CN117546082A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element Download PDF

Info

Publication number
CN117546082A
CN117546082A CN202280044600.0A CN202280044600A CN117546082A CN 117546082 A CN117546082 A CN 117546082A CN 202280044600 A CN202280044600 A CN 202280044600A CN 117546082 A CN117546082 A CN 117546082A
Authority
CN
China
Prior art keywords
liquid crystal
group
formula
polyamic acid
aligning agent
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
CN202280044600.0A
Other languages
Chinese (zh)
Inventor
慈道圭太
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
Original Assignee
Nissan Chemical Corp
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 Nissan Chemical Corp filed Critical Nissan Chemical Corp
Publication of CN117546082A publication Critical patent/CN117546082A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Landscapes

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

Abstract

The invention provides a liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display element, wherein the liquid crystal aligning agent can obtain the liquid crystal alignment film which has small non-uniformity of twist angle of liquid crystal, can inhibit AC residual image and is difficult to generate substrate peeling. A liquid crystal aligning agent comprising the following component (A) and component (B). Component (A): a polyamic acid ester (A) having a structural unit (a-1 Ta) represented by the following formula (1 Ta) and two structural units (a-1 Da) represented by the following formula (1 Da); component (B): a polyamic acid (B) having a structural unit (B-1 Tb) represented by the following formula (1 Tb) and a structural unit (B-1 Db) represented by the following formula (1 Db). (R) 11 ～R 14 Represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the like, R 11 ～R 14 At least one of which represents a group other than a hydrogen atom. Two R 1 Represents a hydrogen atom or a tertiary alkyl group, at least one of which represents a tertiary alkyl group. Y is Y 1 Is of the formula (H) 1 ) Divalent organic groups are shown. Z represents a hydrogen atom or the like. ) (Ar) 1 、Ar 1’ Represents a benzene ring, etc. A represents a divalent organic group having an alkylene structure and having 1 to 10 carbon atoms. L (L) 1 、L 1’ Represents a single bond or the like. ) (X) b Represents tetravalent organic radicals, Y b Represents a divalent organic group, Z represents a hydrogen atom or the like. )

