Classifications

• • 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
  • 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

Definitions

• the present invention relates to a liquid crystal alignment treatment agent, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film.
• Liquid crystal display elements are now widely used as display devices that are thin and light.
• a liquid crystal alignment film is used to determine the alignment state of the liquid crystal.
• the pretilt angle of the liquid crystal As one of the characteristics required for the liquid crystal alignment film, there is control of the so-called pretilt angle of the liquid crystal in which the alignment tilt angle of the liquid crystal molecules with respect to the substrate surface is maintained at an arbitrary value. It is known that the magnitude of the pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film.
• the method using a diamine compound having a side chain as a part of the polyimide raw material can control the pretilt angle according to the proportion of the diamine compound used. Is relatively easy and is useful as means for increasing the pretilt angle (see Patent Document 1).
• the diamine compound for increasing the pretilt angle of the liquid crystal has been studied for improving the stability and process dependency of the pretilt angle, and the side chain structure used here is phenyl. Those containing a ring structure such as a group or a cyclohexyl group have been proposed (see Patent Document 2).
• liquid crystal filling has been generally performed by a vacuum injection method in which a liquid crystal is filled between two substrates using a pressure difference between atmospheric pressure and vacuum.
• the liquid crystal injection port is provided only on one side of the substrate, it takes a long time to fill the liquid crystal, and it is difficult to simplify the manufacturing process of the liquid crystal display element. This has been a big problem particularly in the production of liquid crystal TVs and large monitors that have been put into practical use in recent years.
• a liquid crystal dropping method (ODF (One Drop Drop Filling) method
• ODF One Drop Drop Filling
• a liquid crystal is dropped on a substrate on which a liquid crystal alignment film is formed, bonded to the other substrate in a vacuum, and then the sealing material is UV cured to fill the liquid crystal.
• the liquid crystal dropping method has been solved by optimizing the manufacturing process so as to reduce the influence of adsorbed water and impurities, such as reducing the dropping amount of liquid crystal and improving the degree of vacuum at the time of bonding.
• the liquid crystal display element production line becomes larger, it is no longer possible to suppress display unevenness by optimizing the manufacturing process so far, and a liquid crystal alignment film that can reduce alignment unevenness more than before has been demanded.
• the liquid crystal alignment film used there also has a high voltage holding ratio and a direct current voltage, from the viewpoint of suppressing the reduction in contrast of the liquid crystal display elements and reducing the afterimage phenomenon.
• the characteristic that the accumulated charge at the time of applying a small amount of charge or that the charge accumulated by the DC voltage is quickly relaxed has become increasingly important.
• a liquid crystal alignment treatment agent containing a tertiary amine having a specific structure in addition to polyamic acid or an imide group-containing polyamic acid is assumed to have a short time until an afterimage generated by a DC voltage disappears.
• Patent Document 3 those using a liquid crystal alignment treatment agent containing a soluble polyimide using a specific diamine compound having a pyridine skeleton or the like as a raw material (see Patent Document 4), and the like are known. .
• the liquid crystal alignment film is also used for controlling the angle of the liquid crystal with respect to the substrate, that is, the pretilt angle of the liquid crystal.
• the liquid crystal alignment film is required to have an ability to align the liquid crystal vertically (also referred to as a vertical alignment property or a high pretilt angle).
• the liquid crystal alignment film has become important not only for high vertical alignment but also for its stability.
• a liquid crystal display element using a backlight that generates a large amount of heat and has a large amount of light to obtain high brightness such as a car navigation system or a large television, is exposed to high temperature and light irradiation for a long time. There are cases where it is used or left in a dark environment. Under such severe conditions, when the vertical alignment property is lowered, problems such as failure to obtain initial display characteristics or occurrence of unevenness in display occur.
• This alignment unevenness is caused by the adsorbed water and impurities adhering to the surface of the liquid crystal alignment film formed on the substrate being swept away by the liquid crystal dropped in the ODF process, so that the liquid crystal dropping part and the liquid crystal droplets are in contact with each other. It is thought that it occurs due to the difference in the amount of adsorbed water and impurities.
• the voltage holding ratio which is one of the electrical characteristics of the liquid crystal display element
• high stability under the above severe conditions is also required. That is, if the voltage holding ratio is reduced by light irradiation from the backlight, a burn-in defect (also referred to as line burn-in), which is one of display defects of the liquid crystal display element, is likely to occur. A high liquid crystal display element cannot be obtained. Therefore, in the liquid crystal alignment film, in addition to good initial characteristics, for example, it is required that the voltage holding ratio does not easily decrease even after being exposed to light irradiation for a long time. Furthermore, there is a need for a liquid crystal alignment film that can quickly relieve residual charges accumulated by a direct current voltage by light irradiation from a backlight, even for another surface burn-in, which is another burn-in defect.
• the present invention exhibits stable vertical stability even after being exposed to high temperature and light irradiation for a long time, suppresses a decrease in voltage holding ratio, and reduces the residual charge accumulated by a DC voltage.
• An object of the present invention is to provide a liquid crystal alignment film that can reduce liquid crystal alignment unevenness generated by the ODF method quickly.
• it is providing the liquid crystal aligning agent for obtaining said liquid crystal aligning film, and a liquid crystal display element provided with said liquid crystal aligning film.
• the present inventor has found that a liquid crystal aligning agent containing three polymers having a specific structure is extremely effective for achieving the above object, and completes the present invention. It came. That is, the present invention has the following gist.
• Liquid crystal aligning agent containing the following (A) component, (B) component, and (C) component.
• (B) Component A polyimide precursor obtained by reaction of a diamine component containing a diamine having the structure of the following formula [2] and a tetracarboxylic acid component or a polyimide obtained by imidizing the polyimide precursor.
• (X 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —CONH—, —NHCO—, —CON (CH 3 ) -, - N (CH 3) CO -, - COO- and .
• X 2 indicating at least one bond group selected from the group consisting of -OCO- a single bond or - (CH 2) b - ( b 1 X 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— and —
• X 4 represents at least one selected from the group consisting of OCO—, and X 4 has at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a carbon number of 17 to 17
• X 5 may be a benzene ring, Represents at least one cyclic group selected from the group consisting of a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, It may be substituted with a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom, n represents an integer of
• X 6 represents 1 to 18 carbon atoms. Selected from the group consisting of alkyl groups having 2 to 18 carbon atoms, fluorine-containing alkyl groups having 1 to 18 carbon atoms, alkoxy groups having 1 to 18 carbon atoms and fluorine-containing alkoxy groups having 1 to 18 carbon atoms.
