Photoalignable polymer material for forming liquid crystal alignment films

Abstract

A photoalignable polymeric material for forming a liquid crystal alignment film, comprising recurring units represented by formula (I), (I), wherein P is a divalent residue of a diamine HN2-Ar -X -NH2; and recurring units represented by formula (II), (II), wherein P is a divalent residue of a diamine HN2-Ar -X -Ar -NH2; and wherein Q is a tetravalent residue of a cyclobutane tetra-carboxylic dianhydride. Also provided are methods for producing the photoalignable polymeric material, a liquid crystal alignment film and a method for forming the film, and a liquid crystal alignment film optical device comprising the liquid crystal alignment film. The photoalignable polymeric material minimizes light leakage and improves the dark state of a liquid crystal display. 1 1 1 2 2 2 3 Also provided are methods for producing the photoalignable polymeric material, a liquid crystal alignment film and a method for forming the film, and a liquid crystal alignment film optical device comprising the liquid crystal alignment film. The photoalignable polymeric material minimizes light leakage and improves the dark state of a liquid crystal display.​​​​​​

Description

[0001] The present invention relates to a photo-alignable polymer material for forming a liquid crystal alignment film, a photo-alignable polymer material composition comprising the photo-alignable polymer material, a method for producing the photo-alignable polymer material, a method for forming a liquid crystal alignment film, a liquid crystal alignment film, and an optical device comprising the liquid crystal alignment film.

[0002] Liquid crystal display (LCD) devices provide a display by controlling the alignment of liquid crystal molecules contained in a liquid crystal layer disposed between two display substrates. Specifically, LCDs generate an electric field by applying a voltage to electrodes disposed on the side surface of the liquid crystal layer of the substrate, thereby reorienting the liquid crystal molecules in the liquid crystal layer and controlling the light transmittance to display an image.

[0003] To provide high-quality liquid crystal display devices, excellent initial alignment of liquid crystal (LC) molecules is essential. The alignment of liquid crystal molecules significantly affects display characteristics, including light leakage, response time, and viewing angle.

[0004] Liquid crystal display devices typically include a liquid crystal alignment layer disposed on the liquid crystal layer side surface of a substrate to control the alignment orientation of liquid crystal molecules. In particular, the alignment layer material critically affects the orientation and uniformity of the liquid crystal molecules.

[0005] Known alignment film materials include resins such as polyamic acid, polyimide, polyamide, polysiloxane, polymaleimide, and polyacrylate. For example, alignment films containing polyamic acid and / or polyimide have been found to exhibit excellent physical properties, such as heat resistance, compatibility with liquid crystals, and mechanical strength.

[0006] Friction-coated polyimide films remain the mainstream alignment layer for common liquid crystal displays. Polyimide is coated as a thin alignment film and dried. Then, the surface of the film is mechanically rubbed with a specially manufactured cloth. However, friction is not suitable for alignment over large areas.

[0007] In photoalignment methods, the alignment layer is given an alignment direction by irradiating a substrate coated with a photoalignment material with alignment light (especially linearly polarized UV light (LPUV)). In polyimide-based photoalignment materials, exposure to alignment light induces partial decomposition of the polyimide backbone in a specific direction, thereby inducing anisotropic angular distribution and achieving photoalignment properties.

[0008] In planar modes (such as IPS and FFS), the liquid crystal director in the dark state is aligned parallel to or perpendicular to the polarization direction of the attached, typically orthogonal, polarizing film. Liquid crystal domains that are not perfectly aligned in the desired direction leak light due to depolarization. Therefore, well-defined planar alignment of the liquid crystal on the alignment layer is crucial for achieving low dark-state brightness in planar LCDs, especially when operating in normal black mode.

[0009] When a voltage is applied to an LCD to switch it to a grayscale or brightscale state, the liquid crystal layer deforms. Once the applied voltage falls below the LCD's threshold voltage, the alignment layer must again provide a strong anchoring force to the liquid crystals to drive them back to their initial off-state configuration. Any deviation from the initial off-state configuration will be observed as image retention and thus degrade display quality. Because alternating current (AC) voltage is applied to switch the LCD to different grayscale levels, the image retention that appears after the AC voltage is changed or removed is also known as AC memory.

[0010] EP 2 527 916 A2 describes alignment film materials comprising rigid polyimide and flexible polyimide.

[0011] WO 2024 / 029576 A1 relates to a liquid crystal alignment film comprising a polyimide having repeating units derived from two different diamines, one of which is a diether compound.

[0012] Improved alignment materials are desired. In particular, alignment materials that minimize light leakage in liquid crystal displays are desired. Specifically, an object of the present invention is to provide photoalignment materials and photoalignment layers for planar LCD modes.

[0013] This invention provides a photo-alignable polymer material for forming a liquid crystal alignment film, comprising repeating units represented by formula (I).

[0014] (I)

[0015] Where P 1 It is a diamine HN2-Ar 1 -X 1 -NH2 divalent residues;

[0016] and the repeating unit represented by equation (II)

[0017] (II)

[0018] Where P 2 It is a diamine HN2-Ar 2 -X 2 -Ar 3 -NH2 divalent residues;

[0019] Ar 1 Ar 2 and Ar 3 Independently selected from C6-C 14 -Aspartic acid, of which Ar 1 Ar 2 and Ar 3It can be independently substituted by one or more of OH, O-C1-C6-alkyl, C1-C6-alkyl, COOH, COO-C1-C6-alkyl and C1-C6-fluoroalkyl;

[0020] X 1 Independently selected from bonds, C1-C6-alkylene, O-C1-C6-alkylene and NH-C1-C6-alkylene, wherein each C1-C6-alkylene may be independently substituted by one or more of OH, O-C1-C6-alkyl and F;

[0021] X 2 Independently selected from bond, O, NH, C1-C6-alkylene, O-C1-C6-alkylene, NH-C1-C6-alkylene, NH-C1-C6-alkylene-NH, NH-CO-(C1-C6-alkylene), NH-CO-(C1-C6-alkylene)-CO-NH, CO-NH-(C1-C6-alkylene)-NH-CO, wherein each C1-C6-alkylene may be independently substituted by one or more of OH, O-C1-C6-alkyl and F;

[0022] Q is a tetravalent residue of a tetracarboxylic dianhydride, and at least a portion of Q is represented by formula (A).

[0023] (A)

[0024] R 1 Independently selected from H and C1-C6-alkyl;

[0025] Y is independently selected from OH and O. – M + and O-C1-C6-alkyl, wherein M + It is an alkali metal cation.

[0026] It has been surprisingly discovered that this photo-alignable polymer material allows the formation of liquid crystal alignment films, which induce improved initial alignment of liquid crystals (especially liquid crystal displays), thereby improving light leakage.

[0027] The photo-orientable polymer material comprises repeating units represented by formulas (I) and (II), and thus constitutes a polyamic acid or a polyamic acid derivative depending on the definition of the structural part Y. Polyamic acids and polyamic acid derivatives can be subjected to heat treatment to obtain polyimides.

[0028] Polyimides derived from cyclobutanetetracarboxylic dianhydride and diamine can undergo UV-induced cyclobutane fragmentation, thereby inducing the photoorientation properties of the polyimides. In particular, due to the absorption dichroism of the photosensitive polyimide fragments, UV polarization exposure produces an anisotropic angular distribution of broken and unreacted imide fragments.

[0029] As a result, anisotropy is induced in the alignment film. The liquid crystal contained in the layer formed on the alignment film can be aligned under the influence of such a light-induced alignment film.

[0030] In the photo-alignable polymer material of the present invention, the repeating unit represented by formula (I) includes the structural portion P. 1 It is a diamine HN2-Ar 1 -X 1 -NH2 divalent residues, while the repeating unit represented by formula (II) contains the structural part P. 2 It is a diamine HN2-Ar 2 -X 2 -Ar 3 -NH2 divalent residues. Divalent residue P 1 and P 2 Each is understood to be equivalent to a diamine minus two amino residues.

[0031] Not wanting to be bound by theory, it is believed that the advantageous properties of photo-oriented polymer materials originate from diamine HN2-Ar. 1 -X 1 -NH2 divalent residues and diamine HN2-Ar 2 -X 2 -Ar 3 Both -NH2 divalent residues exist simultaneously.

[0032] Ar 1 Ar 2 and Ar 3 Independently selected from C6-C 14 -Aspartic acid, of which Ar 1 Ar 2 and Ar 3 It can be independently substituted by one or more of OH, O-C1-C6-alkyl, C1-C6-alkyl, COOH, COO-C1-C6-alkyl and C1-C6-fluoroalkyl, especially one or more C1-C6-alkyl.

