WO2015016121A1 - 液晶表示装置の製造方法 - Google Patents
液晶表示装置の製造方法 Download PDFInfo
- Publication number
- WO2015016121A1 WO2015016121A1 PCT/JP2014/069518 JP2014069518W WO2015016121A1 WO 2015016121 A1 WO2015016121 A1 WO 2015016121A1 JP 2014069518 W JP2014069518 W JP 2014069518W WO 2015016121 A1 WO2015016121 A1 WO 2015016121A1
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- WO
- WIPO (PCT)
- Prior art keywords
- liquid crystal
- crystal display
- display device
- photo
- manufacturing
- Prior art date
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- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
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- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 24
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- WWSJZGAPAVMETJ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethoxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OCC WWSJZGAPAVMETJ-UHFFFAOYSA-N 0.000 description 12
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 11
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- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 8
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- 238000002834 transmittance Methods 0.000 description 6
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 5
- LPZOCVVDSHQFST-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CC LPZOCVVDSHQFST-UHFFFAOYSA-N 0.000 description 5
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 5
- VXZBYIWNGKSFOJ-UHFFFAOYSA-N 2-[4-[5-(2,3-dihydro-1H-inden-2-ylamino)pyrazin-2-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC=1N=CC(=NC=1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 VXZBYIWNGKSFOJ-UHFFFAOYSA-N 0.000 description 5
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- 229910052738 indium Inorganic materials 0.000 description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 4
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 3
- 229910007541 Zn O Inorganic materials 0.000 description 3
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005264 High molar mass liquid crystal Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
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- 239000007857 degradation product Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000006358 imidation reaction Methods 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
- G02F1/13378—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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
Definitions
- the present invention relates to a method for manufacturing a liquid crystal display device. More specifically, the present invention relates to a method for manufacturing a liquid crystal display device related to the conditions for forming an alignment film.
- liquid crystal display devices are rapidly spreading, and not only for television applications, but also electronic books, photo frames, IA (Industrial Appliances), PCs (Personal Computers), tablet PCs. Widely used in smartphone applications. In these applications, various performances are required, and various liquid crystal display modes have been developed.
- in-plane switching In-Plane switching
- IPS switching
- FFS fringe field switching
- an alignment treatment method for an alignment film for aligning liquid crystal molecules include a rubbing method and a photo alignment method.
- the rubbing method of rubbing the surface of the alignment film with a cloth has been widely adopted.
- foreign matter defects and display unevenness due to dust generation on the cloth, and destruction of the thin film transistor element due to static electricity when rubbing with the cloth have become problems.
- a photo-alignment method that gives anisotropy to the alignment film by irradiating light such as ultraviolet rays and generates an alignment regulating force has been recently studied instead of the rubbing method. Yes.
- Non-Patent Documents 2 to 4 there is known a document disclosing that the alignment order of the polymer is improved by sequentially performing preheating, irradiation with polarized ultraviolet rays, and main heating (for example, see Non-Patent Documents 2 to 4).
- the said nonpatent literature 4 is related with formation of a photo-alignment film.
- JP-A-8-179328 Japanese Patent No. 4459417 International Publication No. 2012/093682
- a photo alignment film As described above, alignment processing of an alignment film (hereinafter also referred to as a photo alignment film) by a photo alignment method has been studied.
- the photo-alignment method (1) the voltage holding ratio of the liquid crystal display device is lowered and the display quality is lowered when used for a long period of time, and (2) a sufficient alignment regulating force cannot be obtained. High contrast cannot be obtained, or the burn-in characteristic is deteriorated, and (3) the exposure sensitivity of the photo-alignment film is poor, and a large amount of energy (irradiation amount) is required for light irradiation (for example, ultraviolet irradiation).
- irradiation amount for example, ultraviolet irradiation
- the present inventors have found that the above-mentioned defect (1) occurs remarkably when used for a long time in a state of being energized at a high temperature.
- the present inventors have found that the above-mentioned problem (2) is that even when the photo-alignment treatment is performed, the alignment order of the polymer contained in the photo-alignment film is not sufficiently increased and the alignment disorder of the liquid crystal molecules is caused.
- the alignment order indicates, for example, the degree of anisotropy of a polymer that has been photo-aligned so as to be aligned in a predetermined direction.
- the degree of anisotropy can be measured, for example, by refractive index anisotropy or absorptance anisotropy.
- the present inventors have found that the above-mentioned defect (3) occurs remarkably particularly in a photolytic photo-alignment film.
- Patent Document 1 discloses a method for manufacturing a liquid crystal alignment film, which can achieve uniform alignment by high pretilt uniformly and prevent liquid crystal display defects when aligning chiral smectic liquid crystal using an alignment film, and liquid crystal An element manufacturing method is provided.
- the invention described in Patent Document 1 aligns chiral smectic liquid crystal by a rubbing method, and there is room for contrivance to solve the above problems.
- the invention described in Patent Document 1 is aimed at achieving a high pretilt angle.
- the viewing angle characteristics are varied depending on the high pretilt angle. Etc. deteriorates and the display quality deteriorates.
- Patent Document 2 provides a liquid crystal alignment processing method and a liquid crystal display element capable of expressing a liquid crystal pretilt angle necessary for the liquid crystal alignment element without performing oblique irradiation.
- the invention described in Patent Document 2 does not disclose any IPS mode or FFS mode liquid crystal display device that is the subject of the present invention, and there is room for contrivance to solve the above problems.
- the invention described in Patent Document 2 is intended to develop a pretilt angle by vertical irradiation.
- the viewing angle is varied depending on the pretilt angle. The characteristics and the like are deteriorated, and the display quality is lowered.
- the said patent document 3 is providing the composition for photo-alignment films containing the photoreactive compound with a high freedom degree of material selection.
- the invention described in Patent Document 3 does not disclose in detail the firing process of the alignment film, and optimizes the conditions for this heating and further improves the alignment order of the polymer and the electrical characteristics. There was room for contrivance to solve the above problems.
- Non-Patent Document 1 when the alignment order of a polyimide alignment film containing azobenzene in the main chain is measured, the alignment order after the main heating is higher than the alignment order before the main heating.
- the non-patent document 1 only discloses 250 ° C. for 1 hour as to the condition of the main heating, and is a device for solving the above problem in that the condition of the main heating is optimized. There was room.
- the said nonpatent literature 1 is not disclosing at all about preheating. When preheating is not performed, the film thickness unevenness of the photo-alignment film is generated, and the display quality is deteriorated.
- Non-Patent Documents 2 to 4 describe that preheating, irradiation with polarized ultraviolet rays, and main heating are effective in order to increase the orientation order of the polymer.
- Non-Patent Documents 2 to 4 do not disclose any case where the photo-alignment film material contains two or more types of polymers, so that the electrical characteristics are poor and alignment defects such as alignment blots and uneven alignment occur. In this respect, there is room for improvement.
- the said nonpatent literatures 2 and 3 are not disclosed regarding formation of alignment film.
- Non-Patent Document 5 discloses that in an acrylic polymer having a liquid crystal structure, a high degree of orientation is born by liquid crystallinity (self-organization) and hydrogen bonding resulting from an amide group. It shows that it is effective to heat-treat. However, Non-Patent Document 5 discloses only a single treatment at a specific temperature for the main heating condition, and does not disclose any preheating. When preheating is not performed, the film thickness unevenness of the photo-alignment film is generated, and the display quality is deteriorated.
- the present invention has been made in view of the above situation, and an object of the present invention is to provide a method of manufacturing a liquid crystal display device that includes a photo-alignment film and can sufficiently improve display quality.
- the inventors of the present invention have studied various causes for the problem (1) that occur remarkably when used for a long time in a state of being energized at a high temperature. And the impurities contained in the sealing material and the like are eluted into the liquid crystal and behave as mobile ions, so that the voltage holding ratio is lowered.
- the present inventors have made various studies on methods for producing a liquid crystal display device that can solve the above problem (1), have a photo-alignment film, and can sufficiently improve display quality, and have a polyamic acid skeleton.
- a photo-alignment film material containing a polymer having a polyamic acid skeleton —NH groups and —COOH groups are present on the surface of the photo-alignment film, as described above.
- the present inventors have found that it is possible to adsorb various impurities (movable ions), and thus it is possible to sufficiently prevent a decrease in voltage holding ratio, and as a result, it is possible to sufficiently improve display quality.
- the present inventors have made various studies on the reason why the orientation order of the polymer is not sufficiently increased with respect to the problem (2). As a result, light irradiation is performed after the thermochemical reaction of the polymer proceeds by this heating. It has been found that the orientation order of the polymer does not increase sufficiently even if it is performed. This is considered to be because the polymer cannot be completely oriented only by light irradiation. Further, the present inventors have found that even when light irradiation is performed before the main heating, the orientation order of the polymer is not sufficiently increased if the temperature of the main heating is too low.
- the polymer immediately after the light irradiation includes those deviated from the predetermined orientation direction, and the orientation order of the polymer is not sufficiently increased. State. Therefore, if the temperature of the main heating is too low, the molecular motion of the polymer immediately after light irradiation in which the alignment order is not sufficiently increased does not become active, and the polymer deviated from the predetermined orientation direction as described above is This is considered to be because it becomes difficult to re-orientate in the orientation direction.
- the present inventors have studied various methods for manufacturing a liquid crystal display device that can solve the above-mentioned problem (2), have a photo-alignment film, and can sufficiently improve display quality.
- the solvent remains to some extent in the state before the main heating, and the preheating is performed to such an extent that the film quality and display quality of the photo-alignment film are not affected. It has been found that the orientation order of the polymer by self-organization can be sufficiently improved by lowering the temperature. From the above, it has been found that the display quality can be sufficiently improved.
- the present inventors have made various studies on the cause of the remarkable occurrence in the photodecomposition type photo-alignment film with respect to the problem (3).
- a low molecular weight decomposition product is generated by light irradiation, and a liquid crystal display
- the degradation product is agglomerated after being eluted in the liquid crystal, thereby causing deterioration in display quality (for example, poor bright spot).
- the present inventors have studied various methods for manufacturing a liquid crystal display device that can solve the above-mentioned problem (3), have a photo-alignment film, and can sufficiently improve display quality. Attention has been focused on using a photo-alignment film that has at least one chemical reaction selected from the group consisting of photonic transition and optical fleece transition as a main mechanism for forming the alignment anisotropy. If a photo-alignment film material containing a polymer having a photofunctional group capable of at least one chemical reaction selected from the group consisting of photodimerization, photoisomerization, and photofleece transition is used, It has been found that the display quality can be sufficiently improved because no low molecular weight decomposition products are produced.
- a method for manufacturing a liquid crystal display device including a photo-alignment film the method for manufacturing the liquid crystal display device comprising a group consisting of photodimerization, photoisomerization, and optical fleece transition.
- a photo-alignment film material comprising a polymer having a photofunctional group capable of at least one chemical reaction selected from the above, a polymer having a polyamic acid skeleton and not having the photofunctional group, and a solvent
- the liquid crystal display device includes a step (4) of performing main heating on the polarized film and the liquid crystal display device has an in-plane switching mode or fringe field switching in which the pretilt angle is substantially 0 °.
- Mo It is de may be a method of manufacturing a liquid crystal display device.
- the manufacturing method of the liquid crystal display device according to one embodiment of the present invention is not particularly limited by other steps.
- a method for manufacturing a liquid crystal display device that includes a photo-alignment film and can sufficiently improve display quality can be provided.
- the photo-alignment film material has a polymer having a photofunctional group capable of at least one chemical reaction selected from the group consisting of photodimerization, photoisomerization, and photofleece transition, and a polyamic acid skeleton,
- the polymer contains a polymer having no photofunctional group and a solvent, and constitutes a photo-alignment film after the steps (1) to (4). That is, the photo-alignment film generates at least one chemical reaction selected from the group consisting of photo-dimerization, photo-isomerization, and photo-fleece transition when irradiated with light. It is a film that expresses orientation regulating power.
- the photo-alignment film material may contain a different type of polymer from the two types of polymers.
- the two types of polymers have a photofunctional group capable of at least one chemical reaction selected from the group consisting of photodimerization, photoisomerization, and photofleece transition, and a polyamic acid skeleton.
- a photofunctional group capable of at least one chemical reaction selected from the group consisting of photodimerization, photoisomerization, and photofleece transition
- a polyamic acid skeleton it does not specifically limit if it does not have the said photofunctional group, It is preferable that it has a sufficient characteristic calculated
- the photo-alignment film material contains a polyamic acid, from the viewpoint of solubility in the solvent and affinity with the substrate, the coating property when forming the film on the substrate is improved. Can do. From the viewpoint of electrical characteristics, burn-in due to residual DC (direct current) can be reduced by taking into account the dielectric constant and specific resistance of the liquid crystal layer. From this viewpoint, it is also effective to cause a part of the poly
- the solvent is not particularly limited as long as it is a liquid (at room temperature) that can dissolve or disperse the two types of polymers, and is removed from the photo-alignment film material by the steps (2) and (4). .
- the solvent is not only a component suitable for dissolving the two types of polymers (good solvent) but also a component suitable for spreading the photo-alignment film material on the substrate with a uniform thickness (poor solvent). ) And the like, and a mixture thereof is preferable.
- step (1) (hereinafter also referred to as a step of forming a film made of a photo-alignment film material), for example, a method of applying by an ink jet method or a spin coating method, or a method of printing (transferring) by a flexo method. Etc. are used. Then, by using these methods, the film may be formed on the substrate using the photo-alignment film material so that it can function as a photo-alignment film in the subsequent steps.
- the film formation conditions may be appropriately set according to the film formation method and the like. Further, the film thickness and the like of the film may be the same as the film thickness and the like of the photo-alignment film that is normally set.
- the substrate on which the film is formed may be a substrate on which a process for forming a photo-alignment film is performed, and may be a substrate on which various processes have been performed.
- the film is heated / dried to evaporate the solvent.
- the solvent may be partially removed or substantially completely removed by the preheating step.
- the preheating step is performed by a heating device such as a hot plate or a baking furnace set to a predetermined temperature, for example.
- the preheated film is subjected to photo-alignment treatment with, for example, ultraviolet rays, visible rays, or both, and polarized light.
- UV rays are preferably used.
- the light irradiation conditions in a light irradiation process can be made into the conditions set when forming a normal photo-alignment film.
- step (4) for example, self-assembly is advanced, the thermochemical reaction of the polymer is advanced, or the remaining solvent is volatilized. Moreover, this heating process is performed by heating apparatuses, such as a hot plate and a baking furnace, which were set to predetermined temperature, for example.
- the liquid crystal display device is in an in-plane switching (IPS) mode or a fringe field switching (FFS) mode in which the pretilt angle is substantially 0 °.
- the photo-alignment film constituting such a liquid crystal display device may be one that aligns liquid crystal molecules in a direction horizontal to the main surface of the substrate (hereinafter also referred to as a horizontal photo-alignment film).
- the horizontal photo-alignment film may be any film as long as at least adjacent liquid crystal molecules are aligned substantially horizontally with respect to the film surface of the horizontal photo-alignment film.
- the pretilt angle being substantially 0 ° means, for example, that the pretilt angle of the liquid crystal molecules is 1 ° or less with respect to the film surface of the horizontal photo-alignment film.
- Example 1 is a case where a photo-alignment film material containing two types of polymers is used. The manufacturing method of the liquid crystal display device according to the first embodiment will be sequentially described below.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- a solvent a mixture of N-methyl-pyrrolidone and butyl cellosolve at a weight ratio of 50:50 was used.
- the solid content concentration was 4% by weight.
- the cinnamate group is a photofunctional group capable of photodimerization and photoisomerization.
- a film made of a photo-alignment film material was formed on two substrates by spin coating.
- Preheating was performed at 70 ° C. for 150 seconds on the film after the step of forming the film made of the photo-alignment film material on the two substrates.
- the preheating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the film thickness of the photo-alignment film material after the preheating step was about 100 nm.
- the film after the preheating step on the two substrates was irradiated with polarized ultraviolet rays.
- the irradiation amount of polarized ultraviolet rays was 5 mJ / cm 2 in the wavelength range of 280 to 330 nm.
- the main heating was performed at 140 ° C. for 10 minutes on the film after the light irradiation process on the two substrates. This heating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the two substrates after the main heating step were bonded to each other through a sealing material so that the polarization directions of the irradiated polarized ultraviolet rays were parallel to each other.
- An FFS mode liquid crystal display device was obtained by pasting the two substrates and then passing through a seal thermosetting process.
- the liquid crystal material for forming the liquid crystal layer is dropped in advance on one of the two substrates, but may be sealed after the substrates are bonded together.
- the liquid crystal material a material containing liquid crystal molecules having positive dielectric anisotropy was used, and the thickness of the liquid crystal layer was 3.5 ⁇ m.
- the sealing material, the liquid crystal layer, and the like may be formed in the same manner as in the process of manufacturing a normal liquid crystal display device, for example.
- the liquid crystal display device according to Example 1 was obtained by appropriately arranging members such as a polarizing plate and a backlight on the liquid crystal display panel.
- the comparative example 1 is a case where the photo-alignment film material which does not contain the polyamic acid which does not have a photofunctional group and a side chain in Example 1 is used. Since the manufacturing method of the liquid crystal display device according to Comparative Example 1 is the same as that of Example 1 except for the photo-alignment film material, the description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a polymer having a methacrylic skeleton and a photoreactive cinnamate group in a side chain was used. As a solvent, a mixture of N-methyl-pyrrolidone and butyl cellosolve at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- Example 1 and Comparative Example 1 The voltage holding ratio of the liquid crystal display devices manufactured by the method for manufacturing the liquid crystal display device according to Example 1 and Comparative Example 1 was evaluated.
- the voltage holding ratio of Example 1 was 97% or more, which was higher than that of Comparative Example 1 of less than 95%.
- the voltage holding ratio is a ratio at which charges charged during one frame period are held.
- the thermochemical reaction by the main heating is insufficient, the voltage holding ratio may be lowered.
- a decrease in voltage holding ratio may cause display unevenness in the liquid crystal display device. Therefore, according to the method of manufacturing the liquid crystal display device according to the first embodiment, the voltage holding ratio can be sufficiently improved, and as a result, the display quality can be sufficiently improved.
- Example 1 The reason why the voltage holding ratio of Example 1 is higher than that of Comparative Example 1 will be described. If it is used for a long time in a state of being energized at a high temperature, impurities contained in the photo-alignment film and the sealing material are eluted into the liquid crystal and behave as mobile ions, which may cause a decrease in voltage holding ratio.
