halogen, such as fluorine, chlorine and bromine; cyano; C1-C4-alkoxy; carboxyl groups; linear or branched C1-C4 alkyl groups optionally substituted with fluorine or cyano groups. 12 -alkyl-containing ester groups, including linear or branched alkyl and cycloalkyl groups having 1 to 12 carbon atoms, optionally substituted with fluorine or cyano groups, and / or aromatic groups having 6 to 18 carbon atoms, optionally substituted with the aforementioned groups. In a preferred embodiment, the side chain contains one or more fluorine atoms.

[0040] The backbone of the photo-alignable polymer material is not particularly limited and can be selected from polyamic acid, polyimide, polyamide, polysiloxane, polymaleimide, and polyacrylate. However, particularly preferred photo-alignable polymer materials are polysiloxane and polyamic acid polymer, preferably homopolymer and copolymer, more preferably copolymer. Polyamic acid polymer and polysiloxane exhibit excellent film-forming properties. Polyamic acid polymer can be converted into polyimide by heat treatment. Next, polyimide and polysiloxane have been found to exhibit excellent physical properties, such as heat resistance, compatibility with liquid crystal, and mechanical strength.

[0041] Therefore, in one embodiment, the polymeric photoalignment material for forming liquid crystal alignment is represented by the formula (1): [ka] [In the formula, Q is a tetravalent residue of a tetracarboxylic dianhydride; P is a divalent residue of a diamine, where at least a portion of P has a side chain containing a photoalignable group. The repeating unit includes a repeating unit represented by the formula:

[0042] The tetravalent residue Q is understood to be equivalent to the residue of a tetracarboxylic acid (based on a tetracarboxylic dianhydride) minus the four carboxyl groups.

[0043] The divalent residue P is understood to be equivalent to the residue of a diamine minus two amino groups, and at least some of the Ps have side chains containing photoalignable groups.

[0044] Preferably, the photo-orientable group is selected from cinnamates of formula (I), azo groups of formula (III), coumarins of formula (V), and stilbenes of formula (IV), which may be optionally substituted. In one embodiment, P comprises one or two cinnamate groups of formula (I), each independently containing up to three substituents "subst."

[0045] In a preferred embodiment, the side chains contain, in addition to the photoalignable group, one or more aromatic or alicyclic groups. Suitable aromatic groups include phenylene. Suitable alicyclic groups include cyclohexyl, bicyclohexyl, and tricyclohexyl.

[0046] Polymeric photoalignable materials containing repeating units represented by formula (I) are typically obtained by polymerizing at least one diamine with an acid dianhydride, where at least a portion of the diamine has at least one photoalignable group.

[0047] The diamine preferably has the general formula [ka] [In the formula, residue P A preferably includes a photoalignable group represented by one of formulas (I) to (VI), more preferably formula (I), wherein the optional substituent is a methyl, ethyl, halogen, or methoxy group. The compound is selected from optionally substituted compounds of the formula:

[0048] In one embodiment, residue P A teeth, [ka] [In the formula, A represents an optionally substituted aromatic or heteroaromatic ring having 5 or 6 atoms, preferably an optionally substituted phenylene; each B independently represents an optionally substituted aromatic, heteroaromatic or alicyclic group selected from a monocyclic ring of 5 or 6 ring atoms, a bicyclic ring system of 8, 9 or 10 ring atoms, a tricyclic ring system of 13 or 14 ring atoms, a fused ring system of 8 to 20 ring atoms or a bridged ring system comprising 8 to 20 ring atoms and a bridging group selected from -O-, -CO-, -CO-O-, -O-CO-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-CO-O-, -O-CO-NR'-, -NR'-CO-NR'-, -CH=CH-, -C≡C-, -O-CO-O- and -(CH3)2Si-O-Si(CH3)2-, where R' represents a hydrogen atom or a C1-C6-alkyl group; Z 1 and Z 2 each independently represents a bridging group selected from -O-, -CO-, -CO-O-, -O-CO-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-CO-O-, -O-CO-NR'-, -NR'-CO-NR'-, -CH=CH-, -C≡C-, -O-CO-O- and -(CH3)2Si-O-Si(CH3)2- (wherein R' represents a hydrogen atom or a C1-C6 alkyl group), R 1 and R 2 are each independently hydrogen, halogen or nitrile; R 3 is an optionally substituted C1-C 30 -Alkyl or O-C1-C 30 -alkyl, which may be substituted by at least one of halogen or nitrile, preferably fluorine, m is an integer of 0 to 4, preferably 1 or 2; n is an integer of 0 to 6, preferably 1 or 2, more preferably 2; o is an integer of 0 to 2, preferably 0 or 1, more preferably 0. It is expressed as:

[0049] In preferred embodiments, each B independently represents an optionally substituted aromatic or alicyclic group selected from a monocyclic ring of 5 or 6 ring atoms, a bicyclic ring system of 8, 9 or 10 ring atoms, or a tricyclic ring system of 13 or 14 ring atoms. More preferably, each B independently represents optionally substituted phenylene, cyclohexyl, bicyclohexyl, or tricyclohexyl, especially optionally substituted phenylene, cyclohexyl, or bicyclohexyl.

[0050] Preferably, Z 1 and Z 2 is selected from -O- and O-CO-. More preferably, Z 1 is -O-CO-.

[0051] In a preferred embodiment, R 1 and R 2 are each independently hydrogen, nitrile or fluorine. More preferably, R 1 and R 2 is hydrogen.

[0052] Preferably, R 3 represents optionally substituted C1-C6-alkyl, where the substituents are selected from nitrile and halogen, preferably fluorine, where the substituents are preferably located in the terminal position. 3 is selected from C1-C6-alkyl and fluorinated C1-C6-alkyl, in particular unsubstituted C2-C6-alkyl and C2-C6-alkyl containing a terminal trifluoromethyl moiety.

[0053] In a preferred embodiment, the residue P A teeth, [ka] is selected from.

[0054] The tetravalent organic residue Q of the tetracarboxylic dianhydride can be obtained from an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, or an aromatic tetracarboxylic dianhydride. Preferably, the tetravalent organic residue Q of the tetracarboxylic dianhydride is obtained from an alicyclic tetracarboxylic dianhydride.

