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WO2025089307A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides Download PDF

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WO2025089307A1
WO2025089307A1 PCT/JP2024/037751 JP2024037751W WO2025089307A1 WO 2025089307 A1 WO2025089307 A1 WO 2025089307A1 JP 2024037751 W JP2024037751 W JP 2024037751W WO 2025089307 A1 WO2025089307 A1 WO 2025089307A1
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liquid crystal
crystal alignment
hydrogen atom
polymer
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Japanese (ja)
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直己 肥田
大貴 古賀
萌 境田
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
    • 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
    • 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 agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, a liquid crystal display element having the liquid crystal alignment film, and a novel diamine and polymer suitable for them.
  • Liquid crystal display elements are widely used as display units for personal computers, mobile phones, smartphones, televisions, etc.
  • Liquid crystal display elements include, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, pixel electrodes and a common electrode that apply an electric field to the liquid crystal layer, an alignment film that controls the liquid crystal orientation of the liquid crystal molecules in the liquid crystal layer, and thin film transistors (TFTs) that switch the electrical signals supplied to the pixel electrodes.
  • Known methods for driving liquid crystal molecules include vertical electric field methods such as the TN (Twisted Nematic) method and the VA (Vertical Alignment) method, and horizontal electric field methods such as the IPS (In-Plane Switching) method and the FFS (Fringe Field Switching) method.
  • the horizontal electric field method in which electrodes are formed on only one side of the substrate and an electric field is applied parallel to the substrate, is known as a liquid crystal display element that has a wider viewing angle characteristic and is capable of high-quality display compared to the conventional vertical electric field method, in which a voltage is applied to electrodes formed on the top and bottom substrates to drive the liquid crystal.
  • Patent Document 1 discloses a liquid crystal alignment agent containing a polymer obtained using a diamine component containing a diamine whose terminal amino group is alkylated, as a liquid crystal alignment agent for use in a lateral electric field type liquid crystal display element.
  • the object of the present invention is to provide a liquid crystal alignment film that can reduce the absolute value of the accumulated charge while reducing the generated charge in a short period of time, and a liquid crystal alignment agent that can obtain a liquid crystal alignment film in which charge accumulation and flicker caused by backlight are reduced.
  • a liquid crystal aligning agent comprising at least one polymer (P0) selected from the group consisting of a polyimide precursor having a partial structure (a0) represented by the following formula (0) and a polyimide which is an imidized product of the polyimide precursor: (In the formula, ** represents a bond bonded to a saturated hydrocarbon group.
  • A3 represents a branched alkyl group having 3 to 6 carbon atoms, or * -A4 - Y2 .
  • A4 represents an alkylene group having 1 to 6 carbon atoms, Y2 represents an aromatic group, and * represents a bond.
  • any hydrogen atom of the aromatic group in Y2 may be replaced with a monovalent group.
  • X represents an aromatic group having a valence of (n+2).
  • R D represents a hydrogen atom or a protecting group which is substituted with a hydrogen atom by heat, and when there are a plurality of R D s , each R D may be the same or different.
  • n is an integer from 1 to 8.
  • examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and * represents a bond.
  • the main chain of a polymer refers to the "trunk" portion of the polymer, which is the longest chain of atoms. It is permitted that this "trunk" portion contains a ring structure.
  • the side chain of a polymer refers to the portion branched from the "trunk" of the polymer.
  • liquid crystal aligning agent of the present invention By using the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal alignment film that can reduce the absolute value of the accumulated charge while reducing the generated charge in a short period of time, as well as a liquid crystal alignment film in which charge accumulation and flicker caused by backlight light are reduced.
  • the mechanism by which the above-mentioned effects of the present invention are obtained is not entirely clear, but the following is thought to be one of the reasons.
  • polyamic acid which is the main component of liquid crystal alignment agents, undergoes a thermal imidization reaction.
  • the formation of imide rings makes it easier to absorb light, and also makes it difficult to reduce accumulated charges due to its low polarity.