Description

Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
Technical Field
The invention relates to a liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display element, wherein the liquid crystal aligning agent can obtain the liquid crystal aligning film which has small non-uniformity of twist angle of liquid crystal, can inhibit AC residual image and is difficult to generate substrate stripping.
Background
Liquid crystal display devices are widely used in applications ranging from small-sized applications such as cellular phones and smart phones to larger-sized applications such as televisions and displays. The liquid crystal display device includes, for example: a liquid crystal layer sandwiched between the element substrate and the color filter substrate; a pixel electrode and a common electrode for applying an electric field to the liquid crystal layer; an alignment film for controlling alignment properties of liquid crystal molecules of the liquid crystal layer; a thin film transistor (TFT: thin Film Transistor) for converting an electric signal supplied to the pixel electrode; etc. As a driving method of liquid crystal molecules, a vertical electric field method such as a TN (Twisted Nematic) method and a VA (Vertical Alignment: vertical alignment) method is known; in-Plane Switching (IPS) mode, fringe Field Switching (FFS) mode, and the like.
Currently, the most industrially used liquid crystal alignment film is produced by rubbing the surface of a film formed on an electrode substrate and composed of polyamic acid and/or polyimide obtained by imidizing the polyamic acid with a cloth such as cotton, nylon, or polyester in one direction, so-called rubbing treatment. Friction treatment is a simple and useful method with excellent productivity. However, with the increase in performance, high definition, and large-sized liquid crystal display devices, various problems such as damage to the surface of the alignment film, dust generation, mechanical force, and influence of static electricity generated during rubbing treatment, and non-uniformity in the alignment treatment surface become apparent. As an alignment treatment method in place of the rubbing treatment, a photo-alignment method is known in which polarized radiation is irradiated to impart alignment ability to liquid crystals. As the photo-alignment 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, refer to non-patent document 1, patent document 2).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 9-297313
Patent document 2: japanese patent application laid-open No. 2004-206091
Non-patent literature
Non-patent document 1: "liquid crystal photo-alignment film", functional material, 1997, 11-month Vol.17, no.11, pages 13-22
Disclosure of Invention
Problems to be solved by the invention
A liquid crystal alignment film used in an IPS drive mode or FFS drive mode liquid crystal display device needs to have a high alignment regulating force for suppressing an afterimage (hereinafter, also referred to as an AC afterimage) generated by long-term AC drive. In addition, in the case of performing the alignment treatment by the photo-alignment method, the irradiation amount of light is a factor that affects the energy consumption and the production speed, and therefore, it is preferable to perform the alignment treatment with a small irradiation amount of light. On the other hand, as the size of the liquid crystal display device increases, there is a problem that the twist angle of the liquid crystal in the liquid crystal display device surface is slightly uneven due to the unevenness in the manufacturing process. When such unevenness is black display in the liquid crystal display element, the brightness becomes uneven in the plane, and the quality of the liquid crystal display element is lowered.
In recent years, in a liquid crystal display device of a touch panel type, it has been demanded that the durability against external pressure such as pressure by a pointing device such as a finger or a pen is high, that is, alignment failure and bright point failure are less likely to occur even when external pressure is applied. In addition, in flat terminals and mobile terminals, weight reduction and thickness reduction are advancing, and in a panel assembly process at the time of manufacturing a liquid crystal display device, a stress is applied to the inside of the panel by deformation of the panel. Such deformation and stress of the panel cause peeling of the liquid crystal alignment film from the substrate, and cause occurrence of bright-spot failure and alignment failure. Therefore, a high film strength is required for the liquid crystal alignment film, which is less likely to cause peeling of the substrate.
Accordingly, an object of the present invention is to provide a liquid crystal aligning agent which can provide a liquid crystal alignment film having small variation (unevenness) in twist angle of liquid crystal in a liquid crystal alignment film plane, which can suppress AC afterimage, and which can provide a liquid crystal alignment film which is less likely to be peeled off from a substrate at the time of manufacturing a liquid crystal display device or the like, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element using the liquid crystal alignment film.
Solution for solving the problem
As a result of intensive studies, the present inventors have found that the above problems can be solved by using a liquid crystal aligning agent containing a specific component, and have completed the present invention.
Specifically, the present invention includes the following aspects.
A liquid crystal aligning agent characterized by comprising the following component (A) and component (B).
(A) The components are as follows: the polyamide acid ester (A) has a structural unit (a-1 Ta) represented by the following formula (1 Ta) as a structural unit derived from a tetracarboxylic acid derivative, and has two or more structural units (a-1 Da) represented by the following formula (1 Da) as structural units derived from diamine.
(B) The components are as follows: a polyamide acid (B) having a structural unit (B-1 Tb) represented by the following formula (1 Tb) as a structural unit derived from a tetracarboxylic acid derivative and a structural unit (B-1 Db) represented by the following formula (1 Db) as a structural unit derived from a diamine.
(in the formula (1 Ta), R is 11 ～R 14 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, R 11 ～R 14 At least one of which represents a group other than a hydrogen atom in the above definition. Two R 1 Each independently represents a hydrogen atom or a tertiary alkyl group, at least one of which represents a tertiary alkyl group.
In the formula (1 Da), Y 1 Is of the formula (H) 1 ) Divalent organic groups are shown. Each Z independently represents a hydrogen atom or a monovalent organic group. )
＊-Ar 1 -L 1 -A-L 1′ -Ar 1′ -＊ (H 1 )
(A (H) 1 ) Ar in (1) 1 、Ar 1’ Each independently represents a benzene ring, a biphenyl structure, or a naphthalene ring. Ar (Ar) 1 、Ar 1’ Optionally substituted with monovalent groups. A represents a divalent organic group having an alkylene structure and having 1 to 10 carbon atoms. L (L) 1 、L 1’ Each independently represents a single bond, -O-, -S-, -C (=o) -, -O-C (=o) -, -C (=o) -NR- (R represents a hydrogen atom or a monovalent organic group), or-NR-C (=o) - (R represents a hydrogen atom or a monovalent organic group). * Representing a bond. )
(in the formula (1 Tb), X b Represents a tetravalent organic group of the formula (1 Db), Y b Represents a divalent organic group, and Z each independently represents a hydrogen atom or a monovalent organic group. )
In the present specification, the following terms and abbreviations have the meanings described below, respectively. The halogen atom is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like. "tert-" representing a tertiary is also denoted "t-". The Boc group represents a t-butoxycarbonyl group. * Representing a bond.
Effects of the invention
According to the present invention, even when the alignment treatment is performed with a small amount of light irradiation, a liquid crystal alignment agent that can provide a liquid crystal alignment film having small variation (unevenness) in twist angle of liquid crystal in the liquid crystal alignment film surface, and that can suppress AC afterimage, and that can provide a liquid crystal alignment film that is less likely to be peeled off from the substrate at the time of manufacturing a liquid crystal display device, and a liquid crystal display element using the liquid crystal alignment film can be obtained.
The mechanism by which the above-described effects are obtained by the present invention is not necessarily clear, but it is considered that the following is one of the reasons. The liquid crystal aligning agent of the present invention contains specific polyamic acid ester (A) and polyamic acid (B) as polymer components. Since the polyamic acid ester (a) has a tertiary alkyl ester structure having high hydrophobicity, formation of hydrogen bonds with the polyamic acid (B) can be suppressed, and transfer of components to an air interface becomes high when a liquid crystal alignment film is formed, and bias of the polyamic acid ester in the liquid crystal interface becomes high. In addition, the polyamide acid ester (a) having a bulky structure is liable to be detached from the tertiary alkyl ester when the coating film is baked, and therefore, thermal imidization is easier than a usual methyl ester structure, and the tertiary alkyl ester is not liable to remain in the obtained liquid crystal alignment film.
Accordingly, since a high liquid crystal alignment property is uniformly obtained in the plane, it is considered that even with a small amount of light irradiation, a liquid crystal alignment film in which the variation (unevenness) in twist angle of liquid crystal in the plane of the liquid crystal alignment film is small and the AC afterimage is suppressed can be obtained. In addition, the polyamic acid ester (A) may be represented by, for example, R 1 In the case of t-butyl, the isobutylene is released during firing, and imidization proceeds through polyamic acid, so that the film strength of the obtained liquid crystal alignment film is also improved. In addition, it is considered that the liquid crystal alignment agent of the present invention contains the polyamic acid (B) and has a structure with high polarity, and thus a liquid crystal alignment film which is less likely to cause peeling of the substrate can be obtained.
Drawings
Fig. 1 is a schematic partial cross-sectional view showing an example of a transverse electric field liquid crystal display element according to the present invention.
Fig. 2 is a schematic partial cross-sectional view showing another example of the transverse electric field liquid crystal display element of the present invention.
Detailed Description
Polyamic acid ester (A) >, a process for producing the same
The liquid crystal aligning agent of the invention comprises a polyamide acid ester (A) which has a structural unit (a-1 Ta) shown in the formula (1 Ta) as a structural unit derived from a tetracarboxylic acid derivative and has two or more structural units (a-1 Da) shown in the formula (1 Da) as structural units derived from diamine. The polymer (a) may be one or two or more kinds.
The polyamic acid ester (a) has two or more structural units (a-1 Da) represented by the above formula (1 Da), and thus can provide a liquid crystal alignment film having a proper balance between various characteristics such as a high alignment regulating force and a high photosensitivity, and thus can provide a liquid crystal alignment film capable of suppressing an AC afterimage and reducing the amount of light irradiation required for alignment treatment.
The polyamic acid ester (a) of the present invention may have a amic acid ester structure in its entire repeating units or may have a amic acid ester structure in a part of its repeating units. In the case where a part of the repeating units has an amic acid ester structure, the remaining repeating units may have an amic acid structure or may have an imidized structure. The remaining repeating units may have a repeating unit having an amic acid structure and a repeating unit having an imidized structure.
R of the above formula (1 Ta) representing a structural unit derived from a tetracarboxylic acid derivative as the polyamic acid ester (A) 11 ～R 14 Specific examples of the alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and the like. As R as above 11 ～R 14 Specific examples of the alkenyl group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, include: vinyl, propenyl, butenyl, and the like, and they may be linear or branched. As R as above 11 ～R 14 The number of carbon atoms in the (C) is 2-6,specific examples of the alkynyl group preferably having 2 to 4 include: ethynyl, 1-propynyl, 2-propynyl, and the like. As R as above 11 ～R 14 Examples of the monovalent organic group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, which contains a fluorine atom include: fluoromethyl, trifluoromethyl, pentafluoroethyl, pentafluoropropyl, and the like.
R is as follows 11 ～R 14 In a more preferred combination of (2), R is from the viewpoint of high photoreactivity 11 ～R 14 Is a hydrogen atom or a methyl group, preferably R 11 ～R 14 At least one of which is methyl, more preferably R 11 ～R 14 At least two of which are methyl groups. Further preferred is R 11 And R is 14 Is methyl, R 12 And R is 13 In the case of a hydrogen atom.
R as polyamic acid ester (A) 1 The tertiary alkyl group is a tertiary alkyl group having 4 to 10 carbon atoms, preferably 4 to 7 carbon atoms. Specifically, examples are shown as follows: tertiary butyl, tertiary amyl, tertiary hexyl, tertiary heptyl. Among them, tert-butyl is preferable.
From the viewpoint of properly obtaining the effect of the present invention, the structural unit (a-1 Ta) of the polyamic acid ester (a) of the present invention is preferably 5 mol% or more, more preferably 25 mol% or more, and even more preferably 60 mol% or more, based on 1 mol of the total structural units derived from the tetracarboxylic acid derivative of the polyamic acid ester (a).
The polyamic acid ester (A) of the present invention may have a structural unit (a-2 Ta) represented by the following formula (2 Ta) as a structural unit derived from a tetracarboxylic acid derivative.
(two R) 2 Each independently represents a hydrogen atom or a monovalent organic group. X is X 2a Represents a tetravalent organic group. Wherein, at X 2a In the case of a tetravalent organic group represented by the following formula (g), R 2 Represents a hydrogen atom. )
(R 11’ ～R 14’ Including their preferred embodiments, R is the same as R of the above formula (1 Ta) 11 ～R 14 Making the meaning the same. )
R in the above formula (2 Ta) 2 Examples of the monovalent organic group include: monovalent hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms; the methylene group of the hydrocarbon group is replaced by-O-, -S-, and-CO-, -COO-, -COS-, -NR 3 - (wherein R 3 Is hydrogen atom or monovalent hydrocarbon group having 1 to 10 carbon atoms), -CO-NR 3 - (wherein R 3 Is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms), -Si (R) 3 ) 2 - (wherein R 3 Is hydrogen atom or monovalent hydrocarbon group with 1-10 carbon atoms), -SO 2 -an isosubstituted monovalent group a; a monovalent group in which at least one of the hydrogen atoms bonded to the monovalent hydrocarbon group or the carbon atom of the monovalent group a is substituted with a halogen atom, a hydroxyl group, an alkoxy group, a nitro group, an amino group, a mercapto group, a nitroso group, an alkylsilyl group, an alkoxysilane group, a silanol group, a sulfinyl group, a phosphine group, a carboxyl group, a cyano group, a sulfo group, an acyl group or the like; or a monovalent group having a heterocyclic ring.
R in the above formula (2 Ta) 2 Among them, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, t-butoxycarbonyl group or 9-fluorenylmethoxycarbonyl group is preferable, alkyl group having 1 to 3 carbon atoms is more preferable, and methyl group is still more preferable.
From the viewpoint of suitably obtaining the effect of the present invention, two R 2 Each independently is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.
As X in the above formula (2 Ta) 2a Specific examples of the tetravalent organic group of (a) include, in addition to the tetravalent organic group represented by the above formula (g), the following tetracarboxylic dianhydride (hereinafter, it is also referred to asCollectively referred to as other tetracarboxylic dianhydrides) from which two anhydride groups have been removed.
Acyclic aliphatic tetracarboxylic dianhydrides such as 1,2,3, 4-butane tetracarboxylic dianhydride; 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, 3', 4' -dicyclohexyltetracarboxylic dianhydride, 2,3, 5-tricarboxyl cyclopentylacetic dianhydride, 4- (2, 5-dioxatetrahydrofuran-3-yl) tetrahydronaphthalene-1, 2-dicarboxylic dianhydride, 5- (2, 5-dioxatetrahydrofuran-3-yl) -3a,4,5,9 b-tetrahydronaphtho [1,2-c ] furan-1, 3-dione, 5- (2, 5-dioxatetrahydrofuran-3-yl) -8-methyl-3 a,4,5,9 b-tetrahydronaphtho [1,2-c ] furan-1, 3-dione, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2, 3, 6-tetracarboxylic dianhydride, 2, 6-tetracarboxylic acid, 4, 3-dicarboxyl) 2, 3-dicarboxyl: 4,6: alicyclic tetracarboxylic dianhydrides such as 8-dianhydride; pyromellitic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, 3', 4' -diphenyl sulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 3',4,4' -diphenyl ether tetracarboxylic dianhydride, 3', 4' -perfluoroisopropylidene bis (phthalic anhydride), 3', 4' -biphenyl tetracarboxylic dianhydride, 2', aromatic tetracarboxylic dianhydrides such as 3,3' -biphenyltetracarboxylic dianhydride, 4' -bis (3, 4-dicarboxyphenoxy) -2, 2-diphenylpropane dianhydride, ethylene glycol bis-trimellitic anhydride, 4' - (hexafluoroisopropylidene) dianhydride, 4' -carbonyl dianhydride, 4' -oxydi (1, 4-phenylene) bis (phthalic) dianhydride, or 4,4' -methylenebis (1, 4-phenylene) bis (phthalic) dianhydride; and tetracarboxylic dianhydrides described in JP-A2010-97188.
More preferable examples of the other tetracarboxylic dianhydrides include: 1,2,3, 4-butanetetracarboxylic acid dianhydride, 1,2,3, 4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4, 5-cyclohexanedicarboxylic acid dianhydride, 3', 4' -dicyclohexyltetracarboxylic acid dianhydride, 2,3, 5-tricarboxycyclopentylacetic acid dianhydride, 5- (2, 5-dioxatetrahydrofuran-3-yl) -3a,4,5,9 b-tetrahydronaphtho [1,2-c ] furan-1, 3-dione, 5- (2, 5-dioxatetrahydrofuran-3-yl) -8-methyl-3 a,4,5,9 b-tetrahydronaphtho [1,2-c ] furan-1, 3-dione, 2,4,6, 8-tetracyclobicyclo [3.3.0] octane-2: 4,6: 8-dianhydride, pyromellitic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, 3', 4' -diphenyl sulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 3',4,4' -diphenyl ether tetracarboxylic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 2', 3' -biphenyl tetracarboxylic dianhydride.
From the viewpoint of suitably obtaining the effect of the present invention, X in the above formula (2 Ta) 2a More preferably, the tetravalent organic group represented by the above formula (g).
The proportion of the structural unit represented by the formula (2 Ta) in the polyamic acid ester (a) is preferably 95 mol% or less, more preferably 75 mol% or less, and even more preferably 40 mol% or less, based on 1 mol of the total structural units derived from the tetracarboxylic acid derivative in the polyamic acid ester (a).
Y in the above formula (1 Da) 1 Is of the above formula (H) 1 ) Divalent organic groups are shown. In (H) 1 ) Wherein L is 1 、L 1’ As described above. In addition, as the expression L 1 、L 1’ -C (=o) -NR-or-NR-C (=o) monovalent organic groups of R in (a), there may be mentioned: an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, an acyl group having 2 to 3 carbon atoms, an alkylsilane group having 1 to 3 carbon atoms, an alkoxysilane group having 1 to 3 carbon atoms, or a monovalent organic group in which a part of hydrogen atoms contained in these groups is substituted with at least one of a halogen atom and a hydroxyl group.
As the above formula (H) 1 ) Ar in (3) 1 And Ar is a group 1’ Examples of the monovalent group of the substituent of any hydrogen atom on the ring include: a halogen atom; alkyl having 1 to 3 carbon atoms; alkyl groups having 1 to 3 carbon atoms, each of which is substituted with a halogen atom or a hydroxyl group as at least a part of a hydrogen atom; alkoxy having 1 to 3 carbon atoms, wherein at least a part of the alkoxy group or the hydrogen atom is substituted with at least any one of the halogen atom and the hydroxyl group; alkenyl of 2 to 3 carbon atoms; acyl with 2-3 carbon atoms; alkylsilane groups having 1 to 3 carbon atoms; an alkoxysilane group having 1 to 3 carbon atoms; hydroxyl, nitrile, and the like.
