WO2022014470A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides - Google Patents

Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides Download PDF

Info

Publication number
WO2022014470A1
WO2022014470A1 PCT/JP2021/025836 JP2021025836W WO2022014470A1 WO 2022014470 A1 WO2022014470 A1 WO 2022014470A1 JP 2021025836 W JP2021025836 W JP 2021025836W WO 2022014470 A1 WO2022014470 A1 WO 2022014470A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystal
group
crystal alignment
diamine
formula
Prior art date
Application number
PCT/JP2021/025836
Other languages
English (en)
Japanese (ja)
Inventor
達也 結城
敏行 日向野
一平 福田
Original Assignee
日産化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学株式会社 filed Critical 日産化学株式会社
Priority to JP2022536312A priority Critical patent/JP7311047B2/ja
Priority to CN202180063541.7A priority patent/CN116234856B/zh
Priority to KR1020237004491A priority patent/KR20230038513A/ko
Publication of WO2022014470A1 publication Critical patent/WO2022014470A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

  • the present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element.
  • liquid crystal displays have been widely used as display units for personal computers, smartphones, mobile phones, television receivers, and the like.
  • the liquid crystal display device is, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode that apply an electric field to the liquid crystal layer, and a liquid crystal alignment film that controls the orientation of liquid crystal molecules in the liquid crystal layer.
  • a thin film transistor (TFT) for switching an electric signal supplied to a pixel electrode is provided.
  • a vertical electric field method such as a TN method and a VA method
  • a horizontal electric field method such as an IPS method and an FFS (fringe field switching) method are known.
  • liquid crystal alignment film in industry is a polymer film formed on an electrode substrate, which is represented by a polyamic acid and / or a polyimide obtained by imidizing the polyamic acid. It is manufactured by performing a so-called rubbing process of rubbing in one direction with a cloth such as.
  • the rubbing process is a simple and highly productive industrially useful method.
  • scratches on the surface of the alignment film generated by the rubbing process, dust generation, the effects of mechanical force and static electricity, and the in-plane alignment process Various problems such as non-uniformity of the above have been clarified.
  • a photo-alignment method for imparting a liquid crystal alignment ability by irradiating with polarized radiation is known.
  • the photoalignment method a method using a photoisomerization reaction, a method using a photocrosslinking reaction, a method using a photodecomposition reaction, and the like have been proposed (for example, Non-Patent Document 1, Patent Document 1, and Patent Document 2). reference).
  • PSA Polymer Sutained Selected
  • One of the characteristics required for the liquid crystal alignment film is high display quality with few display defects of the liquid crystal display element.
  • high display quality is regarded as important, and there are specifications for display defects such as so-called “afterimage phenomenon” or simply "afterimage”. It is getting tougher and harder.
  • it is required to realize a liquid crystal alignment film having a property of quickly disappearing even if an afterimage is generated.
  • Patent Document 4 a specific diamine and a specific aromatic tetracarboxylic acid derivative are reacted in a predetermined amount.
  • a liquid crystal alignment agent containing a polyimide precursor obtained by the above-mentioned is disclosed.
  • the conventional liquid crystal alignment film did not have sufficient characteristics to quickly eliminate the afterimage. That is, the conventional liquid crystal alignment film exhibits sufficient characteristics as long as the environment in which it is used is limited, but in recent years, liquid crystal display devices have been used in a wide temperature range from extremely low temperature (-20 ° C) to high temperature. It is required that the characteristics can be fully exhibited. In addition, as the liquid crystal display device has become higher in definition, the visibility of the afterimage has become higher than in the past. From the above, there is a demand for a liquid crystal alignment film that eliminates afterimages more quickly than ever before.
  • an object of the present invention is to provide a liquid crystal alignment film capable of quickly eliminating an afterimage and exhibiting high display quality in a high-definition liquid crystal display device. Further, it is also an object of the present invention to provide a liquid crystal alignment agent for obtaining the liquid crystal alignment film and a liquid crystal display element using the liquid crystal alignment film.
  • the present inventor has conducted diligent research to achieve the above problems, and as a result, a liquid crystal alignment agent containing a polymer obtained by using a specific amount of a specific diamine component and an aromatic tetracarboxylic acid dianhydride as essential components.
  • a liquid crystal alignment film formed by using the above-mentioned is extremely effective for achieving the above object, and completed the present invention.
  • the present invention includes the following aspects. Obtained using a diamine represented by the following formula (1a), a diamine component containing a diamine represented by the following formula (1b), and a tetracarboxylic acid derivative component containing an aromatic tetracarboxylic acid dianhydride or a derivative thereof.
  • Y represents a divalent organic group having at least one structure selected from the group consisting of a nitrogen atom-containing heterocycle which may be substituted and an amine structure represented by the following formula (b) in the molecule.
  • R represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, or a group having —O— between carbon-carbon bonds of the chain hydrocarbon group having 1 to 10 carbon atoms.
  • Any hydrogen atom can be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom-containing alkyl group having 1 to 3 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 3 carbon atoms, and fluorine. It may be substituted with at least one selected from the group consisting of atoms.
  • the present invention it is possible to provide a liquid crystal alignment film capable of quickly eliminating an afterimage and exhibiting high display quality in a high-definition liquid crystal display device. Further, according to the present invention, it is possible to provide a liquid crystal alignment agent for obtaining the liquid crystal alignment film and a liquid crystal display element using the liquid crystal alignment film.
  • the mechanism by which the above effects of the present invention are obtained is not always clear, but it is considered that the following is one of the causes. That is, it is considered that the electron mobility is improved and the relaxation rate is improved by directly connecting the phenyl group or nitrogen atom-containing heterocycle and the urea group to expand the conjugated system.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Boc represents a tert-butoxycarbonyl group.
  • liquid crystal alignment agent containing a polymer obtained by using a specific amount of a specific diamine component and an aromatic tetracarboxylic acid dianhydride as essential components, a liquid crystal alignment film formed by using the liquid crystal alignment agent, and a liquid crystal alignment film.
  • the liquid crystal display element having the liquid crystal alignment film will be described in detail, but the description of the constituent requirements described below is an example as an embodiment of the present invention, and is not specified in these contents.
  • the liquid crystal alignment agent of the present invention contains the polymer (A).
  • Preferred embodiments of the liquid crystal alignment agent of the present invention include a liquid crystal alignment agent containing a polymer (A) and an organic solvent. Further, the liquid crystal alignment agent of the present invention can also contain a polymer other than the polymer (A) (for example, the polymer (B) described later).
