CN112602013A - Liquid crystal aligning agent, method for producing same, liquid crystal alignment film, and liquid crystal display element - Google Patents
Liquid crystal aligning agent, method for producing same, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
- Publication number
- CN112602013A CN112602013A CN201980055005.5A CN201980055005A CN112602013A CN 112602013 A CN112602013 A CN 112602013A CN 201980055005 A CN201980055005 A CN 201980055005A CN 112602013 A CN112602013 A CN 112602013A
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- China
- Prior art keywords
- liquid crystal
- group
- aligning agent
- crystal aligning
- diamine
- Prior art date
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Classifications
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- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
-
- 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
- C08G73/14—Polyamide-imides
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- 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
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- 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
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
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Abstract
Providing: a liquid crystal aligning agent which can obtain good afterimage characteristics even in a liquid crystal display element of an IPS drive system or an FFS drive system, a method for producing the same, a liquid crystal alignment film obtained therefrom, and a liquid crystal display element provided with the same. A liquid crystal aligning agent characterized by containing a polyimide which is an imide compound of a polyimide precursor obtained by a polycondensation reaction of a tetracarboxylic acid component containing a tetracarboxylic dianhydride represented by the following formula (1) or a derivative thereof and a diamine component containing a 1 st diamine represented by the following formula (3) and a 2 nd diamine represented by the following formula (4). (X)1Is represented by the formula (X1-1) or (X1-2). R3～R12Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or the like, R3～R6At least one of them is other than a hydrogen atom. ) (A)1Is C2-10 alkylene, a is an integer of 0-4, A2A plurality of A's being present as halogen atoms or the like2In the case of (A)2Optionally the same or different. b and c are 1 or 2, and d is 0 or 1. )
Description
Technical Field
The present invention relates to a liquid crystal aligning agent, a method for producing the same, a liquid crystal alignment film obtained therefrom, and a liquid crystal display element provided with the obtained liquid crystal alignment film.
Background
Liquid crystal display elements used in liquid crystal televisions, liquid crystal displays, and the like are generally provided with a liquid crystal alignment film for controlling the alignment state of liquid crystal in the element. The most popular liquid crystal alignment film in industry at present is produced as follows: the surface of a film formed on an electrode substrate and made of polyamic acid and/or polyimide obtained by imidizing the polyamic acid is subjected to a rubbing treatment, so-called brushing treatment, with a cloth made of cotton, nylon, polyester, or the like in one direction.
The brushing treatment is a simple and industrially useful method with excellent productivity. However, as the liquid crystal display element has been improved in performance, refined in precision, and increased in size, various problems have become apparent, such as scratches on the surface of the alignment film, dust generation, mechanical force, and influence of static electricity, and further, in-plane unevenness of the alignment treatment. As a method for replacing the brushing treatment, the following photo-alignment method is known: the liquid crystal alignment ability is imparted by irradiating polarized ultraviolet rays. In the liquid crystal alignment treatment by the photo-alignment method, there are proposed: a treatment using a photoisomerization reaction, a treatment using a photocrosslinking reaction, a treatment using a photodissociation reaction, and the like.
Patent document 1 proposes the following: a polyimide film having an alicyclic structure such as a cyclobutane ring in its main chain is used in the photo-alignment method. The photo-alignment method is expected to improve the contrast and viewing angle characteristics of liquid crystal display elements of IPS drive system and FFS drive system (boundary electric field switching) as compared with the rubbing treatment method, and therefore has attracted attention as a promising liquid crystal alignment treatment method.
In a liquid crystal alignment film used in a liquid crystal display device of the IPS driving method or the FFS driving method, an alignment regulating force for suppressing afterimages generated by long-term driving is required in addition to basic characteristics such as excellent liquid crystal alignment properties and electric characteristics, but a liquid crystal alignment film obtained by a photo alignment method has a problem that the alignment regulating force is weak as compared with a liquid crystal alignment film obtained by a rubbing treatment. In addition, in the liquid crystal alignment film obtained by the photo-decomposition reaction, a low molecular weight component generated by photo-decomposition causes a reduction in alignment regulating force, and a method of removing the low molecular weight component by a heating treatment or a cleaning treatment has been proposed (patent document 2).
However, in the production of the liquid crystal display element, as described above, in order to remove the low molecular weight component, a heating treatment step and a cleaning treatment step need to be added, which leads to an increase in the production steps of the liquid crystal display element. In contrast, the following methods for producing a liquid crystal alignment film are proposed: even with a small number of steps, afterimage due to long-term driving can be suppressed, and there is no problem due to low molecular weight components (patent document 3).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 9-297313
Patent document 2: japanese patent laid-open publication No. 2011-107266
Patent document 3: WO2018/117239
Disclosure of Invention
Problems to be solved by the invention
In the case of performing the alignment treatment by the photo-alignment method, the amount of light irradiation is a factor that affects energy cost and production speed, and therefore, it is preferable that the alignment treatment can be performed with a small amount of irradiation. However, even in the case of a liquid crystal aligning agent which can obtain good image sticking characteristics, there is a problem that the image sticking characteristics are insufficient when the light irradiation amount is reduced.
Accordingly, an object of the present invention is to provide: a liquid crystal aligning agent which can obtain good afterimage characteristics even when the light irradiation amount in the alignment treatment by the photo-alignment method is reduced and can obtain good and stable liquid crystal alignment capability, a manufacturing method thereof, a liquid crystal alignment film obtained by the liquid crystal aligning agent, and a liquid crystal display element provided with the liquid crystal alignment film.