As the above formula (H) 1 ) Ar in (3) 1 And Ar is a group 1’ Specific examples of (a) include: benzene rings optionally having substituents such as 1, 4-phenylene, 1, 3-phenylene, 2-methyl-1, 4-phenylene, 2-ethyl-1, 4-phenylene, 2-propyl-1, 4-phenylene, 2-butyl-1, 4-phenylene, 2-isopropyl-1, 4-phenylene, 2-t-butyl-1, 4-phenylene, 2-methoxy-1, 4-phenylene, 2-ethoxy-1, 4-phenylene, 2-propoxy-1, 4-phenylene, 2-butoxy-1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-dimethyl-1, 4-phenylene, 4-methyl-1, 3-phenylene, 5-methyl-1, 3-phenylene, 4-fluoro-1, 3-phenylene, 2,3,5, 6-tetramethyl-1, 4-phenylene; 4,4' -biphenylene, 2-methyl-4, 4' -biphenylene, 2-ethyl-4, 4' -biphenylene, 2-propyl-4, 4' -biphenylene, 2-butyl-4, 4' -biphenylene, 2-tert-butyl-4, 4' -biphenylene, 2-methoxy-4, 4' -biphenylene, 2-ethoxy-4, 4' -biphenylene, 2-fluoro-4, 4' -biphenylene, 3-methyl-4, 4' -biphenylene, 3-ethyl-4, 4' -biphenylene, 3-propyl-4, 4' -biphenylene, 3-butyl-4, 4' -biphenylene, 3-tert-butyl-4, 4' -biphenylene, 3-methoxy-4, 4' -biphenylene, 3-ethoxy-4, 4' -biphenylene, 3-fluoro-4, 4' -biphenylene, 2' -dimethyl-4, 4' -biphenylene Biphenyl structure optionally having a substituent such as 3,3 '-dimethyl-4, 4' -biphenylene, 3 '-biphenylene, 5-methyl-3, 3' -biphenylene, 5 '-dimethyl-3, 3' -biphenylene and the like; naphthalene rings optionally substituted with 1, 5-naphthylene, 2, 6-naphthylene, 1-methyl-2, 6-naphthylene and the like.
The above-mentioned formula (H) 1 ) A in (2) is a divalent organic group having an alkylene structure. In the case where the alkylene structure has three or more carbon-carbon bonds, any carbon-carbon bond constituting the alkylene structure is optionally substituted with a carbon-carbon double bond. A is preferably (q 0), (q 1), (q 2) as follows: an alkylene group (q 0) having 1 to 10 carbon atoms; a divalent organic group (q 1) having-O-, -C (=o) -, -NH-, -O-C (=o) -or-C (=o) -O-interposed between carbon-carbon bonds of the alkylene group; or a divalent organic group (q 2) having at least one-NR-C (=O) -NR- (R represents a hydrogen atom or a monovalent organic group) between carbon-carbon bonds of the alkylene group.
The monovalent organic group represented by R in the above-mentioned-NR-C (=O) -NR-includes those represented by the above-mentioned formula (H) 1 ) L of (2) 1 And L 1’ R in-C (=O) -NR-by way of example.
Preferred specific examples of the above (q 0), (q 1) and (q 2) are as follows.
*－(CH 2 ) n －*。
*－(CH 2 ) n1 －O－(CH 2 ) n2 －*。
*－(CH 2 ) m1 －O－C(＝O)－(CH 2 ) n’ －C(＝O)－O－(CH 2 ) m2 －*。
*－(CH 2 ) m1 －C(＝O)－O－(CH 2 ) n’ －O－C(＝O)－(CH 2 ) m2 －*。
*－(CH 2 ) n1 －NR－C(＝O)－NR－(CH 2 ) n2 －*。
In the above chemical formula, R represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include those represented by the formula (H) 1 ) L of (2) 1 And L 1’ R in-C (=O) -NR-by way of example. The two R's are optionally identical or different from each other. n is an integer of 1 to 10, more preferably an integer of 2 to 10, and still more preferably an integer of 2 to 6. m1 and m2 are each independently an integer of 0 to 4, n 'is an integer of 1 to 6, and the total of m1, m2, and n' is 1 to 8.* - (CH) 2 ) n1 －O－(CH 2 ) n2 N1 and n2 in the above are each independently an integer of 1 to 6, and the total of n1 and n2 is 2 to 10.* - (CH) 2 ) n1 －NR－C(＝O)－NR－(CH 2 ) n2 N1 and n2 in the above are each independently an integer of 1 to 6, and the total of n1 and n2 is 2 to 9.
From the standpoint of suitably obtaining the effects of the present invention, L 1 －A－L 1’ The following is preferred. In the following formulae, m1, m2, n', n1, n2 are as defined in the above formulae. In addition, in the case of the optical fiber, R in the formula-C (=O) -NR-or-NR-C (=O) -NR-represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include those represented by the formula (H) 1 ) L of (2) 1 And L 1’ R in-C (=O) -NR-by way of example.
*－(CH 2 ) n －*、－O－(CH 2 ) n －O－*。
*－O－(CH 2 ) n1 －O－(CH 2 ) n2 －O－*。
*－C(＝O)－(CH 2 ) n －C(＝O)－*。
*－C(＝O)－NR－(CH 2 ) n －O－*。
*－O－C(＝O)－(CH 2 ) n －O－*。
*－O－C(＝O)－(CH 2 ) n －O－C(＝O)－*。
*－O－C(＝O)－(CH 2 ) n －C(＝O)－O－*。
*－(CH 2 ) m1 －O－C(＝O)－(CH 2 ) n’ －C(＝O)－O－(CH 2 ) m2 －*。
*－S－(CH 2 ) n －S－*。
*－C(＝O)－NR－(CH 2 ) n －NR－C(＝O)－*。
*－C(＝O)－O－(CH 2 ) n －O－C(＝O)－*。
*－(CH 2 ) m1 －C(＝O)－O－(CH 2 ) n’ －O－C(＝O)－(CH 2 ) m2 －*。
*－O－(CH 2 ) n －*、*－S－(CH 2 ) n －*。
*－NR－C(＝O)－(CH 2 ) n －C(＝O)－NR－*。
*－(CH 2 ) n1 －NR－C(＝O)－NR－(CH 2 ) n2 －*。
Further, from the viewpoint of suitably obtaining the effect of the present invention, it is preferably- (CH) 2 ) n －*、*－O－(CH 2 ) n －O－*、*－O－(CH 2 ) n －*。
From the viewpoint of suitably obtaining the effect of the present invention, the polyamic acid ester (A) preferably contains at least one structural unit represented by the above formula (1 Da) in which Y is as a structural unit derived from diamine 1 Is a divalent organic group having three or more benzene rings.
Here, the benzene ring in the "divalent organic group having three or more benzene rings" also includes benzene rings constituting condensed rings. Then, the above formula (H) is counted 1 ) In the case of the number of benzene rings, the naphthalene ring is each provided with two benzene rings, the anthracene ring is provided with three benzene rings, and the biphenyl structure is counted as having two benzene rings.
From the viewpoint of suitably obtaining the effect of the present invention, the polyamic acid ester (A) preferably has a structural unit represented by the formula (1 Da) in which Y 1 At least one of which is Ar 1 With Ar 1’ Of the formula (H) 1 ) By a means ofDivalent organic groups shown, other Y 1 At least one of which is Ar 1 With Ar 1’ Is of a different structure formula (H) 1 ) Divalent organic groups are shown.
As Ar 1 With Ar 1’ Preferred combinations in the case of the same structure include: a combination of a biphenyl structure optionally having the above substituent and a biphenyl structure optionally having the above substituent, a combination of a naphthalene ring optionally having the above substituent and a naphthalene ring optionally having the above substituent. In addition, as Ar 1 With Ar 1’ Preferred combinations of the different structures are as follows: a combination of a benzene ring optionally having the above substituent and a biphenyl structure optionally having the above substituent, a combination of a benzene ring optionally having the above substituent and a naphthalene ring optionally having the above substituent, a combination of a biphenyl structure optionally having the above substituent and a naphthalene ring optionally having the above substituent.
From the viewpoint of suitably obtaining the effects of the present invention, Y in the above formula (1 Da) 1 The divalent organic group represented by any of the following formulas (h 1-1) to (h 1-13) is preferable. In the formulae (h 1-1) to (h 1-13), the bonding positions of the benzene ring are preferably 1-position and 4-position, and the bonding positions of the naphthalene ring are preferably 2-position and 6-position. In the formula (h 1-4), -CH 2 -a sum of 10 or less. Of the formula (h 1-7), (h 1-8), -CH 2 -the sum of the numbers is below 8, the two m optionally being identical or different from each other.
The proportion of the structural unit (a-1 Da) contained in the polyamic acid ester (A) is preferably 5 to 95 mol%, more preferably 10 to 95 mol%, and even more preferably 20 to 80 mol% based on 1 mol% of the total structural units derived from diamine contained in the polyamic acid ester (A).
Examples of the monovalent organic group of Z in the above formula (1 Da) include: monovalent hydrocarbon groups having 1 to 6 carbon atoms; the methylene group of the hydrocarbon group is replaced by-O-, -)S－、－CO－、－COO－、－COS－、－NR 3 －、－CO－NR 3 －、－Si(R 3 ) 2 - (wherein R 3 Is hydrogen atom or monovalent hydrocarbon group with 1-6 carbon atoms), -SO 2 -an isosubstituted monovalent group a; a monovalent group in which at least one of the hydrogen atoms bonded to the monovalent hydrocarbon group or the carbon atom of the monovalent group a is substituted with a halogen atom, a hydroxyl group, an alkoxy group, a nitro group, an amino group, a mercapto group, a nitroso group, an alkylsilyl group, an alkoxysilane group, a silanol group, a sulfinyl group, a phosphine group, a carboxyl group, a cyano group, a sulfo group, an acyl group or the like; monovalent groups having a heterocyclic ring.
Among them, the monovalent organic group of Z in the above formula (1 Da) is preferably 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 or a t-butoxycarbonyl group, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group.
From the viewpoint of suitably obtaining the effects of the present invention, each of the two Z in the above formula (1 Da) is independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
The polyamic acid ester (A) used in the present invention may contain a structural unit (a-1 Da-2) derived from another diamine other than the structural unit (a-1 Da) as a structural unit derived from a diamine. The structural units (a-1 Da-2) may be one or two or more.
Examples of the other diamine in the structural unit (a-1 Da-2) derived from the other diamine include the following.
There may be mentioned: p-phenylenediamine, 2,3,5, 6-tetramethyl-p-phenylenediamine, 2, 5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2, 4-dimethyl-m-phenylenediamine, 1, 4-diamino-2, 5-methoxybenzene, 2, 5-diaminotoluene, 2, 6-diaminotoluene, 4-aminobenzylamine, 2- (4-aminophenyl) ethylamine, 4- (2- (methylamino) ethyl) aniline, 4- (2-aminoethyl) aniline, 2- (6-aminonaphthyl) ethylamine, 2 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-dimethoxy-4, 4' -diaminobiphenyl, 3 '-dihydroxy-4, 4' -diaminobiphenyl, 3-trifluoromethyl-4, 4 '-diaminobiphenyl, and 2-trifluoromethyl-4, 4' -diaminobiphenyl, 3-fluoro-4, 4 '-diaminobiphenyl, 2' -difluoro-4, 4 '-diaminobiphenyl, 3' -difluoro-4, 4 '-diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl 3,3' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 3,4' -diaminobiphenyl, 4 '-diaminobiphenyl, 3' -diaminobiphenyl, 2 '-diaminobiphenyl, 2,3' -diaminobiphenyl, 1, 5-diaminonaphthalene, 1, 6-diaminonaphthalene, 1, 7-diaminonaphthalene, 2, 5-diaminonaphthalene, 2, 6-diaminonaphthalene, 2, specific diamines such as 7-diaminonaphthalene (hereinafter, these will also be referred to as specific diamines (1)).
1, 4-phenylenebis (4-aminobenzoate), 1, 4-phenylenebis (3-aminobenzoate), 1, 3-phenylenebis (4-aminobenzoate), 1, 3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate; 4,4' -diaminoazobenzene, diaminodiphenylacetylene, 4-diaminochalcone, or 4- (4, 4-trifluorobutoxy) benzoic acid [4- [ (E) -3- [2- (2, 4-diaminophenyl) ethoxy ]]-3-oxo-prop-1-enyl]Phenyl group]Esters or 4- (4, 4-trifluorobutoxy) benzoic acid [4- [ (E) -3- [ [ 5-amino-2- [ 4-amino-2- [ [ (E) -3- [4- [4- (4, 4-trifluorobutoxy) benzoyl]Oxyphenyl radical]Prop-2-enoyl]Oxymethyl group]Phenyl group]Phenyl group]Methoxy group]-3-oxo-prop-1-enyl]Phenyl group]Diamines having a photo-alignment group such as aromatic diamines having a cinnamate structure represented by esters; diamines having a photopolymerizable group at the terminal such as 2- (2, 4-diaminophenoxy) ethyl methacrylate and 2, 4-diamino-N, N-diallylaniline; 1- (4- (2, 4-diaminophenoxy) ethoxy) phenyl) -2-hydroxy-) Diamines having a radical polymerization initiator function such as 2-methyl acetone and 2- (4- (2-hydroxy-2-methylpropanoyl) phenoxy) ethyl-3, 5-diaminobenzoate; diamines having an amide bond such as 4,4' -diaminobenzanilide; diamines having urea bonds such as 1, 3-bis (4-aminophenyl) urea; h 2 N－Y D －NH 2 (Y D A divalent organic group having-N (D) - (D) in the molecule and a protecting group which is released by heating and substituted with a hydrogen atom).
3,3' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3' -diaminodiphenyl methane 3,4' -diaminodiphenylmethane, 4' -sulfonyldiphenylamine, 3' -sulfonyldiphenylamine bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4' -thiodiphenylamine, 3' -thiodiphenylamine, 1, 4-bis (4-aminophenyl) benzene 1, 3-bis (4-aminophenyl) benzene, 2' -bis [4- (4-aminophenoxy) phenyl ] propane, 2' -bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2' -bis (4-aminophenyl) hexafluoropropane, 2' -bis (3-aminophenyl) hexafluoropropane 2,2' -bis (3-amino-4-methylphenyl) hexafluoropropane, 2' -bis (4-aminophenyl) propane, 2' -bis (3-amino-4-methylphenyl) propane, 4' -diaminobenzophenone, 1, 4-bis (4-aminobenzyl) benzene; 2, 6-diaminopyridine, 3, 4-diaminopyridine, 2, 4-diaminopyrimidine, 3, 6-diaminocarbazole, N-methyl-3, 6-diaminocarbazole, 1, 4-bis- (4-aminophenyl) -piperazine, 3, 6-diaminoacridine, N-ethyl-3, 6-diaminocarbazole, N-phenyl-3, 6-diaminocarbazole, N- (3- (1H-imidazol-1-yl) propyl-3, 5-diaminobenzamide, 4- [4- [ (4-aminophenoxy) methyl ] -4, 5-dihydro-4-methyl-2-oxazolyl ] -aniline, 4- [4- [ (4-aminophenoxy) methyl ] -4, 5-dihydro-2-oxazolyl ] -aniline 1, 4-bis (p-aminobenzyl) piperazine, 4' - [4,4' -propane-1, 3-diylbis (piperidine-1, 4-diyl) ] diphenylamine, 4- (4-aminophenoxycarbonyl) -1- (4-aminophenyl) piperidine, 2, 5-bis (4-aminophenyl) pyrrole, 4' - (1-methyl-1H-pyrrole-2, 5-diyl) bis [ aniline ], 1, 4-bis- (4-aminophenyl) -piperazine, 2-N- (4-aminophenyl) pyridine-2, 5-diamine, 2-N- (5-aminopyridin-2-yl) pyridine-2, 5-diamine, 2- (4-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl) -6-aminobenzimidazole, A heterocyclic ring-containing diamine such as 5- (1H-benzimidazol-2-yl) benzene-1, 3-diamine, or a diamine represented by the following formulas (z-1) to (z-5); or a diamine having at least one nitrogen atom structure (wherein, in the following, amino groups derived from-N (D) - (D represent protecting groups which are detached and substituted with hydrogen atoms by heating), which is represented by a diamine having a diphenylamine structure such as 4,4' -diaminodiphenylamine, 4' -diaminodiphenyl-N-methylamine, N ' -bis (4-aminophenyl) -benzidine, N ' -bis (4-aminophenyl) -N, N ' -dimethyl-1, 4-phenylenediamine, or the like, and which is selected from the group consisting of a heterocyclic ring having a nitrogen atom, a secondary amino group and a tertiary amino group.
2, 4-diaminophenol, 3, 5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4, 6-diaminoresorcinol, 4 '-diamino-3, 3' -dihydroxybiphenyl; 2, 4-diaminobenzoic acid, 2, 5-diaminobenzoic acid, 3, 5-diaminobenzoic acid, 4' -diaminobiphenyl-3-carboxylic acid, 4' -diaminodiphenylmethane-3-carboxylic acid, 4' -diaminodiphenylethane-3-carboxylic acid, 4' -diaminobiphenyl-3, 3' -dicarboxylic acid, 4' -diaminobiphenyl-2, 2' -dicarboxylic acid diamines having a carboxyl group such as 3,3' -diaminobiphenyl-4, 4' -dicarboxylic acid, 3' -diaminobiphenyl-2, 4' -dicarboxylic acid, 4' -diaminodiphenylmethane-3, 3' -dicarboxylic acid, 4' -diaminodiphenylethane-3, 3' -dicarboxylic acid, and 4,4' -diaminodiphenylether-3, 3' -dicarboxylic acid; 1- (4-aminophenyl) -1, 3-trimethyl-1H-indan-5-amine, 1- (4-aminophenyl) -2, 3-dihydro-1, 3-trimethyl-1H-inden-6-amine; diamines having a steroid skeleton such as cholesteryl-3, 5-diaminobenzene, cholesteryloxy-2, 4-diaminobenzene, 3, 5-diaminobenzoate cholesteryl ester, 3, 5-diaminobenzoate lanostanyl ester, and 3, 6-bis (4-aminobenzoyloxy) cholestane; diamines represented by the following formulas (V-1) to (V-2); diamines having a siloxane bond such as 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane; acyclic aliphatic diamines such as m-xylylenediamine, 1, 3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc., alicyclic diamines such as 1, 3-bis (aminomethyl) cyclohexane, 1, 4-diaminocyclohexane, 4' -methylenebis (cyclohexylamine), etc.; diamine in which two amino groups are bonded to a group represented by any of the formulae (Y-1) to (Y-167) described in WO2018/117239, and the like.
(in the formula (V-1), m and n are integers of 0 to 3 (wherein, m+n is 1.ltoreq.m.ltoreq.4), j is 0 or an integer of 1, X 1 Represents- (CH) 2 ) a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N (CH) 3 )－、－NH－、－O－、－CH 2 O－、－CH 2 -OCO-, -COO-or-OCO-. R is R 1 Represents a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 10 carbon atoms, a carbon atom-3 to 10 alkyl group, a carbon atom-3 to 10 alkoxy group or a carbon atom-3 to 10 alkoxyalkyl group. In the formula (V-2), X 2 represents-O-, -CH 2 O－、－CH 2 －OCO－、－COO-or-OCO-, in m, n, X 1 、R 1 In the case where there are two, each independently has the above definition. )
In the-N (D) -of the other diamine, D is preferably a urethane-based organic group represented by a benzyloxycarbonyl group, a 9-fluorenylmethoxycarbonyl group, an allyloxycarbonyl group, a Boc group, or the like. The Boc group is particularly preferable from the viewpoint of good heat release efficiency, release at a relatively low temperature, and discharge as a harmless gas during release.
Preferable examples of the diamine having a heat-releasable group, which is exemplified as the other diamine, are preferably selected from diamines of the following formulas (d-1) to (d-7).
(in the formulae (d-2), (d-6) and (d-7), R represents a hydrogen atom or a Boc group.)
In the case where the polyamic acid ester (A) used in the present invention has the structural unit (a-1 Da-2), it is more preferable to contain the structural unit derived from the above-mentioned specific diamine (1) from the viewpoint of suitably obtaining the effect of the present invention. The structural unit derived from the specific diamine (1) is preferably 5 to 95 mol%, more preferably 5 to 90 mol%, and even more preferably 20 to 80 mol% based on 1 mol of the total structural units derived from the diamine contained in the polyamic acid ester (a).
In addition, the polyamic acid ester (A) may contain, as the structural unit (a-1 Da-2), a structural unit derived from the diamine having a heat-peelable group, from the viewpoint of improving the double-layer separation from the polyamic acid (B). The structural unit derived from the diamine having a heat-peelable group is preferably 5 to 40 mol%, more preferably 5 to 35 mol%, and even more preferably 5 to 30 mol% based on 1 mol of the total structural units derived from the diamine contained in the polyamic acid ester (a).
< Polyamic acid (B) >)
The liquid crystal aligning agent of the invention contains the polyamic acid ester (A) and the polyamic acid (B), wherein the polyamic acid (B) has a structural unit (B-1 Tb) shown in the formula (1 Tb) as a structural unit derived from a tetracarboxylic acid derivative, and has a structural unit (B-1 Db) shown in the formula (1 Db) as a structural unit derived from diamine. The polyamic acid (B) may be one kind or two or more kinds. The structural units constituting the polyamic acid (B) may be one or two or more types. The polyamic acid (B) preferably does not have the structural unit (a-1 Ta) and the structural unit (a-1 Da) of the polyamic acid ester (A) in the same molecule.
X is represented by the above formula (1 Tb) b Examples of the tetravalent organic group in (a) include: specific examples of the tetravalent organic group obtained by removing two acid dianhydride groups from the acyclic aliphatic tetracarboxylic dianhydride, the tetravalent organic group obtained by removing two acid dianhydride groups from the alicyclic tetracarboxylic dianhydride, or the tetravalent organic group obtained by removing two acid dianhydride groups from the aromatic tetracarboxylic dianhydride include the above-mentioned X 2a Tetravalent organic groups are shown by way of example.
The aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an aromatic ring.
The acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. The aromatic hydrocarbon compound may have an alicyclic structure or an aromatic ring structure in a part thereof, without being composed of only a chain hydrocarbon structure.
The alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an alicyclic structure. Wherein none of the four carboxyl groups is bonded to an aromatic ring. Further, the structure need not be composed of only an alicyclic structure, and may have a chain hydrocarbon structure or an aromatic ring structure in a part thereof.
From the viewpoint of suitably obtaining the effects of the present invention, X is as described above b The tetravalent organic group in (2) is preferably derived from a compound having a structure selected from the group consisting of benzene rings, cyclobutane rings, and cyclopenteneAn alkane ring structure and a cyclohexane ring structure. More preferably X b Examples thereof include a tetravalent organic group represented by the above formula (g), X in the above formula (2 Ta) 2a The structure shown in the above example is more preferably a tetravalent organic group obtained by removing two acid dianhydride groups from the other tetracarboxylic dianhydrides shown in the above polyamide acid ester (a). Among them, from the viewpoint of improving the liquid crystal alignment, the acyclic aliphatic or alicyclic tetracarboxylic dianhydride is preferably a tetracarboxylic dianhydride having at least one partial structure selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure and a cyclohexane ring structure.
In the polyamide acid (B), from the viewpoint of suitably obtaining the effect of the present invention, the structural unit (B-1 Tb) is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, based on 1 mol% or more of all structural units derived from the tetracarboxylic acid derivative contained in the polyamide acid (B), and the structural unit (B-1 Tb) is X b The quaternary organic group is a quaternary organic group obtained by removing two acid anhydride groups from acyclic aliphatic tetracarboxylic dianhydride, a quaternary organic group obtained by removing two acid anhydride groups from alicyclic tetracarboxylic dianhydride, or a quaternary organic group obtained by removing two acid anhydride groups from aromatic tetracarboxylic dianhydride.