  • the polymer (A) is a diamine represented by the above formula (1a) (hereinafter, also referred to as a specific diamine (1a)) and a diamine represented by the above formula (1b) (hereinafter, also referred to as a specific diamine (1b)).
  • a polymer include a polyimide precursor having an imide precursor structure such as polyamic acid and a polyamic acid ester, and polyimide which is an imidized product of the polyimide precursor.
  • Specific diamine (1a) is represented by the following formula (1a). (Any hydrogen atom on the benzene ring may be substituted with a monovalent substituent.)
  • Examples of the monovalent substituent on the benzene ring 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, and 1 to 10 carbon atoms. Fluoroalkyl group, fluoroalkenyl group having 2 to 10 carbon atoms, fluoroalkoxy group having 1 to 10 carbon atoms, carboxyl group, alkyloxycarbonyl group having 1 to 10 carbon atoms, cyano group, nitro group and the like.
  • preferred specific examples of the specific diamine (1a) include diamines represented by the following formulas (1a-1) to (1a-3). Not limited.
  • the specific diamine (1b) used in the present invention is represented by the following formula (1b).
  • (Y represents a divalent organic group having at least one structure selected from the group consisting of a nitrogen atom-containing heterocycle which may be substituted and an amine structure represented by the following formula (b) in the molecule.
  • (R represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, or a group having —O— between carbon-carbon bonds of the chain hydrocarbon group having 1 to 10 carbon atoms.
  • Any hydrogen atom can be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom-containing alkyl group having 1 to 3 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 3 carbon atoms, and fluorine. It may be substituted with at least one selected from the group consisting of atoms.
  • nitrogen atom-containing heterocycle examples include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indol, benzoimidazole, purine, quinoline, isoquinoline, naphthylidine, quinoxaline, phthalazine, triazine, carbazole, and acridin.
  • examples thereof include piperidine, piperazine, pyrridine, hexamethyleneimine and the like. Of these, pyrrole, pyridine, pyrimidine, pyrazine, benzimidazole, piperidine, piperazine, quinoline, carbazole or acridine are preferable.
  • Any hydrogen atom on the nitrogen atom-containing heterocycle has an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom-containing alkyl group having 1 to 3 carbon atoms, and fluorine having 1 to 3 carbon atoms. It may be substituted with at least one selected from the group consisting of an atom-containing alkoxy group and a fluorine atom.
  • Examples of the chain hydrocarbon group having 1 to 10 carbon atoms in R include an alkyl group such as a methyl group and an ethyl group, an alkenyl group such as a vinyl group, and an alkynyl group such as an ethynyl group. Of these, an alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.
  • the above Y is preferably a divalent organic group represented by the following formulas (y1) to (y8).
  • the Y contains an amine structure represented by the formula (b), the structures represented by the following formulas (y5) to (y8) are preferable.
  • R is synonymous with the above formula (b).
  • Q represents a nitrogen atom-containing heterocycle which may be substituted.
  • n represents an integer of 2 to 12
  • Any hydrogen atom on the benzene ring has an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a carbon number of carbon atoms. It may be substituted with at least one selected from the group consisting of 1 to 3 fluorine atom-containing alkyl groups, 1 to 3 carbon atoms-containing alkoxy groups and fluorine atoms.
  • L, Q, R and L' are substituted. When there are a plurality of them in one formula, they may be the same or different independently.
  • preferred specific examples of the specific diamine (1b) include diamines represented by the following formulas (1b-1) to (1b-20) and the following formula (1b'-). 1)-Diamine represented by (1b'-11), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole and N-methyl-3,6 -Includes, but is not limited to, diaminocarbazole.
  • the diamine component for obtaining the polymer (A) contains 5 to 95 mol% of the diamine represented by the specific diamine (1a) with respect to 1 mol of the diamine component used, and contains the specific diamine (1b). include.
  • the specific diamine (1a) and the specific diamine (1b) may each be composed of one kind of diamine or two kinds of diamines.
  • the ratio of the diamine represented by the specific diamine (1a) in the diamine component for obtaining the polymer (A) is more preferably 10 to 90 mol% with respect to 1 mol of the diamine component used. It is more preferable to contain 80 mol%.
  • the ratio of the specific diamine (1b) in the diamine component for obtaining the polymer (A) is preferably 5 to 95 mol% and 10 to 90 mol% with respect to 1 mol of the diamine component used. It is more preferable, and it is further preferable to contain 20 to 90 mol%.
  • the diamine component for obtaining the polymer (A) other diamines other than the above-mentioned specific diamine (1a) and specific diamine (1b) may be used. Examples of other diamines include the following diamines.
  • Diamines having photoorienting groups such as 4,4'-diaminoazobenzene and diamines represented by the following formulas (d T -1) to (d T -3); 2,4-diaminophenol, 3,5-diamino Phenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol; 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid and: Diamines having a carboxy group such as the diamine compounds represented by the formulas (3b-1) to (3b-4); 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4- (2- (Methylamino) ethyl) aniline, 4,4'-diaminobenz
  • Diamine having a photopolymerizable group at the end a diamine having a siloxane bond such as 1,3-bis (3-aminopropyl) -tetramethyldisiloxane; Diamine having an oxazoline structure; a diamine represented by the following formula (2) or formula (2i), or the like.
  • 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 independently represent an integer of 0 to 4, and m1 + m2 represent an integer of 1 to 4. Equation (3b-2).
  • m3 and m4 each independently represent an integer of 1 to 5.
  • a 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms
  • m5 represents 1 to 5.
  • a 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- represents, m6 is an integer of 1-4).
  • Y 2 represents a divalent organic group represented by the following formula (O).
  • Two Rs independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • Two Y 2i are each.
  • Independently represents a divalent organic group represented by the following formula (O').
  • Ar represents a divalent benzene ring, biphenyl structure, or naphthalene ring.
  • the two Ars may be the same or different, and any hydrogen atom of the benzene ring, biphenyl structure, or naphthalene ring is a monovalent substitution. It may be substituted with a group.
  • P is an integer of 0 or 1.
  • Q 2 is ⁇ (CH 2 ) n ⁇ (n is an integer of 2 to 18), or the ⁇ (CH 2 ) n.
  • Examples of the substituent of the benzene ring, the biphenyl structure or the naphthalene ring in the above formulas (O) and (O') include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and carbon.
  • Examples thereof include an alkyloxycarbonyl group, a cyano group and a nitro group.
  • the divalent organic group represented by the above formula (O) is preferably a divalent organic group represented by the following formulas (o-1) to (o-16) from the viewpoint of enhancing the liquid crystal orientation.
  • * represents a bond.
  • the divalent organic group represented by the above formula (O') is a divalent organic group represented by the above formulas (o-7) to (o-16) from the viewpoint of enhancing the liquid crystal orientation. preferable.