[0033] In this paper, the term “independently selected” is understood to mean selecting a structural part for each occurrence in a repeating unit and for each instance of a repeating unit, independently of its definition in other repeating units and independently of the definition of other such structural parts.

[0034] In this document, each C1-C6-alkyl group may be a branched or straight-chain C1-C6-alkyl group, preferably a C1-C3-alkyl group, such as methyl or ethyl, especially methyl.

[0035] In the preferred embodiment, Ar 1 Ar 2 and Ar 3 Independently selected from phenylene and naphthylene, wherein Ar 1 Ar 2 Ar 3 It can be independently substituted with one or more C1-C3-alkyl groups. In a particularly preferred embodiment, Ar 1 Selected from phenylene and naphthylene; and Ar 2 and Ar 3 It is a phenylene oxide.

[0036] X 1 Independently selected from C1-C6-alkylene, O-C1-C6-alkylene, and NH-C1-C6-alkylene, wherein each C1-C6-alkylene may be independently substituted with one or more of OH, O-C1-C6-alkyl, and F. In a preferred embodiment, X 1 Independently selected from bonds and C1-C6-alkylene groups. In a particularly preferred embodiment, X 1 It is a key.

[0037] In this document, each C1-C6-alkylene may be a branched or straight-chain C1-C6-alkylene, preferably a C1-C4-alkylene, such as methylene, ethylene, propylene or butylene, particularly ethylene or propylene, preferably ethylene.

[0038] X 2 Independently selected from the groups X, O, NH, C1-C6-alkylene, O-C1-C6-alkylene, NH-C1-C6-alkylene, NH-C1-C6-alkylene-NH, NH-CO-(C1-C6-alkylene), NH-CO-(C1-C6-alkylene)-CO-NH, CO-NH-(C1-C6-alkylene), and CO-NH-(C1-C6-alkylene)-NH-CO, wherein each C1-C6-alkylene may be independently substituted by one or more of OH, O-C1-C6-alkyl, and F. In a preferred embodiment, X 2 Independently selected from bonds, O, NH and C1-C6-alkylene groups.

[0039] In the preferred embodiment, Ar 1 Ar 2 and Ar 3 Independently selected from phenylene and naphthylene; and X 1 and X2 Each is a key; among them Ar 1 Ar 2 Ar 3 It can be independently substituted with one or more C1-C3-alkyl groups. In a particularly preferred embodiment, Ar 1 Independently selected from phenylene and naphthylene; Ar 2 and Ar 3 Each is a phenylene oxide; and X 1 and X 2 Each is a key; among them Ar 1 Ar 2 Ar 3 It can be independently substituted with one or more C1-C3-alkyl groups.

[0040] Q is a tetravalent residue of a tetracarboxylic dianhydride, and at least a portion of Q is represented by formula (A).

[0041] (A)

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

[0043] R 1 Independently selected from H and C1-C6-alkyl groups. In one embodiment, R 1 The two structural parts are H, and R 1 Both structural moieties are C1-C6-alkyl. In a particularly preferred embodiment, R 1 The two structural parts are H, and R 1 The two structural parts are C1-C6-alkyl, wherein the two C1-C6-alkyl structural parts are arranged to be isolated from each other, i.e., not in the adjacent position.

[0044] Y is independently selected from OH and O. – M + and O-C1-C6-alkyl (where M + (These are alkali metal cations), particularly selected from OH and O. – M + M + Preferably selected from lithium cations, sodium cations and potassium cations, especially sodium cations and potassium cations.

[0045] In one embodiment, the molar ratio of the repeating unit of formula (I) to the repeating unit of formula (II) is in the range of 1:100 to 100:1, preferably 1:10 to 10:1, more preferably 1:5 to 5:1, and most preferably 1:4 to 4:1.

[0046] In one implementation, a portion of Q is represented by equation (B).

[0047] (B)

[0048] Here, n is an integer independently selected from 0 and 1.

[0049] In one implementation, a portion of Q is represented by equation (B-1).

[0050] (B-1).

[0051] In one embodiment, the molar ratio of the portion of Q represented by formula (A) to the portion of Q represented by formula (B) is in the range of 1:10 to 10:1, preferably 1:5 to 5:1, and more preferably 1:4 to 4:1.

[0052] The present invention further provides photo-orientable polymeric material compositions comprising photo-orientable polymeric materials and polyamic acid and / or polyimide.

[0053] Preferred are photo-orientable polymeric material compositions, wherein the polyamic acid and / or polyimide and the photo-orientable polymeric material independently comprise repeating units represented by formula (II), which have the same meaning and preferences as described above.

[0054] Further preferred is a photo-orientable polymer material composition, wherein the content of the photo-orientable polymer material is 90% to 10% by weight, and the content of polyamic acid and / or polyimide is 10% to 90% by weight, provided that the total amount of the photo-orientable polymer material and the polyamic acid and / or polyimide is 100% by weight. ...

[0056] The present invention further provides a photo-orientable polymer material composition comprising a photo-orientable polymer material or a photo-orientable polymer material composition and at least one solvent.

[0057] Suitable solvents include:

[0058] (i) Aprotic polar solvents, such as N-methylpyrrolidone; N-ethylpyrrolidone; N-vinylpyrrolidone; N,N-dimethylformamide; N,N-dimethylacetamide; 1,3-dimethyl-2-imidazolium ketone; and dimethyl sulfoxide;

[0059] (ii) Esters, such as methyl acetate; ethyl acetate; n-propyl acetate; isopropyl acetate; n-butyl acetate; isobutyl acetate; n-pentyl acetate; isoamyl acetate; isopropyl propionate; n-butyl propionate; n-pentyl propionate; isobutyl propionate; isobutyl isobutyrate; 2-ethylhexyl acetate; propylene glycol monomethyl ether acetate; propylene glycol monoethyl ether acetate; propylene glycol monobutyl ether acetate; 1-methoxypropyl acetate; 2-hydroxyethyl acetate; 2-hydroxyethyl propionate; 2-hydroxy-2-methylpropionate (2-hydroxy-2-methyl ethyl) Propionate; Cyclohexanol acetate; Propylene glycol diacetate; Dipropylene glycol methyl ether acetate; 1,4-Butanediol diacetate; 1,6-Hexanediol diacetate; Butyl cellosolve acetate; Ethyl lactate; n-Propyl lactate; Isopropyl lactate; Methyl 3-methoxypropionate; Methyl 3-ethoxypropionate; Ethyl 3-methoxypropionate; and Ethyl 3-ethoxypropionate;

[0060] (iii) Lactones, such as γ-butyrolactone; and caprolactone;

[0061] (iv) Ketones, such as acetone; methyl ethyl ketone; methyl propyl ketone; methyl isobutyl ketone; 2-heptanone; 3-heptanone; 4-heptanone; methyl isopentyl ketone (2-methyl-5-hexanone); diisobutyl ketone; 5-methyl-3-heptanone; 2-octanone; isophorone; isopropylidene acetone; cyclohexanone; 3,3,5-trimethylcyclohexanone; and cyclopentanone;

[0062] (v) Carbonates, such as diethyl carbonate; dipropyl carbonate; and methyl propyl carbonate;

[0063] (vi) Diols and glycol ethers, such as ethylene glycol monoethyl ether; ethylene glycol monobutyl ether; ethylene glycol monohexyl ether; ethylene glycol monoisopropyl ether; ethylene glycol monopropyl ether; diethylene glycol monoethyl ether; diethylene glycol monobutyl ether; diethylene glycol monohexyl ether; diethylene glycol monoisopropyl ether; propylene glycol monomethyl ether; propylene glycol monoethyl ether; propylene glycol monopropyl ether; propylene glycol monobutyl ether; dipropylene glycol monomethyl ether; dipropylene glycol monobutyl ether; diethylene glycol dimethyl ether; diethylene glycol diethyl ether; diethylene glycol diethyl ether; dipropylene glycol dimethyl ether; dipropylene glycol dimethyl ether; and dipropylene glycol methyl n-propyl ether;

[0064] (vii) Ethers, such as anisole; tetrahydrofuran; 2-methyltetrahydrofuran; dioxane; and methyl tert-butyl ether;

[0065] (viii) Nitriles, such as acetonitrile; isovaleronitrile; and 2-methylbutyronitrile;

[0066] (ix) Acetals, such as ethyl acetal (formaldehyde diethyl acetal); propyl acetal (formaldehyde di-n-propyl acetal); butyl acetal (formaldehyde di-n-butyl acetal); 1,3-dioxolane; and 2,5,7,10-tetraoxaundecane;

[0067] (x) Alcohols, such as isopropanol; isobutanol; butanol; pentanol; isopentanol; cyclohexanol; n-hexanol; methyl isobutyl alcohol; 1-methoxypropanol; 2-ethyl-1-hexanol; and 2-methyl-1-pentanol;

[0068] (xi) Halogenated hydrocarbon solvents, such as dichloromethane; 1,2-dichloroethane; 1,4-dichlorobutane; trichloroethane; chlorobenzene; o-dichlorobenzene; and α,α,α-trifluorotoluene;

[0069] (xii) Hydrocarbons, such as hexane; heptane; octane; nonane; decane; undecane; benzene; toluene; and xylene;

[0070] and its mixtures.