Y as the above formula (1 Tb) b Examples of the divalent organic group include the above Y 1 And a divalent organic group obtained by removing two amino groups from the other diamine shown by way of example in the polyamic acid ester (A). From the viewpoint of few afterimages derived from residual DC, Y is the polyamic acid (B) b Preferably a diamine having a urea bond (for example, the above formula (H) 1 ) Wherein A represents a divalent organic group (q 2), in the formula (H) 1 ) A diamine in which two amino groups are bonded to the divalent organic group shown; or a diamine having a urea bond or the like as exemplified in the other diamines), the diamine having an amide bond, the diamine having a specific nitrogen atom-containing structure, the diamine having a carboxyl group, 4 '-diaminodiphenylmethane, 3,4' -diaminodiphenylmethaneDivalent organic groups (also referred to as specific divalent organic groups) obtained by removing two amino groups from 3,3 '-dimethyl-4, 4' -diaminodiphenylmethane, p-phenylenediamine and m-phenylenediamine.
From the viewpoint of less residual image originating from residual DC, the polyamide acid (B) may contain 5 mol% or more, preferably 10 mol% or more, and more preferably 20 mol% or more of the structural unit (B-1 Db) represented by the formula (1 Db) with respect to 1 mol% or more of the total structural units originating from diamine of the polyamide acid (B), wherein Y in the formula (1 Db) b Is a divalent organic group as specified above.
Examples of the monovalent organic group of Z in the formula (1 Db) include structures shown by way of example for Z in the formula (1 Da).
In the liquid crystal aligning agent of the present invention, the content ratio of the polyamic acid ester (a) to the polyamic acid (B) may be 10/90 to 90/10, may be 20/80 to 90/10, or may be 20/80 to 80/20 in terms of the mass ratio of [ polyamic acid ester (a)/polyamic acid (B) ] from the viewpoint of less residual image derived from residual DC.
< production of Polyamic acid and Polyamic acid ester >
The polyamic acid esters such as the polyamic acid ester (a) and the polyamic acid esters such as the polyamic acid (B) contained in the liquid crystal aligning agent of the present invention can be produced by, for example, the following methods. In this case, as the tetracarboxylic acid derivative, not only tetracarboxylic dianhydride but also a tetracarboxylic dihalide compound, a tetracarboxylic dialkyl ester dihalide, or the like as a derivative thereof may be used.
(production of Polyamic acid)
By reacting the tetracarboxylic dianhydride component with the diamine component, a polymer having an amic acid structure (polyamic acid) can be obtained. In the case where the polyamic acid has a structure represented by the above formula (1 Db), for example, a diamine component having a structure of-N (Z) -Y is used 1 -structure of N (Z) -structure (Y 1 The definition of Z is the same as that of the above), and the tetracarboxylic acid derivative component having X is used b (X b The definition of (c) is the same as that of the above).
The polyamic acid ester (A) may be, for example, a polyamide ester containing the following formula (T) 1 ) The tetracarboxylic acid derivative component of the tetracarboxylic dianhydride shown and the composition containing the compound of formula (D 1 ) The diamine component of the diamine is reacted to obtain a polyamic acid, and then the polyamic acid ester is obtained by a method described below.
(R 11 ～R 14 R of the formula (1 Ta) 11 ～R 14 Meaning is the same, Y 1 And Z is respectively equal to Y of formula (1 Ta) 1 The same meaning as Z of formula (1 Da). )
The ratio of the tetracarboxylic dianhydride to the diamine used for producing the polyamic acid is preferably 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents of the acid anhydride group of the tetracarboxylic dianhydride relative to 1 equivalent of the amino group of the diamine. The molecular weight of the polyamide acid to be produced increases as the equivalent of the acid anhydride group of the tetracarboxylic dianhydride approaches 1 equivalent, as in the usual polycondensation reaction.
The reaction temperature in the production of the polyamic acid is preferably-20 to 150 ℃, more preferably 0 to 100 ℃. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.
The polyamic acid can be produced at any concentration, and is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction may be performed at a high concentration at the beginning of the reaction, and then a solvent may be added.
Specific examples of the organic solvent used for producing the polyamic acid include: cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, 1, 3-dimethyl-2-imidazolidinone. In addition, when the solvent solubility of the produced polyamic acid is high, a solvent such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, or diethylene glycol monoethyl ether may be used.
(production of Polyamic acid ester)
The polyamic acid ester can be obtained by, for example, the following known methods: [I] a method of reacting the polyamic acid obtained by the above-described method with an esterifying agent; [ II ] a method in which a tetracarboxylic acid diester is reacted with a diamine, preferably in an organic solvent, in the presence of a dehydration catalyst (e.g., 4- (4, 6-dimethoxy-1, 3, 5-triazin-2-yl) -4-methylmorpholinium halide, carbonylimidazole, phosphorus-based condensing agent, etc.); [ III ] A method in which a tetracarboxylic acid diester dihalide and a diamine are reacted, preferably in an organic solvent, in the presence of a base (for example, a tertiary amine such as pyridine or triethylamine, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium, potassium or other alkali metals); and a method in which the polyamic acid is reacted with a dehydration condensing agent (such as trifluoroacetic anhydride) to effect imidization, and then an alcohol (for example, an aliphatic alcohol such as methanol, ethanol, n-propanol, isopropanol, butanol, or t-butanol) is reacted.
The tetracarboxylic acid diester used in the above [ II ] can be obtained by ring-opening a tetracarboxylic acid dianhydride with an alcohol or the like. The tetracarboxylic acid diester dihalide used in the above [ III ] can be obtained by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride. In the case where the polyamic acid ester is obtained as a solution by the above-mentioned reaction, the solution may be used for preparing a liquid crystal aligning agent while maintaining the state, or may be used for preparing a liquid crystal aligning agent on the basis of isolating the polyamic acid ester contained in the reaction solution.
As a more preferable method of the above [ I ], there is a method of obtaining a polyamic acid ester by adding an esterifying agent to a solution of a polyamic acid and stirring. The solvent used in the reaction may be the same as the organic solvent exemplified as the solvent used in the production of the polyamic acid. The reaction is carried out in an organic solvent, preferably at a reaction temperature of 0 to 100 ℃, more preferably 0 to 50 ℃ for 0.5 to 48 hours. The esterification agent may be added at the time of preparing a liquid crystal alignment agent described later to form a polyamic acid ester.
Above [ I ] ]In the method of (2), the esterification rate can be arbitrarily adjusted by changing the addition amount of the esterifying agent to be used. The term "esterification rate" as used herein means, for example, in the case of the polyamic acid ester (A), the ratio of the polyamic acid ester structure obtained by esterification is expressed in% based on the total amic acid structure of the polyamic acid before esterification. The esterification rate can be used 1 H-NMR was estimated from the amount of change in the peak intensity of the carboxyl group. The esterification rate of the polyamic acid ester (a) used in the present invention is preferably 5 to 100%, more preferably 25 to 100%, and even more preferably 25 to 65%.
The amount of the esterifying agent added in the method of the above [ I ] is 0.01 to 50 molar equivalents, more preferably 0.1 to 20 molar equivalents, still more preferably 1 to 10 molar equivalents, to 1 molar equivalent of the constituent unit of the amic acid contained in the polyamic acid.
In the case of obtaining a polyamide acid ester having a tertiary butyl ester structure, examples of the esterifying agent include: tert-butyl 2, 2-trichloroacetimidate, O-tert-butyl-N, N' -diisopropylisourea, N-dimethylformamide di-tert-butyl acetal.
Solution viscosity/molecular weight of Polyamic acid and Polyamic acid ester
When the polyamic acid or polyamic acid ester used in the present invention is prepared into a solution having a concentration of 10 to 15 mass%, a solution having a solution viscosity of 10 to 1000mpa·s is preferable from the viewpoint of workability. The solution viscosity (mpa·s) of the polymer is a value measured at 25 ℃ using an E-type rotational viscometer on a polymer solution having a concentration of 10 to 15 mass% prepared using a good solvent (for example, γ -butyrolactone, N-methyl-2-pyrrolidone, etc.) for the polymer.
The weight average molecular weight (Mw) of the polyamic acid and the polyamic acid ester in terms of polystyrene as measured by Gel Permeation Chromatography (GPC) is preferably 1000 to 500000, more preferably 2000 to 300000. 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. By falling within such a molecular weight range, good alignment and stability of the liquid crystal display element can be ensured.
< blocking agent >
In the polyamic acid ester and polyamic acid in the present invention, when producing them, a polymer having a terminal end can be produced by using an appropriate terminal-blocking agent together with the tetracarboxylic acid derivative component and the diamine component as described above. The end-capped polymer has the effect of improving the film hardness of the liquid crystal alignment film obtained from the coating film and improving the adhesion property between the sealant and the liquid crystal alignment film.
Examples of the terminal ends of the polyamic acid ester (a) and the polyamic acid (B) in the present invention include: amino, carboxyl, acid anhydride groups or groups derived from a capping agent described below. The amino group, carboxyl group, acid anhydride group can be obtained by a general condensation reaction or by capping with the following capping agent.
Examples of the blocking agent include: acid monoanhydrides such as acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxy phthalic anhydride, trimellitic anhydride, 3- (3-trimethoxysilyl) propyl-3, 4-dihydrofuran-2, 5-dione, 4,5,6, 7-tetrafluoroisobenzofuran-1, 3-dione, and 4-ethynylphthalic anhydride; dicarbonate diester compounds such as di-t-butyl dicarbonate and diallyl dicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride and nicotinyl chloride; monoamine compounds such as 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, n-heptylamine, and n-octylamine; monoisocyanate compounds such as isocyanate having an unsaturated bond, e.g., ethyl isocyanate, phenyl isocyanate, naphthalene isocyanate, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate; isothiocyanate compounds such as ethyl isothiocyanate and allyl isothiocyanate.
The ratio of the end-capping agent is preferably 0.01 to 20 parts by mol, more preferably 0.01 to 10 parts by mol, based on 100 parts by mol of the total diamine components used in the production of the polymer.
< liquid Crystal alignment agent >)
The liquid crystal aligning agent of the present invention contains a polyamic acid ester (A) and a polyamic acid (B). The liquid crystal aligning agent of the present invention may contain other polymers in addition to the polyamic acid ester (a) and the polyamic acid (B).
Specific examples of the other polymer include: and a polymer selected from the group consisting of polyimide precursors other than the polyamic acid ester (a) and the polyamic acid (B), polyimide, polysiloxane, polyester, polyamide, polyurea, polyurethane, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-maleic anhydride) copolymer, poly (isobutylene-maleic anhydride) copolymer, poly (vinyl ether-maleic anhydride) copolymer, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, and the like.
Specific examples of the poly (styrene-maleic anhydride) copolymer include: SMA1000, SMA2000, SMA3000 (manufactured by Cray Valley company), GSM301 (manufactured by Gifu Shellac Manufacturing company), and the like. As a specific example of the poly (isobutylene-maleic anhydride) copolymer, ISOBAM-600 (manufactured by Kuraray Co., ltd.) can be given. As a specific example of the poly (vinyl ether-maleic anhydride) copolymer, gantrez AN-139 (methyl vinyl ether-maleic anhydride resin, manufactured by Ashland Co., ltd.) is given. Two or more other polymers may be used in combination.
The content of the other polymer is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, and still more preferably 20 to 80 parts by mass, based on 100 parts by mass of the total polymer contained in the liquid crystal aligning agent.
The liquid crystal aligning agent is used for producing a liquid crystal alignment film, and is in the form of a coating liquid from the viewpoint of forming a uniform thin film. In the liquid crystal aligning agent of the present invention, a coating liquid containing the polymer component and an organic solvent is also preferable. In this case, the concentration of the polymer in the liquid crystal aligning agent may be appropriately changed according to the setting of the thickness of the coating film to be formed. The concentration of the polymer in the liquid crystal aligning agent 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 storage stability of the solution. The concentration of the particularly preferred polymer is 2 to 8 mass%.
The organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as the polymer component is uniformly dissolved. Specific examples thereof include: n, N-dimethylformamide, N-dimethylacetamide, N-dimethylformamide, N-dimethylpropionamide, N-diethylpropionamide, tetramethylurea, N-diethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, gamma-butyrolactone, gamma-valerolactone, 1, 3-dimethyl-2-imidazolidinone, methylethylketone, cyclohexanone, cyclopentanone, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-N-propyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-N-butyl-2-pyrrolidone, N-t-butyl-2-pyrrolidone, N-N-pentyl-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone (also collectively referred to as "good solvents"). Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide or gamma-butyrolactone is 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 of the entire solvent contained in the liquid crystal aligning agent.
The organic solvent contained in the liquid crystal aligning agent is preferably a mixed solvent of the above solvents and a solvent (also referred to as a poor solvent) that improves the coatability and surface smoothness of the coating film when the liquid crystal aligning agent is applied. 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 of the entire solvent contained in the liquid crystal aligning agent. The type and content of the poor solvent are appropriately selected according to the application apparatus, application conditions, application environment, and the like of the liquid crystal aligning agent.
Specific examples of the poor solvent to be used in combination are described below, but the present invention is not limited thereto.
For example, there may be mentioned: diisopropyl ether, diisobutyl methanol (2, 6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1, 2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentanyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisopentyl ether, ethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 1- (2-butoxyethoxy) -2-propanol 2- (2-butoxyethoxy) -1-propanol, propylene glycol monomethyl ether acetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, 4-methyl-2-pentyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, diisobutylketone (2, 6-dimethyl-4-heptanone) and the like.
Among these, diisobutylmethanol, 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 acetate, or diisobutylketone are preferable as the poor solvent.
Preferable combinations of the good solvent and the poor solvent include: n-methyl-2-pyrrolidone and ethylene glycol monobutyl ether; n-methyl-2-pyrrolidone, gamma-butyrolactone, and ethylene glycol monobutyl ether; n-methyl-2-pyrrolidone, gamma-butyrolactone, and propylene glycol monobutyl ether; n-ethyl-2-pyrrolidone and propylene glycol monobutyl ether; n-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone; n-ethyl-2-pyrrolidone and propylene glycol diacetate; n, N-dimethyl lactamide and diisobutyl ketone; n-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate; n-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate; n-methyl-2-pyrrolidone, ethyl 3-ethoxypropionate, dipropylene glycol monomethyl ether; n-ethyl-2-pyrrolidone, ethyl 3-ethoxypropionate, and propylene glycol monobutyl ether; n-methyl-2-pyrrolidone, ethyl 3-ethoxypropionate, and diethylene glycol monopropyl ether; n-ethyl-2-pyrrolidone, ethyl 3-ethoxypropionate, and diethylene glycol monopropyl ether; n-methyl-2-pyrrolidone with ethylene glycol monobutyl ether acetate; n-ethyl-2-pyrrolidone and dipropylene glycol dimethyl ether; n, N-dimethyl lactamide with ethylene glycol monobutyl ether; n, N-dimethyl lactamide with propylene glycol diacetate; n-ethyl-2-pyrrolidone and diethylene glycol diethyl ether; n-ethyl-2-pyrrolidone, diethylene glycol monoethyl ether, and butyl cellosolve acetate; n-methyl-2-pyrrolidone, diethylene glycol monomethyl ether, and butyl cellosolve acetate; n, N-dimethyl lactamide and diethylene glycol diethyl ether; n-methyl-2-pyrrolidone, gamma-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol diethyl ether; n-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, and 4-hydroxy-4-methyl-2-pentanone; n-ethyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol monobutyl ether; n-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and diisobutyl ketone; n-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, dipropylene glycol monomethyl ether; n-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol monobutyl ether; n-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol diacetate; n-ethyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, dipropylene glycol dimethyl ether; gamma-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, diisobutylketone; gamma-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol diacetate; n-methyl-2-pyrrolidone, gamma-butyrolactone, propylene glycol monobutyl ether, and diisobutyl ketone; n-methyl-2-pyrrolidone, gamma-butyrolactone, propylene glycol monobutyl ether, and diisopropyl ether; n-methyl-2-pyrrolidone, gamma-butyrolactone, propylene glycol monobutyl ether, and diisobutyl methanol; n-methyl-2-pyrrolidone, gamma-butyrolactone, and dipropylene glycol dimethyl ether; n-methyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol dimethyl ether; n-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether; n-ethyl-2-pyrrolidone, diethylene glycol diethyl ether, and dipropylene glycol monomethyl ether; n-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and propylene glycol diacetate; n-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and diisobutyl ketone; n-ethyl-2-pyrrolidone, gamma-butyrolactone, and diisobutyl ketone; n-ethyl-2-pyrrolidone, N-dimethyl lactamide, and diisobutyl ketone; n-methyl-2-pyrrolidone, ethylene glycol monobutyl ether, and ethylene glycol monobutyl ether acetate; gamma-butyrolactone, ethylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether; n-ethyl-2-pyrrolidone, ethylene glycol monobutyl ether acetate, and propylene glycol dimethyl ether; n-methyl-2-pyrrolidone, 4-methyl-2-pentyl acetate, and ethylene glycol monobutyl ether; n-ethyl-2-pyrrolidone, cyclohexyl acetate, diacetone alcohol cyclohexanone, and propylene glycol monomethyl ether; cyclopentanone and propylene glycol monomethyl ether; n-methyl-2-pyrrolidone, cyclohexanone, propylene glycol monomethyl ether, and the like.
The liquid crystal aligning agent of the present invention may contain components other than the polymer component and the organic solvent (hereinafter, also referred to as additive components). The additive components include: an adhesion promoter for improving adhesion between the liquid crystal alignment film and the substrate and adhesion between the liquid crystal alignment film and the sealant; a compound for improving the strength of the liquid crystal alignment film (hereinafter, also referred to as a crosslinkable compound); a compound for promoting imidization; a dielectric or conductive material for adjusting the dielectric constant and resistance of the liquid crystal alignment film.
From the viewpoint of suitably obtaining the effect of the present invention, the crosslinkable compound may be at least one compound selected from the group consisting of: a compound having at least one group selected from the group consisting of an oxirane group, an oxetane group, a protected isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, a group containing a Mi acid structure, a cyclic carbonate group, and a hydroxyalkylamide bond; phenol compounds having at least one of alkoxymethyl and hydroxymethyl; and a compound having a polymerizable unsaturated group.
Specific examples of the above-mentioned compound having an oxirane group include: bisphenol A type epoxy resins such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2-dibromoneopentyl glycol diglycidyl ether, 1,3,5, 6-tetraglycidyl-2, 4-hexanediol, EPIKOTE 828 (manufactured by Mitsubishi Chemical), bisphenol F type epoxy resins such as EPIKOTE 807 (manufactured by Mitsubishi Chemical), hydrogenated bisphenol A type epoxy resins such as YX-8000 (manufactured by Mitsubishi Chemical), epoxy resins containing a biphenyl skeleton such as YX6954BH30 (manufactured by Mitsubishi Chemical), phenol novolac type epoxy resins such as EPPN-201 (manufactured by Japanese chemical Co., ltd.), triglycidyl isocyanurate such as EOCN-102S (manufactured by Japanese chemical Co., ltd.), and triglycidyl isocyanurate such as TEIKOTE 2021 (manufactured by Japanese chemical Co., ltd.), and Cell chemical Co., ltd.), N, N ' -tetraglycidyl m-xylylenediamine, 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane, tetrakis (glycidyloxymethyl) methane.
