WO2018110354A1 - 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子 - Google Patents
液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子 Download PDFInfo
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- WO2018110354A1 WO2018110354A1 PCT/JP2017/043515 JP2017043515W WO2018110354A1 WO 2018110354 A1 WO2018110354 A1 WO 2018110354A1 JP 2017043515 W JP2017043515 W JP 2017043515W WO 2018110354 A1 WO2018110354 A1 WO 2018110354A1
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- liquid crystal
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- aligning agent
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- 0 */C1=C\C=C\C(\N(*)c(cc2)cc3c2[n](*)c2ccccc32)=C/C=C1 Chemical compound */C1=C\C=C\C(\N(*)c(cc2)cc3c2[n](*)c2ccccc32)=C/C=C1 0.000 description 4
- BUKAUZSZPXOJQU-UHFFFAOYSA-O CC(C(C(c(c1c(C)cc2)c2[OH2+])=O)=C(C(O)=C)C1=O)=C Chemical compound CC(C(C(c(c1c(C)cc2)c2[OH2+])=O)=C(C(O)=C)C1=O)=C BUKAUZSZPXOJQU-UHFFFAOYSA-O 0.000 description 1
- LLGVAYCUTPGFLM-UHFFFAOYSA-N CC1C=C(CNC(O)OC(C)(C)C)C(C)=CC1 Chemical compound CC1C=C(CNC(O)OC(C)(C)C)C(C)=CC1 LLGVAYCUTPGFLM-UHFFFAOYSA-N 0.000 description 1
- YXBIAYXZUDJVEB-UHFFFAOYSA-N Cc(c(C)c1)ccc1-c1cc(C)c(C)cc1 Chemical compound Cc(c(C)c1)ccc1-c1cc(C)c(C)cc1 YXBIAYXZUDJVEB-UHFFFAOYSA-N 0.000 description 1
- GLFKFHJEFMLTOB-UHFFFAOYSA-N Cc1c(C)cc(C(C(F)(F)F)(C(F)(F)F)c2cc(C)c(C)cc2)cc1 Chemical compound Cc1c(C)cc(C(C(F)(F)F)(C(F)(F)F)c2cc(C)c(C)cc2)cc1 GLFKFHJEFMLTOB-UHFFFAOYSA-N 0.000 description 1
- KTLQPZLKEPQFBT-UHFFFAOYSA-N Cc1ccc(C)c(CCCNC(O)=O)c1 Chemical compound Cc1ccc(C)c(CCCNC(O)=O)c1 KTLQPZLKEPQFBT-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
Definitions
- the present invention relates to a liquid crystal aligning agent using a novel polymer, a liquid crystal aligning film, and a liquid crystal display element using the same.
- Liquid crystal display elements are widely used as display units for personal computers, mobile phones, smartphones, televisions and the like.
- the liquid crystal display element includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode that apply an electric field to the liquid crystal layer, an alignment film that controls the alignment of liquid crystal molecules in the liquid crystal layer, A thin film transistor (TFT) for switching an electric signal supplied to the pixel electrode is provided.
- TFT thin film transistor
- As a driving method of liquid crystal molecules a vertical electric field method such as a TN method and a VA method, and a horizontal electric field method such as an IPS method and an FFS method are known.
- the horizontal electric field method in which an electrode is formed only on one side of the substrate and an electric field is applied in a direction parallel to the substrate is wider than the vertical electric field method in which voltage is applied to the electrodes formed on the upper and lower substrates to drive the liquid crystal. It is known as a liquid crystal display element having viewing angle characteristics and capable of high-quality display.
- the horizontal electric field type liquid crystal cell is excellent in viewing angle characteristics, since there are few electrode portions formed in the substrate, if the voltage holding ratio is low, a sufficient voltage is not applied to the liquid crystal and the display contrast is lowered. Further, if the stability of the liquid crystal alignment is small, the liquid crystal does not return to the initial state when the liquid crystal is driven for a long time, which causes a decrease in contrast and an afterimage. Therefore, the stability of the liquid crystal alignment is important. Furthermore, static electricity is likely to be accumulated in the liquid crystal cell, and charges are accumulated in the liquid crystal cell even when a positive / negative asymmetric voltage generated by driving is applied, and these accumulated charges affect the display as a disorder of liquid crystal alignment or an afterimage. The display quality of the liquid crystal element is significantly reduced. In addition, charges are accumulated by irradiating the liquid crystal cell with backlight light immediately after driving, and afterimages are generated even during short-time driving, and the size of flicker (flicker) changes during driving. It will occur.
- Patent Document 1 discloses that a specific diamine and an aliphatic tetracarboxylic acid derivative are combined.
- a liquid crystal aligning agent containing a polymer obtained by condensation is disclosed.
- the present invention provides a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element that can obtain a liquid crystal aligning film that has an excellent voltage holding ratio, quickly reduces accumulated charges, and is less likely to flicker during driving. This is the issue.
- the present inventors have found that various properties can be improved simultaneously by introducing a specific structure into the polymer contained in the liquid crystal aligning agent. Completed the invention.
- the present invention is based on this finding and has the following gist.
- the liquid crystal aligning agent characterized by including the polymer obtained from the diamine which has a structure represented by following formula (1), and an organic solvent.
- R 1 represents hydrogen or a monovalent organic group
- R 2 represents a monovalent organic group
- * represents a site bonded to another group. Any hydrogen atom in the benzene ring may be substituted with a monovalent organic group.
- the liquid crystal aligning agent of this invention is a liquid crystal aligning agent containing the novel polymer obtained from the diamine (henceforth a specific diamine) which has a structure of following formula (1).
- R 1 and R 2 are as defined above.
- the monovalent organic group is preferably an alkyl group, alkenyl group, alkoxy group, fluoroalkyl group, fluoroalkenyl group or fluoroalkoxy group having 1 to 3 carbon atoms.
- R 1 is preferably a hydrogen atom or a methyl group
- R 2 is preferably a methyl group.
- the bonding position between the carbazole structure and the nitrogen atom in Formula (1) is preferably bonded as in Formula (1-1) from the viewpoint of steric hindrance.
- the specific diamine can be represented by, for example, the following formula (1-2), particularly preferably a diamine represented by the following formula (1-3), and further represented by the formula (1-4). Diamine is more preferred.
- R 1 and R 2 are the same as those in the case of the formula (1), and Q 1 and Q 2 are each independently a single bond or a divalent organic group, that is, Q 1 and Q 2 may have different structures. Further, the two Q 2 in the formula (1-4) may have different structures. Furthermore, any hydrogen atom of the benzene ring may be substituted with a monovalent organic group as in the case of the above formula (1).