Means for solving the problems
The present inventors have made extensive studies to achieve the above object, and as a result, have found that: the above object can be achieved by the present invention having the following gist.
A liquid crystal aligning agent characterized by containing a polyimide which is an imide compound of a polyimide precursor obtained by a polycondensation reaction of a tetracarboxylic acid component containing a tetracarboxylic dianhydride represented by the following formula (1) or a derivative thereof and a diamine component containing a 1 st diamine represented by the following formula (3) and a 2 nd diamine represented by the following formula (4).
Wherein, in the formula (1), X1Is a structure represented by the following formula (X1-1) or (X1-2).
Wherein, in the formulas (X1-1) and (X1-2), R3～R12Each 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 1-valent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, R3～R6At least one of them is a group other than a hydrogen atom in the above definition.
Wherein, in the formula (3), A1Is an alkylene group having 2 to 10 carbon atoms or-CH which is contained in the alkylene group2-a group in which at least one of the groups is replaced with-O-or-S-under discontinuous conditions. A. the2A halogen atom, a hydroxyl group, an amino group, a mercapto group, a nitro group, a phosphoric acid group, or a 1-valent organic group having 1 to 20 carbon atoms, a is an integer of 0 to 4, and a plurality of A's are present2In the case of (A)2Optionally the same or different. b and c are each independently an integer of 1 or 2, and d is an integer of 0 or 1.
ADVANTAGEOUS EFFECTS OF INVENTION
The liquid crystal aligning agent of the present invention can greatly reduce the light irradiation amount, and can obtain a liquid crystal alignment film with good afterimage characteristics. Further, the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention has a high yield in the production of liquid crystal panels, and can reduce the afterimage caused by ac drive generated in the liquid crystal display elements of the IPS drive system and the FFS drive system, and can obtain the liquid crystal display elements of the IPS drive system and the FFS drive system having excellent afterimage characteristics.
Detailed Description
The liquid crystal aligning agent of the present invention is characterized by containing a polyimide (hereinafter, also referred to as a specific polymer) which is an imide compound of a polyimide precursor obtained by a polycondensation reaction of a tetracarboxylic acid component (hereinafter, also referred to as a tetracarboxylic acid component) containing a tetracarboxylic dianhydride or a derivative thereof having a specific structure and a diamine component (hereinafter, also referred to as a diamine component) containing 2 kinds of diamines having a specific structure.
< specific Polymer >
The specific polymer used in the present invention is polyimide which is an imide compound of a polyimide precursor having a specific structure. The polyimide precursor is not particularly limited as long as it is a polyimide precursor which forms an imide ring by chemical imidization with heat or a catalyst. From the viewpoint of ease of imidization by heating or chemical imidization, polyamic acid or polyamic acid ester is preferable as the polyimide precursor.
The imidization ratio of the polyimide is not particularly limited, but is preferably 10 to 100%, more preferably 50 to 100%, and further preferably 50 to 80%.
Hereinafter, each component to be a raw material for obtaining the above-mentioned specific polymer will be described in detail.
< tetracarboxylic acid derivative component >
As the tetracarboxylic acid component used in the polymerization of the specific polymer used in the liquid crystal aligning agent of the present invention, not only tetracarboxylic dianhydride but also tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid dialkyl ester dihalide as a derivative thereof can be used.
The tetracarboxylic dianhydride or the derivative thereof is preferably represented by the following formula (1).
Wherein, X1Is a structure represented by the following formula (X1-1) or (X1-2).
Wherein R is3～R12Each 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 1-valent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group. In addition, R is3～R6At least one of them is a group other than a hydrogen atom in the above definition.
From the viewpoint of liquid crystal alignment, X1The above formula (X1-1) is preferable, at least 1 type selected from the following formulae (X1-1-1) to (X1-1-5) is more preferable, and the following formula (X1-1-1) is particularly preferable. The tetracarboxylic dianhydride represented by the formula (1) or its derivative may be used in combination of 2 or more.
The ratio of the tetracarboxylic dianhydride represented by the above formula (1) or a derivative thereof to be used is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 80 mol% or more, based on 1 mol of the total tetracarboxylic acid component used in the specific polymer.
In addition, in the case where the tetracarboxylic acid dianhydride or the derivative thereof represented by the following formula (2) is contained in addition to the tetracarboxylic acid dianhydride or the derivative thereof represented by the above formula (1), the tetracarboxylic acid component used for polymerization of the specific polymer described in the present invention is more preferable from the viewpoint of suppression of a bright point generated by a decomposition product and liquid crystal alignment properties.
Wherein, X2Selected from the following formulae (X2-1) to (X2-6).
Wherein, X2The above-mentioned formula (X2-1), (X2-5) or (X2-6) is preferable, and the formula (X2-1) is particularly preferable. The tetracarboxylic dianhydride represented by the formula (2) and the derivative thereof may be used in combination of 2 or more.
The use ratio of the tetracarboxylic dianhydride represented by the formula (2) or the derivative thereof is preferably 1 to 30 mol%, more preferably 10 to 30%, and still more preferably 10 to 20% based on 1 mol of the total tetracarboxylic acid component used in the specific polymer.
The tetracarboxylic dianhydride component used for the polymerization of the specific polymer described in the present invention may contain tetracarboxylic dianhydrides other than the above formulas (1) and (2) and derivatives thereof.