Specific examples of the oxetanyl group-containing compound include compounds having two or more oxetanyl groups described in paragraphs 0170 to 0175 of WO 2011/132751.
Specific examples of the compound having a protected isocyanate group include: the compounds having two or more protected isocyanate groups described in paragraphs 0046 to 0047 of JP-A2014-224978, the compounds having three or more protected isocyanate groups described in paragraphs 0119 to 0120 of WO2015/141598, and the like. As commercially available products, for example, CORONATE AP stable M, CORONATE 2503, 2515, 2507, 2513, 2555, MILLIONATE MS-50 (manufactured by Tosoh Co., ltd., above), TAKENATE B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (manufactured by Mitsui Co., ltd., above) and the like can be preferably used. Further, a compound having two or more protecting isothiocyanate groups described in Japanese patent application laid-open No. 2016-200798 is exemplified.
Specific examples of the compound having a group containing an oxazoline ring structure include: the compound having two or more oxazoline ring structures described in paragraph 0115 of japanese patent application laid-open No. 2007-286597 is preferably an oxazoline group-containing compound such as 2,2' -bis (2-oxazoline), 2' -bis (4-methyl-2-oxazoline), 2' -bis (5-methyl-2-oxazoline), 1,2, 4-tris- (2-oxazolinyl-2) -benzene, eporos (manufactured by japan catalyst corporation).
Specific examples of the compound having a group containing a Mi's acid structure include compounds having two or more Mi's acid structures described in WO 2012/091088.
Specific examples of the compound having a cyclic carbonate group include compounds described in WO 2011/155577. Specific examples of the compound having a hydroxyalkylamide bond include: a compound described in paragraph 0058 of Japanese patent application laid-open No. 2016-118753, WO 2015/072554; the compound described in Japanese patent application laid-open No. 2016-200798 is preferably N, N, N ', N' -tetrakis (2-hydroxyethyl) adipamide or the like.
Specific examples of the phenol compound having at least one of an alkoxyalkyl group and a hydroxymethyl group include compounds described in WO2010/074269, and preferably 2, 2-bis (4-hydroxy-3, 5-dihydroxymethylphenyl) propane, 2-bis (4-hydroxy-3, 5-dimethoxymethylphenyl) propane, and 2, 2-bis (4-hydroxy-3, 5-dihydroxymethylphenyl) -1, 3-hexafluoropropane. Examples of the compound having a polymerizable unsaturated bond include: glycerol mono (meth) acrylate, glycerol di (meth) acrylate (1, 2-, 1, 3-type mixture), glycerol tri (meth) acrylate, glycerol 1, 3-diglycerol alkyd di (meth) acrylate, pentaerythritol tri (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, pentaethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, and the like. The above-mentioned compound is an example of a crosslinkable compound, and is not limited thereto. For example, there may be mentioned: components other than those disclosed in paragraph 0105 to 0116 on pages 55 of WO2015/060357, etc. Further, two or more kinds of crosslinkable compounds may be combined.
Among the crosslinkable compounds, N, N, N ', N ' -tetraglycidyl m-xylylenediamine, 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, N, N, N ', N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane, TAKENATE B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N, 1,3, 5-tris (2-hydroxyethyl) isocyanurate, triglycidyl isocyanurate, N, N, N ', N ' -tetrakis (2-hydroxyethyl) adipamide, 2-bis (4-hydroxy-3, 5-dihydroxymethylphenyl) propane, 2-bis (4-hydroxy-3, 5-dimethoxymethylphenyl) propane, 2-bis (4-hydroxy-3, 5-dihydroxymethylphenyl) -1, 3-hexafluoropropane are preferable.
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, more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent, from the viewpoint of suitably obtaining the effect of the present invention.
Examples of the adhesion promoter include: 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl diethoxymethyl silane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxy silane, 3-ureidopropyl trimethoxysilane, 3-ureidopropyl triethoxysilane, N-ethoxycarbonyl-3-aminopropyl trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-epoxypropoxy propylmethyldimethoxy silane, 3-epoxypropoxy propyltrimethoxysilane, p-styryl trimethoxysilane, 3-methacryloxypropylmethyldimethoxy silane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxy silane, 3-mercapto propyl silane, 3-glycidoxypropyl silyl (mercapto) coupling agent, 3-mercapto propyl silane, etc. In the case of using the silane coupling agent, the amount of the silane coupling agent is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the polymer component contained in the liquid crystal aligning agent, from the viewpoint of exhibiting good resistance to an AC residual image.
The compound for promoting imidization is preferably a compound having a basic site (for example, a primary amino group, an aliphatic heterocycle (for example, a pyrrolidine skeleton), an aromatic heterocycle (for example, an imidazole ring, an indole ring), a guanidino group, or the like) (excluding the crosslinkable compound and the adhesion promoter), or a compound that generates the basic site at the time of firing. More preferably, the compound is a compound which generates the above-mentioned basic site at the time of firing, and specific examples thereof include amino acids in which a part or all of the basic site of the amino acid is protected with a protecting group (for example, a urethane protecting group such as a Boc group or a 9-fluorenylmethoxycarbonyl group). Specific examples of the amino acid include: glycine, alanine, cysteine, methionine, asparagine, glutamic acid, valine, leucine, phenylalanine, tyrosine, tryptophan, proline, hydroxyproline, arginine, histidine, lysine, ornithine. More preferable specific examples of the compound for promoting imidization include N-. Alpha. - (9-fluorenylmethoxycarbonyl) -N-. Tau. - (t-butoxycarbonyl) -L-histidine.
The content of the compound for promoting imidization is preferably 2 parts by mole or less, more preferably 1 part by mole or less, and still more preferably 0.5 part by mole or less, with respect to the polyamic acid ester or the amic acid site of the polyamic acid or 1 part by mole of the amic acid ester site.
The solid content concentration (the ratio of the total mass of the components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) in the liquid crystal aligning agent is appropriately selected in consideration of viscosity, volatility, and the like, and is preferably in the range of 1 to 10 mass%.
The particularly preferable range of the solid content concentration varies depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, in the case of spin coating, the solid content concentration is particularly preferably in the range of 1.5 to 4.5 mass%. When the printing method is used, it is particularly preferable to set the solid content concentration to a range of 3 to 9 mass%, and thereby set the solution viscosity to a range of 12 to 50mpa·s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration to a range of 1 to 5 mass%, and thereby set the solution viscosity to a range of 3 to 15mpa·s. The temperature at which the polymer composition is prepared is preferably 10 to 50℃and more preferably 20 to 30 ℃.
Liquid crystal alignment film/liquid crystal display element
The liquid crystal alignment film of the present invention is obtained from the liquid crystal alignment agent. The liquid crystal alignment film of the present invention can be used for a liquid crystal display element of a horizontal alignment type or a vertical alignment type (VA type), but is preferably used for a liquid crystal display element of a horizontal alignment type such as an IPS type or FFS type. The liquid crystal alignment film of the present invention is preferably used for a liquid crystal alignment film for a photo-alignment treatment method.
The liquid crystal display element of the present invention includes the liquid crystal alignment film, and can be manufactured by a method including the following steps (1) to (3) and (5) or steps (1) to (2) and (5), for example. More preferably, the method includes steps (1) to (5).
< procedure (1): process of applying liquid Crystal alignment agent to substrate
The step (1) is a step of applying a liquid crystal aligning agent to a substrate. Specific examples of the step (1) are as follows.
The liquid crystal aligning agent is applied to one surface of the substrate provided with the patterned transparent conductive film by a suitable application method such as a roll coater method, a spin coating method, a printing method, an inkjet method, or the like. The material of the substrate is not particularly limited as long as it is a substrate having high transparency, and plastics such as acrylic, polycarbonate, and the like may be used together with glass and silicon nitride. In the reflective liquid crystal display element, an opaque body such as a silicon wafer may be used as the substrate on only one side, and a material reflecting light such as aluminum may be used as the electrode in this case. In the case of manufacturing an IPS mode or FFS mode liquid crystal display device, a substrate provided with an electrode formed of a transparent conductive film or a metal film patterned into a comb-teeth shape and a counter substrate provided with no electrode are used.
Examples of the method of applying the liquid crystal aligning agent to the substrate and forming a film include: screen printing, offset printing, flexography, inkjet or spray printing, and the like. Among them, a coating method and a film forming method using an inkjet method can be preferably used.
< procedure (2): firing the applied liquid crystal aligning agent
The step (2) is a step of forming a film by baking a liquid crystal aligning agent applied to a substrate. Specific examples of the step (2) are as follows.
After the liquid crystal alignment agent is coated on the substrate in the step (1), the solvent may be evaporated by a heating means such as a heating plate, a thermal cycle oven, or an IR (infrared) oven; or thermal imidization of the polyamic acid or polyamic acid ester. The drying and firing steps after the application of the liquid crystal aligning agent of the present invention may be performed at any temperature and for any time or may be performed a plurality of times. The firing temperature may be, for example, 40 to 180 ℃. From the viewpoint of shortening the process, it may be carried out at 40 to 150 ℃. The firing time in this case is not particularly limited, and may be 1 to 10 minutes or 1 to 5 minutes. In the case of thermal imidization of the polyamic acid or polyamic acid ester, for example, a step of baking at 150 to 300℃or 150 to 250℃may be added. The firing time in this case is not particularly limited, and examples thereof include firing times of 5 to 40 minutes or 5 to 30 minutes.
If the film after firing is too thin, the reliability of the liquid crystal display element may be lowered, and thus it is preferably 5 to 300nm, more preferably 10 to 200nm.
< procedure (3): process for orientation treatment
The step (3) is a step of optionally subjecting the fired film (coating film) obtained in the step (2) to an orientation treatment. That is, in a liquid crystal display element of a horizontal alignment type such as an IPS type or FFS type, the coating film is subjected to an alignment ability imparting treatment. On the other hand, in a vertically aligned liquid crystal display element such as a VA system or PSA system (Polymer Sustained Alignment: polymer stabilized alignment), a formed coating film may be used as a liquid crystal alignment film while maintaining the state, or the coating film may be subjected to an alignment ability imparting treatment. As the alignment treatment method of the liquid crystal alignment film, a rubbing treatment method and a photo-alignment treatment method are exemplified, and a photo-alignment treatment method is more preferable. As the photo-alignment treatment method, the following method can be mentioned: the surface of the film is irradiated with radiation biased in a predetermined direction, and in some cases, it is preferable to heat the film at a temperature of 150 to 250 ℃ to impart liquid crystal alignment (also referred to as liquid crystal alignment ability). As the radiation, ultraviolet or visible light having a wavelength of 100 to 800nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400nm are preferable, and ultraviolet rays having a wavelength of 200 to 400nm are more preferable.
The radiation is preferably applied in an amount of 1 to 10000mJ/cm 2 More preferably 100 to 5000mJ/cm 2 Further preferably 100 to 1500mJ/cm 2 Particularly preferably from 100 to 1000mJ/cm 2 More preferably 100 to 400mJ/cm 2 . When a usual liquid crystal aligning agent is used, the light irradiation amount in the aligning treatment is 100 to 5000mJ/cm 2 However, in the liquid crystal aligning agent of the present invention, even if the amount of light irradiation during the alignment treatment is reduced, a liquid crystal alignment film in which unevenness (non-uniformity) in the alignment of liquid crystal in the plane of the liquid crystal alignment film is suppressed can be obtained.
In the case of irradiation with radiation, the substrate having the film may be irradiated while being heated at 50 to 250 ℃ in order to improve the alignment of liquid crystals. The liquid crystal alignment film thus produced can stably align liquid crystal molecules in a certain direction.
In the above method, the liquid crystal alignment film irradiated with the polarized radiation may be subjected to a contact treatment using a solvent; or heat-treating the liquid crystal alignment film irradiated with radiation.
The solvent used in the contact treatment is not particularly limited as long as it is a solvent that dissolves a decomposition product formed from a film-like material upon irradiation with radiation. As specific examples, there may be mentioned: water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate, and the like. Among them, water, 2-propanol, 1-methoxy-2-propanol or ethyl lactate is preferable in terms of versatility and safety of solvents. More preferably water, 1-methoxy-2-propanol or ethyl lactate. The solvent may be one kind, or two or more kinds may be combined.
< procedure (4): process for performing a heating treatment >
The step (4) is a step of heating the liquid crystal alignment film subjected to the alignment treatment in the step (3). The irradiation film (coating film) irradiated with the radiation may be subjected to a heat treatment. The temperature of the heat treatment of the above-mentioned coating film irradiated with radiation is preferably 50 to 300 ℃, more preferably 120 to 250 ℃. The time of the heat treatment is preferably 1 to 30 minutes.
< procedure (5): process for manufacturing liquid Crystal cell
As described above, two substrates on which liquid crystal alignment films are formed are prepared, and liquid crystal is disposed between the two substrates disposed to face each other. Specifically, the following two methods are exemplified.
In the first method, first, two substrates are arranged to face each other with a gap (cell gap) therebetween so that the liquid crystal alignment films face each other. Next, the peripheral portions of the two substrates are bonded with a sealant, a liquid crystal composition is injected into a cell gap defined by the substrate surface and the sealant, and the liquid crystal composition is brought into contact with the film surface, and then the injection hole is sealed.
The liquid crystal composition is not particularly limited, and various liquid crystal compositions containing at least one liquid crystal compound (liquid crystal molecule) and having positive or negative dielectric anisotropy can be used. Hereinafter, a liquid crystal composition having positive dielectric anisotropy will be referred to as a positive liquid crystal, and a liquid crystal composition having negative dielectric anisotropy will be referred to as a negative liquid crystal.
The liquid crystal composition may contain a liquid crystal compound having a fluorine atom, a hydroxyl group, an amino group, a group containing a fluorine atom (for example, trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocycle, a cycloalkane, a cycloalkene, a steroid skeleton, a benzene ring, or a naphthalene ring, or may contain a compound having two or more rigid sites (mesogenic skeletons) exhibiting liquid crystallinity in the molecule (for example, a bimesogenic compound in which two rigid biphenyl structures or a terphenyl structure are linked by an alkyl group). The liquid crystal composition may be a nematic liquid crystal composition, a smectic liquid crystal composition or a cholesteric liquid crystal composition.
In addition, from the viewpoint of improving the alignment property of the liquid crystal, the liquid crystal composition may further contain an additive. Such additives may be exemplified by: a photopolymerizable monomer such as a compound having a polymerizable group described below; optically active compounds (for example, S-811 manufactured by Merck Co., ltd.); an antioxidant; an ultraviolet absorber; a pigment; a defoaming agent; a polymerization initiator; or a polymerization inhibitor, etc.
The positive liquid crystal includes: ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, MLC-7081, etc. manufactured by Merck corporation.
Examples of the negative liquid crystal include: MLC-6608, MLC-6609, MLC-6610, MLC-6882, MLC-6886, MLC-7026-000, MLC-7026-100, or MLC-7029, etc. manufactured by Merck corporation.
In the PSA mode, MLC-3023 manufactured by Merck corporation is used as a liquid crystal containing a compound having a polymerizable group.
The second method is a method called an ODF (One Drop Fill) method. For example, a uv-curable sealant is applied to a predetermined portion on one of two substrates on which a liquid crystal alignment film is formed, and a liquid crystal composition is further dropped onto predetermined portions on the liquid crystal alignment film surface. Then, the other substrate is bonded so that the liquid crystal alignment films face each other, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface. Then, ultraviolet light is irradiated to the entire surface of the substrate, and the sealant is cured. In either method, it is desirable to remove the flow alignment at the time of filling the liquid crystal by further heating to a temperature at which the liquid crystal composition to be used becomes an isotropic phase and then slowly cooling to room temperature.
When the coating film is subjected to the rubbing treatment, the two substrates are disposed so that the rubbing directions of the respective coating films are at a predetermined angle, for example, orthogonal or antiparallel.
As the sealant, for example, an epoxy resin containing a curing agent and alumina balls as spacers, or the like can be used. The liquid crystal includes nematic liquid crystal and smectic liquid crystal, and among them, nematic liquid crystal is preferable.
The liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell as necessary. As the polarizing plate attached to the outer surface of the liquid crystal cell, there may be mentioned: a polarizing plate formed by sandwiching a polarizing film called "H film" with a cellulose acetate protective film; or a polarizing plate composed of an H film itself, wherein the H film is formed by absorbing iodine while stretching and orienting polyvinyl alcohol.
An IPS substrate as a comb electrode substrate used in the IPS system has: a substrate; a plurality of linear electrodes formed on the substrate and arranged in a comb-like shape; and a liquid crystal alignment film formed on the substrate so as to cover the linear electrode.
The FFS substrate, which is a comb-teeth electrode substrate used in the FFS method, includes: a substrate; a surface electrode formed on the substrate; an insulating film formed on the surface electrode; a plurality of linear electrodes formed on the insulating film and arranged in a comb-like shape; and a liquid crystal alignment film formed on the insulating film so as to cover the linear electrode.
Fig. 1 is a schematic partial cross-sectional view showing an example of a transverse electric field liquid crystal display element according to the present invention, and is an example of an IPS mode liquid crystal display element.
In the transverse electric field liquid crystal display element 1 shown in fig. 1, the liquid crystal 3 is sandwiched between the comb-teeth electrode substrate 2 provided with the liquid crystal alignment film 2c and the counter substrate 4 provided with the liquid crystal alignment film 4 a. The comb-teeth electrode substrate 2 has: a base material 2a; a plurality of linear electrodes 2b formed on the base material 2a and arranged in a comb-tooth shape; and a liquid crystal alignment film 2c formed on the substrate 2a so as to cover the linear electrode 2 b. The counter substrate 4 has: a base material 4b; and a liquid crystal alignment film 4a formed on the substrate 4 b. The liquid crystal alignment film 2c is, for example, a liquid crystal alignment film of the present invention. The liquid crystal alignment film 4a is also the liquid crystal alignment film of the present invention.