  • the liquid crystal alignment agent containing the polymer having the specific partial structure of the present invention has the above-mentioned effect because the imidization reaction is inhibited even after the baking process, suppressing light absorption and making it highly polar.
  • FIG. 1 is a schematic cross-sectional view showing an example of a horizontal electric field liquid crystal display element of the present invention.
  • FIG. 4 is a schematic cross-sectional view showing another example of a horizontal electric field liquid crystal display element of the present invention.
  • One embodiment of the polymer contained in the liquid crystal aligning agent of the present invention is at least one polymer (P0) selected from the group consisting of polyimide precursors having the partial structure (a0) represented by the above formula (0) and polyimides which are imidized products of the polyimide precursors.
  • the polymer (P0) may have the partial structure (a0) in the main chain of the polymer (P0) or in the side chain of the polymer (P0).
  • ** represents a bond bonded to a saturated hydrocarbon group.
  • A3 represents a branched alkyl group having 3 to 6 carbon atoms, or * -A4 - Y2 .
  • A4 represents an alkylene group having 1 to 6 carbon atoms
  • Y2 represents an aromatic group
  • * represents a bond. Any hydrogen atom of the aromatic group in Y2 may be replaced with a monovalent group.
  • X represents an aromatic group having a valence of (n+2).
  • R D represents a hydrogen atom or a protecting group which is substituted with a hydrogen atom by heat, and when there are a plurality of R D s , each R D may be the same or different.
  • n is an integer from 1 to 8.
  • the polymer (P0) preferably has a divalent organic group similar to X2 in the formula (2) described below, that is, a divalent organic group having 2 to 42 carbon atoms and a saturated hydrocarbon group.
  • X in the above formula (0) represents an (n+2)-valent aromatic group.
  • Specific preferred examples of the aromatic group include (n+2)-valent aromatic groups obtained by removing (n+1) hydrogen atoms from the specific examples of the aromatic group in Y2 of * -A4 - Y2 described below.
  • A3 in the above formula (0) has the same meaning as A3 in the below-described formula (2).
  • R 3 D in -COOR D in the above formula (0) represents a hydrogen atom or a protecting group which is substituted with a hydrogen atom by heat.
  • the protecting group is preferably a protecting group that is removed by heat of 80° C. or more, and more preferably a protecting group that is removed by heat of 100° C. or more. From the viewpoint of suitably obtaining the effects of the present invention, a protecting group that is removed by heat of 300° C. or less is preferable, a protecting group that is removed by heat of 250° C. or less is more preferable, and a protecting group that is removed by heat of 200° C. or less is even more preferable.
  • Preferred specific examples of the protecting group that is substituted with a hydrogen atom by heat include structures selected from the group consisting of the following formulae (a-1) to (a-6).
  • R 1 represents an alkyl group having 1 to 5 carbon atoms.
  • polymer contained in the liquid crystal aligning agent of the present invention is at least one polymer (P) selected from the group consisting of a polyimide precursor obtained by using a tetracarboxylic acid component containing a tetracarboxylic dianhydride represented by the following formula (1) (also referred to as a specific aromatic tetracarboxylic acid component (p) in the present invention) and a diamine component containing a diamine represented by the following formula (2) (also referred to as a specific diamine (p) in the present invention) and a polyimide which is an imidized product of the polyimide precursor.
  • a polyimide precursor obtained by using a tetracarboxylic acid component containing a tetracarboxylic dianhydride represented by the following formula (1) (also referred to as a specific aromatic tetracarboxylic acid component (p) in the present invention) and a diamine component containing a diamine represented by the following formula (2) (also referred to
  • the polymer (P) contained in the liquid crystal aligning agent of the present invention may be one type or two or more types.
  • the polyimide precursor is a polymer that can give a polyimide by imidizing a polyamic acid, a polyamic acid ester, or the like.
  • Xa represents a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride or a derivative thereof.
  • X2 represents a divalent organic group having 2 to 42 carbon atoms and having a saturated hydrocarbon group. However, at least one of the amino groups bonded to X2 is bonded to the saturated hydrocarbon group of X2.
