Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
A liquid crystal aligning agent with specific compounds and polymers addresses the issues of pretilt angle and AC afterimages in liquid crystal display elements, enhancing viewing angle characteristics and reducing image retention.
Patent Information
- Application Number
- PCT/JP2025/011803
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-03-27
- Filing Date
- 2025-03-25
- Publication Date
- 2025-10-02
AI Technical Summary
Existing liquid crystal display elements face challenges in achieving a low pretilt angle and suppressing AC afterimages, particularly in IPS and FFS modes, which affect viewing angle characteristics and long-term image retention.
A liquid crystal aligning agent containing specific compounds and polymers, such as polyimides, is used to create a liquid crystal alignment film with enhanced flexibility and alignment control, thereby achieving a low pretilt angle and reducing AC afterimages.
The solution results in a liquid crystal alignment film that effectively manages pretilt angles and suppresses AC afterimages, improving viewing angle characteristics and reducing long-term image retention in liquid crystal display elements.
Smart Images
Figure JP2025011803_02102025_PF_FP_ABST
Abstract
Description
Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
[0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display device using the liquid crystal alignment film.
[0002] Liquid crystal display elements are widely used in a wide range of applications, from small devices such as mobile phones and smartphones to relatively large devices such as televisions and monitors. Various driving methods have been developed, each differing in electrode structure and physical properties of the liquid crystal molecules used. Known liquid crystal display elements use various modes, such as twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), and fringe field switching (FFS). These liquid crystal display elements generally have a liquid crystal alignment film, which is essential for controlling the alignment state of the liquid crystal molecules. Polyamic acid and its derivatives (e.g., polyimide) are commonly used as materials for the liquid crystal alignment film (see Patent Document 1).
[0003] WO2022 / 220199 publication
[0004] A liquid crystal display element generally includes a liquid crystal layer sandwiched between an element substrate and a color filter substrate, pixel electrodes and a common electrode that apply an electric field to the liquid crystal layer, a liquid crystal alignment film that controls the orientation of liquid crystal molecules in the liquid crystal layer, and thin film transistors (TFTs) that switch electrical signals supplied to the pixel electrodes.
[0005] A liquid crystal alignment film used in a liquid crystal display element, typically an IPS mode or an FFS mode, may be required to have a low pretilt angle in order to improve viewing angle characteristics. Furthermore, a liquid crystal alignment film used in such a liquid crystal display element may also be required to have a high alignment control force in order to suppress image retention caused by long-term AC driving (hereinafter also referred to as AC image retention).
[0006] In view of the above, an object of the present invention is to provide a liquid crystal aligning agent that can obtain a liquid crystal alignment film that can obtain a low pretilt angle and suppress AC afterimages, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element using the liquid crystal alignment film.
[0007] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved by using a specific compound, thereby completing the present invention. The present invention relates to a liquid crystal aligning agent characterized by containing the following components (A) and (B), a liquid crystal alignment film obtained from the liquid crystal aligning agent, a liquid crystal display device having the liquid crystal alignment film, and further, a novel compound used in the liquid crystal aligning agent. Component (A): Polymer (A) capable of aligning liquid crystals Component (B): Compound (B) represented by the following formula (1) (In formula (1), Ar １ , and Ar １’ each independently represents a benzene ring, a biphenyl structure, or a naphthalene ring, and one or more hydrogen atoms on the benzene ring, the biphenyl structure, or the naphthalene ring may be substituted with a monovalent group (excluding (q1) to (q4)). X is a divalent organic group represented by the following formula (2). *-X １ -(Y １ -L) ｎ -Y ２ -X ２ -* (2) (In formula (2), X １ , X ２ are each independently a single bond, —O—, *1-O—CO—*2 (*1 and *2 represent a bond, and *1 is Ar １ or Ar １’ L represents a single bond, -O-, -O-C(=O)- or -C(=O)-O-, and when there are multiple Ls, the multiple Ls may be the same or different from one another, provided that at least one L represents -O-C(=O)- or -C(=O)-O-. n is an integer of 1 to 6. Y １ , Y ２each independently represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and some of the hydrogen atoms in the divalent hydrocarbon group may be substituted with a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxy group. １ If there are multiple Y １ may be the same or different.) Q and Q' each independently represent a hydrogen atom or a monovalent group selected from the group consisting of the following (q1) to (q4) and a maleimide group. When formula (1) has a plurality of (q1) to (q4), the plurality of R １ ~R ４ may be the same as or different from each other. (In formula (q1), R １ represents a monovalent organic group, and the monovalent organic group is a carbonyl group, a sulfonyl group, and *1-C(R ｑ１ ) ２ - *2 is bonded to the nitrogen atom via a linking group. ２ represents a hydrogen atom or a monovalent organic group. ｑ１ ) ２ *1 in -*2 represents a bond to the nitrogen atom, and multiple R ｑ１ each independently represents a hydrogen atom or a monovalent organic group. ｑ１ ) ２ *2 in -*2 bonds to a monovalent organic group having a heteroatom-containing group. ３ represents a hydrogen atom or a monovalent organic group. ４ represents a hydrogen atom, a hydroxy group, a halogen atom, or a monovalent organic group. ５ represents a hydrogen atom, a hydroxyl group, or a monovalent organic group. １ or Ar １’ represents the bond that bonds to
[0008] In this specification, * represents a bond in all cases. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Preferred examples of carbamate protecting groups include tert-butoxycarbonyl groups and 9-fluorenylmethoxycarbonyl groups.
[0009] According to the present invention, a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film capable of obtaining a low pretilt angle and suppressing AC afterimages, the liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film are obtained. The mechanism by which the above-mentioned effects of the present invention are obtained is not necessarily clear, but the following is thought to be one of the reasons. First, compound (B) has high flexibility and plasticity due to the presence of an alkylene chain and an ester bond in its structure. The presence of compound (B) in the vicinity of polymer (A) or the introduction of compound (B) into the structure of polymer (A) increases the stretchability of the entire alignment film during alignment treatment, resulting in high liquid crystal alignment, which is thought to be the reason for the above-mentioned effects.
[0010] <Component (A)> The liquid crystal aligning agent of the present invention, like known ones, contains a polymer (A) that is a polymer capable of aligning liquid crystals. However, such a polymer is not particularly limited as long as it has the ability to align liquid crystals. The liquid crystal aligning agent of the present invention may contain one or more such polymers. Examples of the polymer (A) include polyimide precursors, polyimides that are imidized products of polyimide precursors, acrylic polymers, methacrylic polymers (hereinafter, acrylic polymers and methacrylic polymers are also collectively referred to as "(meth)acrylic polymers"), acrylamide polymers, methacrylamide polymers (hereinafter, acrylamide polymers and methacrylamide polymers are also collectively referred to as "(meth)acrylamide polymers"), polystyrene, polysiloxane, polyamide, polyester, polyurethane, polycarbonate, polyurea, polyphenol (novolac resin), maleimide polymers, and polymers into which a compound having an isocyanuric acid skeleton or a triazine skeleton has been introduced.
[0011] The raw materials for producing these polymers include the following. When the polymer is a polyimide precursor or polyimide such as polyamic acid or polyamic acid ester, at least one tetracarboxylic acid dianhydride selected from tetracarboxylic acids or their derivatives and a diamine; when the polymer is a (meth)acrylic polymer, (meth)acrylic acid or a derivative thereof, or a (meth)acrylic acid ester or a derivative thereof; when the polymer is a (meth)acrylamide polymer, (meth)acrylamide or a derivative thereof; when the polymer is polystyrene, styrene or a derivative thereof; when the polymer is polysiloxane, a silane compound having a methoxy group or an ethoxy group; when the polymer is polyamide, at least one dicarboxylic acid component selected from dicarboxylic acids and their derivatives and a diamine component; when the polymer is polyester, at least one dicarboxylic acid component selected from dicarboxylic acids and their derivatives and a diol component; when the polymer is polyurethane, a compound having an isocyanate group and a compound having a hydroxyl group; when the polymer is polycarbonate, a bisphenol derivative and phosgene or a phosgene equivalent (e.g., trichlorophosgene) or diphenyl carbonate; when the polymer is polyurea, a bisisocyanate derivative and a diamine component; If the polymer is a polyphenol (novolac resin), it is a phenol compound component and an aldehyde compound component; if the polymer is a maleimide polymer, it is a maleimide derivative alone or copolymerized with styrene; if the polymer is a polymer into which a compound having an isocyanuric acid skeleton or a triazine skeleton has been introduced, it is a compound having an isocyanuric acid skeleton or a triazine skeleton.
[0012] <Polyimide-Based Polymer> As the polymer (A) contained in the liquid crystal aligning agent of the present invention, from the viewpoints of practicality as a liquid crystal aligning agent, mechanical strength of the coating film, and liquid crystal alignment property, at least one polymer selected from the group consisting of polyimide precursors and polyimides, which are imidized products of polyimide precursors (hereinafter also referred to as "polyimide-based polymers"). The polyimide-based polymer can be produced by a known method. For example, a polyamic acid, which is a polyimide precursor, can be obtained by polymerizing (condensing) a tetracarboxylic acid component consisting of a tetracarboxylic acid dianhydride or a derivative thereof with a diamine component, and a polyimide can be obtained by imidizing this polyimide precursor. Examples of derivatives of tetracarboxylic acid dianhydrides include tetracarboxylic acid dihalides, tetracarboxylic acid dialkyl esters, and tetracarboxylic acid dialkyl ester dihalides.
[0013] <Tetracarboxylic Acid Component> Examples of polyamic acids, which are polyimide precursors, include those obtained from tetracarboxylic acid components containing aromatic tetracarboxylic acid dianhydrides, acyclic aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, or derivatives thereof. The above tetracarboxylic acid dianhydrides or derivatives thereof may be used alone or in combination of two or more. The aromatic tetracarboxylic acid dianhydrides are acid dianhydrides obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to an aromatic ring. The acyclic aliphatic tetracarboxylic acid dianhydrides are acid dianhydrides obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, the chain hydrocarbon structure does not necessarily have to be composed solely of a chain hydrocarbon structure, and may partially contain an alicyclic structure or an aromatic ring structure.
[0014] Alicyclic tetracarboxylic acid dianhydrides are acid dianhydrides obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to an alicyclic structure. However, none of these four carboxy groups are bonded to an aromatic ring. Furthermore, they do not necessarily have to be composed solely of an alicyclic structure, and may partially contain a chain hydrocarbon structure or an aromatic ring structure.
[0015] Among these, the polyamic acid is preferably one obtained using a tetracarboxylic acid component containing a tetracarboxylic dianhydride represented by the following formula (2) or a derivative thereof. (In formula (2), Z represents a structure selected from the following formulas (x-1) to (x-13).) (In the above formula, R １ ~R ４ R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, or a phenyl group. ５ and R ６ each independently represents a hydrogen atom or a methyl group; j and k are integers of 0 or 1; A １ and A ２ each independently represents a single bond, —O—, —CO—, —COO—, phenylene, a sulfonyl group, or an amide group. ２ may be the same or different. *1 is a bond bonded to one acid anhydride group, and *2 is a bond bonded to the other acid anhydride group.)
[0016] Preferred specific examples of the tetracarboxylic dianhydride or derivative thereof represented by the above formula (2) include those in which X is selected from the above formulae (x-1) to (x-8) and (x-10) to (x-13).
[0017] The above formula (x-1) is preferably selected from the group consisting of the following formulae (x1-1) to (x1-6). (In the above formula, *1 is a bond bonded to one acid anhydride group, and *2 is a bond bonded to the other acid anhydride group.)
[0018] Preferred specific examples of the above formulae (x-12) and (x-13) include the following formulae (x-14) to (x-29), in which "*" indicates the bonding position.
[0019] The amount of the tetracarboxylic dianhydride represented by the above formula (2) or a derivative thereof used is preferably 60 to 100 mol %, more preferably 80 to 100 mol %, and even more preferably 90 to 100 mol %, relative to 1 mol of the total tetracarboxylic acid components to be reacted with the diamine component.
[0020] <Diamine Component> The diamine component used in the production of the polyimide precursor is not particularly limited, but a diamine component containing at least one diamine selected from diamines represented by the following formula (3) and the following formula (3A) (hereinafter, these may also be referred to as diamine (H)). The diamine contained in the diamine component may be used alone or in combination of two or more. (In formula (3), Y ３ represents a divalent organic group represented by the following formula (O), and in formula (3A), Y ３ａ represents a divalent organic group represented by the following formula (a), and each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In formula (O), Ar represents a divalent benzene ring, biphenyl structure, naphthalene ring, or aromatic heterocycle. When a plurality of Ars are present, the two Ars may be the same or different, and any hydrogen atom of the benzene ring, biphenyl structure, naphthalene ring, or aromatic heterocycle may be substituted with a monovalent substituent. p is an integer of 0 or 1. Q ３ Ha-(CH ２ ) ｎ -(n is an integer of 2 to 18), or the above-(CH ２ ) ｎ -of-CH ２ represents a group in which at least a portion of - has been replaced with either -O-, -C(=O)- or -O-C(=O)-. (In formula (a), a hydrogen atom on the benzene ring may be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, or a fluoroalkoxy group having 1 to 10 carbon atoms. P is an aromatic ring selected from a benzene ring or a biphenyl structure, and a hydrogen atom on the benzene ring or the biphenyl structure may be substituted with a methyl group or a fluorine atom. n is an integer of 0 to 5. When n is an integer of 2 or greater, n Ps independently have the above definition.)
[0021] Examples of the substituents on the benzene ring, biphenyl structure, naphthalene ring, or aromatic heterocycle in the above formula (O) include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, a fluoroalkenyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, a carboxy group, a hydroxy group, an alkyloxycarbonyl group having 1 to 10 carbon atoms, a cyano group, and a nitro group. Specific preferred examples of the aromatic heterocycle in the above formula (O) include the aromatic heterocycles exemplified below as nitrogen-containing heterocycles. Among these, a pyridine ring, a pyrimidine ring, a pyrazine ring, a benzimidazole ring, or a quinoline ring is preferred.
[0022] From the viewpoint of enhancing liquid crystal alignment properties, the divalent organic group represented by the formula (O) is preferably a divalent organic group represented by any one of the following formulae (o-1) to (o-12): In addition, the hydrogen atoms on the rings in the following formulae (o-1) to (o-10) and (o-12) may be substituted with the substituents exemplified for the diamine (H) above.
[0023] (In the formula, X １ , X ２ each independently represents a single bond or —O—.
[0024] (In formula (o-7), X ７ Each independently represents a single bond or —O—. However, when n is 1, two X ７At least one of the groups represents —O—. In formula (o-12), two m's each independently have the above definition.
[0025] The divalent organic group represented by formula (a) in formula (3A) is preferably a divalent organic group represented by any of the following formulae (A-1) to (A-5) from the viewpoint of enhancing liquid crystal alignment properties.
[0026] The total proportion of at least one diamine selected from the diamines represented by formula (3) and formula (3A) is preferably 1 to 95 mol %, more preferably 1 to 90 mol %, and even more preferably 5 to 90 mol %, relative to 1 mol of the diamine component.
[0027] In order to increase the voltage holding ratio of the resulting liquid crystal alignment film, the polyimide polymer used in the present invention may have at least one nitrogen atom-containing structure (hereinafter also referred to as a specific nitrogen atom-containing structure) selected from the group consisting of a nitrogen atom-containing heterocycle (excluding imide rings contained in polyimides), a secondary amino group, and a tertiary amino group. The polyimide polymer having the specific nitrogen atom-containing structure can be obtained by using a monomer having a nitrogen atom-containing structure, for example, a diamine having the specific nitrogen atom-containing structure, as at least a part of the raw material.
[0028] Examples of the nitrogen atom-containing heterocycle that the diamine having the specific nitrogen atom-containing structure may have include a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, an indole ring, a benzimidazole ring, a purine ring, a quinoline ring, an isoquinoline ring, a naphthyridine ring, a quinoxaline ring, a phthalazine ring, a triazine ring, a carbazole ring, an acridine ring, a piperidine ring, a piperazine ring, a pyrrolidine ring, a hexamethyleneimine ring, etc. Among these, a pyridine ring, a pyrimidine ring, a pyrazine ring, a benzimidazole ring, a piperidine ring, a piperazine ring, a quinoline ring, a carbazole ring, or an acridine ring is preferred.
[0029] The secondary amino group and tertiary amino group that the diamine having the specific nitrogen atom-containing structure may have are, for example, represented by the following formula (n).
[0030] In the above formula (n), R represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. "*1, *2" represent bonds bonded to the hydrocarbon group.
[0031] Examples of the monovalent hydrocarbon group represented by R in the above formula (n) include alkyl groups such as methyl, ethyl, and propyl; cycloalkyl groups such as cyclohexyl; and aryl groups such as phenyl and methylphenyl. R is preferably a hydrogen atom or a methyl group.
[0032] Specific examples of diamines having a specific nitrogen atom-containing structure include, in addition to the above-mentioned diamine (H) having an aromatic heterocycle, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, compounds represented by the following formulae (Dp-1) to (Dp-7), and compounds represented by the following formulae (z-1) to (z-19). (X ３ , X ４ are each independently a single bond or -(CH ２ ) n-(n is an integer of 1 to 4).
[0033]
[0034]
[0035] From the viewpoint of increasing the voltage holding ratio of the liquid crystal display element, the use ratio of the diamine having the specific nitrogen atom-containing structure is preferably 1 mol % or more, more preferably 2 mol % or more, based on the total amount of diamines used in the synthesis, and the use ratio is preferably 90 mol % or less, more preferably 80 mol % or less.
[0036] The polyimide polymer used in the present invention may contain diamines other than the diamines described above (hereinafter also referred to as "other diamines"). Examples of other diamines are given below, but the present invention is not limited to these. Diamines having a group "-N(D)- (D represents a carbamate protecting group)" in the molecule and having 6 to 30 carbon atoms excluding D; 4,4'-diaminoazobenzene and diamines of the following formula (d Ｔ -1) to (d Ｔdiamines having a photoalignment group such as diamines represented by the following formulas (3i-1) to (3i-5): 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 1,4-bis(4-aminobenzyl)benzene, diamines represented by the following formulas (3i-1) to (3i-5), 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol; 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid diamines having a carboxy group such as diamine compounds represented by the following formulae (3b-1) to (3b-4): 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzanilide, 4,4'-diaminoazobenzene, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indan-5-amine, 1-(4- diamines having a urea bond such as diamines represented by the following formulas (h-1) to (h-3); diamines having an amide bond such as diamines represented by the following formulas (h-4) to (h-6); diamines having a photopolymerizable group at the terminal such as 2-(2,4-diaminophenoxy)ethyl methacrylate and 2,4-diamino-N,N-diallylaniline; cholestanyloxy-3,5-diaminobenzene, ... diamines having a steroid skeleton such as 2,4-nyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestanyl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, and 3,6-bis(4-aminobenzoyloxy)cholestane; diamines represented by the following formulae (V-1) to (V-6); diamines having a siloxane bond such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane; diamines having an oxazoline ring structure such as those represented by the following formulae (Ox-1) to (Ox-2);Diamines in which two amino groups are bonded to a group represented by any one of formulas (Y-1) to (Y-167) described in WO 2018 / 117239, etc.;
[0037] (In formulas (3i-1) to (3i-3), two n's may be the same or different.)
[0038] (In formula (3b-1), A １ is a single bond, -CH ２ -, -C ２ H ４ -, -C(CH ３ ) ２ -, -CF ２ -, -C(CF ３ ) ２ -, -O-, -CO-, -NH-, -N(CH ３ )-, -CONH-, -NHCO-, -CH ２ O-, -OCH ２ -, -COO-, -OCO-, -CON(CH ３ ) - or -N(CH ３ )CO—, m1 and m2 each independently represent an integer of 0 to 4, and m1+m2 represents an integer of 1 to 4. In formula (3b-2), m3 and m4 each independently represent an integer of 1 to 5. In formula (3b-3), A ２ represents a linear or branched alkyl group having 1 to 5 carbon atoms, and m5 represents an integer of 1 to 5. ３ and A ４ are each independently a single bond, —CH ２ -, -C ２ H ４ -, -C(CH ３ ) ２ -, -CF ２ -, -C(CF ３ ) ２ -, -O-, -CO-, -NH-, -N(CH ３ )-, -CONH-, -NHCO-, -CH ２ O-, -OCH ２ -, -COO-, -OCO-, -CON(CH ３ ) - or -N(CH ３) CO—, and m6 represents an integer of 1 to 4.
[0039]
[0040] (In the above formulas (V-1) to (V-6), X ｖ１ ~X ｖ４ , X ｐ１ ~X ｐ２ are each independently -(CH ２ ) ａ -(a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ３ )-, -NH-, -O-, -CH ２ O-, -CH ２ represents —OCO—, —COO—, or —OCO—; X ｖ５ is -O-, -CH ２ O-, -CH ２ represents —OCO—, —COO—, or —OCO—. ａ represents a single bond, —O—, —NH—, —O—(CH ２ ) ｍ -O-, -C(CH ３ ) ２ -, -CO-, -(CH ２ ) ｍ -, -SO ２ -, -O-C(CH ３ ) ２ -, -CO-(CH ２ ) ｍ -, -NH-(CH ２ ) ｍ -, -SO ２ - (CH ２ ) ｍ -, -CONH-(CH ２ ) ｍ -, -CONH-(CH ２ ) ｍ -NHCO-, -COO-(CH ２ ) ｍ -OCO-, -CONH-, -NH-(CH ２ ) ｍ -NH- or -SO ２ - (CH ２ ) ｍ -SO ２ - (where m represents an integer of 1 to 6), R ｖ１ ~Rｖ４ , R １ａ ~R １ｂ each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms. In formula (V-6), two k's may be the same or different.
[0041]
[0042] Examples of diamines having the above group "-N(D)- (D represents a carbamate protecting group)" in the molecule and having 6 to 30 carbon atoms excluding D include compounds represented by the following formulas (5-1) to (5-15) and (5-18) to (5-20). (Preferably, (5-2) includes compounds (5-16) to (5-17).)
[0043] (Boc represents a tert-butoxycarbonyl group.)
[0044] <Component (B)> The liquid crystal aligning agent of the present invention contains a compound (B) represented by the following formula (1). (In formula (1), Ar １ , and Ar １’ each independently represents a benzene ring, a biphenyl structure, or a naphthalene ring, and one or more hydrogen atoms on the benzene ring, the biphenyl structure, or the naphthalene ring may be substituted with a monovalent group (excluding (q1) to (q4)). X is a divalent organic group represented by the following formula (2). *-X １ -(Y １ -L) ｎ -Y ２ -X ２ -* (2) (In formula (2), X １ , X ２ are each independently a single bond, —O—, *1-O—CO—*2 (*1 and *2 represent a bond, and *1 is Ar １ or Ar １’L represents a single bond, -O-, -O-C(=O)- or -C(=O)-O-, and when there are multiple Ls, the multiple Ls may be the same or different from one another, provided that at least one L represents -O-C(=O)- or -C(=O)-O-. n is an integer of 1 to 6. Y １ , Y ２ each independently represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and some of the hydrogen atoms in the divalent hydrocarbon group may be substituted with a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxy group. １ If there are multiple Y １ may be the same as or different from each other. * represents Ar １ or Ar １’ Each of Q and Q' independently represents a hydrogen atom or a monovalent group selected from the group consisting of (q1) to (q4) below. When formula (1) has a plurality of (q1) to (q4), a plurality of R １ ~R ４ may be the same as or different from each other. (In formula (q1), R １ represents a monovalent organic group, and the monovalent organic group is a carbonyl group, a sulfonyl group, and *1-CR ｑ１ - *2 is bonded to the nitrogen atom via a linking group. ２ represents a hydrogen atom or a monovalent organic group. ｑ１ ) ２ *1 in -*2 represents a bond to the nitrogen atom, and multiple R ｑ１ each independently represents a hydrogen atom or a monovalent organic group. ｑ１ may be the same or different. ｑ１ ) ２ *2 in -*2 is bonded to a monovalent organic group having a heteroatom-containing group. Examples of the heteroatom-containing group include a hydroxy group, a carboxy group, and an epoxy group. In formula (q2), R ３ represents a hydrogen atom or a monovalent organic group. ４represents a hydrogen atom, a hydroxy group, a halogen atom, or a monovalent organic group. ５ represents a hydrogen atom, a hydroxyl group, or a monovalent organic group. １ or Ar １’ represents the bond that bonds to
[0045] R in the above formula (q1) １ The monovalent organic group in the formula (I) is a monovalent hydrocarbon group having 1 to 30 carbon atoms, and the methylene group of the hydrocarbon group may be -O-, -S-, -CO-, -COO-, -COS-, -NR ６ --CO-NR ６ -, -Si(R ６ ) ２ - (However, R ６ When a plurality of groups are present, each group independently represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms.), —SO ２ - or the like (R １ｂ ), the monovalent hydrocarbon group, or the monovalent group (R １ｂ and a monovalent group in which at least one hydrogen atom bonded to a carbon atom of R is replaced with a substituent (x), and a monovalent group having a heterocycle. １ is a carbonyl group, a sulfonyl group, and *1-C(R ｑ１ ) ２ -*2. R in the above formula (q1) is bonded to the nitrogen atom via any one of the linking groups ２、 R in formula (q2) ３ , R in formula (q3) ４ and R in formula (q4) ５ The monovalent organic group in the formula (I) is a monovalent hydrocarbon group having 1 to 30 carbon atoms, and the methylene group of the hydrocarbon group may be -O-, -S-, -CO-, -COO-, -COS-, -NR ６ --CO-NR ６ -, -Si(R ６ ) ２ - (However, R ６ When a plurality of groups are present, each group independently represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms.), —SO ２ - or the like (R ｂ ), the monovalent hydrocarbon group, or the monovalent group (Rｂ and monovalent groups having a heterocycle, in which at least one hydrogen atom bonded to a carbon atom of the formula (I) is replaced with a substituent (x). Examples of the substituent (x) include a halogen atom, a hydroxy group, a nitro group, an amino group, a mercapto group, a nitroso group, a silanol group, a sulfino group, a phosphino group, a carboxy group, a cyano group, and a sulfo group.
[0046] In the above formula (2), Y １ and Y ２ are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms, and examples of the divalent hydrocarbon group include, but are not limited to, a linear or branched alkylene group, —CH═CH—, a phenylene group, or a cyclohexylene group. １ and Y ２ From the viewpoint of suitably achieving the effects of the present invention, Y is preferably a hydrocarbon group having 2 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and even more preferably an alkylene group having 2 or 4 carbon atoms. Some of the hydrogen atoms in the divalent hydrocarbon group may be substituted with halogen atoms, methyl groups, trifluoromethyl groups, or hydroxy groups, and the halogen atoms substituting the hydrogen atoms in the divalent hydrocarbon group are preferably fluorine atoms. １ If there are multiple Y １ may be the same as or different from each other. L represents -O-, -C(=O)-, -O-C(=O)-, or -C(=O)-O-. When multiple Ls are present, the multiple Ls may be the same as or different from each other. However, it is preferable that at least one L represents -O-C(=O)- or -C(=O)-O-, and at least two Ls represent -O-C(=O)- or -C(=O)-O-. n represents an integer of 1 to 6, preferably an integer of 1 to 4, more preferably an integer of 2 to 4, and even more preferably an integer of 2 or 4.
[0047] The group "*-(Y １ -L) ｎ -Y ２More preferred examples of "-*" include the following structures: *-(CH ２ ) ｐ -OC(=O)-(CH ２ ) ｑ -C(=O)-O-(CH ２ ) ｒ - *, * - (CH ２ ) ｐ -C(=O)-O-(CH ２ ) ｑ -OC(=O)-(CH ２ ) ｒ - *, * - (CH ２ ) ｎ１ -OC(=O)-(CH ２ ) ｎ２ -C(=O)-O-(CH ２ ) ｎ３ -OC(=O)-(CH ２ ) ｎ４ -C(=O)-O-(CH ２ ) ｎ５ - *; * - (CH ２ ) ｎ１ -C(=O)-O-(CH ２ ) ｎ２ -OC(=O)-(CH ２ ) ｎ３ -C(=O)-O-(CH ２ ) ｎ４ -OC(=O)-(CH ２ ) ｎ５ *: In the above structure, p, q, and r are each independently an integer of 1 to 6. n1 to n5 are each independently an integer of 1 to 6. However, when n1 to n5 are each an integer of 1 to 6, the total number of carbon atoms in the divalent hydrocarbon group is 20 or less.
[0048] A preferred example of formula (q1) is *-NH-C(=O)-R Ｏ (R Ｏ represents a monovalent organic group bonded to the carbon atom of a carbonyl group via an oxygen atom; *—NH—C(═O)—R Ｎ (However, R Ｎ represents a monovalent organic group bonded to the carbon atom of a carbonyl group via a nitrogen atom; *—NH—C(═O)—R Ｃ (However, Rｃ represents a monovalent organic group bonded to the carbon atom of the carbonyl group via a carbon atom; *—NH—(CH ２ ) ｎ -OH (n is an integer of 1 to 6); or the following formulae (q1-a) to (q1-d): R ０ Preferred examples of R include organic groups in which one hydrogen atom has been removed from the hydroxy group of an alcohol compound, an oxime compound, or a phenol compound. Ｎ Preferred examples of R include organic groups in which one hydrogen atom has been removed from the nitrogen atom of a nitrogen-containing compound such as a lactam compound, an amine compound, a pyrazole compound, an imidazole compound, or an imide compound. Ｃ Preferred examples of the alkyl group, the alkenyl group, the organic group in which one hydrogen atom has been removed from the carbon atom of an active methylene compound, or -(CH ２ ) ｎ -COOH (n is an integer of 1 to 6).
[0049] Examples of the alcohol compounds include saturated alcohols such as methanol, ethanol, propanol, butanol (preferred examples include n-butanol, i-butanol, sec-butanol, and tert-butanol), cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate; acyclic unsaturated alcohols such as allyl alcohol; and alcohols having an aromatic ring such as benzyl alcohol and 9-fluorenylmethanol. Examples of the oxime compounds include acetoxime, formaldoxime, cyclohexaneoxime, methyl ethyl ketoneoxime, cyclohexanoneoxime, and benzophenoneoxime. Examples of the lactam compounds include ε-caprolactam and γ-butyrolactam. Examples of the phenol compounds include phenol, naphthol, cresol, xylenol, and halogen-substituted phenols. Examples of the amine compounds include primary amines and secondary amines. The amine compound may be any of aromatic amines, aliphatic amines, and alicyclic amines, and may be a monoalkylamine (methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc.), a dialkylamine (preferably dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, methylethylamine, methylpropylamine, ethylpropylamine) group, a H ２ N (Boc), HN (Boc) ２Examples of the active methylene compounds include diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate. Examples of the pyrazole compounds include pyrazole, methylpyrazole, and dimethylpyrazole. Examples of the imidazole compounds include imidazole, 1-methylimidazole, 1-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-phenylimidazole. Examples of the imide compounds include maleimide, succinimide, phthalimide, and derivatives thereof.
[0050] R in formula (q2) ３ Preferred specific examples of the alkyl group include a hydrogen atom; a linear alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; a carbamate-based organic group typified by a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, a Boc group, and the like; a glycidyl group; an epoxycyclohexylmethyl group (preferably a 2,3-epoxycyclohexylmethyl group or a 3,4-epoxycyclohexylmethyl group); a group having an oxetane ring represented by the following formula (q2-a); and an N-hydroxysuccinimide ester group. (In formula (q2-a), R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms.)
[0051] R in formula (q3) ４ Preferred examples of the group include a hydroxy group; ｑ３ (R ｑ３ represents an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms, or a group having an aromatic ring (for example, a benzyl group, a 9-fluorenylmethyl group, etc.); a glycidyl group; an epoxycyclohexylmethyl group (preferably a 2,3-epoxycyclohexylmethyl group or a 3,4-epoxycyclohexylmethyl group); and a group having an oxetane ring represented by the above formula (q2-1).