In the transverse electric field liquid crystal display element 1, when a voltage is applied to the linear electrodes 2b, an electric field is generated between the linear electrodes 2b as indicated by the electric lines of force L.
Fig. 2 is a schematic partial cross-sectional view showing another example of the transverse electric field liquid crystal display element of the present invention, and is an example of an FFS mode liquid crystal display element.
In the transverse electric field liquid crystal display element 1 shown in fig. 2 by way of example, the liquid crystal 3 is sandwiched between the comb-teeth electrode substrate 2 provided with the liquid crystal alignment film 2h and the counter substrate 4 provided with the liquid crystal alignment film 4 a. The comb-teeth electrode substrate 2 has: a base material 2d; a surface electrode 2e formed on the substrate 2d; an insulating film 2f formed on the surface electrode 2 e; a plurality of linear electrodes 2g formed on the insulating film 2f and arranged in a comb-tooth shape; and a liquid crystal alignment film 2h formed on the insulating film 2f so as to cover the linear electrode 2 g. The counter substrate 4 has: a base material 4b; and a liquid crystal alignment film 4a formed on the substrate 4 b. The liquid crystal alignment film 2h is, for example, the liquid crystal alignment film of the present invention. The liquid crystal alignment film 4a is also the liquid crystal alignment film of the present invention.
In the transverse electric field liquid crystal display element 1, when a voltage is applied to the surface electrode 2e and the linear electrode 2g, an electric field is generated between the surface electrode 2e and the linear electrode 2g as indicated by the electric field lines L.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples. The abbreviations of the compounds used and the measurement methods of the respective physical properties are as follows.
(diamine)
(tetracarboxylic dianhydride)
(esterifying agent)
(additive)
(solvent)
NMP: n-methyl-2-pyrrolidone, GBL: gamma-butyrolactone.
BCS: ethylene glycol monobutyl ether.
(measurement of viscosity)
The sample size was 1.1mL using an E-type viscometer TVE-22H (manufactured by eastern machine industry Co., ltd.) and was measured at a temperature of 25℃using a conical rotor TE-1 (1℃34', R24).
( 1 Determination of H-NMR
A Fourier transform superconducting nuclear magnetic resonance apparatus (FT-NMR) (manufactured by AVANCE III, BRUKER Co.) was 500MHz.
(measurement of esterification Rate)
To an NMR sample tube (NMR standard sampling tube phi 5 manufactured by Bruhnese science Co., ltd.) was added 150mg of a polyamic acid ester NMP solution having a solid content of 12% by mass, and deuterated dimethyl sulfoxide (DMSO-d) 6 0.05% tms (tetramethylsilane) mixture) 0.53mL, and was completely dissolved by applying ultrasonic waves. Measuring the solution 1 H-NMR. The esterification rate was determined by using the peak integrated value of protons derived from structures which did not change before and after esterification as a reference proton and the peak integrated value of protons derived from carboxylic acid COOH groups which appeared in the vicinity of 11 to 13.5ppm as a reference proton.
Esterification ratio (%) = (1- α·x/y) ×100
In the above formula, x is a proton peak integral value of COOH groups derived from carboxylic acid, y is a peak integral value of reference protons, and α is a number ratio of reference protons to protons of one COOH group of carboxylic acid in the case of polyamic acid (esterification rate is 0%).
< determination of imidization Rate >)
To an NMR sample tube (NMR standard sample tube, phi 5 (manufactured by Bruhnia Co.), 20mg of polyimide powder was added, deuterated dimethyl sulfoxide (0.05% TMS mixture) (0.53 mL) was added, and ultrasonic wave was applied to dissolve it completely. Measuring the solution 1 H-NMR. The imidization rate was determined by using the peak integrated value of protons derived from the structure that did not change before and after imidization as a reference proton and the peak integrated value of protons derived from NH groups of amic acid that appeared in the vicinity of 9.5 to 10.0ppm as a reference proton.
Imidization ratio (%) = (1- α·x/y) ×100
In the above formula, x is a proton peak integral value of NH group derived from amic acid, y is a peak integral value of reference proton, and α is a number ratio of reference proton to one NH group proton of amic acid in the case of polyamic acid (imidization ratio is 0%).
< Synthesis of Polyamic acid >
Synthesis example 1
A100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube was charged with A1 (0.541 g,5.00 mmol), A2 (1.83 g,7.50 mmol), A3 (2.40 g,7.50 mmol), A4 (1.99 g,5.00 mmol), B1 (5.31 g,23.7 mmol) and NMP (88 g), and the mixture was stirred at 40℃for 20 hours to obtain a solution (viscosity: 400 mPa.s) of polyamic acid (PAA-1) having a solid content of 12% by mass.
Synthesis example 2
A100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube was charged with A5 (2.99 g,15.0 mmol), A6 (2.11 g,5.00 mmol), A7 (1.49 g,5.00 mmol), B2 (6.91 g,23.5 mmol) and NMP (99 g), and the mixture was stirred at 40℃for 20 hours to obtain a solution (viscosity: 380 mPas) of polyamic acid (PAA-2) having a solid concentration of 12% by mass.
Synthesis example 3
A100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube was charged with A1 (0.541 g,5.00 mmol), A2 (1.83 g,7.50 mmol), A3 (2.40 g,7.50 mmol), A8 (1.71 g,5.00 mmol), B1 (5.31 g,23.7 mmol) and NMP (86 g), and stirred at 40℃for 20 hours to obtain a solution (viscosity: 400 mPa.s) of polyamic acid (PAA-3) having a solid content of 12% by mass.
< Synthesis of Polyamic acid ester >
Synthesis example 4
A solution (30.0 g) of polyamic acid (PAA-1) was separated into a 100mL Erlenmeyer flask equipped with a nitrogen inlet, and C1 (12.7 g) was added thereto, followed by stirring at room temperature for 12 hours, whereby a solution of polyamic acid ester (PAE-1) was obtained. The esterification rate of the polyamic acid ester was 60%.
Synthesis example 5
A solution (42.7 g) of the polyamic acid ester (PAE-1) was injected into isopropyl alcohol (214 g), and the resultant precipitate was filtered off. The precipitate was washed with isopropyl alcohol and dried under reduced pressure at 80℃to obtain a polyamic acid ester powder. NMP (26.4 g) was added to the obtained polyamic acid ester powder (3.6 g), and the mixture was stirred at 70℃for 20 hours to dissolve the powder, thereby obtaining a polyamic acid ester solution (PAE-1A).
Synthesis example 6
A solution of a polyamic acid ester (PAE-2) was obtained in the same manner as in Synthesis example 4, except that the amount of C1 added was changed to 6.35 g. The esterification rate of the polyamic acid ester was 28%.
< Synthesis of polyimide >
Synthesis example 7
A200 mL Erlenmeyer flask was charged with NMP (20.0 g) and then acetic anhydride (4.65 g) and pyridine (0.60 g) were added to separate a solution (60.0 g) of polyamic acid (PAA-3), and the mixture was reacted at 55℃for 2 hours. The reaction solution was poured into methanol (341 g), and the precipitate formed was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 80℃to obtain a polyimide powder. The imidization rate of the polyimide was 66%. NMP (48.4 g) was added to the obtained polyimide powder (6.6 g), and the mixture was stirred at 60℃for 24 hours to dissolve the polyimide powder, thereby obtaining a polyimide (SPI-1) solution.
The types and amounts of the diamine component and the tetracarboxylic anhydride component used in synthesis examples 1 to 7 are summarized in table 1. In table 1, the values in parentheses indicate the amounts of monomers used (parts by mole) in each component relative to 100 parts by mole in total.
TABLE 1
< preparation of liquid Crystal alignment agent >
Example 1
To the polyamic acid ester (PAE-1) solution (2.75 g) obtained in Synthesis example 4, the polyamic acid (PAA-2) solution (6.42 g), NMP (4.83 g) and BCS (6.00 g) obtained in Synthesis example 2 were added, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (V-1).
Examples 2 to 3
The same procedure as in example 1 was repeated except that the polyamic acid ester solution used was changed from (PAE-1) to (PAE-1A) and (PAE-2), thereby obtaining liquid crystal aligning agents (V-2) and (V-3).
Reference example 1
To the polyamic acid ester (PAE-1A) solution (9.17 g) obtained in Synthesis example 5, NMP10 mass% diluted solution (0.550 g) of AD-1, NMP (4.28 g) and BCS (6.00 g) were added, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (SV-1).
Comparative example 1
The procedure of example 1 was repeated except that the polymer solution used was changed from the polyamic acid ester (PAE-1) solution to the polyamic acid (PAA-1) solution, to thereby obtain a liquid crystal aligning agent (RV-1).
Comparative example 2
To the polyimide (SPI-1) solution (5.83 g) obtained in Synthesis example 7, the polyamic acid (PAA-2) solution (2.50 g), NMP (2.77 g), GBL (4.90 g) and BCS (4.00 g) obtained in Synthesis example 2 were added, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (RV-2).
Comparative example 3
The procedure of reference example 1 was repeated except that the polymer solution used was changed from the polyamic acid ester (PAE-1A) solution to the polyamic acid (PAA-1) solution, to thereby obtain a liquid crystal aligning agent (RV-3).
Comparative example 4
To a polyimide (SPI-1) solution (8.33 g) obtained in Synthesis example 7, NMP10 mass% diluted solution (0.50 g) of AD-1, NMP (4.93 g), GBL (2.33 g) and BCS (4.00 g) were added, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (RV-4).
Table 2 shows the specifications of the liquid crystal aligning agents obtained in examples 1 to 3, reference example 1 and comparative examples 1 to 4.
TABLE 2
Using each of the liquid crystal aligning agents obtained in the above, FFS-driven liquid crystal cells were prepared in the following procedure, and various evaluations were performed.
< FFS drive liquid Crystal cell Structure >
A liquid crystal cell having a structure of FFS mode liquid crystal display element was manufactured.
First, a substrate with electrodes is prepared. The substrate was a glass plate having a rectangular shape of 30mm×50mm and a thickness of 0.7 mm. An ITO electrode having a dense pattern, which constitutes a counter electrode, is formed as a first layer on a substrate. On the opposite electrode of the first layer, a SiN (silicon nitride) film formed by a CVD (chemical vapor deposition) method is formed as the second layer. The SiN film of the second layer was 300nm thick and functioning as an interlayer insulating film. On the SiN film of the second layer, a comb-shaped pixel electrode formed by patterning an ITO film was disposed as a third layer, and two kinds of pixels, i.e., a first pixel and a second pixel, were formed, each having a length of 10mm and a width of 5mm. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the SiN film of the second layer.
The pixel electrode of the third layer has a comb-tooth shape in which a plurality of electrode elements of 3 μm width bent at an inner angle of 160 ° at intervals of 6 μm are arranged in parallel, and one pixel has a first region and a second region, respectively, with a line connecting the bent portions of the plurality of electrode elements as a boundary.
Next, the liquid crystal aligning agents (V-1) to (V-3) and (RV-1) to (RV-2) obtained in examples 1 to 3 and comparative examples 1 to 2 were each filtered by a filter having a pore diameter of 1.0 μm, and then coated on the surface of the above-mentioned prepared electrode-equipped substrate (first glass substrate) and the surface of the glass substrate (second glass substrate) having a columnar spacer having a height of 4 μm and having an ITO film formed on the back surface thereof by spin coating. Subsequently, the resultant was dried on a hot plate at 80℃for 2 minutes, and then baked in a hot air circulating oven at 230℃for 30 minutes, to thereby form a coating film having a thickness of 100 nm. The coated surface was subjected to alignment treatment by irradiating with ultraviolet light having a wavelength of 254nm, which was linearly polarized at an extinction ratio of 26:1, at each irradiation amount shown in Table 3 via a polarizing plate, to obtain a substrate with a liquid crystal alignment film. In the liquid crystal alignment film formed on the electrode-attached substrate, alignment treatment is performed so that the direction of the inner corner of the pixel bending portion is perpendicular to the alignment direction of the liquid crystal, and in the liquid crystal alignment film formed on the second glass substrate, alignment treatment is performed so that the alignment direction of the liquid crystal on the first glass substrate coincides with the alignment direction of the liquid crystal on the second glass substrate when the liquid crystal cell is manufactured. The two substrates were combined, and a sealant (XN-1500T, sanjing chemical Co., ltd.) was printed on each of the substrates, and the other substrate was bonded so that the liquid crystal alignment layers faced each other and the alignment direction became 0 degrees. Thereafter, the sealant was subjected to a heat treatment at 150 ℃ for 60 minutes to cure the sealant, thereby producing an empty case. The liquid crystal MLC-3019 (manufactured by Merck Co.) was injected into the empty cell by vacuum injection, and the injection port was sealed to obtain an FFS-driven liquid crystal cell. Thereafter, the resulting liquid crystal cell was heated at 120℃for 1 hour, and left for evaluation after one minute.
< evaluation of in-plane uniformity of contrast >)
The evaluation of the unevenness in twist angle of the liquid crystal display element was performed using AxoStep manufactured by axome corporation. The liquid crystal cell manufactured as described above was set in a measuring table, and the distribution of Circular Retardance in the pixel plane was measured in a state where no voltage was applied, and 3 times the standard deviation σ, that is, 3σ was calculated. The smaller the value of 3σ is, the better the in-plane uniformity can be said to be. As an evaluation criterion, the 3 σ value of 1.10 or less was "excellent", the 3 σ value of more than 1.10 and 1.20 or less was "good", and the 3 σ value of more than 1.20 was "poor".
The evaluation results of the liquid crystal display elements using the liquid crystal aligning agents of the examples and comparative examples are shown in table 3.
< evaluation of stability of liquid Crystal alignment >
The present evaluation evaluates an afterimage (also referred to as an AC afterimage) generated due to a decrease in alignment performance of the liquid crystal alignment film in long-term AC driving. The better the stability of the liquid crystal alignment, the higher the suppression effect of the AC afterimage is considered.
The FFS-driven liquid crystal cell manufactured as described above was applied with an ac voltage of ±4v at a frequency of 60Hz for 120 hours under a constant temperature environment of 60 ℃. Then, the state of short-circuiting between the pixel electrode and the counter electrode of the liquid crystal cell was maintained, and the liquid crystal cell was left at room temperature for one day. The liquid crystal cell subjected to the above-described process was subjected to calculation of the deviation between the alignment direction of the liquid crystal in the first region and the alignment direction of the liquid crystal in the second region of the pixel in the state where no voltage was applied in terms of angle. Specifically, the liquid crystal cell is placed between two polarizing plates having orthogonal polarization axes, the backlight is turned on, the arrangement angle of the liquid crystal cell is adjusted so that the transmitted light intensity in the first region of the pixel is minimized, and then the rotation angle required for rotating the liquid crystal cell so that the transmitted light intensity in the second region of the pixel is minimized is obtained. It can be said that the smaller the value of the rotation angle is, the better the stability of the alignment of the liquid crystal. As an evaluation criterion, the values of the rotation angles were "excellent" when the values were smaller than 0.10 °, and "good" when the values were not smaller than 0.10 ° but not larger than 0.20 °, and "poor" when the values were larger than 0.20 °.
The evaluation results of the liquid crystal display elements using the liquid crystal aligning agents of examples 1 to 3 and comparative examples 1 to 2 are shown in table 3.
TABLE 3
As shown in table 3, the liquid crystal alignment film obtained from the liquid crystal alignment agent which is a mixture of a specific polyamic acid ester and a specific polyamic acid showed high in-plane uniformity or high stability of liquid crystal alignment with a smaller amount of irradiation of ultraviolet rays than the liquid crystal alignment film obtained from the liquid crystal alignment agent which is a mixture of two polyamic acids or a mixture of polyimide and a polyamic acid.
< test of abrasion resistance >)
Next, in order to confirm the strength of the liquid crystal alignment film formed using each of the liquid crystal alignment agents obtained in reference example 1 and comparative examples 3 to 4, a rubbing resistance test was performed. The better the evaluation of the rubbing resistance test, the less likely the peeling of the liquid crystal alignment film from the substrate occurs.
The liquid crystal aligning agents (SV-1) and (RV-3) to (RV-4) obtained in reference example 1 and comparative examples 3 to 4 were applied to the ITO surface of the glass substrate having the ITO electrode on the whole surface by spin coating. After drying on a heating plate at 80℃for 2 minutes, baking was performed at 230℃for 30 minutes using an IR oven, and a coating film having a thickness of 100nm was formed. The film surface was irradiated with polarized ultraviolet light to 300mJ/cm 2 The orientation treatment is performed by irradiating the substrate. The substrate with the liquid crystal alignment film was obtained by firing again using an IR oven at 230 ℃ for 30 minutes.
The substrate with the liquid crystal alignment film obtained as described above was subjected to a rubbing treatment (roll diameter: 120mm, roll rotation speed: 1000rpm, moving speed: 20mm/sec, press-in length: 0.6 mm) with a rayon cloth, and then observed with a microscope, and the rubbing resistance of the liquid crystal alignment film was evaluated.
The case where no streak was observed on the liquid crystal alignment film surface due to the rubbing treatment was evaluated as "good", and the case where streak was observed was evaluated as "x".
The evaluation results of the rubbing resistance test of the liquid crystal alignment films formed using the liquid crystal alignment agents obtained in reference example 1 and comparative examples 3 to 4 are shown in table 4 below.
TABLE 4
As shown in table 4, the liquid crystal alignment film obtained from the liquid crystal alignment agent of the polyamic acid ester (PAE-1A) showed the rubbing resistance equivalent to that of the liquid crystal alignment film obtained from the polyamic acid (PAA-1), and showed the rubbing resistance higher than that of the liquid crystal alignment film obtained from the polyimide (SPI-1). Therefore, it is suggested that the liquid crystal alignment film of the present invention obtained from the liquid crystal alignment agent containing the polyamic acid ester (a) and the polyamic acid (B) shows a high rubbing resistance comparable to that obtained from the liquid crystal alignment agent containing the polyamic acid, and further shows a high rubbing resistance compared to that obtained from the liquid crystal alignment agent containing the polyimide and the polyamic acid.
Industrial applicability
The liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention can be effectively used for various applications other than liquid crystal display elements of various modes for display purposes, light control windows for controlling light transmission and blocking, light shutters, and the like. For example, the liquid crystal alignment film can be widely used for a retardation film; scanning antenna, liquid crystal alignment film for array antenna; a liquid crystal alignment film for a transmission scattering type liquid crystal light adjusting element; other uses such as a protective film (e.g., a protective film for a color filter), a spacer film, an interlayer insulating film, an antireflection film, a wiring coating film, a antistatic film, a motor insulating film (a gate insulating film of a flexible display), and the like.
Description of the reference numerals
1: a lateral electric field liquid crystal display element; 2: comb electrode base plate; 2a, 4b, 2d: a substrate; 2b, 2g: a linear electrode; 2c, 2h, 4a: a liquid crystal alignment film; 2e: a surface electrode; 2f: an insulating film; 3: a liquid crystal; 4: an opposite substrate; l: a power line.
The entire contents of the specification, claims, drawings and abstract of japanese patent application No. 2021-105052 filed on 24 th 6 th year 2021 are incorporated herein by reference as the disclosure of the present invention.