- the photo-alignment film material used in Example 1 when a polyamic acid having no photofunctional group and side chain is contained, the surface of the photo-alignment film has —NH groups, and — It is thought that a COOH group is present.
- the —NH group and —COOH group can serve as the adsorption sites for impurities (mobile ions) as described above, the mobile ions are fixed, and as a result, a decrease in voltage holding ratio can be sufficiently prevented. it is conceivable that. Therefore, according to the manufacturing method of the liquid crystal display device according to the first embodiment, the voltage holding ratio can be sufficiently improved.
- Example 2-1 the preheating temperature in Example 1 was set to 60 ° C. Since the manufacturing method of the liquid crystal display device according to Example 2-1 is the same as that of Example 1 except for the preheating step, description of overlapping points is omitted.
- Preheating was performed at 60 ° C. for 150 seconds on the film after the step of forming a film made of the photo-alignment film material on the two substrates.
- Example 2-2 is a case where the preheating temperature is set to 70 ° C. in Example 2-1, and is the same as Example 1. Since the manufacturing method of the liquid crystal display device according to Example 2-2 is the same as that of Example 1, the description of overlapping points is omitted.
- Example 2-3 is a case where the preheating temperature in Example 2-1 was set to 80 ° C. Since the manufacturing method of the liquid crystal display device according to Example 2-3 is the same as that of Example 2-1 except for the preheating step, description of overlapping points is omitted.
- Preheating was performed at 80 ° C. for 150 seconds on the film after the step of forming a film made of the photo-alignment film material on the two substrates.
- Example 2-4 is a case where the preheating temperature in Example 2-1 was 90 ° C. Since the manufacturing method of the liquid crystal display device according to Example 2-4 is the same as that of Example 2-1 except for the preheating step, description of overlapping points is omitted.
- Preheating was performed at 90 ° C. for 150 seconds on the film after the step of forming the film made of the photo-alignment film material on the two substrates.
- Example 2-5 is a case where the preheating temperature in Example 2-1 was 100 ° C. Since the manufacturing method of the liquid crystal display device according to Example 2-5 is the same as that of Example 2-1 except for the preheating step, description of overlapping points is omitted.
- Preheating was performed at 100 ° C. for 150 seconds on the film after the step of forming a film made of the photo-alignment film material on the two substrates.
- Example 2-6 is a case where the preheating temperature was 110 ° C. in Example 2-1. Since the manufacturing method of the liquid crystal display device according to Example 2-6 is the same as that of Example 2-1 except for the preheating step, description of overlapping points is omitted.
- Preheating was performed at 110 ° C. for 150 seconds on the film after the step of forming a film made of the photo-alignment film material on the two substrates.
- Table 1 summarizes the preheating temperature and the display quality evaluation results of the liquid crystal display devices manufactured by the liquid crystal display device manufacturing methods according to Examples 2-1 to 2-6.
- Level 1 Contrast is 1200 or more
- Level 2 Contrast is 1000 or more, less than 1200
- Level 3 Contrast is 500 or more, less than 1000
- Level 4 Contrast is less than 500, or alignment failure is visually recognized. Evaluation was made in four stages. Here, when the evaluation result is level 1 to 3, it is determined that the level is suitable for the product, and when the evaluation result is level 4, it is determined that the level suitable for the product is not reached.
- Example 2-1 The evaluation result of the display quality was level 1, which was very good as compared with those of Examples 2-3 to 2-6. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 2-1, the display quality can be sufficiently improved.
- Example 2-2 The evaluation result of the display quality was level 1, which was very good as compared with those of Examples 2-3 to 2-6. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 2-2, the display quality can be sufficiently improved.
- Example 2-3 The evaluation result of the display quality was level 2, which was better than those of Example 2-5 and Example 2-6. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the method for manufacturing the liquid crystal display device according to Example 2-3, the display quality can be sufficiently improved.
- Example 2-4 The evaluation result of the display quality was level 2, which was better than those of Example 2-5 and Example 2-6. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 2-4, the display quality can be sufficiently improved.
- Example 2-5 The evaluation result of the display quality was level 3, which was good. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 2-5, the display quality can be sufficiently improved.
- Example 2-6 The evaluation result of the display quality was level 3, which was good. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 2-6, the display quality can be sufficiently improved.
- Examples 2-1 to 2-6 by performing the main heating after the irradiation with the polarized ultraviolet rays, the molecular motion of the polymer by the heating is facilitated by using the anisotropy formed by the irradiation with the polarized ultraviolet rays as a trigger. Therefore, it is considered that the orientation order of the polymer by self-organization can be sufficiently improved. In addition, the improvement of the orientational order of the polymer by self-organization is caused not only by the polymer having a photofunctional group but also by the interaction with the polyamic acid. Thus, the ease of molecular motion of the polymer is important.
- Example 2-1 and Example 2-2 The reason why the display quality of Example 2-1 and Example 2-2 was very good compared to that of Examples 2-3 to 2-6 will be described. This is because the preheating temperature in Example 2-1 and Example 2-2 is lower than that in Examples 2-3 to 2-6, and as a result, the residual amount of solvent is relatively large. This is considered to be because the molecular motion of the polymer accompanying this heating became relatively active, and the orientation order of the polymer due to self-organization was sufficiently improved. Therefore, in order to advance the self-assembly, it is advantageous that the solvent remains to some extent in the state before performing the main heating, and if the preheating temperature is too high, the self-assembly may be inhibited. it is conceivable that.
- the preheating may be performed so that the liquid fluidity of the film made of the photo-alignment film material is eliminated, and it is preferable to lower the temperature of the preheating so as to achieve the effect of one embodiment of the present invention.
- the reason why the display quality of Example 2-3 and Example 2-4 was better than that of Example 2-5 and Example 2-6 was the same as the reason described above. It is. From the above, it was found that the preheating temperature is preferably 90 ° C. or lower, and more preferably 70 ° C. or lower.
- the preheating temperature is more preferably 40 ° C. or higher and 70 ° C. or lower.
- Example 3-1 is a case where the main heating temperature is 80 ° C. in Example 2-2. Since the manufacturing method of the liquid crystal display device according to Example 3-1 is the same as that of Example 2-2 except for the main heating step, description of overlapping points is omitted.
- the main heating was performed at 80 ° C. for 10 minutes on the film after the light irradiation process on the two substrates.
- Example 3-2 is a case where the main heating temperature is 90 ° C. in Example 3-1. Since the manufacturing method of the liquid crystal display device according to Example 3-2 is the same as that of Example 3-1 except for this heating step, description of overlapping points is omitted.
- the main heating was performed at 90 ° C. for 10 minutes on the film after the light irradiation process on the two substrates.
- Example 3-3 is a case where the main heating temperature is 100 ° C. in Example 3-1. Since the manufacturing method of the liquid crystal display device according to Example 3-3 is the same as that of Example 3-1 except for this heating step, description of overlapping points is omitted.
- the main heating was performed at 100 ° C. for 10 minutes on the film after the light irradiation process on the two substrates.
- Example 3-4 is a case where the main heating temperature is 110 ° C. in Example 3-1. Since the manufacturing method of the liquid crystal display device according to Example 3-4 is the same as that of Example 3-1 except for this heating step, the description of overlapping points is omitted.
- the main heating was performed at 110 ° C. for 10 minutes on the film after the light irradiation process on the two substrates.
- Example 3-5 is a case where the main heating temperature was 120 ° C. in Example 3-1. Since the manufacturing method of the liquid crystal display device according to Example 3-5 is the same as that of Example 3-1 except for this heating step, the description of overlapping points is omitted.
- the main heating was performed at 120 ° C. for 10 minutes on the film after the light irradiation process on the two substrates.
- Example 3-6 is a case where the main heating temperature is 130 ° C. in Example 3-1. Since the manufacturing method of the liquid crystal display device according to Example 3-6 is the same as that of Example 3-1 except for this heating step, the description of the overlapping points is omitted.
- Main heating was performed at 130 ° C. for 10 minutes on the film after the light irradiation process on the two substrates.
- Example 3-7 is the case where the main heating temperature was 140 ° C. in Example 3-1, and was the same as Example 2-2. Since the manufacturing method of the liquid crystal display device according to Example 3-7 is the same as that of Example 2-2, description of overlapping points is omitted.
- Example 3-8 In Example 3-8, the main heating temperature was set to 150 ° C. in Example 3-1. Since the manufacturing method of the liquid crystal display device according to Example 3-8 is the same as that of Example 3-1 except for this heating step, the description of overlapping points is omitted.
- the main heating was performed at 150 ° C. for 10 minutes on the film after the light irradiation process on the two substrates.
- Table 2 summarizes the main heating temperature and the display quality evaluation results of the liquid crystal display devices manufactured by the liquid crystal display device manufacturing methods according to Examples 3-1 to 3-8.
- Display quality was evaluated in the same manner as in Examples 2-1 to 2-6.
- the evaluation result is level 1 to 3
- the evaluation result is level 4
- Example 3-1 The evaluation result of the display quality was level 3, which was good. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the method of manufacturing the liquid crystal display device according to Example 3-1, the display quality can be sufficiently improved.
- Example 3-2 The evaluation result of display quality was level 2, which was better than that of Example 3-1. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 3-2, the display quality can be sufficiently improved.
- Example 3-3 The evaluation result of display quality was level 2, which was better than that of Example 3-1. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 3-3, the display quality can be sufficiently improved.
- Example 3-4 The evaluation result of display quality was level 2, which was better than that of Example 3-1. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 3-4, the display quality can be sufficiently improved.
- Example 3-5 The evaluation result of display quality was level 2, which was better than that of Example 3-1. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 3-5, the display quality can be sufficiently improved.
- Example 3-6 The evaluation result of display quality was level 2, which was better than that of Example 3-1. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 3-6, the display quality can be sufficiently improved.
- Example 3-7 The evaluation result of the display quality was level 1, which was very good as compared with those of Examples 3-1 to 3-6. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 3-7, the display quality can be sufficiently improved.
- Example 3-8 The evaluation result of the display quality was level 1, which was very good as compared with those of Examples 3-1 to 3-6. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 3-8, the display quality can be sufficiently improved.
- Examples 3-1 to 3-8 by performing the main heating after the irradiation with the polarized ultraviolet rays, the molecular motion of the polymer due to the heating is facilitated by using the anisotropy formed by the irradiation with the polarized ultraviolet rays as a trigger. Therefore, it is considered that the orientation order of the polymer by self-organization can be sufficiently improved. In addition, the improvement of the orientational order of the polymer by self-organization is caused not only by the polymer having a photofunctional group but also by the interaction with the polyamic acid. Thus, the ease of molecular motion of the polymer is important.
- Example 3-7 and Example 3-8 were very good compared to that of Examples 3-1 to 3-6.
- the molecular motion of the polymer is easy (active). Therefore, since the main heating temperature in Example 3-7 and Example 3-8 is higher than that in Examples 3-1 to 3-6, the molecular motion of the polymer is relatively active. It is conceivable that. Here, it is considered that the molecular motion of the polymer does not become relatively active if the temperature during self-assembly is too low. Further, the reason why the display quality of Examples 3-2 to 3-6 is better than that of Example 3-1 is the same as the reason described above.
- the main heating temperature is preferably 90 ° C. or higher, and more preferably 140 ° C. or higher.
- the heating temperature is more preferably 140 ° C. or higher and 250 ° C. or lower.
- Example 4 is a case where the liquid crystal material including liquid crystal molecules having negative dielectric anisotropy in Example 1 is used. Since the manufacturing method of the liquid crystal display device according to Example 4 is the same as that of Example 1 except that the dielectric anisotropy of the liquid crystal molecules is different, the description of overlapping points is omitted.
- Comparative Example 2 is a case where the light irradiation process was performed after the main heating process using a decomposition type photo-alignment film. A method for manufacturing a liquid crystal display device according to Comparative Example 2 will be sequentially described below.
- Photo-alignment film material As a solid content, a polyamic acid polymer having a cyclobutane skeleton was used. As a solvent, a mixture of N-methyl-pyrrolidone and butyl cellosolve at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- the photo-alignment film used in Comparative Example 2 causes photodecomposition of the polymer chain near the center wavelength of 254 nm.
- a film made of a photo-alignment film material was formed on two substrates by spin coating.
- Preheating was performed at 90 ° C. for 150 seconds on the film after the step of forming the film made of the photo-alignment film material on the two substrates.
- the preheating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the film thickness of the photo-alignment film material after the preheating step was about 100 nm.
- Main heating was performed at 230 ° C. for 30 minutes on the film after the preliminary heating step on the two substrates. This heating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the film after the main heating process on the two substrates was irradiated with polarized ultraviolet rays.
- the irradiation amount of polarized ultraviolet rays was 1 J / cm 2 near the center wavelength of 254 nm.
- the liquid crystal display device according to Comparative Example 2 was obtained.
- the liquid crystal material a material containing liquid crystal molecules having negative dielectric anisotropy was used, and the thickness of the liquid crystal layer was 3.5 ⁇ m.
- Example 4 and Comparative Example 2 The liquid crystal display device manufactured by the liquid crystal display device manufacturing method according to Example 4 and Comparative Example 2 was evaluated for contrast, image sticking characteristics, and voltage holding ratio.
- the contrast was measured by the same method as in Examples 2-1 to 2-6, and the voltage holding ratio was measured by the same method as in Example 1.
- Example 4 (Contrast measurement result) The contrasts in Example 4 and Comparative Example 2 were both equal to about 1200, which was a level suitable for a product.
- the image sticking property was evaluated by the image sticking rate.
- the voltage at the time of showing the maximum luminance was Vmax
- the voltage at the time of showing 1% of the maximum luminance was the observation voltage V1 (V1 ⁇ Vmax)
- the luminance (L1) when the observation voltage V1 was applied was first measured.
- the luminance (L1 ′) when the observation voltage V1 was applied was measured.
- the change rate of L1 'with respect to L1 was made into the burn-in rate.
- a Canon digital camera (trade name: EOS Kiss Digital NEF-S18-55IIU) was used.
- Example 4 (Evaluation results of seizure characteristics) The burn-in rates in Example 4 and Comparative Example 2 were both equal to about 3%, which was a level suitable for products.
- the bright spot generated in Comparative Example 2 includes liquid crystal molecules having positive dielectric anisotropy when a liquid crystal material including liquid crystal molecules having negative dielectric anisotropy is used. Compared with the case where a liquid crystal material was used, there was a tendency to occur remarkably.
- the transmittance and viewing angle characteristics can be further improved. Therefore, in the method for manufacturing a liquid crystal display device according to one embodiment of the present invention, when a liquid crystal material including a liquid crystal molecule having negative dielectric anisotropy is used, the effect of one embodiment of the present invention is achieved. The transmittance and viewing angle characteristics can be further improved.
- Example 5 is a case where a photo-alignment film material containing two types of polymers is used. A method for manufacturing the liquid crystal display device according to the fifth embodiment will be sequentially described below.
- a solid content a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer containing a photoreactive azobenzene structure, and the other is 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) and biphenyl. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting a diamine containing a structure.
- a solvent a mixture of N-methyl-pyrrolidone and butyl cellosolve at a weight ratio of 50:50 was used.
- the solid content concentration was 4% by weight.
- the azobenzene group is a photofunctional group capable of photoisomerization.
- a film made of a photo-alignment film material was formed on two substrates by spin coating.
- Preheating was performed at 70 ° C. for 150 seconds on the film after the step of forming the film made of the photo-alignment film material on the two substrates.
- the preheating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the film thickness of the photo-alignment film material after the preheating step was about 100 nm.
- the film after the preheating step on the two substrates was irradiated with polarized ultraviolet rays.
- the irradiation amount of polarized ultraviolet rays was 3 J / cm 2 near the center wavelength of 365 nm.
- the main heating was performed at 140 ° C. for 10 minutes on the film after the light irradiation process on the two substrates. This heating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the liquid crystal display device according to Example 5 was obtained.
- the liquid crystal material a material containing liquid crystal molecules having positive dielectric anisotropy was used, and the thickness of the liquid crystal layer was 3.5 ⁇ m.
- the comparative example 3 is a case where the photo-alignment film material which does not contain the polyamic acid which does not have a photofunctional group and a side chain in Example 5 is used. Since the manufacturing method of the liquid crystal display device according to Comparative Example 3 is the same as that of Example 5 except for the photo-alignment film material, the description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a polymer containing a photoreactive azobenzene structure was used. As a solvent, a mixture of N-methyl-pyrrolidone and butyl cellosolve at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- Example 5 and Comparative Example 3 When a voltage of 5 V was continuously applied to the liquid crystal display device manufactured by the method for manufacturing the liquid crystal display device according to Example 5 and Comparative Example 3 in an environment of 60 ° C., 500 hours later was confirmed.
- the voltage holding ratio of Example 5 was about 95 to 97%, which was higher than that of Comparative Example 3 of less than 90%. Since the decrease in the voltage holding ratio may cause display unevenness in the liquid crystal display device, the method for manufacturing the liquid crystal display device according to Example 5 can sufficiently improve the voltage holding ratio, and as a result, The display quality can be sufficiently improved.
- Example 5 The reason why the voltage holding ratio of Example 5 is higher than that of Comparative Example 3 will be described. If it is used for a long time in a state of being energized at a high temperature, impurities contained in the photo-alignment film and the sealing material are eluted into the liquid crystal and behave as mobile ions, which may cause a decrease in voltage holding ratio.
- the photo-alignment film material used in Example 5 when a polyamic acid having no photofunctional group and side chain is contained, the surface of the photo-alignment film has —NH groups, and — It is thought that a COOH group is present.
- the —NH group and —COOH group can serve as the adsorption sites for impurities (mobile ions) as described above, the mobile ions are fixed, and as a result, a decrease in voltage holding ratio can be sufficiently prevented. it is conceivable that. Therefore, according to the method for manufacturing the liquid crystal display device according to Example 5, the voltage holding ratio can be sufficiently improved.
- Example 6 is a case where the liquid crystal material including liquid crystal molecules having negative dielectric anisotropy in Example 5 is used. Since the manufacturing method of the liquid crystal display device according to Example 6 is the same as that of Example 5 except that the dielectric anisotropy of liquid crystal molecules is different, the description of overlapping points is omitted.
- Comparative Example 4 is a case where the light irradiation process was performed after the main heating process using a decomposition type photo-alignment film. A method for manufacturing the liquid crystal display device according to Comparative Example 4 will be sequentially described below.