[0052] R in formula (q4) ５Preferred specific examples of the group include a hydroxyalkyl group having 1 to 6 carbon atoms (preferably a methylol group) and an aliphatic carboxy group having 2 to 6 carbon atoms.
[0053] Ar in the above formula (2) １ and Ar １’ In the above formula, examples of the monovalent group substituting a hydrogen atom on the benzene ring, the biphenyl structure, or the naphthalene ring include a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, a cyano group, and a nitro group.
[0054] The compound (B) is preferably at least one compound selected from the group consisting of the following formulae (q1-1) to (q1-5), (q2-1) to (q2-2), (q3-1) to (q3-3), and (q4-1) to (q4-2):
[0055] The content of the compound (B) represented by the above formula (1) in the liquid crystal aligning agent of the present invention is preferably 0.1 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, and even more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the polymer (A).
[0056] <Method for producing polyamic acid and polyimide> The polyamic acid, which is the polyimide precursor used in the present invention, can be synthesized, for example, by reacting the above-mentioned tetracarboxylic acid component with the above-mentioned diamine component in the presence of an organic solvent (polycondensation). For detailed synthesis methods of the polyimide precursor and polyimide, see, for example, WO2015 / 012368.
[0057] The polyimide precursor or polyimide may be a terminal-modified polymer obtained by using an appropriate terminal-capping agent together with the tetracarboxylic acid component and diamine as described above during production. Examples of the terminal-modifying agent include acid anhydrides such as acetic anhydride, maleic anhydride, succinic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, and trimellitic anhydride; di-tert-butyl dicarbonate; monoamine compounds such as aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, and 4-aminobenzoic acid; and monoisocyanate compounds such as ethyl isocyanate, phenyl isocyanate, and naphthyl isocyanate. The proportion of the terminal modifier used is preferably 40 parts by mol or less, and more preferably 30 parts by mol or less, per 100 parts by mol of the total of the diamine components used.
[0058] <Solution Viscosity and Molecular Weight of Polymer> The polyamic acid, polyamic acid ester, and polyimide used in the present invention preferably have a solution viscosity of, for example, 10 to 1,000 mPa·s when prepared into a solution of 10 to 15 wt % from the viewpoint of workability, but are not particularly limited thereto. The solution viscosity (mPa·s) of the polymer is a value measured at 25°C using an E-type rotational viscometer for a polymer solution of 10 to 15 wt % concentration prepared using a good solvent for the polymer (e.g., γ-butyrolactone, N-methyl-2-pyrrolidone, etc.).
[0059] The weight average molecular weight (Mw) of the polyamic acid, polyamic acid ester, and polyimide, measured by gel permeation chromatography (GPC) in terms of polyethylene glycol oxide, is preferably 1,000 to 500,000, and more preferably 2,000 to 500,000. The molecular weight distribution (Mw / Mn), expressed as the ratio of Mw to the number average molecular weight (Mn) in terms of polyethylene glycol oxide measured by GPC, is preferably 15 or less, and more preferably 10 or less. Having the molecular weight within this range ensures good liquid crystal alignment properties in liquid crystal display elements.
[0060] <Liquid Crystal Aligning Agent> The liquid crystal aligning agent of the present invention contains the polymer (A) capable of aligning liquid crystals and the compound (B) of the above formula (1). The liquid crystal aligning agent of the present invention preferably has a form in which the compound (B) of the above formula (1) is added to a solution in which the polymer (A) capable of aligning liquid crystals is dissolved in a solvent. The content (concentration) of the polymer (A) contained in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the thickness of the coating film to be formed, but is preferably 1% by mass or more from the viewpoint of forming a uniform and defect-free coating film, and is preferably 10% by mass or less from the viewpoint of storage stability of the solution.
[0061] The solvent contained in the liquid crystal alignment agent is not particularly limited as long as it can uniformly dissolve the polymer component. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and methyl ethyl ketone. Examples of suitable good solvents include propanamide, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone (collectively referred to as "good solvents"). Among these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and γ-butyrolactone are preferred. The content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass of the total solvent contained in the liquid crystal aligning agent.
[0062] In addition, the solvent contained in the liquid crystal aligning agent is preferably a mixed solvent containing, in addition to the above solvent, a solvent (also called a poor solvent) that improves the coatability when applying the liquid crystal aligning agent and the surface smoothness of the coating film. Specific examples of the solvent to be used in combination are listed below, but are not limited thereto.
[0063] For example, diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propyl propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2,6-dimethyl-4-heptanone), and the like.
[0064] Among these, diisobutyl carbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, or diisobutyl ketone is preferred. The content of the poor solvent is preferably 1 to 80 mass % of the total solvent contained in the liquid crystal aligning agent, more preferably 10 to 80 mass %, and particularly preferably 20 to 70 mass %. The type and content of the poor solvent are appropriately selected depending on the coating device, coating conditions, coating environment, etc. of the liquid crystal aligning agent.
[0065] Preferred solvent combinations of a good solvent and a poor solvent include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone ... N-methyl-2-pyrrolidone and propylene glycol diacetate, N,N-dimethyl lactamide and diisobutyl ketone, N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate, N-ethyl-2-pyrrolidone and dipropylene glycol dimethyl ether, N,N-dimethyl lactamide and ethylene glycol monobutyl ether, N,N-dimethyl lactamide and propylene glycol diacetate N-ethyl-2-pyrrolidone and diethylene glycol diethyl ether, N,N-dimethyl lactamide and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, N-ethyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether, N-methyl- 2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and 2,6-dimethyl-4-heptanone, N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol diacetate, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, and 2,6-dimethyl-4-heptanone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol diacetate, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, and 2,6-dimethyl-4-heptanone, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, and diisopropyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, and 2,6-dimethyl-4-heptanol, N-methyl-2-pyrrolidone, γ-butyrolactone, and dipropylene glycol dimethyl ether, N N-methyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and propylene glycol diacetate, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and diisobutyl ketone, N-ethyl-2-pyrrolidone, γ-butyrolactone, and diisobutyl ketone, and N-ethyl-2-pyrrolidone, N,N-dimethyl lactamide, and diisobutyl ketone.
[0066] The liquid crystal aligning agent of the present invention may further contain, in addition to the polymer (A) and the compound (B), a component other than the solvent (hereinafter also referred to as an additive component). Examples of such additive components include an adhesion aid for improving the adhesion between the liquid crystal alignment film and the substrate or between the liquid crystal alignment film and the sealant, a compound for increasing the strength of the liquid crystal alignment film (hereinafter also referred to as a crosslinking compound), and a dielectric or conductive substance for adjusting the dielectric constant or electrical resistance of the liquid crystal alignment film. The liquid crystal aligning agent of the present invention may contain one type of such additive component, or may contain two or more types.
[0067] Examples of the crosslinkable compound, from the viewpoint of exhibiting good resistance to AC afterimages and significantly improving film strength, include a compound having at least one group selected from the group consisting of an oxiranyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, a group containing a Meldrum's acid structure, and a cyclocarbonate group; a hydroxyalkylamide compound; or a compound selected from compounds represented by the following formula (e):
[0068] (In formula (e), A represents an (m+n)-valent organic group having an aromatic ring. m represents an integer of 1 to 6, and n represents an integer of 0 to 4. R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Any hydrogen atom in the aromatic ring may be replaced by a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, a fluoroalkenyl group having 2 to 10 carbon atoms, or a fluoroalkoxy group having 1 to 10 carbon atoms. When m is 2 or more, each R independently has the same definition as above.)
[0069] Specific examples of the compound having an oxiranyl group include compounds having two or more oxiranyl groups, such as the compound described in paragraph
[0037] of JP-A-10-338880 and compounds having a triazine ring skeleton described in WO 2017 / 170483. Among these, compounds containing a nitrogen atom, such as N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-p-phenylenediamine, and compounds represented by the following formulas (r-1) to (r-3), may also be used.
[0070]
[0071] Specific examples of the compound having an oxetanyl group include compounds having two or more oxetanyl groups described in paragraphs
[0170] to
[0175] of WO 2011 / 132751.
[0072] Specific examples of the compound having a protected isocyanate group include the compound having two or more protected isocyanate groups described in paragraphs
[0046] to
[0047] of JP 2014-224978 A, and the compound having three or more protected isocyanate groups described in paragraphs
[0119] to
[0120] of WO 2015 / 141598 A, and may also be compounds represented by the following formulas (bi-1) to (bi-3).
[0073]
[0074] Specific examples of compounds having a protected isothiocyanate group include compounds having two or more protected isothiocyanate groups described in JP 2016-200798 A.
[0075] Specific examples of compounds having a group containing an oxazoline ring structure include compounds containing two or more oxazoline ring structures described in paragraph
[0115] of JP-A No. 2007-286597.
[0076] Specific examples of compounds having a group containing a Meldrum's acid structure include compounds having two or more Meldrum's acid structures described in WO 2012 / 091088.
[0077] Specific examples of the compound having a cyclocarbonate group include the compounds described in WO 2011 / 155577.
[0078] Specific examples of the hydroxyalkylamide compound other than the compound represented by formula (1) above include the compounds described in WO 2015 / 072554 and paragraph
[0058] of JP 2016-118753 A, the compounds described in JP 2016-200798 A, and the compounds described in WO 2019 / 142927 A, and may also be compounds represented by the following formulae (hd-1) to (hd-8), and compounds represented by the following formulae (hd1-1) to (hd1-4).
[0079]
[0080]
[0081] Examples of the (m+n)-valent organic group having an aromatic ring for A in formula (e) include an (m+n)-valent aromatic hydrocarbon group having 6 to 30 carbon atoms, an (m+n)-valent organic group to which an aromatic hydrocarbon group having 6 to 30 carbon atoms is bonded directly or via a linking group, and an (m+n)-valent group having an aromatic heterocycle. Examples of the aromatic hydrocarbon include benzene and naphthalene. Examples of the aromatic heterocycle include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a pyridazine ring, a pyrazine ring, a benzimidazole ring, an indole ring, a quinoxaline ring, and an acridine ring. Examples of the linking group include an alkylene group having 1 to 10 carbon atoms, a group obtained by removing one hydrogen atom from the alkylene group, and a divalent or trivalent cyclohexane ring. Any hydrogen atom in the alkylene group may be substituted with an organic group such as an alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a trifluoromethyl group. Specific examples include the compounds described in WO 2010 / 074269 and compounds represented by the following formulas (e-1) to (e-10).
[0082]
[0083] The above compounds are examples of crosslinkable compounds, and are not limited thereto. For example, components other than those described above are disclosed on pages 53
[0105] to 55
[0116] of WO 2015 / 060357. Two or more types of crosslinkable compounds may be combined.