Claims (15)

1. A liquid crystal aligning agent comprising the following components A and B,
component A: a polyamic acid ester A having a structural unit a-1Ta represented by the following formula (1 Ta) as a structural unit derived from a tetracarboxylic acid derivative, and two or more structural units a-1Da represented by the following formula (1 Da) as structural units derived from a diamine;
and the component B comprises the following components: a polyamide acid B having a structural unit B-1Tb represented by the following formula (1 Tb) as a structural unit derived from a tetracarboxylic acid derivative, a structural unit B-1Db represented by the following formula (1 Db) as a structural unit derived from a diamine,
in the formula (1 Ta), R is 11 ～R 14 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, R 11 ～R 14 Represents a group other than a hydrogen atom in the definition; two R 1 Each independently represents a hydrogen atom or a tertiary alkyl group, at least one of which represents a tertiary alkyl group; in the formula (1 Da), Y 1 Is of the formula (H) 1 ) A divalent organic group as shown; z each independently represents a hydrogen atom or a monovalent organic group,
＊-Ar 1 -L 1 -A-L 1′ -Ar 1′ -＊ (H 1 )
(H) 1 ) Ar in (1) 1 、Ar 1’ Each independently represents a benzene ring, a biphenyl structure, or a naphthalene ring; ar (Ar) 1 、Ar 1’ Optionally substituted with monovalent groups; a represents a divalent organic group having an alkylene structure and having 1 to 10 carbon atoms; l (L) 1 、L 1’ Each independently represents a single bond, -O-, -S-, -C (=o) -, -O-C (=o) -, -C (=o) -NR-in which R represents a hydrogen atom or a monovalent organic group, or-NR-C (=o) -in which R represents a hydrogen atom or a monovalent organic group; * The bond is represented by the bond,
in the formula (1 Tb), X b Represents a tetravalent organic group of the formula (1 Db), Y b Represents a divalent organic group, and two Z's each independently represent a hydrogen atom or a monovalent organic group.
2. The liquid crystal aligning agent according to claim 1, wherein,
the formula (H) 1 ) Wherein R represents a hydrogen atom or a monovalent organic group; two R are optionally identical or different from each other; n is an integer of 1 to 10; * - (CH) 2 ) n1 －O－(CH 2 ) n2 N1 and n2 in the formula are each independently integers of 1 to 6, and the total of n1 and n2 is 2 to 10; * - (CH) 2 ) n1 －NR－C(＝O)－NR－(CH 2 ) n2 N1 and n2 in the formula are each independently integers of 1 to 6, and the total of n1 and n2 is 2 to 9; m1 and m2 are each independently an integer of 0 to 4, n 'is an integer of 1 to 6, and the total of m1, m2 and n' is 1 to 8; * The bond is represented by the bond,
*－(CH 2 ) n －*、
*－(CH 2 ) n1 －O－(CH 2 ) n2 －*、
*－(CH 2 ) m1 －O－C(＝O)－(CH 2 ) n’ －C(＝O)－O－(CH 2 ) m2 －*、
*－(CH 2 ) m1 －C(＝O)－O－(CH 2 ) n’ －O－C(＝O)－(CH 2 ) m2 －*、
*－(CH 2 ) n1 －NR－C(＝O)－NR－(CH 2 ) n2 －*。
3. The liquid crystal aligning agent according to claim 1 or 2, wherein,
the polyamic acid ester A has a structural unit represented by the formula (1 Da) as a structural unit derived from diamine, wherein in the formula (1 Da), Y 1 At least one of which is Ar 1 With Ar 1’ Of the formula (H) 1 ) The divalent organic radicals shown, other Y 1 At least one of which is Ar 1 With Ar 1’ Is of a different structure formula (H) 1 ) Divalent organic groups are shown.
4. A liquid crystal aligning agent according to any one of claim 1 to 3, wherein,
the polyamic acid ester A comprises at least one structural unit shown in a formula (1 Da) as a structural unit derived from diamine, wherein in the formula (1 Da), Y 1 Is a divalent organic group having three or more benzene rings.
5. The liquid crystal aligning agent according to any one of claims 1 to 4, wherein,
y in formula (1 Da) 1 Is a divalent organic group represented by any of the following formulas (h 1-1) to (h 1-13),
in the formula (h 1-4), -CH 2 -a sum of 10 or less; of the formula (h 1-7), (h 1-8), -CH 2 -the sum of the numbers is below 8, the two m optionally being identical or different from each other; * Representation keyAnd (5) bonding.
6. The liquid crystal aligning agent according to any one of claims 1 to 5, wherein,
X in the formula (1 Tb) b The tetravalent organic group is a tetravalent organic group obtained by removing two acid dianhydride groups from an acyclic aliphatic tetracarboxylic dianhydride, a tetravalent organic group obtained by removing two acid dianhydride groups from an alicyclic tetracarboxylic dianhydride, or a tetravalent organic group obtained by removing two acid dianhydride groups from an aromatic tetracarboxylic dianhydride, and is derived from a tetracarboxylic dianhydride having at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure, or a derivative thereof.
7. The liquid crystal aligning agent according to any one of claims 1 to 6, wherein,
the polyamic acid ester A contains 5 mol% or more of the structural unit a-1Ta relative to 1 mol of the total structural units derived from the tetracarboxylic acid derivative.
8. The liquid crystal aligning agent according to any one of claims 1 to 7, wherein,
the polyamic acid ester A contains 5 to 95 mol% of the structural unit a-1Da relative to 1 mol% of all structural units derived from diamine that the polyamic acid ester A has.
9. The liquid crystal aligning agent according to any one of claims 1 to 8, wherein,
the liquid crystal aligning agent is used for forming a liquid crystal alignment film for a photo-alignment treatment method.
10. A liquid crystal alignment film obtained from the liquid crystal alignment agent according to any one of claims 1 to 9.
11. A liquid crystal display element comprising the liquid crystal alignment film according to claim 10.
12. A method for manufacturing a liquid crystal display element, comprising the following steps 1 to 3:
step 1: a step of applying the liquid crystal aligning agent according to any one of claims 1 to 9 to a substrate;
step 2: a step of baking the coated liquid crystal aligning agent;
and step 3: and (2) a step of performing an orientation treatment on the fired film obtained in the step (2).
13. The method for manufacturing a liquid crystal display element according to claim 12, wherein,
the orientation treatment is a photo-orientation treatment.
14. The method for manufacturing a liquid crystal display element according to claim 13, wherein,
the irradiation amount of the radioactive rays in the photo-orientation treatment is 100-1500 mJ/cm 2 。
15. The method for manufacturing a liquid crystal display element according to any one of claims 12 to 14, wherein,
further comprising a step 4 of,
and 4, step 4: and a step of further performing a heat treatment at 50 to 300 ℃ on the fired film subjected to the orientation treatment in the step 3.
CN202280044600.0A 2021-06-24 2022-06-06 Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element Pending CN117546082A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2021-105052 2021-06-24
JP2021105052 2021-06-24
PCT/JP2022/022806 WO2022270287A1 (en) 2021-06-24 2022-06-06 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Publications (1)