- Photo-alignment film material As a solid content, a polyamic acid polymer having a cyclobutane skeleton was used. As a solvent, a mixture of N-methyl-pyrrolidone and butyl cellosolve at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- the photo-alignment film used in Comparative Example 4 causes photodecomposition of the polymer chain near the center wavelength of 254 nm.
- a film made of a photo-alignment film material was formed on two substrates by spin coating.
- Preheating was performed at 90 ° C. for 150 seconds on the film after the step of forming the film made of the photo-alignment film material on the two substrates.
- the preheating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the film thickness of the photo-alignment film material after the preheating step was about 100 nm.
- Main heating was performed at 230 ° C. for 30 minutes on the film after the preliminary heating step on the two substrates. This heating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the film after the main heating process on the two substrates was irradiated with polarized ultraviolet rays.
- the irradiation amount of polarized ultraviolet rays was 1 J / cm 2 near the center wavelength of 254 nm.
- the liquid crystal display device according to Comparative Example 4 was obtained.
- the liquid crystal material a material containing liquid crystal molecules having negative dielectric anisotropy was used, and the thickness of the liquid crystal layer was 3.5 ⁇ m.
- Example 6 and Comparative Example 4 The liquid crystal display device manufactured by the liquid crystal display device manufacturing method according to Example 6 and Comparative Example 4 was evaluated for contrast, image sticking characteristics, and voltage holding ratio.
- the contrast was measured by the same method as in Examples 2-1 to 2-6, the burn-in characteristics were evaluated by the same method as in Example 4, and the voltage holding ratio was measured by the same method as in Example 1.
- Example 6 (Contrast measurement result) The contrasts in Example 6 and Comparative Example 4 were both equal to about 1200, which was a level suitable for a product.
- Example 6 (Evaluation results of seizure characteristics) The burn-in rates in Example 6 and Comparative Example 4 were both about 3%, which was the same level and suitable for the product.
- the bright spots generated in Comparative Example 4 include liquid crystal molecules having positive dielectric anisotropy when a liquid crystal material including liquid crystal molecules having negative dielectric anisotropy is used. Compared with the case where a liquid crystal material was used, there was a tendency to occur remarkably.
- the transmittance and viewing angle characteristics can be further improved. Therefore, in the method for manufacturing a liquid crystal display device according to one embodiment of the present invention, when a liquid crystal material including a liquid crystal molecule having negative dielectric anisotropy is used, the effect of one embodiment of the present invention is achieved. The transmittance and viewing angle characteristics can be further improved.
- Example 7-1 is a case where the main heating was performed twice at different temperatures in the above step (4). A method for manufacturing the liquid crystal display device according to Example 7-1 will be sequentially described below.
- a solid content a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer containing a photoreactive azobenzene structure, and the other is 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) and biphenyl. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting a diamine containing a structure.
- a solvent a mixture of N-methyl-pyrrolidone and butyl cellosolve at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- a film made of a photo-alignment film material was formed on two substrates by spin coating.
- Preheating was performed at 60 ° C. for 150 seconds on the film after the step of forming a film made of the photo-alignment film material on the two substrates.
- the preheating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the film thickness of the photo-alignment film material after the preheating step was about 100 nm.
- the film after the preheating step on the two substrates was irradiated with polarized ultraviolet rays.
- the irradiation amount of polarized ultraviolet rays was 1 J / cm 2 near the center wavelength of 365 nm.
- the main heating was performed at 110 ° C. for 10 minutes on the film after the light irradiation process on the two substrates. This heating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the main heating was performed at 200 ° C. for 30 minutes on the film after the first main heating step on the two substrates. This heating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- a liquid crystal display device according to Example 7-1 was obtained by appropriately arranging the members.
- the liquid crystal material a material containing liquid crystal molecules having negative dielectric anisotropy was used, and the thickness of the liquid crystal layer was 3.5 ⁇ m.
- Example 7-2 is a case where the preheating temperature in Example 7-1 was set to 70 ° C. Since the manufacturing method of the liquid crystal display device according to Example 7-2 is the same as that of Example 7-1 except for the preheating step, description of overlapping points is omitted.
- Preheating was performed at 70 ° C. for 150 seconds on the film after the step of forming the film made of the photo-alignment film material on the two substrates.
- Example 7-3 is a case where the preheating temperature in Example 7-1 was set to 80 ° C. Since the manufacturing method of the liquid crystal display device according to Example 7-3 is the same as that of Example 7-1 except for the preheating step, description of overlapping points is omitted.
- Preheating was performed at 80 ° C. for 150 seconds on the film after the step of forming a film made of the photo-alignment film material on the two substrates.
- Example 7-4 is a case where the preheating temperature in Example 7-1 was 90 ° C. Since the manufacturing method of the liquid crystal display device according to Example 7-4 is the same as that of Example 7-1 except for the preheating step, description of overlapping points is omitted.
- Preheating was performed at 90 ° C. for 150 seconds on the film after the step of forming the film made of the photo-alignment film material on the two substrates.
- Example 7-5 is a case where the preheating temperature in Example 7-1 was 100 ° C. Since the manufacturing method of the liquid crystal display device according to Example 7-5 is the same as that of Example 7-1 except for the preheating step, the description of overlapping points is omitted.
- Preheating was performed at 100 ° C. for 150 seconds on the film after the step of forming a film made of the photo-alignment film material on the two substrates.
- Example 7-6 is a case where the preheating temperature is 110 ° C. in Example 7-1. Since the manufacturing method of the liquid crystal display device according to Example 7-6 is the same as that of Example 7-1 except for the preheating step, description of overlapping points is omitted.
- Preheating was performed at 110 ° C. for 150 seconds on the film after the step of forming a film made of the photo-alignment film material on the two substrates.
- Table 3 summarizes the preheating temperature and the display quality evaluation results of the liquid crystal display devices manufactured by the liquid crystal display device manufacturing methods according to Examples 7-1 to 7-6.
- Display quality was evaluated in the same manner as in Examples 2-1 to 2-6.
- the evaluation result is level 1 to 3
- the evaluation result is level 4
- Example 7-1 The evaluation result of the display quality was level 1, which was very good compared with those of Examples 7-3 to 7-6. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 7-1, the display quality can be sufficiently improved.
- Example 7-2 The evaluation result of the display quality was level 1, which was very good compared with those of Examples 7-3 to 7-6. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 7-2, the display quality can be sufficiently improved.
- Example 7-3 The evaluation result of the display quality was level 2, which was better than those of Example 7-5 and Example 7-6. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the method of manufacturing the liquid crystal display device according to Example 7-3, the display quality can be sufficiently improved.
- Example 7-4 The evaluation result of the display quality was level 2, which was better than those of Example 7-5 and Example 7-6. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the method of manufacturing the liquid crystal display device according to Example 7-4, the display quality can be sufficiently improved.
- Example 7-5 The evaluation result of the display quality was level 3, which was good. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 7-5, the display quality can be sufficiently improved.
- Example 7-6 The evaluation result of the display quality was level 3, which was good. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 7-6, the display quality can be sufficiently improved.
- Example 7-1 and Example 7-2 The reason why the display quality of Example 7-1 and Example 7-2 was very good compared to that of Examples 7-3 to 7-6 will be described. This is because the preheating temperature in Example 7-1 and Example 7-2 is lower than that in Examples 7-3 to 7-6, and as a result, the residual amount of solvent is relatively large. This is considered to be because the molecular motion of the polymer accompanying this heating became relatively active, and the orientation order of the polymer due to self-organization was sufficiently improved. Therefore, in order to advance the self-assembly, it is advantageous that the solvent remains to some extent in the state before performing the main heating, and if the preheating temperature is too high, the self-assembly may be inhibited. it is conceivable that.
- the preheating may be performed so that the liquid fluidity of the film made of the photo-alignment film material is eliminated, and it is preferable to lower the temperature of the preheating so as to achieve the effect of one embodiment of the present invention.
- the reason why the display quality of Example 7-3 and Example 7-4 was better than that of Example 7-5 and Example 7-6 is the same as the reason described above. It is. From the above, it was found that the preheating temperature is preferably 90 ° C. or lower, and more preferably 70 ° C. or lower.
- the preheating temperature is more preferably 40 ° C. or higher and 70 ° C. or lower.
- Example 8-1 In Example 8-1, the temperature of the first main heating in Example 7-1 was set to 70 ° C. Since the manufacturing method of the liquid crystal display device according to Example 8-1 is the same as that of Example 7-1 except for the first main heating step, description of overlapping points is omitted.
- the main heating was performed at 70 ° C. for 10 minutes on the film after the light irradiation process on the two substrates.
- Example 8-2 is a case where the temperature of the first main heating in Example 8-1 was 80 ° C. Since the manufacturing method of the liquid crystal display device according to Example 8-2 is the same as that of Example 8-1 except for the first main heating step, the description of overlapping points is omitted.
- the main heating was performed at 80 ° C. for 10 minutes on the film after the light irradiation process on the two substrates.
- Example 8-3 is a case where the temperature of the first main heating in Example 8-1 was 90 ° C. Since the manufacturing method of the liquid crystal display device according to Example 8-3 is the same as that of Example 8-1 except for the first main heating step, description of overlapping points is omitted.
- the main heating was performed at 90 ° C. for 10 minutes on the film after the light irradiation process on the two substrates.
- Example 8-4 is a case where the temperature of the first main heating in Example 8-1 was 100 ° C. Since the manufacturing method of the liquid crystal display device according to Example 8-4 is the same as that of Example 8-1 except for the first main heating step, description of overlapping points is omitted.
- the main heating was performed at 100 ° C. for 10 minutes on the film after the light irradiation process on the two substrates.
- Example 8-5 is the case where the temperature of the first main heating in Example 8-1 was 110 ° C., and is the same as Example 7-1. Since the manufacturing method of the liquid crystal display device according to Example 8-5 is the same as that of Example 7-1, description of overlapping points is omitted.
- Example 8-6 is a case where the temperature of the first main heating in Example 8-1 was 120 ° C. Since the manufacturing method of the liquid crystal display device according to Example 8-6 is the same as that of Example 8-1 except for the first main heating step, description of overlapping points is omitted.
- the main heating was performed at 120 ° C. for 10 minutes on the film after the light irradiation process on the two substrates.
- Example 8-7 In Example 8-7, the temperature of the first main heating in Example 8-1 was set to 130 ° C. Since the manufacturing method of the liquid crystal display device according to Example 8-7 is the same as that of Example 8-1 except for the first main heating step, description of overlapping points is omitted.
- Example 8-8 is a case where the temperature of the first main heating in Example 8-1 was 140 ° C. Since the manufacturing method of the liquid crystal display device according to Example 8-8 is the same as that of Example 8-1 except for the first main heating step, description of overlapping points is omitted.
- the main heating was performed at 140 ° C. for 10 minutes on the film after the light irradiation process on the two substrates.
- Example 8-9 is a case where the temperature of the first main heating in Example 8-1 was 150 ° C. Since the manufacturing method of the liquid crystal display device according to Example 8-9 is the same as that of Example 8-1 except for the first main heating step, description of overlapping points is omitted.
- the main heating was performed at 150 ° C. for 10 minutes on the film after the light irradiation process on the two substrates.
- Example 8-10 is a case where the temperature of the first main heating in Example 8-1 was 160 ° C. Since the manufacturing method of the liquid crystal display device according to Example 8-10 is the same as that of Example 8-1 except for the first main heating step, description of overlapping points is omitted.
- the main heating was performed at 160 ° C. for 10 minutes on the film after the light irradiation process on the two substrates.
- Table 4 summarizes the temperature of the first main heating and the evaluation results of the display quality of the liquid crystal display devices manufactured by the manufacturing method of the liquid crystal display device according to Examples 8-1 to 8-10.
- Display quality was evaluated in the same manner as in Examples 2-1 to 2-6.
- Example 8-1 The evaluation result of display quality was level 2, which was good. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 8-1, the display quality can be sufficiently improved.
- Example 8-2 The evaluation result of display quality was level 2, which was good. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 8-2, the display quality can be sufficiently improved.
- Example 8-3 The evaluation result of the display quality was level 1, which was very good. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 8-3, the display quality can be sufficiently improved.
- Example 8-4 The evaluation result of the display quality was level 1, which was very good. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 8-4, the display quality can be sufficiently improved.
- Example 8-5 The evaluation result of the display quality was level 1, which was very good. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 8-5, the display quality can be sufficiently improved.
- Example 8-6 The evaluation result of the display quality was level 1, which was very good. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 8-6, the display quality can be sufficiently improved.
- Example 8-7 The evaluation result of the display quality was level 1, which was very good. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 8-7, the display quality can be sufficiently improved.
- Example 8-8 The evaluation result of the display quality was level 1, which was very good. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 8-8, the display quality can be sufficiently improved.
- Example 8-9 The evaluation result of display quality was level 2, which was good. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 8-9, the display quality can be sufficiently improved.
- Example 8-10 The evaluation result of display quality was level 2, which was good. This is considered to be because the orientation order of the polymer by self-organization has been sufficiently improved. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 8-10, the display quality can be sufficiently improved.
- Examples 8-3 to 8-8 The reason why the display quality of Examples 8-3 to 8-8 was very good as compared with those of other Examples will be described.
- the temperature at the time of self-assembly for example, the temperature of the first main heating
- the temperature at the time of self-assembly is too low, it is considered that the molecular motion of the polymer does not become relatively active.
- the temperature during self-assembly is too high, anisotropy is formed due to self-assembly, and the thermochemical reaction of the polymer and the volatilization of the remaining solvent also occur simultaneously. Does not progress sufficiently. Therefore, the temperature of the first main heating (about 90 to 140 ° C.) in Examples 8-3 to 8-8 is considered to be a temperature at which self-organization occurs predominantly.
- the display quality of 3-8-8 was very good compared with that of the other examples.
- the temperature of the first main heating is preferably 90 ° C. or higher and 140 ° C. or lower.
- the temperature of the first main heating is less than 90 ° C.
- the molecular motion of the polymer may not be active.
- the temperature of the first main heating exceeds 140 ° C.
- the thermochemical reaction of the polymer and the volatilization of the remaining solvent may be remarkably started, which may hinder self-organization.
- the time of the first main heating is preferably 1 minute or longer, and more preferably 10 minutes or longer. If the time of the first main heating is less than 1 minute, the self-assembly may not proceed sufficiently.
- Example 5 since no additional main heating is performed, it is considered that a large amount of solvent remains, and in the process of using the liquid crystal display device for a long time, it elutes into the liquid crystal and behaves as an impurity. This is considered to cause a decrease in voltage holding ratio. Therefore, according to the method for manufacturing a liquid crystal display device according to Examples 7-1 to 7-6 and Examples 8-1 to 8-10, compared with the method for manufacturing a liquid crystal display device according to Example 5, The voltage holding ratio can be further improved.
- the second main heating step is performed after the light irradiation step, that is, the film after the preheating step is applied.
- the thermochemical reaction thermal imidation
- the polyamic acid and the remaining solvent volatilize at the same time. Will occur.
- the polymer chain in which the thermochemical reaction has sufficiently progressed has rigidity compared to polyamic acid, it has low thermal mobility and may inhibit self-assembly.
- the main heating is performed at a temperature at which self-organization occurs predominantly. It is preferable to cause the remaining solvent to volatilize after it has progressed sufficiently.
- the main heating was performed using two hot plates set at different temperatures.
- the second main heating step can be performed by changing the temperature to the temperature of the second main heating step after the first main heating step.
- the main heating is substantially performed even at a temperature between the temperature of the first main heating step and the temperature of the second main heating step, but the display quality can be sufficiently improved. This is presumably because self-organization and volatilization of the remaining solvent proceeded simultaneously during the hot plate temperature rising process.
- the installation area of the heating device increases. However, as in the case where one hot plate is used, the temperature of the hot plate is changed after the second main heating step.
- the production efficiency can be further improved.
- the substrate temperature may drop momentarily when the substrate is transferred between the hot plates, but this does not give a problem to the solution of the problem of the present invention. Absent.
- the installation area of the heating device can be further reduced, and the degree of freedom of device layout can be improved.
- Example 9-1 In Example 9-1, the main heating is performed twice at different temperatures in the step (4), and the first main heating (first main heating step) and the second main heating (second main heating). In this case, light irradiation (second light irradiation step) is performed on the film that has been subjected to the first main heating.
- first main heating step first main heating step
- second main heating second main heating
- a method for manufacturing the liquid crystal display device according to Example 9-1 will be sequentially described below.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- a solvent a mixture of N-methyl-pyrrolidone and butyl cellosolve at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- a film made of a photo-alignment film material was formed on two substrates by spin coating.
- Preheating was performed at 70 ° C. for 150 seconds on the film after the step of forming the film made of the photo-alignment film material on the two substrates.
- the preheating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the film thickness of the photo-alignment film material after the preheating step was about 100 nm.
- UV irradiation step The film after the first main heating step on the two substrates was irradiated with ultraviolet rays.
- the amount of UV irradiation was 1 J / cm 2 near the center wavelength of 313 nm.
- the main heating was performed at 180 ° C. for 5 minutes on the film after the second light irradiation process on the two substrates. This heating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- a liquid crystal display device according to Example 9-1 was obtained by appropriately arranging the members.
- the liquid crystal material a material containing liquid crystal molecules having positive dielectric anisotropy was used, and the thickness of the liquid crystal layer was 3.5 ⁇ m.
- Example 9-2 is a case where the second light irradiation step was not performed in Example 9-1. Since the manufacturing method of the liquid crystal display device according to Example 9-2 is the same as that of Example 9-1 except that the second light irradiation step does not exist, description of overlapping points is omitted.
- Example 9-1 and Example 9-2 A voltage of 5 V was continuously applied to the liquid crystal display device manufactured by the method for manufacturing the liquid crystal display device according to Example 9-1 and Example 9-2 in an environment of 60 ° C., and confirmed after 500 hours. As a result, in both cases, the voltage holding ratio was 97% or more. Table 5 summarizes the evaluation results of the display quality of the liquid crystal display devices manufactured by the liquid crystal display device manufacturing method according to Example 9-1 and Example 9-2.
- Display quality was evaluated in the same manner as in Examples 2-1 to 2-6.