< diamine >
The diamine component used for polymerization of the specific polymer used in the liquid crystal aligning agent of the present invention contains at least 1 st diamine selected from diamines represented by the following formula (3) and at least 12 nd diamine selected from diamines represented by the following formula (4).
Wherein A is1Is an alkylene group having 2 to 10 carbon atoms or-CH of the alkylene group2-a group in which at least one of the groups is replaced with-O-or-S-under discontinuous conditions. A. the2Each independently represents a halogen atom, a hydroxyl group, an amino group, a mercapto group, a nitro group, a phosphoric acid group, or a 1-valent organic group having 1 to 20 carbon atoms. a is an integer of 0 to 4, and a plurality of A exist2In the case of (A)2Optionally the same or different. b and c are each independently an integer of 1 or 2, and d is 0 or 1.
Preferred specific examples of the 1 st diamine shown in the formula (3) will be described below, but the present invention is not limited thereto. Among them, the formula (3-1), (3-3), (3-5) to (3-7) or (3-12) is particularly preferable. The 1 st diamine represented by the formula (3) may be used in combination of 2 or more.
The content of the 1 st diamine represented by the formula (3) is preferably 40 to 90 mol%, more preferably 40 to 75 mol%, based on the total diamine components used in the specific polymer.
Preferred specific examples of the 2 nd diamine shown in the formula (4) will be described below, but the present invention is not limited thereto.
The 2 nd diamine represented by the formula (4) may be used by mixing 2 or more kinds.
The content of the 2 nd diamine represented by the formula (4) is preferably 10 to 40 mol%, more preferably 20 to 40 mol%, based on the total diamine components used in the specific polymer.
The diamine component used for polymerization of the specific polymer contained in the liquid crystal aligning agent of the present invention may contain a diamine other than the 1 st diamine and the 2 nd diamine (hereinafter, also referred to as another diamine).
The following examples of other diamines include, but are not limited to, these.
M-phenylenediamine, 4- (2- (methylamino) ethyl) aniline, 3, 5-diaminobenzoic acid, 4 ' -diaminodiphenylmethane, 3 ' -diaminodiphenylmethane, 4 ' -diaminodiphenyl ether, 3 ' -diaminodiphenyl ether, 4 ' -diaminobenzophenone, 3 ' -diaminobenzophenone, 1, 4-diaminonaphthalene, 1, 5-diaminonaphthalene, 2, 6-diaminonaphthalene, 2, 7-diaminonaphthalene, 2 ' -bis [4- (4-aminophenoxy) phenyl ] propane, 2 ' -bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2 ' -bis (4-aminophenyl) propane, 1, 3-bis (4-aminophenylethyl) urea, and the like.
In addition, from the viewpoint of improving the solvent solubility of polyimide and making it easier for the specific polymer component to be unevenly distributed in the vicinity of the surface layer of the liquid crystal alignment film when a polymer other than the specific polymer is contained in the liquid crystal alignment agent of the present invention, it is preferable to use at least 1 of the diamines represented by the following formula (5) as the other diamine.
H2N-Y1-NH2 (5)
Wherein, in the formula (5), Y1Is a 2-valent organic group having a structure represented by the following formula (6).
Wherein in formula (6), D represents a protecting group which is removed by heating and is substituted with a hydrogen atom, and represents a bonding site to another structure. A preferred structure of D is tert-butoxycarbonyl.
Preferred specific examples of the diamine represented by the formula (5) are given below, but the diamine is not limited thereto. In the following structure, Boc represents a tert-butoxycarbonyl group.
The preferable content of the diamine represented by the formula (5) is 5 to 30 mol% of the diamine represented by the formula (5) with respect to the total diamine components used in the specific polymer.
< production methods of polyamic acid ester, polyamic acid, and polyimide >
Polyamic acid esters and polyamic acids which are polyimide precursors used in the present invention, and polyimides which are imide compounds of these polyimide precursors can be synthesized by known methods. An example thereof is a method described in WO 2013/157586.
The molecular weight of the specific polymer is not particularly limited as long as a good coating film can be formed, and is, for example, 2000 to 500000, more preferably 5000 to 300000, and further preferably 10000 to 100000 in terms of a weight average molecular weight (hereinafter also referred to as Mw). The number average molecular weight (hereinafter also referred to as Mn) is preferably 1000 to 250000, more preferably 2500 to 150000, and further preferably 5000 to 50000.
< liquid Crystal Aligning agent >
The liquid crystal aligning agent of the present invention is a composition containing the above-mentioned specific polymer and an organic solvent, and may contain 2 or more kinds of specific polymers having different structures. The liquid crystal aligning agent of the present invention may contain a polymer other than the specific polymer (hereinafter, also referred to as "2 nd polymer") and various additives.
When the liquid crystal aligning agent of the present invention contains the 2 nd polymer, the ratio of the 2 nd polymer to the whole polymer components is preferably 5% by mass or more, and examples thereof include 5 to 95% by mass.
Examples of the 2 nd polymer include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or a derivative thereof, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, and the like.
Particularly, polyamic acid (hereinafter, also referred to as "2 nd polyamic acid") obtained from a tetracarboxylic dianhydride component and a diamine component is preferable as the 2 nd polymer.
Examples of the tetracarboxylic dianhydride component for obtaining the 2 nd polyamic acid include compounds represented by the following formula (7).
Wherein, in the formula (7), A is a 4-valent organic group, preferably a 4-valent organic group having 4 to 30 carbon atoms.
