Classifications

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

Definitions

• the present invention relates to a liquid crystal alignment agent for producing a liquid crystal alignment film and a liquid crystal alignment film obtained from the liquid crystal alignment agent. More specifically, in place of rubbing treatment, a liquid crystal alignment agent used for forming a liquid crystal alignment film capable of imparting liquid crystal alignment ability by photo-alignment treatment, that is, irradiation with polarized ultraviolet rays, and the liquid crystal alignment agent. It relates to a liquid crystal alignment film obtained from the above.
• the liquid crystal alignment film is made of a polyamic acid formed on an electrode substrate and / or a surface of a film made of polyimide obtained by imidizing this with cotton, nylon, It is produced by carrying out a so-called rubbing treatment that rubs in one direction with a cloth such as polyester.
• the method of rubbing the film surface in the alignment process of the liquid crystal alignment film is an industrially useful method that is simple and excellent in productivity.
• demands for higher performance, higher definition, and larger size of liquid crystal display elements are increasing, and the surface of the alignment film caused by rubbing treatment, dust generation, the influence of mechanical force and static electricity, Various problems such as non-uniformity in the orientation processing surface have been revealed.
• Patent Document 1 proposes that a polyimide film having an alicyclic structure such as a cyclobutane ring in the main chain is used for the photo-alignment method.
• the photo-alignment method as described above has been attracting attention as a rubbing-less alignment treatment method, and has an advantage that it can be produced by an industrially simple manufacturing process.
• the obtained liquid crystal alignment film can improve performance such as the contrast and viewing angle characteristics of the liquid crystal display element can be improved as compared with the liquid crystal alignment film obtained by the rubbing treatment method. It is.
• the liquid crystal alignment film used for the liquid crystal display element of the IPS driving method or the FFS driving method in addition to the basic characteristics such as excellent liquid crystal alignment property and electrical characteristics, It is necessary to suppress the afterimage by the generated AC drive.
• a liquid crystal alignment film obtained by a photo-alignment method has insufficient alignment regulating power of liquid crystal and its stability, and it has been difficult to satisfy the above characteristics.
• the present invention relates to a liquid crystal alignment film for a photo-alignment processing method capable of suppressing an afterimage due to alternating current driving that occurs in a liquid crystal display element of an IPS drive system or an FFS drive system, and a photo-alignment process for obtaining the liquid crystal alignment film It aims at providing the liquid crystal aligning agent for a method.
• the present inventor has conducted extensive research to achieve the above object, and as a result of irradiating polarized radiation, any one of the reactions of photolysis, photodimerization, or photoisomerization proceeds, and polarization
• polarization A polymer having anisotropy in the same direction as the direction or perpendicular to the polarization direction, a polymer having both a rigid aromatic group and a flexible alkylene group, and an organic solvent. It has been found that the above object can be achieved by a liquid crystal aligning agent.
• the present invention has the following gist. 1.
• the following (A) component, (B) component, and an organic solvent are contained, Content of (B) component is 0.1-15 mass parts with respect to 100 mass parts of (A) component, It is characterized by the above-mentioned.
• (B) Component A polymer containing a structure represented by the following formula (1).
• W 1 and W 2 are each independently a divalent organic group having an aromatic group having 6 to 30 carbon atoms, and A has an alkylene group having 2 to 20 carbon atoms. It is a divalent organic group.
• the component (A) is a polymer of one or more types that undergoes a photolysis reaction when irradiated with polarized radiation and imparts anisotropy in a direction perpendicular to the polarization direction.
• the component (A) contains a structural unit represented by the following formula (2), and at least one polymer selected from the group consisting of a polyimide precursor and an imidized polymer of the polyimide precursor 3.
• the liquid crystal aligning agent according to 1 or 2 above.
• X 1 is at least one selected from the group consisting of structures represented by the following formulas (X1-1) to (X1-9), and Y 1 is a divalent organic group.
• R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, An alkenyl group or a phenyl group, which may be the same or different. 4).
• A From the group which a component consists of a polyimide precursor which contains 60 mol% or more of structural units represented by said Formula (2) with respect to 1 mol of all the structural units, and the imidation polymer of this polyimide precursor. 4.
• X 1 is at least one selected from the group consisting of a structure represented by the formula (X1-1). 6). 6. The liquid crystal according to any one of 3 to 5 above, wherein in the formula (2), X 1 is at least one selected from the group consisting of structures represented by the following formulas (X1-10) to (X1-11) Alignment agent.
• Y 1 is at least one selected from the group consisting of structures represented by the following formulas (4) and (5).
• Z 1 is a single bond, an ester bond, an amide bond, a thioester bond, or a divalent organic group having 2 to 10 carbon atoms.
• 8 The liquid crystal aligning agent according to 7, wherein Y 1 is a structure represented by the above formula (4) in the above formula (2).
• the component (B) is at least one polymer selected from the group consisting of a polyimide precursor having a structural unit represented by the following formula (3) and an imidized polymer of the polyimide precursor.
• the liquid crystal aligning agent in any one of.
• X 2 is a tetravalent organic group having an aromatic group having 6 to 20 carbon atoms and having a bond in the aromatic group.
• Y 2 represents the following formula (Y2-1) and (Y2-2) is at least one divalent organic group selected from the group consisting of, and A 1 and A 2 are each independently a hydrogen atom or a C 1 -C which may have a substituent.
• 10 is an alkyl group, an alkenyl group, or an alkynyl group, and R 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• a 3 is a divalent organic group having an alkylene group having 2 to 20 carbon atoms.
• a 4 represents —O—, —S—, —NR 12 —, ester bond, amide bond, thioester bond, urea bond, carbonate bond, carbamate bond, R 12 is a hydrogen atom, methyl group, or t-butoxycarbonyl group, and A 5 has 2 carbon atoms. ⁇ 20 alkylene groups.
• the component (B) is selected from the group consisting of a polyimide precursor containing 60 mol% or more of the structural unit represented by the above formula (3) with respect to 1 mol of all structural units and an imidized polymer of the polyimide precursor. 10.
• the liquid crystal aligning agent according to 9 above which is at least one polymer.
• the liquid crystal aligning agent according to 9 or 10 above, wherein X 2 in the formula (3) is at least one selected from the group consisting of structures represented by the following formulas (X2-1) to (X2-3).
• R 13 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, which may be the same or different.
• R 13 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, which may be the same or different.
• 14 14.
• 15. 14 A liquid crystal alignment film obtained by applying and baking the liquid crystal aligning agent according to any one of the above 1 to 13, and further irradiating with polarized radiation.
• 16. 14 A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of 1 to 13 above, firing, irradiating with polarized radiation, and then heating at 150 ° C. to 250 ° C. 17.
• a liquid crystal display device comprising the liquid crystal alignment film according to any one of 14 to 16 above.
• the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention can suppress afterimages caused by alternating current drive generated in an IPS drive type or FFS drive type liquid crystal display element.
• the reason why the problems of the present invention are solved in the liquid crystal alignment film of the present invention is not necessarily clear, but is considered as follows. In general, afterimages due to alternating current drive generated in liquid crystal display elements of IPS drive type and FFS drive type are suppressed by increasing the anisotropy of the liquid crystal alignment film and / or increasing the interaction between the liquid crystal alignment film and the liquid crystal. It is known that it can be done.
• the liquid crystal alignment film obtained by the photo-alignment method can provide sufficient anisotropy, a specific portion that reacts by irradiation with radiation requires a certain ratio or more, and the interaction with the liquid crystal is enhanced. It was difficult. Specifically, when a structure capable of enhancing the interaction with the liquid crystal is introduced into the polymer, sufficient anisotropy is caused by a decrease in the reactivity of the photoreactive site and a decrease in the density of the photoreactive site. In some cases, it could not be obtained.
• the inventors of the present application provide a liquid crystal having both a rigid skeleton containing an aromatic group and a flexible skeleton containing an alkylene group as the component (A) to which anisotropy is imparted by irradiating polarized radiation. While maintaining the anisotropy when irradiated with polarized radiation, the polymer (component (B)) containing a similar structure is preferably mixed with the component (A) in a specific amount.
• the present inventors have found that the interaction between the liquid crystal alignment film obtained by the photo-alignment method and the liquid crystal can be enhanced. Since the component (B) having a skeleton similar to liquid crystal has a flexible skeleton, it is expected to have high mobility when heated.
• the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has high liquid crystal alignment properties and can suppress an afterimage caused by alternating current drive generated in an IPS drive type or FFS drive type liquid crystal display element. It is considered possible.
• ⁇ (A) component The component (A) contained in the liquid crystal aligning agent of the present invention undergoes a reaction of photodecomposition, photodimerization, or photoisomerization by irradiating polarized radiation, and is in the same direction as the polarization direction. Or one or two or more polymers imparted with anisotropy in the direction perpendicular to the polarization direction.
• the component (A) of the present invention is not particularly limited as long as it is a polymer having a site where any of the reactions of photolysis, photodimerization, or photoisomerization proceeds upon irradiation with radiation.
• examples of the structure in which the photodimerization reaction proceeds include a polymer containing a structure having a cinnamoyl group represented by the following formula (A-1).
• examples of the structure in which the photoisomerization reaction proceeds include a polymer containing an azobenzene skeleton represented by the following formula (A-2).
• the structure in which the photolysis reaction proceeds is at least one selected from the group consisting of a polymer containing an imide skeleton having an alicyclic group represented by the following formula (A-3) and a precursor of the polymer.
• the polymer of this is mentioned.
• Q is a divalent aromatic group.
• X is a tetravalent alicyclic group, and Y is a divalent organic group.
• Q is a divalent aromatic group.
• X is a tetravalent alicyclic group, and Y is a divalent organic group.
• a polymer containing an imide structure having an alicyclic skeleton and a precursor of the polymer have high photoreaction sensitivity, and the obtained liquid crystal alignment film has high anisotropy.
• a polyimide precursor having a structural unit represented by the following formula (2) and an imidized polymer of the polyimide precursor are preferable. From the viewpoint of solubility in an organic solvent, a polyimide precursor containing a structural unit represented by the following formula (2) is particularly preferable.
• R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of ease of imidization by heating, a hydrogen atom or a methyl group is particularly preferable.
• X 1 is at least one selected from the group consisting of structures represented by the following formulas (X1-1) to (X1-9).
• R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, An alkenyl group or a phenyl group, which may be the same or different.
• R 1 , R 2 , R 3 , and R 4 are preferably a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, more preferably a hydrogen atom or a methyl group, and still more preferably, At least one selected from the group consisting of structures represented by the following formulas (X1-10) to (X1-11).
• Y 1 is a divalent organic group, and its structure is not particularly limited. Since the obtained liquid crystal alignment film has high anisotropy, it is preferably at least one selected from the group consisting of structures represented by the following formulas (4) and (5).
• Z 1 is a single bond, an ester bond, an amide bond, a thioester bond, or a divalent organic group having 2 to 10 carbon atoms.
• the ester bond is represented by —C (O) O— or —OC (O) —.
• the amide bond a structure represented by —C (O) NH— or —C (O) NR—, —NHC (O) —, —NRC (O) — can be shown.
• R is an alkyl group, alkenyl group, alkynyl group, aryl group, or a combination thereof having 1 to 10 carbon atoms.
• alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, and a bicyclohexyl group.
• alkenyl group examples include those obtained by replacing one or more CH—CH structures present in the above alkyl group with C ⁇ C structures, and more specifically, vinyl groups, allyl groups, 1-propenyl groups.
• Alkynyl groups include those in which one or more CH 2 —CH 2 structures present in the alkyl group are replaced with C ⁇ C structures, and more specifically, ethynyl groups, 1-propynyl groups, 2 -Propynyl group and the like.
• Examples of the aryl group include a phenyl group.
• thioester bond a structure represented by —C (O) S— or —SC (O) — can be shown.
• Z 1 is an organic group having 2 to 10 carbon atoms, it can be represented by the structure of the following formula (6).
• Z 4 , Z 5 and Z 6 are each independently a single bond, —O—, —S—, —NR 11 —, an ester bond, an amide bond, a thioester bond, a urea bond, or a carbonate bond. Or a carbamate bond.
• R 11 is a hydrogen atom, a methyl group, or a t-butoxycarbonyl group.
• the ester bond, amide bond, and thioester bond can have the same structures as the ester bond, amide bond, and thioester bond described above.
• urea bond a structure represented by —NH—C (O) NH— or —NR—C (O) NR— can be shown.
• R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof, and examples thereof are the same as the above-described alkyl group, alkenyl group, alkynyl group, and aryl group.
• carbonate bond a structure represented by —O—C (O) —O— can be shown.
• the carbamate bond is —NH—C (O) —O—, —O—C (O) —NH—, —NR—C (O) —O—, or —O—C (O) —NR—.
• R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof, and examples thereof are the same as the above-described alkyl group, alkenyl group, alkynyl group, and aryl group.
• R 9 and R 10 in the formula (6) are each independently a single bond or a structure selected from an alkylene group having 1 to 10 carbon atoms, an alkenylene group, an alkynylene group, an arylene group, and a group obtained by combining these. is there. If one of R 9 and R 10 is a single bond, R 9 or R 10 is a structure selected from the group formed by combining an alkylene group having 2 to 10 carbon atoms, an alkenylene group, an alkynylene group, an arylene group, and these .
• alkylene group examples include a structure in which one hydrogen atom is removed from the alkyl group. More specifically, a methylene group, 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, 1,2-butylene group 1,2-pentylene group, 1,2-hexylene group, 2,3-butylene group, 2,4-pentylene group, 1,2-cyclopropylene group, 1,2-cyclobutylene group, 1,3- Examples thereof include a cyclobutylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group and the like.
• alkenylene group examples include a structure in which one hydrogen atom is removed from the alkenyl group. More specifically, 1,1-ethenylene group, 1,2-ethenylene group, 1,2-ethenylenemethylene group, 1-methyl-1,2-ethenylene group, 1,2-ethenylene-1,1- Ethylene group, 1,2-ethenylene-1,2-ethylene group, 1,2-ethenylene-1,2-propylene group, 1,2-ethenylene-1,3-propylene group, 1,2-ethenylene-1, Examples include 4-butylene group and 1,2-ethenylene-1,2-butylene group.
• the alkynylene group includes a structure in which one hydrogen atom is removed from the alkynyl group. More specifically, an ethynylene group, an ethynylene methylene group, an ethynylene-1,1-ethylene group, an ethynylene-1,2-ethylene group, an ethynylene-1,2-propylene group, an ethynylene-1,3-propylene group, Examples include ethynylene-1,4-butylene group, ethynylene-1,2-butylene group and the like.
• the arylene group includes a structure in which one hydrogen atom is removed from the aryl group. More specific examples include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group and the like.
• Y 1 has a structure with high linearity or a rigid structure, a liquid crystal alignment film having good liquid crystal alignment can be obtained. Therefore, Z 1 can be a single bond, The structure of 25) is more preferable.
• Y 1 Since Y 1 has a more rigid structure, a liquid crystal alignment film having excellent liquid crystal alignment can be obtained. Therefore, Y 1 is particularly preferably a structure represented by the above formula (4).
• the ratio of the structural unit represented by the above formula (2) is the total structure in the polymer. 60 mol% to 100 mol% is preferable with respect to 1 mol of the unit. Since the higher the ratio of the structural unit represented by the above formula (2), the better the liquid crystal alignment film having liquid crystal alignment properties, 80 mol% to 100 mol% is more preferable, and 90 mol% to 100 mol% is preferable. Is more preferable.
• the component (A) of the present invention may be a polyimide precursor having a structural unit represented by the following formula (7) and the polyimide precursor.
• R 1 is the same as defined for R 1 in the formula (2).
• X 3 is a tetravalent organic group, and its structure is not particularly limited. Specific examples include structures of the following formulas (X-9) to (X-42). From the viewpoint of availability of the compound, X includes X-17, X-25, X-26, X-27, X-28, X-32, or X-39.
• a tetracarboxylic dianhydride having an aromatic ring structure it is preferable to use a tetracarboxylic dianhydride having an aromatic ring structure, and X is X-26, X-- 27, X-28, X-32, X-35, or X-37 are more preferred.
• Y 3 is a divalent organic group, and its structure is not particularly limited. Specific examples of Y 3 include the following formulas (Y-1) to (Y-74).
• the structures other than the formulas (4) and (5) include Y-8, Y-20, Y-21, Y-22, Y— 28, Y-29, Y-30, Y-72, Y-73, or Y-74.
• the ratio of the structural unit represented by the above formula (7) in the component (A) is high, the ratio of the structural unit represented by the above formula (7) is The amount is preferably 0 to 40 mol%, more preferably 0 to 20 mol%, relative to 1 mol of the structural unit.
• the component (B) of the present invention is a polymer containing a structure represented by the following formula (1).
• W 1 and W 2 are each independently a divalent organic group having an aromatic group having 6 to 30 carbon atoms, and may be the same or different. Examples of the aromatic group contained in W 1 and W 2 include benzene, naphthalene, anthracene, biphenyl, and terphenyl.
• A is a divalent organic group having an alkylene group having 2 to 20 carbon atoms.
• the alkylene group having 2 to 20 carbon atoms examples include 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, 1,5-butylene group, Examples include pentylene group, 1,6-hexylene group, 2,3-butylene group, 2,4-pentylene group and the like.
• the component (B) is selected from the group consisting of a polyimide precursor containing a structure represented by the above formula (1) and an imidized polymer of the polyimide precursor. It is preferable that it is at least one polymer selected. Specifically, at least one selected from the group consisting of a polyimide precursor having a structural unit represented by the following formula (3) and an imidized polymer of the polyimide precursor is more preferable.
• R 2 is the same definition as R 1 in Formula (2), including preferred examples.
• a 1 and A 2 are each independently a hydrogen atom or an optionally substituted alkyl group, alkenyl group, or alkynyl group having 1 to 10 carbon atoms. The same structure as a group can be mentioned.
• the above alkyl group, alkenyl group, and alkynyl group may have a substituent as long as it has 1 to 10 carbon atoms as a whole, and may further form a ring structure by the substituent.
• forming a ring structure with a substituent means that the substituents or a substituent and a part of the mother skeleton are combined to form a ring structure.
• this substituent include halogen groups, hydroxyl groups, thiol groups, nitro groups, aryl groups, organooxy groups, organothio groups, organosilyl groups, acyl groups, ester groups, thioester groups, phosphate ester groups, amide groups, alkyls.
• the halogen group as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• a phenyl group is mentioned as an aryl group which is a substituent. This aryl group may be further substituted with the other substituent described above.
• the organooxy group which is a substituent can have a structure represented by OR.
• the R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
• alkyloxy group examples include methoxy group, ethoxy group, propyloxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like.
• the organothio group which is a substituent can have a structure represented by —S—R.
• R include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
• Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, and an octylthio group.
• the organosilyl group as a substituent can have a structure represented by —Si— (R) 3 .
• the R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
• Specific examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tripentylsilyl group, a trihexylsilyl group, a pentyldimethylsilyl group, and a hexyldimethylsilyl group.
• the acyl group as a substituent can have a structure represented by —C (O) —R.
• R examples include the alkyl groups, alkenyl groups, and aryl groups described above. These Rs may be further substituted with the substituent described above.
• Specific examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group and the like.
• As the ester group which is a substituent a structure represented by —C (O) O—R or —OC (O) —R can be shown.
• R examples include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
• the thioester group as a substituent can have a structure represented by —C (S) O—R or —OC (S) —R.
• R examples include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
• the phosphate group which is a substituent can have a structure represented by —OP (O) — (OR) 2 .
• the R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
• Examples of the amide group as a substituent include —C (O) NH 2 , —C (O) NHR, —NHC (O) R, —C (O) N (R) 2 , or —NRC (O) R.
• the structure represented by can be shown.
• the R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
• Examples of the aryl group as a substituent include the same aryl groups as described above. This aryl group may be further substituted with the other substituent described above.
• Examples of the alkyl group as a substituent include the same alkyl groups as described above.
• This alkyl group may be further substituted with the other substituent described above.
• Examples of the alkenyl group as a substituent include the same alkenyl groups as described above. This alkenyl group may be further substituted with the other substituent described above.
• Examples of the alkynyl group that is a substituent include the same alkynyl groups as described above. This alkynyl group may be further substituted with the other substituent described above.
• a 1 and A 2 a hydrogen atom or a carbon atom that may have a substituent is 1
• An alkyl group of 1 to 5 is more preferable, and a hydrogen atom, a methyl group or an ethyl group is particularly preferable.
• X 2 is a tetravalent organic group having an aromatic group having 6 to 20 carbon atoms and having a bond in the aromatic group. Examples of the aromatic group having 6 to 20 carbon atoms include benzene, naphthalene, anthracene, biphenyl, and terphenyl.
• X 2 is preferably a tetravalent organic group consisting only of an aromatic group, more preferably a compound represented by the following formulas (X2-1) to (X) because the interaction with the liquid crystal is enhanced and the effect of suppressing the afterimage is enhanced. And a structure represented by X2-3). Among these, a structure represented by the formula (X2-1) is particularly preferable.
• Y 2 is at least one divalent organic group selected from the group consisting of the following formulas (Y2-1) to (Y2-2).
• a 3 is a divalent organic group having an alkylene group having 2 to 20 carbon atoms, and may have a plurality of alkylene groups.
• alkylene group having 2 to 20 carbon atoms include 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, 1,5-butylene group, Examples include pentylene group, 1,6-hexylene group, 2,3-butylene group, 2,4-pentylene group and the like.
• a 3 is preferably a divalent organic group having an alkylene group having 2 to 10 carbon atoms.
• a 4 is a single bond, —O—, —S—, —NR 12 —, ester bond, amide bond, thioester bond, urea bond, carbonate bond, or carbamate bond
• R 4 12 is a hydrogen atom, a methyl group, or a t-butoxycarbonyl group, and these can have the same structure as described above.
• a 5 is an alkylene group having 2 to 20 carbon atoms, and can exhibit the same structure as the above-described alkylene group.
• a 4 is preferably a single bond, and A 5 is preferably an alkylene group having 2 to 6 carbon atoms.
• Specific examples of Y 2 that can enhance the interaction with the liquid crystal and improve the liquid crystal alignment include structures represented by the following formulas (Y2-3) to (Y2-12). Among these, a structure represented by the following formula (Y2-3) is particularly preferable.
• the ratio of the structural unit represented by the above formula (3) is the total structure in the polymer. 60 mol% to 100 mol% is preferable with respect to 1 mol of the unit. As the ratio of the structural unit represented by the above formula (3) is higher, a liquid crystal alignment film having better liquid crystal alignment can be obtained. Therefore, 80 mol% to 100 mol% is more preferable, and 90 mol% to 100 mol% is obtained. Is more preferable.