- R 1 and R 2 are the same as those in the above formula (1)
- R 3 each independently represents a single bond or the structure of the following formula (3)
- n is 1 to 3 Represents an integer. Any hydrogen atom in the benzene ring may be substituted with a monovalent organic group.
- R 4 represents a single bond, —O—, —COO—, —OCO—, — (CH 2 ) 1 —, —O (CH 2 ) m O—, —CONR—, and —NRCO—.
- Such a monovalent organic group is preferably an alkyl group having 1 to 3 carbon atoms.
- * 1 represents a site that binds to the benzene ring in formulas (2-1) to (2-3), and * 2 binds to an amino group in formulas (2-1) to (2-3) Represents a site.
- the method for synthesizing the specific diamine of the present invention is not particularly limited.
- a dinitro compound (2-1-N) which is a precursor of the diamine of the above formula (2-1-1) is synthesized, and the nitro group is synthesized.
- the method of reducing is mentioned.
- the catalyst used in the reduction reaction is preferably an activated carbon-supported metal available as a commercial product, and examples thereof include palladium-activated carbon, platinum-activated carbon, rhodium-activated carbon and the like. Further, palladium catalyst, platinum oxide, Raney nickel or the like may not necessarily be an activated carbon supported metal catalyst. Palladium-activated carbon, which is generally widely used, is preferred because good results are obtained.
- the reaction may be carried out in the presence of activated carbon.
- the amount of the activated carbon to be used is not particularly limited, but is preferably in the range of 1 to 30% by mass, more preferably 10 to 20% by mass with respect to the dinitro compound X1.
- the reaction may be carried out under pressure. In this case, in order to avoid reduction of benzene nuclei, it is carried out in a pressure range up to 20 atm. The reaction is preferably carried out in the range up to 10 atm.
- a solvent does not react with each raw material, it can be used without a restriction
- aprotic polar organic solvents dimethylformamide (DMF), dimethylsulfoxide (DMSO), dimethyl acetate (DMAc), N-methylpyrrolidone (NMP), etc.
- ethers diethyl ether (Et 2 O), diisopropyl, etc.
- solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used singly or in combination of two or more. If necessary, the solvent can be dried using a suitable dehydrating agent or desiccant and used as a non-aqueous solvent.
- the amount of the solvent used is not particularly limited, but is usually 0.1 to 10 times, preferably 0.5 to 30 times, more preferably 1 to 10 times the dinitro compound. Is double.
- the reaction temperature is not particularly limited, but is usually in the range from ⁇ 100 ° C. to the boiling point of the solvent used, and preferably ⁇ 50 to 150 ° C.
- the reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.
- the dinitro compound (2-1-N) can be easily synthesized by a known reaction using diiodocarbazole and the corresponding nitrobenzene derivative.
- the polymer contained in the liquid crystal aligning agent of this invention is a polymer obtained using the said specific diamine.
- Specific examples include polyamic acid, polyamic acid ester, polyimide, polyurea, polyamide and the like.
- a polyimide precursor having a structural unit represented by the following formula (4), And / or at least one polymer selected from polyimide which is an imidized product thereof (hereinafter also referred to as a specific polymer) is more preferable.
- X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative
- Y 1 is a divalent organic group derived from a specific diamine.
- R 5 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- R 5 is preferably a hydrogen atom, a methyl group or an ethyl group from the viewpoint of easy imidization by heating.
- Said X 1 is coatability solubility and liquid crystal alignment agent in the solvent of the polymer liquid crystal orientation in the case where the liquid crystal alignment film, the voltage holding ratio, such stored charge, depending on the degree of the properties required May be appropriately selected, and two or more kinds may be included in the same polymer.
- Specific examples of X 1 include the structures of formulas (X-1) to (X-46) and the like, which are described on pages 13 to 14 of International Publication No. 2015/119168.
- (A-1) and (A-2) are particularly preferable from the viewpoint of further improving the rubbing resistance, and (A-4) is particularly preferable from the viewpoint of further improving the relaxation rate of the accumulated charge.
- (A-15) to (A-17) are particularly preferred from the viewpoint of further improving the liquid crystal orientation and the rate of relaxation of the accumulated charges.
- the polyimide precursor may have a structural unit represented by the following formula (5) in addition to the structural unit represented by the formula (4).
- X 2 is the same as the definition of X 1 in the formula (4). Specific examples of X 2 include the same examples as exemplified for X 1 in formula (4), including preferred examples.
- R 6 has the same definition as R 5 in the formula (4).
- R 7 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Moreover, it is preferable that at least one of two R ⁇ 7 > is a hydrogen atom.
- Y 2 is a divalent organic group derived from a diamine that does not include the structure of formula (1) in the main chain direction, and the structure is not particularly limited.
- Y 2 is appropriately selected according to the degree of required properties such as the solubility of the polymer in the solvent, the coating property of the liquid crystal aligning agent, the orientation of the liquid crystal when the liquid crystal alignment film is used, the voltage holding ratio, and the accumulated charge. Two or more types may be mixed in the same polymer.
- (B-28), (B-29) and the like are particularly preferable from the viewpoint of further improving the rubbing resistance, and (B-1) to (B-3) and the like are liquid crystal alignment properties.
- (B-14) to (B-18), (B-27) and the like are particularly preferable from the viewpoint of further improving the relaxation rate of the accumulated charge, and (B-26) and the like. Is preferable from the viewpoint of further improving the voltage holding ratio.
- the structural unit represented by the formula (4) is represented by the formula (4).
- 10 mol% or more with respect to the total of the formula (5) more preferably 20 mol% or more, and particularly preferably 30 mol% or more.
- the molecular weight of the polyimide precursor used in the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100 in terms of weight average molecular weight (Mw). , 000.
- the polyimide of the specific polymer is obtained by ring-closing the polyimide precursor represented by formula (4) or formula (5).
- the imidation ratio is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.
- a known method can be used as a method for imidizing the polyimide precursor.
- Chemical imidization in which a basic catalyst is added to the polyimide precursor solution is simple. Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer does not easily decrease during the imidization process.
- Chemical imidization can be performed by stirring the polyimide precursor in the presence of a basic catalyst in an organic solvent.
- the solvent used at the time of the polymerization reaction mentioned above can be used.
- the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, triethylamine is preferred because it has sufficient basicity to allow the reaction to proceed.
- the temperature for carrying out the imidization reaction is ⁇ 20 to 140 ° C., preferably 0 to 100 ° C., and the reaction time can be preferably 1 to 100 hours.
- the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amic acid ester group.
- the imidation rate of the obtained polymer can be controlled by adjusting the amount of catalyst, temperature, reaction time and the like. Since the added catalyst or the like remains in the solution after the imidation reaction, the obtained imidized polymer is recovered by the means described below, redissolved in an organic solvent, and the liquid crystal alignment according to the present invention. It is preferable to use an agent.
- the obtained imidized polymer is recovered by the means described below, and redissolved in an organic solvent. It is preferable to use the liquid crystal aligning agent of the invention.
- the polyimide solution obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, washed with a poor solvent, and then dried at room temperature or by heating to obtain a purified polyimide powder.
- liquid crystal aligning agent of this invention contains a specific polymer, in the limit which has an effect as described in this invention, you may contain 2 or more types of specific polymers of a different structure. In addition to the specific polymer, other polymers may be contained. Other polymer types include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or derivatives thereof, poly (styrene-phenylmaleimide) derivative, poly (meta ) Acrylate and the like. Moreover, the polyimide etc. which are chosen from the polyimide precursor represented by the said Formula (5) and / or the polyimide which imidated this polyimide precursor may be contained.
- the ratio of the specific polymer to the total polymer components is preferably 5% by mass or more, more preferably 5 to 95% by mass.
- the liquid crystal aligning agent is used for producing a liquid crystal aligning film, and generally takes the form of a coating liquid from the viewpoint of forming a uniform thin film. Also in the liquid crystal aligning agent of this invention, it is preferable that it is a coating liquid containing an above-described polymer component and the organic solvent in which this polymer component is dissolved. At that time, the concentration of the polymer in the liquid crystal aligning agent can be appropriately changed by setting the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, the content is preferably 1% by mass or more, and from the viewpoint of storage stability of the solution, it is preferably 10% by mass or less. A particularly preferred polymer concentration is 2 to 8% by mass.
- the organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as the polymer component is uniformly dissolved.
- Specific examples are N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, ⁇ -butyrolactone, 1,3-dimethyl.
- -Imidazolidinone methyl ethyl ketone, cyclohexanone, cyclopentanone and the like.
- N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or ⁇ -butyrolactone is preferably used.
- the organic solvent contained in the liquid crystal aligning agent uses a mixed solvent that is used in combination with a solvent that improves the coating properties and the surface smoothness of the coating film when the liquid crystal aligning agent is applied in addition to the above-described solvents.
- a mixed solvent is also preferably used in the liquid crystal aligning agent of the present invention. Specific examples of the organic solvent to be used in combination are listed below, but are not limited to these examples.
- ethanol isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Ethane All, 1,2-propanediol, 1,3-propan
- D 1 represents an alkyl group having 1 to 3 carbon atoms
- D 2 represents an alkyl group having 1 to 3 carbon atoms
- D 3 represents an alkyl group having 1 to 4 carbon atoms.
- 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether or Dipropylene glycol dimethyl ether is preferred.
- the kind and content of such a solvent are appropriately selected according to the application device, application conditions, application environment, and the like of the liquid crystal aligning agent.
- the liquid crystal aligning agent of the present invention may additionally contain components other than the polymer component and the organic solvent.
- additional components include an adhesion aid for increasing the adhesion between the liquid crystal alignment film and the substrate and the adhesion between the liquid crystal alignment film and the sealing material, a crosslinking agent for increasing the strength of the liquid crystal alignment film, and the liquid crystal alignment.
- additional components include dielectrics and conductive materials for adjusting the dielectric constant and electric resistance of the film. Specific examples of these additional components are as disclosed in various known literatures relating to liquid crystal alignment agents. For example, International Publication No. 2015/060357, pages 53 [0105] to 55 [ [0116] and the like.
- the liquid crystal aligning film of the present invention is obtained from the liquid crystal aligning agent of the present invention. If an example of the method of obtaining a liquid crystal aligning film from a liquid crystal aligning agent is given, a liquid crystal aligning agent in the form of a coating solution is applied to a substrate, dried and baked on a film obtained by rubbing or photo-aligning. And a method of performing an alignment treatment.
- the substrate on which the liquid crystal aligning agent is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can also be used.
- a substrate on which an ITO electrode or the like for driving the liquid crystal is used from the viewpoint of simplification of the process.
- an opaque object such as a silicon wafer can be used as long as only one substrate is used, and a material that reflects light such as aluminum can be used for the electrode in this case.
- the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, screen printing, offset printing, flexographic printing, inkjet method, and the like are common. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spray method, and these may be used depending on the purpose.
- the solvent is evaporated and baked by a heating means such as a hot plate, a thermal circulation oven, an IR (infrared) oven, or the like.
- a heating means such as a hot plate, a thermal circulation oven, an IR (infrared) oven, or the like.
- Arbitrary temperature and time can be selected for the drying and baking steps after applying the liquid crystal aligning agent.
- the thickness of the liquid crystal alignment film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be lowered, so that it is preferably 5 to 300 nm, more preferably 10 to 200 nm.
- the liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film of a horizontal electric field type liquid crystal display element such as an IPS mode or an FFS mode, and is particularly useful as a liquid crystal alignment film of an FFS mode liquid crystal display element.
- the liquid crystal display device of the present invention is a device in which a liquid crystal cell is prepared by a known method after obtaining a substrate with a liquid crystal alignment film obtained from the liquid crystal aligning agent, and the liquid crystal cell is used as an element.
- a liquid crystal display element having a passive matrix structure will be described as an example.
- an active matrix structure liquid crystal display element in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion constituting the image display may be used.
- a transparent glass substrate is prepared, a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate.
- These electrodes can be ITO electrodes, for example, and are patterned so as to display a desired image.
- an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode.
- the insulating film can be, for example, a film made of SiO 2 —TiO 2 formed by a sol-gel method.
- a liquid crystal alignment film is formed on each substrate under the above conditions.
- an ultraviolet curable sealing material is disposed at a predetermined position on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystals are disposed at predetermined positions on the liquid crystal alignment film surface.
- the other substrate is bonded and pressure-bonded so that the liquid crystal alignment film faces, and the liquid crystal is spread on the front surface of the liquid crystal alignment film, and then the entire surface of the substrate is irradiated with ultraviolet rays to cure the sealing material. Get a cell.