Publication Number Publication Date
CN117546082A true CN117546082A (en) 2024-02-09

Family

ID=84544538

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202280044600.0A Pending CN117546082A (en) 2021-06-24 2022-06-06 Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element

Country Status (5)

Country Link
JP (1) JPWO2022270287A1 (en)
KR (1) KR20240023525A (en)
CN (1) CN117546082A (en)
TW (1) TW202317740A (en)
WO (1) WO2022270287A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024157869A1 (en) * 2023-01-23 2024-08-02 日産化学株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3893659B2 (en) 1996-03-05 2007-03-14 日産化学工業株式会社 Liquid crystal alignment treatment method
WO2004053582A1 (en) 2002-12-09 2004-06-24 Hitachi Displays, Ltd. Liquid crystal display and method for manufacturing same
CN102445790B (en) * 2010-10-06 2016-05-18 株式会社日本显示器 Alignment films, composition for forming alignment film and liquid crystal indicator
JP5939614B2 (en) * 2012-02-01 2016-06-22 株式会社ジャパンディスプレイ Alignment film and liquid crystal display device using the same
JP7114856B2 (en) * 2016-02-15 2022-08-09 日産化学株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Also Published As

Publication number Publication date
TW202317740A (en) 2023-05-01
KR20240023525A (en) 2024-02-22
JPWO2022270287A1 (en) 2022-12-29
WO2022270287A1 (en) 2022-12-29

Similar Documents

Publication Publication Date Title
WO2022176680A1 (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
CN116529290A (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
CN117546082A (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
CN117280277A (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
WO2024122359A1 (en) Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
CN116615689B (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
CN116234856B (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
JP7497782B2 (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
WO2024154728A1 (en) Liquid crystal display element and method for manufacturing same
WO2024157869A1 (en) Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
WO2024219400A1 (en) Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
WO2023210532A1 (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
WO2022220199A1 (en) Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
WO2022190896A1 (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element
WO2024166693A1 (en) Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, compound and polymer
TW202436600A (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element
WO2023219112A1 (en) Novel diamine compound, polymer obtained using diamine, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
CN118355319A (en) Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, and compound
WO2022250007A1 (en) Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, diamine, and polymer
CN118401888A (en) Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, compound and polymer
CN118451361A (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
TW202436599A (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element
CN117716282A (en) Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, compound and polymer
CN117957488A (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
CN116917798A (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination