CN117850102A - Liquid crystal aligning agent for photo-alignment, liquid crystal alignment film, and liquid crystal element using same - Google Patents
Liquid crystal aligning agent for photo-alignment, liquid crystal alignment film, and liquid crystal element using same Download PDFInfo
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- CN117850102A CN117850102A CN202311121415.XA CN202311121415A CN117850102A CN 117850102 A CN117850102 A CN 117850102A CN 202311121415 A CN202311121415 A CN 202311121415A CN 117850102 A CN117850102 A CN 117850102A
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- liquid crystal
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- aligning agent
- alignment film
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- VSQYNPJPULBZKU-UHFFFAOYSA-N mercury xenon Chemical compound [Xe].[Hg] VSQYNPJPULBZKU-UHFFFAOYSA-N 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
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- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
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- SJPFBRJHYRBAGV-UHFFFAOYSA-N n-[[3-[[bis(oxiran-2-ylmethyl)amino]methyl]phenyl]methyl]-1-(oxiran-2-yl)-n-(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC=1C=C(CN(CC2OC2)CC2OC2)C=CC=1)CC1CO1 SJPFBRJHYRBAGV-UHFFFAOYSA-N 0.000 description 1
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- 125000004957 naphthylene group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- HLEWRNFSHDSFFF-UHFFFAOYSA-N octa-2,6-dienedioic acid Chemical compound OC(=O)C=CCCC=CC(O)=O HLEWRNFSHDSFFF-UHFFFAOYSA-N 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1017—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)amine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/542—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Nonlinear Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials Engineering (AREA)
- Mathematical Physics (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention relates to a liquid crystal aligning agent for photo-alignment, a liquid crystal alignment film and a liquid crystal element using the same, and provides a liquid crystal alignment film which can form a liquid crystal display element having less film peeling, less cutting, excellent adhesion with a sealing agent and good contrast even when exposure energy of photo-alignment treatment is small, and a liquid crystal alignment agent capable of forming the liquid crystal alignment film. The liquid crystal aligning agent contains tetracarboxylic acidThe polyamide acid or its derivative obtained by reacting a derivative, a diamine and a monoamine having two or more hydroxyl groups, and contains a compound represented by the formula (I) as a tetracarboxylic acid derivative. In the formula (I), 1', 2 and 2' are chemical bonds, each independently bond to a hydroxyl group or the like, and at least one of the group of 1 and 1 'and the group of 2 and 2' can bond to the same oxygen atom; r is R b1 、R b2 、R b3 And R is b4 Each independently is a hydrogen atom or a methyl group, at least one of which is a methyl group.
Description
Technical Field
The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal element using the same. More specifically, the present invention relates to a liquid crystal alignment agent for photo-alignment (hereinafter, abbreviated as a liquid crystal alignment agent) for forming a liquid crystal alignment film of photo-alignment type (hereinafter, abbreviated as a photo-alignment film), a liquid crystal alignment film of photo-alignment type formed by using the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film (hereinafter, abbreviated as a liquid crystal element).
Background
A liquid crystal device is known in which an optical phenomenon such as refraction, scattering, reflection, etc. of electromagnetic waves incident into the device can be caused by controlling or modulating an alignment state of a liquid crystal layer in the device. Specifically, a liquid crystal antenna, a dimming window, an optical compensation material, and a variable phase shifter are known in addition to the liquid crystal display element described below.
As liquid crystal display elements, various driving modes such as a TN (Twisted Nematic) mode, a STN (Super Twisted Nematic) mode, an IPS (In-Plane Switching) mode, an FFS (Fringe Field Switching) mode, and a VA (Multi-domain Vertical Alignment) mode In which vertical alignment is performed are known. These liquid crystal display elements are used in image display devices of various electronic devices such as televisions and mobile phones, and have been developed with a view to further improving display quality. Specifically, the performance of the liquid crystal display element is improved not only by the driving method and the improvement of the element structure but also by the structural members used in the element. Among the structural members used in liquid crystal display devices, particularly, a liquid crystal alignment film is one of important materials related to display quality, and in order to cope with the demand for higher quality of liquid crystal display devices, research has been actively conducted on the liquid crystal alignment film.
Here, the liquid crystal alignment film has the following functions: a pair of substrates provided on both sides of a liquid crystal layer of a liquid crystal display element are provided so as to be in contact with the liquid crystal layer, and liquid crystal molecules constituting the liquid crystal layer are aligned with respect to the substrates with a certain regularity. By using a liquid crystal alignment film having high liquid crystal alignment properties, a liquid crystal display element having high contrast and improved afterimage characteristics can be realized (for example, refer to patent documents 1 and 2).
In the formation of such a liquid crystal alignment film, a solution (varnish) obtained by dissolving a polyamic acid, a soluble polyimide or a polyamic acid ester in an organic solvent has been mainly used. In order to form a liquid crystal alignment film using these varnishes, the varnish is applied to a substrate, and then the coating film is cured by heating or the like to form a polyimide-based liquid crystal alignment film, and if necessary, an alignment treatment suitable for the display mode is performed. As the alignment treatment method, there are known a rubbing method of rubbing the surface of an alignment film with cloth or the like to adjust the direction of polymer molecules, and a photo-alignment method of irradiating the alignment film with ultraviolet rays of linearly polarized light to cause photochemical changes such as photoisomerization and dimerization of polymer molecules to impart anisotropy to the film. Among them, the photo alignment method has advantages such as high uniformity of alignment compared with the rubbing method, no damage to the film due to the non-contact alignment treatment method, and reduction of the cause of defective display of the liquid crystal display element due to dust, static electricity, and the like.
As a liquid crystal alignment film using such a photo-alignment method, for example, patent documents 1 to 5 describe a technique of applying photoisomerization using azobis (diazosulfide) or the like as a raw material to obtain a photo-alignment film having a large anchoring energy (anchoring energy) and good liquid crystal alignment. Patent document 6 describes that a photo-alignment film having high transparency and good liquid crystal alignment is obtained by applying a photo-decomposition technique. However, when a liquid crystal alignment film using such a technique is produced into a panel, peeling and cutting of the film are likely to occur, and there is a problem that the display quality of the panel is degraded by foreign matter generated.
In addition, in a liquid crystal display element using a liquid crystal alignment film using a photo-alignment method, in order to improve the efficiency of manufacturing the liquid crystal display element, it is required to use a liquid crystal alignment film which can exhibit a good contrast even in a short photo-alignment treatment time, that is, a photo-alignment treatment with a small exposure energy.
In addition, in the liquid crystal display element, a frame is narrowed in order to enlarge a display screen. In order to form a narrow frame, it is necessary to print a liquid crystal alignment film on an end portion of the substrate, and to apply a sealant to the liquid crystal alignment film, and it is necessary to provide a liquid crystal alignment film having high adhesion to the sealant.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2010-197999;
patent document 2: international publication No. 2013/157463;
patent document 3: japanese patent laid-open publication No. 2005-275364;
patent document 4: japanese patent laid-open No. 2007-248637;
patent document 5: international publication No. 2015/016118;
patent document 6: japanese patent application laid-open No. 2012-155311;
patent document 7: japanese patent application laid-open No. 2013-235130.
Disclosure of Invention
The invention provides a liquid crystal alignment film which can form a liquid crystal display element having less film peeling and cutting which are causes of poor display in the liquid crystal display element, excellent adhesion with a sealing agent and good contrast even if exposure energy of photo-alignment treatment is smaller than that of the prior art, and a liquid crystal alignment agent which can form the liquid crystal alignment film.
The present inventors have conducted intensive studies and as a result, have found that a liquid crystal alignment film having high sensitivity to exposure energy, suppressed film peeling and cutting, excellent adhesion to a sealant, and providing a liquid crystal display element having high display quality can be formed by using a compound represented by the formula (I) and a monoamine having two or more hydroxyl groups as raw materials of a liquid crystal alignment agent for photo-alignment, and have completed the present invention.
[1] A liquid crystal aligning agent for photo-alignment, which comprises a polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic acid derivative, a diamine, and a monoamine having two or more hydroxyl groups, wherein the liquid crystal aligning agent comprises a compound represented by the formula (I) as the tetracarboxylic acid derivative.
In the formula (I), 1', 2 and 2' are chemical bonds, and each is independently bonded to a hydroxyl group, a chlorine atom or an alkoxy group having 1 to 6 carbon atoms, and at least one of the group of 1 and 1 'and the group of 2 and 2' is capable of bonding to the same oxygen atom;
R b1 、R b2 、R b3 and R is b4 Each independently is a hydrogen atom or a methyl group, at least one of which is a methyl group.
[2] The liquid crystal aligning agent for photo-alignment according to [1], wherein the monoamine having two or more hydroxyl groups is at least one selected from the following formulas (Xa) to (Xf).
In the formulas (Xa), (Xb), R x Independently a hydrogen atom or a methyl group.
[3] The liquid crystal aligning agent for photo-alignment according to [2], wherein the monoamine having two or more hydroxyl groups is at least one selected from the following formulas (Xa-1), (Xa-2), (Xb-1), (Xb-2), (Xc-1), (Xc-2) and (Xe).
[4] The liquid crystal aligning agent for photo-alignment according to any one of [1] to [3], further comprising an additive.
[5] A liquid crystal alignment film formed by the liquid crystal alignment agent for photo-alignment of any one of [1] to [4 ].
[6] A liquid crystal element having the liquid crystal alignment film of [5 ].
[7] A method for producing a liquid crystal alignment film, comprising the steps of: coating the liquid crystal aligning agent for photo-alignment of any one of [1] to [4] on a substrate; firing the substrate; and irradiating the substrate with polarized ultraviolet rays.
By using the liquid crystal aligning agent for photo-alignment of the present invention, a liquid crystal alignment film having high sensitivity to exposure energy, less likely to cause film peeling and cutting, and exhibiting high seal adhesion can be obtained.
Detailed Description
The present invention will be described in detail below. The following description of the structural elements is sometimes made based on the representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present invention, the "liquid crystal aligning agent" is a liquid crystal aligning agent capable of imparting anisotropy by irradiation of polarized ultraviolet rays when forming a film thereof on a substrate, and is also referred to as a "liquid crystal aligning agent" in the present specification, or a "liquid crystal aligning agent for photo-alignment" in some cases. In the present invention, the term "tetracarboxylic acid derivative" means a tetracarboxylic dianhydride, a tetracarboxylic diester, or a tetracarboxylic diester dihalide. The tetracarboxylic acid diester and the tetracarboxylic acid diester dihalide are sometimes collectively referred to as derivatives of tetracarboxylic acid dianhydride. In the present invention, diamine and dihydrazide (dihydrazide) are sometimes referred to as "diamines". In the chemical formula of the present specification, chemical bonds are represented.
< liquid Crystal alignment agent for photo-alignment of the invention >
The liquid crystal aligning agent for photo-alignment is characterized by comprising at least one polymer selected from the group consisting of polyamic acid and polyamic acid derivatives, wherein the polyamic acid and the polyamic acid derivatives are obtained by reacting tetracarboxylic acid derivatives comprising at least one compound shown in a formula (I), diamines and monoamines with more than two hydroxyl groups. This polymer is sometimes referred to as the polymer of the present invention. In the present invention, the polyamic acid derivative refers to polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer and polyamideimide.
In the formula (I), 1', 2 and 2' are chemical bonds, and each is independently bonded to a hydroxyl group, a chlorine atom or an alkoxy group having 1 to 6 carbon atoms, and at least one of the group of 1 and 1 'and the group of 2 and 2' is capable of bonding to the same oxygen atom;
R b1 、R b2 、R b3 and R is b4 Each independently ofThe site is a hydrogen atom or a methyl group, at least one of which is a methyl group.
< kind of Polymer >
The polyamic acid and the polyamic acid derivative will be described in detail below.
Here, the polyamic acid is a polymer synthesized by polymerization reaction of tetracarboxylic dianhydride represented by formula (AN) and diamine represented by formula (DI), and has a structural unit represented by formula (PAA). When the liquid crystal aligning agent containing polyamide acid is heated and fired in the step of forming the liquid crystal aligning film, the polyamide acid is imidized, and a polyimide liquid crystal aligning film having a structural unit represented by formula (PI) can be formed.
In the formula (AN), the formula (PAA) and the formula (PI), X 1 Is a 4-valent organic group. In the formula (DI), the formula (PAA) and the formula (PI), X 2 Is a 2-valent organic group. Regarding X 1 The preferable range and specific examples of the 4-valent organic group can be referred to the corresponding structures of the tetracarboxylic dianhydrides described in the present specification. Regarding X 2 The preferable range and specific examples of the 2-valent organic group can be referred to the corresponding structures of diamine or dihydrazide described in the present specification.
The polyamic acid derivative is a compound having properties changed by replacing a part of the polyamic acid with another atom or group of atoms, and particularly preferably has improved solubility in a solvent used for the liquid crystal aligning agent. Specific examples of such polyamic acid derivatives include 1) polyimide in which all amino groups and carboxyl groups of a polyamic acid have undergone a dehydrative ring closure reaction, 2) partially polyimide in which a dehydrative ring closure reaction has been partially performed, 3) polyamic acid ester in which a carboxyl group of a polyamic acid has been converted into an ester, 4) polyamic acid-polyamide copolymer in which a part of an acid dianhydride contained in a tetracarboxylic acid dianhydride compound has been replaced with an organic dicarboxylic acid and reacted, and 5) polyamideimide in which a part or all of the polyamic acid-polyamide copolymer has undergone a dehydrative ring closure reaction. Among these derivatives, for example, as polyimide, a compound having a structural unit represented by the above formula (PI) is exemplified, and as polyamic acid ester, a compound having a structural unit represented by the following formula (PAE) is exemplified.
In the formula (PAE), X 1 Is a 4-valent organic group, X 2 Is a 2-valent organic group, and Y is independently an alkyl group. Regarding X 1 、X 2 Reference may be made to the preferred ranges and specific examples relating to X in formula (PAA) 1 、X 2 The description of (2). In Y, a linear or branched alkyl group having 1 to 6 carbon atoms is preferable, and methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl is more preferable.
The tetracarboxylic dianhydride and the diamine used for the synthesis of the polyamic acid may be either one or two or more.
In the case of producing a polyimide as a polyamic acid derivative from a polyamic acid, the obtained polyamic acid solution is subjected to imidization reaction at a temperature of 20 to 150 ℃ together with an acid anhydride such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride, or the like as a dehydrating agent, and a tertiary amine such as triethylamine, pyridine, or collidine, or the like, as a dehydrating ring-closure catalyst. Alternatively, a polyimide may be obtained by precipitating a polyamic acid from the obtained polyamic acid solution using a large amount of a poor solvent (an alcoholic solvent such as methanol, ethanol, or isopropanol, or a glycol solvent), and subjecting the precipitated polyamic acid to imidization reaction in a solvent such as toluene or xylene together with the dehydrating agent and the dehydration ring-closure catalyst at a temperature of 20 to 150 ℃.
In the imidization reaction, the ratio of the dehydrating agent to the dehydration ring-closing catalyst is preferably 0.1 to 10 (molar ratio). The total amount of the dehydrating agent and the dehydrating ring-closing catalyst to be used is preferably 1.5 to 10 times by mol based on the total amount of the molar amount of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid. By adjusting the amount of the dehydrating agent, the catalyst, the reaction temperature and the reaction time used in the imidization reaction, the degree of imidization can be controlled, whereby a part of polyimide obtained by imidizing only a part of polyamic acid can be obtained. The polyimide thus obtained may be separated from the solvent used in the reaction and dissolved in another solvent to be used as a liquid crystal aligning agent, or may be used as a liquid crystal aligning agent without separation from the solvent.
The polyamic acid ester can be obtained by a method of synthesizing a polyamic acid by reacting with a hydroxyl group-containing compound, a halide, an epoxy group-containing compound, or the like, or a method of synthesizing a tetracarboxylic acid diester derived from a tetracarboxylic acid dianhydride or a tetracarboxylic acid diester dichloride by reacting with diamines. The tetracarboxylic acid diester derived from the tetracarboxylic acid dianhydride can be obtained, for example, by ring-opening by reacting the tetracarboxylic acid dianhydride with 2 equivalents of alcohol, and the tetracarboxylic acid diester dichloride can be obtained by reacting the tetracarboxylic acid diester with 2 equivalents of a chlorinating agent (for example, thionyl chloride, etc.). The polyamic acid ester may have only an amic acid ester structure, or may be a partial ester in which the amic acid structure and the amic acid ester structure coexist.
The polyamic acid or derivative thereof used in the liquid crystal aligning agent for photo-alignment of the present invention can be produced in the same manner as the known polyamic acid or derivative thereof used for film formation of polyimide.
The liquid crystal aligning agent for photo-alignment of the present invention may contain only one kind of these polyamic acid, polyamic acid ester, and polyimide obtained by imidizing these, or may contain two or more kinds.
The molecular weight of the polyamic acid or derivative thereof is preferably 5000 to 500000, more preferably 5000 to 50000, in terms of weight average molecular weight (Mw) in terms of polystyrene. The molecular weight of the polyamic acid or derivative thereof can be determined by measurement using Gel Permeation Chromatography (GPC).
The presence of the polyamic acid or its derivative can be confirmed by analyzing a solid content obtained by precipitating the polyamic acid or its derivative with a large amount of a poor solvent by IR (infrared spectroscopy) or NMR (nuclear magnetic resonance analysis). Further, the monomers used can be confirmed by forming an extract from the decomposed product of the polyamic acid or derivative thereof formed from an aqueous solution of a strong base such as KOH or NaOH by an organic solvent, and analyzing the extract by GC (gas chromatography), HPLC (high performance liquid chromatography), or GC-MS (gas chromatography mass spectrometry).
< monoamine having two or more hydroxyl groups >
The monoamine having two or more hydroxyl groups used in the present invention will be described.
The monoamine having two or more hydroxyl groups used in the present invention may be one kind or two or more kinds may be mixed and used.
Examples of the monoamine having two or more hydroxyl groups include monoamines represented by the following formulas (Xa) to (Xf).
In the formulas (Xa), (Xb), rx is independently a hydrogen atom or a methyl group.
As the monoamines represented by the formulae (Xa) to (Xf), specifically, the following formulae (Xa-1), (Xa-2), (Xb-1), (Xb-2), (Xc-1) and (Xc-2) can be mentioned.
By using the monoamines represented by the formulas (Xa) to (Xf), an alignment film which maintains a good contrast as a liquid crystal display element and has good film hardness and sealing adhesion can be obtained. Of these, the formula (Xd) or the formula (Xe) is preferable, and the formula (Xe) is particularly preferable.
The polymer of the present invention is a polyamic acid and a derivative thereof obtained by reacting a tetracarboxylic acid derivative containing at least one of the compounds represented by the formula (I), a diamine, and a monoamine having two or more hydroxyl groups. Monoamines having two or more hydroxyl groups are used as the blocking agent.
The polymer of the present invention can be obtained, for example, by the following steps. First, a tetracarboxylic acid derivative is reacted with a diamine. Then, a monoamine having two or more hydroxyl groups is added to react with unreacted sites of the tetracarboxylic acid derivative, thereby forming a cap. Alternatively, the compound may be produced by simultaneously reacting a tetracarboxylic acid derivative, a diamine, and a monoamine having two or more hydroxyl groups, or may be produced by first reacting a tetracarboxylic acid derivative with a monoamine having two or more hydroxyl groups and then reacting diamines.
The total amount of the diamine to be added is preferably 0.80 to 0.99 mole based on 1 mole of the total of the tetracarboxylic acid derivatives. The total amount of monoamine having two or more hydroxyl groups to be added is preferably 0.02 to 0.40 relative to 1 mol of the total of the tetracarboxylic acid derivatives.
< Compound represented by formula (I) >
The compound represented by the formula (I) used as a raw material for the polymer of the present invention will be described.
In the formula (I), 1', 2 and 2' are chemical bonds, and each is independently bonded to a hydroxyl group, a chlorine atom or an alkoxy group having 1 to 6 carbon atoms, and at least one of the group of 1 and 1 'and the group of 2 and 2' is capable of bonding to the same oxygen atom;
R b1 、R b2 、R b3 and R is b4 Each independently is a hydrogen atom or a methyl group, at least one of which is a methyl group.
Specific examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and tert-butoxy groups. Methoxy is preferable from the viewpoint of the easiness of imidization.
The formula (I) contains a form in which all of 4 chemical bonds are bonded to any one of a hydroxyl group, a chlorine atom, and an alkoxy group having 1 to 6 carbon atoms; * A form in which any one of the group 1 and 1 'and the group 2 and 2' is bonded to the same oxygen atom, and two chemical bonds of the remaining group are bonded to any one of a hydroxyl group, a chlorine atom, and an alkoxy group having 1 to 6 carbon atoms; and a form in which both the groups of 1 and 1 'and the groups of 2 and 2' are bonded to the same oxygen atom, respectively. Of these, a form in which all of 4 chemical bonds are bonded to any one of a hydroxyl group, a chlorine atom, and an alkoxy group having 1 to 6 carbon atoms is preferable; and a form in which both the groups of 1 and 1 'and the groups of 2 and 2' are bonded to the same oxygen atom, respectively.
From the viewpoint of obtaining a liquid crystal alignment film having high sensitivity to exposure energy, R is preferable b1 And R is b4 Is methyl, R b2 And R is b3 Is a hydrogen atom. The following examples are preferred.
In the polymer of the present invention, the compound represented by the formula (I) is preferably used in an amount of 50 mol% or more based on the total amount of the tetracarboxylic acid derivative used.
< other tetracarboxylic acid derivatives >
The polymer of the present invention may be a tetracarboxylic acid derivative other than the compound represented by the formula (I). Hereinafter, a tetracarboxylic dianhydride which can be used in combination with the compound represented by the formula (I) is exemplified. These tetracarboxylic dianhydrides can also be derivatized to tetracarboxylic diesters, tetracarboxylic diester dichlorides, and used as starting materials for polymers.
[ tetracarboxylic dianhydride represented by the formula (AN-1) ]
In the formula (AN-1), G 11 Is a single bond, an alkylene group having 1 to 12 carbon atoms, a 1,4-phenylene group (1, 4-phenylene), a 1,4-cyclohexylene group (1, 4-cyclohexylene) or a formula (G11-1). R is R 11 Independently a hydrogen atom or a methyl group.
In the formula (G11-1), X is independently a single bond, -O-, -S-, or-NR 1 -，R 1 Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is independently an integer of 1 to 5, and m is an integer of 1 to 3The number of groups not having a bonding position fixed to any carbon atom constituting the ring indicates a group capable of bonding to any carbon bondable to the ring.
The tetracarboxylic dianhydride represented by the following formula (AN-1) is exemplified.
In the formulae (AN-1-2) and (AN-1-5), each m is independently AN integer of 1 to 12.
[ tetracarboxylic dianhydride represented by the formula (AN-2) ]
In the formula (AN-2), G 11 Is a single bond, an alkylene group having 1 to 12 carbon atoms, a 1, 4-phenylene group or a 1, 4-cyclohexylene group. X is X 11 Is a single bond or-CH 2 -。G 12 Independently any of the following 3-valent groups.
At G 12 When > N-, G 11 Not a single bond and-CH 2 -，X 11 Is not a single bond.
The tetracarboxylic dianhydride represented by the following formula (AN-2) is exemplified.
In the formula (AN-2-2), m is AN integer of 1 to 12.
[ tetracarboxylic dianhydride represented by the formula (AN-3) ]
In the formula (AN-3), the ring A 11 Is cyclohexane ring or benzene ring.
As examples of the tetracarboxylic dianhydride represented by the formula (AN-3), compounds represented by the following formulas (AN-3-1) and (AN-3-2) are given.
[ tetracarboxylic dianhydride represented by the formula (AN-4) ]
In the formula (AN-4), G 13 Is a single bond, - (CH) 2 )m-、-O-、-S-、-C(CH 3 ) 2 -、-SO 2 -、-CO-、-C(CF 3 ) 2 Or a 2-valent group represented by the following formula (G13-1), m being an integer of 1 to 12. Ring A 11 Each independently is a cyclohexane ring or a benzene ring. G 13 Can be combined with ring A 11 Is bonded at any position of the substrate.
In the formula (G13-1), G 13a And G 13b Each independently is a single bond, -O-, -CONH-, or-NHCO-, a 2-valent group. The phenylene group is preferably a 1, 4-phenylene group or a 1, 3-phenylene group.
As examples of the tetracarboxylic dianhydride represented by the formula (AN-4), compounds represented by the following formulas (AN-4-1) to (AN-4-31) are given.
In the formula (AN-4-17), m is AN integer of 1 to 12.
[ tetracarboxylic dianhydride represented by the formula (AN-5) ]
In the formula (AN-5), R 11 Independently a hydrogen atom or a methyl group. Two R 11 R in the benzene ring 11 Bonded to any of the substitutable positions of the benzene ring.
As examples of the tetracarboxylic dianhydride represented by the formula (AN-5), compounds represented by the following formulas (AN-5-1) to (AN-5-3) are given.
[ tetracarboxylic dianhydride represented by the formula (AN-6) ]
In the formula (AN-6), X 11 Independently a single bond or-CH 2 -。X 12 is-CH 2 -、-CH 2 CH 2 -or-ch=ch-. n is 1 or 2. When n is 2, two X 12 May be the same as or different from each other.
As examples of the tetracarboxylic dianhydride represented by the formula (AN-6), compounds represented by the following formulas (AN-6-1) to (AN-6-12) are given.
[ tetracarboxylic dianhydride represented by the formula (AN-7) ]
In the formula (AN-7), X 11 Is a single bond or-CH 2 -。
As examples of the tetracarboxylic dianhydride represented by the formula (AN-7), compounds represented by the following formulas (AN-7-1) and (AN-7-2) are given.
[ tetracarboxylic dianhydride represented by the formula (AN-8) ]
In the formula (AN-8), X 11 Is a single bond or-CH 2 -。R 12 Is a hydrogen atom, methyl, ethyl or phenyl. Ring A 12 Is cyclohexane or cyclohexene.
As examples of the tetracarboxylic dianhydride represented by the formula (AN-8), compounds represented by the following formulas (AN-8-1) and (AN-8-2) are given.
[ tetracarboxylic dianhydride represented by the formula (AN-9) ]
In the formula (AN-9), r is each independently 0 or 1.
As examples of the tetracarboxylic dianhydride represented by the formula (AN-9), compounds represented by the following formulas (AN-9-1) to (AN-9-3) are given.
[ tetracarboxylic dianhydrides represented by the formulae (AN-10-1) and (AN-10-2) ]
[ tetracarboxylic dianhydride represented by the formula (AN-11) ]
In the formula (AN-11), the ring A11 is independently a cyclohexane ring or a benzene ring.
As examples of the tetracarboxylic dianhydride represented by the formula (AN-11), compounds represented by the following formulas (AN-11-1) to (AN-11-3) are given.
[ tetracarboxylic dianhydride represented by the formula (AN-12) ]
In the formula (AN-12), the ring A 11 Each independently is a cyclohexane ring or a benzene ring.
As examples of the tetracarboxylic dianhydride represented by the formula (AN-12), compounds represented by the following formulas (AN-12-1) to (AN-12-3) are given.
[ tetracarboxylic dianhydride represented by the formula (AN-15) ]
In the formula (AN-15), w is AN integer of 1 to 10.
As examples of the tetracarboxylic dianhydride represented by the formula (AN-15), compounds represented by the following formulas (AN-15-1) to (AN-15-3) are given.
[ tetracarboxylic dianhydrides represented by the formulae (AN-16-1) to (AN-16-19) ]
As the tetracarboxylic dianhydride other than the above, compounds represented by the following formulas (AN-16-1) to (AN-16-19) are mentioned.
< diamines of the formulae (DI-1) to (DI-17) and (DIH-1) to (DIH-3) >)
The diamine used as the raw material of the polymer of the present invention may be any known diamine. As specific examples, diamines represented by the formulas (DI-1) to (DI-17) and the formulas (DIH-1) to (DIH-3) will be described.
In the formula (DI-1), G 20 Is an alkylene group having 1 to 12 carbon atoms or a group represented by the formula (DI-1-a). When G 20 In the case of an alkylene group having 1 to 12 carbon atoms, -CH 2 At least one of them may be substituted by-NH-or-O-but they are not adjacent, -CH 2 At least one hydrogen atom of the group may be substituted by hydroxy or methyl.
In the formula (DI-1-a), v is an integer of 1 to 6 independently of each other.
In the formula (DI-3), the formula (DI-6) and the formula (DI-7), G 21 Independently a single bond, -NH-, -NCH 3 -、-O-、-S-、-S-S-、-SO 2 -、-CO-、-COO-、-CONCH 3 -、-CONH-、-C(CH 3 ) 2 -、-C(CF 3 ) 2 -、-(CH 2 ) m -、-O-(CH 2 ) m -O-、-N(CH 3 )-(CH 2 ) k -N(CH 3 )-、-(O-C 2 H 4 ) m -O-、-O-CH 2 -C(CF 3 ) 2 -CH 2 -O-、-O-CO-(CH 2 ) m -CO-O-、-CO-O-(CH 2 ) m -O-CO-、-(CH 2 ) m -NH-(CH 2 ) m -、-CO-(CH 2 ) k -NH-(CH 2 ) k -、-(NH-(CH 2 ) m ) k -NH-、-CO-C 3 H 6 -(NH-C 3 H 6 ) n -CO-, or-S- (CH) 2 ) m-S-, m is independently an integer of 1 to 12, k is an integer of 1 to 5, and n is 1 or 2.
In the formula (DI-4), s is independently an integer of 0 to 2.
In the formula (DI-5), G 33 Is a single bond, -NH-, -NCH 3 -、-O-、-S-、-S-S-、-SO 2 -、-CO-、-COO-、-CONCH 3 -、-CONH-、-C(CH 3 ) 2 -、-C(CF 3 ) 2 -、-(CH 2 ) m -、-O-(CH 2 ) m -O-、-(O-C 2 H 4 ) m -O-、-O-CH 2 -C(CF 3 ) 2 -CH 2 -O-、-O-CO-(CH 2 ) m -CO-O-、-CO-O-(CH 2 ) m -O-CO-、-(CH 2 ) m -NH-(CH 2 ) m -、-CO-(CH 2 ) k -NH-(CH 2 ) k -、-CO-C 3 H 6 -(NH-C 3 H 6 ) n -CO-, or-S- (CH) 2 ) m -S-、-N(Boc)-(CH 2 ) e -、-(CH 2 ) m -N(Boc)-CONH-(CH 2 ) m -、-(CH 2 ) m -N(Boc)-(CH 2 ) m Or a group represented by the following formula (DI-5-a) or (DI-5-b), m is independently an integer of 1 to 12, k is an integer of 1 to 5, e is an integer of 2 to 10, and n is 1 or 2.Boc is t-butoxycarbonyl (tertiary butoxycarbonyl).
In the formula (DI-5-a), q is an integer of 0 to 6 independently of each other. R is R 44 Is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
In the formula (DI-6) and the formula (DI-7), G 22 Independently a single bond, -O-, -S-, -CO-, -C (CH) 3 ) 2 -、-C(CF 3 ) 2 Or an alkylene group having 1 to 10 carbon atoms.
At least one hydrogen atom of the cyclohexane ring and the benzene ring in the formulae (DI-2) to (DI-7) may be substituted with a fluorine atom, a chlorine atom, an alkyl group having 1 to 3 carbon atoms, a methoxy group, a hydroxyl group, a trifluoromethyl group, a carboxyl group, a carbamoyl group, a phenylamino group, a phenyl group or a benzyl group, and furthermore, in the formula (DI-4), at least one hydrogen atom of the benzene ring may be substituted with one selected from the group of groups represented by any one of the following formulae (DI-4-a) to (DI-4-i), in the formula (DI-5), in G 33 In the case of a single bond, at least one hydrogen atom of the benzene ring may be bonded to NHBoc or N (Boc) 2 And (3) substitution.
In the formula (DI-4-a) and the formula (DI-4-b), R 20 Independently a hydrogen atom or a methyl group. In the formula (DI-4-f) and the formula (DI-4-g), m is an integer of 0 to 12 independently of each otherBoc is t-butoxycarbonyl.
In the formulae (DI-2) to (DI-7), the group in which the bonding position is not fixed to the carbon atom constituting the ring means that the bonding position in the ring is arbitrary.
In the formula (DI-11), r is 0 or 1. In the formulae (DI-8) to (DI-11), the bonding position of the amino group bonded to the ring is arbitrary.
In the formula (DI-12), R 21 And R is 22 Each independently is an alkyl group having 1 to 3 carbon atoms or a phenyl group, G 23 Independently is an alkylene group having 1 to 6 carbon atoms, a phenylene group or a phenylene group substituted with an alkyl group, and w is an integer of 1 to 10.
In the formula (DI-13), R 23 Independently is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a chlorine atom, and p and q are each independently integers of 0 to 4.
In the formula (DI-14), ring B is a monocyclic heterocyclic aromatic group, R 24 Is hydrogen atom, fluorine atom, chlorine atom, alkyl group, alkoxy group, alkenyl group or alkynyl group having 1 to 6 carbon atoms, q is an integer of 0 to 4. When q is 2 or more, a plurality of R 24 May be the same as or different from each other. In the formula (DI-15), the ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group. In the formula (DI-16), G 24 Is a single bond, an alkylene group having 2 to 6 carbon atoms, or a 1, 4-phenylene group, and r is 0 or 1.
In the formula (DI-17), R 23 Independently is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a chlorine atom, p is independently an integer of 0 to 4, R 25 Independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a t-butoxycarbonyl group, and Z is a 2-valent group containing an alkylene group having 1 to 5 carbon atoms. Any position in alkylene group having 1 to 5 carbon atoms and any number of CH 2 NH may be substituted but NH is not adjacent.
R 25 The preferred example of the alkyl group having 1 to 4 carbon atoms is a methyl group. A preferred example of the 2-valent group containing an alkylene group having 1 to 5 carbon atoms in Z is- (CH) 2 ) m -、-Ph-(CH 2 ) m Ph-, m is an integer from 1 to 5. Among them, preferred is- (CH) 2 ) m -, further preferred is- (CH) 2 ) 2 - (ethylene). Here, ph is 1, 4-phenylene.
In the formulae (DI-13) to (DI-17), the group in which the bonding position is not fixed to the carbon atom constituting the ring means that the bonding position in the ring is arbitrary. The bonding position of the amino groups in the two terminal rings may be arbitrary, and para (para-) and meta (meta-) are preferred, and para is more preferred.
In the formula (DIH-1), G 25 Is a single bond, alkylene group with 1-20 carbon atoms, -CO-, -O-, -S-, -SO 2 -、-C(CH 3 ) 2 -or-C (CF) 3 ) 2 -。
In the formula (DIH-2), the ring D is a cyclohexylene group, a phenylene group or a naphthylene group, at least one hydrogen atom of which may be substituted with a methyl group, an ethyl group or a phenyl group.
In the formula (DIH-3), the rings E are each independently cyclohexylene or phenylene, at least one hydrogen atom of which may be replaced by methyl, ethyl or phenyl. The two rings E may be identical to or different from each other. Y is a single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO 2 -、-C(CH 3 ) 2 -, or-C (CF) 3 ) 2 -. In the formulae (DIH-2) and (DIH-3), the bonding position of the-hydrazide group bonded to the ring is arbitrary.
Examples of the diamine represented by the formula (DI-1) are shown by the following formulas (DI-1-1) to (DI-1-9).
In the formula (DI-1-7) and the formula (DI-1-8), k is an integer of 1 to 3 independently of each other. In the formula (DI-1-9), v is an integer of 1 to 6 independently of each other.
Examples of the diamines of the formulae (DI-2) to (DI-3) are shown in the following formulae (DI-2-1), (DI-2-2) and (DI-3-1) to (DI-3-3).
Examples of the diamine represented by the formula (DI-4) are shown by the following formulas (DI-4-1) to (DI-4-27).
In the formula (DI-4-20) and the formula (DI-4-21), m is an integer of 1 to 12, respectively.
Examples of the diamine represented by the formula (DI-5) are represented by the following formulas (DI-5-1) to (DI-5-29), formulas (DI-5-31) to (DI-5-38), formulas (DI-5-40), formulas (DI-5-41) and formulas (DI-5-44) to (DI-5-50).
In the formula (DI-5-1), m is an integer of 1 to 12.
In the formula (DI-5-12) and the formula (DI-5-13), m is an integer of 1 to 12 independently of each other.
In the formula (DI-5-16), v is an integer of 1 to 6.
In the formulae (DI-5-35) to (DI-5-37), m is an integer of 1 to 12, in the formula (DI-5-38), k is an integer of 1 to 5, in the formula (DI-5-40), and n is 1 or 2.
In the formula (DI-5-44), e is an integer of 2 to 10, R in the formula (DI-5-45) 43 Independently a hydrogen atom, (t-butoxycarbonyl) amino group or a bis (t-butoxycarbonyl) amino group.
Examples of the diamine represented by the formula (DI-6) are shown by the following formulas (DI-6-1) to (DI-6-7).
Examples of the diamine represented by the formula (DI-7) are shown by the following formulas (DI-7-1) to (DI-7-11).
In the formula (DI-7-3) and the formula (DI-7-4), m is an integer of 1 to 12, and n is 1 or 2.
Examples of the diamine represented by the formula (DI-8) are shown by the following formulas (DI-8-1) to (DI-8-4).
Examples of the diamine represented by the formula (DI-9) are shown by the following formulas (DI-9-1) to (DI-9-3).
Examples of the diamine represented by the formula (DI-10) are represented by the following formulas (DI-10-1) and (DI-10-2).
Examples of the diamine represented by the formula (DI-11) are shown by the following formulas (DI-11-1) to (DI-11-3).
An example of the diamine represented by the formula (DI-12) is represented by the following formula (DI-12-1).
Examples of the diamine represented by the formula (DI-13) are shown by the following formulas (DI-13-1) to (DI-13-13).
Examples of the diamine represented by the formula (DI-14) are shown by the following formulas (DI-14-1) to (DI-14-9).
Examples of the diamine represented by the formula (DI-15) are shown by the following formulas (DI-15-1) to (DI-15-12).
An example of the diamine represented by the formula (DI-16) is represented by the following formula (DI-16-1).
Examples of the diamine represented by the formula (DI-17) are shown by the following formulas (DI-17-1) to (DI-17-4).
In the formula (DI-17-1), k is an integer of 1 to 5. In the formulae (DI-17-2) to (DI-17-3), e is an integer of 1 to 10, and Boc is t-butoxycarbonyl. In the formula (DI-17-4), each m is independently an integer of 1 to 5, and k is 1 or 2.
Examples of the compounds represented by any one of the formulae (DIH-1) to (DIH-3) are represented by the following formulae (DIH-1-1), formula (DIH-1-2), formula (DIH-2-1) to formula (DIH-2-3), and formula (DIH-3-1) to formula (DIH-3-6).
In the formula (DIH-1-2), m is an integer of 1 to 12.
Preferred materials for improving the respective characteristics of the liquid crystal alignment film described later among the diamines will be described. In order to improve the afterimage characteristics, it is preferable to use the compounds represented by the formulas (DI-5), (DI-13) and (DI-17). Of the compounds represented by the formula (DI-5), a compound represented by m=2 is more preferable. Among the compounds represented by the formula (DI-13), the compound represented by the formula (DI-13-1) is preferably used. Among the compounds represented by the formula (DI-17), the compound represented by the formula (DI-17-1) is preferably used, and k=2 is more preferably used.
The liquid crystal aligning agent for photo-alignment of the present invention may be composed of one kind of the polymer of the present invention, or may be mixed with a polymer other than the present invention. In the present specification, a liquid crystal aligning agent composed of one of the above polymers is sometimes referred to as a single layer liquid crystal aligning agent. A liquid crystal aligning agent in which two or more of the above polymers are mixed is sometimes referred to as a blended liquid crystal aligning agent. The blend type liquid crystal aligning agent is used particularly when VHR (Voltage Holding Ratio ) reliability and other electric characteristics are important.
The polymer other than the present invention used for the blended liquid crystal aligning agent is preferably one or more of polyamic acid and a polyamic acid derivative. As the polymer other than the present invention, the polyamic acid and the polyamic acid derivative may be referred to as the description of the polymer of the present invention described above, except that the compound represented by the formula (I) is not included as the raw material composition.
In the case of using a polymer of two components, for example, there is a method of selecting a polymer having excellent properties for liquid crystal alignment ability and selecting a polymer having excellent properties for improving electric characteristics of a liquid crystal display element, and it is suitable to obtain a liquid crystal alignment agent having a good balance between liquid crystal alignment property and electric characteristics.
In this case, by controlling the structure and molecular weight of each polymer, and applying a liquid crystal aligning agent obtained by dissolving these polymers in a solvent to a substrate as described later and pre-drying the same to form a thin film, it is possible to segregate a polymer having excellent properties for liquid crystal aligning ability in an upper layer of the thin film and a polymer having excellent properties for improving the electrical characteristics of a liquid crystal display element in a lower layer of the thin film. Thus, among the polymers mixed with each other, a phenomenon in which a polymer having a small surface energy is separated into an upper layer and a polymer having a large surface energy is separated into a lower layer can be applied. The confirmation of such layer separation can be confirmed by the fact that the surface energy of the formed liquid crystal alignment film is the same or similar to the surface energy of a film formed of a liquid crystal alignment agent containing only a polymer intended to segregate in the upper layer.
As a method for exhibiting layer separation, there is also mentioned a method for reducing the molecular weight of a polymer to be segregated in an upper layer.
In a liquid crystal aligning agent composed of a mixture of polyamic acid and a polyamic acid derivative, layer separation may be expressed by using a polymer that is desired to segregate in an upper layer as a polyamic acid ester or polyimide.
The polymer of the present invention may be used as a raw material of a polymer segregated in the upper layer of the film, or as a raw material of a polymer segregated in the lower layer of the film, or may be used as a raw material of two polymers, and more preferably as a raw material of a polymer segregated in the upper layer of the film.
The proportion of the polyamic acid or derivative thereof segregated in the upper layer of the film is preferably 5 to 80% by weight, more preferably 20 to 80% by weight, based on the total amount of the polyamic acid or derivative thereof segregated in the upper layer of the film and the polyamic acid or derivative thereof segregated in the lower layer of the film.
The liquid crystal aligning agent for photo-alignment of the present invention may further contain a solvent from the viewpoints of the coatability of the liquid crystal aligning agent and the adjustment of the concentration of the polyamic acid or derivative thereof. The solvent is not particularly limited as long as it has an ability to dissolve the polymer component. The solvent is generally used in the production process and the use of the polymer component such as polyamic acid and soluble polyimide, and may be appropriately selected according to the purpose of use. The solvent may be one kind or a mixed solvent of two or more kinds.
Examples of the solvent include a good solvent for the polyamic acid or derivative thereof and other solvents for the purpose of improving coatability.
Examples of the aprotic polar organic solvent which is a good solvent for the polyamic acid or its derivative include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl imidazolidinone, N-methylcaprolactam, N-methylpropanamide, N-dimethylacetamide, dimethylsulfoxide, N-dimethylformamide, N-diethylformamide, diethylacetamide, N-dimethylisobutyl amide, γ -butyrolactone, and γ -valerolactone. Of these, N-methyl-2-pyrrolidone, dimethylimidazolidinone, gamma-butyrolactone or gamma-valerolactone is preferable.
Examples of other solvents for the purpose of improving coatability and the like include ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether and ethylene glycol mono tertiary butyl ether; diethylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether; diethylene glycol dialkyl ethers such as diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether and diethylene glycol butyl methyl ether. Further, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and 1-butoxy-2-propanol; dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether; triethylene glycol monoalkyl ether; butyl cellosolve acetate, phenyl acetate, and ester compounds such as these acetates. Further, examples thereof include dialkyl malonates such as diethyl malonate; alkyl lactate, diisobutyl ketone, diacetone alcohol, 3-methyl-3-methoxybutanol, 4-methyl-2-pentanol, diisobutyl methanol, tetrahydronaphthalene and isophorone.
Of these, diisobutyl ketone, 4-methyl-2-pentanol, diisobutyl methanol, ethylene glycol monobutyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, 1-butoxy-2-propanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether or butyl cellosolve acetate is preferred.
The concentration of the solid content in the liquid crystal aligning agent for photo-alignment of the present invention is not particularly limited, and the optimum value can be selected according to various coating methods described below. In general, in order to suppress unevenness, pinholes, and the like at the time of coating, the amount is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight, relative to the varnish weight.
The viscosity of the liquid crystal aligning agent for photo-alignment of the present invention varies depending on the method of coating, the concentration of the polyamic acid or derivative thereof, the kind of the polyamic acid or derivative thereof used, the kind and ratio of the solvent. For example, when the coating is performed by a printer, the thickness is 5 to 100 mPas (more preferably 10 to 80 mPas). When the thickness is 5 mPas or more, a sufficient film thickness is easily obtained, and when the thickness is 100 mPas or less, printing unevenness is easily suppressed. When the coating is performed by spin coating, it is preferably 5 to 200 mPas (more preferably 10 to 100 mPas). When the coating is performed by using an inkjet coating device, the thickness is preferably 5 to 50 mPas (more preferably 5 to 20 mPas). The viscosity of the liquid crystal aligning agent is measured by a rotational viscosity measurement method, for example, using a rotational viscometer (TVE-20L type viscometer manufactured by DONGMACHINESE Co., ltd.) (measurement temperature: 25 ℃ C.).
The liquid crystal aligning agent for photo-alignment of the present invention may further contain various additives. In order to improve various characteristics of the liquid crystal alignment film, various additives may be selectively used according to respective purposes. Examples are shown below.
< alkenyl substituted nadic imide (nadimide) compound >
For example, the liquid crystal aligning agent for photoalignment of the present invention may further contain an alkenyl-substituted nadic imide compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The alkenyl-substituted nadic imide compound may be used singly or in combination. From the above-mentioned object, the content of the alkenyl-substituted nadic imide compound is preferably 1 to 50% by weight, more preferably 1 to 30% by weight, still more preferably 1 to 20% by weight, relative to the polyamic acid or derivative thereof. The alkenyl-substituted nadic imide compound is preferably a compound that can be dissolved in a solvent in which the polyamic acid or derivative thereof used in the present invention is dissolved. Preferred examples of the alkenyl-substituted nadic imide compound include alkenyl-substituted nadic imide compounds disclosed in japanese patent laid-open publication nos. 2008-096979, 2009-109987, and 2013-242526. Particularly preferred alkenyl-substituted nadic imide compounds include bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) phenyl } methane, N '-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) or N, N' -hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide).
< Compound having radically polymerizable unsaturated double bond >
For example, the liquid crystal aligning agent for photoalignment of the present invention may further contain a compound having a radically polymerizable unsaturated double bond, for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The compound having a radical polymerizable unsaturated double bond may be one compound or two or more compounds. In addition, the compound having a radical polymerizable unsaturated double bond does not contain an alkenyl-substituted nadic imide compound. Examples of the compound having a radical polymerizable unsaturated double bond include, as preferable compounds, N ' -methylenebisacrylamide, N ' -dihydroxyethylene-bisacrylamide, ethylenebisacrylate, 4' -methylenebis (N, N-dihydroxyethyleneacryiamine), triallylcyanurate, other Japanese patent application laid-open No. 2009-109987, japanese patent application laid-open No. 2013-242526, international publication No. 2014/119682, and International publication No. 2015/152014, which have a radical polymerizable unsaturated double bond. From the above-mentioned object, the content of the compound having a radical polymerizable unsaturated double bond is preferably 1 to 50% by weight, more preferably 1 to 30% by weight, relative to the polyamic acid or derivative thereof.
< oxazine Compound >
For example, the liquid crystal aligning agent for photo-alignment of the present invention may further contain an oxazine compound for the purpose of stabilizing the electrical characteristics in the liquid crystal display element for a long period of time. The oxazine compound may be one compound or two or more compounds. From the above-mentioned object, the content of the oxazine compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, still more preferably 1 to 20% by weight, relative to the polyamic acid or derivative thereof.
The oxazine compound is soluble in a solvent for dissolving the polyamic acid or derivative thereof, and an oxazine compound having ring-opening polymerization is preferable. Preferred oxazine compounds include oxazine compounds represented by the formula (OX-3-1), the formula (OX-3-9) or the formula (OX-3-10), and oxazine compounds disclosed in other Japanese patent application laid-open No. 2007-286597 and Japanese patent application laid-open No. 2013-242526.
< oxazoline Compound >
For example, the liquid crystal aligning agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the electrical characteristics in the liquid crystal display element for a long period of time. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one compound or two or more compounds. From the above-mentioned object, the content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, still more preferably 1 to 20% by weight, relative to the polyamic acid or derivative thereof. Preferable oxazoline compounds include those disclosed in JP-A2010-054872 and JP-A2013-242526. More preferably 1, 3-bis (4, 5-dihydro-2-oxazolyl) benzene.
< epoxy Compound >
For example, the liquid crystal aligning agent for photo-alignment of the present invention may further contain an epoxy compound for the purpose of stabilizing electrical characteristics in a liquid crystal display element for a long period of time, for the purpose of improving the hardness of a film, or for the purpose of improving the adhesion with a sealant. The epoxy compound may be one kind of compound or two or more kinds of compounds. From the above-mentioned object, the content of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 1 to 20% by weight, and even more preferably 1 to 10% by weight, relative to the polyamic acid or derivative thereof.
As the epoxy compound, various compounds having one or more epoxy rings in the molecule can be used.
In order to improve the hardness of the film or to improve the adhesion to the sealant, a compound having two or more epoxy rings in the molecule is preferable, and a compound having 3 or 4 epoxy rings is more preferable.
Examples of the epoxy compound include those disclosed in Japanese patent application laid-open No. 2009-175715, japanese patent application laid-open No. 2013-242526, japanese patent application laid-open No. 2016-170409, and International publication No. 2017/217413. Preferred epoxy compounds include N, N, N ', N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane, 3-glycidoxypropyl trimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, (3, 3', 4' -diepoxy) dicyclohexyl, 1, 4-butanediol glycidyl ether, tris (2, 3-epoxypropyl) isocyanurate, 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, and N, N, N ', N ' -tetraglycidyl-m-xylylenediamine. More preferred are 3-glycidoxypropyl trimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, and 2- (3, 4-epoxycyclohexyl) ethyl triethoxysilane. In addition to the above, an oligomer or polymer having an epoxy ring may be added. As the oligomer and polymer having an epoxy ring, those disclosed in Japanese patent application laid-open No. 2013-242526 can be used.
< silane Compound >
For example, the liquid crystal aligning agent for photo-alignment of the present invention may further contain a silane compound for the purpose of improving adhesion to a substrate and a sealant. From the above-mentioned object, the content of the silane compound is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and even more preferably 0.5 to 10% by weight, relative to the polyamic acid or derivative thereof.
As the silane compound, there can be used a silane coupling agent disclosed in Japanese patent application laid-open No. 2013-242526, japanese patent application laid-open No. 2015-212807, japanese patent application laid-open No. 2018-173545, and International publication No. 2018/181566. Preferred silane coupling agents include 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, p-aminophenyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, 3-isocyanatopropyl triethoxysilane, and 3-ureidopropyl triethoxysilane.
In addition to the above-described additives, a compound having a cyclic carbonate group, a compound having a hydroxyalkylamide moiety, or a hydroxyl group may be added for the purpose of improving the strength of a liquid crystal alignment film or for the purpose of stabilizing the electrical characteristics in a liquid crystal display element for a long period of time. Specific examples of the compound include those disclosed in Japanese patent application laid-open No. 2016-118753 and International publication No. 2017/110976. Preferable examples of the compound include the following formulae (HD-1) to (HD-4). These compounds are preferably 0.5 to 50% by weight, more preferably 1 to 30% by weight, and even more preferably 1 to 10% by weight, relative to the polyamic acid or derivative thereof.
In addition, when it is necessary to improve the antistatic property, an antistatic agent may be used, and in the case of imidization at a low temperature, an imidization catalyst may be used. As the imidization catalyst, there is mentioned an imidization catalyst disclosed in Japanese patent application laid-open No. 2013-242526.
< liquid Crystal alignment film >
The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the liquid crystal alignment agent for photo-alignment of the present invention. The liquid crystal alignment film of the present invention can be obtained by a usual method for producing a liquid crystal alignment film from a liquid crystal alignment agent. For example, the liquid crystal alignment film of the present invention can be obtained through a process of forming a coating film of the liquid crystal alignment agent for photo-alignment of the present invention, a process of heat drying, and a process of heat firing. The liquid crystal alignment film of the present invention is subjected to a treatment for imparting anisotropy. As the treatment, friction treatment may be performed to impart anisotropy, but it is preferable to impart anisotropy by light irradiation.
Hereinafter, a method for forming a liquid crystal alignment film of the liquid crystal alignment agent for photo-alignment of the present invention will be described.
The coating film can be formed by coating the liquid crystal alignment agent for photo-alignment of the present invention on a substrate in a liquid crystal display element in the same manner as in the production of a usual liquid crystal alignment film. The substrate may be provided with ITO (Indium Tin Oxide), IZO (In 2 O 3 -ZnO)、IGZO(In-Ga-ZnO 4 ) Electrodes such as electrodes, and substrates such as glass, silicon nitride, acrylic, polycarbonate, polyimide, and the like for color filters.
As a method of applying a liquid crystal aligning agent to a substrate, spin coating, printing, dip coating, dropping, inkjet, and the like are generally known. These methods are equally applicable in the present invention.
In general, a method of performing a heat treatment in an oven or an infrared oven, a method of performing a heat treatment on a heating plate, and the like are known in the heat drying step. The heat drying step is preferably performed at a temperature within a range where the solvent can evaporate, and more preferably at a temperature lower than the temperature in the heat firing step. Specifically, the heating and drying temperature is preferably in the range of 30 to 150 ℃, and more preferably in the range of 50 to 120 ℃.
The heating and firing step may be performed under conditions required for imidization of the polyamic acid or derivative thereof. The firing of the coating film is generally known as a method of heat-treating in an oven or an infrared oven, a method of heat-treating on a heating plate, or the like. These methods are equally applicable to the present invention. Generally, the temperature is preferably about 90 to 300 ℃, more preferably 120 to 280 ℃, and still more preferably 150 to 250 ℃. The firing time is not particularly limited, but is preferably 1 minute to 2 hours, more preferably 10 minutes to 40 minutes.
The heating may be performed in several times, or may be performed by changing the temperature at this time.
In order to orient the liquid crystal in one direction with respect to the horizontal and/or vertical directions, a known photo-alignment method can be preferably used as a means for imparting anisotropy to the liquid crystal alignment film.
As the light used in the light irradiation step in the photo-alignment method, for example, ultraviolet or visible light including light having a wavelength of 150 to 800nm may be used. The light is not particularly limited as long as it can impart liquid crystal alignment ability to the film, and if it is intended to cause the liquid crystal to exhibit strong alignment regulating force, polarized light is preferable, and linearly polarized light is more preferable.
The wavelength of the polarized light in the light irradiation step is preferably 150 to 400nm, more preferably 200 to 400nm, and even more preferably 200 to 300nm. The irradiation amount of the polarized light is preferably 0.001 to 10J/cm 2 More preferably 0.1 to 5J/cm 2 . The irradiation angle of the polarized light to the film surface is not particularly limited, and in the case where it is desired to exhibit a strong alignment regulating force to the liquid crystal, it is preferable to be as perpendicular as possible to the film surface from the viewpoint of shortening the alignment treatment time. In addition, the liquid crystal alignment film of the present invention can align liquid crystals in a direction perpendicular to the polarization direction of linearly polarized light by irradiating the linearly polarized light.
The light source used in the light irradiation step may be, without limitation, an ultra-high pressure mercury lamp, a low pressure mercury lamp, a Deep UV (Deep UV) lamp, a halogen lamp, a metal halide lamp, a high power metal halide lamp, a xenon lamp, a mercury-xenon lamp, an excimer lamp, a KrF excimer laser (KrF excimer laser), a fluorescent lamp, an LED (Lighting Emitting Diode, a light emitting diode) lamp, a sodium lamp, a microwave excitation electrodeless lamp, or the like.
In order to improve the liquid crystal alignment ability of the liquid crystal alignment film, light irradiation may be performed while heating the liquid crystal alignment film. In this case, the heating temperature is preferably in the range of 50℃to 250 ℃.
The light irradiation step may be performed after the heat drying step or after the heat firing step, and is preferably performed after the heat firing step. The heat drying step may be performed simultaneously with the heating drying step.
The liquid crystal alignment film of the present invention is preferably additionally heated after the light irradiation step. The heating temperature is preferably 150 to 300 ℃, more preferably 150 to 250 ℃, and even more preferably 200 to 250 ℃ at the same temperature or higher than the temperature of the heating and firing step. The additional heating time is preferably 5 minutes to 2 hours, more preferably 5 minutes to 60 minutes, and still more preferably 5 minutes to 30 minutes.
The cleaning step may be provided after the light irradiation step or after the additional heating step. Specifically, the liquid crystal alignment film is immersed in a solvent. The temperature at the time of impregnation is preferably 10 to 80 ℃, more preferably 20 to 50 ℃. In addition, ultrasonic treatment is also preferable. The treatment time is preferably 1 minute to 1 hour, more preferably 1 minute to 30 minutes. The solvent to be used is not particularly limited as long as it is a solvent that dissolves a decomposed product formed from the liquid crystal alignment film by irradiation with ultraviolet rays, and examples thereof include 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 from the viewpoint of versatility and safety. After impregnation, heating or rinsing is preferably carried out. Alternatively, both may be performed. The heating temperature is preferably 150 to 300 ℃, more preferably 200 to 230 ℃. The heating time is preferably 10 seconds to 30 minutes, more preferably 1 to 10 minutes. The solvent used for the flushing is preferably a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone or methyl ethyl ketone.
The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 to 300nm, more preferably 30 to 150nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as a step gauge or ellipsometer (ellipsometer).
The liquid crystal alignment film of the present invention can be suitably used for alignment control of a liquid crystal composition in a liquid crystal display element. In addition to the alignment application of the liquid crystal composition of the liquid crystal display element, the composition can be used for the alignment control of the liquid crystal material in all other liquid crystal elements such as a liquid crystal antenna, a dimming window, an optical compensation material, a variable phase shifter and the like.
< liquid Crystal display element >
Next, a liquid crystal display element of the present invention will be described. The liquid crystal display device of the present invention is characterized by having the liquid crystal alignment film of the present invention, and by having a good contrast, a high display quality can be achieved.
The liquid crystal display element of the present invention will be described in detail. The present invention provides a liquid crystal display element comprising a pair of substrates disposed to face each other, electrodes formed on one or both of the facing surfaces of the pair of substrates, a liquid crystal alignment film formed on the facing surface of each of the pair of substrates, a liquid crystal layer formed between the pair of substrates, and a pair of polarizing films, a backlight, and a driving device disposed so as to sandwich the pair of substrates, wherein the liquid crystal alignment film is composed of the liquid crystal alignment film of the present invention.
The electrode is not particularly limited as long as it is formed on one surface of the substrate. Examples of such electrodes include ITO and metal vapor deposited films. The electrode may be formed on the entire surface of one surface of the substrate, or may be formed in a desired shape, for example, by patterning. The desired shape of the electrode is for example a comb-like or saw-tooth structure. The electrode may be formed on one substrate or on both substrates of the pair of substrates. The formation mode of the electrode varies depending on the type of the liquid crystal display element, and for example, in the case of an IPS type liquid crystal display element (in-plane switching type liquid crystal display element), the electrode is disposed on one of the pair of substrates, and in the case of the other liquid crystal display element, the electrode is disposed on both of the pair of substrates. The liquid crystal alignment film is formed on the substrate or electrode.
The liquid crystal layer is formed by sandwiching a liquid crystal composition between the pair of substrates facing each other on which the liquid crystal alignment film is formed. In the formation of the liquid crystal layer, spacers having appropriate intervals may be formed using fine particles, resin sheets, or the like interposed between the pair of substrates as needed.
As a method for forming a liquid crystal layer, a vacuum injection method and an ODF (One Drop Fill) method are known.
In the vacuum injection method, a gap (cell gap) is provided so that the liquid crystal alignment film faces, an injection port of liquid crystal is left, and a sealing agent is printed and bonded to a substrate. After filling liquid crystal is injected into a cell gap partitioned by a substrate surface and a sealant by vacuum pressure difference, an injection port is sealed, and a liquid crystal display element is manufactured.
In the ODF method, a sealant Zhou Yinshua is applied to the outer side of one liquid crystal alignment film surface of a pair of substrates, and after dropping liquid crystal into the inner region of the sealant, the other substrate is bonded so that the liquid crystal alignment film surfaces face each other. Then, the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal display element.
A thermosetting type sealant is known as a sealant for bonding substrates, in addition to UV (Ultraviolet) curing type sealant. The sealing agent may be printed by, for example, screen printing.
The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy may be used. Among preferred liquid crystal compositions having a positive dielectric anisotropy, there are liquid crystal compositions disclosed in Japanese patent application laid-open No. 3086228, japanese patent application laid-open No. 2635435, japanese patent application laid-open No. 5-501735, japanese patent application laid-open No. 8-157826, japanese patent application laid-open No. 8-231960, japanese patent application laid-open No. 9-241644 (EP 885272A 1), japanese patent application laid-open No. 9-302346 (EP 806466A 2), japanese patent application laid-open No. 8-199168 (EP 722998A 1), japanese patent application laid-open No. 9-235552, japanese patent application laid-open No. 9-255956, japanese patent application laid-open No. 9-241643 (EP 885271A 1), japanese patent application laid-open No. 10-204016 (EP 844229A 1), japanese patent application laid-open No. 10-204436, japanese patent application laid-open No. 10-231482, japanese patent application laid-open No. 2000-087040, japanese patent application laid-open No. 2001-48822 and the like.
As a preferable example of the liquid crystal composition having negative dielectric anisotropy, examples thereof include Japanese patent application laid-open No. 57-114532, japanese patent application laid-open No. 2-4725, japanese patent application laid-open No. 4-224885, japanese patent application laid-open No. 8-40953, japanese patent application laid-open No. 8-104869, japanese patent application laid-open No. 10-168076, japanese patent application laid-open No. 10-168453, japanese patent application laid-open No. 10-236989, japanese patent application laid-open No. 10-236990, japanese patent application laid-open No. 10-236992, japanese patent application laid-open No. 10-236993, japanese patent application laid-open No. 10-236994, japanese patent application laid-open No. 10-237000, japanese patent application laid-open No. 10-237004, japanese patent application laid-open No. 10-237024, japanese patent application laid-open No. 10-237035, japanese patent application laid-open No. 10-237075, japanese patent application laid-open No. 10-237076, japanese patent application laid-open No. 10-237448 (EP 967261A 1), japanese patent application laid-open No. 10-287874, japanese patent application laid-open No. 10-287875, japanese patent application laid-open No. 2001-7235, japanese patent application laid-open No. 2001-open No. 2010-5, japanese patent application laid-5-open No. 2010-5, 2001, and/inspection, japanese patent application laid-5, and so on top-5, and/on top-quality of the like.
One or more optically active compounds may be added to a liquid crystal composition having positive or negative dielectric anisotropy.
In addition, for example, from the viewpoint of improving the alignment property, the liquid crystal composition used in the liquid crystal display element of the present invention may further contain additives. Such additives are photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerization initiators, polymerization inhibitors, and the like. Preferred examples of the photopolymerizable monomer, optically active compound, antioxidant, ultraviolet absorber, pigment, defoamer, polymerization initiator and polymerization inhibitor include those disclosed in International publication No. 2015/146330.
To suit the liquid crystal display element of PSA (polymer sustained alignment, polymer stabilized alignment) mode, a polymerizable compound may be mixed in the liquid crystal composition. Preferred examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (ethylene oxide, oxetane), ketene and the like. Preferred compounds include those disclosed in International publication No. 2015/146330 and the like.
Examples
The present invention will be described below with reference to examples. In addition, the evaluation methods and compounds used in the examples are as follows.
< weight average molecular weight (Mw) >)
The weight average molecular weight of the polyamic acid was measured by GPC using a 2695 separation module (Separations Module). 2414 differential refractive index detector (manufactured by Waters), and converted to polystyrene. The resultant polyamic acid was diluted with a phosphoric acid-DMF (N, N-Dimethylformamide, N-Dimethylformamide) mixed solution (phosphoric acid/dmf=0.6/100, weight ratio) so that the concentration of the polyamic acid became about 2 weight%. The column was subjected to measurement using HSP gel RT MB-M (HSPgel RT MB-M) (manufactured by Wolter company) with the mixed solution as a developing agent at a column temperature of 50℃and a flow rate of 0.40 mL/min. The standard polystyrene used was TSK standard polystyrene manufactured by Tosoh corporation.
< pencil hardness >
The method of scratch hardness (pencil method) according to JIS standard "JIS-K-5600,5.4". The result is expressed in terms of hardness of the pencil lead. If the pencil hardness is low, peeling and abrasion are likely to occur, and if the value is more than 2H, an alignment film which is less likely to cause cutting or the like can be obtained.
< sealing Property >
The ends of the upper and lower substrates of the sample for measuring seal adhesion described later were fixed to a glass substrate manufactured by IMADA corporationThe manufactured electric test bench MX2-500N was press-fitted from the upper part of the center of the substrate by using a digital push-pull tester ZTS-100N manufactured by Yimenda Co., ltd, and the pressure (N) at the time of peeling was measured. The pressure (N) is then divided by the area (cm) estimated from the measured diameter of the sealant 2 ) Calculate the adhesion strength (N/cm) 2 ). It can be said that the higher the value of the adhesion strength is, the higher the adhesion to the sealant is. The calculated adhesion strength was divided by the adhesion strength of the reference liquid crystal alignment film, and the seal adhesion of each liquid crystal alignment film was compared.
< tetracarboxylic dianhydride >
< diamine >
< monoamine >
< solvent >
NMP: n-methyl-2-pyrrolidone
BC: butyl cellosolve (ethylene glycol monobutyl ether)
Preparation of varnish
Preparation example of varnish A1 preparation
Into a 100mL three-necked flask equipped with a stirring blade and a nitrogen inlet tube, 0.268g of the compound represented by the formula (DI-4-1), 1.052g of the compound represented by the formula (DI-5-1) and m=2, and 1.330g of the compound represented by the formula (DI-13-1) were charged, and 74.0g of NMP was added and stirred. To this solution was added 3.058g of the compound represented by the formula (I-1) under a nitrogen atmosphere, and the mixture was stirred at room temperature for 12 hours. To this was added 0.297g of the compound represented by the formula (Xe), and the mixture was stirred at room temperature for 12 hours. To this solution, 20.0g of BC was added, and the solution was heated and stirred at 70℃until the weight average molecular weight of the polymer of the solute reached the desired weight average molecular weight, to obtain varnish A1 having a weight average molecular weight of the solute of about 25100 and a resin component concentration (solid component concentration) of 6 wt%.
Preparation examples 2 to 4 preparation of varnishes A2 to A4
Varnishes A2 to A4 having a solid content concentration of 6 wt% were prepared in the same manner as in preparation example 1, except that the compounds used as diamine, tetracarboxylic dianhydride, and monoamine were changed as shown in table 1. In table 1, in the preparation examples in which two or more compounds are described as diamines, it is meant that all of the compounds are used together as diamines. The numbers in brackets indicate the compounding ratio (mol%) and the blank indicates that no compound corresponding to that column is used.
TABLE 1
Example 1
The varnish A1 was diluted with NMP-BC mixed solution (NMP/bc=7/3 weight ratio) so as to have a solid content of 4 weight%, and stirred to prepare a liquid crystal aligning agent 1. The prepared liquid crystal aligning agent 1 was coated on a glass substrate by spin coating. After the coating, the substrate was heated at 60℃for 80 seconds to evaporate the solvent, and then baked at 230℃for 30 minutes to form a liquid crystal alignment film. A substrate was irradiated with linearly polarized Light of ultraviolet rays from a vertical direction via a polarizing plate having a polarizing band of 230nm to 310nm using Multi Light ML-501C/B manufactured by Bull tail (Ushio) motor (Inc.). At this time, the light quantity was measured by using an ultraviolet cumulative light meter UIT-150 (light receiver: UVD-S254) manufactured by Niuwei motor Co., ltd.) for exposure energy, and the exposure time of the linearly polarized light was adjusted so as to be 0.3.+ -. 0.03J/cm at a wavelength of 254nm 2 . Then, additional heating was performed at 230℃for 30 minutes. The pencil hardness of the obtained substrate was measured and found to be 2H.
Two glass substrates of the same size were prepared. The liquid crystal aligning agent 1 was coated on one glass substrate by spin coating.After the coating, the substrate was heated at 60℃for 80 seconds to evaporate the solvent, and then baked at 230℃for 30 minutes to form a liquid crystal alignment film. A substrate was irradiated with linearly polarized light of ultraviolet rays from a vertical direction via a polarizing plate having a polarizing band of 230nm to 310nm using multi-light ML-501C/B manufactured by Niuwei motor (Inc.). At this time, the light quantity was measured by using an ultraviolet cumulative light meter UIT-150 (light receiver: UVD-S254) manufactured by Niuwei motor Co., ltd.) for exposure energy, and the exposure time of the linearly polarized light was adjusted so as to be 0.3.+ -. 0.03J/cm at a wavelength of 254nm 2 . Then, additional heating was performed at 230℃for 30 minutes. A sealant (XN-1500T, manufactured by Co-chemical industries, ltd.) in which bead spacers of 5 μm were dispersed was dropped onto the surface of the substrate on which the alignment film was formed. Next, using a glass substrate to which no alignment agent was applied, bonding was performed so that the overlapping width of the substrates was 1cm and the sealant was interposed therebetween. At this time, the amount of the sealant to be added was adjusted so that the diameter of the sealant after lamination became about 3 mm. After the two bonded substrates were fixed with a jig, the two bonded substrates were subjected to 3J/cm 2 Subsequently, the sealing agent was cured by heating at 120℃for 1 hour, thereby producing a sample for measuring the sealing adhesion. The adhesion strength was calculated by the above-described evaluation method.
Comparative orientation agent 1 was prepared using varnish A4 instead of varnish A1, and a sample for measuring seal adhesion was prepared in the same manner. The adhesion strength was calculated by the above-described evaluation method.
The ratio of the adhesion strength to the comparative alignment agent 1 was calculated by dividing the adhesion strength of the liquid crystal alignment agent 1 prepared from varnish A1 by the adhesion strength of the comparative alignment agent 1 prepared from varnish A4, and as a result, the ratio was 2.3.
Examples 2 and 3 and comparative example 1
The varnishes A2 to A4 were diluted and stirred with NMP-BC mixed solution (NMP/bc=7/3 weight ratio) so that the solid concentration was 4 weight%, respectively, to prepare a liquid crystal aligning agent 2, a liquid crystal aligning agent 3, and a comparative aligning agent 1. The pencil hardness and the adhesion strength to the sealant were evaluated in the same manner as in example 1, except that the liquid crystal aligning agent shown in table 2 was used instead of the liquid crystal aligning agent 1. The measurement results of the pencil hardness and the adhesion strength (ratio) of the varnish used are shown in table 2.
TABLE 2
| Liquid crystal aligning agent | Varnish | Hardness of pencil | Sealing strength (ratio) | |
| Example 1 | Liquid crystal aligning agent 1 | A1 | 2H | 2.3 |
| Example 2 | Liquid crystal aligning agent 2 | A2 | 2H | 1.8 |
| Example 3 | Liquid crystal aligning agent 3 | A3 | 2H | 1.5 |
| Comparative example 1 | Comparative alignment agent 1 | A4 | HB | 1.0 |
As shown in table 2, in examples 1 to 3, the pencil hardness was 2H, the adhesion strength (ratio) was 1.5 to 2.3, and in comparative example 1 in which formula (Xe) was not used, the pencil hardness was HB.
It is found that a liquid crystal alignment film having high pencil hardness and sealing adhesion can be produced by using the compound represented by the formula (Xe).
Industrial applicability
When the liquid crystal aligning agent for photo-alignment of the present invention is used, a liquid crystal alignment film having high sensitivity to exposure energy, less likely to cause film peeling or cutting, and exhibiting high sealing adhesion can be produced. The liquid crystal aligning agent for photo-alignment of the present invention can be applied to a lateral electric field type liquid crystal display element.
Claims (7)
1. A liquid crystal aligning agent comprising a polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic acid derivative, a diamine, and a monoamine having two or more hydroxyl groups, the liquid crystal aligning agent comprising a compound represented by the formula (I) as the tetracarboxylic acid derivative,
in the formula (I), 1', 2 and 2' are chemical bonds, and each is independently bonded to a hydroxyl group, a chlorine atom or an alkoxy group having 1 to 6 carbon atoms, and at least one of the group of 1 and 1 'and the group of 2 and 2' is capable of bonding to the same oxygen atom;
R b1 、R b2 、R b3 And R is b4 Each independently is a hydrogen atom or a methyl group, at least one of which is a methyl group.
2. The liquid crystal aligning agent according to claim 1, wherein the monoamine having two or more hydroxyl groups is at least one selected from the following formulas (Xa) to (Xf),
in the formulas (Xa), (Xb), R x Independently a hydrogen atom or a methyl group.
3. The liquid crystal aligning agent according to claim 2, wherein the monoamine having two or more hydroxyl groups is at least one selected from the following formulas (Xa-1), (Xa-2), (Xb-1), (Xb-2), (Xc-1), (Xc-2) and (Xe),
4. a liquid crystal aligning agent according to any one of claims 1 to 3, further comprising an additive.
5. A liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 4.
6. A liquid crystal element comprising the liquid crystal alignment film according to claim 5.
7. A method for producing a liquid crystal alignment film, comprising the steps of:
applying the liquid crystal aligning agent of any one of claims 1 to 4 to a substrate;
firing the substrate; and
the substrate is irradiated with polarized ultraviolet rays.
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