- an opening that can be filled with liquid crystal from the outside is provided when a sealing material is disposed at a predetermined location on one substrate.
- a liquid crystal material is injected into the liquid crystal cell through an opening provided in the sealing material, and then the opening is sealed with an adhesive to obtain a liquid crystal cell.
- the liquid crystal material may be injected by a vacuum injection method or a method utilizing capillary action in the atmosphere.
- liquid crystal material examples include a nematic liquid crystal and a smectic liquid crystal.
- a nematic liquid crystal is preferable, and either a positive liquid crystal material or a negative liquid crystal material may be used.
- a polarizing plate is installed. Specifically, it is preferable to attach a pair of polarizing plates to the surfaces of the two substrates opposite to the liquid crystal layer.
- the liquid crystal alignment film and the liquid crystal display element of the present invention are not limited to the above description as long as the liquid crystal aligning agent of the present invention is used, and may be manufactured by other known methods. good.
- the process from the liquid crystal aligning agent to obtaining the liquid crystal display element is disclosed in, for example, paragraph 17 of page 17 to paragraph 0081 of page 19 of Japanese Unexamined Patent Publication No. 2015-135393.
- NMP N-methyl-2-pyrrolidone
- NEP N-ethyl-2-pyrrolidone
- GBL ⁇ -butyrolactone
- BCS butyl cellosolve
- PB propylene glycol monobutyl ether
- DME dipropylene glycol dimethyl ether
- DAA 4-hydroxy-4-methyl- 2-pentanone
- DEDG diethylene glycol diethyl ether
- DIBK 2,6-dimethyl-4-heptanone
- DIPE diisopropyl ether
- DIBC 2,6-dimethyl-4-heptanol
- Pd / C palladium carbon
- DMSO dimethyl sulfoxide
- THF Tetrahydrofuran
- Boc represents a group represented by the following.
- the imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid that appear in the vicinity of 9.5 ppm to 10.0 ppm. It calculated
- Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
- x is the accumulated proton peak value derived from NH group of amic acid
- y is the accumulated peak value of reference proton
- ⁇ is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.
- the viscosity of the polyamic acid solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), with a sample amount of 1.1 mL and cone rotor TE-1 (1 ° 34 ′, R24 ) At a temperature of 25 ° C.
- GPC apparatus manufactured by Shodex (GPC-101), column: manufactured by Shodex (KD803, series of KD805), column temperature: 50 ° C.
- eluent N, N-dimethylformamide (as an additive, lithium bromide-water) 30 mmol / L (liter) of Japanese product (LiBr ⁇ H 2 O), 30 mmol / L of phosphoric acid / anhydrous crystals (o-phosphoric acid), 10 ml / L of tetrahydrofuran (THF), flow rate: 1.0 ml / min.
- Standard sample for preparing calibration curve TSK standard polyethylene oxide (weight average molecular weight (Mw); about 900,000, 150,000, 100,000 and 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (peak top) manufactured by Polymer Laboratories Molecular weight (Mp); about 12,000, 4,000 and 1,000).
- Mw weight average molecular weight
- Mp polyethylene glycol
- a glass substrate with an electrode having a size of 30 mm length ⁇ 35 mm width and a thickness of 0.7 mm was prepared.
- an IZO electrode having a solid pattern constituting a counter electrode as a first layer is formed on the substrate.
- a SiN (silicon nitride) film formed by the CVD method is formed as the second layer.
- the second layer SiN film has a thickness of 500 nm and functions as an interlayer insulating film.
- a comb-like pixel electrode formed by patterning an IZO film as the third layer is arranged to form two pixels, a first pixel and a second pixel. ing.
- the size of each pixel is 10 mm long and about 5 mm wide.
- the first-layer counter electrode and the third-layer pixel electrode are electrically insulated by the action of the second-layer SiN film.
- the pixel electrode of the third layer has a comb-like shape configured by arranging a plurality of “U” -shaped electrode elements having a bent central portion (FIG. 3 of Japanese Patent Application Laid-Open No. 2014-77845). reference).
- the width in the short direction of each electrode element is 3 ⁇ m, and the distance between the electrode elements is 6 ⁇ m.
- the pixel electrode forming each pixel is formed by arranging a plurality of bent “bow” -shaped electrode elements at the center, so the shape of each pixel is not rectangular but is the same as that of the electrode element. It has a shape that resembles a bold “Kugi” that bends in part.
- Each pixel is divided into upper and lower portions with a central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side.
- the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 10 ° (clockwise) in the first region of the pixel, and the pixel in the second region of the pixel.
- the electrode elements of the electrode are formed so as to form an angle of ⁇ 10 ° (clockwise).
- the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode in the substrate surface are mutually It is comprised so that it may become a reverse direction.
- the polyimide film surface is rubbed with a rayon cloth under the conditions of a roll diameter of 120 mm, a roller rotation speed of 500 rpm, a stage moving speed of 30 mm / sec, and a rubbing cloth indentation pressure of 0.3 mm, and then in pure water for 1 minute. Ultrasonic irradiation was performed, and drying was performed at 80 ° C. for 10 minutes.
- liquid crystal alignment film Using the two types of substrates with the above-mentioned liquid crystal alignment film, the rubbing directions were combined to be antiparallel, the periphery was sealed leaving the liquid crystal injection port, and an empty cell with a cell gap of 3.8 ⁇ m was produced. .
- Liquid crystals (MLC-3019, manufactured by Merck & Co., Inc.) were vacuum-injected into this empty cell at room temperature, and the injection port was sealed to obtain an anti-parallel alignment liquid crystal cell.
- the obtained liquid crystal cell constitutes an FFS mode liquid crystal display element. Thereafter, the liquid crystal cell was heated at 120 ° C. for 1 hour and allowed to stand overnight before being used for evaluation.
- a DC voltage of 1 V was applied at the same time while driving the liquid crystal cell by applying an AC voltage of 30 Hz with a relative transmittance of 23%, and the liquid crystal cell was driven for 30 minutes. Thereafter, the applied DC voltage value was set to 0 V, and only the application of the DC voltage was stopped, and the driving was continued for 15 minutes in that state.
- the time during which the relative transmittance decreased to 30% or less by the time 30 minutes elapsed from the start of application of the DC voltage was quantified.
- the relative transmittance dropped to 30% or less within 5 minutes it was evaluated as “ ⁇ ”, and when within 6 to 30 minutes, it was evaluated as “ ⁇ ”.
- the afterimage was not erased and was evaluated as “x”.