[0071] The type and proportion of solvent or solvent mixture in the compositions of the present invention depend primarily on the coating or printing method used to prepare the liquid crystal alignment film or coating layer for manufacturing optical and electro-optic components and devices.

[0072] Furthermore, to improve processing performance, coating quality, or to adjust viscosity, the formulation may further include polar or aprotic poor solvents or nonpolar poor solvents. Examples of polar or aprotic poor solvents include acetals, alcohols, monoalkylated or dialkylated glycols, carboxylic acid esters (preferably highly branched), alkoxy-aliphatic carboxylic acid esters, lactates, ketones (preferably highly branched), ethers, carbonates, and nitriles, provided that the dissolved photooriented polymer material does not precipitate. Examples of nonpolar poor solvents are hydrocarbons and haloalkanes, provided that the dissolved photooriented polymer material does not precipitate. Particularly preferred polar or aprotic poor solvents include monoalkylated or dialkylated glycol ethers and alkoxy-aliphatic carboxylic acid esters, such as ethyl 3-ethoxypropionate.

[0073] In one embodiment, the photooriented polymeric material composition has a solids content of 3.0 to 10.0 wt%, preferably 3.5 to 8.0 wt%, more preferably 4.0 to 7.0 wt%, and most preferably 4.5 to 6.7 wt%. The solids comprise the photooriented polymeric material, as well as additional polymeric materials. It should be understood that the composition may contain more than one photooriented polymeric material.

[0074] Suitable photo-alignable polymeric materials are well known in the field of liquid crystal alignment materials. Such materials are used to prepare liquid crystal alignment films for the manufacture of optical and electro-optic devices, and are disclosed, for example, in the following publications: O. Yaroshuk, Y. Renikov, J. Mater. Chem., 2012, 22, 286-300 and references cited therein; US 5,389,698; US 5,838,407; US 5,602,661; US ​​6,160,597; US 6,369,869; US 6,717,644; US 6,215,539; US 6,300,991 and US 6,608,661.

[0075] Furthermore, the photo-alignable polymeric material compositions of the present invention may optionally contain one or more additives. Such additives are typically used in small amounts to improve certain performance properties of the compositions of the present invention, such as coating and printing behavior, storage stability and inhibition of color formation, as well as, for example, improving the mechanical and thermal properties and photo-alignable properties of the alignment layers produced from the compositions of the present invention.

[0076] Optional additives are typically grouped into categories such as antioxidants, inhibitors, stabilizers, surfactants, flow improvers, defoamers, sensitizers, adhesion promoters, thixotropic agents, pigments, initiators, nucleating agents, clarifying agents, antistatic agents, slip agents, silica, talc, stabilizers, UV stabilizers, lubricants, coupling agents, antimicrobial agents, crosslinking agents, surfactants, photosensitizers, photosensitizers, and other substances.

[0077] Additives, such as those containing silanes and those containing epoxy crosslinking agents, can be added. Suitable silane-containing additives are described in Plast. Eng. 36 (1996), (Polyimides, fundamentals and applications), Marcel Dekker, Inc. Suitable epoxy crosslinking additives include 4,4'-methylenebis(N,N-diglycidylaniline), trimethylolpropane triglycidyl ether, phenyl-1,2,4,5-tetracarboxylic acid-1,2,4,5-N,N'-diglycidyl diimide, polyethylene glycol diglycidyl ether, N,N-diglycidylcyclohexylamine, (3-glycidyloxypropyl)triethoxysilane, and N,N,N',N'-tetra(2-hydroxyethyl)hexamethylenediamide.

[0078] Other suitable additives include 2,2-dimethoxyphenyl ethyl ketone, mixtures of diphenyl ketone with N,N-dimethylaniline or ethyl 4-(dimethylamino)benzoate, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, and Irgacure. ® 500 (a 1:1 weight mixture of 1-hydroxycyclohexylphenyl ketone and benzophenone), 2,2-dimethoxy-1,2-diphenylethane-1-one, or Michlechne. Non-limiting examples are hydroquinone, 2,6-di-tert-butyl-4-methylphenol (BHT), 4-ethoxyphenol, 4-methoxyphenol, phenothiazine, and N-phenyl-2-naphthylamine.

[0079] The amount of additive in the composition is typically less than 25% of the total weight of the photooriented polymeric material, preferably less than 15%, and more preferably less than 10%.

[0080] The present invention further provides a method for producing a photo-alignable polymeric material for forming a liquid crystal alignment film, comprising copolymerizing a mixture comprising a diamine of formula (1), a diamine of formula (2), and a cyclobutanetetracarboxylic dianhydride or a derivative thereof of formula (3).

[0081] HN2-Ar 1 -X 1 -NH2 (1)

[0082] HN2-Ar 2 -X 2 -Ar 3 -NH2 (2)

[0083] (3)

[0084] in

[0085] Ar 1 Ar 2 and Ar 3 Independently selected from C6-C 14 -Aspartic acid, of which Ar 1 Ar 2 and Ar 3 It can be independently substituted by one or more of OH, O-C1-C6-alkyl, C1-C6-alkyl, COOH, COO-C1-C6-alkyl and C1-C6-fluoroalkyl;

[0086] X 1 Independently selected from bonds, C1-C6-alkylene, O-C1-C6-alkylene and NH-C1-C6-alkylene, wherein each C1-C6-alkylene may be independently substituted by one or more of OH, O-C1-C6-alkyl and F;

[0087] X 2 Independently selected from bond, O, NH, C1-C6-alkylene, O-C1-C6-alkylene, NH-C1-C6-alkylene, NH-C1-C6-alkylene-NH, NH-CO-(C1-C6-alkylene), NH-CO-(C1-C6-alkylene)-CO-NH, CO-NH-(C1-C6-alkylene), and CO-NH-(C1-C6-alkylene)-NH-CO, wherein each C1-C6-alkylene may be independently substituted by one or more of OH, O-C1-C6-alkyl, and F; and

[0088] R 1 Independently selected from H and C1-C6-alkyl.

[0089] The embodiments of the photo-alignable polymer materials of the present invention discussed above are to be understood to also apply to the methods of the present invention where applicable.

[0090] In one embodiment, the molar ratio of the first diamine of formula (1) to the second diamine of formula (2) is in the range of 1:10 to 10:1, preferably 1:10 to 5:1, more preferably 1:5 to 2:1, and most preferably 1:4 to 2:1.

[0091] In one embodiment, the mixture comprises cyclopentanetetracarboxylic dianhydride of formula (4) or a derivative thereof.

[0092] (4).

[0093] Here, n is an integer independently selected from 0 and 1.

[0094] In one embodiment, the molar ratio of cyclobutanetetracarboxylic dianhydride and its derivatives of formula (3) to cyclopentanetetracarboxylic dianhydride and its derivatives of formula (4) is in the range of 1:10 to 10:1, preferably 1:5 to 5:1, and more preferably 1:4 to 4:1.

[0095] Suitable diamines of formula (1) include:

[0096] 1,2-Diaminobenzene;

[0097] 1,3-Diaminobenzene;

[0098] 1,4-Diaminobenzene;

[0099] 3-Methyl-1,2-diaminobenzene;

[0100] 4-Methyl-1,2-diaminobenzene;

[0101] 2-Methyl-1,3-diaminobenzene;

[0102] 4-Methyl-1,3-diaminobenzene;

[0103] 5-Methyl-1,3-diaminobenzene; hk

[0104] 2-Methyl-1,4-diaminobenzene;

[0105] 2,5-Dimethyl-1,4-diaminobenzene;

[0106] 4-(2-Aminoethyl)aniline;

[0107] 1,5-Diaminonaphthalene; and

[0108] 1,8-Diaminonaphthalene.

[0109] Preferred diamines of formula (1) include:

[0110] 1,2-Diaminobenzene;

[0111] 1,3-Diaminobenzene;

[0112] 1,4-Diaminobenzene;

[0113] 4-Methyl-1,2-diaminobenzene;

[0114] 2-Methyl-1,3-diaminobenzene;

[0115] 4-Methyl-1,3-diaminobenzene;

[0116] 2,5-Dimethyl-1,4-diaminobenzene;

[0117] 4-(2-aminoethyl)aniline; and

[0118] 1,5-Diaminonaphthalene.

[0119] It should be understood that the divalent diamine residue P in the repeating unit represented by formula (I) in the photo-orientable polymer material of the present invention 1 It can be derived from the diamine of formula (1).

[0120] Suitable diamines of formula (2) include:

[0121] 4,4'-Methylenediphenylamine;

[0122] 3,3'-Methylenediphenylamine;

[0123] 3,4'-Methylenediphenylamine;

[0124] 4,4'-Ethylenediphenylamine;

[0125] 4,4'-Diamino-2,2'-Dimethylbiphenyl;

[0126] 4,4'-Diamino-3,3'-Dimethylbiphenyl;

[0127] 4,4'-Diphenylamine oxide;

[0128] 3,4'-Diphenylamine oxide;

[0129] N-(4-aminophenyl)phenyl-1,4-diamine;

[0130] N-(4-aminophenyl)phenyl-1,3-diamine;

[0131] 2,2-Bis(4-aminophenyl)hexafluoropropane;

[0132] 2-Amino-4-[1-(3-Amino-4-hydroxyphenyl)-1-methylethyl]phenol;

[0133] 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline;

[0134] 4-[(4-amino-2-methylphenyl)methyl]-2-methylaniline;

[0135] 4,4'-Methylenebis(2-chloroaniline); and

[0136] Bis(4-aminophenoxy)-2,2-dimethylpropane.

[0137] Preferred diamines of formula (2) include:

[0138] 4,4'-Diamino-2,2'-Dimethylbiphenyl;

[0139] 4-[(4-amino-2-methylphenyl)methyl]-2-methylaniline;

[0140] N-(4-aminophenyl)phenyl-1,4-diamine; and

[0141] 4,4'-Diphenylamine oxide.

[0142] It should be understood that the divalent diamine residue P in the repeating unit represented by formula (II) in the photo-orientable polymer material of the present invention 2 It can be derived from the diamine of formula (2).

[0143] Suitable cyclobutanetetracarboxylic dianhydrides of formula (3) include:

[0144] 1,2,3,4-Cyclobutanetetracarboxylic acid dianhydride (4,9-dioxatricyclo[5.3.0.0]) 2,6 Decane-3,5,8,10-tetraone (CBDA);

[0145] 1,3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride (1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0]) 2,6 ] Decane-3,5,8,10-tetraone (DM-CBDA); and

[0146] 1,2,3,4-Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride.

[0147] Preferred cyclobutanetetracarboxylic dianhydrides of formula (3) include:

[0148] 1,2,3,4-Cyclobutanetetracarboxylic acid dianhydride (4,9-dioxatricyclo[5.3.0.0]) 2,6 ] Decane-3,5,8,10-tetraone (CBDA); and

[0149] 1,3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride (1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0]) 2,6 Decane-3,5,8,10-tetraone, DM-CBDA).

[0150] The derivatives of cyclobutanetetracarboxylic dianhydride of formula (3) include its acid, C1-C6-ester and acyl chloride.

[0151] It should be understood that the portion (A) of the tetravalent organic residue Q in repeating units (I) and (II) can be derived from cyclobutanetetracarboxylic anhydride and its derivatives of formula (3).

[0152] Suitable cyclopentanetetracarboxylic dianhydrides of formula (4) include:

[0153] 1,2,3,4-Cyclopentanetetracarboxylic acid dianhydride and 3-(carboxymethyl)-1,2,4-cyclopentanetricarboxylic acid-1,4:2,3-dianhydride (TCA-AH).

[0154] The derivatives of the cyclopentanetetracarboxylic dianhydride of formula (4) include its acid, C1-C6-ester and acyl chloride.

[0155] It should be understood that optional portion (B) of the tetravalent organic residue Q in repeating units (I) and (II) may be derived from cyclopentanetetracarboxylic anhydride of formula (4) and its derivatives.

[0156] The photo-alignable polymer material can be prepared according to methods known to those skilled in the art, for example by the methods described in Plast. Eng. 36 (1996), “Polyimides, Fundamentals and Application”, MarcelDekker, Inc.

[0157] The present invention further relates to a method for forming a liquid crystal alignment film, comprising:

[0158] - Apply the photo-alignable polymer material of the present invention, or the photo-alignable polymer material obtained by the method of the present invention, onto the substrate;

[0159] - Dry the resulting wet film, and

[0160] - Irradiate the dried film to impart liquid crystal alignment capability.

[0161] The substrate can be transparent or opaque, and is preferably selected from glass and plastic substrates, polymer films (e.g., polyethylene terephthalate (PET), triacetyl cellulose (TAC), polypropylene), optionally coated with indium tin oxide (ITO). In particular, the composition can be applied to a support optionally coated with electrodes (e.g., a glass plate coated with indium tin oxide (ITO)) to produce a uniform layer with a thickness of 0.005 to 50 µm, preferably 0.025 to 1.00 µm, more preferably 0.050 to 0.200 µm.

[0162] The composition can be applied to the substrate using 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, casting coating, spray coating, slot-orifice coating, calendering coating, electrodeposition coating, dip coating, or die coating. Printing methods include letterpress printing (e.g., flexographic printing, inkjet printing), gravure printing (e.g., direct gravure printing or offset gravure printing), lithography (e.g., offset printing), or stencil printing (e.g., screen printing). Preferred printing methods are offset and inkjet printing.

[0163] After the composition is applied to the substrate, the wet film is dried and the area to be oriented is 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 generate an image of the structure.

[0164] The method suitably includes a heat treatment step of the dried film at a temperature ranging from 80 to 230°C. This heat treatment step allows most or all of the polyamic acid groups to be converted into polyimide groups. The resulting polyimide film exhibits excellent physical properties, such as heat resistance, compatibility with liquid crystals, and mechanical strength.

[0165] In one embodiment, alignment light is used. Preferably, the wavelength is in the UV-A, UV-B, and / or UV-C range, or in the visible light range. A suitable wavelength can be in the range of 100 to 350 nm, preferably 100 to 280 nm. The instantaneous direction of the alignment light can be perpendicular to the substrate or at any tilt angle. Irradiation with alignment light can be performed in a single step or in several separate steps. In a preferred embodiment of the invention, the treatment with alignment light is performed in a single step.

[0166] More preferably, the alignment light is at least partially linearly polarized, elliptically polarized (e.g., circularly polarized), or unpolarized; most preferably, it is at least circularly polarized or partially linearly polarized light, or unpolarized light exposed at an angle. In particular, the most preferred alignment light refers to substantially polarized light, especially linearly polarized light.

[0167] The direction of polarization is understood to refer to the line of intersection between the alignment layer surface and the polarization plane of the polarized light during exposure. If the polarized light is elliptically polarized, then the polarization plane should refer to the plane defined by the incident direction of the light and the major axis of the polarization ellipse.

[0168] In the context of this invention, the term polarization direction is used not only to describe the direction during the exposure process, but also to refer to the direction of polarized light applied to the alignment layer during exposure after exposure.

[0169] Irradiation time depends on the output power of a single lamp and can vary from seconds to hours. Irradiation of the homogeneous layer can also be performed using a filter that, for example, only allows certain wavelengths to pass through, such as wavelengths suitable for inducing [2+2] inverse ring addition.

[0170] The present invention further relates to liquid crystal alignment films obtained by the method of the present invention.

[0171] This invention further relates to optical devices comprising the liquid crystal alignment film of this invention. Optical devices are understood to include structured or unstructured optical and electro-optic elements and devices comprising the liquid crystal alignment film obtained by the method of this invention. Examples of structured or unstructured optical and electro-optic 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.

[0172] The present invention will be described in more detail through the following embodiments.

[0173] Polyamic acid and its orientation formulation were prepared. The orientation formulation was then tested.

[0174] Method A: Intrinsic viscosity

[0175] The intrinsic viscosity of polyamic acid was determined using an Ubbelohde viscometer, which consists of a capillary tube through which the sample flows under gravity. The time (t) it takes for a given volume to pass through the capillary tube was measured, and the intrinsic viscosity (η) was calculated. intr ] = [dL / g]).

[0176] Method B: Alignment Quality

[0177] The alignment quality of the cells obtained from this alignment formulation is quantified by evaluating the output ellipticity of each cell on a polarizing optical microscope (POM) between the polarizer and analyzer. The cell is illuminated with white light from a linear polarizer having polarization parallel to the in-plane optical axis. Using a photomultiplier tube as the voltage, the maximum intensity "a" when the analyzer is parallel to the polarizer and the minimum intensity "b" when the analyzer is perpendicular to the polarizer are measured. The leakage factor is calculated using the formula a / b.

[0178] Alignment quality is defined as excellent for an a / b value greater than 3500, good for an a / b value greater than 2500 and between 3500, moderate for an a / b value greater than 1500 and between 2500, and poor for an a / b value less than or equal to 1500.

[0179] Example

[0180] In the following text, the abbreviation NMP refers to 1-methyl-2-pyrrolidone (CAS: 872-50-4). The abbreviation BC refers to 2-butoxyethanol (butyl cellosolve, CAS: 11-76-2).

[0181] The following compounds were used to obtain the polymers of the examples:

[0182]

[0183] Comparative Example 1: Preparation of polyamic acid CP1 and the corresponding orientation formulation CF1

[0184] 1813 mg (9.247 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 1000 mg (9.247 mmol) of phenyl-1,3-diamine in 11254 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.34 dL / g was obtained. intrPolyamic acid CP1. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give the orientation formulation CF1.

[0185] Comparative Example 2: Preparation of polyamic acid CP2 and the corresponding orientation formulation CF2

[0186] 2073 mg (9.247 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 1000 mg (9.247 mmol) of phenyl-1,3-diamine in 12292 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.43 dL / g was obtained. intr Polyamic acid CP2. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give the orientation formulation CF2.

[0187] Comparative Example 3: Preparation of polyamic acid CP3 and the corresponding orientation formulation CF3

[0188] 924 mg (4.711 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 1000 mg (4.711 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 7695 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.52 dL / g was obtained. intr Polyamic acid CP3. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give the orientation formulation CF3.

[0189] Comparative Example 4: Preparation of polyamic acid CP4 and the corresponding orientation formulation CF4

[0190] 2112 mg (9.421 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0℃.2,6 Decane-3,5,8,10-tetraone was added to a solution of 2000 mg (9.421 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 16448 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.74 dL / g was obtained. intr Polyamic acid CP4. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give the orientation formulation CF4.

[0191] Example 1: Preparation of polyamic acid P1 and the corresponding orientation formulation F1

[0192] 1232 mg (6.281 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 170 mg (1.570 mmol) phenyl-1,3-diamine and 1000 mg (4.711 mmol) 4-(4-amino-2-methylphenyl)-3-methylaniline in 11254 mg NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.63 dL / g was obtained. intr Polyamic acid P1. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F1.

[0193] Example 2: Preparation of polyamic acid P2 and the corresponding orientation formulation F2

[0194] 1.848 mg (9.421 mmol) of 4,9-dioxatricyclo[5.3.0.0] was released at 0 °C. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 509 mg (4.711 mmol) of phenyl-1,3-diamine and 1000 mg (4.711 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 13428 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.41 dL / g was obtained. intrPolyamic acid P2. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F2.

[0195] Example 3: Preparation of polyamic acid P3 and the corresponding orientation formulation F3

[0196] 1408 mg (6.281 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0 °C. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 170 mg (1.570 mmol) of phenyl-1,3-diamine and 1000 mg (4.711 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 10311 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.53 dL / g was obtained. intr Polyamic acid P3. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F3.

[0197] Example 4: Preparation of polyamic acid P4 and the corresponding orientation formulation F4

[0198] 2112 mg (9.421 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 509 mg (4.711 mmol) of phenyl-1,3-diamine and 1000 mg (4.711 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 14485 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.39 dL / g was obtained. intr Polyamic acid P4. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F4.

[0199] Example 5: Preparation of polyamic acid P5 and the corresponding orientation formulation F5

[0200] 907 mg (4.624 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 [Decane-3,5,8,10-tetraone and 3109 mg (13.871 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] 2,6 A mixture of decane-3,5,8,10-tetraone was added to a solution of 500 mg (4.624 mmol) phenyl-1,3-diamine and 2945 mg (13.871 mmol) 4-(4-amino-2-methylphenyl)-3-methylaniline in 29843 mg NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.55 dL / g was obtained. intr Polyamic acid P5. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F5.

[0201] Example 6: Preparation of polyamic acid P6 and the corresponding orientation formulation F6

[0202] 453 mg (2.312 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 [Decane-3,5,8,10-tetraone and 1555 mg (6.935 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] 2,6 A mixture of decane-3,5,8,10-tetraone was added to a solution of 500 mg (4.624 mmol) phenyl-1,3-diamine and 982 mg (4.624 mmol) 4-(4-amino-2-methylphenyl)-3-methylaniline in 13959 mg NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow to react for an additional 72 hours. An intrinsic viscosity η of 0.46 dL / g was obtained. intr Polyamic acid P6. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F6.

[0203] Example 7: Preparation of polyamic acid P7 and the corresponding orientation formulation F7

[0204] 1232 mg (6.281 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 170 mg (1.570 mmol) of phenyl-1,2-diamine and 1000 mg (4.711 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 11254 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.43 dL / g was obtained. intr Polyamic acid P7. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F7.

[0205] Example 8: Preparation of polyamic acid P8 and the corresponding orientation formulation F8

[0206] 1.848 mg (9.421 mmol) of 4,9-dioxatricyclo[5.3.0.0] was released at 0 °C. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 509 mg (4.711 mmol) of phenyl-1,2-diamine and 1000 mg (4.711 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 13428 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.23 dL / g was obtained. intr Polyamic acid P8. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F8.

[0207] Example 9: Preparation of polyamic acid P9 and the corresponding orientation formulation F9

[0208] 1408 mg (6.281 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0 °C. 2,6Decane-3,5,8,10-tetraone was added to a solution of 170 mg (1.570 mmol) of phenyl-1,2-diamine and 1000 mg (4.711 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 10311 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.38 dL / g was obtained. intr Polyamic acid P9. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F9.

[0209] Example 10: Preparation of polyamic acid P10 and the corresponding orientation formulation F10

[0210] 1605 mg (8.185 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 250 mg (2.046 mmol) of 4-methylphenyl-1,2-diamine and 1303 mg (6.139 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 12634 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.42 dL / g was obtained. intr Polyamic acid P10. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F10.

[0211] Example 11: Preparation of polyamic acid P11 and the corresponding orientation formulation F11

[0212] 803 mg (4.093 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 250 mg (2.046 mmol) of 4-methylphenyl-1,2-diamine and 434 mg (2.046 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 5948 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.40 dL / g was obtained.intr Polyamic acid P11. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F11.

[0213] Example 12: Preparation of polyamic acid P12 and the corresponding orientation formulation F12

[0214] 1835 mg (8.185 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0 °C. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 250 mg (2.046 mmol) of 4-methylphenyl-1,2-diamine and 1303 mg (6.139 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 13553 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.69 dL / g was obtained. intr Polyamic acid P12. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F12.

[0215] Example 13: Preparation of polyamic acid P13 and the corresponding orientation formulation F13

[0216] 917 mg (4.093 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 250 mg (2.046 mmol) of 4-methylphenyl-1,2-diamine and 434 mg (2.046 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 6407 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.43 dL / g was obtained. intr Polyamic acid P13. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F13.

[0217] Example 14: Preparation of polyamic acid P14 and the corresponding orientation formulation F14

[0218] 1605 mg (8.185 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 250 mg (2.046 mmol) of 2-methylphenyl-1,3-diamine and 1303 mg (6.139 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 12634 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.58 dL / g was obtained. intr Polyamic acid P14. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F14.

[0219] Example 15: Preparation of polyamic acid P15 and the corresponding orientation formulation F15

[0220] 803 mg (4.093 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 250 mg (2.046 mmol) of 2-methylphenyl-1,3-diamine and 434 mg (2.046 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 5948 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.42 dL / g was obtained. intr Polyamic acid P15. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F15.

[0221] Example 16: Preparation of polyamic acid P16 and the corresponding orientation formulation F16

[0222] 1835 mg (8.185 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0 °C. 2,6Decane-3,5,8,10-tetraone was added to a solution of 250 mg (2.046 mmol) of 2-methylphenyl-1,3-diamine and 1303 mg (6.139 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 13553 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.49 dL / g was obtained. intr Polyamic acid P16. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F16.

[0223] Example 17: Preparation of polyamic acid P17 and the corresponding orientation formulation F17

[0224] 917 mg (4.093 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 250 mg (2.046 mmol) of 2-methylphenyl-1,3-diamine and 434 mg (2.046 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 6407 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.38 dL / g was obtained. intr Polyamic acid P17. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F17.

[0225] Example 18: Preparation of polyamic acid P18 and the corresponding orientation formulation F18

[0226] 1605 mg (8.185 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6Decane-3,5,8,10-tetraone was added to a solution of 250 mg (2.046 mmol) of 4-methylphenyl-1,3-diamine and 1303 mg (6.139 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 12634 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.79 dL / g was obtained. intr Polyamic acid P18. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F18.

[0227] Example 19: Preparation of polyamic acid P19 and the corresponding orientation formulation F19

[0228] 803 mg (4.093 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 250 mg (2.046 mmol) of 4-methylphenyl-1,3-diamine and 434 mg (2.046 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 5948 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.40 dL / g was obtained. intr Polyamic acid P19. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F19.

[0229] Example 20: Preparation of polyamic acid P20 and the corresponding orientation formulation F20

[0230] 1835 mg (8.185 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0 °C. 2,6Decane-3,5,8,10-tetraone was added to a solution of 250 mg (2.046 mmol) of 4-methylphenyl-1,3-diamine and 1303 mg (6.139 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 13553 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.59 dL / g was obtained. intr Polyamic acid P20. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F20.

[0231] Example 21: Preparation of polyamic acid P21 and the corresponding orientation formulation F21

[0232] 917 mg (4.093 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 250 mg (2.046 mmol) of 4-methylphenyl-1,3-diamine and 434 mg (2.046 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 6407 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.44 dL / g was obtained. intr Polyamic acid P21. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F21.

[0233] Example 22: Preparation of polyamic acid P22 and the corresponding orientation formulation F22

[0234] 1232 mg (6.281 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 170 mg (1.570 mmol) of phenyl-1,4-diamine and 1000 mg (4.711 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 11254 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.50 dL / g was obtained.intr Polyamic acid P22. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F22.

[0235] Example 23: Preparation of polyamic acid P23 and the corresponding orientation formulation F23

[0236] 1.848 mg (9.421 mmol) of 4,9-dioxatricyclo[5.3.0.0] was released at 0 °C. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 509 mg (4.711 mmol) of phenyl-1,4-diamine and 1000 mg (4.711 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 13428 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.41 dL / g was obtained. intr Polyamic acid P23. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F23.

[0237] Example 24: Preparation of polyamic acid P24 and the corresponding orientation formulation F24

[0238] 1408 mg (6.281 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0 °C. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 170 mg (1.570 mmol) of phenyl-1,4-diamine and 1000 mg (4.711 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 10311 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.53 dL / g was obtained. intr Polyamic acid P24. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F24.

[0239] Example 25: Preparation of polyamic acid P25 and the corresponding orientation formulation F25

[0240] 907 mg (4.624 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 [Decane-3,5,8,10-tetraone and 3109 mg (13.871 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] 2,6 A mixture of decane-3,5,8,10-tetraone was added to a solution of 500 mg (4.624 mmol) phenyl-1,4-diamine and 2945 mg (13.871 mmol) 4-(4-amino-2-methylphenyl)-3-methylaniline in 29843 mg NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.63 dL / g was obtained. intr Polyamic acid P25. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F25.

[0241] Example 26: Preparation of polyamic acid P26 and the corresponding orientation formulation F26

[0242] 1440 mg (7.343 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 250 mg (1.836 mmol) of 2,5-dimethylphenyl-1,4-diamine and 1169 mg (5.507 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 11436 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.59 dL / g was obtained. intr Polyamic acid P26. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F26.

[0243] Example 27: Preparation of polyamic acid P27 and the corresponding orientation formulation F27

[0244] 1646 mg (7.343 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0 °C. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 250 mg (1.836 mmol) of 2,5-dimethylphenyl-1,4-diamine and 1169 mg (7.343 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 12260 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.68 dL / g was obtained. intr Polyamic acid P27. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F27.

[0245] Example 28: Preparation of polyamic acid P28 and the corresponding orientation formulation F28

[0246] 823 mg (3.671 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0 °C. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 250 mg (1.836 mmol) of 2,5-dimethylphenyl-1,4-diamine and 390 mg (1.836 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 5851 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.62 dL / g was obtained. intr Polyamic acid P28. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F28.

[0247] Example 29: Preparation of polyamic acid P29 and the corresponding orientation formulation F29

[0248] 1232 mg (6.281 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6Decane-3,5,8,10-tetraone was added to a solution of 248 mg (1.570 mmol) of naphthyl-1,5-diamine and 1000 mg (4.711 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 9920 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.51 dL / g was obtained. intr Polyamic acid P29. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F29.

[0249] Example 30: Preparation of polyamic acid P30 and the corresponding orientation formulation F30

[0250] 1408 mg (6.281 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0 °C. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 248 mg (1.570 mmol) of naphthyl-1,5-diamine and 1000 mg (4.711 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 10625 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.47 dL / g was obtained. intr Polyamic acid P30. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F30.

[0251] Example 31: Preparation of polyamic acid P31 and the corresponding orientation formulation F31

[0252] 2112 mg (9.421 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6Decane-3,5,8,10-tetraone was added to a solution of 745 mg (4.711 mmol) of naphthyl-1,5-diamine and 1000 mg (4.711 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 15.429 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.45 dL / g was obtained. intr Polyamic acid P31. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F31.

[0253] Example 32: Preparation and alignment quality quantification of F1-based boxes

[0254] Formulation F1 was spin-coated onto two ITO-coated glass substrates at approximately 2500 rpm for 30 seconds. Following spin-coating, the substrates were subjected to a baking process consisting of a pre-baking at 120°C for 130 seconds and a baking at 230°C for 30 minutes. The substrates were then exposed to linearly polarized light (500 mJ) at an incident angle of 0° relative to the substrate surface normal. cm -2 -LPUVC). The substrate is post-baked at 230°C for 30 minutes. A cell is manufactured by assembling the two substrates, with the exposed polymer layer facing the inside of the cell. The substrates are adjusted relative to each other so that the induced alignment directions are parallel to each other. The cell is capillarily filled with a liquid crystal having the following properties: T S→N <40 ℃, T N→I =80 ℃, Δn (589 nnm, 25 ℃) = 0.103 and Δε (1kHz, 25 ℃) = 10.1, K11 (25 ℃) = 11.6, K11 (25 ℃) = 6.9, K33 (25 ℃) = 14.7. Finally, the filled box is further heat-annealed at 90 ℃ for 30 minutes, thereby completing the box assembly process. The alignment quality of the obtained box is quantified using the method described above.

[0255] The liquid crystals in the cells prepared using F1 exhibited well-defined and uniform planar orientation before and after thermal annealing of the cells. Tilt angles below 1° were measured using a rotating analyzer method from Shintech, and excellent light leakage factors were also measured.

[0256] Comparative Example 5: Preparation and alignment quality quantification of CF1-based boxes

[0257] Except for coating formulation CF1, the cell was prepared as in Example 32 using F1. The liquid crystal in the cell exhibited poor orientation before thermal annealing and planar orientation after thermal annealing. Tilt angles below 1° were measured using a rotating analyzer method from Shintech, and poor light leakage factors were also measured.

[0258] Example 33: Preparation and alignment quality comparison of boxes using CF2 to CF4 and F2 to F31

[0259] Except for coating formulations CF2 to CF4 and F2 to F31, the boxes were prepared as in Example 32. The tilt angle of all boxes below 1° was measured using a rotating analyzer method from Shintech, and the alignment quality was measured. The results are shown in Table 1 below.

[0260] Table 1

[0261]

[0262]

[0263] Comparative Example 6: Preparation of polyamic acid CP5 and the corresponding orientation formulation CF5

[0264] 867 mg (4.419 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to 1000 mg (4.419 mmol) of a solution of 4-[(4-amino-2-methylphenyl)methyl]-2-methylaniline in 7466 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.48 dL / g was obtained. intr Polyamic acid CP5. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give the orientation formulation CF5.

[0265] Comparative Example 7: Preparation of polyamic acid CP6 and the corresponding orientation formulation CF6

[0266] 991 mg (4.419 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0 °C. 2,6Decane-3,5,8,10-tetraone was added to 1000 mg (4.419 mmol) of a solution of 4-[(4-amino-2-methylphenyl)methyl]-2-methylaniline in 7962 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.42 dL / g was obtained. intr Polyamic acid CP6. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give the orientation formulation CF6.

[0267] Comparative Example 8: Preparation of polyamic acid CP7 and the corresponding orientation formulation CF7

[0268] 1125 mg (5.019 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0 °C. 2,6 Decane-3,5,8,10-tetraone was added to 1000 mg (5.019 mmol) of a solution of 4-[(4-amino-2-methylphenyl)methyl]-2-methylaniline in 8500 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.73 dL / g was obtained. intr Polyamic acid CP7. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give the orientation formulation CF7.

[0269] Comparative Example 9: Preparation of polyamic acid CP8 and the corresponding orientation formulation CF8

[0270] 984 mg (5.019 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 500 mg (2.509 mmol) of N1-(4-aminophenyl)benzene-1,4-diamine and 502 mg (2.509 mmol) of 4-(4-aminophenoxy)aniline in 7947 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow to react for an additional 72 hours. An intrinsic viscosity η of 0.42 dL / g was obtained. intrPolyamic acid CP8. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give the orientation formulation CF8.

[0271] Comparative Example 10: Preparation of polyamic acid CP9 and the corresponding orientation formulation CF9

[0272] 984 mg (5.019 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 500 mg (2.509 mmol) of N1-(4-aminophenyl)benzene-1,4-diamine and 533 mg (2.509 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 8068 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.74 dL / g was obtained. intr Polyamic acid CP9. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give the orientation formulation CF9.

[0273] Example 34: Preparation of polyamic acid P32 and the corresponding orientation formulation F32

[0274] 1813 mg (9.247 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 250 mg (2.312 mmol) of phenyl-1,3-diamine and 1382 mg (6.935 mmol) of 4N1-(4-aminophenyl)phenyl-1,4-diamine in 13781 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.55 dL / g was obtained. intr Polyamic acid P32. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F32.

[0275] Example 35: Preparation of polyamic acid P33 and the corresponding orientation formulation F33

[0276] 907 mg (4.624 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 250 mg (2.312 mmol) of phenyl-1,3-diamine and 461 mg (2.312 mmol) of 4N1-(4-aminophenyl)phenyl-1,4-diamine in 8087 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.51 dL / g was obtained. intr Polyamic acid P33. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F33.

[0277] Comparative Example 11: Preparation of polyamic acid CP10 and the corresponding orientation formulation CF10

[0278] 1120 mg (4.994 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 1000 mg (4.994 mmol) of 4-(4-aminophenoxy)aniline in 8478 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.45 dL / g was obtained. intr Polyamic acid CP10. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give the orientation formulation CF10.

[0279] Example 36: Preparation of polyamic acid P34 and the corresponding orientation formulation F34

[0280] 1306 mg (6.659 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6Decane-3,5,8,10-tetraone was added to a solution of 263 mg (1.665 mmol) of naphthalene-1,5-diamine and 1000 mg (4.994 mmol) of 4-(4-aminophenoxy)aniline in 10277 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.47 dL / g was obtained. intr Polyamic acid P34. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F34.

[0281] Example 37: Preparation of polyamic acid P35 and the corresponding orientation formulation F35

[0282] 1959 mg (9.988 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 790 mg (4.994 mmol) of naphthalene-1,5-diamine and 1000 mg (4.994 mmol) of 4-(4-aminophenoxy)aniline in 14995 mg of NMP. After 2 hours at 0°C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. Polyamic acid P35 has an intrinsic viscosity η of 0.46 dL / g. intr Add 4650 mg of NMP and 2850 mg of BC to 2500 mg of the 20% NMP solution. Stir the resulting mixture at room temperature for 30 minutes and filter it through a 0.2 µm PTFE filter to give orientation formulation F35.

[0283] Example 38: Preparation of polyamic acid P36 and the corresponding orientation formulation F36

[0284] 1679 mg (7.491 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0 °C. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 593 mg (3.746 mmol) of naphthalene-1,5-diamine and 593 mg (3.746 mmol) of 4-(4-aminophenoxy)aniline in 12087 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.24 dL / g was obtained. intrPolyamic acid P36. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F36.

[0285] Example 39: Preparation of boxes using CF5 to CF10 and F32 to F36 and comparison of alignment quality

[0286] Except for coating formulations CF5 to CF10 and F32 to F36, the boxes were prepared as in Example 32. The alignment quality of each box was measured, and the results are shown in Table 2 below.

[0287] Table 2

[0288]

[0289] Comparative Example 12: Preparation of polyamic acid CP11 and the corresponding orientation formulation CF11

[0290] 1440 mg (7.343 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 1000 mg (7.343 mmol) of 4-(2-aminoethyl)aniline in 9760 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.48 dL / g was obtained. intr Polyamic acid CP11. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give the orientation formulation CF11.

[0291] Comparative Example 13: Preparation of polyamic acid CP12 and the corresponding orientation formulation CF12

[0292] 1646 mg (7.343 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0 °C. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 1000 mg (7.343 mmol) of 4-(2-aminoethyl)aniline in 10584 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.62 dL / g was obtained. intrPolyamic acid CP12. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give the orientation formulation CF12.

[0293] Example 40: Preparation of polyamic acid P37 and the corresponding orientation formulation F37

[0294] 1440 mg (7.343 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 500 mg (3.671 mmol) of 4-(2-aminoethyl)aniline and 779 mg (3.671 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 10877 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow to react for an additional 72 hours. An intrinsic viscosity η of 0.82 dL / g was obtained. intr Polyamic acid P37. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F37.

[0295] Example 41: Preparation of polyamic acid P38 and the corresponding orientation formulation F38

[0296] 1646 mg (7.343 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] was added at 0 °C. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 500 mg (3.671 mmol) of 4-(2-aminoethyl)aniline and 779 mg (3.671 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 11702 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.81 dL / g was obtained. intr Polyamic acid P38. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F38.

[0297] Example 42: Preparation of polyamic acid P39 and the corresponding orientation formulation F39

[0298] 720 mg (3.671 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 [Decane-3,5,8,10-tetraone and 2469 mg (11.014 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] 2,6 A mixture of decane-3,5,8,10-tetraones was added to a solution of 1000 mg (7.343 mmol) of 4-(2-aminoethyl)aniline and 1559 mg (7.343 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 22991 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. An intrinsic viscosity η of 0.57 dL / g was obtained. intr Polyamic acid P39. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F39.

[0299] Example 43: Preparation of polyamic acid P40 and the corresponding orientation formulation F40

[0300] 1440 mg (7.343 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 [Decane-3,5,8,10-tetraone and 1646 mg (7.343 mmol) of 1,6-dimethyl-4,9-dioxatricyclo[5.3.0.0] 2,6 A mixture of decane-3,5,8,10-tetraones was added to a solution of 1000 mg (7.343 mmol) of 4-(2-aminoethyl)aniline and 1559 mg (7.343 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 22579 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow to react for an additional 72 hours. An intrinsic viscosity η of 0.52 dL / g was obtained. intr Polyamic acid P40. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F40.

[0301] Example 44: Preparation of polyamic acid P41 and the corresponding orientation formulation F41

[0302] 1440 mg (7.343 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 500 mg (3.671 mmol) of 4-(2-aminoethyl)aniline, 199 mg (1.836 mmol) of phenyl-1,3-diamine, and 390 mg (1.836 mmol) of 4-(4-amino-2-methylphenyl)-3-methylaniline in 10113 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and allow for an additional 72 hours of reaction. An intrinsic viscosity η of 0.65 dL / g was obtained. intr Polyamic acid P41. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give orientation formulation F41.

[0303] Comparative Example 45: Preparation of polyamic acid CP13 and the corresponding orientation formulation CF13

[0304] 802 mg (4.092 mmol) of 4,9-dioxatricyclo[5.3.0.0] was added at 0℃. 2,6 Decane-3,5,8,10-tetraone was added to a solution of 1000 mg (4.092 mmol) of 4-[2-(4-aminophenoxy)ethoxy]aniline in 7052 mg of NMP. After 2 hours at 0 °C, the reaction mixture was allowed to warm to room temperature and react for an additional 72 hours. Polyamic acid CP13 with a specific logarithmic viscosity [η] of 0.71 dL / g was obtained. 4650 mg of NMP and 2850 mg of BC were added to 2500 mg of this 20 wt% NMP solution. The resulting mixture was stirred at room temperature for 30 minutes and filtered through a 0.2 µm PTFE filter to give the orientation formulation CF13.

[0305] Example 46: Preparation of boxes using CF11, CF12, CF13 and F37 to F41 and comparison of alignment quality

[0306] Except for coating formulations CF11, CF12, CF13, and F37 to F41, the boxes were prepared as in Example 32. The alignment quality of each box was measured, and the results are shown in Table 3 below.

[0307] Table 3

[0308]

[0309] Example 47: Preparation of orientation formulation F43

[0310] Mix 3500 mg of alignment formulation F3 and 1500 mg of alignment formulation CF13 together at room temperature for 30 minutes and filter through a 0.2 µm PTFE filter to give alignment formulation F43.

[0311] Example 48: Preparation of alignment formulation F44

[0312] Mix 3000 mg of alignment formulation F3 and 2000 mg of alignment formulation CF13 together at room temperature for 30 minutes and filter through a 0.2 µm PTFE filter to give alignment formulation F44.

[0313] Example 49: Preparation of alignment formulation F45

[0314] Mix 3500 mg of alignment formulation F1 and 1500 mg of alignment formulation CF13 together at room temperature for 30 minutes and filter through a 0.2 µm PTFE filter to give alignment formulation F45.

[0315] Example 50: Preparation of orientation formulation F46

[0316] Mix 3500 mg of alignment formulation F3 and 1500 mg of alignment formulation CF5 together at room temperature for 30 minutes and filter through a 0.2 µm PTFE filter to give alignment formulation F46.

[0317] Example 51: Preparation of alignment formulation F47

[0318] Mix 3500 mg of alignment formulation F3 and 1500 mg of alignment formulation CF6 together at room temperature for 30 minutes and filter through a 0.2 µm PTFE filter to give alignment formulation F47.

[0319] Example 52: Preparation of orientation formulation F48

[0320] Mix 3500 mg of alignment formulation F3 and 1500 mg of alignment formulation CF10 together at room temperature for 30 minutes and filter through a 0.2 µm PTFE filter to give alignment formulation F48.

[0321] Example 53: Preparation of alignment formulation F49

[0322] Mix 3000 mg of alignment formulation F3 and 3000 mg of alignment formulation CF13 together at room temperature for 30 minutes and filter through a 0.2 µm PTFE filter to give alignment formulation F49.

[0323] Example 54: Preparation and alignment quality comparison of boxes using CF5, CF6, CF10, CF13, and F43 to F49

[0324] Except for coating formulations CF5, CF6, CF10, and CF13, and F43 to F49, the boxes were prepared as in Example 32 using F1. The alignment quality of each box was measured and summarized in Table 4 below.

[0325] Table 4

[0326]

[0327] It is evident that the photo-orientable polymer materials of the present invention exhibit moderate to excellent orientation quality.

Claims

1. A photo-alignable polymeric material for forming a liquid crystal alignment film, comprising repeating units represented by formula (I). (I) Where P 1 It is a diamine HN2-Ar 1 -X 1 -NH2 divalent residues; and the repeating unit represented by equation (II) (II) Where P 2 It is a diamine HN2-Ar 2 -X 2 -Ar 3 -NH2 divalent residues; Ar 1 Ar 2 and Ar 3 Independently selected from C6-C 14 -Aspartic acid, of which Ar 1 Ar 2 and Ar 3 It can be independently substituted by one or more of OH, O-C1-C6-alkyl, C1-C6-alkyl, COOH, COO-C1-C6-alkyl and C1-C6-fluoroalkyl; X 1 Independently selected from bonds, C1-C6-alkylene, O-C1-C6-alkylene and NH-C1-C6-alkylene, wherein each C1-C6-alkylene may be independently substituted by one or more of OH, O-C1-C6-alkyl and F; X 2 Independently selected from bond, O, NH, C1-C6-alkylene, O-C1-C6-alkylene, NH-C1-C6-alkylene, NH-C1-C6-alkylene-NH, NH-CO-(C1-C6-alkylene), NH-CO-(C1-C6-alkylene)-CO-NH, CO-NH-(C1-C6-alkylene)-NH-CO, wherein each C1-C6-alkylene may be independently substituted by one or more of OH, O-C1-C6-alkyl and F; Q is a tetravalent residue of a tetracarboxylic dianhydride, and at least a portion of Q is represented by formula (A). (A) in R 1 Independently selected from H and C1-C6-alkyl; Y is independently selected from OH and O. – M + and O-C1-C6-alkyl, wherein M + It is an alkali metal cation.

2. The photo-alignable polymer material according to claim 1, wherein... Ar 1 Ar 2 and Ar 3 Independently selected from phenylene and naphthylene; X 1 and X 2 Each is a key; Among them, Ar 1 Ar 2 Ar 3 It can be independently substituted with one or more C1-C3-alkyl groups.

3. The photo-alignable polymer material according to claim 2, wherein... Ar 1 Independently selected from phenylene and naphthylene; and Ar 2 and Ar 3 Each is a phenylene oxide.

4. The photo-alignable polymer material according to any one of the preceding claims, wherein, The molar ratio of the repeating unit in formula (I) to the repeating unit in formula (II) is in the range of 1:10 to 10:

1.

5. The photo-orientable polymeric material according to any one of the preceding claims, wherein a portion of Q is represented by formula (B). (B) Where n is an integer independently selected from 0 and 1.

6. A photo-orientable polymeric material composition comprising the photo-orientable polymeric material as described above, and polyamic acid and / or polyimide.

7. A photo-orientable polymeric material composition comprising the photo-orientable polymeric material and at least one solvent.

8. A method for producing a photo-alignable polymeric material for forming a liquid crystal alignment film, comprising copolymerizing a mixture comprising a diamine of formula (1), a diamine of formula (2), and a cyclobutanetetracarboxylic dianhydride or a derivative thereof of formula (3). HN2-Ar 1 -X 1 -NH2 (1) HN2-Ar 2 -X 2 -On 3 -NH2 (2) (3) in Ar 1 Ar 2 and Ar 3 Independently selected from C6-C 14 -Aspartic acid, of which Ar 1 Ar 2 and Ar 3 It can be independently substituted by one or more of OH, O-C1-C6-alkyl, C1-C6-alkyl, COOH, COO-C1-C6-alkyl and C1-C6-fluoroalkyl; X 1 Independently selected from bonds, C1-C6-alkylene, O-C1-C6-alkylene and NH-C1-C6-alkylene, wherein each C1-C6-alkylene may be independently substituted by one or more of OH, O-C1-C6-alkyl and F; X 2 Independently selected from bond, O, NH, C1-C6-alkylene, O-C1-C6-alkylene, O-C1-C6-alkylene-O, NH-C1-C6-alkylene, NH-C1-C6-alkylene-NH, NH-CO-(C1-C6-alkylene), NH-CO-(C1-C6-alkylene)-CO-NH, CO-NH-(C1-C6-alkylene)-NH-CO, wherein each C1-C6-alkylene may be independently substituted by one or more of OH, O-C1-C6-alkyl and F; and R 1 Independently selected from H and C1-C6-alkyl.

9. The method according to claim 8, wherein Ar 1 Ar 2 and Ar 3 Independently selected from phenylene and naphthylene; X 1 and X 2 Each is a key; Among them, Ar 1 Ar 2 Ar 3 It can be independently substituted with one or more C1-C3-alkyl groups.

10. The method of claim 9, wherein Ar 1 Independently selected from phenylene and naphthylene; and Ar 2 and Ar 3 Each is a phenylene oxide.

11. The method according to any one of claims 8 to 10, wherein, The molar ratio of the first diamine of formula (1) to the second diamine of formula (2) is in the range of 1:10 to 10:

1.

12. The method according to any one of claims 8 to 11, wherein, The mixture comprises cyclopentanetetracarboxylic anhydride or a derivative thereof of formula (4). (4) Where n is an integer independently selected from 0 and 1.

13. A method for forming a liquid crystal alignment film, comprising: - Apply the photo-alignable polymer material according to any one of claims 1 to 5, the photo-alignable polymer material composition according to claims 6 and / or 7, or the photo-alignable polymer material obtained by the method according to any one of claims 8 to 12 to a substrate; - To dry the resulting wet film; and - Irradiate the dried film to impart liquid crystal alignment capability.

14. A liquid crystal alignment film obtained by the method according to claim 13.

15. An optical device comprising the liquid crystal alignment film according to claim 14.

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