[0084] The content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent, and more preferably 1 to 15 parts by mass from the viewpoint of proceeding with the crosslinking reaction and exhibiting good resistance to AC afterimages.
[0085] Examples of the adhesion aid include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, and N-trimethoxysilylpropyltriethoxysilane. triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,Examples of silane coupling agents include 4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. When a silane coupling agent is used, it is preferably used in an amount of 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the polymer component contained in the liquid crystal alignment agent, from the viewpoint of exhibiting good resistance to AC afterimages. Examples of dielectric or conductive substances for adjusting the dielectric constant or electrical resistance of the liquid crystal alignment film include monoamines having a nitrogen-containing aromatic heterocycle, such as 3-picolylamine.
[0086] <Liquid Crystal Alignment Film / Liquid Crystal Display Element> The liquid crystal alignment film of the present invention is formed from the liquid crystal aligning agent described above. The liquid crystal alignment film of the present invention can be used as a liquid crystal alignment film for horizontal alignment type or vertical alignment type (VA type) liquid crystal display elements, and is particularly suitable for horizontal alignment type liquid crystal display elements such as IPS type or FFS type. The liquid crystal display element of the present invention comprises the liquid crystal alignment film described above. The liquid crystal display element of the present invention can be produced, for example, by a method including the following steps (1) to (4) or steps (1) to (2) and (4).
[0087] <Step (1): Step of Applying Liquid Crystal Alignment Agent> The liquid crystal alignment agent of the present invention is applied to one side of a substrate having a patterned transparent conductive film by an appropriate application method, such as a roll coater method, a spin coat method, a printing method, or an inkjet method. The substrate is not particularly limited as long as it is highly transparent. In addition to glass substrates and silicon nitride substrates, plastic substrates such as acrylic substrates and polycarbonate substrates can also be used. In addition, in reflective liquid crystal display elements, an opaque material such as a silicon wafer can be used for only one substrate. In this case, a light-reflecting material such as aluminum can also be used for the electrode. Furthermore, when manufacturing IPS or FFS liquid crystal elements, a substrate having an electrode made of a comb-shaped patterned transparent conductive film or metal film and an opposing substrate having no electrode are used.
[0088] Examples of a method for applying the liquid crystal alignment agent to a substrate and forming a film include screen printing, offset printing, flexographic printing, an inkjet method, and a spray method. Among these, the application and film formation method by the inkjet method is preferably used.
[0089] <Step (2): Step of Baking the Applied Liquid Crystal Alignment Agent> Step (2) is a step of baking the liquid crystal alignment agent applied to the substrate to form a film. After applying the liquid crystal alignment agent to the substrate, the solvent can be evaporated or the amic acid or amic acid ester in the polymer can be thermally imidized using a heating means such as a hot plate, a heat circulation oven, or an IR (infrared) oven. The drying and baking steps after applying the liquid crystal alignment agent of the present invention can be performed at any temperature and for any time, and may be performed multiple times. The temperature for removing the solvent from the liquid crystal alignment agent can be, for example, 40 to 180°C. To shorten the process, the temperature can be 40 to 150°C. The baking time is not particularly limited, but can be 1 to 10 minutes or 1 to 5 minutes. When thermally imidizing the amic acid or amic acid ester in the polymer, a baking step can be performed at a temperature range of, for example, 150 to 300°C or 150 to 250°C after the organic solvent removal step. The baking time is not particularly limited, but may be 5 to 40 minutes or 5 to 30 minutes. If the thickness of the film-like substance after baking is too thin, the reliability of the liquid crystal display element may decrease, so the thickness is preferably 5 to 300 nm, and more preferably 10 to 200 nm.
[0090] <Step (3): Alignment Treatment of the Film Obtained in Step (2)> Step (3) is a step of optionally aligning the film obtained in Step (2). That is, in horizontal alignment type liquid crystal display devices such as IPS mode or FFS mode, the coating film is subjected to an alignment ability imparting treatment. On the other hand, in vertical alignment type liquid crystal display devices such as VA mode or PSA mode, the formed coating film can be used as a liquid crystal alignment film as is, but the coating film may also be subjected to an alignment ability imparting treatment. Preferred alignment treatment methods for liquid crystal alignment films include rubbing treatment and photo-alignment treatment. Examples of photo-alignment treatment methods include irradiating the surface of the film-like material with radiation polarized in a certain direction, and optionally performing a heat treatment at a temperature preferably between 150 and 250°C to impart liquid crystal alignment (also referred to as liquid crystal alignment ability). The radiation can be ultraviolet light or visible light having a wavelength of 100 to 800 nm. Among these, ultraviolet light having a wavelength of 100 to 400 nm is preferred, and more preferably between 200 and 400 nm.
[0091] The radiation dose is 1 to 10,000 mJ / cm ２ is preferable, and among these, 100 to 5,000 mJ / cm ２ is more preferable. When irradiating with radiation, the substrate having the film-like material may be irradiated while being heated at 50 to 250°C in order to improve the liquid crystal alignment. The liquid crystal alignment film produced in this manner can stably align the liquid crystal molecules in a fixed direction. Furthermore, the liquid crystal alignment film irradiated with polarized radiation by the above method can be contact-treated with water or a solvent, or the liquid crystal alignment film irradiated with radiation can be heat-treated.
[0092] The solvent used in the contact treatment is not particularly limited, as long as it dissolves the decomposition products generated from the film-like material by irradiation with radiation. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate. Among these, water, 2-propanol, 1-methoxy-2-propanol, and ethyl lactate are preferred from the viewpoints of versatility and solvent safety. Water, 1-methoxy-2-propanol, and ethyl lactate are more preferred. The solvent may be one type or a combination of two or more types.
[0093] The heat treatment of the coating film irradiated with the radiation is preferably carried out at 50 to 300° C. for 1 to 30 minutes, more preferably at 120 to 250° C. for 1 to 30 minutes.
[0094] <Step (4): Step of preparing a liquid crystal cell> Two substrates on which a liquid crystal alignment film has been formed are prepared as described above, and a liquid crystal is placed between the two substrates arranged opposite each other. Specifically, the following two methods can be mentioned. In the first method, the two substrates are first arranged opposite each other with a gap (cell gap) between them so that the liquid crystal alignment films face each other. Next, the peripheries of the two substrates are bonded together using a sealant, and a liquid crystal composition is injected into the substrate surfaces and the cell gap defined by the sealant to contact the film surface, and then the injection hole is sealed.
[0095] The second method is called the ODF (One Drop Fill) method. A UV-curable sealant, for example, is applied to a predetermined location on one of two substrates on which a liquid crystal alignment film has been formed, and a liquid crystal composition is then dropped onto several predetermined locations on the liquid crystal alignment film. The other substrate is then attached so that the liquid crystal alignment film faces the other substrate, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface. The entire surface of the substrate is then irradiated with UV light to cure the sealant. In either method, it is preferable to further heat the liquid crystal composition used to a temperature at which it assumes an isotropic phase and then slowly cool it to room temperature to remove flow alignment that occurs during liquid crystal filling. If the coating film is subjected to a rubbing treatment, the two substrates are positioned opposite each other so that the rubbing directions on each coating film are at a predetermined angle to each other, for example, perpendicular or antiparallel. Examples of sealants that can be used include epoxy resins containing a curing agent and aluminum oxide spheres as spacers. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, with nematic liquid crystals being preferred.
[0096] A liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell as needed. Examples of the polarizing plate to be attached to the outer surface of the liquid crystal cell include a polarizing film called an "H film" made by stretching and aligning polyvinyl alcohol and absorbing iodine, sandwiched between cellulose acetate protective films, and a polarizing plate made of the H film itself.
[0097] The liquid crystal display element of the present invention can be effectively applied to various devices, and can be used in various display devices such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions, information displays, etc. In addition, the polymer composition contained in the liquid crystal aligning agent can be used as a liquid crystal alignment film for a retardation film, a liquid crystal alignment film for a scanning antenna or a liquid crystal array antenna, or a liquid crystal alignment film for a transmissive / scattering liquid crystal dimming element, or for other applications such as a protective film for a color filter, a gate insulating film for a flexible display, or a substrate material.
[0098] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The abbreviations of the compounds used and the methods for measuring the properties are as follows. (Organic solvents) NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone BCS: butyl cellosolve THF: tetrahydrofuran (Tetracarboxylic acid dianhydrides) CA-1 to CA-4: Compounds represented by the following formulas (CA-1) to (CA-4), respectively (Diamine) DA-1 to DA-9: Compounds represented by the following formulas (DA-1) to (DA-9), respectively (In the above formula, Boc represents a tert-butoxycarbonyl group.) (Additives) AD-1 to AD-11: Compounds represented by the following formulas (AD-1) to (AD-11), respectively. Among the above additives, AD-3 to AD-7, AD-10, and AD-11 are included in the range of specific additives corresponding to compound (B) of the present application. (In the above formula, Boc represents a tert-butoxycarbonyl group.)
[0099] (Reaction Reagent) Boc ２ O: di-tert-butyl dicarbonate SAH: succinic anhydride Ac ２ O: acetic anhydride
[0100] <Measurement of Viscosity> Measurement was carried out at 25°C using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL and a cone rotor TE-1 (1°34', R24).
[0101] <Measurement of molecular weight> Measurement was carried out using the following room temperature GPC (gel permeation chromatography) apparatus under the following conditions, and Mn and Mw were calculated as polyethylene glycol oxide equivalent values. GPC apparatus: GPC-101 (manufactured by Resonac Corporation), Column: GPC KD-803 and GPC KD-805 (manufactured by Resonac Corporation) connected in series, Column temperature: 50°C, Eluent: N,N-dimethylformamide (containing lithium bromide monohydrate (LiBr.H) as an additive), ２ o-Phosphoric acid (o-Phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 mL / L), flow rate: 1.0 mL / min. Standard sample for preparing a calibration curve: EasiVial PEG / PEO polyethylene glycol oxide PL2080-0201 (molecular weight: about 1,500, about 4,000, about 13,000, about 30,000, about 70,000, about 130,000, about 500,000, about 1,000,000, about 1,500,000) (GL Sciences).