• (W 1 is —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCO—, —CON (CH 3 ) — and —N (CH 3 )
• W 3 represents a single bond, —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH 3 ) —, At least one selected from the group consisting of —N (CH 3 ) CO— and —O (CH 2 ) m — (m represents an integer of 1 to 5), W 4 represents a nitrogen-containing aromatic heterocyclic ring; Show.
• Y represents the structure of the following formula [3-1] or [3-2].
• M1 represents an integer of 1 to 4.
• a and b each represents an integer of 0 to 4)
• Z represents at least one structure selected from the group consisting of the structures of the following formulas [4a] to [4k].
• Z 1 to Z 4 each independently represents at least one selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom and a benzene ring.
• Z 5 and Z 6 each independently represent a hydrogen atom or methyl Group.
• liquid crystal aligning agent according to any one of the above (1) to (10), which contains at least one solvent selected from the group consisting of solvents.
• 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.
• a crosslinkable compound selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group and a cyclocarbonate group, a crosslinkable compound selected from the group consisting of a hydroxy group, a hydroxyalkyl group and a lower alkoxyalkyl group.
• a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of (1) to (12).
• a liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates.
• the liquid crystal alignment film according to (13) or (14) which is used for a liquid crystal display device produced through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.
• a liquid crystal alignment film having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates.
• the liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film exhibiting stable vertical alignment even after being exposed to high temperature and light irradiation for a long time.
• a liquid crystal alignment film that can reduce liquid crystal alignment unevenness generated by the ODF method.
• a liquid crystal alignment film that suppresses the decrease in the voltage holding ratio and quickly relaxes the residual charges accumulated by the DC voltage.
• the specific structure (1) in the specific polymer (A) has a divalent organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring, a heterocyclic ring or a steroid skeleton.
• the side chain structure of these rings and organic groups is a structure that is more rigid than a long-chain alkyl group that is a conventional technique for vertically aligning liquid crystals and is stable to light such as ultraviolet rays.
• the liquid crystal alignment film obtained from the liquid crystal aligning agent having the specific structure (1) exhibits higher vertical alignment than the prior art, and further, even when exposed to light irradiation for a long time, the vertical alignment Can be suppressed. In addition, even when exposed to light irradiation, it is possible to reduce the voltage holding ratio and to suppress the decomposition products of side chain components that accumulate residual charges due to a direct current voltage.
• the specific structure (1) is a highly hydrophobic structure, it is possible to suppress adsorbed water and impurities generated in the liquid crystal display element manufacturing process from adhering to the surface of the liquid crystal alignment film. Therefore, liquid crystal alignment unevenness generated by the ODF method can be reduced.
• the nitrogen-containing heterocycle of the specific structure (2) in the specific polymers (A) and (B) is an electrostatic such as salt formation or hydrogen bonding with the carboxy group or hydroxy group in the specific polymer (C). By being linked by the interaction, charge transfer easily occurs between the nitrogen-containing aromatic heterocycle and the carboxy group or the hydroxy group.
• the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has excellent reliability.
• the specific diamine (1) in this invention has the specific structure (1) of following formula [1].
• X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and n are as defined above, but X 1 is a single bond, from the viewpoint of availability of raw materials and ease of synthesis, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O— or —COO— is preferable.
• a single bond — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
• X 2 is preferably a single bond or — (CH 2 ) b — (b is an integer of 1 to 10).
• X 3 is preferably a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O— or —COO— from the viewpoint of ease of synthesis. More preferred is a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
• X 4 is preferably an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton from the viewpoint of ease of synthesis.
• X 5 is preferably a benzene ring or a cyclohexane ring.
• X 6 represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine containing 1 to 10 carbon atoms Alkoxy groups are preferred.
• it is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
• Particularly preferred is an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkoxy group having 1 to 9 carbon atoms.
• n is preferably 0 to 3 in view of availability of raw materials and ease of synthesis. More preferred is 0-2.
• the organic group having 17 to 51 carbon atoms having a steroid skeleton in the present invention has 12 to 20 carbon atoms having a steroid skeleton.
• An organic group having 12 to 25 carbon atoms having a steroid skeleton is to be read as an organic group having 17 to 51 carbon atoms having a steroid skeleton.
• (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) to (2-315) , (2-364) to (2-387), (2-436) to (2-483), or (2-603) to (2-615) are preferred.
• Particularly preferred combinations are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-603) to (2- 606), (2-607) to (2-609), (2-611), (2-612) or (2-624).
• X represents the structure of the formula [1].
• the details and preferred combinations of X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , and n in the formula [1a] are as described in the formula [1].
• n1 represents an integer of 1 to 4. Among these, an integer of 1 is preferable.
• a 4 in the formula [2-13] represents a linear or branched alkyl group having 3 to 18 carbon atoms.
• R 3 in the formulas [2-4] to [2-6] represents at least one selected from the group consisting of —O—, —CH 2 O—, —COO—, and —OCO—. .
• preferred diamines can exhibit a stable pretilt angle, can reduce liquid crystal alignment unevenness generated by the ODF method, and have a high effect of suppressing a decrease in voltage holding ratio after being exposed to light irradiation for a long time.
• the specific diamine (1) is preferably used in an amount of 10 to 70 mol% with respect to the entire diamine component in the specific polymer (A). More preferred is 15 to 70 mol%, and particularly preferred is 20 to 60 mol%.
• the specific polymer (B) 0 to 40 mol% is preferable with respect to the entire diamine component. More preferred is 0 to 30 mol%, and particularly preferred is 0 to 25 mol%.
• the specific polymer (C) 0 to 20 mol% is preferable. More preferred is 0 to 10 mol%.
• specific diamine (1) is 1 type or depending on characteristics, such as the solubility to the solvent of a polyimide-type polymer, the liquid crystal aligning property at the time of making a liquid crystal aligning film, and the optical characteristic of a liquid crystal display element. Two or more kinds can be mixed and used.
• the specific diamine (2) of the present invention has a specific structure represented by the following formula [2].
• W 1 , W 2 , W 3 and W 4 are as defined above. Among these, the following are preferable.
• W 1 is preferably —O—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCO—, —CON (CH 3 ) — or —N (CH 3 ) CO—. More preferred is —O—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCO— or —CON (CH 3 ) — from the viewpoint of ease of synthesis. Particularly preferred is —O—, —CONH— or —CH 2 O—.
• W 2 represents at least one selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring and an aromatic ring.
• the alkylene group having 1 to 20 carbon atoms may be linear or branched. Moreover, you may have an unsaturated bond. Among these, an alkylene group having 1 to 10 carbon atoms is preferable from the viewpoint of ease of synthesis.
• non-aromatic ring examples include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, and a cyclotridecane ring.
• a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, or an adamantane ring is preferable.
• aromatic ring examples include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring and phenalene ring.
• a benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring or anthracene ring is preferred.