Hereinafter, a preferred structure of a is shown, but the present invention is not limited to this.
Of the above structures, (A-1) and (A-2) are preferable from the viewpoint of further improving the photo-alignment properties, (A-4) is preferable from the viewpoint of improving the relaxation rate of charge accumulation, and (A-15) to (A-17) are preferable from the viewpoint of further improving the liquid crystal alignment properties and improving the relaxation rate of charge accumulation. The tetracarboxylic dianhydride component used to obtain the 2 nd polyamic acid may be one kind of tetracarboxylic dianhydride, or 2 or more kinds of tetracarboxylic dianhydrides may be used in combination.
Examples of the diamine component for obtaining the 2 nd polyamic acid include the diamine represented by the formula (3), the diamine represented by the formula (4), and other diamines exemplified above.
In addition, from the viewpoint of improving the relaxation rate of charge accumulation, it is preferable to use at least 1 kind of diamine represented by the following formula (8). The diamine component for obtaining the 2 nd polyamic acid may be 2 or more kinds of diamines in combination.
H2N-Y2-NH2 (8)
Wherein, in the formula (8), Y2Is an organic group having a nitrogen atom bonded to an aromatic group or a valence of 2 having a nitrogen-containing aromatic heterocyclic ring.
In the following, preferred Y is shown2The present invention is not limited to the above.
The molecular weight of the 2 nd polyamic acid is not particularly limited, and is, for example, 2000 to 500000, preferably 5000 to 300000, and more preferably 10000 to 100000 in terms of Mw. Further, the Mn content is 1000 to 250000, preferably 2500 to 150000, more preferably 5000 to 50000.
The content (concentration) of the polymer in the liquid crystal aligning agent of the present invention can be appropriately changed by setting the thickness of a coating film to be formed, and is preferably 1 mass% or more in terms of forming a uniform and defect-free coating film, and is preferably 10 mass% or less in terms of the storage stability of the solution. The concentration of the polymer is particularly preferably 2 to 8 mass%.
The organic solvent contained in the liquid crystal aligning agent of the present invention is not particularly limited as long as the polymer component is uniformly dissolved. Specific examples thereof include N, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, γ -butyrolactone, 1, 3-dimethyl-imidazolidinone, and 3-methoxy-N, N-dimethylpropionamide. These may be used in a mixture of 1 or 2 or more. In addition, even if the solvent alone is a solvent which cannot uniformly dissolve the polymer component, the solvent may be mixed with the organic solvent as long as the polymer is not precipitated.
The liquid crystal aligning agent of the present invention may contain, in addition to an organic solvent for dissolving the polymer component: a solvent for improving the uniformity of a coating film when the liquid crystal aligning agent is coated on a substrate. As the solvent, a solvent having a lower surface tension than the organic solvent is usually used. Specific examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, butyl cellosolve acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and isoamyl lactate. These solvents may be used in combination of 2 or more.
In addition to the above, the liquid crystal aligning agent of the present invention may further comprise: a dielectric or conductive material for the purpose of changing electrical characteristics such as dielectric constant and conductivity of the liquid crystal alignment film, a silane coupling agent for the purpose of improving adhesion between the liquid crystal alignment film and the substrate, a crosslinkable compound for the purpose of increasing hardness and density of the film when the liquid crystal alignment film is formed, an imidization accelerator for the purpose of efficiently imidizing the polyamic acid when the coating film is fired, and the like.
< method for producing liquid crystal alignment film >
The method for producing a liquid crystal alignment film using the liquid crystal alignment agent of the present invention is not particularly limited, and the liquid crystal alignment film can be produced through the steps (a) to (D) shown below, thereby more effectively exhibiting the excellent properties of the liquid crystal alignment agent of the present invention.
Step (A): and a step of applying the liquid crystal aligning agent of the present invention to a substrate.
A step (B): and heating the coated liquid crystal aligning agent at a temperature at which thermal imidization does not substantially proceed to obtain a film.
Step (C): irradiating the film obtained in the step (B) with polarized ultraviolet rays.
A step (D): and (C) firing the film obtained in step (C) at a temperature of 100 ℃ or higher and higher than that in step (B).
The respective steps (a) to (D) will be described in more detail below.
< Process (A) >
The substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acryl substrate or a polycarbonate substrate, or the like can be used. In this case, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed, in view of simplifying the process. In the reflective liquid crystal display element, if only one substrate is formed, an opaque material such as a silicon wafer may be used, and a material that reflects light such as aluminum may be used for the electrodes.
The method of applying the liquid crystal aligning agent is not particularly limited, and is generally a method performed by screen printing, offset printing, flexographic printing, inkjet method, or the like. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinning machine method, a spray coating method, and the like, and they can be used according to the purpose.
< Process (B) >
The step (B) is a step of heating the liquid crystal aligning agent applied to the substrate without substantially performing thermal imidization to form a film. After coating the liquid crystal aligning agent on the substrate, the solvent is evaporated by heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven to form a film. In this step, any temperature and time may be selected as long as the organic solvent contained in the liquid crystal aligning agent can be removed without substantially performing thermal imidization. In general, in order to sufficiently remove the solvent contained, the heating is preferably performed at 50 to 150 ℃ for 1 to 10 minutes, and more preferably at 50 to 120 ℃ for 1 to 5 minutes.
< Process (C) >
The step (C) is a step of irradiating the film obtained in the step (B) with polarized ultraviolet rays. The ultraviolet ray preferably has a wavelength of 200 to 400nm, and more preferably has a wavelength of 200 to 300 nm. In order to improve the liquid crystal alignment properties, the substrate coated with the liquid crystal alignment agent may be irradiated with ultraviolet rays while being heated at 50 to 250 ℃. The dose of the ultraviolet ray is, for example, 1 to 2000mJ/cm2Preferably 10 to 1000mJ/cm2More preferably 100 to 600mJ/cm2. Further, the higher the extinction ratio of the polarized ultraviolet ray, the higher the anisotropy can be imparted, and therefore, the higher the extinction ratio is, the preferable. Specifically, the extinction ratio of ultraviolet rays polarized along a straight line is preferably 10: 1 or more, more preferably 20: 1 or more.
< Process (D) >
The step (D) is a step of firing the film irradiated with ultraviolet rays in the step (C). Specifically, the step (B) is a step of firing at a temperature of 100 ℃ or higher and higher than the temperature of heating in the step (B). The firing temperature is not particularly limited as long as it is 100 ℃ or higher and higher than the heating temperature in the step (B), and is preferably 150 to 300 ℃, more preferably 150 to 250 ℃, and still more preferably 200 to 250 ℃. The firing time is preferably 5 to 120 minutes, more preferably 5 to 60 minutes, and further preferably 5 to 30 minutes. If the thickness of the liquid crystal alignment film after firing is too thin, the reliability of the liquid crystal display device may be lowered, and therefore, the thickness is preferably 5 to 300nm, more preferably 10 to 200 nm.
The liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film for a liquid crystal display element of a transverse electric field system such as an IPS system or an FFS system, and is particularly useful as a liquid crystal alignment film for a liquid crystal display element of an FFS system. The liquid crystal display element can be produced as follows: after a substrate with a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is obtained, a liquid crystal cell is produced by a known method, and the liquid crystal cell is used to produce the liquid crystal cell.
As an example of a method for manufacturing a liquid crystal cell, a liquid crystal display element having a passive matrix structure will be described. Note that the liquid crystal display element may be an active matrix liquid crystal display element in which a switching element such as a tft (thin Film transistor) is provided in each pixel portion constituting an image display.
Specifically, a transparent glass substrate is prepared, a common electrode is provided on one substrate, and segment electrodes are provided on the other substrate. These electrodes may be formed as ITO electrodes, for example, and patterned so as to be able to display a desired image. Next, an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode. The insulating film may be made of, for example, SiO formed by a sol-gel method2-TiO2The film of (1).
Next, liquid crystal alignment films are formed on the respective substrates, one substrate is stacked on the other substrate so that the liquid crystal alignment films face each other, and the periphery is bonded with a sealant. In order to control the substrate gap, it is generally preferable to mix the spacers in the sealant in advance, and it is preferable to spread the spacers for controlling the substrate gap also in the surface portion where the sealant is not provided. An opening portion capable of being filled with liquid crystal from the outside is provided in advance in a part of the sealant. Next, a liquid crystal material was injected into a space surrounded by the 2 substrates and the sealant through an opening provided in the sealant, and then the opening was sealed with an adhesive. The injection may be performed by a vacuum injection method or a method using a capillary phenomenon in the atmosphere. As the liquid crystal material, any of positive type liquid crystal materials and negative type liquid crystal materials can be used. Subsequently, a polarizing plate was disposed. Specifically, a pair of polarizing plates was attached to the surface of 2 substrates opposite to the liquid crystal layer.
As described above, the liquid crystal aligning agent of the present invention can provide a liquid crystal alignment film comprising: can suppress image sticking due to long-term AC drive generated in a liquid crystal display element of an IPS drive system or an FFS drive system, has no defects such as bright spots generated by the residue of a low molecular weight compound, and can be manufactured in a fewer number of steps than ever before.
Examples
The present invention will be further specifically described below with reference to examples, but the present invention is not limited to these examples.
Hereinafter, the abbreviation of the compound and the method for measuring each property are as follows. The numerical values and units in the following are based on mass unless otherwise specified.
NMP: n-methyl-2-pyrrolidone, GBL: gamma-butyrolactone,
BCS: butyl cellosolve,
[ viscosity ]
The sample size was measured using an E-type viscometer TVE-22H (manufactured by Toyobo Co., Ltd.) at 25 ℃ with a conical rotor TE-1(1 ℃ C., 34' and R24) in an amount of 1.1 mL.
[ molecular weight ]
The Mn and Mw were calculated by measurement using a GPC (gel permeation chromatography at room temperature) apparatus and as values converted to polyethylene glycol and polyethylene oxide.
GPC apparatus: shodex (GPC-101), column: shodex (series of KD803 and KD 805), column temperature: 50 ℃ and eluent: n, N-dimethylformamide (lithium bromide-hydrate (LiBr. H) as additive2O) 30mmol/L, phosphoric acid anhydrous crystal (orthophosphoric acid) 30mmol/L, Tetrahydrofuran (THF) 10ml/L), flow rate: 1.0 ml/min
Standard curve preparation standard samples: TSK standard polyethylene oxide (Mw: about 900000, 150000, 100000, 30000) manufactured by Tosoh corporation, and polyethylene glycol (peak top molecular weight (Mp) of about 12000, 4000, 1000) manufactured by Polymer Laboratories Limited. In the measurement, 4 samples of 900000, 100000, 12000, and 1000 and 2 samples of 150000, 30000, and 4000 were mixed to avoid overlapping peaks.
< measurement of imidization Rate >
20mg of polyimide powder was charged into an NMR sample tube (NMR standard sample tube,. phi.5 (manufactured by Softy scientific Co.), a mixture of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) (0.53ml) was added thereto, and the mixture was dissolved completely by applying ultrasonic waves, and the proton NMR and imidization ratios at 500MHz were measured with an NMR measuring machine (JNW-ECA500) (manufactured by JEOL DATUM LTD.) in this solution, and the peak accumulation value of the proton of the NH group derived from amic acid appearing in the vicinity of 9.5ppm to 10.0ppm were determined by the following formula.
Imidization ratio (%) - (1-. alpha.x/y). times.100
In the above formula, x is a peak cumulative value of a proton derived from an NH group of amic acid, y is a peak cumulative value of a reference proton, and α is a ratio of the number of protons of the reference proton to 1 NH group of amic acid in the case of polyamic acid (imidization ratio of 0%).
[ constitution of FFS-driven liquid Crystal cell ]
In a liquid crystal cell for Fringe Field Switching (FFS) mode, a set of a 1 st glass substrate having an fop (finger on plate) electrode layer formed on the front surface thereof and including a common electrode, an insulating layer, and a comb-teeth-shaped pixel electrode having a surface shape, and a set of a 2 nd glass substrate having a column spacer having a height of 4 μm on the front surface thereof and an ITO film for preventing static electricity on the back surface thereof are used. The pixel electrode has a comb-tooth shape in which a plurality of electrode elements of 3 μm width whose central portions are bent at an internal angle of 160 ° are arranged in parallel at intervals of 6 μm, and 1 pixel has a 1 st region and a 2 nd region with a line connecting the bent portions of the plurality of electrode elements as a boundary.
The liquid crystal alignment film formed on the 1 st glass substrate was subjected to alignment treatment so that the direction of the inner angle of the bent portion of the pixel was equally divided and the alignment direction of the liquid crystal was orthogonal to each other, and the liquid crystal alignment film formed on the 2 nd glass substrate was subjected to alignment treatment so that the alignment direction of the liquid crystal on the 1 st substrate and the alignment direction of the liquid crystal on the 2 nd substrate were aligned when the liquid crystal cell was produced.
On each surface of the above-mentioned pair of glass substrates, a liquid crystal aligning agent filtered through a filter having a pore size of 1.0 μm was applied by spin coating, and dried on a hot plate at 80 ℃ for 2 minutes. Then, the film surface was irradiated with a predetermined amount of a polarizing plate having an extinction ratio of 26: 1, and then, the substrate was fired in a hot air circulating oven at 230 ℃ for 30 minutes to obtain a substrate with a liquid crystal alignment film having a film thickness of 100 nm.
Next, a sealant was printed on one of the pair of glass substrates with the liquid crystal alignment film, and the other substrate was bonded with the liquid crystal alignment film surface facing each other, and the sealant was cured to prepare an empty cell. Liquid crystal MLC-3019 (manufactured by Merck) was injected into the empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell. Then, the obtained liquid crystal cell was heated at 120 ℃ for 1 hour, and after standing overnight, the residual image characteristics were evaluated.
[ evaluation of afterimage characteristics by Long-term AC drive ]
The FFS-driven liquid crystal cell fabricated as described above was applied with an ac voltage of ± 5V at a frequency of 60Hz for 120 hours in a constant temperature environment of 60 ℃. After that, the liquid crystal cell was placed in a state in which the pixel electrode and the counter electrode were short-circuited, and the liquid crystal cell was left at room temperature for one day.
In the liquid crystal cell subjected to the above-described processing, the deviation between the alignment direction of the liquid crystal in the 1 st region and the alignment direction of the liquid crystal in the 2 nd region of the pixel in the voltage-non-applied state was calculated at an angle.
Specifically, a liquid crystal cell was placed between 2 polarizing plates arranged so that the polarization axes were orthogonal to each other, the backlight was turned on, the arrangement angle of the liquid crystal cell was adjusted so that the transmission light intensity in the 1 st region of the pixel became minimum, and then the rotation angle required to rotate the liquid crystal cell so that the transmission light intensity in the 2 nd region of the pixel became minimum was obtained.
The smaller the value of the rotation angle is, the better the afterimage characteristics due to the long-term ac driving can be said to be. When the value of the angle Δ of the liquid crystal cell was 0.1 ° or less, the evaluation was "good".
Examples of synthesis of polyamic acid and polyimide are shown below.
< Synthesis example 1 >
In a 300mL four-necked flask equipped with a stirrer and a nitrogen inlet, 15.86 g (24.0mmol) of DA, 21.73 g (16.0mmol) of DA, 37.02 g (24.0mmol) of DA and 53.80 g (16.0mmol) of DA were weighed out, 205.7g of NMP was added, and the mixture was dissolved by stirring while feeding nitrogen. While stirring this diamine solution, CA-114.88 g (66.4mmol) and CA-23.00 g (12.0mmol) were added thereto, and the mixture was stirred at 40 ℃ for 24 hours to obtain a polyamic acid solution (A-1) (viscosity: 445 mPas). The polyamic acid had Mn of 11200 and Mw of 33900.
< Synthesis examples 2 to 7 >
The same operations as in Synthesis example 1 were carried out with respect to the diamine component and the tetracarboxylic acid component shown in Table 1 below, to obtain polyamic acid solutions (A-2) to (A-5) and (B-1) to (B-2) shown in Table 1 below. The viscosity, Mn, and Mw of the obtained polyamic acid are shown in table 1 below.
The polyamic acid solutions obtained in synthesis examples 1 to 7 each had a polyamic acid concentration of 15 mass%.
[ Table 1]
< Synthesis example 8 >
In a 300mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 100g of the obtained polyamic acid solution (A-1) was weighed, 50g of NMP was added, and the mixture was stirred for 30 minutes. To the polyamic acid solution thus obtained were added 16.78g of acetic anhydride and 5.20g of pyridine, and the mixture was heated at 50 ℃ for 3 hours to effect chemical imidization. The obtained reaction solution was poured into 600ml of methanol while stirring, and the precipitated precipitate was obtained by filtration, and the resin powder was washed and dried at 60 ℃ for 12 hours by performing the same operation 2 times, to obtain a polyimide resin powder. The polyimide resin powder had an imidization ratio of 71%, Mn 12600 and Mw 33900. 3.60g of the obtained polyimide resin powder was taken in a 100ml Erlenmeyer flask, 26.4g of NMP was added so that the solid content concentration became 12%, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NMP, thereby obtaining a polyimide solution (A-1-PI) (see Table 2 below).
In table 2, the concentration (%) under the imidization conditions indicates the polymer concentration in the solution during the imidization reaction.
< Synthesis examples 8 to 12 >
Polyimide solutions (A-2-PI) to (A-5-PI) were obtained by chemical imidization in the same manner as in Synthesis example 8, except that acetic anhydride and pyridine shown in Table 2 below were used, and polyamide acid solutions (A-2) to (A-5) were used instead of the polyamide acid solution (A-1). The imidization ratio and Mn/Mw of the obtained polyimide are shown in Table 2 below.
[ Table 2]
< example 1 >
4.0g of the 12% by mass polyimide solution (A-1-PI) obtained in Synthesis example 8 and 4.8g of the 15% by mass polyamide acid solution (B-1) obtained in Synthesis example 6 were taken in a50 ml Erlenmeyer flask, and NMP3.24g, GBL 3.96g and BCS 4.00g were added thereto and mixed at 25 ℃ for 8 hours to obtain a liquid crystal aligning agent (1) (see Table 3 below). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as clouding and precipitation.
In table 3, a/B represents a mass% ratio of the polyimide solution/the polyamic acid solution, and a solid content ratio (mass%) represents a content ratio of the polymer in the liquid crystal alignment agent.
< examples 2 to 6, comparative example 1 >
Liquid crystal alignment agents (2) to (8) were obtained in the same manner as in example 1, except that the polyamic acid solution and the polyimide solution shown in table 3 below were used. These liquid crystal aligning agents were confirmed to be homogeneous solutions without any abnormality such as clouding and precipitation.
[ Table 3]
< example 11 >
The afterimage characteristics were evaluated based on the above [ evaluation of afterimage by long-term ac drive ]. That is, the liquid crystal aligning agent (1) obtained in example 1 was filtered through a filter having a pore diameter of 1.0 μm, and then applied to the prepared electrode-carrying substrate and a glass substrate having an ITO film formed on the back surface thereof and having a columnar spacer having a height of 4 μm by spin coating. After drying on a hot plate at 80 ℃ for 2 minutes, the coated surface was irradiated with a polarizing plate having an extinction ratio of 26: 1, and then fired in a hot air circulating oven at 230 ℃ for 30 minutes to obtain a substrate with a liquid crystal alignment film having a film thickness of 100 nm.
The obtained 2 substrates were used as a set, a sealant was printed on the substrates, and another 1 substrate was bonded so that the liquid crystal alignment films face each other and the alignment direction was 0 °, and then the sealant was cured to prepare an empty cell. Liquid crystal MLC-3019 (manufactured by Merck) was injected into the empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell. Then, the resulting liquid crystal cell was heated at 120 ℃ for 1 hour, and placed at night, and the evaluation of the residual image due to the long-time ac driving was performed.
The value (°) of the angle Δ of the liquid crystal cell after long-term ac driving is shown in table 4 below, i.e., the amount of the ultraviolet light irradiation is 0.2J/cm2The angle Δ of the lower liquid crystal cell was 0.09 °. Since the minimum value of the respective separation angles Δ is 0.1 ° or less, good liquid crystal alignment properties are obtained by the liquid crystal aligning agent (1).
< examples 12 to 16 and comparative example 11 >
In examples 12 to 16 and comparative example 11, an FFS-driven liquid crystal cell was produced in exactly the same manner as in example 11 except that the liquid crystal aligning agent shown in table 4 below was used instead of the liquid crystal aligning agent (1), and the evaluation of the residual image due to long-term ac driving was performed.
The values of the angle Δ of the liquid crystal cell after long-term ac driving are shown in table 4 for examples 12 to 16 and comparative example 11.
[ Table 4]
As shown in Table 4, in examples 11 to 16, the amount of ultraviolet irradiation was 0.2J/cm at an angle Δ (deg.) of 0.1 ° or less2The angle Δ is optimized below with a small amount of polarized ultraviolet irradiation. The liquid crystal display element is excellent in shortening of the production time because of its good afterimage characteristics.
Industrial applicability
The liquid crystal aligning agent of the present invention is useful for forming a liquid crystal alignment film in a wide variety of liquid crystal display devices such as IPS drive systems and FFS drive systems.
The entire contents of the specification, claims, drawings, and abstract of japanese patent application No. 2018-154227, which was filed on 8/20/2018, are incorporated herein as the disclosure of the specification of the present invention.
Claims (13)
1. A liquid crystal aligning agent characterized by containing a polyimide which is an imide compound of a polyimide precursor obtained by a polycondensation reaction of a tetracarboxylic acid component containing a tetracarboxylic dianhydride represented by the following formula (1) or a derivative thereof and a diamine component containing a 1 st diamine represented by the following formula (3) and a 2 nd diamine represented by the following formula (4),
wherein, X1Is as followsA structure represented by the formula (X1-1) or (X1-2),
wherein R is3～R12Each 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 1-valent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, R3～R6At least one of which is a group other than a hydrogen atom in the above definition,
wherein A is1Is an alkylene group having 2 to 10 carbon atoms or-CH which the alkylene group has2-a group in which at least one of the groups is replaced under discontinuous conditions by-O-or-S-, A2A halogen atom, a hydroxyl group, an amino group, a mercapto group, a nitro group, a phosphoric acid group, or a 1-valent organic group having 1 to 20 carbon atoms, a is an integer of 0 to 4, and a plurality of A's are present2In the case of (A)2Optionally identical or different, b and c are each independently an integer of 1 or 2, d is an integer of 0 or 1,
2. the liquid crystal aligning agent according to claim 1, wherein X in the following formula (1)1Is at least 1 selected from the following formulas (X1-1-1) to (X1-1-5),
3. the liquid crystal aligning agent according to claim 1 or 2, wherein the 1 st diamine represented by the following formula (3) is at least 1 diamine selected from the group consisting of the following formulas (3-1) to (3-12),
4. the liquid crystal aligning agent according to any one of claims 1 to 3, wherein the 1 st diamine represented by the following formula (4) is at least 1 diamine selected from the group consisting of the following formulas (4-1) to (4-3),
5. the liquid crystal aligning agent according to any one of claims 1 to 4, wherein the 1 st diamine represented by the formula (3) is contained in an amount of 40 to 90 mol% based on the diamine component.
6. The liquid crystal aligning agent according to any one of claims 1 to 5, wherein the 2 nd diamine represented by the formula (4) is contained in an amount of 10 to 40 mol% based on the diamine component.
7. The liquid crystal aligning agent according to any one of claims 1 to 6, wherein the tetracarboxylic acid component further comprises at least 1 selected from the group consisting of tetracarboxylic dianhydrides represented by the following formula (2) and derivatives thereof,
wherein, X2Is a structure selected from the following formulae (X2-1) to (X2-6),
8. the liquid crystal aligning agent according to claim 7, wherein the tetracarboxylic dianhydride represented by the formula (2) or the derivative thereof is contained in an amount of 1 to 30 mol% based on the tetracarboxylic acid component.
9. A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to any one of claims 1 to 8.
10. A liquid crystal display element comprising the liquid crystal alignment film according to claim 9.
11. A method for producing a liquid crystal alignment film, comprising the following steps (A), (B), (C) and (D),
step (A): a step of coating the liquid crystal aligning agent according to any one of claims 1 to 8 on a substrate;
a step (B): heating the coated liquid crystal aligning agent under the condition of not substantially carrying out thermal imidization to obtain a film;
step (C): irradiating the film obtained in the step (B) with polarized ultraviolet rays;
a step (D): and (C) firing the film obtained in step (C) at a temperature of 100 ℃ or higher and higher than that in step (B).
12. The method of producing a liquid crystal alignment film according to claim 11, wherein the heating is performed at 50 to 150 ℃ in the step (B).
13. The method for producing a liquid crystal alignment film according to claim 11 or 12, wherein in the step (D), the film is fired at 150 to 300 ℃.
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| PCT/JP2019/032286 WO2020040089A1 (en) | 2018-08-20 | 2019-08-19 | Liquid crystal alignment agent, production method thereof, liquid crystal alignment film, and liquid crystal display element |
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| CN113930247A (en) * | 2020-07-13 | 2022-01-14 | 奇美实业股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
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| JP5654228B2 (en) | 2009-11-13 | 2015-01-14 | 株式会社ジャパンディスプレイ | Liquid crystal display device and method of manufacturing liquid crystal display device |
| WO2014057945A1 (en) * | 2012-10-09 | 2014-04-17 | 日産化学工業株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| JP6375789B2 (en) * | 2013-09-02 | 2018-08-22 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, retardation film and method for producing the same |
| CN105849631B (en) * | 2013-10-23 | 2019-04-16 | 日产化学工业株式会社 | Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element |
| KR20180063294A (en) * | 2015-10-07 | 2018-06-11 | 닛산 가가쿠 고교 가부시키 가이샤 | A liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element |
| WO2017170681A1 (en) * | 2016-03-30 | 2017-10-05 | 日産化学工業株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| CN111279255B (en) * | 2017-10-26 | 2023-03-14 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
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| CN104024932A (en) * | 2011-10-27 | 2014-09-03 | 日产化学工业株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| CN104419429A (en) * | 2013-09-02 | 2015-03-18 | Jsr株式会社 | Liquid crystal aligning agent and film thereof, display component, film and manufacturing method thereof, polymer and compound |
| WO2018117239A1 (en) * | 2016-12-21 | 2018-06-28 | 日産化学工業株式会社 | Method for producing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element |
| CN107698761A (en) * | 2017-11-03 | 2018-02-16 | 杭州超通科技有限公司 | A kind of preparation method of polyimides |
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