- the afterimage evaluation according to the method mentioned above was performed on the temperature conditions of the state whose temperature of a liquid crystal cell is 23 degreeC.
- the liquid crystal cell produced above is placed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, and the LED backlight is turned on with no voltage applied, so that the brightness of transmitted light is minimized. Further, the arrangement angle of the liquid crystal cell was adjusted. Next, a VT curve (voltage-transmittance curve) was measured while applying an AC voltage with a frequency of 30 Hz to the liquid crystal cell, and an AC voltage with a relative transmittance of 23% was calculated as a drive voltage.
- VT curve voltage-transmittance curve
- the LED backlight that was turned on is temporarily turned off and left to block light for 72 hours, and then the LED backlight is turned on again.
- the frequency at which the relative transmittance becomes 23% at the same time when the backlight turns on is 30 Hz.
- the AC voltage was applied and the liquid crystal cell was driven for 60 minutes to track the flicker amplitude.
- the flicker amplitude is a data collection / data logger switch unit 34970A (Agilent technologies) that connects the transmitted light of the LED backlight that has passed through the two polarizing plates and the liquid crystal cell therebetween, via a photodiode and an IV conversion amplifier. ).
- z is a value obtained by reading the luminance when driven by an AC voltage with a frequency of 30 Hz with a relative transmittance of 23% by the data collection / data logger switch unit 34970A.
- the evaluation of the flicker level is defined as “ ⁇ ” when the flicker level is maintained at less than 3% by 60 minutes after the start of the LED backlight lighting and the application of the AC voltage. went. When the flicker level reached 3% or more in 60 minutes, the evaluation was defined as “x”. Evaluation of the flicker level according to the above-described method was performed under temperature conditions where the temperature of the liquid crystal cell was 23 ° C.
- the liquid crystal display elements using the liquid crystal aligning agents of Examples 1 to 3 and 5 have a fast relaxation of accumulated charges and are less likely to cause a flicker shift that occurs immediately after the start of driving. I understand.
- the substrate was baked at 230 ° C. for 20 minutes to obtain a substrate with a liquid crystal alignment film.
- the two substrates are combined as a set, a sealant is printed on the substrate, and the other substrate is bonded so that the liquid crystal alignment film faces and the alignment direction is 0 °, and then the sealant is added.
- An empty cell was produced by curing. Liquid crystal (MLC-3019, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell by vacuum injection at normal temperature, and the inlet was sealed to obtain an FFS drive liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 120 ° C. for 1 hour and allowed to stand overnight before being used for each evaluation.
- Table 9 shows the results of the evaluation of the afterimage erasing time and the evaluation of the flicker level immediately after the driving performed for the liquid crystal display elements using the liquid crystal aligning agents obtained in Examples 3, 4, 13 and Comparative Example 6. Shown in In Table 9, * 1 indicates the content (parts by mass) of each polymer with respect to 100 parts by mass of all polymers.