• W 2 includes a single bond, an alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, and a tetrahydronaphthalene ring , A fluorene ring or an anthracene ring is preferred.
• a single bond an alkylene group having 1 to 5 carbon atoms, cyclohexane, because of the ease of synthesis and quickening of the residual charge accumulated by direct current voltage after exposure to light irradiation for a long time.
• a ring or a benzene ring is preferred.
• W 3 is preferably a single bond, —O—, —COO—, —OCO—, or —O (CH 2 ) m — (m represents an integer of 1 to 5). More preferable is a single bond, —O—, —OCO— or —O (CH 2 ) m — (m is 1 to 5) from the viewpoint of ease of synthesis.
• W 4 represents a nitrogen-containing aromatic heterocycle and contains at least one structure selected from the group consisting of the following formula [a], formula [b] and formula [c]. (Z represents an alkyl group having 1 to 5 carbon atoms.)
• a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, or a benzimidazole ring is preferable. More preferable is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring from the viewpoint that relaxation of residual charges accumulated by direct current voltage after being exposed to light irradiation for a long time is accelerated.
• W 3 in the formula [2], expressions included in the W 4 [a], is preferably bonded with a substituent nonadjacent the formula [b] and the formula [c].
• Tables 1 to 31 show preferable combinations of W 1 , W 2 , W 3 , and W 4 .
• (a-43) to (a-49), (a-57) to (a-63), (a-218) to (a-224), (a-232) to (a-238) , (A-323) to (a-329), (a-337) to (a-343), (a-428) to (a-434), or (a-442) to (a-448) Is preferred. More preferably, (a-44), (a-45), (a-58) or (A-59) combination.
• W represents the structure of the formula [2]. Details and preferred combinations of W 1 , W 2 , W 3 , and W 4 are as described in the above formula [2].
• p1 represents an integer of 1 to 4. Among these, 1 is preferable from the viewpoint of ease of synthesis.
• the use ratio of the specific diamine (2) is preferably the following use ratio.
• 1 to 60 mol% is preferable with respect to the entire diamine component. More preferred is 5 to 50 mol%, and particularly preferred is 10 to 50 mol%.
• 5 to 100 mol% is preferable based on the entire diamine component. More preferred is 10 to 95 mol%, and particularly preferred is 15 to 95 mol%.
• specific polymer (C) 0 to 20 mol% is preferable. More preferred is 0 to 10 mol%, and particularly preferred is 0 mol%.
• specific diamine (2) is 1 type or according to characteristics, such as the solubility to the solvent of a polyimide-type polymer, the liquid crystal aligning property at the time of setting it as a liquid crystal aligning film, and the optical characteristic of a liquid crystal display element. Two or more kinds can be mixed and used.
• the specific diamine (3) in the present invention has at least one substituent selected from the group consisting of a carboxy group (COOH group) and a hydroxy group (OH group).
• Y represents the structure of the following formula [3-1] or [3-2].
• m1 represents an integer of 1 to 4.
• a represents an integer of 0 to 4.
• the integer of 0 or 1 is preferable from the point of the availability of a raw material or the ease of a synthesis
• b represents an integer of 0 to 4.
• the integer of 0 or 1 is preferable from the point of the availability of a raw material or the ease of a synthesis
• 2,4-diaminophenol, 3,5 is preferable because it suppresses a decrease in the voltage holding ratio after being exposed to light irradiation for a long time and accelerates the relaxation of residual charges accumulated by a DC voltage.
• -Diaminophenol, 3,5-diaminobenzyl alcohol or 3,5-diaminobenzoic acid are preferred.
• the use ratio of the specific diamine (3) is preferably the following use ratio.
• the specific polymer (A) 0 to 20 mol% is preferable with respect to the entire diamine component. More preferred is 0 to 10 mol%, and particularly preferred is 0 mol%.
• the specific polymer (B) 0 to 20 mol% is preferable based on the entire diamine component. More preferred is 0 to 10 mol%, and particularly preferred is 0 mol%.
• the specific polymer (C) 40 to 100 mol% is preferable. More preferred is 50 to 100 mol%, and particularly preferred is 60 to 100 mol%.
• specific diamine (3) is 1 type or depending on characteristics, such as the solubility to the solvent of a polyimide-type polymer, the liquid crystal aligning property at the time of setting it as a liquid crystal aligning film, and the optical characteristic of a liquid crystal display element. Two or more kinds can be mixed and used.
• the specific polymers (A), (B) and (C) in the present invention mean the components (A), (B) and (C), respectively, and are polyimide precursors or polyimides (collectively polyimides). Also referred to as a polymer). They are preferably a polyimide precursor or polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.
• the polyimide precursor has a structure of the following formula [A].
• R 1 represents a tetravalent organic group.
• R 2 represents a divalent organic group.
• a 1 and A 2 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
• a 3 And A 4 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acetyl group, and nA represents a positive integer.
• Examples of the diamine component include diamines having two primary or secondary amino groups in the molecule.
• Examples of the tetracarboxylic acid component include tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds, and tetracarboxylic acid dialkyl ester dihalide compounds.
• the polyimide-based polymer is obtained by using the tetracarboxylic dianhydride represented by the following formula [B] and the diamine represented by the following formula [C] as raw materials.
• Polyamic acid composed of a structural formula of repeating units or polyimide obtained by imidizing the polyamic acid is preferable.
• R 1 , R 2 and nA are as defined in the formula [A].
• the polymer of the formula [D] obtained above by an ordinary synthesis method is added to the alkyl group having 1 to 8 carbon atoms of A 1 and A 2 in the formula [A] and the formula [A]. It is also possible to introduce an alkyl group having 1 to 5 carbon atoms or an acetyl group of A 3 and A 4 .
• diamines may be used for the diamine component of any one of the specific polymers (A), (B) and (C). It can be used for the diamine component of the coalescence.
• other diamines may be used alone or in combination of two or more depending on the solubility of the polyimide polymer in the solvent, the liquid crystal alignment when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. Can be used in combination.
• the tetracarboxylic acid component in at least one of the specific polymers (A), (B), and (C) includes a tetracarboxylic dianhydride represented by the following formula [4] (also referred to as a specific tetracarboxylic acid component). Is preferably used. More preferably, a specific tetracarboxylic acid component is used for all the specific polymers.
• Z represents at least one structure selected from the group consisting of the structures of the formulas [4a] to [4k].
• Z represents the formula [4a], the formula [4c], the formula [4d], the formula [4e], the formula [4f], the formula from the viewpoint of the ease of synthesis and the ease of polymerization reactivity when producing the polymer.
• [4g] or formula [4k] is preferred. More preferable is the formula [4a], the formula [4e], the formula [4f], the formula [4g], or the formula [4k]. Particularly preferable is the formula [4e], the formula [4f], the formula [4g], or the formula [4k].