- the evaluation result is level 1 to 3
- the evaluation result is level 4
- Example 9-1 The evaluation result of the display quality was level 1, which was very good. This is considered to be because after the self-organization has sufficiently progressed, the remaining solvent has sufficiently volatilized, and the orientational order of the polymer improved by the self-organization has been sufficiently fixed. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 9-1, the display quality can be sufficiently improved.
- Example 9-2 The evaluation result of the display quality was level 3, which was good. This is considered to be because after the self-organization has sufficiently progressed, the remaining solvent has sufficiently volatilized, and the orientational order of the polymer improved by the self-organization has been sufficiently fixed. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 9-2, the display quality can be sufficiently improved.
- Example 9-1 the dimerization of the cinnamate group further proceeds by performing the second light irradiation step, and then the alignment order of the polymer is sufficiently fixed by performing the second main heating step. It is thought.
- Example 9-2 since the second light irradiation step does not exist, it is considered that the alignment order of the polymer is not relatively improved as compared with Example 9-1. Therefore, the display quality of Example 9-1 was better than that of Example 9-2.
- Example 10-1 is a case in which one of the two substrates is a thin film transistor array substrate having thin film transistor elements and the other is a color filter substrate in Example 1.
- a semiconductor layer included in the thin film transistor element an oxide semiconductor (In—Ga—Zn—O) including indium (In), gallium (Ga), zinc (Zn), and oxygen (O) is used.
- oxide semiconductor In—Ga—Zn—O
- Example 10-1 Since the manufacturing method of the liquid crystal display device according to Example 10-1 is the same as that of Example 1 except for the configuration of the liquid crystal display device, description of overlapping points is omitted.
- the semiconductor layer included in the thin film transistor element an oxide semiconductor (In—Ga—Zn—O) was used.
- the screen size is 10 inches (2048 ⁇ 1560 pixels).
- Example 10-2 is a case in which one of the two substrates is a thin film transistor array substrate having thin film transistor elements and the other is a color filter substrate in Example 1. Here, amorphous silicon was used as a semiconductor layer included in the thin film transistor element. Since the manufacturing method of the liquid crystal display device according to Example 10-2 is the same as that of Example 1 except for the configuration of the liquid crystal display device, description of overlapping points is omitted.
- the semiconductor layer included in the thin film transistor element amorphous silicon was used.
- the screen size is 10 inches (2048 ⁇ 1560 pixels).
- Example 10-1 and Example 10-2 For the liquid crystal display devices manufactured by the liquid crystal display device manufacturing method according to Example 10-1 and Example 10-2, the image sticking characteristics and the voltage holding ratio characteristics were evaluated by display quality. Regarding burn-in characteristics, white (255 gradation) and black (0 gradation) checker patterns were displayed, and the burn-in level was evaluated in a state where the entire surface was turned on with 32 gradations after 1 hour. Regarding the voltage holding ratio characteristics, white and black checker patterns were displayed, and the level of blotches and unevenness was evaluated in a state where the entire surface was turned on with 32 gradations after 500 hours.
- burn-in characteristics white (255 gradation) and black (0 gradation) checker patterns were displayed, and the burn-in level was evaluated in a state where the entire surface was turned on with 32 gradations after 1 hour.
- the voltage holding ratio characteristics white and black checker patterns were displayed, and the level of blotches and unevenness was evaluated in a state where the entire surface was turned on with 32 gradations after 500 hours
- the liquid crystal display device is turned on in the dark room, and the display quality is visually evaluated through the naked eye and a neutral density (ND) filter. Evaluation was made in four stages: level C: non-uniformity is not visible over ND filter 20%, level D: orientation non-uniformity is visible over 20% ND filter.
- level C non-uniformity is not visible over ND filter 20%
- level D orientation non-uniformity is visible over 20% ND filter.
- Example 10-1 and Example 10-2 were both level B.
- Example 10-1 and Example 10-2 were both level B.
- Example 10-1 the aperture ratio of the liquid crystal display panel in Example 10-1 was 50%, which was higher than 40% in Example 10-2.
- the contrast and transmittance of Example 10-1 were both improved by 20% compared to those of Example 10-2. Therefore, according to the method for manufacturing the liquid crystal display device according to Example 10-1, the display quality can be further improved as compared with the method for manufacturing the liquid crystal display device according to Example 10-2.
- Example 10-1 The reason why the aperture ratio of Example 10-1 is higher than that of Example 10-2 will be described.
- An oxide semiconductor has a feature of higher mobility than amorphous silicon. Therefore, the ratio of the thin film transistor element including an oxide semiconductor to one pixel can be reduced as compared with the thin film transistor element including amorphous silicon. Therefore, according to the method for manufacturing the liquid crystal display device according to Example 10-1, the aperture ratio can be further improved as compared with the method for manufacturing the liquid crystal display device according to Example 10-2. The quality can be further improved.
- Example 11-1 is a case where a solvent in which the photo-alignment film material contains a mixture of N-methyl-pyrrolidone (good solvent) and butyl cellosolve (poor solvent) at a weight ratio of 50:50. The same as in the first embodiment. Since the manufacturing method of the liquid crystal display device according to Example 11-1 is the same as that of Example 1, description of overlapping points is omitted.
- Example 11-2 N-ethyl-pyrrolidone (good solvent) and butyl cellosolve (poor solvent) were mixed at a weight ratio of 50:50 as the solvent contained in the photo-alignment film material in Example 11-1. This is the case when a thing is used. Since the manufacturing method of the liquid crystal display device according to Example 11-2 is the same as that of Example 11-1, except for the photo-alignment film material, the description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- a solvent a mixture of N-ethyl-pyrrolidone and butyl cellosolve at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- Example 11-3 is a mixture of ⁇ -butyllactone (good solvent) and butyl cellosolve (poor solvent) in a weight ratio of 50:50 as the solvent contained in the photo-alignment film material in Example 11-1. This is the case. Since the manufacturing method of the liquid crystal display device according to Example 11-3 is the same as that of Example 11-1, except for the photo-alignment film material, description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- solvent a mixture of ⁇ -butyl lactone and butyl cellosolve at a weight ratio of 50:50 was used.
- the solid content concentration was 4% by weight.
- Example 11-4 uses a mixture of acetone (good solvent) and butyl cellosolve (poor solvent) in a weight ratio of 50:50 as the solvent contained in the photo-alignment film material in Example 11-1. Is the case. Since the manufacturing method of the liquid crystal display device according to Example 11-4 is the same as that of Example 11-1, except for the photo-alignment film material, the description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- a solvent a mixture of acetone and butyl cellosolve at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- Example 11-5 used a mixture of chloroform (good solvent) and butyl cellosolve (poor solvent) in a weight ratio of 50:50 as the solvent contained in the photo-alignment film material in Example 11-1. Is the case. Since the manufacturing method of the liquid crystal display device according to Example 11-5 is the same as that of Example 11-1, except for the photo-alignment film material, the description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- a solvent a mixture of chloroform and butyl cellosolve at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- Example 11-6 is a mixture of cyclopentanone (good solvent) and butyl cellosolve (poor solvent) mixed in a weight ratio of 50:50 as the solvent contained in the photo-alignment film material in Example 11-1. This is the case. Since the manufacturing method of the liquid crystal display device according to Example 11-6 is the same as that of Example 11-1, except for the photo-alignment film material, the description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- solvent a mixture of cyclopentanone and butyl cellosolve at a weight ratio of 50:50 was used.
- the solid content concentration was 4% by weight.
- Example 11-7 N-methyl-pyrrolidone (good solvent) and diethylene glycol diethyl ether (poor solvent) were mixed at a weight ratio of 50:50 as the solvent contained in the photo-alignment film material in Example 11-1. This is a case where a mixture is used. Since the manufacturing method of the liquid crystal display device according to Example 11-7 is the same as that of Example 11-1, except for the photo-alignment film material, the description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- a solvent a mixture of N-methyl-pyrrolidone and diethylene glycol diethyl ether at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- Example 11-8 N-methyl-pyrrolidone (good solvent) and diisobutyl ketone (poor solvent) were mixed at a weight ratio of 50:50 as the solvent contained in the photo-alignment film material in Example 11-1. This is the case of using. Since the manufacturing method of the liquid crystal display device according to Example 11-8 is the same as that of Example 11-1, except for the photo-alignment film material, the description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- diamine containing a biphenyl structure As the solvent, a mixture of N-methyl-pyrrolidone and diisobutyl ketone at a weight ratio of 50:50 was used.
- the solid content concentration was 4% by weight.
- Example 11-9 N-methyl-pyrrolidone (good solvent) and propylene glycol monobutyl ether (poor solvent) are used in a weight ratio of 50:50 as the solvent contained in the photo-alignment film material in Example 11-1. It is a case where what was mixed with is used. Since the manufacturing method of the liquid crystal display device according to Example 11-9 is the same as that of Example 11-1, except for the photo-alignment film material, the description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- solvent a mixture of N-methyl-pyrrolidone and propylene glycol monobutyl ether in a weight ratio of 50:50 was used.
- the solid content concentration was 4% by weight.
- Example 11-10 N-methyl-pyrrolidone (good solvent) and diacetone alcohol (poor solvent) are mixed at a weight ratio of 50:50 as the solvent contained in the photo-alignment film material in Example 11-1. This is a case where a mixture is used. Since the manufacturing method of the liquid crystal display device according to Example 11-10 is the same as that of Example 11-1, except for the photo-alignment film material, the description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- diamine containing a biphenyl structure As a solvent, a mixture of N-methyl-pyrrolidone and diacetone alcohol at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- Example 11-11 N-methyl-pyrrolidone (good solvent) and hexane (poor solvent) as a solvent contained in the photo-alignment film material in Example 11-1 were mixed at a weight ratio of 50:50. This is the case when a thing is used. Since the manufacturing method of the liquid crystal display device according to Example 11-11 is the same as that of Example 11-1, except for the photo-alignment film material, the description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- a solvent a mixture of N-methyl-pyrrolidone and hexane at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- Example 11-12 N-methyl-pyrrolidone (good solvent) and methanol (poor solvent) were mixed at a weight ratio of 50:50 as the solvent contained in the photo-alignment film material in Example 11-1. This is the case when a thing is used. Since the manufacturing method of the liquid crystal display device according to Example 11-12 is the same as that of Example 11-1, except for the photo-alignment film material, the description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- a solvent a mixture of N-methyl-pyrrolidone and methanol at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- Example 11-13 In Example 11-13, N-methyl-pyrrolidone (good solvent) and isopropyl alcohol (poor solvent) were mixed at a weight ratio of 50:50 as the solvent contained in the photo-alignment film material in Example 11-1. This is the case of using. Since the manufacturing method of the liquid crystal display device according to Example 11-13 is the same as that of Example 11-1, except for the photo-alignment film material, the description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- a solvent in which N-methyl-pyrrolidone and isopropyl alcohol were mixed at a weight ratio of 50:50 was used.
- the solid content concentration was 4% by weight.
- Example 11-14 In Example 11-14, a mixture of acetone (good solvent) and hexane (poor solvent) at a weight ratio of 50:50 was used as the solvent contained in the photo-alignment film material in Example 11-1. Is the case. Since the manufacturing method of the liquid crystal display device according to Example 11-14 is the same as that of Example 11-1, except for the photo-alignment film material, the description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- diamine containing a biphenyl structure As the solvent, a mixture of acetone and hexane at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- Example 11-15 In Example 11-15, a mixture of chloroform (good solvent) and methanol (poor solvent) at a weight ratio of 50:50 was used as the solvent contained in the photo-alignment film material in Example 11-1. Is the case. Since the manufacturing method of the liquid crystal display device according to Example 11-15 is the same as that of Example 11-1, except for the photo-alignment film material, the description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- a solvent a mixture of chloroform and methanol at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- Example 11-16 is a mixture of cyclopentanone (good solvent) and isopropyl alcohol (poor solvent) in a weight ratio of 50:50 as the solvent contained in the photo-alignment film material in Example 11-1. Is used. Since the manufacturing method of the liquid crystal display device according to Example 11-16 is the same as that of Example 11-1, except for the photo-alignment film material, the description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- solvent a mixture of cyclopentanone and isopropyl alcohol at a weight ratio of 50:50 was used.
- the solid content concentration was 4% by weight.
- Table 6 summarizes the evaluation results of the solvent components (good solvent and poor solvent) and display quality of the liquid crystal display devices manufactured by the method of manufacturing liquid crystal display devices according to Examples 11-1 to 11-16.
- the liquid crystal display device is turned on in the dark room, and the display quality is visually evaluated through the naked eye and a neutral density (ND) filter. Evaluation was made in four stages: level C: non-uniformity is not visible over ND filter 20%, level D: orientation non-uniformity is visible over 20% ND filter.
- level C non-uniformity is not visible over ND filter 20%
- level D orientation non-uniformity is visible over 20% ND filter.
- Example 11-1 The evaluation result of the display quality was level A, which was very good. This is presumably because the occurrence of film thickness unevenness was sufficiently prevented after the preheating step. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 11-1, the display quality can be sufficiently improved.
- Example 11-2 The evaluation result of the display quality was level A, which was very good. This is presumably because the occurrence of film thickness unevenness was sufficiently prevented after the preheating step. Therefore, according to the method of manufacturing the liquid crystal display device according to Example 11-2, the display quality can be sufficiently improved.
- Example 11-3 The evaluation result of the display quality was level A, which was very good. This is presumably because the occurrence of film thickness unevenness was sufficiently prevented after the preheating step. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 11-3, the display quality can be sufficiently improved.
- Example 11-4 The evaluation result of the display quality was level B, which was good. This is presumably because the occurrence of film thickness unevenness was sufficiently prevented after the preheating step. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 11-4, the display quality can be sufficiently improved.
- Example 11-5 The evaluation result of the display quality was level B, which was good. This is presumably because the occurrence of film thickness unevenness was sufficiently prevented after the preheating step. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 11-5, the display quality can be sufficiently improved.
- Example 11-6 The evaluation result of the display quality was level B, which was good. This is presumably because the occurrence of film thickness unevenness was sufficiently prevented after the preheating step. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 11-6, the display quality can be sufficiently improved.
- Example 11-7 The evaluation result of the display quality was level A, which was very good. This is presumably because the occurrence of film thickness unevenness was sufficiently prevented after the preheating step. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 11-7, the display quality can be sufficiently improved.
- Example 11-8 The evaluation result of the display quality was level A, which was very good. This is presumably because the occurrence of film thickness unevenness was sufficiently prevented after the preheating step. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 11-8, the display quality can be sufficiently improved.
- Example 11-9 The evaluation result of the display quality was level A, which was very good. This is presumably because the occurrence of film thickness unevenness was sufficiently prevented after the preheating step. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 11-9, the display quality can be sufficiently improved.
- Example 11-10 The evaluation result of the display quality was level A, which was very good. This is presumably because the occurrence of film thickness unevenness was sufficiently prevented after the preheating step. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 11-10, the display quality can be sufficiently improved.
- Example 11-11 The evaluation result of the display quality was level B, which was good. This is presumably because the occurrence of film thickness unevenness was sufficiently prevented after the preheating step. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 11-11, it is possible to sufficiently improve the display quality.
- Example 11-12 The evaluation result of the display quality was level B, which was good. This is presumably because the occurrence of film thickness unevenness was sufficiently prevented after the preheating step. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 11-12, the display quality can be sufficiently improved.
- Example 11-13 The evaluation result of the display quality was level B, which was good. This is presumably because the occurrence of film thickness unevenness was sufficiently prevented after the preheating step. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 11-13, the display quality can be sufficiently improved.
- Example 11-14 The evaluation result of the display quality was level C. This is presumably because the occurrence of film thickness unevenness was sufficiently prevented after the preheating step. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 11-14, the display quality can be sufficiently improved.
- Example 11-15 The evaluation result of the display quality was level C. This is presumably because the occurrence of film thickness unevenness was sufficiently prevented after the preheating step. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 11-15, the display quality can be sufficiently improved.
- Example 11-16 The evaluation result of the display quality was level C. This is presumably because the occurrence of film thickness unevenness was sufficiently prevented after the preheating step. Therefore, according to the manufacturing method of the liquid crystal display device according to Example 11-16, the display quality can be sufficiently improved.
- the solvent contained in the photo-alignment film material is preferably a mixture of a good solvent with high solubility and a poor solvent with low surface tension and high coatability from the viewpoint of further improving display quality.
- at least one compound selected from the group consisting of acetone, chloroform, and cyclopentanone as the good solvent is used, and at least one compound selected from the group consisting of hexane, methanol, and isopropyl alcohol is used as the poor solvent.
- the solvent contained in the photo-alignment film material is preferably a mixture of a good solvent and a poor solvent, and the good solvent is selected from N-methyl-pyrrolidone, N-ethyl-pyrrolidone, and ⁇ -butyllactone.
- the good solvent is selected from N-methyl-pyrrolidone, N-ethyl-pyrrolidone, and ⁇ -butyllactone.
- One compound was found to be preferred.
- Comparative Example 5 is a case where the light irradiation process is performed after the main heating process using a decomposition type photo-alignment film and a liquid crystal material including liquid crystal molecules having positive dielectric anisotropy. A method for manufacturing a liquid crystal display device according to Comparative Example 5 will be sequentially described below.
- Photo-alignment film material As a solid content, a polyamic acid polymer having a cyclobutane skeleton was used. As a solvent, a mixture of N-methyl-pyrrolidone and butyl cellosolve at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- a film made of a photo-alignment film material was formed on two substrates by spin coating.
- Preheating was performed at 70 ° C. for 150 seconds on the film after the step of forming the film made of the photo-alignment film material on the two substrates.
- the preheating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the film thickness of the photo-alignment film material after the preheating step was about 100 nm.
- the film after the first main heating step on the two substrates was irradiated with polarized ultraviolet rays.
- the irradiation amount of polarized ultraviolet rays was 1 J / cm 2 in the wavelength range of 220 to 260 nm.
- the main heating was performed at 230 ° C. for 30 minutes on the film after the light irradiation process on the two substrates. This heating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- a liquid crystal display device according to Comparative Example 5 was obtained by appropriately arranging the members.
- the liquid crystal material a material containing liquid crystal molecules having positive dielectric anisotropy was used, and the thickness of the liquid crystal layer was 3.5 ⁇ m.
- Comparative Example 6 is a case where the liquid crystal material including liquid crystal molecules having negative dielectric anisotropy is used in Comparative Example 5. Since the manufacturing method of the liquid crystal display device according to Comparative Example 6 is the same as that of Comparative Example 5 except that the dielectric anisotropy of the liquid crystal molecules is different, the description of overlapping points is omitted.