- the liquid crystal aligning agent of the present invention is widely used for a liquid crystal display element of a vertical electric field method such as a TN method or a VA method, particularly a horizontal electric field method such as an IPS method or an FFS method.
- a vertical electric field method such as a TN method or a VA method
- a horizontal electric field method such as an IPS method or an FFS method.
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Abstract
Description
具体例としては以下が例示できるが、これらに限定されない。なかでも、蓄積電荷の緩和の点から、(2―1―1)~(2―1-7)、(2―1-10)~(2―1-17)が好ましく、(2―1―1)~(2―1-7)、又は(2―1-15)~(2―1-17)が特に好ましい。
溶媒の使用量(反応濃度)は特に限定されないが、ジニトロ化合物に対し、通常、0.1~10質量倍であり、好ましくは0.5~30質量倍であり、さらに好ましくは1~10質量倍である。反応温度は特に限定されないが、通常、-100℃から使用する溶媒の沸点までの範囲であり、好ましくは、-50~150℃である。反応時間は、通常、0.05~350時間であり、好ましくは0.5~100時間である。
本発明の液晶配向剤に含有される重合体は、上記特定ジアミンを用いて得られる重合体である。具体例としては、ポリアミック酸、ポリアミック酸エステル、ポリイミド、ポリウレア、ポリアミドなどが挙げられるが、液晶配向剤としての使用の観点から、下記式(4)で表される構造単位を有するポリイミド前駆体、及び/又はそのイミド化物であるポリイミドから選ばれる少なくとも1種の重合体(以下、特定重合体ともいう。)がより好ましい。
上記X1は、重合体の溶媒への溶解性や液晶配向剤の塗布性、液晶配向膜とした場合における液晶の配向性、電圧保持率、蓄積電荷など、必要とされる特性の程度に応じて適宜選択され、同一重合体中に2種類以上であってもよい。
X1の具体例を示すならば、国際公開公報2015/119168の13頁~14頁に掲載される、式(X-1)~(X-46)の構造などが挙げられる。
また、Y2は、式(1)の構造を主鎖方向に含まないジアミンに由来する二価の有機基であり、その構造は特に限定されない。Y2は重合体の溶媒への溶解性や液晶配向剤の塗布性、液晶配向膜とした場合における液晶の配向性、電圧保持率、蓄積電荷など、必要とされる特性の程度に応じて適宜選択され、同一重合体中に2種類以上が混在していてもよい。
以下に、好ましいY2の構造を示すが、本発明はこれらに限定されるものではない。
本発明に用いるポリイミド前駆体の分子量は、重量平均分子量(Mw)で2,000~500,000が好ましく、より好ましくは5,000~300,000であり、さらに好ましくは、10,000~100,000である。
特定重合体のうちのポリイミドは、式(4)、式(5)で表されるポリイミド前駆体を閉環させて得られる。この場合のイミド化率は必ずしも100%である必要はなく、用途や目的に応じて任意に調整できる。
ポリイミド前駆体をイミド化させる方法としては、既知の方法が使用できる。ポリイミド前駆体の溶液に、塩基性触媒を添加する化学的イミド化が簡便である。化学的イミド化は、比較的低温でイミド化反応が進行し、イミド化の課程で重合体の分子量低下が起こりにくいので好ましい。
化学的イミド化は、ポリイミド前駆体を、有機溶媒中において、塩基性触媒の存在下で撹拌することにより行うことができる。有機溶媒としては、前述した重合反応時に用いる溶媒を使用することができる。塩基性触媒としては、ピリジン、トリエチルアミン、トリメチルアミン、トリブチルアミン、トリオクチルアミン等を挙げることができる。中でもトリエチルアミンは反応を進行させるのに充分な塩基性を持つので好ましい。
上記のようにして得られるポリイミドの溶液は、よく撹拌させながら貧溶媒に注入することで、重合体を析出させることができる。析出を数回行い、貧溶媒で洗浄後、常温あるいは加熱乾燥して、精製されたポリイミドの粉末を得ることができる。
貧溶媒としては、特に限定されないが、メタノール、アセトン、ヘキサン、ブチルセルソルブ、ヘプタン、メチルエチルケトン、メチルイソブチルケトン、エタノール、トルエン、ベンゼン等が挙げられる。
本発明の液晶配向剤は、特定重合体を含有するものであるが、本発明に記載の効果を奏する限度において、異なる構造の特定重合体を2種以上含有していてもよい。また、特定重合体に加えて、その他の重合体を含有していてもよい。その他の重合体の種類としては、ポリアミック酸、ポリイミド、ポリアミック酸エステル、ポリエステル、ポリアミド、ポリウレア、ポリオルガノシロキサン、セルロース誘導体、ポリアセタール、ポリスチレンまたはその誘導体、ポリ(スチレン-フェニルマレイミド)誘導体、ポリ(メタ)アクリレートなどを挙げることができる。また、上記式(5)で表されるポリイミド前駆体及び/又は該ポリイミド前駆体をイミド化したポリイミドから選ばれるポリイミドなどを含有していてもよい。
液晶配向剤は、液晶配向膜を作製するために用いられるものであり、均一な薄膜を形成させるという観点から、一般的には塗布液の形態をとる。本発明の液晶配向剤においても前記した重合体成分と、この重合体成分を溶解させる有機溶媒とを含有する塗布液であることが好ましい。その際、液晶配向剤中の重合体の濃度は、形成させようとする塗膜の厚みの設定によって適宜変更することができる。均一で欠陥のない塗膜を形成させるという点からは、1質量%以上であることが好ましく、溶液の保存安定性の点からは、10質量%以下とすることが好ましい。特に好ましい重合体の濃度は、2~8質量%である。
また、液晶配向剤に含有される有機溶媒は、上記のような溶媒に加えて液晶配向剤を塗布する際の塗布性や塗膜の表面平滑性を向上させる溶媒を併用した混合溶媒を使用することが一般的であり、本発明の液晶配向剤においてもこのような混合溶媒は好適に用いられる。併用する有機溶媒の具体例を下記に挙げるが、これらの例に限定されない。
本発明の液晶配向膜は、上記本発明の液晶配向剤から得られる。液晶配向剤から液晶配向膜を得る方法の一例を挙げるなら、塗布液形態の液晶配向剤を基板に塗布し、乾燥し、焼成して得られた膜に対してラビング処理法又は光配向処理法で配向処理を施す方法が挙げられる。
液晶配向剤を塗布する基板としては、透明性の高い基板であれば特に限定されず、ガラス基板、窒化珪素基板、アクリル基板やポリカーボネート基板などのプラスチック基板等を用いることもできる。その際、液晶を駆動させるためのITO電極などが形成された基板を用いると、プロセスの簡素化の点から好ましい。また、反射型の液晶表示素子では、片側の基板のみにならば、シリコンウエハーなどの不透明な物でも使用でき、この場合の電極にはアルミニウムなどの光を反射する材料も使用できる。
液晶配向剤を基板上に塗布した後は、ホットプレート、熱循環型オーブン、IR(赤外線)型オーブンなどの加熱手段により、溶媒を蒸発させ、焼成する。液晶配向剤を塗布した後の乾燥、焼成工程は、任意の温度と時間を選択することができる。通常は、含有される溶媒を十分に除去するために、50~120℃で1~10分焼成し、その後、150~300℃で、5~120分焼成する条件が挙げられる。
本発明の液晶配向膜は、IPS方式やFFS方式などの横電界方式の液晶表示素子の液晶配向膜として好適であり、特に、FFS方式の液晶表示素子の液晶配向膜として有用である。