• the use ratio of the specific tetracarboxylic acid component is preferably 1 mol% or more with respect to the total tetracarboxylic acid component. More preferably, it is 5 mol% or less. Particularly preferred is 10 mol% or more, and most preferred is 10 to 90 mol% from the viewpoint of suppressing a decrease in voltage holding ratio after being exposed to light irradiation for a long time.
• the usage-amount shall be 20 mol% or more of the whole tetracarboxylic-acid component.
• tetracarboxylic acid component may be a tetracarboxylic acid component having a structure of the formula [4e], the formula [4f], the formula [4g], or the formula [4k].
• tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used as long as the effects of the present invention are not impaired.
• Specific examples include other tetracarboxylic acid components described on pages 27 to 28 of International Publication No. WO2013 / 125595 (published 2013.8.29).
• the specific tetracarboxylic acid component and other tetracarboxylic acid components can be used alone or in combination of two or more according to the respective characteristics.
• the specific polymer (A) is a polyimide precursor obtained by a reaction between a diamine component containing the specific diamine (1) and the specific diamine (2) and a tetracarboxylic acid component or a polyimide obtained by imidizing the polyimide precursor. is there.
• the use ratio of specific diamine (1) and specific diamine is as follows. That is, the specific diamine (1) is preferably 10 to 70 mol% with respect to the entire diamine component. More preferred is 15 to 70 mol%, and particularly preferred is 20 to 60 mol%.
• the specific diamine (2) is preferably 1 to 60 mol% with respect to the entire diamine component. More preferred is 5 to 50 mol%, and particularly preferred is 10 to 50 mol%.
• the specific diamine (3) is preferably 0 to 20 mol% with respect to the entire diamine component, because liquid crystal alignment unevenness generated by the ODF method can be reduced. More preferable is 0 to 10 mol%, and particularly preferable is 0 mol%, that is, the specific diamine (3) is not used.
• the specific polymer (B) is a polyimide precursor obtained by a reaction between a diamine component containing the specific diamine (2) and a tetracarboxylic acid component or a polyimide obtained by imidizing the polyimide precursor.
• the usage-amount of specific diamine (2) is as follows. That is, the specific diamine (2) is preferably 5 to 100 mol% with respect to the entire diamine component. More preferred is 10 to 95 mol%, and particularly preferred is 15 to 95 mol%. In the specific diamine (1), 0 to 40 mol% is preferable with respect to the entire diamine component. More preferred is 0 to 30 mol%, and particularly preferred is 0 to 25 mol%.
• the usage ratio (mol%) of the specific diamine (1) in the specific polymer (B) to the entire diamine component is 1.0% of the usage ratio (mol%) of the specific diamine (1) in the specific polymer (A).
• the use ratio (mol%) is such that the ratio is less than 1.0.
• the ratio is preferably 0.01 to 0.9.
• the specific diamine (3) is preferably 0 to 20 mol% with respect to the total diamine component. More preferably, it is 0 to 10 mol%, and particularly preferable is 0 mol%, that is, the specific diamine is added to the diamine component of the specific polymer (B) from the viewpoint that liquid crystal alignment unevenness generated by the ODF method can be reduced. (3) is not used.
• the specific polymer (C) is a polyimide precursor obtained by a reaction of a diamine component containing the specific diamine (3) and a tetracarboxylic acid component or a polyimide obtained by imidizing the polyimide precursor.
• the usage-amount of specific diamine (3) is as follows. That is, the specific diamine (3) is preferably 40 to 100 mol% with respect to the entire diamine component. More preferred is 50 to 100 mol%, and particularly preferred is 60 to 100 mol%.
• the content is preferably 0 to 20 mol% with respect to the entire diamine component. More preferred is 0 to 10 mol%.
• the usage ratio (mol%) of the specific diamine (1) in the specific polymer (C) to the entire diamine component is 1.0% of the usage ratio (mol%) of the specific diamine (1) in the specific polymer (A).
• the use ratio (mol%) is such that the ratio is less than 1.0.
• the ratio is preferably 0.01 to 0.4.
• the specific diamine (3) is preferably 0 to 20 mol% based on the entire diamine component. More preferably, it is 0 to 10 mol%, and particularly preferable is that the reduction of the voltage holding ratio after being exposed to light irradiation for a long time is suppressed and the residual charge accumulated by the DC voltage is alleviated. From the point of speed, it is 0 mol%, that is, the specific diamine (3) is not used for the diamine component of the specific polymer (C).
• the method for producing all the specific polymers is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, by reacting at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydride and its derivative, a diamine component consisting of one or more diamines, The method of obtaining a polyamic acid is mentioned. Specifically, tetracarboxylic dianhydride and primary or secondary diamine are polycondensed to obtain polyamic acid, tetracarboxylic acid and primary or secondary diamine are subjected to dehydration polycondensation reaction. A method of obtaining a polyamic acid or a method of obtaining a polyamic acid by reacting a tetracarboxylic acid dihalide with a primary or secondary diamine is used.
• a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group and a primary or secondary diamine, a tetracarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group, and a primary a method of reacting with a secondary diamine or a method of converting a carboxy group of a polyamic acid into an ester is used.
• polyimide a method is used in which the polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.
• the reaction between the diamine component and the tetracarboxylic acid component is usually performed in an organic solvent with the diamine component and the tetracarboxylic acid component.
• the organic solvent used at that time is not particularly limited as long as the produced polyimide precursor is dissolved. Although the specific example of the organic solvent used for reaction below is given, it is not limited to these examples.
• N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-imidazolidinone, etc. Can be mentioned.
• the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or a solvent represented by the following formula [D-1] to formula [D-3] Can be used.
• 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.
• a solvent that does not dissolve the polyimide precursor may be used by mixing with the above solvent as long as the generated polyimide precursor does not precipitate.
• moisture content in an organic solvent inhibits a polymerization reaction and also causes the produced polyimide precursor to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent.
• the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic acid component is added as it is, or dispersed in the organic solvent or Examples include a method of adding by dissolving, a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent, and a method of adding a diamine component and a tetracarboxylic acid component alternately. Any of these methods may be used.
• the polymerization temperature can be selected from -20 ° C to 150 ° C, but is preferably in the range of -5 ° C to 100 ° C.
• the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. It becomes.
• the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to the normal polymerization reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyimide precursor produced.
• Polyimide is a polyimide obtained by ring closure of the polyimide precursor, and the ring closure rate (also referred to as imidation rate) of the amic acid group does not necessarily need to be 100%, and can be arbitrarily adjusted according to the application and purpose. can do.
• the specific polymers are the polyimides which imidated the polyimide precursor.