  • Tetracarboxylic acid derivative component When the above polymer (A) is produced, the tetracarboxylic acid derivative component to be reacted with the diamine component is not only tetracarboxylic acid dianhydride, but also tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid dialkyl ester. Derivatives of tetracarboxylic acid dianhydride such as dihalide can also be used. As the tetracarboxylic acid derivative component, one kind of tetracarboxylic dianhydride or a derivative thereof may be used alone, or two or more kinds thereof may be used in combination.
  • the tetracarboxylic acid derivative component for obtaining the polymer (A) contains an aromatic tetracarboxylic acid dianhydride or a derivative thereof, and comprises one kind of aromatic tetracarboxylic acid dianhydride or a derivative thereof. It may be composed of two or more kinds of aromatic tetracarboxylic acid dianhydrides or derivatives thereof.
  • the aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to the aromatic ring. However, it does not have to be composed only of an aromatic ring structure, and may have a chain hydrocarbon structure or an alicyclic structure as a part thereof.
  • the aromatic tetracarboxylic dianhydride or a derivative thereof include an aromatic tetracarboxylic dianhydride represented by the following formula (Ta) or a derivative thereof.
  • (Xa represents a structure selected from the group consisting of the following formulas (a-1) to (a-9).)
  • J and k are integers of 0 or 1
  • a 1 and A 2 are independent, single bond, -O-, -CO-, -COO-, phenylene, -SO 2-, or-, respectively.
  • NRCO- R represents. a hydrogen atom or a methyl group in representing the.
  • * represents a bond that binds to the acid anhydride group.
  • formula (a-2) 2 two a 2 is be the same or different good.
  • Preferred specific examples of the above formulas (a-1) and (a-2) include the following formulas (a-10) to (a-25).
  • "*" in the formula represents a bond that binds to an acid anhydride group.
  • the ratio of the aromatic tetracarboxylic dianhydride or its derivative represented by the above formula (Ta) is 10 to 10 to 1 mol of the total tetracarboxylic dianhydride component used in the synthesis of the polymer (A). 100 mol% is preferable, 20 to 100 mol% is more preferable, and 50 to 100 mol% is further preferable.
  • the tetracarboxylic acid dianhydride and its derivative used in the production of the polymer (A) are the aromatic tetracarboxylic acid dianhydride represented by the above formula (Ta) or a tetracarboxylic acid dianhydride other than the derivative thereof.
  • the derivative (hereinafter, other tetracarboxylic acid dianhydride or a derivative thereof) may be contained.
  • examples of other tetracarboxylic dianhydrides or derivatives thereof include acyclic aliphatic or alicyclic tetracarboxylic dianhydrides or derivatives thereof.
  • the acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. However, it does not have to be composed only of a chain hydrocarbon structure, and may have a heteroatom such as an alicyclic structure, an aromatic ring structure, or an oxygen atom as a part thereof.
  • the alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to the alicyclic structure. However, none of these four carboxyl groups are bonded to the aromatic ring. Further, it does not have to be composed only of an alicyclic structure, and may have a chain hydrocarbon structure or an aromatic ring structure as a part thereof.
  • Preferred examples of the other tetracarboxylic dianhydrides or derivatives thereof include tetracarboxylic dianhydrides represented by the following formulas (T) and the following formulas (2T) or derivatives thereof.
  • the above-mentioned other tetracarboxylic dianhydrides or derivatives thereof may be used alone or in combination of two or more.
  • acyclic aliphatic or alicyclic tetracarboxylic dianhydride represented by the following formula (T) is preferable.
  • (X represents a structure selected from the group consisting of the following formulas (x-1) to (x-11).
  • X 2 is selected from the group consisting of the following formulas (t-1) to (t-19).
  • R 1 to R 4 each independently contain 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, and a fluorine atom. It represents a monovalent organic group or a phenyl group having 1 to 6 carbon atoms.
  • R 5 and R 6 each independently represent a hydrogen atom or a methyl group. * Is a bond that binds to an acid anhydride group. show.) (* Represents a bond that binds to an acid anhydride group.
  • the six Rs are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, and a carbon number of carbon atoms.
  • R is hydrogen.
  • An atom, a halogen atom, a methyl group, or an ethyl group is preferable, and a hydrogen atom or a methyl group is more preferable.
  • X is the above formulas (x-1) to (x-6). ..
  • the above formula (x-1) is preferably selected from the group consisting of the following formulas (x1-1) to (x1-6). (* Represents a bond that binds to an acid anhydride group.)
  • the tetracarboxylic acid derivative component for obtaining the polymer (A) is represented by the above formula (T), wherein X represents a structure selected from the group consisting of the above formulas (x-1) to (x-7). It does not have to contain the alicyclic tetracarboxylic dianhydride.
  • the liquid crystal aligning agent of the present invention is selected from the group consisting of a polyimide precursor obtained by using a tetracarboxylic acid derivative component and a diamine component and a polyimide which is an imidized product of the polyimide precursor, from the viewpoint of enhancing the liquid crystal orientation.
  • the polymer (B) (however, excluding the polymer (A)) may be contained.
  • Specific examples of such a polymer include a polyimide precursor obtained by using a tetracarboxylic acid derivative component and a diamine component not containing the specific diamine (1a), and a polyimide which is an imidized product of the polyimide precursor. Examples thereof include polymers selected from the group consisting of.
  • Specific examples of the polyimide precursor include polyamic acid and polyamic acid ester.
  • the polymer (B) one type may be used alone, or two or more types may be used in combination.
  • Examples of the tetracarboxylic dianhydride component for obtaining the polymer (B) include acyclic aliphatic tetocarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride or derivatives thereof. Can be mentioned. Specific examples of the acyclic aliphatic tetracarboxylic dianhydride, the alicyclic tetracarboxylic dianhydride, and the aromatic tetocarboxylic dianhydride include the tetracarboxylic dianhydride exemplified in the polymer (A). Can be mentioned.
  • the preferred tetcarboxylic acid derivative component is an aromatic tetracarboxylic acid dianhydride represented by the above formula (Ta) or a derivative thereof, an alicyclic tetracarboxylic acid dianhydride represented by the above formula (T) or a derivative thereof.
  • Derivatives hereinafter, these are also collectively referred to as a specific tetracarboxylic acid derivative component (b)
  • the tetracarboxylic acid derivative component one kind of tetracarboxylic dianhydride or a derivative thereof may be used alone, or two or more kinds thereof may be used in combination.
  • the ratio of the specific tetracarboxylic acid derivative component (b) used is preferably 1 to 100 mol% with respect to 1 mol of the total tetracarboxylic acid derivative component used in the synthesis of the polymer (B), preferably 5 to 100. More preferably mol%, more preferably 10-100 mol%.
  • Examples of the diamine component for obtaining the polymer (B) include the diamine exemplified in the polymer (A).
  • diamines having photoalignant groups such as 4,4'-diaminoazobenzene and diamines represented by the above formulas (d T -1) to (d T -3); 3, 3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4- (2- (methylamino) ethyl) aniline, 4,4'-diaminobenzophenone, 1,4-bis (4) -Aminobenzyl) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4'-diaminodiphenyl ether; the above formulas (h-1) to (
  • a diamine having a urea bond such as a diamine represented by -3); a diamine having an amide bond represented by the above formulas (h-4) to (h-6); 2- (2,4-diaminophenoxy) methacrylate.
  • Diamine having a photopolymerizable group such as ethyl and 2,4-diamino-N, N-diallylaniline at the end; Diamine having a siloxane bond such as 1,3-bis (3-aminopropyl) -tetramethyldisiloxane
  • a diamine having an oxazoline structure such as the above formulas (Ox-1) to (Ox-2); a diamine represented by the above formula (2) or the above formula (2i) is preferable.
  • the preferred embodiment of the diamine represented by the above formula (2) or the above formula (2i) is the same as the above.
  • Y 2 is the above formulas (o-1) to (o-14).
  • the diamine of the above formula (2) which is a divalent organic group represented by the above formula, and the above formula (the above formula) where Y 2 is a divalent organic group represented by the above formulas (o-15) to (o-16). It may be a combination with the diamine of 2).
  • Preferred specific examples of the diamine represented by the above formula (2i) include compounds represented by the following formulas (2i-1) to (2i-5).
  • the two ns independently represent an integer of 1 to 6.
  • the two ns are independent of each other. Represents an integer of 2 to 6)
  • the polymer (B) is 4,4'-diaminoazobenzene, a diamine represented by the above formulas (d T -1) to (d T -3), and 3,3'-diamino.
  • At least one diamine may be used in an amount of 1 to 95 mol%, 30 to 95 mol%, or 40 to 90 mol% with respect to 1 mol of the diamine component used for the synthesis of the polymer (B). You may use it.
  • At least one of the polymer (A) and the polymer (B) has a group "-N (D)-(D is a carbamate-based protecting group) in the molecule from the viewpoint of increasing the voltage holding ratio of the obtained liquid crystal orientation display element. It represents.) ”.
  • a polymer having the group "-N (D)-(D represents a carbamate-based protecting group)" is a single amount having a group "-N (D)-(D represents a carbamate-based protecting group)".
  • a method using a body for example, a diamine having a group "-N (D)-(D represents a carbamate-based protecting group)" as at least a part of a raw material, or a method using a terminal encapsulant described later.
  • a carbamate-based protecting group include a tert-butoxycarbonyl group and a 9-fluorenylmethoxycarbonyl group.
  • the diamine having the group "-N (D)-(D represents a carbamate-based protecting group)" is more preferably having at least one aromatic group such as a benzene ring. More preferably, the residue excluding the group "(D)” is a diamine having 6 to 30 carbon atoms.
  • Specific examples of the diamine having the group "-N (D)-(D represents a carbamate-based protecting group)” include compounds represented by the following formulas (5-1) to (5-10). Can be mentioned. (Boc represents a tert-butoxycarbonyl group.)
  • the ratio of the diamine having the group "-N (D)-(D represents a carbamate-based protecting group)" is the diamine component used in the synthesis of the polymer from the viewpoint of increasing the voltage retention rate of the liquid crystal display element. 1 mol% or more is preferable with respect to 1 mol, and 2 mol% or more is more preferable.
  • the usage ratio is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 35 mol% or less.
  • the content ratio of the polymer (A) to the polymer (B) is 10/90 in terms of the mass ratio of [polymer (A)] / [polymer (B)]. It may be ⁇ 90/10, 20/80 to 90/10, or 20/80 to 80/20.
  • the polymer (A) or (B) is produced by reacting the diamine component and the tetracarboxylic acid derivative component in a solvent (condensation).
  • a part of the polymer (A) or (B) contains an amic acid structure, for example, a polymer having an amic acid structure (polyamic acid) by reacting a tetracarboxylic acid dianhydride component with a diamine component. Is obtained.
  • the solvent is not particularly limited as long as it dissolves the produced polymer.
  • the above solvent examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl.
  • -2-Imidazolidinone can be mentioned.
  • the polymer has high solvent solubility, it is represented by methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3].
  • a solvent can be used.
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • D-3 represents an alkyl group having 1 to 4 carbon atoms.
  • the reaction can be carried out at any concentration, preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial reaction can be carried out at a high concentration and then the solvent can be added.
  • the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid derivative component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weights of the polymer (A) and the polymer (B) produced.
  • the polymer containing an amic acid ester structure is, for example, [I] a method of reacting the polyamic acid obtained by the above method with an esterifying agent, [II] a tetracarboxylic acid diester and a diamine. It can be obtained by a known method such as a method of reacting, a method of reacting a tetracarboxylic acid diester dihalide with a diamine, and the like.
  • the imidized product in the polymer (A) or (B) contained in the liquid crystal alignment agent of the present invention is obtained by ring-closing the polymer obtained above.
  • the ring closure rate (also referred to as imidization rate) of the functional group of the amic acid group or its derivative does not necessarily have to be 100%, and the imidized product can be arbitrarily adjusted according to the intended use and purpose.
  • the imidization ratio of the polymer (B) is preferably 20 to 100%, preferably 50 to 95%, and even more preferably 60 to 90%.
  • Examples of the method for obtaining an imidized product include thermal imidization in which the polymer solution obtained in the above reaction is heated as it is, or catalytic imidization in which a catalyst is added to the polymer solution.
  • the temperature for thermal imidization in the solution is preferably 100 to 400 ° C, more preferably 120 to 250 ° C, and it is preferable to remove the water produced by the imidization reaction from the system.
  • the catalyst imidization is carried out by adding a basic catalyst and an acid anhydride to a solution of the polymer obtained by the reaction, and stirring the mixture at preferably ⁇ 20 to 250 ° C., more preferably 0 to 180 ° C. be able to.
  • the amount of the basic catalyst is preferably 0.5 to 30 mol times, more preferably 2 to 20 mol times, and the amount of acid anhydride is preferably 1 to 50 mol times, more than the amic acid group. It is preferably 3 to 30 mol times.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, and tributylamine trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity for advancing the reaction.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like, and among them, acetic anhydride is preferable because it facilitates purification after the reaction is completed.
  • the imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, the reaction temperature, and the reaction time.
  • the reaction solution may be added to a solvent for precipitation.
  • the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like.
  • the polymer put into a solvent and precipitated can be collected by filtration and then dried at room temperature or by heating under normal pressure or reduced pressure.
  • impurities in the polymer can be reduced.
  • the solvent at this time include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more kinds of solvents selected from these, because the purification efficiency is further improved.
  • the polymer (A) or (B) used in the present invention preferably has a solution viscosity of, for example, 10 to 1000 mPa ⁇ s when it is used as a solution having a concentration of 10 to 15% by mass from the viewpoint of workability.
  • the solution viscosity (mPa ⁇ s) of the polymer is a polymer having a concentration of 10 to 15% by mass prepared by using a good solvent of the polymer (for example, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, etc.).
  • the values of the solution were measured at 25 ° C. using an E-type rotational viscometer.
  • the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polymer (A) or (B) is preferably 1,000 to 500,000, more preferably 2,. It is 000 to 500,000.
  • the molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. Within such a molecular weight range, good orientation and stability of the liquid crystal display element can be ensured.
  • an end-sealed polymer is prepared by using an appropriate end-sealing agent together with the tetracarboxylic acid derivative component and the diamine component as described above. It may be synthesized.
  • the end-sealed polymer has the effects of improving the film hardness of the liquid crystal alignment film obtained by the coating film and improving the adhesion characteristics between the sealant and the liquid crystal alignment film.
  • Examples of the terminal of the polymer (A) and the polymer (B) in the present invention include an amino group, a carboxy group, an acid anhydride group or a derivative thereof.
  • Amino groups, carboxy groups, acid anhydride groups or derivatives thereof can be obtained by a usual condensation reaction or by sealing the ends with the following terminal encapsulants, wherein the derivatives are, for example, , Can also be obtained in the same manner using the following terminal encapsulants.
  • terminal encapsulant examples include acetic anhydride, maleic anhydride, nagic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-( (3-Trimethoxysilyl) propyl) -3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynylphthalic anhydride, etc.
  • Dicarbonate diester compounds such as di-tert-butyl dicarbonate, diallyl dicarbonate
  • Chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride, nicotinic acid chloride; aniline, 2-aminophenol, 3-aminophenol, 4-Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, Monoamine compounds such as n-heptylamine and n-octylamine; monoisocyanate compounds such as ethyl isocyanate, phenylisocyanate and naphthylisocyanate can be mentioned.
  • the ratio of the terminal encapsulant to be used is preferably 0.01 to 20 mol parts, more preferably 0.01 to 10 mol parts, based on 100 mol parts of the total diamine component used.
  • the liquid crystal alignment agent of the present invention contains a polymer (A) and, if necessary, a polymer (B).
  • the liquid crystal alignment agent of the present invention may contain other polymers in addition to the polymer (A) and the polymer (B).
  • examples of other types of polymers include polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, polyacetal, polystyrene or its derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates and the like.
  • the liquid crystal alignment agent is used for producing a liquid crystal alignment film, and takes the form of a coating liquid from the viewpoint of forming a uniform thin film.
  • the liquid crystal alignment agent of the present invention is also preferably a coating liquid containing the above-mentioned polymer component and an organic solvent.
  • the concentration of the polymer in the liquid crystal alignment agent can be appropriately changed by setting the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, 1% by mass or more is preferable, and from the viewpoint of storage stability of the solution, 10% by mass or less is preferable. A particularly preferable concentration of the polymer is 2 to 8% by mass.
  • the content of the polymer (A) in the liquid crystal alignment agent can be appropriately changed depending on the application method of the liquid crystal alignment agent and the film thickness of the target liquid crystal alignment film, but it may be 2 to 10% by mass. It is preferable, and particularly preferably 3 to 7% by mass.
  • the organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as the polymer component is uniformly dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethyllactamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, and ⁇ -butyrolactone.
  • ⁇ -Valerolactone 1,3-dimethyl-2-imidazolidinone, methylethylketone, cyclohexanone, cyclopentanone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropaneamide, 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, N-cyclohexyl-2-pyrrolidone (collectively "good solvent”) Also known as).
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide or ⁇ -butyrolactone are preferable.
  • 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 based on the total amount of the solvent contained in the liquid crystal alignment agent.
  • the organic solvent contained in the liquid crystal alignment agent is a mixture in which a solvent (also referred to as a poor solvent) for improving the coatability when applying the liquid crystal alignment agent and the surface smoothness of the coating film is used in combination with the above solvent.
  • a solvent also referred to as a poor solvent
  • the use of solvent is preferred. Specific examples of the poor solvent used in combination are described below, but the present invention is not limited thereto.
  • the content of the poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent.
  • the type and content of the poor solvent are appropriately selected according to the liquid crystal alignment agent coating device, coating conditions, coating environment, and the like.
  • diisopropyl ether diisobutyl ether, diisobutylcarbinol (2,6-dimethyl-4-heptanol)
  • ethylene glycol dimethyl ether ethylene glycol diethyl ether
  • ethylene glycol dibutyl ether 1,2-butoxyetan
  • diethylene glycol dimethyl ether diethylene glycol diethyl ether.
  • diisobutylcarbinol diisobutylcarbinol, 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.
  • Preferred combinations of good and poor solvents include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and ⁇ -butyrolactone and ethylene glycol monobutyl ether, and N-methyl-2-.
  • Examples thereof include diisobutylketone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone and diisobutylketone, N-ethyl-2-pyrrolidone and N, N-dimethyllactamide and diisobutylketone.
  • the liquid crystal alignment agent of the present invention may additionally contain a component other than the polymer component and the organic solvent (hereinafter, also referred to as an additive component).
  • additive components include an adhesion aid for enhancing the adhesion between the liquid crystal alignment film and the substrate and the adhesion between the liquid crystal alignment film and the sealing agent, and a compound for increasing the strength of the liquid crystal alignment film (hereinafter,).
  • Also referred to as a crosslinkable compound a dielectric for adjusting the dielectric constant and electrical resistance of the liquid crystal alignment film, a conductive substance, and the like can be mentioned.
  • an oxylanyl group an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, and a meldrum.
  • R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or "* -CH 2- OH". * Indicates a bond.
  • R is 1 carbon atom. Represents an alkyl group of up to 6; an alkenyl group of 2 to 6 carbon atoms, or an alkynyl group of 2 to 6 carbon atoms.
  • Z represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms. , Or an alkynyl group having 2 to 6 carbon atoms.
  • A represents a (m + n) valent organic group having an aromatic ring.
  • R' represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • M represents 1 Represents an integer of ⁇ 6, and n represents an integer of 0 to 4.
  • the compound having an oxylanyl group examples include the compound described in paragraph [0037] of JP-A-10-338880 and the compound having a triazine ring as a skeleton described in International Publication No. 2017/170483. Examples thereof include compounds having more than one oxylanyl group.
  • the compound having an oxetanyl group include the compounds having two or more oxetanyl groups described in paragraphs [0170] to [0175] of International Publication No. 2011/132751.
  • the compound having a protected isocyanate group include the compounds having two or more protected isocyanate groups described in paragraphs [0046] to [0047] of Japanese Patent Application Laid-Open No. 2014-224978, International Publication No. 2015/141598.
  • the compounds having three or more protected isocyanate groups described in paragraphs [0119] to [0120] of the above are mentioned, and the compounds represented by the following formulas (bi-1) to (bi-3) may be used. ..
  • Specific examples of the compound having a protected isothiocyanate group include the compounds having two or more protected isothiocyanate groups described in Japanese Patent Application Laid-Open No. 2016-2000798.
  • Specific examples of the compound having a group containing an oxazoline ring structure include compounds containing two or more oxazoline structures described in paragraph [0115] of Japanese Patent Application Laid-Open No. 2007-286597.
  • Specific examples of the compound having a group containing a Meldrum's acid structure include the compound having two or more Meldrum's acid structures described in International Publication No. 2012/091088.
  • Specific examples of the compound having a cyclocarbonate group include the compound described in International Publication No. 2011/155577.
  • R 2 an alkyl group having 1 to 3 carbon atoms R 3 group represented by the above formula (d), a methyl group, an ethyl group, a propyl group.
  • the compound having a group represented by the above formula (d) include the above formula (d) described in International Publication No. 2015/072554 and paragraph [0058] of Japanese Patent Application Laid-Open No. 2016-118753.
  • Examples thereof include compounds having two or more groups represented by (2) and compounds described in Japanese Patent Application Laid-Open No. 2016-209458, which are compounds represented by the following formulas (hd-1) to (hd-8). May be good.
  • the compound having a group represented by the above (d1) include the compounds described in International Publication No. 2019/142927, and more preferably the following formulas (hd1-1) to (hd1-4). It may be a compound represented.
  • Examples of the (m + n) -valent organic group having an aromatic ring in A of the above formula (e) include an (m + n) -valent aromatic hydrocarbon group having 6 to 30 carbon atoms and an aromatic hydrocarbon group having 6 to 30 carbon atoms. Examples thereof include (m + n) valent organic groups bonded directly or via a linking group, and (m + n) valent groups having an aromatic heterocycle.
  • Examples of the aromatic hydrocarbon include benzene and naphthalene.
  • Examples of the aromatic heterocycle include the aromatic heterocycle exemplified in the above nitrogen atom-containing structure.
  • 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, a divalent or trivalent cyclohexane ring, and the like. Any hydrogen atom of the alkylene group may be substituted with an organic group such as a fluorine atom or a trifluoromethyl group.
  • Examples of the alkyl group having 1 to 5 carbon atoms in R'of the above formula (e) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Examples include the n-pentyl group. Specific examples include the compounds described in International Publication No. 2010/074269 and the compounds represented by the following formulas (e-1) to (e-10).
  • the above compound is an example of a crosslinkable compound, and is not limited thereto.
  • components other than the above disclosed in International Publication No. 2015/060357 on pages 53 [0105] to 55 [0116] can be mentioned.
  • two or more kinds of crosslinkable compounds may be combined.
  • 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 with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent, and the crosslinking reaction proceeds. In addition, from the viewpoint of exhibiting good resistance to AC afterimages, it is more preferably 1 to 15 parts by mass.
  • adhesion aid examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N.
  • silane coupling agent when used, it should be 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent from the viewpoint of exhibiting good resistance to AC afterimage. It is preferable, more preferably 0.1 to 20 parts by mass.
  • the liquid crystal alignment film of the present invention is obtained from the above liquid crystal alignment agent.
  • the liquid crystal alignment film of the present invention can be used for a horizontally oriented type or a vertically oriented type (VA type) liquid crystal alignment film, and among them, a liquid crystal alignment suitable for a horizontally oriented type liquid crystal display element such as an IPS method or an FFS method. It is a membrane.
  • the liquid crystal display element of the present invention includes the liquid crystal alignment film.
  • the liquid crystal display element of the present invention can be manufactured, for example, by a method including the following steps (1) to (4) or steps (1) to (2) and (4).
  • the liquid crystal alignment agent of the present invention is applied to one surface of a substrate provided with a patterned transparent conductive film by an appropriate coating method such as a roll coater method, a spin coating method, a printing method, or an inkjet method.
  • the substrate is not particularly limited as long as it is a highly transparent substrate, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used together with the glass substrate and the silicon nitride substrate.
  • a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used together with the glass substrate and the silicon nitride substrate.
  • an opaque object such as a silicon wafer can be used, and in this case, a material that reflects light such as aluminum can also be used for the electrode.
  • a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb tooth shape, and a facing substrate not provided with an electrode Is used.
  • Examples of the method of applying the liquid crystal alignment agent to the substrate to form a film include screen printing, offset printing, flexographic printing, inkjet method, spray method and the like. Among them, the coating and film forming methods by the inkjet method can be preferably used.
  • Step (2) is a step of firing the liquid crystal alignment agent applied on the substrate to form a film.
  • the solvent is evaporated or the polyamic acid or polyamic acid ester is thermally imidized by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven. Can be done.
  • the drying and firing steps after applying the liquid crystal alignment agent of the present invention can be performed at any temperature and time, and may be performed a plurality of times.
  • the drying temperature can be, for example, 40 to 180 ° C. From the viewpoint of shortening the process, it may be carried out at 40 to 150 ° C.
  • the drying time is not particularly limited, and examples thereof include 1 to 10 minutes or 1 to 5 minutes.
  • a step of firing in a temperature range of, for example, 150 to 300 ° C. or 150 to 250 ° C. may be added after the above drying step.
  • the firing time is not particularly limited, and examples thereof include a firing time of 5 to 40 minutes or 5 to 30 minutes. If the film-like material after firing is too thin, the reliability of the liquid crystal display element may decrease, so 5 to 300 nm is preferable, and 10 to 200 nm is more preferable.
  • the step (3) is, in some cases, a step of orienting the film obtained in the step (2). That is, in a horizontally oriented liquid crystal display element such as an IPS system or an FFS system, an alignment ability imparting process is performed on the coating film. On the other hand, in a vertically oriented liquid crystal display element such as a VA method or a PSA mode, the formed coating film can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to an alignment ability imparting treatment. Examples of the liquid crystal alignment film alignment treatment method include a rubbing treatment method and a photoalignment treatment method.
  • the surface of the film-like material is irradiated with radiation deflected in a certain direction, and in some cases, heat treatment is performed at a temperature of 150 to 250 ° C. to achieve liquid crystal orientation (liquid crystal alignment).
  • heat treatment is performed at a temperature of 150 to 250 ° C. to achieve liquid crystal orientation (liquid crystal alignment).
  • the radiation ultraviolet rays having a wavelength of 100 to 800 nm or visible light can be used. Among them, ultraviolet rays having a wavelength of preferably 100 to 400 nm, more preferably 200 to 400 nm.
  • the irradiation amount of the above radiation is preferably 1 to 10,000 mJ / cm 2. Of these, 100 to 5,000 mJ / cm 2 is preferable.
  • the substrate having the film-like substance may be irradiated while being heated at 50 to 250 ° C.
  • the liquid crystal alignment film thus produced can stably orient liquid crystal molecules in a certain direction.