[0055] Suitable tetracarboxylic dianhydrides are well known in the field of liquid crystal alignment materials and are used as monomers or comonomers to prepare liquid crystal alignment films for rubbing or photoalignment techniques. Suitable dianhydrides are represented by the formula (VII): [ka] This includes dianhydrides represented by the formula:

[0056] Examples of suitable aliphatic or alicyclic tetracarboxylic dianhydrides are: 4,9-Dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone; 4,10-Dioxtrisacyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone; 2,3,5-Tricarboxy-cyclopentylacetic acid-1,2:3,4-dianhydride (all isomers); 1,2,3,4-Cyclobutanetetracarboxylic dianhydride; 1,3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride; 1,3-Dimethyl-1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride; 1,2,3,4-Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride; 1,2,3,4-Cyclopentanetetracarboxylic dianhydride; 2,3,5-Tricarboxycyclopentylacetic dianhydride; 3,5,6-Tricarboxynorbornane-2-acetic dianhydride; 2,3,4,5-Tetrahydrofurantetracarboxylic dianhydride; 5-(2,5-dioxotetrahydro-3-furanyl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione; 5-(2,5-dioxotetrahydro-3-furanyl)-5-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione; 5-(2,5-dioxotetrahydro-3-furanyl)-5-ethyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione; 5-(2,5-dioxotetrahydro-3-furanyl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione; 5-(2,5-dioxotetrahydro-3-furanyl)-7-ethyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione; 5-(2,5-dioxotetrahydro-3-furanyl)-6-methylhexahydro-2-benzofuran-1,3-dione; 6-(2,5-dioxotetrahydro-3-furanyl)-4-methylhexahydro-2-benzofuran-1,3-dione; 5-(2,5-dioxotetrahydrofural)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride; Bicyclo[2.2.2]octan-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 acid dianhydride; Tetrahydro-4,8-methanofuro[3,4-d]oxepin-1,3,5,7-tetrone; 3-(Carboxymethyl)-1,2,4-cyclopentanetricarboxylic acid 1,4:2,3-dianhydride; Hexahydrofuro[3',4':4,5]cyclopenta[1,2-c]pyran-1,3,4,6-tetrone; 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 acid dianhydride; 5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride; 4-tert-butyl-6-(2,5-dioxotetrahydro-3-furanyl)-2-benzofuran-1,3-dione; 9-Isopropyloctahydro-4,8-ethenofuro[3',4':3,4]cyclobuta[1,2-f][2]benzofuran-1,3,5,7-tetrone; 1,2,5,6-cyclooctanetetracarboxylic dianhydride; Octahydro-4,8-ethenofuro[3',4':3,4]cyclobuta[1,2-f][2]benzofuran-1,3,5,7-tetrone; Octahydrofuro[3',4':3,4]cyclobuta[1,2-f][2]benzofuran-1,3,5,7-tetrone; Tetrahydro-3,3'-bifuran-2,2',5,5'-tetrone and Tetrahydro-5,9-methano-1H-pyrano[3,4-d]oxepin-1,3,6,8(4H)-tetrone Includes.

[0057] Examples of suitable 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)diphenyl 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; 4,4'-methylenedi(1,4-phenylene)bis(phthalic)dianhydride and 4-tert-butyl-6-(2,5-dioxotetrahydro-3-furanyl)-2-benzofuran-1,3-dione Includes.

[0058] Particularly preferred examples of suitable tetracarboxylic dianhydrides are: 4,9-Dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone; 4,10-Dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone; 1,2,3,4-Cyclobutanetetracarboxylic dianhydride; 1,2,3,4-Cyclopentanetetracarboxylic dianhydride; 2,3,5-Tricarboxycyclopentylacetic dianhydride; Tetrahydro-4,8-methanofuro[3,4-d]oxepin-1,3,5,7-tetrone; 3-(Carboxymethyl)-1,2,4-cyclopentanetricarboxylic acid 1,4:2,3-dianhydride; Hexahydrofuro[3',4':4,5]cyclopenta[1,2-c]pyran-1,3,4,6-tetrone; 5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride; Pyromellitic dianhydride; 4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride; 5-(2,5-dioxotetrahydro-3-furanyl)-5-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione; 5-(2,5-dioxotetrahydro-3-furanyl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione; 5-(2,5-dioxotetrahydro-3-furanyl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione; 4-tert-butyl-6-(2,5-dioxotetrahydro-3-furanyl)-2-benzofuran-1,3-dione; 4,4'-(Hexafluoroisopropylidene)diphthalic dianhydride and Bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and Tetrahydro-5,9-methano-1H-pyrano[3,4-d]oxepin-1,3,6,8(4H)-tetrone Includes.

[0059] Most preferably, the tetracarboxylic dianhydride is selected from 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone and 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone.

[0060] In one embodiment, the composition contains a polymeric material other than the specific photoalignable polymeric material described above (hereinafter, "additional polymeric material").

[0061] In a preferred embodiment, the additional polymeric material can be obtained by reacting the above-described tetracarboxylic dianhydride with a diamine. The diamine typically has 6 to 40 carbon atoms. Suitable diamines include aliphatic diamines, alicyclic diamines, and / or diamines containing aryl groups. These can be used alone or in combination of two or more.

[0062] Suitable aliphatic diamines include those of formula (VIII): H2N-Alkylene-NH2(VIII) wherein the term "alkylene" means C1 to C 24 Alkylene, preferably C1-C 12 It has the meaning of alkylene, which is branched, straight chain, optionally substituted, optionally interrupted by a linking group as defined above, or an alicyclic group, such as cyclohexylene or C 17 ~C 40 is an alicyclic group, or Si(R c )2- or -O-Si(R c )2-, where R c is hydrogen, fluorine, chlorine, nitrile, unsubstituted or fluorine-substituted C1-C 12 alkyl (wherein one or more carbon atoms, -CH= or CH2- groups may be replaced by a linking group); preferably represents hydrogen, methyl or fluorine, more preferably hydrogen); The present invention includes compounds represented by the formula:

[0063] Suitable cycloaliphatic diamines are represented by the formulae (IX) and (X): [ka] [where, X 4is a linking group as defined above, preferably -COO-, -CONH-; a single bond, -O-, -S-, methylene, ethylene, propylene, more preferably a single bond or methylene, ethylene, propylene, butylene or pentylene optionally substituted by CF3, OCF3, F, in which the cyclohexylene groups are unsubstituted or each independently substituted by hydrogen, halogen, hydroxyl, a carbocyclic or heterocyclic non-aromatic group or a C1-C 30 It may be mono- or polysubstituted by alkyl, which may be branched, straight-chain, optionally substituted, optionally interrupted by a linking group as defined above, more preferably a carbocyclic or heterocyclic non-aromatic group, such as cyclohexylene or C 17 ~C 40 The cycloaliphatic groups, more preferably the cyclohexylene groups, are each independently substituted by halogen or optionally substituted by methylene, ethylene or propylene. The present invention includes compounds represented by the formula:

[0064] Suitable aromatic diamines or diamines containing aryl groups are optionally substituted and have the formula (XI): [ka] [where, X 5 is a single bond or C1-C 30 alkyl, where C1-C 30 Alkyl is preferably methyl, ethyl, propyl, butyl or pentyl. or a compound represented by (XII) [ka] [where, X 6 is a linking group as defined above, preferably X 6 is, for example, a single bond, -O-, -S- or optionally linear or branched C1-C6 alkylene, -O-(CH2CH2O)n-; -O-(C1-C 12Alkyl)nO-, -S-(C1-C 12 Alkyl)nS-, triazine, 1,3,5-triazinane-2,4,6-trione, 1,1'-cyclohexylene, NR 5 ((C1-C6 alkyl) n NR 6 ), -(piperidine) n1 -(C1-C6 alkyl) n -(piperidine) n (wherein n is an integer of 1 to 6, and n1 is an integer of 0 to 6), and preferably, X 6 is a single bond, a linear or branched C1-C6 alkylene, or -O-, where R 5 and R 6 each independently represents hydrogen or C1-C6 alkyl, preferably hydrogen. or a compound represented by formula (XIII) [ka] [where, X 7 and X 8 is a linking group as defined above. or a compound of formula (XIV) [ka] [where, X 9 , X 10 and X 11 is a linking group as defined above. or a compound represented by formula (XV) [ka] [where, X 5 has the meaning given above, and X 17 is CH, O or NH] or a compound of formula (XVI) [ka] [In the formula, R9 and R 10 is C1~C 30 alkyl, preferably methyl; R 20 is 2-methylheptane, y is 0 or 1, and X 17 , X 18 and X 19 is a single bond, carbonyl, or NH] The compounds include those selected from the group consisting of:

[0065] In the compounds of formula (XI), (XII), (XIII), (XIV), (XV) and (XVI), the aryl group, in particular the phenylene ring, may be substituted with halogen, hydroxyl, a carbocyclic or heterocyclic non-aromatic group or a C1-C 30 Alkyl or O-C1~C 30 alkyl, wherein C1-C 30 Alkyl is preferably methyl, ethyl, propyl, butyl, pentyl or 2-methylheptyl or an aryl group, in particular a phenylene ring, such as hexyl, 1,1'-cyclohexyl, 4-(C1-C 30 alkyl)-cyclohexyl, 3,4''-bis[4'-(C1-C 30 alkyl)-1,1'-bi(cyclohexyl)-4-yl], 1,1'-bi(cyclohexyl)-4-yl, 2-pyridine, pyrrolidine-2,5-dione, which may be substituted with at least one of CF3, OCF3, F, benzyl, pentyl, benzoate, 4-(phenoxycarbonyl), carboxylic acid, -SO3H, -PO3H, or -OR 15 where R 15 is C1~C 30 alkyl or optionally substituted benzyl.

[0066] Diamines containing at least one optionally substituted aryl group are preferred.

[0067] Examples of aliphatic and cycloaliphatic diamines are: Trimethylenediamine; Tetramethylenediamine; Hexamethylenediamine; Octamethylenediamine; 1,4-diaminocyclohexane; 4,4'-methylenebis(cyclohexylamine); 4,4'-methylenebis(2-methylcyclohexylamine); Isophoronediamine; Tetrahydrodicyclopentadienylenediamine and 1,3-Adamantanediamine Includes.

[0068] Examples of preferred diamines containing aryl groups are: 1,3-bis(aminomethyl)benzene; 1,4-bis(aminomethyl)benzene; m-phenylenediamine; p-phenylenediamine; 2-methylbenzene-1,3-diamine; 1,5-diaminonaphthalene; 4,4'-diaminodiphenyl ether; 3,4'-diaminodiphenyl ether; 4,4'-Diaminodiphenyl sulfide; 4,4-Diamino-2,2'-dichlorodiphenyl disulfide; 4,4'-diaminodiphenyl sulfone; 3,3'-diaminodiphenyl sulfone; 4,4'-diaminodiphenylmethane; 3,3'-diaminodiphenylmethane; 3,4'-diaminodiphenylmethane; 4,4'-Diamino-2,2'-dimethylbiphenyl; 4,4'-Diamino-3,3'-dimethyldiphenylmethane; 4,4'-diaminodiphenylethane; 3,3'-Diaminobenzophenone; 4,4'-Diaminobenzophenone; 3,4'-Diaminobenzophenone; 2,2-bis(4-aminophenyl)hexafluoropropane; 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane; 2,2-bis[4-(4-aminophenoxy)phenyl]propane; 1,4-bis(4-aminophenoxy)benzene; 1,3-bis(4-aminophenoxy)benzene; 4,4'-Diamino-diphenylene-cyclohexane; 3,5-Diamino-3'-trifluoromethylbenzanilide; 3,5-Diamino-4'-trifluoromethylbenzanilide; 4,4'-Diaminobenzanilide; 2-amino-4-[1-(3-amino-4-hydroxy-phenyl)-1-methyl-ethyl]phenol; Diaminofluorene derivatives, such as 2,7-diaminofluorene and 9,9-bis(4-aminophenyl)fluorene; Diaminoanthraquinone derivatives, for example, 1,5-diaminoanthraquinone; Benzidine derivatives, for example, 4,4'-diaminobiphenyl; 4,4'-diamino-3,3'-dimethylbiphenyl; tetramethylbenzidine; 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl; 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl; 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl; 3,3'-dimethoxy-4,4'-diaminobiphenyl; 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane; 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane; 4-(4-amino-2-methyl-phenyl)-3-methyl-aniline; 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline; 4,4'-methylene-bis(2-chloroaniline); 4,4'-(p-phenyleneisopropylidene)bisaniline; 4,4'-(m-phenyleneisopropylidene)bisaniline; 2-(4-aminophenyl)-1H-benzimidazol-5-amine; Bis(4-aminophenoxy)-2,2-dimethylpropane and 1,5-diaminonaphthalene, 2,7-diaminofluorene Includes.

[0069] Examples of more preferred diamines containing aryl groups are: m-phenylenediamine; p-phenylenediamine; 2-methylbenzene-1,3-diamine; 1,5-diaminonaphthalene; 4,4'-diaminodiphenyl ether; 3,4'-diaminodiphenyl ether; 4,4'-Diaminodiphenyl sulfide; 4,4'-diaminodiphenyl sulfone; 4,4'-diaminodiphenylmethane; 4,4'-diaminodiphenylethane; 2,2-bis(4-aminophenyl)hexafluoropropane; 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane; 2,2-bis[4-(4-aminophenoxy)phenyl]propane; 1,4-bis(4-aminophenoxy)benzene; 1,3-bis(4-aminophenoxy)benzene; 2,7-diaminofluorene; 4,4'-diaminobiphenyl; 4,4'-diamino-3,3'-dimethylbiphenyl; 4,4'-Diamino-2,2'-dimethylbiphenyl; 4-(4-amino-2-methyl-phenyl)-3-methyl-aniline; 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline; 4,4'-(p-phenylenebisisopropylidene)bisaniline; 4,4'-(m-phenylenebisisopropylidene)bisaniline; 2-(4-aminophenyl)-1H-benzimidazol-5-amine; Bis(4-aminophenoxy)-2,2-dimethylpropane and 2-amino-4-[1-(3-amino-4-hydroxyphenyl)-1-methyl-ethyl]phenol Includes.

[0070] Particularly preferred diamines containing aryl groups are: p-phenylenediamine; 2-methylbenzene-1,3-diamine; 4,4'-diaminodiphenyl ether; 3,4'-diaminodiphenyl ether; 4,4'-Diaminodiphenyl sulfide; 4,4'-diaminodiphenylmethane; 4,4'-diaminodiphenylethane; 2,2-bis[4-(4-aminophenoxy)phenyl]propane; 1,4-bis(4-aminophenoxy)benzene; 1,3-bis(4-aminophenoxy)benzene; 4,4'-diamino-3,3'-dimethylbiphenyl; 4,4'-Diamino-2,2'-dimethylbiphenyl; 4-(4-amino-2-methyl-phenyl)-3-methyl-aniline; 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline; 4,4'-(p-phenylenebisisopropylidene)bisaniline; 4,4'-(m-phenylenebisisopropylidene)bisaniline; 2-(4-aminophenyl)-1H-benzimidazol-5-amine; Bis(4-aminophenoxy)-2,2-dimethylpropane and 2-amino-4-[1-(3-amino-4-hydroxyphenyl)-1-methyl-ethyl]phenol Includes.

[0071] Further preferred diamines containing aryl groups are: 4,4'-diaminodiphenyl ether; 3,4'-diaminodiphenyl ether; 4,4'-Diamino-2,2'-dimethylbiphenyl; 2-amino-4-[1-(3-amino-4-hydroxyphenyl)-1-methyl-ethyl]phenol is.

[0072] Furthermore, the compositions of the present invention can optionally contain one or more additives, which are generally used in minor amounts to improve certain performance criteria of the compositions, such as coating and printing behavior, storage stability and color inhibition, and to improve, for example, the mechanical and thermal properties and photoalignment properties of alignment layers made from the compositions.

[0073] The optional additives are generally classified into groups such as antioxidants, inhibitors, stabilizers, surfactants, flow improvers, defoamers, sensitizers, adhesion promoters, thixotropic agents, pigments, initiators, nucleating agents, clarifiers, antistatic agents, slip agents, silica, talc, stabilizers, UV stabilizers, lubricants, coupling agents, antimicrobial agents, crosslinkers, surfactants, photoactivators, photosensitizers, photogenerators, and the like.

[0074] Additives such as silane-containing compounds and epoxy-containing crosslinkers can be added. Suitable silane-containing additives are described in Plast. Eng. 36 (1996), (Polyimides, fundamentals and applications), Marcel Dekker, Inc. 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-diglycidylcyclohexylamine, etc.

[0075] Other suitable additives include 2,2-dimethoxyphenylethanone, a mixture of diphenylmethanone and N,N-dimethylbenzenamine or ethyl 4-(dimethylamino)benzoate, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, Irgacure® 500 (a 1:1 weight ratio mixture of 1-hydroxycyclohexylphenylketone and benzophenone), 2,2-dimethoxy-1,2-diphenylethan-1-one, or Michler's ketone. Non-limiting examples are hydroquinone, 2,6-di-tert-butyl-4-methylphenol (BHT), 4-ethoxyphenol, 4-methoxyphenol, phenothiazine, and N-phenyl-2-naphthylamine.

[0076] The amount of additives in the composition is generally less than 20%, preferably less than 10%, more preferably less than 5%, more preferably less than 2%, based on the total weight of the composition.

[0077] Furthermore, the present invention provides a method for forming a liquid crystal alignment film, comprising: - applying the composition of the present invention onto a substrate; - drying the wet membrane thus obtained; - irradiating the dried film to impart liquid crystal alignment ability.

[0078] The substrate may be transparent or non-transparent and is preferably selected from glass and plastic substrates, polymer films such as polyethylene terephthalate (PET), triacetyl cellulose (TAC), and polypropylene, and is optionally coated with indium tin oxide (ITO). In particular, the composition can be applied to a support, optionally coated with an electrode, such as a glass plate coated with indium tin oxide (ITO), to produce a homogeneous layer having a thickness of 0.050 to 50 μm, preferably 0.050 to 1.00 μm, and more preferably 0.080 to 0.120 μm.

[0079] The composition can be applied to a substrate by common coating and printing methods known in the art. Coating methods include, for example, spin coating, blade coating, knife coating, reverse roll coating, transfer roll coating, gravure roll coating, kiss roll coating, cast coating, spray coating, slot orifice coating, calendar coating, electrodeposition coating, dip coating, and die coating. Printing methods include relief printing, such as flexographic printing, inkjet printing, intaglio printing, such as direct gravure printing or offset gravure printing, lithographic printing, such as offset printing, and stencil printing, such as screen printing. A preferred printing method is inkjet printing.

[0080] After the composition is applied to a substrate, the wet film is dried and the regions to be oriented are irradiated, for example, with a high-pressure mercury vapor lamp, a xenon lamp or a pulsed UV laser, using a polarizer and, optionally, a mask to create an image of the structure.

[0081] This process suitably includes a step of heat-treating the dried film at a temperature in the range of 80 to 230°C. When the photoalignable polymeric material is a polyamic acid polymer or copolymer, this heat-treating step can convert most or all of the polyamic acid groups into polyimide groups. The polyimide film thus obtained exhibits excellent physical properties, such as heat resistance, compatibility with liquid crystals, and mechanical strength.

[0082] In one embodiment, aligning light is used. Preferably, the wavelength is in the UV-A, UVB and / or UV / C range or the visible range. The appropriate wavelength depends on the photo-aligning compound. Preferably, the photo-aligning group is sensitive to visible light and / or UV light. The irradiation direction of the aligning light may be perpendicular to the substrate or at any oblique angle except 0°. Irradiation with the aligning light may be carried out in a single step or in multiple separate steps. In a preferred embodiment of the present invention, treatment with the aligning light is carried out in a single step.

[0083] More preferably, the orienting light is at least partially linearly polarized, elliptically polarized, e.g., circularly polarized, or unpolarized light, and most preferably at least partially circularly polarized or partially linearly polarized or obliquely exposed unpolarized light. In particular, the most preferred orienting light is substantially polarized light, especially linearly polarized light.

[0084] The polarization direction is understood to mean the line of intersection between the surface of the alignment layer and the plane of polarization of the polarized light during exposure. If the polarized light is elliptically polarized, the plane of polarization is taken to mean the plane defined by the direction of incidence of the light and the major axis of the polarization ellipse.

[0085] In the context of the present invention, the term polarization direction is used not only to describe the direction during the exposure process, but also after exposure to refer to the direction of polarization on an alignment layer applied during exposure.

[0086] The irradiation time depends on the power of the individual lamps and can vary from a few seconds to several hours. The homogeneous layer can also be irradiated using, for example, a filter that allows only certain wavelengths to pass, e.g., wavelengths suitable for inducing a crosslinking reaction.

[0087] Furthermore, the present invention relates to a liquid crystal alignment film obtained by the method of the present invention.

[0088] Furthermore, the present invention relates to structured or unstructured optical and electro-optical elements and devices comprising a liquid crystal alignment film obtained by the method of the present invention. Examples of structured or unstructured optical and electro-optical elements and devices include optical films, retarders, liquid crystal displays (LCDs), organic field effect transistors (OFETs), organic light emitting diodes (OLEDs), smart windows and sensors.

[0089] The invention will now be described in more detail by way of the following examples.

[0090] The following abbreviations were used: 1 H NMR: 1 H nuclear magnetic resonance spectroscopy m: multiplet, d: doublet, dd: doublet doublet, t: triplet, s: singlet, b: broad DMSO-d6: Deuterated dimethyl sulfoxide MS: Mass spectroscopy ITO: Indium tin oxide IBIB: Isobutyl isobutyrate PTFE: Polytetrafluoroethylene MeOH: Methanol DMF: N,N-dimethylformamide NMP: N-methyl-2-pyrrolidone BL or GBL: gamma-butyrolactone DEE: Diethylene glycol diethyl ether EEP: Ethyl 3-ethoxypropionate BC: Ethylene glycol monobutyl ether (Butyl CELLOSOLVE™) MIBK: Methyl isobutyl ketone

[0091] 4,9-Dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone refers to the compound with CAS number 4415-87-6.

[0092] 4,10-Dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone refers to the compound with CAS number 6053-46-9.

[0093] 4-(4-aminophenoxy)-aniline refers to the compound with CAS number 101-80-4.

[0094] (trans,trans)-4'-(4,4,4-trifluorobutyl)[1,1'-bicyclohexyl]-4-carboxylic acid refers to the compound with CAS number 1887749-09-8.

[0095] method As described in detail below, various compositions for forming liquid crystal alignment films were prepared and investigated using the following method. The inks were printed onto a 0.7 mm Kuramato polished soda glass / SiO2 (20 nm) / ITO (160 nm) substrate using an LP50 Suss Micro Tec inkjet printer, with the printer parameters adjusted to obtain a coating thickness of 107 nm in the center of the printed area. Heat treatment was performed on a hot plate with a pin (6 mm height) at 25°C for 50 seconds, then at 100°C for 90 seconds, and finally at 200°C for 10 minutes on a hot plate without a pin.

[0096] A. Viscosity Viscosity was measured at 25°C using a Brookfield DV-II+pro viscometer.

[0097] B. Surface tension Surface tension was measured at 20°C using a Kibron AquaPi microtensiometer.

[0098] C. Spread Spread was measured by measuring the final dimension of the printed area after heat treatment with a ruler in the cross-scan direction (perpendicular to the printing direction), subtracting the print width (40 mm) and dividing the result by 2 to obtain the spread value (mm).

[0099] D. Minimum thickness in the boundary region The minimum thickness in the border region was measured using an Alpha-Step® D-100 profiler (KLA-Tencor).

[0100] Preparation of monomers 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 was added slowly 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 was distilled off under reduced pressure. The reaction mixture was 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 were added.

[0101] After stirring for 2 hours at room temperature, 26.53 g (254.9 mmol) malonic acid and 7.3 g (102.6 mmol) pyrrolidine were added and the reaction mixture was heated to 80° C. After 4 hours at 80° C., the reaction mixture was cooled to 40° C., 150 mL of MeOH was added, and the reaction mixture was cooled to 0° C. After 1 hour at 0° C., the precipitate was filtered off, washed with 100 mL of chilled methanol, and dried in vacuo at 40° C. to give 53.0 g (90%) (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).

[0102] Preparation of (E)-3-[4-(4-pentylcyclohexanecarbonyl)oxyphenyl]prop-2-enoic acid 11.63 g (97.74 mmol) of thionyl chloride was added slowly over 30 minutes to a suspension of 17.62 g (88.86 mmol) of 4-pentylcyclohexanecarboxylic acid in 75 mL of toluene and 0.06 mL of DMF at 75° C. After 2 hours at 75° C., excess thionyl chloride was distilled off under reduced pressure. The reaction mixture was 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 were added.

[0103] After stirring for 2 hours at room temperature, 15.81 g (151.95 mmol) malonic acid and 3.22 g (45.32 mmol) pyrrolidine were added and the reaction mixture was heated to 80° C. After 4 hours at 80° C., the reaction mixture was cooled to 40° C., 150 mL of MeOH was added, and the reaction mixture was cooled to 0° C. After 1 hour at 0° C., the precipitate was filtered off, washed with 100 mL of chilled methanol, and dried in vacuo at 40° C. to give 24.5 g (80%) (E)-3-[4-(4-pentylcyclohexanecarbonyl)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), 2.50 (m, 1H), 2.08 (m, 2H), 1.80 (m, 2H), 1.5-0.7 (m, 13H), 0.85 (t, 3H).

[0104] Preparation of (E)-3-[4-[4-(4-pentylcyclohexyl)cyclohexanecarbonyl]oxyphenyl]prop-2-enoic acid 11.63 g (97.74 mmol) of thionyl chloride was added slowly over 30 minutes to a suspension of 24.92 g (88.86 mmol) of 4-(4-pentylcyclohexyl)cyclohexanecarboxylic acid in 75 mL of toluene and 0.06 mL of DMF at 75° C. After 2 hours at 75° C., excess thionyl chloride was distilled off under reduced pressure. The reaction mixture was 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 were added.

[0105] After stirring for 2 hours at room temperature, 15.81 g (151.95 mmol) malonic acid and 3.22 g (45.32 mmol) pyrrolidine were added and the reaction mixture was heated to 80° C. After 4 hours at 80° C., the reaction mixture was cooled to 40° C., 150 mL of MeOH was added, and the reaction mixture was cooled to 0° C. After 1 hour at 0° C., the precipitate was filtered off, washed with 100 mL of chilled methanol, and dried in vacuo at 40° C. to give 31.54 g (83%) (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).

[0106] Preparation of (E)-3-[4-[4-[4-(4,4,4-trifluorobutyl)cyclohexyl]cyclohexanecarbonyl]-oxyphenyl]prop-2-enoic acid 2.82 g (23.69 mmol) thionyl chloride was added slowly over 30 min to a suspension of 6.90 g (21.54 mmol) (trans,trans)-4'-(4,4,4-trifluorobutyl)[1,1'-bicyclohexyl]-4-carboxylic acid in 18 mL of toluene and 0.06 mL of DMF at 75 °C. After 2 h at 75 °C, excess thionyl chloride was distilled off under reduced pressure. The reaction mixture was then cooled to room temperature, and 2.74 g (22.40 mmol) 4-hydroxybenzaldehyde, 0.13 g (1.08 mmol) 4-dimethylaminopyridine, and 7.39 g (93.43 mmol) pyridine were added.

[0107] After stirring for 2 hours at room temperature, 3.83 g (36.83 mmol) malonic acid and 0.78 g (10.98 mmol) pyrrolidine were added, and the reaction mixture was heated to 80 °C. After 4 hours at 80 °C, the reaction mixture was cooled to 40 °C, 150 mL of MeOH was added, and the reaction mixture was cooled to 0 °C. After 1 hour at 0 °C, the precipitate was filtered off and washed with 100 mL of chilled methanol. The solid was suspended in a mixture of 18 mL of MeOH, 6 mL of water, and 3 g of HCl solution (25%). After stirring for 2 hours, the solid was filtered off, washed with MeOH, water, and heptane, and dried at 40 °C for 48 hours to give 4.90 g (48.7%) (E)-3-[4-[4-[4-(4,4,4-trifluorobutyl)cyclohexyl]cyclohexanecarbonyl]-oxyphenyl]prop-2-enoic acid as a white powder. 1 H NMR (300 MHz) in DMSO-D6: 12.38 (s, 1H), 7.73 (d, 2H), 7.59 (d, 1H), 7.14 (d, 2H), 6.50 (d, 1H), 2.91 (m, 1H), 2.3 (m, 3H), 1.73-0.7 (m, 22H).

[0108] 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) 2-(2,4-dinitrophenyl)ethanol, 4.65 g (11.8 mmol) (E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoic acid, and 144 mg (1.2 mmol) 4-dimethylaminopyridine were dissolved in 30 mL of dichloromethane. 2.48 g (13.0 mmol) N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC hydrochloride) was added at 0°C. The solution was stirred at 0°C for 1 hour and then at room temperature overnight.

[0109] After 22 hours at room temperature, the reaction mixture was partitioned between dichloromethane and water. The organic phase was washed repeatedly with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was chromatographed on silica gel using toluene:ethyl acetate (95:5) as the eluent. Crystallization from an ethyl acetate:hexane (1:1) mixture yielded 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).

[0110] Preparation of [4-(E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]-4-pentyl cyclohexanecarboxylate 2.50 g (11.8 mmol) of 2-(2,4-dinitrophenyl)ethanol, 4.06 g (11.8 mmol) of (E)-3-[4-(4-pentylcyclohexanecarbonyl)oxyphenyl]prop-2-enoic acid, and 144 mg (1.2 mmol) of 4-dimethylaminopyridine were dissolved in 30 mL of dichloromethane. 2.48 g (13.0 mmol) of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC hydrochloride) was added at 0°C. The solution was stirred at 0°C for 1 hour and then at room temperature overnight.

[0111] After 22 hours at room temperature, the reaction mixture was partitioned between dichloromethane and water. The organic phase was washed repeatedly with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was chromatographed on silica gel using toluene:ethyl acetate (95:5) as the eluent. Crystallization from an ethyl acetate:hexane (1:1) mixture yielded 4.44 g (70%) of [4-[(E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]-4-pentylcyclohexanecarboxylate as colorless crystals. 1 H NMR (300 MHz) in DMSO-D6: 8.73 (d, 1H), 8.51 (dd, 1H), 7.92 (d, 1H), 7.75 (d, 2H), 7.60 (d, 1H), 7.15 (d, 2H), 6.51 (d, 1H), 4.47 (t, 2H), 3.38 (t, 2H), 2.5 (m, 1H), 2.1 (m, 2H), 1.8 (m, 2H), 1.5-0.7 (m, 13H), 0.85 (t, 3H).

[0112] 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) 2-(2,4-dinitrophenyl)ethanol, 5.03 g (11.8 mmol) (E)-3-[4-[4-(4-pentylcyclohexyl)cyclohexanecarbonyl]oxyphenyl]prop-2-enoic acid, and 144 mg (1.2 mmol) 4-dimethylaminopyridine were dissolved in 30 mL of dichloromethane. 2.48 g (13.0 mmol) N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC hydrochloride) was added at 0°C. The solution was stirred at 0°C for 1 hour and then at room temperature overnight.

[0113] After 22 hours at room temperature, the reaction mixture was partitioned between dichloromethane and water. The organic phase was washed repeatedly with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was chromatographed on silica gel using toluene:ethyl acetate (95:5) as the eluent. Crystallization from an ethyl acetate:hexane (1:1) mixture yielded 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).

[0114] 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) ([4-[(E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate was dissolved in a mixture of 54 mL of N,N-dimethylformamide and 6 mL of water. 13.9 g (51.4 mmol) of ferric chloride hexahydrate was added. 5.60 g (85.7 mmol) of zinc powder was added slowly over 60 minutes. The mixture was allowed to react for 2 hours. The reaction mixture was then partitioned between ethyl acetate and water and filtered. The organic phase was washed repeatedly with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was filtered over silica gel using toluene:ethyl acetate (1:3) as the eluent, and crystallization from ethyl acetate:hexane (1:1) afforded 3.20 g (72%) of methyl 2-(4-(4,4,4-trifluorobutoxy)benzoate). [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate was produced 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).

[0115] Preparation of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-pentyl cyclohexanecarboxylate 4.51 g (8.38 mmol) of 4-[(E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-pentylcyclohexanecarboxylate was dissolved in a mixture of 54 mL of N,N-dimethylformamide and 6 mL of water. 13.9 g (51.4 mmol) of ferric chloride hexahydrate was added. 5.60 g (85.7 mmol) of zinc powder was added slowly over 60 minutes. The mixture was allowed to react for 2 hours.

[0116] The reaction mixture was then partitioned between ethyl acetate and water and filtered. The organic phase was washed repeatedly with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was filtered over silica gel using toluene:ethyl acetate (1:3) as the eluent, and crystallization from ethyl acetate:hexane (1:1) afforded 2.88 g (72%) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-pentylcyclohexanecarboxylate as a yellow powder. 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), 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).

[0117] Preparation of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate

[0118] 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 was dissolved in a mixture of 54 mL of N,N-dimethylformamide and 6 mL of water. 13.9 g (51.4 mmol) of ferric chloride hexahydrate was added. 5.60 g (85.7 mmol) of zinc powder was added slowly over 60 minutes. The mixture was allowed to react for 2 hours.