• the imidation ratio in that case is as follows. That is, the specific polymer (A) is preferably 50 to 90%. More preferred is 55 to 90%, and particularly preferred is 60 to 90%.
• the specific polymer (B) is preferably 50 to 95%. More preferred is 55 to 95%, and particularly preferred is 60 to 95%.
• the specific polymer (C) is preferably 50 to 90%. More preferred is 60 to 90%, and particularly preferred is 60 to 80%.
• Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is, or catalytic imidization in which a catalyst is added to the polyimide precursor solution.
• the temperature when the polyimide precursor is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.
• the catalytic imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C.
• 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 amido acid group. Is double.
• the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Of these, pyridine is preferable because it has a basicity suitable for advancing the reaction.
• the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Of these, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
• the imidation ratio by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.
• the reaction solution may be poured into a solvent and precipitated.
• the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water.
• the polymer precipitated in the solvent can be recovered by filtration, and then dried at normal temperature or under reduced pressure at room temperature or by heating.
• the impurities in the polymer can be reduced.
• the solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further improved.
• the molecular weight of the polyimide-based polymer is the weight average molecular weight measured by GPC (Gel Permeation Chromatography) when considering the strength of the liquid crystal alignment film obtained therefrom, the workability at the time of forming the liquid crystal alignment film, and the coating properties. It is preferably 5,000 to 1,000,000. Of these, 10,000 to 150,000 is preferable. As described above, all the specific polymers in the present invention exhibit stable vertical stability even after being exposed to high temperature and light irradiation for a long time, and maintain voltage even after being exposed to light irradiation for a long time. It is preferable that it is the polyimide which carried out the catalyst imidation of the polyimide precursor mentioned above from the point which can suppress the fall of a rate. The imidation ratio at that time is preferably in the above-described range.
• the use ratio of the specific polymers (A), (B), and (C) in the liquid crystal aligning agent is 30 to 300 parts of the specific polymer (B) with respect to 100 parts of the specific polymer (A).
• the polymer (C) is preferably 60 to 500 parts. More preferably, the specific polymer (B) is 50 to 250 parts, the specific polymer (C) is 100 to 350 parts, and particularly preferably the specific polymer (B) is 50 to 200 parts.
• the specific polymer (C) is 100 to 300 parts.
• All of the polymer components in the liquid crystal aligning agent may be specific polymers, or other polymers may be mixed. At that time, the content of other polymers is preferably 0.5 to 15 parts with respect to 100 parts of all the specific polymers. More preferred is 1 to 10 parts. Examples of other polymers include cellulosic polymers, acrylic polymers, methacrylic polymers, polystyrenes, polyamides, and polysiloxanes.
• the solvent in the liquid crystal aligning agent is preferably 70 to 99.9% in terms of forming a uniform liquid crystal aligning film by coating. This content can be appropriately changed depending on the film thickness of the target liquid crystal alignment film.
• the solvent used for the liquid-crystal aligning agent of this invention will not be specifically limited if it is a solvent (it is also called a good solvent) which dissolves all the specific polymers.
• a good solvent is given to the following, it is not limited to these.
• N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone is preferably used.
• the good solvent in the liquid crystal aligning agent is preferably 10 to 100% of the total solvent contained in the liquid crystal aligning agent. More preferred is 20 to 90%. Particularly preferred is 30 to 80%.
• a solvent also referred to as a poor solvent
• a poor solvent that improves the coating properties and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied is used as the liquid crystal alignment treatment agent. it can.
• the specific example of a poor solvent is given to the following, it is not limited to these.
• 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, or the above formulas [D-1] to [D -3] is preferably used.
• These poor solvents are preferably 1 to 70% of the total solvent contained in the liquid crystal aligning agent. More preferred is 1 to 60%. Particularly preferred is 5 to 60%.
• the liquid crystal aligning agent includes a crosslinkable compound selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group and a cyclocarbonate group, a hydroxy group, a hydroxyalkyl group and a lower alkoxyalkyl group. It is preferable to introduce a crosslinkable compound selected from the group consisting of the above or a crosslinkable compound having a polymerizable unsaturated bond group (also collectively referred to as a specific crosslinkable compound). In that case, it is necessary to have two or more of these groups in the compound.
• crosslinkable compound having an epoxy group or an isocyanate group specifically, an epoxy group or an isocyanate group described on pages 37 to 38 of International Publication WO2013 / 125595 (published 2013.8.29) is used.
• crosslinkable compound having an oxetane group examples include crosslinkable compounds represented by the formulas [4a] to [4k] described on pages 58 to 59 of International Publication WO2011 / 132751.
• crosslinkable compound having a cyclocarbonate group examples include the crosslinkability represented by the formulas [5-1] to [5-42] described on pages 76 to 82 of International Publication WO2012 / 014898. Compounds.
• crosslinkable compound having at least one group selected from the group consisting of a hydroxy group, a hydroxyalkyl group and a lower alkoxyalkyl group, specifically, International Publication No. 2013/125595 (published 2013.8.29) Melamine derivatives or benzoguanamine derivatives described on pages 39 to 40, and formulas [6-1] to formulas described on pages 62 to 66 of International Publication No. WO2011 / 132751 (published 2011.10.20) And a crosslinkable compound represented by [6-48].
• crosslinkable compound having a polymerizable unsaturated bond examples include crosslinks having a polymerizable unsaturated bond described on pages 40 to 41 of International Publication No. WO2013 / 125595 (published 2013.8.29). Compound.
• the content of the specific crosslinkable compound in the liquid crystal aligning agent is preferably 0.1 to 100 parts with respect to 100 parts of all polymer components. More preferably, the amount is 0.1 to 50 parts because the crosslinking reaction proceeds and the desired effect is exhibited. Particularly preferred is 1 to 30 parts.
• the liquid crystal alignment treatment agent of the present invention in order to promote charge transfer in the liquid crystal alignment film and promote charge release of the device, pages 69 to 73 of International Publication No. WO2011 / 132751 (2011.10.27 published).
• the nitrogen-containing heterocyclic amine of the formula [M1] to the formula [M156] listed in the above can be added.
• the amine may be added directly to the liquid crystal aligning agent, but it is preferable to add the amine after forming a solution with a suitable solvent at a concentration of 0.1 to 10%, preferably 1 to 7%.
• the solvent is not particularly limited as long as it is an organic solvent that dissolves the specific polymer.
• a compound that improves the uniformity of the thickness of the liquid crystal alignment film and the surface smoothness when the liquid crystal alignment treatment agent is applied can be used as the liquid crystal alignment treatment agent.
• a compound that improves the adhesion between the liquid crystal alignment film and the substrate can be used.