[0102] [Synthesis of Monomer] DA-9 is a novel compound not disclosed in any literature. The product in Monomer Synthesis Example 1 below is １ The product was identified by H-NMR analysis. The analysis conditions were as follows: Apparatus: BRUKER ADVANCE III-500 MHz Measurement solvent: deuterated dimethyl sulfoxide (DMSO-d ６ ) Reference substance: tetramethylsilane (TMS) (δ 0.0 ppm for １ H)
[0103] <Monomer Synthesis Example 1: Synthesis of DA-9> 2-(4-nitrophenoxy)ethanol (50.0 g, 273 mmol) was charged with THF (600 g), 4-dimethylaminopyridine (DMAP, 16.6 g, 13.6 mmol), and succinic anhydride (34.1 g, 341 mmol), and the mixture was stirred at 50°C. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC·HCl, 59.8 g, 312 mmol) and 1,4-butanediol (11.7 g, 130 mmol) were charged into the resulting solution, and the mixture was stirred at room temperature (25°C) for 3 hours. After completion of the reaction, water (1.5 kg) was added to precipitate crystals. The solid obtained by filtration was dried to obtain crude crystals. THF (300 g) was added to the crude crystals, and the mixture was heated and stirred at 65°C. After cooling to room temperature, methanol (1.5 kg) was added and the mixture was recrystallized. The crystals were filtered off and the resulting crystals were dried to obtain DA-9-1 (yield: 60.4 g, 97.2 mmol, 75%). １ H-NMR (500MHz) in DMSO-d ６ δ (ppm) = 8.21 (d, J = 9.2 Hz, 4H), 7.17 (d, J = 9.2 Hz, 4H), 4.37 (q, 8H), 3.99 (s, 4H), 2.58 (m, 8H), 1.57 (m, 4H). To the DA-9-1 (60.3 g, 97.2 mmol) obtained above, THF (1.2 kg) was added and the mixture was purged with nitrogen. Then, carbon-supported palladium (5% Pd carbon powder (hydrated product) K type, manufactured by N.E. Chemcat Corporation) (6.0 g) was added and the mixture was purged with nitrogen again. A Tedlar bag containing hydrogen was attached, and the mixture was stirred at room temperature for 4 days. After completion of the reaction, the carbon-supported palladium was removed by passing it through a membrane filter, and the filtrate was completely concentrated to precipitate crude crystals. The crude crystals were washed with isopropyl alcohol (240 g) and stirred at room temperature. The crystals were filtered off and the resulting crystals were dried to obtain DA-9 (yield: 44.8 g, 79.9 mmol, 82%). １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 6.65 (d, J = 8.9 Hz, 4H), 6.50 (d, J = 8.9 Hz, 4H), 4.62 (s, 4H) 4.27 (m, 4H), 4.00 (m, 8H), 2.57 (m, 8H), 1.59 (m, 4H).
[0104] [Synthesis of Additives] AD-3 to AD-7, AD-10 and AD-11 are novel compounds not disclosed in the literature, and the products in the following Additive Synthesis Examples 1 to 9 are １ The product was identified by H-NMR analysis. The analysis conditions were as follows: Apparatus: BRUKER ADVANCE III-500 MHz Measurement solvent: deuterated dimethyl sulfoxide (DMSO-d ６ ) Reference substance: tetramethylsilane (TMS) (δ 0.0 ppm for １ H)
[0105] Additive Synthesis Example 1: Synthesis of AD-3 NMP (35.0 g) was added to DA-7 (5.00 g, 12.0 mmol) and the mixture was purged with nitrogen. ２ O (7.35 g, 72.0 mmol) was added and the mixture was stirred at room temperature for 1 day to react. After completion of the reaction, the above solution was slowly added dropwise to methanol (300 g) to cause recrystallization, yielding crude crystals. The crude crystals were dispersed in methanol (150 g) and stirred for 30 minutes, and the crystals were filtered off. The obtained crystals were dried to obtain AD-3 (yield: 4.99 g, 9.96 mmol, 83%). １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 9.76 (s, 2H), 7.46 (d, J = 8.6Hz, 4H), 6.87 (d, J = 8.6Hz, 4H), 4.31 (t, 4H), 4.12 (t, 4H), 2.23 (t, 4H), 2.00 (s, 6H), 1.54 (m, 4H).
[0106] Additive Synthesis Example 2: Synthesis of AD-4 NMP (8.50 g) was added to DA-7 (1.50 g, 3.60 mmol) and the mixture was purged with nitrogen. SAH (1.08 g, 10.8 mmol) dissolved in NMP (5.0 g) was then added and the mixture was stirred at room temperature for 1 day to allow the reaction to proceed. After completion of the reaction, the above solution was slowly added dropwise to methanol (300 g) to allow recrystallization, yielding crude crystals. The crude crystals were dispersed in methanol (150 g) and stirred for 30 minutes, and the crystals were filtered off. The obtained crystals were dried to obtain AD-4 (yield: 1.42 g, 2.30 mmol, 64% yield).１ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 12.1 (br, 2H), 9.80 (s, 2H), 7.48 (d, J = 9.1Hz, 4H), 6.87 (d, J = 9.1 Hz, 4H), 4.31 (t, 4H), 4.12 (t, 4H), 2.51 (m, 8H), 2.33 (t, 4H), 1.54 (m, 4H).
[0107] Additive Synthesis Example 3: Synthesis of AD-5 Under a nitrogen atmosphere, DA-7 (3.33 g, 8.00 mmol), Boc ２ O (3.50 g, 16.0 mmol) and THF (33 g) were added and reacted at room temperature with stirring. After the reaction was completed, the solvent was removed using an evaporator, 30 g of isopropyl alcohol was added, and the precipitated solid was filtered off. This was dried to obtain AD-5 (3.50 g, 5.67 mmol, yield 71%, pink-white crystals). １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 9.11 (s, 2H), 7.32 (d, 4H), 6.83 (d, 4H), 4.30 (t, 4H), 4.10 (t, 4H), 2,32 (s, 4H), 1.54 (s, 4H), 1.46 (s, 18H).
[0108] Additive Synthesis Example 4: Synthesis of AD-6 THF (18.4 g) was added to DA-9 (3.60 g, 6.42 mmol) and purged with nitrogen, and then Boc dissolved in THF (8.0 g) was added. ２ O (8.41 g, 38.5 mmol) was added and the mixture was stirred at room temperature for 1 day to react. After completion of the reaction, methanol (3.70 g) was added and the mixture was stirred at 60°C for 1 hour, after which the solvent was removed using an evaporator. The precipitated solid was dispersed in methanol (150 g) and stirred for 30 minutes, and the crystals were separated by filtration. The obtained crystals were dried to obtain AD-6 (yield: 3.57 g, 4.69 mmol, 73%). １ H-NMR (500MHz) in DMSO-d ６: δ (ppm) = 9.12 (s, 2H), 7.34 (d, J = 8.5Hz, 4H), 6.84 (d, J = 9.1Hz, 4H), 4.31 ( t, 4H), 4.10 (t, 4H), 4.00 (t, 4H), 2.57 (m, 8H), 1.57 (m, 4H), 1.46 (s, 18H).
[0109] Additive Synthesis Example 5: Synthesis of AD-7 THF (16 g) was added to DA-8 (2.00 g, 5.20 mmol) and the mixture was purged with nitrogen. ２ 0 (2.62 g, 12.0 mmol) was added, and the mixture was stirred at room temperature for 2 days to react. After completion of the reaction, water (100 g) was added in an ice bath to precipitate crystals. The solid obtained by filtration was dried to obtain crude crystals. Methanol (50 g) was added to the crude crystals, and the mixture was heated and stirred at 70°C, allowed to cool at room temperature, and then recrystallized. The crystals obtained were filtered off and dried to obtain AD-7 (yield: 2.12 g, 3.62 mmol, 70%). １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 9.23 (s, 2H), 7.37 (d, J = 8.5Hz, 4H), 7.11 (d, J = 8.5Hz, 4H), 4.17 (t, 4H), 2.79 (t, 4H), 2.23 (m, 4H), 1.46 (m, 22H).
[0110] Additive Synthesis Example 6: Synthesis of AD-8 THF (20.4 g) was added to DA-6 (3.60 g, 18.0 mmol) and purged with nitrogen. Then, Boc ２ O (23.5 g, 108 mmol) was added and the mixture was stirred at room temperature for 1 day to react. After completion of the reaction, methanol (10.4 g) was added and the mixture was stirred at 60°C for 1 hour, after which the solvent was removed using an evaporator, and the precipitated solid was dispersed in toluene (150 g), stirred for 30 minutes, and filtered. The obtained crystals were dried to obtain AD-8 (yield: 5.69 g, 14.2 mmol, 79%). １ H-NMR (500MHz) in DMSO-d ６: δ (ppm) = 9.27 (s, 2H), 7.41 (d, J = 8.8Hz, 4H), 6.87 (d, J = 9.0Hz, 4H), 1.47 (s, 18H). <Additive Synthesis Example 7 Synthesis of AD-9> THF (20.4 g) was added to DA-5 (3.60 g, 18.0 mmol) and purged with nitrogen. Then, Boc ２ O (8.24 g, 37.8 mmol) was added and the mixture was stirred at room temperature for 1 day to react. After completion of the reaction, methanol (3.63 g) was added and the mixture was stirred at 60°C for 1 hour, after which the solvent was removed using an evaporator, and the precipitated solid was dispersed in toluene (150 g) and stirred for 30 minutes, and the crystals were separated by filtration. The obtained crystals were dried to obtain AD-9 (yield: 5.54 g, 13.9 mmol, 77% yield). １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 9.02 (s, 2H), 7.70 (s, 1H), 7.26 (d, J = 8.1Hz, 4H), 6.89 (d, J = 8.9Hz, 4H), 1.46 (s, 18H).
[0111] Additive Synthesis Example 8: Synthesis of AD-10 To tert-butyl 4-hydroxybenzoate (10.0 g, 51.5 mmol), 10% aqueous NaOH (200 g) was added as a solvent, and the mixture was heated to 80°C. 2-Chloroethanol (41.5 g, 515 mmol) was then added and stirred for 2.5 hours. Ethyl acetate (200 g) was then added, and the organic layer was extracted and washed with purified water and brine (200 g). The organic layer was extracted, and after filtering out the impurities, the mixture was concentrated to leave behind oil and crystals. Acetonitrile (70 g) was added, and after filtering out the impurities, the filtrate was concentrated to obtain the desired AD-10-1 (yield: 9.20 g, 38.5 mmol, 73% yield). H-NMR (500 MHz) in DMSO-d6: 7.83 (d, 2H), 7.01 (d, 2H), 4.91 (s, 1H), 4.05 (t, 2H), 3.73 (m, 2H), 1.52 (s, 9H). To the AD-10-1 obtained above, THF (70 g), 4-dimethylaminopyridine (DMAP, 0.351 g, 2.87 mmol), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC·HCl, 13.2 g, 69 mmol) were added and stirred at room temperature for 10 minutes. Subsequently, adipic acid (2.10 g, 14.4 mmol) was added and stirred at room temperature (25°C) overnight. After the reaction was completed, the mixture was extracted with ethyl acetate (210 g) and purified water (140 g). The organic layer was concentrated and then crystallized with heptane (140 g). The white solid was filtered off, the cake was washed with heptane, and then dried to obtain AD-10 (yield: 5.50 g, 9.46 mmol, 66%). １ H-NMR (500MHz) in DMSO-d ６ : 7.80 (d, 4H), 6.98 (d, 4H), 4.31 (m, 4H), 4.21 (m, 4H), 2.29 (t, 4H), 1.48 (m, 22H).