- the comparative example 6 produced more noticeable bright spots in the screen than the comparative example 5.
- the conditions of the thermal cycle test were set to 1 hour for one cycle in a temperature range of ⁇ 10 ° C. to 70 ° C. Further, when one month later was confirmed after standing at room temperature, in Comparative Example 6, a fine bright spot was generated more remarkably in the screen than in Comparative Example 5.
- Comparative Example 5 and Comparative Example 6 it is considered that a low molecular weight decomposition product was generated by irradiation with polarized ultraviolet rays, and the decomposition product aggregated after eluting into the liquid crystal, thereby becoming a bright spot.
- the case where the liquid crystal material containing liquid crystal molecules having negative dielectric anisotropy is used is compared with the case where the liquid crystal material containing liquid crystal molecules having positive dielectric anisotropy is used. It is considered that the bright spot was generated more remarkably because the decomposition product was dissolved into the liquid crystal. Therefore, from the viewpoint of improving the display quality, it has been found that it is more difficult to use a liquid crystal material including liquid crystal molecules having negative dielectric anisotropy.
- Example 4 etc. According to the method for manufacturing a liquid crystal display device according to one embodiment of the present invention, even when a liquid crystal material containing liquid crystal molecules having negative dielectric anisotropy is used, display quality is sufficient. Can be improved.
- Comparative Example 7 In Comparative Example 7, the same photo-alignment film material as in Example 1 was used, and the light irradiation process was performed after the main heating process. A method for manufacturing a liquid crystal display device according to Comparative Example 7 will be sequentially described below.
- Photo-alignment film material As a solid content, a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer having a methacryl skeleton and a photoreactive cinnamate group in the side chain, and the other is a 1,2,3,4-cyclobutanetetracarboxylic acid dicarboxylic acid. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting an anhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA anhydride
- a solvent a mixture of N-methyl-pyrrolidone and butyl cellosolve at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- a film made of a photo-alignment film material was formed on two substrates by spin coating.
- Preheating was performed at 70 ° C. for 150 seconds on the film after the step of forming the film made of the photo-alignment film material on the two substrates.
- the preheating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the film thickness of the photo-alignment film material after the preheating step was about 100 nm.
- the main heating was performed at 200 ° C. for 30 minutes on the film after the first light irradiation process on the two substrates. This heating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the film after the second main heating step on the two substrates was irradiated with polarized ultraviolet rays.
- the irradiation amount of polarized ultraviolet rays was 5 mJ / cm 2 in the wavelength range of 280 to 330 nm.
- the two substrates after the second light irradiation step were bonded to the FFS mode liquid crystal display panel obtained in the same manner as in the liquid crystal display device manufacturing method according to Example 1, and a polarizing plate, a backlight, etc.
- a liquid crystal display device according to Comparative Example 7 was obtained by appropriately arranging the members.
- the liquid crystal material a material containing liquid crystal molecules having positive dielectric anisotropy was used, and the thickness of the liquid crystal layer was 3.5 ⁇ m.
- Comparative Example 8 is a case where the same photo-alignment film material as in Example 5 was used and the light irradiation process was performed after this heating process. A method for manufacturing a liquid crystal display device according to Comparative Example 8 will be sequentially described below.
- a solid content a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polymer containing a photoreactive azobenzene structure, and the other is 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) and biphenyl. It is a polyamic acid having no photofunctional group and side chain, obtained by reacting a diamine containing a structure.
- a solvent a mixture of N-methyl-pyrrolidone and butyl cellosolve at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- a film made of a photo-alignment film material was formed on two substrates by spin coating.
- Preheating was performed at 60 ° C. for 150 seconds on the film after the step of forming a film made of the photo-alignment film material on the two substrates.
- the preheating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the film thickness of the photo-alignment film material after the preheating step was about 100 nm.
- the main heating was performed at 200 ° C. for 30 minutes on the film after the first main heating step on the two substrates. This heating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the film after the second main heating step on the two substrates was irradiated with polarized ultraviolet rays.
- the irradiation amount of polarized ultraviolet rays was 3 J / cm 2 near the center wavelength of 365 nm.
- the liquid crystal display device according to Comparative Example 8 was obtained.
- the liquid crystal material a material containing liquid crystal molecules having negative dielectric anisotropy was used, and the thickness of the liquid crystal layer was 3.5 ⁇ m.
- Example 12 is a case where the main heating was performed twice at different temperatures in the step (4). A manufacturing method of the liquid crystal display device according to Example 12 will be sequentially described below.
- a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polyamic acid obtained by reacting an acid anhydride (TCA) represented by the following chemical formula (1) and a diamine containing a phenyl ester group having photoreactivity.
- TCA acid anhydride
- the other of the two types of polymers is a photofunctional group and a side chain obtained by reacting 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) and a diamine containing a biphenyl structure.
- CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
- the phenyl ester group is a photofunctional group capable of photo-fleece transition.
- a film made of a photo-alignment film material was formed on two substrates by spin coating.
- Preheating was performed at 60 ° C. for 150 seconds on the film after the step of forming a film made of the photo-alignment film material on the two substrates.
- the preheating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the film thickness of the photo-alignment film material after the preheating step was about 100 nm.
- the film after the preheating step on the two substrates was irradiated with polarized ultraviolet rays.
- the irradiation amount of polarized ultraviolet rays was 1 J / cm 2 near the center wavelength of 254 nm.
- the main heating was performed at 120 ° C. for 20 minutes on the film after the light irradiation process on the two substrates. This heating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the main heating was performed at 220 ° C. for 30 minutes on the film after the first main heating process on the two substrates. This heating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- a liquid crystal display device according to Example 12 was obtained by appropriately arranging the members.
- the liquid crystal material a material containing liquid crystal molecules having negative dielectric anisotropy was used, and the thickness of the liquid crystal layer was 3.5 ⁇ m.
- the comparative example 9 is a case where the photo-alignment film material which does not contain the polyamic acid which does not have a photofunctional group and a side chain in Example 12 is used. Since the manufacturing method of the liquid crystal display device according to Comparative Example 9 is the same as that of Example 12 except for the photo-alignment film material, the description of overlapping points is omitted.
- a polyamic acid obtained by reacting an acid anhydride (TCA) represented by the chemical formula (1) and a diamine containing a phenyl ester group having photoreactivity was used as the solid content.
- TCA acid anhydride
- a diamine containing a phenyl ester group having photoreactivity was used as the solid content.
- a solvent a mixture of N-methyl-pyrrolidone and butyl cellosolve at a weight ratio of 50:50 was used.
- the solid content concentration was 4% by weight.
- Example 12 and Comparative Example 9 The liquid crystal display device manufactured by the liquid crystal display device manufacturing method according to Example 12 was evaluated for contrast and image sticking characteristics.
- the case where the contrast was 500 or more and the burn-in characteristic (burn-in rate) was within 5% was judged to be a level suitable for the product.
- the contrast was measured by the same method as in Examples 2-1 to 2-6, and the burn-in characteristics were evaluated by the same method as in Example 4.
- Example 12 (Contrast measurement result) The contrast in Example 12 was 1200, which was a level suitable for a product.
- Example 12 (Evaluation results of seizure characteristics) The burn-in rate in Example 12 was 3%, which was a level suitable for the product.
- Example 13 is a case where the main heating was performed twice at different temperatures in the step (4). A method for manufacturing the liquid crystal display device according to Example 13 will be described in turn below.
- a mixture of two kinds of polymers at a weight ratio of 50:50 was used.
- One of the two types of polymers is a polyamic obtained by reacting an acid anhydride (TCA) represented by the chemical formula (1) and a diamine containing a phenyl ester group and a cinnamate group having photoreactivity. It is an acid.
- the other of the two types of polymers is a photofunctional group and a side chain obtained by reacting 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) and a diamine containing a biphenyl structure.
- TCA acid anhydride
- CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
- This photo-alignment film material contains a photofunctional group capable of photodimerization, photoisomerization, and photofleece transition.
- a film made of a photo-alignment film material was formed on two substrates by spin coating.
- Preheating was performed at 60 ° C. for 150 seconds on the film after the step of forming a film made of the photo-alignment film material on the two substrates.
- the preheating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the film thickness of the photo-alignment film material after the preheating step was about 100 nm.
- the film after the preheating step on the two substrates was irradiated with polarized ultraviolet rays.
- the irradiation amount of polarized ultraviolet rays was 500 mJ / cm 2 near the center wavelength of 313 nm, and further 100 mJ / cm 2 near the center wavelength of 254 nm.
- the main heating was performed at 120 ° C. for 20 minutes on the film after the light irradiation process on the two substrates. This heating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the main heating was performed at 220 ° C. for 30 minutes on the film after the first main heating process on the two substrates. This heating was performed using a hot plate (trade name: EC-1200N) manufactured by ASONE.
- the two substrates after the second main heating step were bonded to the FFS mode liquid crystal display panel obtained in the same manner as in the liquid crystal display device manufacturing method according to Example 1, and a polarizing plate, a backlight, etc.
- a liquid crystal display device according to Example 13 was obtained by appropriately arranging the members.
- the liquid crystal material a material containing liquid crystal molecules having negative dielectric anisotropy was used, and the thickness of the liquid crystal layer was 3.5 ⁇ m.
- the comparative example 10 is a case where the photo-alignment film material which does not contain the polyamic acid which does not have a photofunctional group and a side chain in Example 13 is used. Since the manufacturing method of the liquid crystal display device according to Comparative Example 10 is the same as that of Example 13 except for the photo-alignment film material, the description of overlapping points is omitted.
- Photo-alignment film material As a solid content, a polyamic acid obtained by reacting an acid anhydride (TCA) represented by the chemical formula (1) and a diamine containing a phenyl ester group and a cinnamate group having photoreactivity was used. As a solvent, a mixture of N-methyl-pyrrolidone and butyl cellosolve at a weight ratio of 50:50 was used. The solid content concentration was 4% by weight.
- TCA acid anhydride
- solvent a mixture of N-methyl-pyrrolidone and butyl cellosolve at a weight ratio of 50:50 was used.
- the solid content concentration was 4% by weight.
- Example 13 and Comparative Example 10 The liquid crystal display device manufactured by the method for manufacturing a liquid crystal display device according to Example 13 was evaluated for contrast and image sticking characteristics.
- the contrast was measured by the same method as in Examples 2-1 to 2-6, and the burn-in characteristics were evaluated by the same method as in Example 4.
- Example 13 (Contrast measurement result) The contrast in Example 13 was 1200, which was a level suitable for a product.
- Example 13 (Evaluation results of seizure characteristics) The burn-in rate in Example 13 was 3%, which was a level suitable for the product.
- the main heating in the step (4) may be performed at a temperature of 90 ° C. or higher.
- the molecular motion of the polymer accompanying the main heating becomes easier, and the alignment order of the polymer by self-organization can be further improved.
- the temperature of the main heating is less than 90 ° C., the molecular motion of the polymer accompanying the main heating may not become active.
- “performing main heating at a temperature of 90 ° C. or higher” means performing the main heating so that the temperature has a constant temperature period of 90 ° C. or higher.
- the constant temperature period of 90 ° C. or higher may mean a period of a heating state maintained for 1 minute or longer within a temperature range of ⁇ 5 ° C., for example.
- the main heating temperature in the step (4) is more preferably 140 ° C. or higher.
- the molecular motion of the polymer accompanying the main heating becomes more active, and the alignment order of the polymer due to self-organization can be further improved.
- the temperature of the main heating is less than 140 ° C.
- the molecular motion of the polymer accompanying the main heating does not become active, and the orientation order of the polymer due to self-organization may not be sufficiently improved.
- the temperature of this heating exceeds 250 degreeC, discoloration of a color filter layer etc. generate
- it is still more preferable that the temperature of the main heating of the said process (4) is 140 degreeC or more and 250 degrees C or less.
- the preheating in the step (2) may be performed at a temperature of 90 ° C. or lower, and more preferably performed at a temperature of 70 ° C. or lower.
- the preheating temperature exceeds 90 ° C., the residual amount of the solvent decreases, so that the molecular motion of the polymer accompanying the main heating does not become active, and the orientation order of the polymer due to self-organization is reduced. There is a possibility that it cannot be improved sufficiently. “Preheating at a temperature of 90 ° C.
- the constant temperature period of 90 ° C. or lower may mean, for example, a period of a heating state maintained for 30 seconds or more within a temperature range of ⁇ 5 ° C.
- the preheating temperature in step (2) is more preferably 40 ° C. or higher and 70 ° C. or lower. Thereby, the molecular motion of the polymer accompanying the subsequent main heating becomes more active, and the alignment order of the polymer by self-organization can be further improved.
- the preheating temperature is lower than 40 ° C., it takes time for the solvent to volatilize, so that the film thickness unevenness due to the convection of the solution is remarkably generated. As a result, the alignment unevenness is visually recognized when the liquid crystal display device is turned on. There is a possibility that.
- the preheating temperature exceeds 70 ° C.
- the residual amount of the solvent decreases, so that the molecular motion of the polymer accompanying the main heating does not become active, and the orientation order of the polymer due to self-organization is reduced. There is a possibility that it cannot be improved sufficiently.
- the preheating temperature in the step (2) is particularly preferably 50 ° C. or higher and 70 ° C. or lower.
- the liquid crystal display device may align liquid crystal molecules having negative dielectric anisotropy with the photo-alignment film. Thereby, the transmittance and viewing angle characteristics can be further improved.
- the main heating in the step (4) may include an operation performed so as to have a plurality of constant temperature periods with different temperatures from a low temperature to a high temperature. Thereby, the main heating can be performed step by step at a plurality of different temperatures, and the display quality can be sufficiently improved.
- the constant temperature period may mean, for example, a period of a heating state maintained for 1 minute or more within a temperature range of ⁇ 5 ° C.
- the main heating in the above step (4) is performed twice at different temperatures, the first main heating is performed at a temperature of 90 ° C. or higher and 140 ° C. or lower, and the second main heating is performed at 180 ° C. or higher. It may be performed at the temperature. Thereby, the molecular motion of the polymer becomes more active, and the alignment order of the polymer due to self-organization can be sufficiently improved.
- the temperature of the first main heating exceeds 140 ° C., the thermochemical reaction of the polymer and the volatilization of the remaining solvent may be remarkably started, which may hinder self-organization.
- the temperature of the first main heating is more preferably 110 ° C. or higher and lower than 120 ° C.
- the temperature of the second main heating is less than 180 ° C., the remaining amount of the solvent cannot be sufficiently reduced, and the display quality may be deteriorated. Further, from the viewpoint of further improving display quality, the temperature of the second main heating is more preferably 180 ° C. or higher and 250 ° C. or lower. When the temperature of the second main heating exceeds 250 ° C., the color filter layer may be discolored and the like, and the display quality of the liquid crystal display device may be deteriorated. Further, from the viewpoint of sufficiently proceeding the thermochemical reaction of the polymer, the temperature of the second main heating is more preferably 200 ° C. or more and 250 ° C. or less.
- the main heating in the above step (4) may be performed using a plurality of heating devices set to different temperatures. Thereby, the operation of main heating the film irradiated with polarized light so as to have a plurality of constant temperature periods with different temperatures from low temperature to high temperature can be suitably performed. Moreover, compared with the case where one heating apparatus is used, manufacturing efficiency can be improved more.
- the main heating in the step (4) may be performed while sequentially changing to different temperatures using a single heating device.
- the operation of main heating the film irradiated with polarized light so as to have a plurality of constant temperature periods with different temperatures from low temperature to high temperature can be suitably performed.
- the installation area of the heating device can be further reduced, and the degree of freedom of device layout can be improved.
- the main heating in the step (4) may be performed while moving the substrate in the heating device using a heating device having a region with a temperature gradient. Thereby, the operation of main heating the film irradiated with polarized light so as to have a plurality of constant temperature periods with different temperatures from low temperature to high temperature can be suitably performed.
- the photofunctional group may be at least one functional group selected from the group consisting of a cinnamate group, a chalcone group, a coumarin group, a stilbene group, a phenyl ester group, and an azobenzene group.
- the polymer skeleton having the photofunctional group may have at least one structure selected from the group consisting of polyamic acid, polyimide, acrylic, methacrylic, maleimide, and polysiloxane.
- a part of the polyamic acid may be subjected to a thermochemical reaction (thermal imidization), thereby adjusting the electrical characteristics such as the specific resistance and dielectric constant of the photo-alignment film.
- thermochemical reaction thermal imidization
- a skeleton combining acrylic or methacryl and maleimide that is, a copolymer structure
- another structure having no photoreactivity can be introduced into the photo-alignment film material.
- transduce a photofunctional group into the polyamic acid or the diamine which forms a polyimide it can also introduce suitably by making another diamine which does not have photoreactivity into a copolymer structure.
- employing the copolymer structure as described above is an effective technique for adjusting the photoreactive sensitivity, electrical characteristics, and orientation characteristics in a well-balanced manner.
- a monomer having a plurality of functional groups such as epoxy, carboxylic acid, amine, acrylate, or methacrylate may be added in advance to the photo-alignment film material. Thereby, long-term reliability can be improved.
- This monomer functions as a crosslinking agent for the polymer contained in the photo-alignment film material, and forms a network structure in the photo-alignment film.
- impurities contained in the photo-alignment film and the substrate are prevented from eluting into the liquid crystal, and the voltage holding ratio is lowered in the process of using the liquid crystal display device for a long period of time. Can be sufficiently suppressed.
- the photofunctional group can be at least photodimerized, and the step (4) performs two main heating at different temperatures, and further between the first main heating and the second main heating. It may include a step (4a) of performing light irradiation on the film that has been subjected to the first main heating.
- the polymer material contained in the photo-alignment film material includes a structure represented by the following chemical formulas (2) to (4) in the main chain or side chain. Is preferred.
- X is not present, and is O, COO, OCO, CO, or C ⁇ C.
- a benzene ring in each chemical formula and any hydrogen atom of cyclohexane may be independently substituted with a fluorine atom (F) or a chlorine atom (Cl).
- the benzene ring and cyclohexane in each chemical formula are heterocyclic rings in which any carbon atom (C) is substituted with an oxygen atom (O), a nitrogen atom (N), or a sulfur atom (S). It may be.
- the polymer material contained in the photo-alignment film material preferably has a carboxyl group and / or an amide group in the main chain or side chain.
- self-organization can be activated by hydrogen bonds acting between C ⁇ O and OH or between NH and C ⁇ O.
- the ability to self-assemble can be improved by introducing a carboxyl group and / or an amide group into the main chain or side chain separately from the portion forming polyamic acid or polyimide.
- the polymer having the polyamic acid skeleton and not having the photofunctional group also includes a structure that activates self-organization as described above.
- the solvent includes at least one compound selected from the group consisting of N-methyl-pyrrolidone, N-ethyl-pyrrolidone, and ⁇ -butyllactone, butyl cellosolve, diethylene glycol diethyl ether, diisobutyl ketone and structural isomers thereof, propylene glycol It may be a mixture with monobutyl ether and at least one compound selected from the group consisting of diacetone alcohol.
- the substrate may include a thin film transistor array substrate including a thin film transistor element, and the thin film transistor element may include a semiconductor layer including an oxide semiconductor.
- An oxide semiconductor is characterized by higher mobility and less characteristic variation than amorphous silicon. For this reason, a thin film transistor element including an oxide semiconductor can be driven at a higher speed than a thin film transistor element including amorphous silicon, has a high driving frequency, and can reduce a ratio of one pixel. This is suitable for driving a next-generation display device.
- the oxide semiconductor film is formed by a simpler process than the polycrystalline silicon film, it has an advantage that it can be applied to a device that requires a large area.
- the substrate includes a thin film transistor array substrate including a thin film transistor element
- the thin film transistor element includes a semiconductor layer including an oxide semiconductor
- a liquid crystal capable of achieving the effect of one embodiment of the present invention and achieving high-speed driving.
- a display device can be manufactured.
- a compound (In—Ga—Zn—O), indium (In), indium (In), gallium (Ga), zinc (Zn), and oxygen (O) is used.
- In tin (Tin), zinc (Zn), and a compound composed of oxygen (O) (In—Tin—Zn—O), or indium (In), aluminum (Al), zinc (Zn) And a compound composed of oxygen (O) (In—Al—Zn—O) or the like.
- the hygroscopic property of the photo-alignment film material is preferably low.
- a polymer having a polyimide skeleton is preferably used.
- polymers having acrylic, methacrylic, maleimide, and polysiloxane skeletons are preferably used.
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Abstract
Description
実施例1は、2種類の高分子を含有する光配向膜材料を用いた場合である。実施例1に係る液晶表示装置の製造方法について、以下に順次説明する。
FFSモード用の電極構造を有する液晶表示装置であり、プレチルト角は0°である。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、N-メチル-ピロリドン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。ここで、シンナメート基は、光二量化及び光異性化が可能な光官能基である。
2枚の基板上に、光配向膜材料による膜をスピンコート法により形成した。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を70℃で150秒間行った。予備加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。また、予備加熱工程後の光配向膜材料による膜の膜厚は、100nm程度であった。
2枚の基板上の予備加熱工程後の膜に対して、偏光紫外線を照射した。偏光紫外線の照射量は、280~330nmの波長範囲で5mJ/cm2とした。
2枚の基板上の光照射工程後の膜に対して、本加熱を140℃で10分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
比較例1は、実施例1において光官能基及び側鎖を有さないポリアミック酸を含有しない光配向膜材料を用いた場合である。比較例1に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例1のそれと同様であるため、重複する点については説明を省略する。
固形分として、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子を用いた。溶媒として、N-メチル-ピロリドン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例1、及び、比較例1に係る液晶表示装置の製造方法により製造された液晶表示装置について、電圧保持率を評価した。
電圧保持率の測定には、東陽テクニカ社製の液晶物性評価システム(商品名:6254型)を用いた。印加電圧は5V、保持時間は16.67ms、測定温度は60℃とした。
60℃の環境下で5Vの電圧を印加し続け、500時間後を確認したところ、実施例1の電圧保持率は97%以上であり、比較例1の95%未満と比べて高かった。ここで、電圧保持率とは、1フレーム期間中に充電された電荷が保持される割合である。通常、本加熱による熱化学反応が不足すると、電圧保持率が低下してしまうことがある。また、電圧保持率の低下は、液晶表示装置における表示むらを引き起こすことがある。よって、実施例1に係る液晶表示装置の製造方法によれば、電圧保持率を充分に向上することができ、その結果、表示品位を充分に向上することができる。
実施例2-1は、実施例1において予備加熱の温度を60℃とした場合である。実施例2-1に係る液晶表示装置の製造方法は、予備加熱工程以外、実施例1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を60℃で150秒間行った。
実施例2-2は、実施例2-1において予備加熱の温度を70℃とした場合であり、実施例1と同様である。実施例2-2に係る液晶表示装置の製造方法は、実施例1のそれと同様であるため、重複する点については説明を省略する。
実施例2-3は、実施例2-1において予備加熱の温度を80℃とした場合である。実施例2-3に係る液晶表示装置の製造方法は、予備加熱工程以外、実施例2-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を80℃で150秒間行った。
実施例2-4は、実施例2-1において予備加熱の温度を90℃とした場合である。実施例2-4に係る液晶表示装置の製造方法は、予備加熱工程以外、実施例2-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を90℃で150秒間行った。
実施例2-5は、実施例2-1において予備加熱の温度を100℃とした場合である。実施例2-5に係る液晶表示装置の製造方法は、予備加熱工程以外、実施例2-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を100℃で150秒間行った。
実施例2-6は、実施例2-1において予備加熱の温度を110℃とした場合である。実施例2-6に係る液晶表示装置の製造方法は、予備加熱工程以外、実施例2-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を110℃で150秒間行った。
実施例2-1~2-6に係る液晶表示装置の製造方法により製造された液晶表示装置について、予備加熱の温度、及び、表示品位の評価結果を表1にまとめた。
表示品位を評価し、レベル1:コントラストが1200以上、レベル2:コントラストが1000以上、1200未満、レベル3:コントラストが500以上、1000未満、レベル4:コントラストが500未満又は配向不良が視認される、の4段階で評価した。ここで、評価結果がレベル1~3である場合を製品に適したレベルであると判断し、評価結果がレベル4である場合を製品に適したレベルに達していないと判断した。
コントラストは、(コントラスト)=(白表示時の輝度)/(黒表示時の輝度)で測定された。白表示時は最大輝度となる電圧印加状態、黒表示時は電圧無印加状態とした。輝度(白表示時及び黒表示時の輝度)の測定には、トプコン社製の分光放射計(商品名:SR-UL2)を用いた。
各例の表示品位の評価結果について、以下に説明する。
表示品位の評価結果はレベル1であり、実施例2-3~2-6のそれと比べて非常に良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例2-1に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル1であり、実施例2-3~2-6のそれと比べて非常に良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例2-2に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル2であり、実施例2-5、及び、実施例2-6のそれと比べて良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例2-3に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル2であり、実施例2-5、及び、実施例2-6のそれと比べて良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例2-4に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル3であり、良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例2-5に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル3であり、良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例2-6に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
実施例3-1は、実施例2-2において本加熱の温度を80℃とした場合である。実施例3-1に係る液晶表示装置の製造方法は、本加熱工程以外、実施例2-2のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光照射工程後の膜に対して、本加熱を80℃で10分間行った。
実施例3-2は、実施例3-1において本加熱の温度を90℃とした場合である。実施例3-2に係る液晶表示装置の製造方法は、本加熱工程以外、実施例3-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光照射工程後の膜に対して、本加熱を90℃で10分間行った。
実施例3-3は、実施例3-1において本加熱の温度を100℃とした場合である。実施例3-3に係る液晶表示装置の製造方法は、本加熱工程以外、実施例3-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光照射工程後の膜に対して、本加熱を100℃で10分間行った。
実施例3-4は、実施例3-1において本加熱の温度を110℃とした場合である。実施例3-4に係る液晶表示装置の製造方法は、本加熱工程以外、実施例3-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光照射工程後の膜に対して、本加熱を110℃で10分間行った。
実施例3-5は、実施例3-1において本加熱の温度を120℃とした場合である。実施例3-5に係る液晶表示装置の製造方法は、本加熱工程以外、実施例3-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光照射工程後の膜に対して、本加熱を120℃で10分間行った。
実施例3-6は、実施例3-1において本加熱の温度を130℃とした場合である。実施例3-6に係る液晶表示装置の製造方法は、本加熱工程以外、実施例3-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光照射工程後の膜に対して、本加熱を130℃で10分間行った。
実施例3-7は、実施例3-1において本加熱の温度を140℃とした場合であり、実施例2-2と同様である。実施例3-7に係る液晶表示装置の製造方法は、実施例2-2のそれと同様であるため、重複する点については説明を省略する。
実施例3-8は、実施例3-1において本加熱の温度を150℃とした場合である。実施例3-8に係る液晶表示装置の製造方法は、本加熱工程以外、実施例3-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光照射工程後の膜に対して、本加熱を150℃で10分間行った。
実施例3-1~3-8に係る液晶表示装置の製造方法により製造された液晶表示装置について、本加熱の温度、及び、表示品位の評価結果を表2にまとめた。
実施例2-1~2-6と同様な方法で表示品位を評価し、レベル1:コントラストが1200以上、レベル2:コントラストが1000以上、1200未満、レベル3:コントラストが500以上、1000未満、レベル4:コントラストが500未満又は配向不良が視認される、の4段階で評価した。ここで、評価結果がレベル1~3である場合を製品に適したレベルであると判断し、評価結果がレベル4である場合を製品に適したレベルに達していないと判断した。
各例の表示品位の評価結果について、以下に説明する。
表示品位の評価結果はレベル3であり、良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例3-1に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル2であり、実施例3-1のそれと比べて良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例3-2に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル2であり、実施例3-1のそれと比べて良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例3-3に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル2であり、実施例3-1のそれと比べて良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例3-4に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル2であり、実施例3-1のそれと比べて良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例3-5に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル2であり、実施例3-1のそれと比べて良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例3-6に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル1であり、実施例3-1~3-6のそれと比べて非常に良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例3-7に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル1であり、実施例3-1~3-6のそれと比べて非常に良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例3-8に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
実施例4は、実施例1において負の誘電率異方性を有する液晶分子を含む液晶材を用いた場合である。実施例4に係る液晶表示装置の製造方法は、液晶分子の誘電率異方性が異なること以外、実施例1のそれと同様であるため、重複する点については説明を省略する。
比較例2は、分解型の光配向膜を用いて、光照射工程を本加熱工程の後に行った場合である。比較例2に係る液晶表示装置の製造方法について、以下に順次説明する。
固形分として、シクロブタン骨格を有するポリアミド酸高分子を用いた。溶媒として、N-メチル-ピロリドン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。ここで、比較例2で用いられた光配向膜は、中心波長254nm付近で高分子鎖の光分解を生じるものである。
2枚の基板上に、光配向膜材料による膜をスピンコート法により形成した。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を90℃で150秒間行った。予備加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。また、予備加熱工程後の光配向膜材料による膜の膜厚は、100nm程度であった。
2枚の基板上の予備加熱工程後の膜に対して、本加熱を230℃で30分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
2枚の基板上の本加熱工程後の膜に対して、偏光紫外線を照射した。偏光紫外線の照射量は、中心波長254nm付近で1J/cm2とした。
実施例4、及び、比較例2に係る液晶表示装置の製造方法により製造された液晶表示装置について、コントラスト、焼き付き特性、及び、電圧保持率を評価した。ここで、コントラストが500以上、焼き付き特性(焼き付き率)が5%以内、電圧保持率が97%以上である場合を製品に適したレベルであると判断した。なお、コントラストは実施例2-1~2-6と同様な方法で測定し、電圧保持率は実施例1と同様な方法で測定した。
実施例4、及び、比較例2におけるコントラストは、ともに1200程度で同等であり、製品に適したレベルであった。
焼き付き特性は、焼き付き率で評価した。最大輝度を示す際の電圧をVmax、最大輝度の1%を示す際の電圧を観察電圧V1とし(V1<Vmax)、まず、観察電圧V1印加時の輝度(L1)を測定した。次に、Vmaxを6時間印加し続けた後に、観察電圧V1印加時の輝度(L1’)を測定した。そして、L1に対するL1’の変化率を焼き付き率とした。輝度の測定には、キヤノン社製のデジタルカメラ(商品名:EOS Kiss Digital NEF-S18-55IIU)を用いた。
実施例4、及び、比較例2における焼き付き率は、ともに3%程度で同等であり、製品に適したレベルであった。
60℃の環境下で5Vの電圧を印加し続け、500時間後を確認したところ、実施例4、及び、比較例2における電圧保持率は、ともに98%以上で同等であり、製品に適したレベルであった。
実施例5は、2種類の高分子を含有する光配向膜材料を用いた場合である。実施例5に係る液晶表示装置の製造方法について、以下に順次説明する。
FFSモード用の電極構造を有する液晶表示装置であり、プレチルト角は0°である。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、光反応性を有するアゾベンゼン構造を含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、N-メチル-ピロリドン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。ここで、アゾベンゼン基は、光異性化が可能な光官能基である。
2枚の基板上に、光配向膜材料による膜をスピンコート法により形成した。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を70℃で150秒間行った。予備加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。また、予備加熱工程後の光配向膜材料による膜の膜厚は、100nm程度であった。
2枚の基板上の予備加熱工程後の膜に対して、偏光紫外線を照射した。偏光紫外線の照射量は、中心波長365nm付近で3J/cm2とした。
2枚の基板上の光照射工程後の膜に対して、本加熱を140℃で10分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
比較例3は、実施例5において光官能基及び側鎖を有さないポリアミック酸を含有しない光配向膜材料を用いた場合である。比較例3に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例5のそれと同様であるため、重複する点については説明を省略する。
固形分として、光反応性を有するアゾベンゼン構造を含む高分子を用いた。溶媒として、N-メチル-ピロリドン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例5、及び、比較例3に係る液晶表示装置の製造方法により製造された液晶表示装置に対して60℃の環境下で5Vの電圧を印加し続け、500時間後を確認したところ、実施例5の電圧保持率は95~97%程度であり、比較例3の90%未満と比べて高かった。電圧保持率の低下は、液晶表示装置における表示むらを引き起こすことがあるため、実施例5に係る液晶表示装置の製造方法によれば、電圧保持率を充分に向上することができ、その結果、表示品位を充分に向上することができる。
実施例6は、実施例5において負の誘電率異方性を有する液晶分子を含む液晶材を用いた場合である。実施例6に係る液晶表示装置の製造方法は、液晶分子の誘電率異方性が異なること以外、実施例5のそれと同様であるため、重複する点については説明を省略する。
比較例4は、分解型の光配向膜を用いて、光照射工程を本加熱工程の後に行った場合である。比較例4に係る液晶表示装置の製造方法について、以下に順次説明する。
固形分として、シクロブタン骨格を有するポリアミド酸高分子を用いた。溶媒として、N-メチル-ピロリドン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。ここで、比較例4で用いられた光配向膜は、中心波長254nm付近で高分子鎖の光分解を生じるものである。
2枚の基板上に、光配向膜材料による膜をスピンコート法により形成した。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を90℃で150秒間行った。予備加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。また、予備加熱工程後の光配向膜材料による膜の膜厚は、100nm程度であった。
2枚の基板上の予備加熱工程後の膜に対して、本加熱を230℃で30分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
2枚の基板上の本加熱工程後の膜に対して、偏光紫外線を照射した。偏光紫外線の照射量は、中心波長254nm付近で1J/cm2とした。
実施例6、及び、比較例4に係る液晶表示装置の製造方法により製造された液晶表示装置について、コントラスト、焼き付き特性、及び、電圧保持率を評価した。ここで、コントラストが500以上、焼き付き特性(焼き付き率)が5%以内、電圧保持率が97%以上である場合を製品に適したレベルであると判断した。なお、コントラストは実施例2-1~2-6と同様な方法で測定し、焼き付き特性は実施例4と同様な方法で評価し、電圧保持率は実施例1と同様な方法で測定した。
実施例6、及び、比較例4におけるコントラストは、ともに1200程度で同等であり、製品に適したレベルであった。
実施例6、及び、比較例4における焼き付き率は、ともに3%程度で同等であり、製品に適したレベルであった。
60℃の環境下で5Vの電圧を印加し続け、500時間後を確認したところ、実施例6、及び、比較例4における電圧保持率は、ともに98%以上で同等であり、製品に適したレベルであった。
実施例7-1は、上記工程(4)で異なる温度での2回の本加熱を行った場合である。実施例7-1に係る液晶表示装置の製造方法について、以下に順次説明する。
FFSモード用の電極構造を有する液晶表示装置であり、プレチルト角は0°である。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、光反応性を有するアゾベンゼン構造を含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、N-メチル-ピロリドン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
2枚の基板上に、光配向膜材料による膜をスピンコート法により形成した。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を60℃で150秒間行った。予備加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。また、予備加熱工程後の光配向膜材料による膜の膜厚は、100nm程度であった。