• the compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specific examples include surfactants described on pages 42 to 43 of International Publication WO2013 / 125595 (published 2013.8.29).
• the amount of these surfactants used is preferably 0.01 to 2 parts by weight, more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of all polymer components contained in the liquid crystal aligning agent. Part.
• Specific examples of compounds that improve the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds and epoxy group-containing compounds. Specific examples include compounds described on pages 43 to 44 of International Publication No. WO2013 / 125595 (published 2013.8.29).
• the use ratio of the compound to be adhered to these substrates is preferably 0.1 to 30 parts, more preferably 1 to 20 parts with respect to 100 parts of all the polymer components contained in the liquid crystal aligning agent. Part. If it is less than 0.1 part, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts, the storage stability of the liquid crystal aligning agent may be deteriorated.
• the liquid crystal aligning agent includes a dielectric or conductive material for changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired. Substances may be added.
• the liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film by applying and baking on a substrate and then performing alignment treatment by rubbing treatment, light irradiation or the like. Further, in the case of vertical alignment use etc., it can be used as a liquid crystal alignment film without alignment treatment.
• the substrate used at this time is not particularly limited as long as it is a highly transparent substrate.
• a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplifying the process, it is preferable to use a substrate on which an ITO electrode or the like for driving the liquid crystal is formed.
• an opaque substrate 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 as an electrode in this case.
• a method for applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, an inkjet method, or the like is generally used. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, or a spray method, and these may be used depending on the purpose.
• After applying the liquid crystal aligning agent on the substrate it is preferably 30 to 300 ° C., depending on the solvent used for the liquid crystal aligning agent, by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven.
• the liquid crystal alignment film can be obtained by evaporating the solvent at a temperature of 30 to 250 ° C.
• the thickness of the liquid crystal alignment film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 10 to 100 nm.
• the fired liquid crystal alignment film is treated by rubbing or irradiation with polarized ultraviolet rays.
• 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 alignment treatment agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
• a method for producing a liquid crystal cell for example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside, There is a method of pasting the other substrate and injecting liquid crystal under reduced pressure, or a method in which the substrate is pasted after the liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed (ODF method), etc. It can be illustrated.
• the liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board
• the composition is also preferably used for a liquid crystal display device produced through a step of polymerizing a polymerizable compound by at least one of irradiation with active energy rays and heating while applying a voltage between electrodes.
• ultraviolet rays are suitable as the active energy ray.
• the wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm.
• the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C.
• the liquid crystal display element controls the pretilt of liquid crystal molecules by the PSA method.
• a small amount of a photopolymerizable compound for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, a predetermined voltage is applied to the liquid crystal layer and an ultraviolet ray is applied to the photopolymerizable compound.
• the pretilt of the liquid crystal molecules is controlled by the produced polymer.
• the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer.
• the PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by the rubbing process. That is, in the liquid crystal display element of the present invention, after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent by the above-described method, a liquid crystal cell is prepared, and a polymerizable compound is polymerized by at least one of ultraviolet irradiation and heating. Thus, the alignment of liquid crystal molecules can be controlled.
• a liquid crystal cell is manufactured by the manufacturing method described above.
• a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed.
• the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule.
• the polymerizable compound is preferably 0.01 to 10 parts, more preferably 0.1 to 5 parts, relative to 100 parts of the liquid crystal component. When the polymerizable compound is less than 0.01 part, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled.
• the polymerizable compound When the polymerizable compound is more than 10 parts, the amount of unreacted polymerizable compound increases and the liquid crystal display element is burned. Characteristics are degraded. After the liquid crystal cell is produced, the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell. Thereby, the alignment of the liquid crystal molecules can be controlled.
• the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates. It can also be used for a liquid crystal display element manufactured through a process of arranging a liquid crystal alignment film containing and applying a voltage between electrodes, that is, an SC-PVA mode.
• ultraviolet rays are suitable as the active energy ray.
• the wavelength of ultraviolet rays is 300 to 400 nm, and more preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, more preferably 60 to 80 ° C.
• a method of adding a compound containing this polymerizable group to the liquid crystal aligning agent A method using a coalescing component may be mentioned.
• An example of the production of an SC-PVA mode liquid crystal cell is as follows. That is, a liquid crystal cell is manufactured by the manufacturing method described above. Thereafter, the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.
• D1 p-phenylenediamine
• D2 m-phenylenediamine
• D3 1,3-diamino-4-octadecyloxybenzene
• E1 1,2,3,4-cyclobutanetetracarboxylic dianhydride
• E2 bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride
• E3 the following formula [E3]
• E4 tetracarboxylic dianhydride of the following formula [E4]
• E5 tetracarboxylic dianhydride of the following formula [E5]
• NMP N-methyl-2-pyrrolidone
• NEP N-ethyl-2-pyrrolidone
• ⁇ -BL ⁇ -butyrolactone
• BCS ethylene glycol monobutyl ether
• PB propylene glycol monobutyl ether
• DME dipropylene glycol dimethyl ether
• DPM Dipropylene glycol monomethyl ether
• 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 the reference proton for one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) The number ratio.
• This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash
• the imidation ratio of this polyimide was 70%, Mn was 18,600, and Mw was 48,800.
• Example 3 and Example 8 “Evaluation of inkjet coating properties of liquid crystal alignment treatment agents" Using the liquid crystal aligning agent obtained in Example 3 and Example 8 which will be described later, the inkjet coating property was evaluated. Specifically, a substrate with an ITO (indium tin oxide) electrode (length: 100 mm) obtained by pressure-filtering these liquid crystal alignment treatment agents with a membrane filter having a pore diameter of 1 ⁇ m and washing with pure water and IPA (isopropyl alcohol).
• ITO indium tin oxide
• the coating was performed on an ITO surface having a width of 100 mm and a thickness of 0.7 mm under the conditions of a coating area of 70 ⁇ 70 mm, a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm, and a coating speed of 40 mm / second.
• HIS-200 manufactured by Hitachi Plant Technology Co., Ltd.
• the time from application to temporary drying was 60 seconds, and the temporary drying was performed on a hot plate at 70 ° C. for 5 minutes. The applicability was evaluated by visually observing the coating surface of the substrate with a liquid crystal alignment film obtained above.
• the coating film surface was visually observed under a sodium lamp to confirm the presence or absence of pinholes.
• the coating film surface was visually observed under a sodium lamp to confirm the presence or absence of pinholes.
• the liquid crystal aligning agent of Example 3 and Example 8 produced a board
• a heat treatment was carried out at 30 ° C. for 30 minutes to obtain an ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm.
• the substrate surface of this substrate is rubbed with a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.1 mm. did.
• a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.1 mm.