[0119] The reaction mixture was then partitioned between ethyl acetate and water and filtered. The organic phase was washed repeatedly with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was filtered over silica gel using toluene:ethyl acetate (1:3) as the eluent, and crystallization from ethyl acetate:hexane (1:1) afforded 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).

[0120] Preparation of [4-[(E)-3-[[5-nitro-2-[4-nitro-2-[[(E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoyl]oxymethyl]phenyl]phenyl]methoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate 3.92 g (12.8 mmol) of 2,2'-bis(hydroxymethyl-4,4'-dinitro-1,1'-biphenyl), 13.20 g (33.5 mmol) of (E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoic acid, and 0.630 mg (5.15 mmol) of 4-dimethylaminopyridine were dissolved in 200 mL of dichloromethane. 6.91 g (11.16 mmol) of N,N'-dicyclohexylcarbodiimide was added at 0°C. The solution was stirred at 0°C for 2 hours and then at room temperature overnight.

[0121] After 22 hours at room temperature, the reaction mixture was partitioned between dichloromethane and water. The organic phase was washed repeatedly with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was chromatographed on 150 g silica gel using toluene:ethyl acetate (9:1) as the eluent to yield 12.0 g of [4-[(E)-3-[[5-nitro-2-[4-nitro-2-[[(E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoyl]oxymethyl]phenyl]phenyl]methoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate as white crystals. MS: 1074.2 M+NH4 + , 1079.2 M+Na +

[0122] Preparation of [4-[(E)-3-[[5-amino-2-[4-amino-2-[[(E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoyl]oxymethyl]phenyl]phenyl]methoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate 2.27 g (2.14 mol) [4-[(E)-3-[[5-nitro-2-[4-nitro-2-[[(E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoyl]oxymethyl]phenyl]phenyl]methoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate was dissolved in a mixture of 40 mL of N,N-dimethylformamide and 3 mL of water. 3.48 g (12.8 mmol) of ferric chloride hexahydrate was added. 1.40 g (21.4 mmol) of zinc powder was added slowly over 40 minutes. The mixture was allowed to react for 2 hours.

[0123] The reaction mixture was then partitioned between ethyl acetate and water and filtered. The organic phase was washed repeatedly with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was chromatographed on 100 g silica gel using toluene:ethyl acetate (7:3) as eluent to yield 1.74 g of [4-[(E)-3-[[5-amino-2-[4-amino-2-[[(E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoyl]oxymethyl]phenyl]phenyl]methoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate as yellowish crystals. MS:997.4 MH + , 1014.4 M+NH4 +

[0124] Preparation of polymer The polymers were synthesized by solution polycondensation of diamines or mixtures of diamines and dianhydrides or mixtures of dianhydrides. Polymer formation was characterized by an increase in the viscosity of the reaction mixture. An intrinsic viscosity greater than 0.1 dL / g evidenced the formation of the polymer backbone.

[0125] Polymer PX1 4.897 g (24.970 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone was added to a solution of 5.000 g (24.970 mmol) of 4-(4-aminophenoxy)aniline in 39.59 g of NMP. Stirring was then carried out at 0°C for 2 hours. The mixture was then allowed to react at room temperature for 72 hours. Polymer PX1 was obtained as a solution (20 wt%) in NMP with an intrinsic viscosity η of 0.48 dL / g.

[0126] Polymer PX2 5.284 g (23.570 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone was 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 was then carried out at 0°C for 2 hours. The mixture was then allowed to react at room temperature for 72 hours. Polyamic acid PX2 was obtained as a 20 wt% NMP solution with an intrinsic viscosity η of 0.47 dL / g.

[0127] Polymer P1 0.840 g (3.74 mmol) 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone in 6.733 g NMP, 2.000 g (3.78 mmol) [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate and 0.038 g (0.03 mmol) To the solution of [4-[(E)-3-[[5-amino-2-[4-amino-2-[[(E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoyl]oxymethyl]phenyl]phenyl]methoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate was added. Stirring was then carried out at 0°C for 2 hours. The mixture was then allowed to react at room temperature for 72 hours. Polymer P1 was obtained as a solution (30% by weight) in NMP with an intrinsic viscosity η of 0.27 dL / g.

[0128] Polymer P2 0.364 g (1.85 mmol) of 4,9-dioxatricyclo[5.3.0.02,6]decane-3,5,8,10-tetrone and 0.424 g (1.89 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone were added to a solution of 2.000 g (3.78 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxoprop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate in 6.514 g of NMP. Stirring was then carried out at 0°C for 2 hours. The mixture was then allowed to react at room temperature for 48 hours. Polymer P2 was obtained as a 30 wt % solution in NMP with an intrinsic viscosity η of 0.42 dL / g.

[0129] Polymer P3 0.468 g (2.08 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone was added to a solution of 0.828 g (1.56 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxoprop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate and 0.250 g (0.52 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxoprop-1-enyl]phenyl]4-pentylcyclohexanecarboxylate in 3.60 g of NMP. The mixture was then stirred at 0° C. for 2 hours. The mixture was then allowed to react at room temperature for 72 hours. Polymer P3 was obtained as a solution (30 wt %) in NMP with an intrinsic viscosity η of 0.35 dL / g.

[0130] Polymer P4 0.499 g (2.22 mmol) of 4,10-dioxatricyclo[6.3.1.02,7]dodecane-3,5,9,11-tetrone was added to a solution of 1.000 g (1.89 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxoprop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate and 0.187 g (0.33 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxoprop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate in 3.93 g of NMP. The mixture was then stirred at 0° C. for 2 hours. The mixture was then allowed to react at room temperature for 72 hours. Polymer P4 was obtained as a solution (30 wt %) in NMP with an intrinsic viscosity η of 0.41 dL / g.

[0131] Polymer P5 50.00 g (0.20 mol) 2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane and 5.00 g (0.05 mol) triethylamine in 250 g MIBK were heated to reflux. 50.00 g (2.77 mol) deionized water was added dropwise to the mixture over 30 minutes. After stirring at 80 °C for 6 hours, the reaction mixture was cooled to room temperature, the organic layer was extracted, washed three times with deionized water, and the solvent was removed under reduced pressure to give poly[2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane P5 as a viscous oil. GPC (MW = 2.5 kDa)

[0132] Polymer P6 2.94 g (13.6 mmol) of polymer P5, 1.61 g (4.08 mmol) of (E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoic acid, and 0.132 g (0.41 mmol) of tetrabutylammonium bromide in 19 mL of MIBK were heated to 110 °C. After stirring at 110 °C for 12 h, the reaction mixture was cooled to room temperature and the MIBK was removed under vacuum. The residue was redissolved in 100 mL of ethyl acetate and washed three times with deionized water. The solvent was removed under vacuum to give polymer P6 as an off-white powder. GPC (MW = 14.3 kDa).

[0133] Polymer P7 1.00 g (4.62 mmol) Polymer P5, 0.215 g (0.46 mmol) (E)-3-[4-[4-[4-(4,4,4-trifluorobutyl)cyclohexyl]cyclohexanecarbonyl]oxyphenyl]prop-2-enoic acid, 0.493 g (1.16 mmol) (E)-3-[4-[4-(4-pentylcyclohexyl)cyclohexanecarbonyl]oxyphenyl]prop-2-enoic acid, and 0.022 g (0.07 mmol) tetrabutylammonium bromide in 10 mL of MIBK were heated to 110 °C. After stirring at 110 °C for 12 h, the reaction mixture was cooled to room temperature and the MIBK was removed under vacuum. The residue was redissolved in 100 mL of ethyl acetate and washed three times with deionized water. The organic layer was removed under reduced pressure to give Polymer P7 as an off-white powder. GPC (16.7 kDa).

[0134] Solutions were prepared by dissolving the polymeric materials in the solvent mixtures specified below.

[0135] solution 1 In a 30 mL plastic flask, 0.739 g P1 and 10.142 g PX1 were mixed with 3.312 g NMP. Then, 11.936 g GBL, 19.098 g BC, and 4.774 g DEE were added. The solution was vigorously stirred at room temperature for 10 minutes and filtered through a series of Sartorius filters (0.45 μm and 0.20 μm).

[0136] solution 2~7 Solutions 2 to 7 were obtained in the same manner as solution 1, using the following polymers and solvents.

[0137] Solution 2: 0.591 g P1 and 8.113 g PX1 were mixed with 4.556 g NMP; 11.468 g GBL; 11.461 g BC and 3.821 g DEE.

[0138] Solution 3: 0.901 g P2 and 7.65 g PX1 were mixed with 4.714 g NMP; 11.459 g GBL; 11.462 g BC and 3.821 g DEE.

[0139] Solution 4: 0.800 g P2 and 6.80 g PX1 were mixed with 5.527 g NMP; 11.524 g GBL; 11.522 g BC, and 3.827 g DEE.

[0140] Solution 5: 0.592g P1 and 8.113g PX1 were mixed with 4.557g NMP; 11.462g GBL; 11.462g BC and 3.82g EEP.

[0141] Solution 6: 0.533g P3 and 7.201g PX1 were mixed with 5.387g NMP; 11.521g GBL; 11.520g BC, and 3.84g DEE.

[0142] Solution 7: 0.400 g P4 and 7.40 g PX1 were mixed with 5.320 g NMP; 11.521 g GBL; 11.521 g BC, and 3.843 g DEE.

[0143] Solution 8: 0.800 g P2 and 6.805 g PX2 were mixed with 5.517 g NMP; 11.520 g GBL; 11.462 g BC, and 3.842 g DEE.

[0144] Solution 9: 0.400 g P6 and 7.601 g PX1 were mixed with 5.121 g NMP; 11.522 g GBL; 11.522 g BC, and 3.840 g DEE.

[0145] Solution 10: 0.016g P7 and 7.920g PX1 were mixed with 5.185g NMP; 11.520g GBL, 9.60g BC and 5.761g DEE.

[0146] [Table 1]

[0147] These solutions were tested according to the methods described above, and the results are shown in the table below.

[0148] [Table 2]

[0149] The variation in film thickness was within ±3 nm for each film. This indicates that the composition of the present invention can provide a uniform liquid crystal alignment film with no visible irregularities compared to the comparative example, and that the composition also suppresses spreading and increases the minimum thickness.

Claims

1. A composition for forming a liquid crystal alignment film, a photoalignable polymer material having a side chain containing a photoalignable group for forming a liquid crystal alignment film; a solvent mixture comprising (i) at least one of an N-alkylpyrrolidone and a lactone in a total amount of 45 to 70% by weight, (ii) a diethylene glycol dialkyl ether in an amount of 5 to 15% by weight, and (iii) an ethylene glycol monoalkyl ether in an amount sufficient to bring the total weight of the solvent mixture to 100% by weight, based on the weight of the solvent mixture; having a solids content of 3.0 to 6.0 wt. %; composition.

2. The composition of claim 1, wherein the solvent mixture comprises both an N-alkylpyrrolidone and a lactone.

3. 3. The composition of claim 2, wherein the solvent mixture comprises 20 to 40% by weight of N-alkylpyrrolidone and 20 to 40% by weight of lactone, based on the weight of the solvent mixture, with the proviso that the sum of the amounts of N-alkylpyrrolidone and lactone is 45 to 70% by weight.

4. The composition according to any one of claims 1 to 3, wherein the N-alkylpyrrolidone is N-methylpyrrolidone, the lactone is γ-butyrolactone, the ethylene glycol monoalkyl ether is ethylene glycol monobutyl ether, and the diethylene glycol dialkyl ether is diethylene glycol diethyl ether.

5. 5. The composition of any one of claims 1 to 4, wherein the photoalignable groups are selected from cinnamates and chalcones; coumarins and quinolones; stilbenes and cyanostilbenes; azo groups; chromones and chromenes; mono- and di-acetylene groups, such as diphenylacetylene groups; benzylidenephthalimide groups, benzylideneacetophene groups, phenylenediacryl groups, wherein the photoalignable groups are optionally substituted.

6. The composition of any one of claims 1 to 5, wherein the side chains further comprise, in addition to the photoalignable group, one or more of an aromatic group or an alicyclic group.

7. 7. The composition according to claim 1, wherein the backbone of the photoalignable polymer material is selected from the group consisting of polyamic acid, polyimide, polyamide, polysiloxane, polymaleimide, and polyacrylate.

8. The polymer material for forming the liquid crystal alignment film is obtained by polymerizing at least one diamine with an acid dianhydride, wherein at least a portion of the diamine has at least one photoalignable group. The composition according to any one of claims 1 to 7.

9. The polymer material for forming the liquid crystal alignment is represented by the formula (1) 【Chemistry 14】 [In the formula, Q is a tetravalent residue of a tetracarboxylic dianhydride; P is a divalent residue of a diamine, wherein at least a portion of P has a side chain containing a photoalignable group. The composition of claim 8, comprising a repeating unit represented by:

10. The composition of any one of claims 1 to 9, further comprising an additional polymeric material.

11. A method for forming a liquid crystal alignment film, comprising: - applying a composition according to claim 1 onto a substrate; drying the wet membrane thus obtained; - irradiating the dried film to impart liquid crystal alignment ability, method.

12. A liquid crystal alignment film obtained by the method according to claim 11.

13. 13. Structured or unstructured optical and electro-optical elements and devices comprising a liquid crystal alignment film according to claim 12.

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