• the component (B) used in the present invention may be a polyimide precursor containing a structural unit represented by the following formula (8) in addition to the structural unit represented by the above formula (3) and the polyimide precursor. .
• R 2, A 1, and A 2 are the same as defined, including preferred examples and R 2, A 1, and A 2 in Formula (3).
• X 4 is a tetravalent organic group having an alicyclic group, and the structure thereof is not particularly limited as long as it is a tetravalent organic group having an alicyclic group. Specific examples thereof include the above formulas (X1-1) to (X1-9), (X-9) to (X-15), (X-22 to 25), (X-39), (X-40).
• Y 4 is a divalent organic group, and its structure is not particularly limited. Specific examples thereof include the above formulas (Y2-3) to (Y2-12), the above formula (4), the above formula (5), and the formulas (Y-1) to (Y-74).
• the ratio of the structural unit represented by the above formula (8) contained in the component (B) is high, the ratio of the structural unit represented by the above formula (8) is decreased in order to reduce the liquid crystal orientation of the liquid crystal alignment film. Is preferably from 0 to 40 mol%, more preferably from 0 to 20 mol%, based on 1 mol of all structural units.
• the polyamic acid ester which is a polyimide precursor used in the present invention can be synthesized by the following methods (1) to (3).
• the polyamic acid ester can be synthesized by esterifying a polyamic acid obtained from tetracarboxylic dianhydride and diamine. Specifically, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 4 hours. Can be synthesized.
• the esterifying agent those that can be easily removed by purification are preferable.
• the addition amount of the esterifying agent is preferably 2 to 6 molar equivalents per 1 mol of the polyamic acid repeating unit.
• the solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone from the solubility of the polymer, and these may be used alone or in combination. Good.
• the concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
• Polyamic acid ester can be synthesized from tetracarboxylic acid diester dichloride and diamine. Specifically, tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. It can be synthesized by reacting.
• a base pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently.
• the addition amount of the base is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.
• the solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or ⁇ -butyrolactone in view of the solubility of the monomer and polymer, and these may be used alone or in combination.
• the polymer concentration at the time of synthesis is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is difficult to occur and a high molecular weight product is easily obtained.
• the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.
• the polyamic acid ester can be synthesized by polycondensation of a tetracarboxylic acid diester and a diamine. Specifically, tetracarboxylic acid diester and diamine in the presence of a condensing agent, a base, and an organic solvent at 0 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., for 30 minutes to 24 hours, preferably 3 to 15 hours. It can be synthesized by reacting.
• condensing agent examples include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazide.
• Nylmethylmorpholinium O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like.
• the addition amount of the condensing agent is preferably 2 to 3 times the molar amount of the tetracarboxylic acid diester.
• tertiary amines such as pyridine and triethylamine can be used.
• the addition amount of the base is preferably 2 to 4 moles relative to the diamine component from the viewpoint of easy removal and easy obtaining of a high molecular weight product.
• the reaction proceeds efficiently by adding Lewis acid as an additive.
• Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
• the addition amount of the Lewis acid is preferably 0 to 1.0 times mol with respect to the diamine component.
• the synthesis method (1) or (2) is particularly preferable.
• the polyamic acid ester solution obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
• a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
• the polyamic acid which is a polyimide precursor used in the present invention can be synthesized by the following method. Specifically, tetracarboxylic dianhydride and diamine are reacted in the presence of an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 12 hours. Can be synthesized.
• the organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone in view of the solubility of the monomer and polymer. These may be used alone or in combination of two or more.
• the concentration of the polymer is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation hardly occurs and a high molecular weight body is easily obtained.
• the polyamic acid obtained as described above can be recovered by precipitating the polymer by pouring into the poor solvent while thoroughly stirring the reaction solution. Moreover, the powder of polyamic acid refine
• a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
• the polyimide used in the present invention can be produced by imidizing the polyimide precursor such as the polyamic acid ester or polyamic acid.
• a polyimide is produced from a polyamic acid ester
• chemical imidization in which a basic catalyst is added to the polyamic acid solution obtained by dissolving the polyamic acid ester solution or the polyamic acid ester resin powder in an organic solvent is simple.
• Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is hardly lowered during the imidization process.
• Chemical imidation can be performed by stirring the polyamic acid ester to be imidized in an organic solvent in the presence of a basic catalyst.
• 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 ° C. to 140 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 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 ratio of the resulting polymer can be controlled by adjusting the catalyst amount, temperature, and reaction time. 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, re-dissolved in an organic solvent, and the liquid crystal alignment according to the present invention. It is preferable to use an agent.
• the chemical imidation which adds a catalyst to the solution of the said polyamic acid obtained by reaction of a diamine component and tetracarboxylic dianhydride is simple.
• Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is hardly lowered during the imidization process.
• Chemical imidation can be performed by stirring a polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride.
• a basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferred because it has an appropriate basicity for proceeding with the reaction.
• the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
• the temperature for carrying out the imidization reaction is ⁇ 20 ° C. to 140 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 1 to 100 hours.
• the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amic acid group. Is double.
• the imidation ratio of the resulting polymer can be controlled by adjusting the catalyst amount, temperature, and reaction time.
• the liquid crystal aligning agent of the present invention is preferable.
• the polyimide solution obtained as described above can be polymerized by pouring into a poor solvent while thoroughly stirring. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
• the poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.
• the liquid crystal aligning agent of this invention has the form of the solution in which (A) component and (B) component were melt
• the molecular weight of the polymer of the component (A) and the component (B) is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably, in terms of weight average molecular weight. 10,000 to 100,000.
• the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
• the concentration of the polymer containing the component (A) and the component (B) contained in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the setting of the thickness of the coating film to be formed.
• the component (A) in the liquid crystal aligning agent of the present invention is organic in order to exhibit high anisotropy when irradiated with polarized radiation and to exhibit good liquid crystal alignment when used as a liquid crystal alignment film.
• the content is usually 1 to 10% by mass, preferably 2 to 8% by mass, based on the solvent.
• the content of component (B) is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, and more preferably 1 to 5 parts by weight with respect to 100 parts by weight of component (A).
• the organic solvent contained in the liquid crystal aligning agent of the present invention is not particularly limited as long as the (A) component and the (B) component are uniformly dissolved.
• Specific examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, Examples include 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, ⁇ -butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like.
• the liquid crystal aligning agent of the present invention may contain a solvent for improving the uniformity of the coating film when the liquid crystal aligning agent is applied to the substrate in addition to the organic solvent for dissolving the polymer.
• a solvent for improving the uniformity of the coating film when the liquid crystal aligning agent is applied to the substrate in addition to the organic solvent for dissolving the polymer.
• a solvent having a surface tension lower than that of the organic solvent is generally used.
• ethyl cellosolve examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2 -Propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, butyl cellosolve acetate, di Propylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactic acid Isoamyl ester, and the like. Two or more
• Dielectrics or conductive materials for the purpose of changing electrical properties such as conductivity
• silane coupling agents for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate
• a crosslinkable compound for the purpose of increasing, and further an imidization accelerator for the purpose of efficiently proceeding imidization of the polyamic acid when baking the coating film may be added.
• the liquid crystal alignment film of the present invention is a coating film obtained by applying a liquid crystal aligning agent to a substrate, drying and baking, and can be obtained by irradiating this coating film surface with radiation polarized almost linearly.
• the substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a 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 be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like is formed.
• an opaque object such as a silicon wafer can be used as long as it is only on one side of the substrate.
• a material that reflects light such as aluminum can be used as the electrode.
• the method for applying the liquid crystal aligning agent of the present invention include a spin coating method, a printing method, and an ink jet method. Arbitrary temperature and time can be selected for the drying and baking steps after applying the liquid crystal aligning agent of the present invention. Usually, in order to sufficiently remove the organic solvent contained, the organic solvent is dried at 50 ° C. to 120 ° C. for 1 minute to 10 minutes, and then baked at 150 ° C. to 300 ° C. for 5 minutes to 120 minutes.
• the thickness of the coating film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be lowered, and therefore it is 5 to 300 nm, preferably 10 to 200 nm.
• the liquid crystal aligning agent of the present invention is particularly useful when used in a photo-alignment treatment method.
• the photo-alignment treatment method there is a method in which the surface of the coating film is irradiated with radiation polarized in a certain direction, and in some cases, a heat treatment is further performed at a temperature of 150 to 250 ° C. to impart liquid crystal alignment ability.
• a heat treatment is further performed at a temperature of 150 to 250 ° C. to impart liquid crystal alignment ability.
• the wavelength of radiation ultraviolet rays and visible rays having a wavelength of 100 nm to 800 nm can be used. Among these, ultraviolet rays having a wavelength of 100 nm to 400 nm are preferable, and those having a wavelength of 200 nm to 400 nm are particularly preferable.
• radiation may be irradiated while heating the coated substrate at 50 to 250 ° C.
• Dose of the radiation is preferably in the range of 1 ⁇ 10,000mJ / cm 2, and particularly preferably in the range of 100 ⁇ 5,000mJ / cm 2.
• the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the above-described method, performing an alignment treatment, and then preparing a liquid crystal cell by a known method. It is.
• the manufacturing method of a liquid crystal cell is not specifically limited. For example, a pair of substrates on which a liquid crystal alignment film is formed are placed with a liquid crystal alignment film surface inside, preferably with a spacer of 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m, and then surroundings. Is generally sealed with a sealant, and liquid crystal is injected and sealed.
• the method for enclosing the liquid crystal is not particularly limited, and examples thereof include a vacuum method of injecting liquid crystal after reducing the pressure inside the produced liquid crystal cell, and a dropping method of sealing after dropping the liquid crystal.
• the molecular weight of the polyamic acid ester is measured by a GPC (normal temperature gel permeation chromatography) apparatus, and is a number average molecular weight (hereinafter also referred to as Mn) and a weight average molecular weight (hereinafter also referred to as Mw) as polyethylene glycol and polyethylene oxide equivalent values. ) was calculated.
• Mn number average molecular weight
• Mw weight average molecular weight
• GPC device manufactured by Shodex (GPC-101) Column: manufactured by Shodex (series of KD803 and KD805) Column temperature: 50 ° C Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr ⁇ H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystals (o-phosphoric acid) 30 mmol / L, tetrahydrofuran) (THF) is 10 ml / L) 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, 30,000) manufactured by Tosoh Corporation, and polymer laboratory Polyethylene glycol manufactured by the company (peak top molecular weight (Mp) of about 12,000, 4,000, 1,000). In order to avoid the overlap of peaks, the measurement was performed by mixing four types of 900,000, 100,000, 12,000, and
• FFS fringe field switching
• a coating film having a thickness of 100 nm.
• This coating film surface was irradiated with 254 nm ultraviolet light through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Further, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 ⁇ m on which no electrode was formed as a counter substrate, and an orientation treatment was performed.
• 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-2041 manufactured by Merck & Co., Inc.
• VT characteristic voltage-transmittance characteristic
• the obtained polyamic acid ester solution was poured into 872 g of 2-propanol with stirring, and the deposited precipitate was collected by filtration, washed with 290 g of 2-propanol five times, and dried to obtain a polyamic acid ester.
• a resin powder was obtained.
• Mn 13462
• Mw 28462.
• PEE-1 polyamic acid ester solution
• Example 1 In a 20 ml sample tube containing a stirrer, 7.13 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1 and 0.29 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2; 4.60 g of NMP and 3.02 g of BCS were added, and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (A-1).
• PAA-1 polyamic acid solution obtained in Synthesis Example 1
• PAA-2 polyamic acid solution obtained in Synthesis Example 2
• 4.60 g of NMP and 3.02 g of BCS were added, and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (A-1).
• Example 2 In a 20 ml sample tube containing a stirrer, 3.95 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1, 0.19 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2, 3.88 g of NMP, 2.00 g of BCS, and 0.02 g of 1-butylimidazole were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-2).
• Example 3 In a 20 ml sample tube containing a stir bar, 3.79 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1 and 0.37 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2; 3.89 g of NMP, 2.00 g of BCS, and 0.02 g of 1-butylimidazole were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-3).
• PAA-1 polyamic acid solution obtained in Synthesis Example 1
• PAA-2 polyamic acid solution obtained in Synthesis Example 2
• 3.89 g of NMP, 2.00 g of BCS, and 0.02 g of 1-butylimidazole were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-3).
• Example 4 In a 20 ml sample tube containing a stirrer, 7.42 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1 and 0.08 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 3 were used. Then, 4.53 g of NMP and 3.03 g of BCS were stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-4).
• Example 5 After the liquid crystal aligning agent (A-1) obtained in Example 1 was filtered through a 1.0 ⁇ m filter, an ITO electrode having a film thickness of 50 nm as a first layer was insulated on a glass substrate as a second layer. Glass on which FFS driving electrodes having comb-like ITO electrodes (electrode width: 3 ⁇ m, electrode interval: 6 ⁇ m, electrode height: 50 nm) are formed as the third layer, silicon nitride having a thickness of 500 nm as a film The substrate was applied by spin coating. After drying on an 80 ° C. hot plate for 5 minutes, baking was performed in a hot air circulation oven at 230 ° C.
• a coating film having a thickness of 100 nm.
• the surface of the coating film was irradiated with 1500 mJ / cm 2 of 254 nm ultraviolet light through a polarizing plate, and further heated in a hot air circulation oven at 230 ° C. for 30 minutes to obtain a substrate with a liquid crystal alignment film.
• a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 ⁇ m on which no electrode was formed as a counter substrate, and an orientation treatment was performed. 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.
• Liquid crystal MLC-2041 manufactured by Merck & Co., Inc.
• ⁇ V 50 was 1.8 mV.
• Example 6 An FFS drive liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (A-2) obtained in Example 2 was used. As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ⁇ V 50 was 1.3 mV.
• Example 7 An FFS drive liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (A-3) obtained in Example 3 was used. As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ⁇ V 50 was 1.2 mV.
• Example 8 An FFS drive liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (A-4) obtained in Example 4 was used. As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ⁇ V 50 was 1.1 mV.
• Comparative Example 2 An FFS drive liquid crystal cell was produced in the same manner as in Example 6 except that the liquid crystal aligning agent (B-1) obtained in Comparative Example 1 was used. As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ⁇ V 50 was 5.0 mV.
• Example 9 In a 50 ml sample tube containing a stir bar, 16.29 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 4 and 0.45 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2 were added. 7.38 g of BCS, 6.05 g of BCS, and 0.23 g of N- ⁇ - (9-fluorenylmethoxycarbonyl) -N- ⁇ -t-butoxycarbonyl-L-histidine as an imidization accelerator, The mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-5).
• PAA-3 polyamic acid solution obtained in Synthesis Example 4
• PAA-2 polyamic acid solution obtained in Synthesis Example 2
• Example 10 In a 50 ml sample tube containing a stirrer, 10.79 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 4, 0.31 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 6 and NMP , BCS 6.05 g, and N- ⁇ - (9-fluorenylmethoxycarbonyl) -N- ⁇ -t-butoxycarbonyl-L-histidine as an imidization accelerator were added for 30 minutes with a magnetic stirrer. By stirring, a liquid crystal aligning agent (A-6) was obtained.
• Example 11 In a 50 ml sample tube containing a stirrer, 10.90 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 5 and 0.10 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2 were added. 5.08 g, BCS 4.26 g, and 0.15 g of N- ⁇ - (9-fluorenylmethoxycarbonyl) -N- ⁇ -t-butoxycarbonyl-L-histidine as an imidization accelerator, The mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-7).
• Example 12 In a 20 ml sample tube containing a stir bar, 7.45 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 5 and 0.08 g of the polyamic acid ester solution (PAE-2) obtained in Synthesis Example 7 were obtained. 4.39 g of NMP, 3.02 g of BCS, and 0.08 g of N- ⁇ - (9-fluorenylmethoxycarbonyl) -N- ⁇ -t-butoxycarbonyl-L-histidine as an imidization accelerator were added. The mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-8).
• Example 13 In a 20-ml sample tube containing a stirrer, 7.43 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 5 and 0.08 g of the polyamic acid ester solution (PAE-3) obtained in Synthesis Example 8 were obtained. 4.38 g of NMP, 3.11 g of BCS, and 0.08 g of N- ⁇ - (9-fluorenylmethoxycarbonyl) -N- ⁇ -t-butoxycarbonyl-L-histidine as an imidization accelerator were added. The mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-9).
• Example 14 In a 20 ml sample tube containing a stir bar, 7.43 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 5 and 0.08 g of the polyamic acid ester solution (PAE-4) obtained in Synthesis Example 9 were obtained. 4.35 g of NMP, 3.02 g of BCS, and 0.08 g of N- ⁇ - (9-fluorenylmethoxycarbonyl) -N- ⁇ -t-butoxycarbonyl-L-histidine as an imidization accelerator were added. The mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-10).
• Example 15 An FFS drive liquid crystal cell was produced in the same manner as in Example 5, except that the liquid crystal aligning agent (A-5) obtained in Example 9 was used and 254 nm ultraviolet rays were irradiated at 500 mJ / cm 2 . As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ⁇ V 50 was 0.8 mV.
• Example 16 An FFS drive liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (A-6) obtained in Example 10 was used and 254 nm ultraviolet rays were irradiated at 500 mJ / cm 2 . As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ⁇ V 50 was 1.0 mV.
• Example 17 An FFS drive liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (A-7) obtained in Example 11 was used and 254 nm ultraviolet rays were irradiated at 500 mJ / cm 2 . As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ⁇ V 50 was 0.8 mV.
• Example 18 An FFS drive liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (A-8) obtained in Example 12 was used and ultraviolet rays of 254 nm were irradiated at 500 mJ / cm 2 . As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ⁇ V 50 was 0.6 mV.
• Example 19 An FFS drive liquid crystal cell was produced in the same manner as in Example 5, except that the liquid crystal aligning agent (A-9) obtained in Example 13 was used and 254 nm ultraviolet rays were irradiated at 500 mJ / cm 2 . As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ⁇ V 50 was 1.1 mV.
• Example 20 An FFS drive liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (A-10) obtained in Example 14 was used and 254 nm ultraviolet rays were irradiated at 500 mJ / cm 2 . As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ⁇ V 50 was 1.1 mV.
• Example 21 In a 50 ml sample tube containing a stirrer, 12.44 g of the polymer solution (M-1) of the methacrylate obtained in Synthesis Example 10 and 0.32 g of the polyamic acid solution (A-2) obtained in Synthesis Example 2 Then, 2.08 g of NMP and 6.19 g of BCS were added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (A-11).
• Example 22 In a 50 ml sample tube containing a stir bar, 12.41 g of the polymer solution (M-1) of the methacrylate obtained in Synthesis Example 10 and 0.54 g of the polyamic acid solution (A-2) obtained in Synthesis Example 2 Then, 2.09 g of NMP and 6.20 g of BCS were added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (A-12).
• Example 23 Using the liquid crystal aligning agent (A-11) obtained in Example 21, a liquid crystal cell was produced according to the procedure shown below.
• the board A glass substrate having a size of 30 mm ⁇ 40 mm and a thickness of 0.7 mm and having a comb-like pixel electrode formed by patterning an ITO film is used.
• the pixel electrode has a comb-like shape configured by arranging a plurality of dog-shaped electrode elements whose central portion is bent. The width of each electrode element in the short direction is 10 ⁇ m, and the distance between the electrode elements is 20 ⁇ m.
• each pixel Since the pixel electrode forming each pixel is formed by arranging a plurality of bent-shaped electrode elements in the center part, the shape of each pixel is not rectangular, but in the center part like the electrode elements. It has a shape that bends and resembles a bold, bold character.
• 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. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different.
• the electrode element of the pixel electrode is formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel.
• the electrode elements of the pixel electrode are formed so as to form an angle of ⁇ 15 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the application of voltage between the pixel electrode and the counter electrode are mutually in the substrate plane. It is comprised so that it may become a reverse direction.
• the liquid crystal aligning agent (A-11) obtained in Example 21 was spin-coated on the prepared substrate with electrodes. Subsequently, after drying for 90 seconds with an 80 degreeC hotplate, it baked for 30 minutes with a 160 degreeC hot-air circulation type oven, and formed the liquid crystal aligning film with a film thickness of 100 nm.
• the coating film surface was irradiated with 313 nm ultraviolet rays through a polarizing plate at 500 mJ / cm 2 and then heated in a hot air circulation oven at 160 ° C. to obtain a substrate with a liquid crystal alignment film. Further, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 ⁇ m on which no electrode was formed as a counter substrate, and an orientation treatment was performed. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one substrate. Next, the other substrate was bonded so that the liquid crystal alignment film faces each other and the alignment direction was 0 °, and then the sealing agent was cured to produce an empty cell.
• a sealant XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.
• a liquid crystal cell having a configuration of an IPS (In-Plane Switching) mode liquid crystal display element is prepared by injecting liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) into the empty cell by a reduced pressure injection method, sealing the injection port. Obtained.
• the liquid crystal cell for IPS mode obtained by the above method is installed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, the backlight is turned on with no voltage applied, and transmitted light is transmitted.
• the arrangement angle of the liquid crystal cell was adjusted so that the luminance was minimized.
• the rotation angle when the liquid crystal cell was rotated from the angle at which the second region of the pixel was darkest to the angle at which the first region was darkest was calculated as the initial orientation azimuth.
• an AC voltage of 8 V PP was applied at a frequency of 30 Hz in an oven at 60 ° C. for 168 hours.
• the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited and left as it was at room temperature for 1 hour.
• the orientation azimuth was measured in the same manner, and the difference in orientation azimuth before and after AC driving was calculated as an angle ⁇ (deg.). It can be judged that the smaller the difference in orientation orientation before and after AC driving, the better the AC driving image sticking characteristics.
• the difference in orientation azimuth angle before and after AC driving is the angle ⁇ (deg.). It was 0.5 °.
• Example 24 An IPS drive liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal aligning agent (A-12) obtained in Example 22 was used. As a result of evaluating the AC drive burn-in characteristics of this IPS drive liquid crystal cell in the same manner as in Example 23, the difference in orientation azimuth angle before and after AC drive is the angle ⁇ (deg.). It was 0.4 °.
• Comparative Example 4 An IPS drive liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal aligning agent (B-2) obtained in Comparative Example 3 was used. As a result of evaluating the AC drive burn-in characteristics of this IPS drive liquid crystal cell in the same manner as in Example 23, the difference in orientation azimuth angle before and after AC drive is the angle ⁇ (deg.). It was 1.7 °.
• the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention reduces afterimages due to AC driving generated in an IPS driving type or FFS driving type liquid crystal display element, and because the residual charge accumulated by the DC voltage is quickly relaxed, It is particularly useful as a liquid crystal alignment film of an IPS driving method or an FFS driving method having excellent afterimage characteristics or a liquid crystal alignment film of a liquid crystal television.

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