  • Each A3 independently represents a branched alkyl group having 3 to 6 carbon atoms or * -A4 - Y2 , where * represents a bond.
  • A4 represents an alkylene group having 1 to 6 carbon atoms, and Y2 represents an aromatic group. Any hydrogen atom of the aromatic group in Y2 may be replaced with a monovalent group.
  • the polyamic acid (P') which is a polyimide precursor of the polymer (P) can be obtained, for example, by a polymerization reaction between a diamine component containing the specific diamine (p) and a tetracarboxylic dianhydride represented by the formula (1).
  • the tetracarboxylic acid component to be reacted with the diamine component may be not only a tetracarboxylic acid dianhydride but also a derivative of a tetracarboxylic acid dianhydride such as a tetracarboxylic acid, a tetracarboxylic acid dihalide, a tetracarboxylic acid dialkyl ester, or a tetracarboxylic acid dialkyl ester dihalide.
  • Xa in the above formula (1) represents a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride or a derivative thereof.
  • the aromatic tetracarboxylic acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to an aromatic ring.
  • Xa in the above formula (1) is preferably a structure selected from the following formulae (Xa-1) and (Xa-2).
  • j and k are integers of 0 or 1
  • R represents a hydrogen atom or a methyl group.
  • a 2 may be the same or different. * represents a bond.
  • Xa is more preferably any of the above formulae (Xa-3) to (Xa-7), and further preferably any of the above formulae (Xa-3) to (Xa-6).
  • the proportion of the specific aromatic tetracarboxylic acid component (p) used is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 50 mol% or more, per mole of the total tetracarboxylic acid components used in the polymer (P).
  • the tetracarboxylic acid component used in the production of the polymer (P) may contain tetracarboxylic acid components other than the specific aromatic tetracarboxylic acid component (p) (hereinafter also referred to as other tetracarboxylic acid components).
  • the amount of the specific aromatic tetracarboxylic acid component (p) used is preferably 90 mol% or less, and more preferably 80 mol% or less, per mole of the total tetracarboxylic acid components used in the polymer (P).
  • the other tetracarboxylic acid components mentioned above include acyclic aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, or derivatives thereof.
  • the acyclic aliphatic tetracarboxylic acid dianhydrides are acid dianhydrides obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, they do not have to be composed of chain hydrocarbon structures only, and may have an alicyclic structure or an aromatic ring structure as part of them.
  • Alicyclic tetracarboxylic acid dianhydrides are acid dianhydrides obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to an alicyclic structure. However, none of these four carboxy groups are bonded to an aromatic ring. In addition, they do not have to be composed of only alicyclic structures, and may have a chain hydrocarbon structure or an aromatic ring structure as part of them.
  • acyclic aliphatic or alicyclic tetracarboxylic acid dianhydrides or derivatives thereof are preferably tetracarboxylic acid dianhydrides having at least one partial structure selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure, or derivatives thereof, from the viewpoint of enhancing the liquid crystal alignment.
  • tetracarboxylic acid components are preferably tetracarboxylic dianhydrides or derivatives thereof represented by the following formula (t):
  • XT is a structure selected from the following formulae (X1-1) to (X1-23).
  • R 1 to R 21 each independently represent 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 alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group.
  • R 1 to R 21 each independently represent preferably a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.
  • formula (X1-1) include the following formulas (1-1) to (1-6). From the viewpoint of improving the liquid crystal alignment property, formulas (1-1) to (1-2) are particularly preferable.
  • the above XT is preferably the above formula (X1-1) to (X1-10), or (X1-18) to (X1-23), more preferably the above formula (X1-1), (X1-5), (X1-7) to (X1-10), (X1-21), or (X1-23), and further preferably the above formula (1-1), (1-2), (X1-5), (X1-7), (X1-8), or (X1-9).
  • aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, and 3,3',4,4'-biphenyl tetracarboxylic dianhydride.
  • aromatic tetracarboxylic acid dianhydrides include water, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, ethylene glycol bisanhydrotrimate, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-oxydi(1,4-phenylene)bis(phthalic acid) dianhydride, and 4,4'-methylenedi(1,4-phenylene)bis(phthalic acid) dianhydride, and derivatives thereof.
  • the specific diamine (p) of the present invention is a diamine represented by the above formula (2).
  • the specific diamine (p) may be used alone or in combination of two or more kinds.
  • the amount of the specific diamine (p) used is preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 20 mol % or more, per mol of the diamine component used in the production of the polymer (P).
  • X2 in the above formula (2) represents a divalent organic group having 2 to 42 carbon atoms and a saturated hydrocarbon group.
  • at least one of the amino groups bonded to X2 is bonded to the saturated hydrocarbon group possessed by X2 .
  • the number of carbon atoms in the above divalent organic group is preferably 2 to 30, and more preferably 2 to 24.
  • X2 in the above formula (2) may be composed of only a chain hydrocarbon structure, or may have one or more ring structures such as an alicyclic structure or an aromatic ring structure, but preferably has one or more ring structures, more preferably has one or more aromatic ring structures.
  • the ring structure may be a nitrogen atom-containing structure that contains a nitrogen atom.
  • X2 in the above formula (2) is preferably a structure represented by the following formula (3):
  • the number of carbon atoms in the structure represented by formula (3) is 2 or more.
  • Y3 represents a divalent organic group having 6 to 30 carbon atoms containing one or more ring structures.
  • Z2 and Z3 each independently represent a divalent chain-like saturated hydrocarbon group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 4 to 6 carbon atoms.
  • n is an integer of 0 to 1. Any hydrogen atom in the ring structure in Y3 may be replaced with a monovalent group.
  • * represents a bond.
  • Examples of the ring structure contained in Y 3 include an alicyclic structure and an aromatic ring structure, and among them, an aromatic ring structure is preferable.
  • the aromatic ring refers to an aromatic hydrocarbon or an aromatic heterocycle, and includes a monocyclic ring, a condensed ring, and a ring in which a monocyclic ring or a condensed ring is connected.
  • Examples of the aromatic ring include a benzene ring, a naphthalene ring, and a biphenyl structure. Any hydrogen atom of the aromatic group may be replaced with a monovalent group.
  • Examples of the monovalent group include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, a fluoroalkenyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, a carboxy group, a hydroxy group, an alkyloxycarbonyl group having 1 to 10 carbon atoms, a cyano group, and a nitro group.
  • alicyclic structure examples include cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, and adamantane.
  • Y3 is preferably bonded to Z2 and/or Z3 through an atom constituting a ring structure, and more preferably bonded to a carbon atom constituting a ring structure. It is more preferable that the polymer (P) has a ring structure possessed by Y3 in the main chain direction of the polymer (P).
  • the polymer (P) has a ring structure possessed by Y3 in the main chain direction of the polymer (P)
  • the ring structure possessed by Y3 constitutes the main chain of the polymer (P).
  • the rings in the ring structures may be bonded to each other via a linking group.
  • the linking group include a single bond, -CH 2 -, -C(CH 3 ) 2 -, -O-, -C( ⁇ O)-, -O-C( ⁇ O)-, -NR-C( ⁇ O)-, -NR- (wherein R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a tert-butoxycarbonyl group), an alkylene group having 2 to 18 carbon atoms, or a divalent organic group in which a portion of the -CH 2 - of the alkylene group has been replaced with -O-, -Si(CH 3 ) 2 -, -C( ⁇ O)-, -O-C( ⁇ O)-, -NR-C( ⁇ O)-, or -NR- (wherein R represents a hydrogen
  • Y3 is preferably a structure represented by the following formula (4).
  • any hydrogen atom on the cyclohexylene group or phenylene group may be substituted with a halogen atom, or an alkyl group or alkoxy group having 1 to 5 carbon atoms.
  • C4 represents an aromatic group, an alicyclic hydrocarbon group, or an alicyclic hydrocarbon group containing a nitrogen atom selected from a piperidinediyl group and a piperazinediyl group. When a plurality of C4s are present, they may be the same or different.