• two substrates after the rubbing treatment were prepared, combined with a 6 ⁇ m spacer sandwiched with the coating surface on the inside, and the periphery was adhered with a sealing agent to produce an empty cell.
• MLC-6608 manufactured by Merck Japan
• the pretilt angle was measured. Specifically, the measurement was performed with a liquid crystal cell after performing an isotropic treatment of liquid crystal (heat treatment at 95 ° C. for 5 minutes) and a liquid crystal cell after heat treatment (heat treatment at 120 ° C. for 5 hours). Further, a liquid crystal cell produced under the same conditions as described above was subjected to isotropic treatment, and then the liquid crystal cell after irradiation with 10 J / cm 2 of ultraviolet rays in terms of 365 nm was also measured. The pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON).
• ultraviolet irradiation was performed using a desktop UV curing device (HCT3B28HEX-1) (manufactured by Senlite). Evaluation is performed after heat treatment (also referred to after high temperature treatment) and after irradiation with ultraviolet rays (also referred to after ultraviolet irradiation) with respect to the pretilt angle after liquid crystal isotropic treatment (also referred to as initial). The smaller the change in the pretilt angle, the better the evaluation. Tables 37 to 39 show the values of the respective pretilt angles.
• liquid crystal alignment unevenness generated by ODF method was evaluated using the liquid crystal aligning agents obtained in Examples and Comparative Examples described later. Specifically, these liquid crystal aligning agents were pressure filtered through a membrane filter having a pore diameter of 1 ⁇ m and washed with pure water and IPA (100 mm long ⁇ 100 mm wide, 0.7 mm thick). The ITO substrate is spin-coated on the ITO surface and heated at 100 ° C. for 5 minutes on a hot plate, and at 230 ° C. for 30 minutes in a heat-circulating clean oven. Got.
• the liquid crystal aligning agent of Example 3 and Example 8 produced a board
• a heat treatment was carried out at 30 ° C. for 30 minutes to obtain an ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm.
• the substrate surface of this substrate is rubbed with a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.1 mm. did.
• a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.1 mm.
• two substrates, the substrate subjected to the rubbing treatment and the substrate not treated, were prepared, and a 6 ⁇ m spacer was sprayed on the coating surface of the substrate not treated.
• an ultraviolet curable sealant is drawn around the substrate, and nematic liquid crystal (MLC-6608, manufactured by Merck Japan Ltd.) is applied in 6 drops onto the inner surface of the sealant by the ODF method.
• MLC-6608 nematic liquid crystal
• liquid crystal cell (2 vertical points ⁇ 3 horizontal points, and the interval between each point was 10 mm in the vertical and horizontal directions), and the rubbed substrate was bonded to obtain a liquid crystal cell. Then, in order to cure the sealant, the liquid crystal cell was cut using a metal halide lamp with an illuminance of 60 mW, the wavelength of 310 nm or less was cut, and ultraviolet rays of 5 J / cm 2 were converted in terms of 365 nm. A liquid crystal cell was obtained by heating at 120 ° C. for 60 minutes. Using the obtained liquid crystal cell, liquid crystal dropping mark unevenness, that is, liquid crystal alignment unevenness was confirmed.
• the liquid crystal cell whose voltage holding ratio was measured immediately after the liquid crystal cell was manufactured was irradiated with ultraviolet rays of 50 J / cm 2 in terms of 365 nm using a desktop UV curing device (HCT3B28HEX-1, manufactured by Senlite).
• the voltage holding ratio was measured under the same conditions as described above. In this evaluation, the value of the voltage holding ratio immediately after the production of the liquid crystal cell is high, and further, the value after the ultraviolet irradiation (also called after the ultraviolet irradiation) with respect to the value of the voltage holding ratio immediately after the production of the liquid crystal cell (also referred to as the initial). ), The smaller the decrease, the better the evaluation.
• Tables 40 to 42 show the values of each VHR.
• the liquid crystal cell for which the measurement of the residual charge immediately after the production of the liquid crystal cell was completed was irradiated with ultraviolet rays of 30 J / cm 2 in terms of 365 nm using a desktop UV curing device (HCT3B28HEX-1, manufactured by Senlite).
• the residual charge was measured under the same conditions as described above.
• Tables 40 to 42 show the values of the residual charges.
• the liquid crystal aligning agent of Example 3 produced a board
• a polymerizable compound (1) of the following formula is added to a nematic liquid crystal (MLC-6608, manufactured by Merck Japan Ltd.) by vacuum injection into this empty cell, and the polymerizable compound (1) is added to 100% of the nematic liquid crystal.
• a liquid crystal cell was obtained by injecting 0.3% mixed liquid crystal and then sealing the injection port.
• the liquid crystal cell obtained in any of the examples confirmed that the alignment direction of the liquid crystal was controlled because the response speed of the liquid crystal cell after ultraviolet irradiation was higher than that of the liquid crystal cell before ultraviolet irradiation. . Further, in any liquid crystal cell, it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL, manufactured by Nikon Corp.) that the liquid crystal was uniformly aligned.
• NEP (3.92 g) was added to the polyimide powder (1) (0.50 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (3.92 g) was added and stirred at 40 ° C. for 4 hours to obtain a solution.
• NEP (5.88 g) was added to the polyimide powder (10) (0.75 g) obtained in Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (5.88 g) was added and stirred at 40 ° C. for 4 hours to obtain a solution.
• NEP (9.79 g) was added to the polyimide powder (14) (1.25 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (9.79 g) was added and stirred at 40 ° C. for 4 hours to obtain a solution.
• the three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (1).
• This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
• NEP (3.92 g) was added to the polyimide powder (2) (0.50 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (2.35 g) and PB (1.57 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• NEP (5.88 g) was added to the polyimide powder (10) (0.75 g) obtained in Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (3.53 g) and PB (2.35 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• NEP (9.79 g) was added to the polyimide powder (14) (1.25 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (5.88 g) and PB (3.92 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• the three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (2).
• This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
• NMP (6.27 g) was added to the polyimide powder (4) (0.80 g) obtained in Synthesis Example 4, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (5.02 g) and DME (1.25 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• NMP (6.27 g) was added to the polyimide powder (12) (0.80 g) obtained in Synthesis Example 12, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (5.02 g) and DME (1.25 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• NMP (8.36 g) was added to the polyimide powder (14) (1.07 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (6.68 g) and DME (1.67 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• the three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (4).
• This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
• NEP (7.52 g) was added to the polyimide powder (5) (0.80 g) obtained in Synthesis Example 5, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (2.51 g) and PB (2.51 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• NEP (7.52 g) was added to the polyimide powder (10) (0.80 g) obtained in Synthesis Example 10 and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (2.51 g) and PB (2.51 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• NEP (10.0 g) was added to the polyimide powder (14) (1.07 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (3.34 g) and PB (3.34 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• the three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (5).