  • the liquid crystal alignment film irradiated with polarized radiation can be contact-treated with a solvent, or the liquid crystal alignment film irradiated with radiation can be heat-treated.
  • the solvent used for the contact treatment is not particularly limited as long as it is a solvent that dissolves the decomposition product generated from the film-like substance 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, 3-.
  • Examples thereof include methyl methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate and the like.
  • water, 2-propanol, 1-methoxy-2-propanol or ethyl lactate is preferable, and water, 1-methoxy-2-propanol or ethyl lactate is more preferable from the viewpoint of versatility and solvent safety.
  • the solvent may be used alone or in combination of two or more.
  • the temperature of the heat treatment for the coating film irradiated with the above radiation is more preferably 50 to 300 ° C, further preferably 120 to 250 ° C.
  • the heat treatment time is preferably 1 to 30 minutes, respectively.
  • Step (4) Step of manufacturing a liquid crystal cell> Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and the liquid crystal is arranged between the two substrates arranged opposite to each other. Specifically, the following two methods can be mentioned. In the first method, first, two substrates are arranged facing each other through a gap (cell gap) so that the liquid crystal alignment films face each other. Next, the peripheral portions of the two substrates are bonded together using a sealant, and the liquid crystal composition is injected and filled into the surface of the substrate and the cell gap partitioned by the sealant to contact the film surface, and then the injection holes are sealed. Stop.
  • the second method is a method called an ODF (One Drop Fill) method.
  • ODF One Drop Fill
  • an ultraviolet light-curable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and the liquid crystal composition is further applied to a predetermined number of places on the liquid crystal alignment film surface. Is dropped. Then, the other substrate is bonded so that the liquid crystal alignment film faces each other, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface. Next, the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant.
  • the two substrates are arranged so as to face each other so that the rubbing directions of the coating films are opposite to each other at a predetermined angle, for example, orthogonal or antiparallel.
  • the sealing agent for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
  • the liquid crystal include a nematic liquid crystal and a smectic liquid crystal, and among them, the nematic liquid crystal is preferable.
  • a liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell.
  • a polarizing plate attached to the outer surface of the liquid crystal cell a polarizing plate called an "H film" in which polyvinyl alcohol is stretched and oriented to absorb iodine is sandwiched between a cellulose acetate protective film or the H film itself.
  • a polarizing plate made of the above can be mentioned.
  • the liquid crystal display element of the present invention can be effectively applied to various devices, for example, a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, a smartphone, and the like. It can be used for various display devices such as various monitors, liquid crystal televisions, and information displays.
  • the polymer composition contained in the liquid crystal alignment agent is 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 transmission scattering type liquid crystal photochromic element. Alternatively, it can also be used for applications other than these, such as a protective film for a color filter, a gate insulating film for a flexible display, and a substrate material.
  • WA-1 A compound represented by the following formula (WA-1) (Other diamines) A1 to A2: Compounds represented by the following formulas (A1) to (A2), respectively.
  • the viscosity of the solution was measured at a temperature of 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). did.
  • a liquid crystal cell having a configuration of a Fringe Field Switching (FFS) mode liquid crystal display element is manufactured.
  • a substrate with electrodes was prepared.
  • the substrate is a glass substrate having a size of 30 mm ⁇ 35 mm and a thickness of 0.7 mm.
  • a SiN (silicon nitride) film formed by a CVD (chemical vapor deposition) method is formed as a second layer on the counter electrode of the first layer.
  • the film thickness of the SiN film of the second layer is 500 nm, and it functions as an interlayer insulating film.
  • a comb-shaped pixel electrode formed by patterning an ITO film as a third layer is arranged to form two pixels, a first pixel and a second pixel. ing.
  • the size of each pixel is 10 mm in length and about 5 mm in width.
  • the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.
  • the pixel electrode of the third layer has a comb-teeth shape in which a plurality of electrode elements having a width of 3 ⁇ m in which the central portion is bent at an internal angle of 160 ° are arranged in parallel with an interval of 6 ⁇ m.
  • the pixel has a first region and a second region with a line connecting the bent portions of the plurality of electrode elements as a boundary.
  • the forming directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, the electrode elements of the pixel electrodes are formed so as to form an angle (clockwise) of + 10 ° in the first region of the pixel, and the pixel is formed in the second region of the pixel.
  • the electrode elements of the electrodes are formed so as to form an angle of ⁇ 10 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (inplane switching) of the liquid crystal in the substrate surface induced by the voltage application between the pixel electrode and the counter electrode are mutual. It is configured to be in the opposite direction.
  • This polyimide film is rubbed with a rayon cloth (roller diameter: 120 mm, roller rotation speed: 500 rpm, moving speed: 30 mm / sec, pushing length: 0.3 mm, rubbing direction: tilted 10 ° with respect to the third layer IZO comb tooth electrode. After that, it was washed by irradiating it with ultrasonic waves for 1 minute in pure water, and water droplets were removed by air blowing. Then, it was dried at 80 degreeC for 15 minutes to obtain a substrate with a liquid crystal alignment film. A set of these two substrates with a liquid crystal alignment film is printed with a sealant with the liquid crystal injection port left on the substrate, and the liquid crystal alignment film surface faces the other substrate and the rubbing direction is antiparallel.
  • the liquid crystal cell produced above is placed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, and the pixel electrode and the counter electrode are short-circuited to have the same potential.
  • the LED backlight was irradiated from below, and the angle of the liquid crystal cell was adjusted so that the brightness of the transmitted light of the LED backlight measured on the two polarizing plates was minimized.
  • the VT curve voltage-transmittance curve
  • the afterimage evaluation according to the above-mentioned method was performed under the temperature condition that the temperature of the liquid crystal cell was 40 ° C.
  • the liquid crystal alignment film obtained from the liquid crystal alignment agent using diamine WA-1 exhibits a relaxation rate of accumulated charge higher than that of the liquid crystal alignment film obtained from the liquid crystal alignment agent using diamine A1. I understood. Specifically, it is shown in the comparison between Example 1 and Comparative Example 1 shown in Table 1.
  • the liquid crystal display element using the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention can be suitably used for the liquid crystal display element. These elements are also useful in liquid crystal displays for display purposes, as well as in dimming windows and optical shutters that control the transmission and blocking of light.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Liquid Crystal (AREA)

Abstract

L'invention fournit un film d'alignement de cristaux liquides qui peut faire disparaître rapidement une rémanence à l'extinction, et qui peut présenter une qualité d'affichage élevée dans un dispositif d'affichage à cristaux liquides haute définition.　En outre, l'invention concerne un agent d'alignement de cristaux liquides qui comprend au moins une sorte de polymère (A) choisie dans un groupe constitué : d'un précurseur de polyimide qui est obtenu à l'aide d'un composant diamine qui contient un diamine représenté par la formule (1a) et un diamine représenté par la formule (1b), et d'un composant de dérivé d'acide tétracarboxylique contenant un dianhydride d'acide tétracarboxylique aromatique ou un dérivé de celui-ci ; et d'un polyimide consistant en un produit imidisé de ce précurseur de polyimide. Cet agent d'alignement de cristaux liquides est caractéristique en ce que ledit composant diamine est contenu à raison de 5 à 95% en moles pour 1 mole de composant diamine mettant en œuvre ledit diamine représenté par la formule (1a). [Formule 1] (Un atome d'hydrogène arbitraire d'un cycle benzène peut être substitué par un substituant monovalent.) [Formule 2] (Y est tel que défini dans la description.)
PCT/JP2021/025836 2020-07-17 2021-07-08 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides WO2022014470A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2022536312A JP7311047B2 (ja) 2020-07-17 2021-07-08 液晶配向剤、液晶配向膜、及び液晶表示素子
CN202180063541.7A CN116234856B (zh) 2020-07-17 2021-07-08 液晶取向剂、液晶取向膜以及液晶显示元件
KR1020237004491A KR20230038513A (ko) 2020-07-17 2021-07-08 액정 배향제, 액정 배향막, 및 액정 표시 소자

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020123004 2020-07-17
JP2020-123004 2020-07-17

Publications (1)

Publication Number Publication Date
WO2022014470A1 true WO2022014470A1 (fr) 2022-01-20

Family

ID=79555438

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/025836 WO2022014470A1 (fr) 2020-07-17 2021-07-08 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides

Country Status (5)

Country Link
JP (1) JP7311047B2 (fr)
KR (1) KR20230038513A (fr)
CN (1) CN116234856B (fr)
TW (1) TW202214829A (fr)
WO (1) WO2022014470A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017217413A1 (fr) * 2016-06-14 2017-12-21 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
WO2018051923A1 (fr) * 2016-09-13 2018-03-22 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2018051956A1 (fr) * 2016-09-13 2018-03-22 日産化学工業株式会社 Agent d'alignement de cristaux liquides, pellicule d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3893659B2 (ja) 1996-03-05 2007-03-14 日産化学工業株式会社 液晶配向処理方法
JP4175826B2 (ja) 2002-04-16 2008-11-05 シャープ株式会社 液晶表示装置
JP5879693B2 (ja) * 2011-02-22 2016-03-08 Jsr株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
KR20190049909A (ko) 2011-10-27 2019-05-09 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
JP6597640B2 (ja) * 2014-12-22 2019-10-30 日産化学株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
KR20230097217A (ko) 2015-03-24 2023-06-30 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
WO2018155674A1 (fr) * 2017-02-27 2018-08-30 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage de cristaux liquides
JP7093059B2 (ja) * 2017-07-14 2022-06-29 日産化学株式会社 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017217413A1 (fr) * 2016-06-14 2017-12-21 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
WO2018051923A1 (fr) * 2016-09-13 2018-03-22 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2018051956A1 (fr) * 2016-09-13 2018-03-22 日産化学工業株式会社 Agent d'alignement de cristaux liquides, pellicule d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides

Also Published As

Publication number Publication date
KR20230038513A (ko) 2023-03-20
JPWO2022014470A1 (fr) 2022-01-20
CN116234856B (zh) 2024-04-09
JP7311047B2 (ja) 2023-07-19
CN116234856A (zh) 2023-06-06
TW202214829A (zh) 2022-04-16

Similar Documents

Publication Publication Date Title
JP7243782B2 (ja) 新規なジアミンから得られる重合体を含有する液晶配向剤
JP7343059B2 (ja) 液晶配向剤、液晶配向膜及び液晶表示素子
WO2022176680A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2023286733A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, procédé de production d'un élément d'affichage à cristaux liquides et élément d'affichage à cristaux liquides
WO2022234820A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
JP7311047B2 (ja) 液晶配向剤、液晶配向膜、及び液晶表示素子
KR20230002449A (ko) 액정 배향제, 액정 배향막, 및 액정 표시 소자
JP7302744B2 (ja) 液晶配向剤、液晶配向膜、及び液晶表示素子
JP7318826B2 (ja) 液晶配向剤、液晶配向膜、及び液晶表示素子
WO2022181311A1 (fr) Agent d'alignment de cristaux liquides, film d'alignment de cristaux liquides et élément d'affichage à cristaux liquides
WO2022085674A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2022107640A1 (fr) Composition polymère, agent d'alignement de cristaux liquides, film de résine, film d'alignement de cristaux liquides, procédé de production d'élément d'affichage à cristaux liquides et élément d'affichage à cristaux liquides
WO2022168722A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, procédé de production d'un élément d'affichage à cristaux liquides et élément d'affichage à cristaux liquides
WO2024029576A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2023210532A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2022190896A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
JP2024022213A (ja) 液晶配向剤、液晶配向膜及び液晶表示素子
WO2021246431A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
TW202321427A (zh) 液晶配向劑、液晶配向膜、液晶顯示元件之製造方法及液晶顯示元件
WO2021206003A1 (fr) Agent d'alignement de cristaux liquides, couche d'alignement de cristaux liquides et élément d'écran à cristaux liquides
TW202146633A (zh) 新穎二胺、聚合物、液晶配向劑、液晶配向膜及使用該膜之液晶顯示元件

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21842590

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022536312

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20237004491

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21842590

Country of ref document: EP

Kind code of ref document: A1