2枚の基板上の予備加熱工程後の膜に対して、偏光紫外線を照射した。偏光紫外線の照射量は、中心波長365nm付近で1J/cm2とした。
2枚の基板上の光照射工程後の膜に対して、本加熱を110℃で10分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
2枚の基板上の第1の本加熱工程後の膜に対して、本加熱を200℃で30分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
実施例7-2は、実施例7-1において予備加熱の温度を70℃とした場合である。実施例7-2に係る液晶表示装置の製造方法は、予備加熱工程以外、実施例7-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を70℃で150秒間行った。
実施例7-3は、実施例7-1において予備加熱の温度を80℃とした場合である。実施例7-3に係る液晶表示装置の製造方法は、予備加熱工程以外、実施例7-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を80℃で150秒間行った。
実施例7-4は、実施例7-1において予備加熱の温度を90℃とした場合である。実施例7-4に係る液晶表示装置の製造方法は、予備加熱工程以外、実施例7-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を90℃で150秒間行った。
実施例7-5は、実施例7-1において予備加熱の温度を100℃とした場合である。実施例7-5に係る液晶表示装置の製造方法は、予備加熱工程以外、実施例7-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を100℃で150秒間行った。
実施例7-6は、実施例7-1において予備加熱の温度を110℃とした場合である。実施例7-6に係る液晶表示装置の製造方法は、予備加熱工程以外、実施例7-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を110℃で150秒間行った。
実施例7-1~7-6に係る液晶表示装置の製造方法により製造された液晶表示装置について、予備加熱の温度、及び、表示品位の評価結果を表3にまとめた。
実施例2-1~2-6と同様な方法で表示品位を評価し、レベル1:コントラストが1200以上、レベル2:コントラストが1000以上、1200未満、レベル3:コントラストが500以上、1000未満、レベル4:コントラストが500未満又は配向不良が視認される、の4段階で評価した。ここで、評価結果がレベル1~3である場合を製品に適したレベルであると判断し、評価結果がレベル4である場合を製品に適したレベルに達していないと判断した。
各例の表示品位の評価結果について、以下に説明する。
表示品位の評価結果はレベル1であり、実施例7-3~7-6のそれと比べて非常に良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例7-1に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル1であり、実施例7-3~7-6のそれと比べて非常に良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例7-2に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル2であり、実施例7-5、及び、実施例7-6のそれと比べて良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例7-3に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル2であり、実施例7-5、及び、実施例7-6のそれと比べて良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例7-4に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル3であり、良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例7-5に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル3であり、良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例7-6に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
実施例8-1は、実施例7-1において1回目の本加熱の温度を70℃とした場合である。実施例8-1に係る液晶表示装置の製造方法は、第1の本加熱工程以外、実施例7-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光照射工程後の膜に対して、本加熱を70℃で10分間行った。
実施例8-2は、実施例8-1において1回目の本加熱の温度を80℃とした場合である。実施例8-2に係る液晶表示装置の製造方法は、第1の本加熱工程以外、実施例8-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光照射工程後の膜に対して、本加熱を80℃で10分間行った。
実施例8-3は、実施例8-1において1回目の本加熱の温度を90℃とした場合である。実施例8-3に係る液晶表示装置の製造方法は、第1の本加熱工程以外、実施例8-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光照射工程後の膜に対して、本加熱を90℃で10分間行った。
実施例8-4は、実施例8-1において1回目の本加熱の温度を100℃とした場合である。実施例8-4に係る液晶表示装置の製造方法は、第1の本加熱工程以外、実施例8-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光照射工程後の膜に対して、本加熱を100℃で10分間行った。
実施例8-5は、実施例8-1において1回目の本加熱の温度を110℃とした場合であり、実施例7-1と同様である。実施例8-5に係る液晶表示装置の製造方法は、実施例7-1のそれと同様であるため、重複する点については説明を省略する。
実施例8-6は、実施例8-1において1回目の本加熱の温度を120℃とした場合である。実施例8-6に係る液晶表示装置の製造方法は、第1の本加熱工程以外、実施例8-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光照射工程後の膜に対して、本加熱を120℃で10分間行った。
実施例8-7は、実施例8-1において1回目の本加熱の温度を130℃とした場合である。実施例8-7に係る液晶表示装置の製造方法は、第1の本加熱工程以外、実施例8-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光照射工程後の膜に対して、本加熱を130℃で10分間行った。
実施例8-8は、実施例8-1において1回目の本加熱の温度を140℃とした場合である。実施例8-8に係る液晶表示装置の製造方法は、第1の本加熱工程以外、実施例8-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光照射工程後の膜に対して、本加熱を140℃で10分間行った。
実施例8-9は、実施例8-1において1回目の本加熱の温度を150℃とした場合である。実施例8-9に係る液晶表示装置の製造方法は、第1の本加熱工程以外、実施例8-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光照射工程後の膜に対して、本加熱を150℃で10分間行った。
実施例8-10は、実施例8-1において1回目の本加熱の温度を160℃とした場合である。実施例8-10に係る液晶表示装置の製造方法は、第1の本加熱工程以外、実施例8-1のそれと同様であるため、重複する点については説明を省略する。
2枚の基板上の光照射工程後の膜に対して、本加熱を160℃で10分間行った。
実施例8-1~8-10に係る液晶表示装置の製造方法により製造された液晶表示装置について、1回目の本加熱の温度、及び、表示品位の評価結果を表4にまとめた。
実施例2-1~2-6と同様な方法で表示品位を評価し、レベル1:コントラストが1200以上、レベル2:コントラストが500以上、1200未満、レベル3:コントラストが500未満又は配向不良が視認される、の3段階で評価した。ここで、評価結果がレベル1又は2である場合を製品に適したレベルであると判断し、評価結果がレベル3である場合を製品に適したレベルに達していないと判断した。
各例の表示品位の評価結果について、以下に説明する。
表示品位の評価結果はレベル2であり、良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例8-1に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル2であり、良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例8-2に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル1であり、非常に良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例8-3に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル1であり、非常に良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例8-4に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル1であり、非常に良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例8-5に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル1であり、非常に良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例8-6に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル1であり、非常に良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例8-7に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル1であり、非常に良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例8-8に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル2であり、良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例8-9に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル2であり、良好であった。これは、自己組織化による高分子の配向秩序が充分に向上したためであると考えられる。よって、実施例8-10に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
実施例7-1~7-6、実施例8-1~8-10、及び、実施例5に係る液晶表示装置の製造方法により製造された液晶表示装置に対して60℃の環境下で5Vの電圧を印加し続け、500時間後を確認したところ、実施例7-1~7-6、及び、実施例8-1~8-10の電圧保持率は98%以上であり、実施例5の95~97%程度と比べて高かった。電圧保持率の低下は、液晶表示装置における表示むらを引き起こすことがあるため、実施例7-1~7-6、及び、実施例8-1~8-10に係る液晶表示装置の製造方法によれば、実施例5に係る液晶表示装置の製造方法と比べて、電圧保持率をより向上することができ、その結果、表示品位をより向上することができる。
実施例9-1は、上記工程(4)で異なる温度での2回の本加熱を行い、1回目の本加熱(第1の本加熱工程)と2回目の本加熱(第2の本加熱工程)との間で、更に、1回目の本加熱が行われた上記膜に対して光照射(第2の光照射工程)を行った場合である。実施例9-1に係る液晶表示装置の製造方法について、以下に順次説明する。
FFSモード用の電極構造を有する液晶表示装置であり、プレチルト角は0°である。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、N-メチル-ピロリドン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
2枚の基板上に、光配向膜材料による膜をスピンコート法により形成した。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を70℃で150秒間行った。予備加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。また、予備加熱工程後の光配向膜材料による膜の膜厚は、100nm程度であった。
2枚の基板上の予備加熱工程後の膜に対して、偏光紫外線を照射した。偏光紫外線の照射量は、中心波長313nm付近で5mJ/cm2とした。
2枚の基板上の第1の光照射工程後の膜に対して、本加熱を140℃で10分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
2枚の基板上の第1の本加熱工程後の膜に対して、紫外線を照射した。紫外線の照射量は、中心波長313nm付近で1J/cm2とした。
2枚の基板上の第2の光照射工程後の膜に対して、本加熱を180℃で5分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
実施例9-2は、実施例9-1において第2の光照射工程を行わなかった場合である。実施例9-2に係る液晶表示装置の製造方法は、第2の光照射工程が存在しないこと以外、実施例9-1のそれと同様であるため、重複する点については説明を省略する。
実施例9-1、及び、実施例9-2に係る液晶表示装置の製造方法により製造された液晶表示装置に対して60℃の環境下で5Vの電圧を印加し続け、500時間後を確認したところ、両者とも、電圧保持率は97%以上であった。また、実施例9-1、及び、実施例9-2に係る液晶表示装置の製造方法により製造された液晶表示装置について、表示品位の評価結果を表5にまとめた。
実施例2-1~2-6と同様な方法で表示品位を評価し、レベル1:コントラストが1200以上、レベル2:コントラストが1000以上、1200未満、レベル3:コントラストが500以上、1000未満、レベル4:コントラストが500未満又は配向不良が視認される、の4段階で評価した。ここで、評価結果がレベル1~3である場合を製品に適したレベルであると判断し、評価結果がレベル4である場合を製品に適したレベルに達していないと判断した。
各例の表示品位の評価結果について、以下に説明する。
表示品位の評価結果はレベル1であり、非常に良好であった。これは、自己組織化が充分に進行した後に、残存した溶媒の揮発が充分に進行し、自己組織化により向上した高分子の配向秩序が充分に固定化されたためであると考えられる。よって、実施例9-1に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベル3であり、良好であった。これは、自己組織化が充分に進行した後に、残存した溶媒の揮発が充分に進行し、自己組織化により向上した高分子の配向秩序が充分に固定化されたためであると考えられる。よって、実施例9-2に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
実施例10-1は、実施例1において、2枚の基板のうちの一方を、薄膜トランジスタ素子を備える薄膜トランジスタアレイ基板とし、他方をカラーフィルタ基板とした場合である。ここで、薄膜トランジスタ素子が有する半導体層としては、インジウム(In)、ガリウム(Ga)、亜鉛(Zn)、及び、酸素(O)から構成される酸化物半導体(In-Ga-Zn-O)を用いた。実施例10-1に係る液晶表示装置の製造方法は、液晶表示装置の構成以外、実施例1のそれと同様であるため、重複する点については説明を省略する。
FFSモード用の電極構造を有する液晶表示装置であり、プレチルト角は0°である。薄膜トランジスタ素子が有する半導体層としては、酸化物半導体(In-Ga-Zn-O)を用いた。画面サイズは10インチ(2048×1560画素)である。
実施例10-2は、実施例1において、2枚の基板のうちの一方を、薄膜トランジスタ素子を備える薄膜トランジスタアレイ基板とし、他方をカラーフィルタ基板とした場合である。ここで、薄膜トランジスタ素子が有する半導体層としては、アモルファスシリコンを用いた。実施例10-2に係る液晶表示装置の製造方法は、液晶表示装置の構成以外、実施例1のそれと同様であるため、重複する点については説明を省略する。
FFSモード用の電極構造を有する液晶表示装置であり、プレチルト角は0°である。薄膜トランジスタ素子が有する半導体層としては、アモルファスシリコンを用いた。画面サイズは10インチ(2048×1560画素)である。
実施例10-1、及び、実施例10-2に係る液晶表示装置の製造方法により製造された液晶表示装置について、焼き付き特性、及び、電圧保持率特性を、表示品位で評価した。焼き付き特性については、白(255階調)及び黒(0階調)のチェッカーパターンを表示させ、1時間後に32階調で全面点灯させた状態で焼き付きレベルを評価した。電圧保持率特性については、白及び黒のチェッカーパターンを表示させ、500時間後に32階調で全面点灯させた状態で、しみやむらのレベルを評価した。
暗室にて液晶表示装置を点灯させて、裸眼及びニュートラルデンシティ(ND)フィルター越しにて表示品位を視認評価し、レベルA:配向むらが裸眼で視認されない、レベルB:配向むらがNDフィルター50%越しで視認されない、レベルC:配向むらがNDフィルター20%越しで視認されない、レベルD:配向むらがNDフィルター20%越しで視認される、の4段階で評価した。ここで、評価結果がレベルA、B又はCである場合を製品に適したレベルであると判断し、評価結果がレベルDである場合を製品に適したレベルに達していないと判断した。
実施例10-1、及び、実施例10-2における焼き付き特性は、ともにレベルBであった。
実施例10-1、及び、実施例10-2における電圧保持率特性は、ともにレベルBであった。
実施例11-1は、光配向膜材料が含有する溶媒として、N-メチル-ピロリドン(良溶媒)、及び、ブチルセロソルブ(貧溶媒)を重量比50:50で混合したものを用いた場合であり、実施例1と同様である。実施例11-1に係る液晶表示装置の製造方法は、実施例1のそれと同様であるため、重複する点については説明を省略する。
実施例11-2は、実施例11-1において、光配向膜材料が含有する溶媒として、N-エチル-ピロリドン(良溶媒)、及び、ブチルセロソルブ(貧溶媒)を重量比50:50で混合したものを用いた場合である。実施例11-2に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例11-1のそれと同様であるため、重複する点については説明を省略する。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、N-エチル-ピロリドン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例11-3は、実施例11-1において、光配向膜材料が含有する溶媒として、γブチルラクトン(良溶媒)、及び、ブチルセロソルブ(貧溶媒)を重量比50:50で混合したものを用いた場合である。実施例11-3に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例11-1のそれと同様であるため、重複する点については説明を省略する。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、γブチルラクトン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例11-4は、実施例11-1において、光配向膜材料が含有する溶媒として、アセトン(良溶媒)、及び、ブチルセロソルブ(貧溶媒)を重量比50:50で混合したものを用いた場合である。実施例11-4に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例11-1のそれと同様であるため、重複する点については説明を省略する。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、アセトン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例11-5は、実施例11-1において、光配向膜材料が含有する溶媒として、クロロホルム(良溶媒)、及び、ブチルセロソルブ(貧溶媒)を重量比50:50で混合したものを用いた場合である。実施例11-5に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例11-1のそれと同様であるため、重複する点については説明を省略する。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、クロロホルム、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例11-6は、実施例11-1において、光配向膜材料が含有する溶媒として、シクロペンタノン(良溶媒)、及び、ブチルセロソルブ(貧溶媒)を重量比50:50で混合したものを用いた場合である。実施例11-6に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例11-1のそれと同様であるため、重複する点については説明を省略する。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、シクロペンタノン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例11-7は、実施例11-1において、光配向膜材料が含有する溶媒として、N-メチル-ピロリドン(良溶媒)、及び、ジエチレングリコールジエチルエーテル(貧溶媒)を重量比50:50で混合したものを用いた場合である。実施例11-7に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例11-1のそれと同様であるため、重複する点については説明を省略する。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、N-メチル-ピロリドン、及び、ジエチレングリコールジエチルエーテルを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例11-8は、実施例11-1において、光配向膜材料が含有する溶媒として、N-メチル-ピロリドン(良溶媒)、及び、ジイソブチルケトン(貧溶媒)を重量比50:50で混合したものを用いた場合である。実施例11-8に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例11-1のそれと同様であるため、重複する点については説明を省略する。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、N-メチル-ピロリドン、及び、ジイソブチルケトンを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例11-9は、実施例11-1において、光配向膜材料が含有する溶媒として、N-メチル-ピロリドン(良溶媒)、及び、プロピレングリコールモノブチルエーテル(貧溶媒)を重量比50:50で混合したものを用いた場合である。実施例11-9に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例11-1のそれと同様であるため、重複する点については説明を省略する。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、N-メチル-ピロリドン、及び、プロピレングリコールモノブチルエーテルを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例11-10は、実施例11-1において、光配向膜材料が含有する溶媒として、N-メチル-ピロリドン(良溶媒)、及び、ジアセトンアルコール(貧溶媒)を重量比50:50で混合したものを用いた場合である。実施例11-10に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例11-1のそれと同様であるため、重複する点については説明を省略する。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、N-メチル-ピロリドン、及び、ジアセトンアルコールを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例11-11は、実施例11-1において、光配向膜材料が含有する溶媒として、N-メチル-ピロリドン(良溶媒)、及び、ヘキサン(貧溶媒)を重量比50:50で混合したものを用いた場合である。実施例11-11に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例11-1のそれと同様であるため、重複する点については説明を省略する。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、N-メチル-ピロリドン、及び、ヘキサンを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例11-12は、実施例11-1において、光配向膜材料が含有する溶媒として、N-メチル-ピロリドン(良溶媒)、及び、メタノール(貧溶媒)を重量比50:50で混合したものを用いた場合である。実施例11-12に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例11-1のそれと同様であるため、重複する点については説明を省略する。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、N-メチル-ピロリドン、及び、メタノールを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例11-13は、実施例11-1において、光配向膜材料が含有する溶媒として、N-メチル-ピロリドン(良溶媒)、及び、イソプロピルアルコール(貧溶媒)を重量比50:50で混合したものを用いた場合である。実施例11-13に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例11-1のそれと同様であるため、重複する点については説明を省略する。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、N-メチル-ピロリドン、及び、イソプロピルアルコールを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例11-14は、実施例11-1において、光配向膜材料が含有する溶媒として、アセトン(良溶媒)、及び、ヘキサン(貧溶媒)を重量比50:50で混合したものを用いた場合である。実施例11-14に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例11-1のそれと同様であるため、重複する点については説明を省略する。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、アセトン、及び、ヘキサンを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例11-15は、実施例11-1において、光配向膜材料が含有する溶媒として、クロロホルム(良溶媒)、及び、メタノール(貧溶媒)を重量比50:50で混合したものを用いた場合である。実施例11-15に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例11-1のそれと同様であるため、重複する点については説明を省略する。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、クロロホルム、及び、メタノールを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例11-16は、実施例11-1において、光配向膜材料が含有する溶媒として、シクロペンタノン(良溶媒)、及び、イソプロピルアルコール(貧溶媒)を重量比50:50で混合したものを用いた場合である。実施例11-16に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例11-1のそれと同様であるため、重複する点については説明を省略する。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、シクロペンタノン、及び、イソプロピルアルコールを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例11-1~11-16に係る液晶表示装置の製造方法により製造された液晶表示装置について、溶媒成分(良溶媒及び貧溶媒)、及び、表示品位の評価結果を表6にまとめた。