[0112] Additive Synthesis Example 9: Synthesis of AD-11 To AD-10 (2.00 g, 3.41 mmol), formic acid (30 g) was added and the mixture was stirred at 40°C for 1 hour. After completion of the reaction, water (60 g) was added to precipitate crystals. The solid obtained by filtration was dried to obtain crude crystals. DMSO (6 g) was added to the crude crystals, and the mixture was heated and stirred at 80°C. After cooling to room temperature, isopropanol (80 g) was added to precipitate crystals. The filtered crystals were dried to obtain AD-11 (yield: 0.590 g, 1.24 mmol, 36% yield). １ H-NMR (500MHz) in DMSO-d ６ :12.6 (s, 2H), 7.88 (d, 4H), 7.03 (d, 4H), 4.36 (m, 4H), 4.26 (m, 4H), 2.33 (t, 4H), 1.53 (m, 4H).
[0113] [Polymer Synthesis] <Synthesis Example 1> DA-1 (2.29 g, 8.00 mmol) and NMP (16.8 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while supplying nitrogen. Thereafter, CA-1 (1.69 g, 7.54 mmol) and NMP (12.4 g) were added, and the mixture was stirred at 40°C for 18 hours to obtain a solution of polyamic acid (A-1) with a solids concentration of 12% by mass (viscosity: 225 mPa s). The Mn of this polyamic acid was 10,382 and the Mw was 32,874.
[0114] Synthesis Example 2 DA-2 (0.977 g, 4.00 mmol), DA-5 (0.797 g, 4.00 mmol), and NMP (10.1 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. Thereafter, CA-2 (1.50 g, 6.00 mmol) and NMP (8.30 g) were added, and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, after cooling to room temperature, CA-3 (0.494 g, 1.68 mmol) and NMP (2.80 g) were added, and the mixture was stirred at 70 ° C. for 18 hours, to obtain a solution of polyamic acid (A-2) with a solids concentration of 15% by mass (viscosity: 304 mPa s). The Mn of this polyamic acid was 9,284, and the Mw was 26,834.
[0115] Synthesis Example 3: DA-1 (9.74 g, 34.0 mmol), DA-3 (1.37 g, 4.01 mmol), DA-4 (1.11 g, 1.99 mmol), and NMP (106 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. Thereafter, CA-1 (7.89 g, 35.2 mmol) and NMP (41.0 g) were added, and the mixture was stirred at room temperature for 18 hours to obtain a solution of polyamic acid (A-3) with a solids concentration of 12% by mass (viscosity: 210 mPa s). The Mn of this polyamic acid was 10,521, and the Mw was 32,302.
[0116] Synthesis Example 4 DA-5 (10.2 g, 51.0 mmol), DA-2 (8.31 g, 34.0 mmol), and NMP (135 g) were added to a 200 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. Thereafter, CA-2 (13.8 g, 55.2 mmol) and NMP (47.6 g) were added, and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, after cooling to room temperature, CA-3 (7.45 g, 25.3 mmol) and NMP (41.1 g) were added, and the mixture was stirred at 70 ° C. for 18 hours, to obtain a solution of polyamic acid (A-4) with a solids concentration of 15% by mass (viscosity: 309 mPa s). The Mn of this polyamic acid was 10,357, and the Mw was 26,452. Synthesis Example 5 DA-1 (1.58 g, 5.50 mmol) and NMP (16.8 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while supplying nitrogen. Thereafter, CA-4 (1.15 g, 5.28 mmol) and NMP (8.10 g) were added, and the mixture was stirred at 50°C for 18 hours, yielding a solution of polyamic acid (A-5) with a solids concentration of 12% by mass (viscosity: 239 mPa s). The Mn of this polyamic acid was 10,094 and the Mw was 33,198.
[0117] The types and amounts of the tetracarboxylic acid components and diamine components used in Synthesis Examples 1 to 5 are shown in Table 1. In Table 1, the numerical values for the tetracarboxylic acid components and diamine components represent the proportions (parts by mole) of each compound used relative to 100 parts by mole of the total amount of the diamine components used in the synthesis of each polyamic acid.
[0118]
[0119] Synthesis Example 6 To the polyamic acid solution A-3 (20 g), 0.11 g (1.13 mmol) of SAH was added and stirred at room temperature for 24 hours to obtain a solution of polyamic acid (A-6) having a non-amino terminal structure.
[0120] [Preparation of Liquid Crystal Alignment Agent] Example 1 To the solution (1.63 g) of the polyamic acid (A-1) obtained in Synthesis Example 1, the solution (3.90 g) of the polyamic acid (A-2) obtained in Synthesis Example 2, NMP (0.90 g), GBL (6.36 g), BCS (6.00 g), AD-1 (1 mass% GBL solution, 0.78 g), AD-2 (10 mass% NMP solution, 0.39 g), and AD-3 (0.04 g) were added, and the mixture was stirred at room temperature for 2 hours, thereby obtaining a liquid crystal aligning agent (AL-1) of the present invention.
[0121] <Examples 2 to 11 and Comparative Examples 1 to 4> By carrying out the same operation as in Example 1 above, except that the type and amount of polymer solution, solvent, and additive used were changed as shown in Table 2, the liquid crystal aligning agent (AL-2) to (AL-11) of Examples 2 to 11 of the present invention and the liquid crystal aligning agent (AL-C1) to (AL-C4) of Comparative Examples 1 to 4 were obtained.
[0122]
[0123] In Table 2, the numerical values for Polymer 1, Polymer 2, Additive 1, Additive 2, Specific Additive, and Other Additives represent the proportions (parts by mass) of each polymer solid content and additive relative to 100 parts by mass of the total polymer components.
[0124] [Preparation of Liquid Crystal Cell] <Preparation of ECB-Type Liquid Crystal Cell> A liquid crystal cell having the configuration of an ECB-mode liquid crystal display element was prepared. First, a substrate with electrodes was prepared. The substrate was a glass substrate measuring 30 mm x 40 mm and 0.7 mm thick. ITO electrodes with a thickness of 35 nm were formed on the substrate, and the electrodes were in a stripe pattern spaced 40 mm vertically and 10 mm horizontally. Next, the liquid crystal alignment agent obtained above was filtered through a filter with a pore size of 1.0 μm and then applied to the substrate with electrodes prepared above by spin coating. The resulting solution was then dried on a hot plate at 80°C for 2 minutes and then baked in an infrared oven at 230°C for 20 minutes to form a coating film with a thickness of 60 nm. This liquid crystal alignment film was subjected to a rubbing alignment treatment (roller diameter: 120 mm, roller rotation speed: 1,000 rpm, movement speed: 20 mm / sec, indentation length: 0.4 mm) using a rayon cloth (HY-5318 manufactured by Hyperflex). Subsequently, the film was washed by ultrasonic irradiation in pure water for 1 minute, water droplets were removed by air blowing, and then the film was dried at 80°C for 10 minutes to obtain a substrate with a liquid crystal alignment film. Two substrates with this liquid crystal alignment film were prepared, and spherical spacers with a particle size of 4 μm were sprayed onto the liquid crystal alignment film surface of one of the substrates. After that, a sealant (XN-1500T manufactured by Mitsui Chemicals) was printed around the periphery, leaving the liquid crystal injection port, and the other substrate was attached with the rubbing direction reversed and the film surfaces facing each other. This was then subjected to a heat treatment at 150°C for 60 minutes to harden the sealant and produce an empty cell. Negative liquid crystal NA-1559 (DIC Corporation) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell. The obtained liquid crystal cell was then heated at 120°C for 1 hour and allowed to stand at 23°C overnight before being used for evaluation.
[0125] <Fabrication of FFS-Driven Liquid Crystal Cell> A liquid crystal cell with the configuration of an FFS-mode liquid crystal display element was fabricated. First, a substrate with electrodes was prepared. The substrate was a rectangular glass substrate measuring 30 mm x 50 mm and 0.7 mm thick. A solid-patterned ITO electrode constituting a common electrode was formed on the substrate as a first layer. A SiN (silicon nitride) film deposited by CVD (chemical vapor deposition) was formed on the first common electrode as a second layer. The second SiN film had a thickness of 300 nm, which served as an interlayer insulating film. A comb-shaped pixel electrode formed by patterning an ITO film as a third layer was disposed on the second SiN film. Two pixels, a first pixel and a second pixel, were formed, each measuring 10 mm long and 5 mm wide. This electrode-equipped substrate had a structure in which the first common electrode and the third pixel electrode were insulated by the second SiN film. The pixel electrode of the third layer had a comb-like shape with the central portion bent at an interior angle of 160° and multiple electrode lines, each 3 μm wide, arranged parallel to each other at intervals of 6 μm. One pixel was formed by multiple electrode lines and had a first region and a second region separated by a line connecting the bent portions.
[0126] Next, the liquid crystal alignment agent obtained above was filtered through a filter with a pore size of 1.0 μm, and then spin-coated onto the electrode-attached substrate (hereinafter referred to as the electrode substrate) and a glass substrate (hereinafter referred to as the counter substrate) having 4 μm-high columnar spacers and an ITO film formed on the backside. After drying for 2 minutes on a hot plate at 80 °C, it was baked for 20 minutes in a hot air circulating oven at 230 °C to form a coating film with a thickness of 60 nm. This coating film was subjected to a rubbing alignment treatment (roller diameter: 120 mm, roller rotation speed: 1,000 rpm, movement speed: 20 mm / sec, indentation length: 0.4 mm) using a rayon cloth (HY-5318 manufactured by Hyperflex). The substrate was then ultrasonically washed in pure water for 1 minute, water droplets were removed by air blowing, and the substrate was dried at 80 °C for 10 minutes to obtain a substrate with a liquid crystal alignment film. The liquid crystal alignment film formed on the electrode substrate was subjected to an alignment treatment so that the direction dividing the interior angle of the pixel bend was parallel to the liquid crystal alignment direction. The liquid crystal alignment film formed on the counter substrate was also subjected to an alignment treatment so that the alignment direction of the liquid crystal on the electrode substrate was aligned with the alignment direction of the liquid crystal on the counter substrate when the liquid crystal cell was fabricated. The two substrates were combined into a pair, and a sealant (Mitsui Chemicals XN-1500T) was printed on one substrate using a dispenser. Another substrate was then attached to the other substrate, facing each other with the alignment directions of the liquid crystal alignment films aligned at 0°. The bonded substrates were then pressed together and heated for 60 minutes in a hot air circulating oven at 150°C to cure the sealant, producing an empty cell. Negative liquid crystal NA-1559 (DIC Corporation) was injected into this empty cell using a vacuum injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell. The resulting liquid crystal cell was then heated at 120°C for 1 hour and left overnight at 23°C before being used for evaluation.
[0127] [Evaluation of Liquid Crystal Cell Characteristics] The characteristics of the ECB-type liquid crystal cell and the FFS-type liquid crystal cell prepared above were evaluated as follows.
[0128] <Evaluation of Alignment Stability by Long-Term AC Drive> This evaluation is to evaluate the afterimage (also called AC afterimage) that occurs due to the deterioration of the alignment performance of the liquid crystal alignment film during long-term AC drive. Using the FFS drive liquid crystal cell prepared above, a high-brightness backlight (light source: LED, brightness: 30,000 cd / m) with a surface temperature of 50°C was used. ２ ) and an AC voltage of ±6.5 V at a frequency of 30 Hz was applied for 120 hours. The pixel electrode and common electrode of the liquid crystal cell were then shorted and left at room temperature (23°C) for one day. After leaving the liquid crystal cell, it was placed between two polarizing plates arranged so that their polarization axes were perpendicular to each other. The backlight was turned on with no voltage applied, and the liquid crystal cell was adjusted to minimize the transmitted light intensity of the first region of the first pixel. The rotation angle Δ required to rotate the liquid crystal cell to minimize the transmitted light intensity of the second region of the first pixel was then calculated. The first and second regions of the second pixel were similarly compared, and the same angle Δ was calculated. The average of the angles Δ for the first and second pixels was then calculated as the rotation angle Δ of the liquid crystal cell. It can be said that the smaller the rotation angle Δ, the better the stability of the liquid crystal alignment.
[0129] <Measurement of Pretilt Angle> The pretilt angle in the ECB-type liquid crystal cell was measured by the Mueller matrix method using an AxoScan manufactured by Axometrics Inc. The lower the pretilt angle, the better the viewing angle characteristics.
[0130] The evaluation results of the alignment stability and pretilt angle using each of the liquid crystal aligning agents of Examples 1 to 6 and Comparative Examples 1 to 4 are shown in Table 3. The numbers in parentheses for the polymer components and additives represent the blending ratio (parts by mass) of each polymer solid content and additive when the total content of the polymer solid content is 100 parts by mass.
[0131]
[0132] As shown in Table 3, the liquid crystal alignment films obtained from the liquid crystal alignment agents containing the specific additives had better alignment stability and viewing angle characteristics than the liquid crystal alignment films obtained from the liquid crystal alignment agents containing neither the specific additive nor other additives (Comparison between Examples 1 to 5 and 8 to 11 and Comparative Example 1, and between Examples 6 and 7 and Comparative Example 4). On the other hand, when other additives were added as additives, some films showed improved alignment stability or viewing angle characteristics compared to the liquid crystal alignment films obtained from the liquid crystal alignment agents containing neither the specific additive nor other additives, but not all of them were good (Comparison between Comparative Examples 2 and 3 and Comparative Example 1).
[0133] The liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention can be suitably used in various liquid crystal display elements, typified by liquid crystal display elements of an IPS drive system or an FFS drive system. These display elements are not limited to liquid crystal displays intended for display purposes, and can also be used as a liquid crystal alignment film for a retardation film, a liquid crystal alignment film for a scanning antenna or a liquid crystal array antenna, or a liquid crystal alignment film for a transmissive / scattering liquid crystal dimming element, or for other purposes, such as a protective film for a color filter, a gate insulating film for a flexible display, or a substrate material.
[0134] The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2024-052112 filed on March 27, 2024 are hereby incorporated by reference as the disclosure of the present invention.
Claims
1. A liquid crystal aligning agent containing the following components (A) and (B): Component (A): a polymer (A) capable of aligning liquid crystals; Component (B): a compound (B) represented by the following formula (1): (In formula (1), Ar １ , and Ar １’ each independently represents a benzene ring, a biphenyl structure, or a naphthalene ring, and one or more hydrogen atoms on the benzene ring, the biphenyl structure, or the naphthalene ring may be substituted with a monovalent group (excluding (q1) to (q4)). X is a divalent organic group represented by the following formula (2). *-X １ -(Y １ -L) ｎ -Y ２ -X ２ -* (2) (In formula (2), X １ , X ２ are each independently a single bond, —O—, *1-O—CO—*2 (*1 and *2 represent a bond, and *1 is Ar １ or Ar １’ L represents a single bond, -O-, -O-C(=O)- or -C(=O)-O-, and when there are multiple Ls, the multiple Ls may be the same or different from one another, provided that at least one L represents -O-C(=O)- or -C(=O)-O-. n is an integer of 1 to 6. Y １ , Y ２ each independently represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and some of the hydrogen atoms in the divalent hydrocarbon group may be substituted with a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxy group. １ If there are multiple Y １ may be the same as or different from each other. * represents Ar １ or Ar １’ Each of Q and Q' independently represents a hydrogen atom or a monovalent group selected from the group consisting of (q1) to (q4) below. When formula (1) has a plurality of (q1) to (q4), a plurality of R １ ~R ４ may be the same as or different from each other. (In formula (q1), R １ represents a monovalent organic group, and the monovalent organic group is a carbonyl group, a sulfonyl group, and *1-C(R ｑ１ ) ２ - *2 is bonded to the nitrogen atom via a linking group. ２ represents a hydrogen atom or a monovalent organic group. ｑ１ ) ２ *1 in -*2 represents a bond to the nitrogen atom, and multiple R ｑ１ each independently represents a hydrogen atom or a monovalent organic group. ｑ１ ) ２ *2 in -*2 bonds to a monovalent organic group having a heteroatom-containing group. ３ represents a hydrogen atom or a monovalent organic group. ４ represents a hydrogen atom, a hydroxy group, a halogen atom, or a monovalent organic group. ５ represents a hydrogen atom, a hydroxyl group, or a monovalent organic group. １ or Ar １’ represents the bond that bonds to 2. The liquid crystal aligning agent according to claim 1, wherein the compound (B) is at least one compound selected from the group consisting of the following formulae (q1-1) to (q1-5), (q2-1) to (q2-2), (q3-1) to (q3-3), and (q4-1) to (q4-2):
3. The liquid crystal aligning agent according to claim 1, wherein the polymer (A) is at least one polymer selected from the group consisting of polyimide precursors and polyimides which are imidized products of the polyimide precursors.
4. The liquid crystal aligning agent according to claim 3, wherein the polyimide precursor is obtained using a tetracarboxylic acid component containing a tetracarboxylic acid dianhydride represented by the following formula (2) or a derivative thereof: (In formula (2), Z represents a structure selected from the following formulas (x-1) to (x-13).) (In the above formula, R １ ~R ４ R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, or a phenyl group. ５ and R ６ each independently represents a hydrogen atom or a methyl group; j and k are integers of 0 or 1; A １ and A ２ each independently represents a single bond, —O—, —CO—, —COO—, phenylene, a sulfonyl group, or an amide group. ２ may be the same or different. *1 is a bond bonded to one acid anhydride group, and *2 is a bond bonded to the other acid anhydride group.) 5. The liquid crystal aligning agent according to claim 4, wherein the formula (x-1) is selected from the group consisting of the following formulas (x1-1) to (x1-6): (In the above formula, *1 is a bond bonded to one acid anhydride group, and *2 is a bond bonded to the other acid anhydride group.) 6. The liquid crystal aligning agent according to claim 3, wherein the polyimide precursor is obtained using a diamine component containing at least one diamine selected from the group consisting of diamines represented by the following formula (3) and the following formula (3A): (In formula (3), Y ３ represents a divalent organic group represented by the following formula (O), and in formula (3A), Y ３ａ represents a divalent organic group represented by the following formula (a), where each of the multiple R's independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In formula (O), Ar represents a divalent benzene ring, biphenyl structure, naphthalene ring, or aromatic heterocycle. When a plurality of Ars are present, the two Ars may be the same or different, and any hydrogen atom of the benzene ring, biphenyl structure, naphthalene ring, or aromatic heterocycle may be substituted with a monovalent substituent. p is an integer of 0 or 1. Q ３ Ha-(CH ２ ) ｎ -(n is an integer of 2 to 18), or the above-(CH ２ ) ｎ -of-CH ２ represents a group in which at least a portion of - has been replaced with either -O-, -C(=O)-, or -O-C(=O)-. * represents a bond. (In formula (a), a hydrogen atom on the benzene ring may be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, or a fluoroalkoxy group having 1 to 10 carbon atoms. P is an aromatic ring selected from a benzene ring or a biphenyl structure, and a hydrogen atom on the benzene ring or the biphenyl structure may be substituted with a methyl group or a fluorine atom. n is an integer of 0 to 5. When n is an integer of 2 or greater, the n Ps independently have the above definition. * represents a bond.) 7. The liquid crystal aligning agent according to claim 6, wherein the divalent organic group represented by formula (O) is any one of the following formulae (o-1) to (o-12): (In the formula, X １ , X ２ each independently represents a single bond or —O—. (In formula (o-7), X ７ Each independently represents a single bond or —O—. However, when n is 1, two X ７ At least one of the groups represents —O—. In formula (o-12), two m's each independently have the above definition.
8. The liquid crystal aligning agent according to claim 3, wherein the polyimide precursor is obtained using a diamine component containing a diamine having at least one nitrogen atom-containing structure selected from the group consisting of a nitrogen atom-containing heterocycle (excluding imide rings contained in polyimides), a secondary amino group, and a tertiary amino group.
9. The liquid crystal aligning agent according to claim 1, wherein the content of the compound (B) is 0.1 to 50 parts by mass relative to 100 parts by mass of the polymer (A).
10. The liquid crystal aligning agent according to claim 1, further comprising at least one additive selected from the group consisting of an adhesion aid, a crosslinking compound, and a dielectric or conductive substance for adjusting the dielectric constant or electrical resistance of the liquid crystal alignment film.
11. A method for producing a liquid crystal alignment film, comprising applying the liquid crystal aligning agent according to any one of claims 1 to 10 to a substrate, baking the applied film, and then subjecting the resulting film to an alignment treatment.
12. A liquid crystal alignment film formed from the liquid crystal aligning agent according to any one of claims 1 to 10.
13. A liquid crystal display device comprising the liquid crystal alignment film according to claim 12.
14. The liquid crystal display element according to claim 12, which is of an IPS drive system or an FFS drive system.
15. A compound represented by any one of the following formulas (q1-1) to (q1-5), (q2-1) to (q2-2), (q3-1) to (q3-3), and (q4-1) to (q4-2).
Citation Information
Patent Citations
Polyoxyalkylene-substituted and bridged triazine, benzotriazole and benzophenone derivatives as UV absorbers
JP2000515141A
Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal element
JP2022136974A
Alignment material composition and alignment layer
US20100213423A1