本発明の液晶表示素子は、上記液晶配向剤から得られる液晶配向膜付きの基板を得た後、既知の方法で液晶セルを作製し、該液晶セルを使用して素子としたものである。
液晶セルの作製方法の一例として、パッシブマトリクス構造の液晶表示素子を例にとり説明する。なお、画像表示を構成する各画素部分にTFT(Thin Film Transistor)などのスイッチング素子が設けられたアクティブマトリクス構え造の液晶表示素子であってもよい。
または、基板の上に液晶配向膜を形成した後の工程として、一方の基板上の所定の場所にシール材を配置する際に、外部から液晶を充填可能な開口部を設けておき、液晶を配置しないで基板を貼り合わせた後、シール材に設けた開口部を通じて液晶セル内に液晶材料を注入し、次いで、この開口部を接着剤で封止して液晶セルを得る。液晶材料の注入には、真空注入法でもよいし、大気中で毛細管現象を利用した方法でもよい。
上記の液晶材料としては、ネマチック液晶、スメクチック液晶を挙げることができ、その中でもネマチック液晶が好ましく、ポジ型液晶材料やネガ型液晶材料のいずれを用いてもよい。次に、偏光板の設置を行う。具体的には、2枚の基板の液晶層とは反対側の面に一対の偏光板を貼り付けることが好ましい。
NMP:N-メチル-2-ピロリドン、NEP:N-エチル-2-ピロリドン
GBL:γ-ブチロラクトン、BCS:ブチルセロソルブ
PB:プロピレングリコールモノブチルエーテル
DME:ジプロピレングリコールジメチルエーテル
DAA:4-ヒドロキシ-4-メチル-2-ペンタノン
DEDG:ジエチレングリコールジエチルエーテル
DIBK:2,6-ジメチル-4-ヘプタノン、DIPE:ジイソプロピルエーテル
DIBC:2,6-ジメチル-4-ヘプタノール、Pd/C:パラジウムカーボン
DMSO:ジメチルスルオキシド、THF:テトラヒドロフラン
装置:Varian NMR system 400NB(400MHz)(Varian社製)、及びJMTC-500/54/SS(500MHz)(JEOL社製)
測定溶媒:CDCl3(重水素化クロロホルム),DMSO-d6(重水素化ジメチルスルホキシド)
基準物質:TMS(テトラメチルシラン)(δ:0.0ppm,1H)及びCDCl3(δ:77.0ppm,13C)
ポリイミド粉末20mgをNMRサンプル管(NMRサンプリングチューブスタンダード,φ5(草野科学社製))に入れ、重水素化ジメチルスルホキシド(DMSO-d6,0.05%TMS(テトラメチルシラン)混合品)を0.53ml添加し、超音波をかけて完全に溶解させた。この溶液をNMR測定機(JNW-ECA500、日本電子データム社製)にて500MHzのプロトンNMRを測定した。イミド化率は、イミド化前後で変化しない構造に由来するプロトンを基準プロトンとして決め、このプロトンのピーク積算値と、9.5ppm~10.0ppm付近に現れるアミド酸のNH基に由来するプロトンピーク積算値とを用い以下の式によって求めた。
イミド化率(%)=(1-α・x/y)×100
上記式中、xはアミド酸のNH基由来のプロトンピーク積算値、yは基準プロトンのピーク積算値、αはポリアミド酸(イミド化率が0%)の場合におけるアミド酸のNH基プロトン1個に対する基準プロトンの個数割合である。
合成例及び比較合成例において、ポリアミド酸溶液の粘度は、E型粘度計TVE-22H(東機産業社製)を用い、サンプル量1.1mL及びコーンロータTE-1(1°34’、R24)にて、温度25℃で測定した。
GPC装置:Shodex社製(GPC-101)、カラム:Shodex社製(KD803、KD805の直列)、カラム温度:50℃、溶離液:N,N-ジメチルホルムアミド(添加剤として、臭化リチウム-水和物(LiBr・H2O)が30mmol/L(リットル)、リン酸・無水結晶(o-リン酸)が30mmol/L、テトラヒドロフラン(THF)が10ml/L)、流速:1.0ml/分。
検量線作成用標準サンプル:東ソー社製 TSK 標準ポリエチレンオキサイド(重量平均分子量(Mw);約900,000、150,000、100,000及び30,000)、及びポリマーラボラトリー社製 ポリエチレングリコール(ピークトップ分子量(Mp);約12,000、4,000及び1,000)。
1H-NMR(DMSO-d6):8.60-8.62(2H,m)、7.74-7.77(2H,dd)、7.46-7.49(2H, m)、3.84(3H,s)
1H-NMR(DMSO-d6):8.17(2H,d)、8.01-8.06(4H,m)、7.77(2H,d)、7.41-7.45(2H,dd)、6.68-6.73(4H,m)、3.97(3H,s)、3.46(6H,s)
1H-NMR(DMSO-d6):7.54(2H,d)、7.33(2H,d)、6.91-6.94(2H,dd)、6.72-6.75(4H,m)、6.51-6.55(4H,m)、4.77(4H,s)、3.75(3H,s)、3.18(6H,s)
撹拌装置付き及び窒素導入管付きの100mLの四つ口フラスコに、DA-1(2.53g,6.0mmol)を加えた後、NMP(30.0g)を加え、窒素を送りながら撹拌し溶解させた。この溶液を撹拌しながら、CA-1(0.87g,4.0mmol)、CA-2(1.08g,5.5mmol)、及びNMP(9.0g)を加えた後、さらに50℃条件下にて12時間攪拌することでポリアミック酸溶液(PAA-A1)を得た。このポリアミック酸溶液の粘度は350mPa・sであった。また、このポリアミック酸の数平均分子量(Mn)=16008であり、重量平均分子量(Mw)=51878であった。
表1にそれぞれ示す、ジアミン成分、テトラカルボン酸成分、及び溶媒を使用した他は、合成例1と同様に実施することにより、ポリアミック酸溶液(PAA-A2)~(PAA-A4)及びポリアミック酸溶液(PAA-B1)~(PAA-B5)を得た。
合成例1~6で得られたポリアミック酸溶液の粘度、及びポリアミック酸のMn、Mwを表2に示す。
撹拌装置付き及び窒素導入管付きの200mLの四つ口フラスコに、DA-6(4.03g,16.5mmol)、DA-7(3.59g、9.0mmol)、及びDA-8(2.51g、4.5mmol)を加えた後、NMP(74.0g)を加え、窒素を送りながら撹拌し溶解させた。この溶液を撹拌しながらCA-4(4.37g、19.5mmol)及びNMP(9.0)gを加え、40℃条件下にて3時間攪拌した。その後、25℃にてCA-2(1.71g,8.7mmol)及びNMP(9.0g)を加えた後、さらに12時間攪拌することでポリアミック酸溶液を得た。このポリアミック酸溶液の粘度は480mPa・sであり、このポリアミック酸のMn=10,660であり、Mw=20,512であった。
撹拌装置及び窒素導入管付きの3Lの四つ口フラスコに、DA-9(17.30g、159.98mmol)、DA-5(58.63g、240.0mmol)、DA-10(76.89g、240.0mmol)及びDA-11(54.63g、159.99mmol)を量り取り、NMP(2458.13g)を加えて、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながら、CA-4(171.27g、764.02mmol)を添加し、更に、固形分濃度が12質量%になるようにNMPを加え、40℃で20時間撹拌して、ポリアミック酸(PAA-4)の溶液を得た。このポリアミック酸溶液の粘度は426mPa・sであり、このポリアミック酸のMn=12,380であり、Mw=33,250であった。
合成例1~9で得られたポリアミック酸溶液、及び合成例10、11で得られたポリイミド溶液を、それぞれ、表3及び表4に示す組成になるように、攪拌しながら、溶媒および添加剤を加え、更に室温で2時間撹拌することにより実施例1~13及び比較例1~6の液晶配向剤を得た。
なお、表3、4中における、※1、※2は、全ての重合体100質量部に対する含有(添加)量(質量部)を示し、※3は、液晶配向剤100質量部に対する溶媒の使用量(質量部)を示す。
縦30mm×横35mmの大きさで、厚さが0.7mmの電極付きのガラス基板を準備した。基板上には第1層目として対向電極を構成する、ベタ状のパターンを備えたIZO電極が形成されている。第1層目の対向電極の上には第2層目として、CVD法により成膜されたSiN(窒化珪素)膜が形成されている。第2層目のSiN膜の膜厚は500nmであり、層間絶縁膜として機能する。第2層目のSiN膜の上には、第3層目としてIZO膜をパターニングして形成された櫛歯状の画素電極が配置され、第1画素及び第2画素の2つの画素を形成している。各画素のサイズは、縦10mmで横約5mmである。このとき、第1層目の対向電極と第3層目の画素電極とは、第2層目のSiN膜の作用により電気的に絶縁されている。
上記で作製した液晶セルを偏光軸が直交するように配置された2枚の偏光板の間に設置し、電圧無印加の状態でLEDバックライトを点灯させておき、透過光の輝度が最も小さくなるように、液晶セルの配置角度を調整した。次に、この液晶セルに周波数30Hzの交流電圧を印加しながらV-Tカーブ(電圧-透過率曲線)を測定し、相対透過率が23%となる交流電圧を駆動電圧として算出した。
残像評価では、相対透過率が23%となる周波数30Hzの交流電圧を印加して液晶セルを駆動させながら、同時に1Vの直流電圧を印加し、30分間駆動させた。その後、印加直流電圧値を0Vにして直流電圧の印加のみを停止しその状態で更に15分駆動した。
上記で作製した液晶セルを偏光軸が直交するように配置された2枚の偏光板の間に設置し、電圧無印加の状態でLEDバックライトを点灯させておき、透過光の輝度が最も小さくなるように、液晶セルの配置角度を調整した。次に、この液晶セルに周波数30Hzの交流電圧を印加しながらV-Tカーブ(電圧-透過率曲線)を測定し、相対透過率が23%となる交流電圧を駆動電圧として算出した。
フリッカーレベル(%)={フリッカー振幅/(2×z)}×100
フリッカーレベルの評価は、LEDバックライトの点灯及び交流電圧の印加を開始した時点から60分間が経過するまでに、フリッカーレベルが3%未満を維持した場合に、「○」と定義して評価を行った。60分間でフリッカーレベルが3%以上に達した場合には、「×」と定義して評価した。
上述した方法に従うフリッカーレベルの評価は、液晶セルの温度が23℃の状態の温度条件下で行った。
上記実施例1~3、5及び比較例1~6の各液晶配向剤を使用する液晶表示素子に関し、上記で実施した残像消去時間、及び駆動開始直後に起こるフリッカーシフトの評価結果を表4~表7に示す。
なお、表5~8中、※1は、全ての重合体100質量部に対する各重合体の含有量(質量部)を示す。
液晶配向剤を孔径1.0μmのフィルターで濾過した後、準備された上記電極付き基板と対向基板として裏面にITO膜が成膜されており、かつ高さ4μmの柱状のスペーサーを有するガラス基板のそれぞれにスピンコートした。次いで、80℃のホットプレート上で5分間乾燥後、230℃で20分間焼成して膜厚100nmの塗膜として、各基板上にポリイミド膜を得た。この塗膜面に偏光板を介して消光比26:1の直線偏光した波長254nmの紫外線を300mJ/cm2照射した。
ラビング法による液晶表示素子の場合と同様にして、上記で作製した光配向法による液晶表示素子の光学系等を用いて残像の評価を行った。
<駆動直後のフリッカーレベルの評価>
ラビング法による液晶表示素子の場合と同様にして、上記で作製した光配向法による液晶表示素子の光学系等を用いて残像の評価を行った。
上記実施例3、4、13及び比較例6で得られた液晶配向剤を使用する液晶表示素子に関し、上記で実施した残像消去時間の評価、及び駆動直後のフリッカーレベルの評価の結果を表9に示す。なお、表9中、※1は、全ての重合体100質量部に対する各重合体の含有量(質量部)を示す。
なお、2016年12月15日に出願された日本特許出願2016-243735号の明細書、特許請求の範囲、図面、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (15)
- 前記重合体が、前記式(1)で表される構造を有するジアミンとテトラカルボン酸二無水物との重縮合物であるポリイミド前駆体及びそのイミド化物であるポリイミドからなる群から選ばれる少なくとも1種の重合体である、請求項1に記載の液晶配向剤。
- 前記ジアミンが、下記式(2-1)、(2-2)、又は(2-3)で表される、請求項1又は2に記載の液晶配向剤。
- 前記式(4)で表される構造単位を有する重合体が、液晶配向剤に含有される全重合体に対して10モル%以上含有される、請求項4又は5に記載の液晶配向剤。
- 前記有機溶媒が、4-ヒドロキシ-4-メチル-2-ペンタノン及びジエチレングリコールジエチルエーテルからなる群から選ばれる少なくとも1種を含有する、請求項1~6のいずれか1項に記載の液晶配向剤。
- 請求項1~7のいずれか1項に記載の液晶配向剤から得られる液晶配向膜。
- 請求項8に記載の液晶配向膜を具備する液晶表示素子。
- 液晶表示素子が横電界駆動方式である請求項9に記載の液晶表示素子。
- 上記ジアミンが、下記式(2-1)、(2-2)、又は(2-3)で表される、請求項11に記載の重合体。
- 下記式(2-1)、(2-2)、または(2-3)で表されるジアミン。
但し、R4は、単結合、-O-、-COO-、-OCO-、-(CH2)l-、-O(CH2)mO-、-CONR-、及び-NRCO-から選ばれる2価の有機基を表し(k、l、mは1から5の整数を表す)、Rは水素もしくは一価の有機基を表し、*1は式(2-1)~式(2-3)中のベンゼン環と結合する部位を表し、*2は式(2-1)~式(2-3)中のアミノ基と結合する部位を表す。
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Citations (3)
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CN105237462A (zh) * | 2015-09-08 | 2016-01-13 | 湖南工业大学 | 一种含咔唑结构的具有高平面性二胺单体及其合成方法和应用 |
CN105622487A (zh) * | 2016-03-08 | 2016-06-01 | 湖南工业大学 | 一种含咔唑结构的新型功能三胺单体及其制备方法和用途 |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN105237462A (zh) * | 2015-09-08 | 2016-01-13 | 湖南工业大学 | 一种含咔唑结构的具有高平面性二胺单体及其合成方法和应用 |
CN105622487A (zh) * | 2016-03-08 | 2016-06-01 | 湖南工业大学 | 一种含咔唑结构的新型功能三胺单体及其制备方法和用途 |
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JP7103232B2 (ja) | 2017-01-13 | 2022-07-20 | 日産化学株式会社 | 芳香族ジアミン化合物前駆体の製造方法 |
WO2020100918A1 (ja) * | 2018-11-14 | 2020-05-22 | 日産化学株式会社 | 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子 |
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WO2020218331A1 (ja) * | 2019-04-24 | 2020-10-29 | 日産化学株式会社 | 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子 |
CN113728270A (zh) * | 2019-04-24 | 2021-11-30 | 日产化学株式会社 | 液晶取向剂、液晶取向膜以及使用了该液晶取向膜的液晶显示元件 |
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