暗室にて液晶表示装置を点灯させて、裸眼及びニュートラルデンシティ(ND)フィルター越しにて表示品位を視認評価し、レベルA:配向むらが裸眼で視認されない、レベルB:配向むらがNDフィルター50%越しで視認されない、レベルC:配向むらがNDフィルター20%越しで視認されない、レベルD:配向むらがNDフィルター20%越しで視認される、の4段階で評価した。ここで、評価結果がレベルA、B又はCである場合を製品に適したレベルであると判断し、評価結果がレベルDである場合を製品に適したレベルに達していないと判断した。
各例の表示品位の評価結果について、以下に説明する。
表示品位の評価結果はレベルAであり、非常に良好であった。これは、予備加熱工程後の状態で膜厚むらの発生を充分に防止できたためであると考えられる。よって、実施例11-1に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベルAであり、非常に良好であった。これは、予備加熱工程後の状態で膜厚むらの発生を充分に防止できたためであると考えられる。よって、実施例11-2に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベルAであり、非常に良好であった。これは、予備加熱工程後の状態で膜厚むらの発生を充分に防止できたためであると考えられる。よって、実施例11-3に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベルBであり、良好であった。これは、予備加熱工程後の状態で膜厚むらの発生を充分に防止できたためであると考えられる。よって、実施例11-4に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベルBであり、良好であった。これは、予備加熱工程後の状態で膜厚むらの発生を充分に防止できたためであると考えられる。よって、実施例11-5に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベルBであり、良好であった。これは、予備加熱工程後の状態で膜厚むらの発生を充分に防止できたためであると考えられる。よって、実施例11-6に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベルAであり、非常に良好であった。これは、予備加熱工程後の状態で膜厚むらの発生を充分に防止できたためであると考えられる。よって、実施例11-7に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベルAであり、非常に良好であった。これは、予備加熱工程後の状態で膜厚むらの発生を充分に防止できたためであると考えられる。よって、実施例11-8に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベルAであり、非常に良好であった。これは、予備加熱工程後の状態で膜厚むらの発生を充分に防止できたためであると考えられる。よって、実施例11-9に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベルAであり、非常に良好であった。これは、予備加熱工程後の状態で膜厚むらの発生を充分に防止できたためであると考えられる。よって、実施例11-10に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベルBであり、良好であった。これは、予備加熱工程後の状態で膜厚むらの発生を充分に防止できたためであると考えられる。よって、実施例11-11に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベルBであり、良好であった。これは、予備加熱工程後の状態で膜厚むらの発生を充分に防止できたためであると考えられる。よって、実施例11-12に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベルBであり、良好であった。これは、予備加熱工程後の状態で膜厚むらの発生を充分に防止できたためであると考えられる。よって、実施例11-13に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベルCであった。これは、予備加熱工程後の状態で膜厚むらの発生を充分に防止できたためであると考えられる。よって、実施例11-14に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベルCであった。これは、予備加熱工程後の状態で膜厚むらの発生を充分に防止できたためであると考えられる。よって、実施例11-15に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
表示品位の評価結果はレベルCであった。これは、予備加熱工程後の状態で膜厚むらの発生を充分に防止できたためであると考えられる。よって、実施例11-16に係る液晶表示装置の製造方法によれば、表示品位を充分に向上することができる。
比較例5は、分解型の光配向膜、及び、正の誘電率異方性を有する液晶分子を含む液晶材を用いて、光照射工程を本加熱工程の後に行った場合である。比較例5に係る液晶表示装置の製造方法について、以下に順次説明する。
FFSモード用の電極構造を有する液晶表示装置であり、プレチルト角は0°である。
固形分として、シクロブタン骨格を有するポリアミド酸高分子を用いた。溶媒として、N-メチル-ピロリドン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
2枚の基板上に、光配向膜材料による膜をスピンコート法により形成した。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を70℃で150秒間行った。予備加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。また、予備加熱工程後の光配向膜材料による膜の膜厚は、100nm程度であった。
2枚の基板上の予備加熱工程後の膜に対して、本加熱を230℃で60分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
2枚の基板上の第1の本加熱工程後の膜に対して、偏光紫外線を照射した。偏光紫外線の照射量は、220~260nmの波長範囲で1J/cm2とした。
2枚の基板上の光照射工程後の膜に対して、本加熱を230℃で30分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
比較例6は、比較例5において負の誘電率異方性を有する液晶分子を含む液晶材を用いた場合である。比較例6に係る液晶表示装置の製造方法は、液晶分子の誘電率異方性が異なること以外、比較例5のそれと同様であるため、重複する点については説明を省略する。
比較例5、及び、比較例6に係る液晶表示装置の製造方法により製造された液晶表示装置について、コントラスト、焼き付き特性、及び、電圧保持率を評価した。ここで、コントラストが500以上、焼き付き特性(焼き付き率)が5%以内、電圧保持率が97%以上である場合を製品に適したレベルであると判断した。なお、コントラストは実施例2-1~2-6と同様な方法で測定し、焼き付き特性は実施例4と同様な方法で評価し、電圧保持率は実施例1と同様な方法で測定した。
比較例5、及び、比較例6におけるコントラストは、ともに1200程度で同等であり、製品に適したレベルであった。
比較例5、及び、比較例6における焼き付き率は、ともに3%程度で同等であり、製品に適したレベルであった。
60℃の環境下で5Vの電圧を印加し続け、500時間後を確認したところ、比較例5、及び、比較例6における電圧保持率は、ともに98%以上で同等であり、製品に適したレベルであった。
比較例7は、実施例1と同じ光配向膜材料を用いて、光照射工程を本加熱工程の後に行った場合である。比較例7に係る液晶表示装置の製造方法について、以下に順次説明する。
FFSモード用の電極構造を有する液晶表示装置であり、プレチルト角は0°である。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、メタクリル骨格を有し、光反応性を有するシンナメート基を側鎖に含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、N-メチル-ピロリドン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
2枚の基板上に、光配向膜材料による膜をスピンコート法により形成した。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を70℃で150秒間行った。予備加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。また、予備加熱工程後の光配向膜材料による膜の膜厚は、100nm程度であった。
2枚の基板上の予備加熱工程後の膜に対して、本加熱を110℃で20分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
2枚の基板上の第1の本加熱工程後の膜に対して、紫外線を照射した。紫外線の照射量は、中心波長313nm付近で200mJ/cm2とした。
2枚の基板上の第1の光照射工程後の膜に対して、本加熱を200℃で30分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
2枚の基板上の第2の本加熱工程後の膜に対して、偏光紫外線を照射した。偏光紫外線の照射量は、280~330nmの波長範囲で5mJ/cm2とした。
比較例8は、実施例5と同じ光配向膜材料を用いて、光照射工程を本加熱工程の後に行った場合である。比較例8に係る液晶表示装置の製造方法について、以下に順次説明する。
FFSモード用の電極構造を有する液晶表示装置であり、プレチルト角は0°である。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、光反応性を有するアゾベンゼン構造を含む高分子であり、他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、N-メチル-ピロリドン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
2枚の基板上に、光配向膜材料による膜をスピンコート法により形成した。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を60℃で150秒間行った。予備加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。また、予備加熱工程後の光配向膜材料による膜の膜厚は、100nm程度であった。
2枚の基板上の予備加熱工程後の膜に対して、本加熱を110℃で20分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
2枚の基板上の第1の本加熱工程後の膜に対して、本加熱を200℃で30分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
2枚の基板上の第2の本加熱工程後の膜に対して、偏光紫外線を照射した。偏光紫外線の照射量は、中心波長365nm付近で3J/cm2とした。
比較例7、及び、比較例8に係る液晶表示装置の製造方法により製造された液晶表示装置について評価した結果、両者ともコントラストが50以下であり、非常に低かった。これは、本加熱工程にて高分子の熱化学反応が進行した後に光照射工程を行ったことで、高分子の配向秩序が高まらなかったためであると考えられる。よって、上述したように、高分子の配向秩序を充分に向上するためには自己組織化を進行させることが重要であり、光照射工程によって形成される異方性を、本加熱工程前にきっかけとして付与することが重要であることが分かった。
実施例12は、上記工程(4)で異なる温度での2回の本加熱を行った場合である。実施例12に係る液晶表示装置の製造方法について、以下に順次説明する。
FFSモード用の電極構造を有する液晶表示装置であり、プレチルト角は0°である。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、下記化学式(1)で表される酸無水物(TCA)、及び、光反応性を有するフェニルエステル基を含むジアミンを反応させて得られるポリアミック酸である。2種類の高分子のうちの他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、N-メチル-ピロリドン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。ここで、フェニルエステル基は、光フリース転移が可能な光官能基である。
2枚の基板上に、光配向膜材料による膜をスピンコート法により形成した。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を60℃で150秒間行った。予備加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。また、予備加熱工程後の光配向膜材料による膜の膜厚は、100nm程度であった。
2枚の基板上の予備加熱工程後の膜に対して、偏光紫外線を照射した。偏光紫外線の照射量は、中心波長254nm付近で1J/cm2とした。
2枚の基板上の光照射工程後の膜に対して、本加熱を120℃で20分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
2枚の基板上の第1の本加熱工程後の膜に対して、本加熱を220℃で30分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
比較例9は、実施例12において光官能基及び側鎖を有さないポリアミック酸を含有しない光配向膜材料を用いた場合である。比較例9に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例12のそれと同様であるため、重複する点については説明を省略する。
固形分として、上記化学式(1)で表される酸無水物(TCA)、及び、光反応性を有するフェニルエステル基を含むジアミンを反応させて得られるポリアミック酸を用いた。溶媒として、N-メチル-ピロリドン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例12に係る液晶表示装置の製造方法により製造された液晶表示装置について、コントラスト、及び、焼き付き特性を評価した。ここで、コントラストが500以上、焼き付き特性(焼き付き率)が5%以内である場合を製品に適したレベルであると判断した。なお、コントラストは実施例2-1~2-6と同様な方法で測定し、焼き付き特性は実施例4と同様な方法で評価した。
実施例12におけるコントラストは1200であり、製品に適したレベルであった。
実施例12における焼き付き率は3%であり、製品に適したレベルであった。
60℃の環境下で5Vの電圧を印加し続け、500時間後を確認したところ、実施例12の電圧保持率は97%以上であり、比較例9の95%未満と比べて高かった。電圧保持率の低下は、液晶表示装置における表示むらを引き起こすことがあるため、実施例12に係る液晶表示装置の製造方法によれば、電圧保持率を充分に向上することができ、その結果、表示品位を充分に向上することができる。
実施例13は、上記工程(4)で異なる温度での2回の本加熱を行った場合である。実施例13に係る液晶表示装置の製造方法について、以下に順次説明する。
FFSモード用の電極構造を有する液晶表示装置であり、プレチルト角は0°である。
固形分として、2種類の高分子を重量比50:50で混合したものを用いた。2種類の高分子のうちの一方は、上記化学式(1)で表される酸無水物(TCA)、及び、光反応性を有するフェニルエステル基及びシンナメート基を含むジアミンを反応させて得られるポリアミック酸である。2種類の高分子のうちの他方は、1,2,3,4-シクロブタンテトラカルボン酸二無水物(CBDA)、及び、ビフェニル構造を含むジアミンを反応させて得られる、光官能基及び側鎖を有さないポリアミック酸である。溶媒として、N-メチル-ピロリドン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。この光配向膜材料は、光二量化、光異性化、及び、光フリース転移が可能な光官能基を含むものである。
2枚の基板上に、光配向膜材料による膜をスピンコート法により形成した。
2枚の基板上の光配向膜材料による膜を形成する工程後の膜に対して、予備加熱を60℃で150秒間行った。予備加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。また、予備加熱工程後の光配向膜材料による膜の膜厚は、100nm程度であった。
2枚の基板上の予備加熱工程後の膜に対して、偏光紫外線を照射した。偏光紫外線の照射量は、中心波長313nm付近で500mJ/cm2とし、更に、中心波長254nm付近で100mJ/cm2とした。
2枚の基板上の光照射工程後の膜に対して、本加熱を120℃で20分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
2枚の基板上の第1の本加熱工程後の膜に対して、本加熱を220℃で30分間行った。本加熱は、アズワン社製のホットプレート(商品名:EC-1200N)を用いて行った。
比較例10は、実施例13において光官能基及び側鎖を有さないポリアミック酸を含有しない光配向膜材料を用いた場合である。比較例10に係る液晶表示装置の製造方法は、光配向膜材料以外、実施例13のそれと同様であるため、重複する点については説明を省略する。
固形分として、上記化学式(1)で表される酸無水物(TCA)、及び、光反応性を有するフェニルエステル基及びシンナメート基を含むジアミンを反応させて得られるポリアミック酸を用いた。溶媒として、N-メチル-ピロリドン、及び、ブチルセロソルブを重量比50:50で混合したものを用いた。また、固形分濃度は4重量%とした。
実施例13に係る液晶表示装置の製造方法により製造された液晶表示装置について、コントラスト、及び、焼き付き特性を評価した。ここで、コントラストが500以上、焼き付き特性(焼き付き率)が5%以内である場合を製品に適したレベルであると判断した。なお、コントラストは実施例2-1~2-6と同様な方法で測定し、焼き付き特性は実施例4と同様な方法で評価した。
実施例13におけるコントラストは1200であり、製品に適したレベルであった。
実施例13における焼き付き率は3%であり、製品に適したレベルであった。
60℃の環境下で5Vの電圧を印加し続け、500時間後を確認したところ、実施例13の電圧保持率は97%以上であり、比較例10の95%未満と比べて高かった。電圧保持率の低下は、液晶表示装置における表示むらを引き起こすことがあるため、実施例13に係る液晶表示装置の製造方法によれば、電圧保持率を充分に向上することができ、その結果、表示品位を充分に向上することができる。
比較例2、4等の分解型の光配向膜を用いる場合であっても、上述した他の実施例と同様に、光照射工程を本加熱工程の前に行って自己組織化を進行させる場合は、偏光紫外線の照射量を大幅に下げられる可能性があり、上述した微小な輝点の発生や、電気特性の低下を防止できる可能性がある。
以下に、上記本発明の一態様に係る液晶表示装置の製造方法における好ましい態様の例を挙げる。各例は、本発明の要旨を逸脱しない範囲において適宜組み合わされてもよい。
Claims (15)
- 光配向膜を備える液晶表示装置の製造方法であって、
前記液晶表示装置の製造方法は、
光二量化、光異性化、及び、光フリース転移からなる群より選択される少なくとも1つの化学反応が可能な光官能基を有する高分子と、ポリアミック酸骨格を有し、前記光官能基を有さない高分子と、溶媒とを含有する光配向膜材料による膜を基板上に形成する工程(1)、
前記膜に対して前記溶媒を蒸発させる予備加熱を行う工程(2)、
予備加熱された前記膜に対して偏光照射を行う工程(3)、及び、
偏光照射された前記膜に対して本加熱を行う工程(4)
を順に含み、
前記液晶表示装置は、プレチルト角が実質的に0°であるイン・プレーン・スイッチングモード又はフリンジ・フィールド・スイッチングモードであることを特徴とする液晶表示装置の製造方法。 - 前記工程(4)の本加熱は、90℃以上の温度で行われることを特徴とする請求項1に記載の液晶表示装置の製造方法。
- 前記工程(2)の予備加熱は、90℃以下の温度で行われることを特徴とする請求項1に記載の液晶表示装置の製造方法。
- 前記液晶表示装置は、前記光配向膜により負の誘電率異方性を有する液晶分子を配向させることを特徴とする請求項1~3のいずれかに記載の液晶表示装置の製造方法。
- 前記工程(4)の本加熱は、低温から高温へ異なる温度の定温期間を複数有するように行う操作を含むことを特徴とする請求項1~4のいずれかに記載の液晶表示装置の製造方法。
- 前記工程(4)の本加熱は、異なる温度での2回の本加熱を行い、1回目の本加熱は90℃以上、140℃以下の温度で行われ、2回目の本加熱は180℃以上の温度で行われることを特徴とする請求項5に記載の液晶表示装置の製造方法。
- 前記工程(4)の本加熱は、異なる温度に設定された複数の加熱装置を用いて行われることを特徴とする請求項1~6のいずれかに記載の液晶表示装置の製造方法。
- 前記工程(4)の本加熱は、1台の加熱装置を用いて異なる温度に順次変化させながら行われることを特徴とする請求項1~6のいずれかに記載の液晶表示装置の製造方法。
- 前記工程(4)の本加熱は、温度勾配のある領域を有する加熱装置を用いて前記加熱装置内で前記基板を移動させながら行われることを特徴とする請求項1~6のいずれかに記載の液晶表示装置の製造方法。
- 前記光官能基は、シンナメート基、カルコン基、クマリン基、スチルベン基、フェニルエステル基、及び、アゾベンゼン基からなる群より選択される少なくとも1つの官能基であることを特徴とする請求項1~9のいずれかに記載の液晶表示装置の製造方法。
- 前記光官能基を有する高分子の骨格は、ポリアミック酸、ポリイミド、アクリル、メタクリル、マレイミド、及び、ポリシロキサンからなる群より選択される少なくとも1つの構造を有することを特徴とする請求項1~10のいずれかに記載の液晶表示装置の製造方法。
- 前記光官能基は、少なくとも光二量化が可能であり、
前記工程(4)は、異なる温度での2回の本加熱を行い、1回目の本加熱と2回目の本加熱との間に、更に、1回目の本加熱が行われた前記膜に対して光照射を行う工程(4a)を含むことを特徴とする請求項1~11のいずれかに記載の液晶表示装置の製造方法。 - 前記光配向膜材料に含有される高分子材料は、主鎖又は側鎖にカルボキシル基及び/又はアミド基を有することを特徴とする請求項1~13のいずれかに記載の液晶表示装置の製造方法。
- 前記溶媒は、N-メチル-ピロリドン、N-エチル-ピロリドン、及び、γブチルラクトンからなる群より選択される少なくとも1つの化合物と、ブチルセロソルブ、ジエチレングリコールジエチルエーテル、ジイソブチルケトン及びその構造異性体、プロピレングリコールモノブチルエーテル、並びに、ジアセトンアルコールからなる群より選択される少なくとも1つの化合物との混合物であることを特徴とする請求項1~14のいずれかに記載の液晶表示装置の製造方法。
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JP7234673B2 (ja) | 2019-02-08 | 2023-03-08 | Jnc株式会社 | 光配向用液晶配向剤、液晶配向膜およびこれを用いた液晶表示素子、並びに、ジアミン、(メタ)アクリレート、およびポリマー |
KR20200102195A (ko) * | 2019-02-21 | 2020-08-31 | 주식회사 엘지화학 | 액정 배향제 조성물, 이를 이용한 액정 배향막의 제조 방법, 이를 이용한 액정 배향막 및 액정표시소자 |
JP2021521487A (ja) * | 2019-02-21 | 2021-08-26 | エルジー・ケム・リミテッド | 液晶配向剤組成物、これを用いた液晶配向膜の製造方法、これを用いた液晶配向膜および液晶表示素子 |
US11332672B2 (en) | 2019-02-21 | 2022-05-17 | Lg Chem, Ltd. | Liquid crystal alignment agent composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film, liquid crystal display using the same |
JP7092442B2 (ja) | 2019-02-21 | 2022-06-28 | エルジー・ケム・リミテッド | 液晶配向剤組成物、これを用いた液晶配向膜の製造方法、これを用いた液晶配向膜および液晶表示素子 |
KR102461121B1 (ko) | 2019-02-21 | 2022-10-28 | 주식회사 엘지화학 | 액정 배향제 조성물, 이를 이용한 액정 배향막의 제조 방법, 이를 이용한 액정 배향막 및 액정표시소자 |
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JPWO2015016121A1 (ja) | 2017-03-02 |
CN105452948A (zh) | 2016-03-30 |
CN105452948B (zh) | 2018-11-13 |
US9977290B2 (en) | 2018-05-22 |
JP5997385B2 (ja) | 2016-09-28 |
US20160178968A1 (en) | 2016-06-23 |
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