• This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
• NMP (3.76 g) and NEP (3.76 g) were added to the polyimide powder (7) (0.80 g) obtained in Synthesis Example 7, and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (2.51 g) and PB (2.51 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• NMP (3.76 g) and NEP (3.76 g) were added to the polyimide powder (10) (0.80 g) obtained in Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours.
• Example 8 Polyimide powder (8) (0.30 g) obtained in Synthesis Example 8, polyimide powder (10) (0.45 g) obtained in Synthesis Example 10, and polyimide powder (14) obtained in Synthesis Example 14 (0) NEP (12.4 g) and ⁇ -BL (6.21 g) were added to .75 g) and dissolved by stirring at 70 ° C. for 24 hours. BCS (8.27g) and PB (14.5g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (8). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
• NEP 5.09 g was added to the polyimide powder (1) (0.50 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (1.18 g) and PB (1.57 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution. On the other hand, NEP (7.64 g) was added to the polyimide powder (11) (0.75 g) obtained in Synthesis Example 11, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (1.76 g) and PB (2.35 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• NEP (12.7 g) was added to the polyimide powder (14) (1.25 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (2.94 g) and PB (3.92 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• the three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (9).
• This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
• NEP (4.70 g) was added to the polyimide powder (5) (0.50 g) obtained in Synthesis Example 5, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (3.13 g) was added and stirred at 40 ° C. for 4 hours to obtain a solution.
• NEP (7.05 g) was added to the polyimide powder (12) (0.75 g) obtained in Synthesis Example 12, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (4.70 g) was added and stirred at 40 ° C. for 4 hours to obtain a solution.
• NEP (11.8 g) was added to the polyimide powder (14) (1.25 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours.
• PB (7.83 g) was added and stirred at 40 ° C. for 4 hours to obtain a solution.
• the three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (10).
• This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
• NEP (4.70 g) was added to the polyimide powder (1) (0.50 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (0.78g) and PB (2.35g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.
• NEP (7.05 g) was added to the polyimide powder (13) (0.75 g) obtained in Synthesis Example 13 and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (1.18 g) and PB (3.53 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• NEP (11.8 g) was added to the polyimide powder (14) (1.25 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (1.96 g) and PB (5.88 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• the three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (11).
• This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
• NMP (6.27 g) was added to the polyimide powder (1) (0.80 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (2.51 g) and PB (3.76 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• NMP (4.18 g) was added to the polyimide powder (10) obtained in Synthesis Example 10 (0.53 g) and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (1.67 g) and PB (2.51 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• NMP (10.4 g) was added to the polyimide powder (15) obtained in Synthesis Example 15 (1.33 g), and the mixture was dissolved by stirring at 70 ° C. for 24 hours.
• BCS (4.18 g) and PB (6.27 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• M1 (0.19 g) was further added, and the mixture was stirred at 40 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (12).
• This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
• Example 13 Polyimide powder (1) (0.80 g) obtained in Synthesis Example 1, polyimide powder (10) (0.80 g) obtained in Synthesis Example 10, and polyimide powder (16) obtained in Synthesis Example 16 (1) 0.07 g) was added NEP (20.9 g) and dissolved by stirring at 70 ° C. for 24 hours. BCS (8.36g) and PB (12.5g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (13). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
• Example 14 Polyimide powder (1) (0.80 g) obtained in Synthesis Example 1, polyimide powder (10) (0.80 g) obtained in Synthesis Example 10, and polyimide powder (16) obtained in Synthesis Example 16 (1) 0.07 g) was added NEP (20.9 g) and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (12.5 g) and DPM (8.36 g) were added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (22). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
• NEP (19.6 g) was added to the polyimide powder (10) (2.50 g) obtained in Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (19.6 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (15).
• This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
• NEP (10.2 g) was added to the polyimide powder (1) (1.30 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 24 hours. BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.
• NEP (10.2 g) was added to the polyimide powder (10) (1.30 g) obtained in Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.
• the two solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (17).
• This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
• NEP (10.2 g) was added to the polyimide powder (1) (1.30 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 24 hours. BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.
• NEP (10.2 g) was added to the polyimide powder (14) (1.30 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours. BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.
• the two solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (18). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
• NEP (10.2 g) was added to the polyimide powder (10) (1.30 g) obtained in Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours. BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.
• NEP (10.2 g) was added to the polyimide powder (14) (1.30 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours. BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.
• the two solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (19). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
• NEP (3.92 g) was added to the polyimide powder (9) (0.50 g) obtained in Synthesis Example 9 and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (2.35 g) and PB (1.57 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• NEP (5.88 g) was added to the polyimide powder (10) (0.75 g) obtained in Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (3.53 g) and PB (2.35 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• NEP (9.79 g) was added to the polyimide powder (14) (1.25 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours.
• BCS (5.88 g) and PB (3.92 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
• the three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (20).
• This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
• Tables 34 to 36 show a summary of the liquid crystal aligning agents obtained in the above Examples and Comparative Examples.
• Tables 37 to 42 show the results of liquid crystal display element evaluation using these liquid crystal alignment treatment agents.
• * 1 An introduction amount (parts) of the specific polymer (A) with respect to 100 parts of all polymers is shown.
• * 2 is the introduction amount (parts) of the specific polymer (B) to 100 parts of all polymers,
• 3 is the introduction amount (parts) of the specific polymer (C) to 100 parts of all polymers, and * 4 is all The amount (parts) of the other polymer introduced relative to 100 parts of the polymer, * 5 indicates the content ratio (solid content concentration) of all the polymers in the liquid crystal aligning agent.
• the liquid crystal aligning agent of the example showed a stable pretilt angle even when the liquid crystal cell was subjected to high temperature treatment and ultraviolet irradiation, as compared with the liquid crystal aligning agent of the comparative example. Further, liquid crystal alignment unevenness generated by the ODF method could be reduced. Furthermore, even when the liquid crystal cell was irradiated with ultraviolet light, the decrease in the voltage holding ratio was suppressed, and the residual charge accumulated by the DC voltage was quickly relaxed.
• Comparative Example 8 shows all the effects of the present invention, in particular, the ODF method. Inferior results were obtained with respect to the occurrence of uneven liquid crystal alignment and a decrease in voltage holding ratio after exposure to light irradiation for a long time.
• the liquid crystal aligning agent of the present invention is useful for liquid crystal display elements using VA mode, PSA mode, and SC-PVA mode, particularly TN elements, STN elements, TFT liquid crystal elements, especially vertical alignment type liquid crystal display elements.
• a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention can be suitably used for a large-screen, high-definition liquid crystal television, a small-sized car navigation system, a smartphone, and the like.

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