  • the piperidinediyl group is preferably a piperidine-1,4-diyl group
  • the piperazinediyl group is preferably a piperazine-1,4-diyl group.
  • R4 represents a halogen atom, or an alkyl or alkoxy group having 1 to 5 carbon atoms, in which any hydrogen atom of the alkyl or alkoxy group may be substituted with a halogen atom, and any hydrocarbon group may be substituted with an amino group protected with a tert-butoxycarbonyl group.
  • Each of the multiple a's is independently an integer of 0 to 4, b is an integer of 1 to 3, b is preferably an integer of 1 to 2, and c is an integer of 0 to 1. b+c is preferably an integer of 1 to 3.
  • the two R's may be the same or different).
  • p is an integer of 1 to 6, and preferably an integer of 2 to 6.
  • q is an integer of 1 to 6, and more preferably an integer of 2 to 6, and even more preferably an integer of 2 to 4.
  • p', q', and r' each independently represents an integer of 0 to 6. In addition, 0 ⁇ p'+q' ⁇ 10 is satisfied, and 2 ⁇ p'+q+r' ⁇ 16 is satisfied.
  • Z 2 and Z 3 are each independently a divalent, linear, saturated hydrocarbon group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 4 to 6 carbon atoms.
  • the divalent, linear, saturated hydrocarbon group having 1 to 6 carbon atoms may be linear or branched. From the viewpoint of improving liquid crystal alignment, a linear alkylene group is preferable, and a methylene group or an ethylene group is more preferable.
  • a 3 each independently represents a branched alkyl group having 3 to 6 carbon atoms or *-A 4 -Y 2 .
  • *A 4 in -A 4 -Y 2 is an alkylene group having a carbon number of 1 to 6. From the viewpoint of improving the liquid crystal alignment property, A 4 is preferably a methylene group or an ethylene group.
  • Y 2 represents an aromatic group, and * represents a bond.
  • Y2 is preferably a monovalent aromatic group having 4 to 30 carbon atoms.
  • the aromatic group of Y2 refers to an aromatic hydrocarbon group or an aromatic heterocyclic group, and includes a monocyclic group, a condensed ring group, and a group in which a monocyclic ring or a condensed ring is linked. Any hydrogen atom of the aromatic group may be replaced with a monovalent group.
  • Examples of the monovalent group include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, a fluoroalkenyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, a carboxy group, a hydroxy group, an alkyloxycarbonyl group having 1 to 10 carbon atoms, a cyano group, and a nitro group.
  • aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and a biphenyl structure
  • 5-membered aromatic heterocycles such as a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, and a triazole ring
  • 6-membered aromatic heterocycles such as a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, and a pyrazine ring
  • polycyclic aromatic heterocycles such as an indole ring, a benzimidazole ring, a purine ring, a quinoline ring, an iso
  • diamine represented by formula (2) above include diamines represented by any of the following formulas (D A -1) to (D A -24).
  • m is an integer of 0 to 6
  • m1, m2, n1, and n2 are each an integer of 1 to 6.
  • the hydrogen atoms on the benzene rings in formulas (D A -1) to (D A -24) may be substituted with a monovalent substituent.
  • the diamine component used in the production of the polymer (P) may contain a diamine other than the specific diamine (p) (hereinafter, also referred to as other diamines).
  • the amount of the specific diamine (p) used relative to the diamine component is preferably 90 mol % or less, more preferably 80 mol % or less, relative to 1 mole of the diamine component used in the production of the polymer (P).
  • Examples of the other diamines include, but are not limited to, the following:
  • the above other diamines may be used alone or in combination of two or more.
  • diamines having a photoalignment group such as 4,4'-diaminoazobenzene or diaminotolane
  • diamines having an amide bond such as 4,4'-diaminobenzanilide
  • diamines having a urea bond such as 1,3-bis(4-aminophenyl)urea, 1,3-bis(4-aminobenzyl)urea, and 1,3-bis(4-aminophenethyl)urea
  • diamines having at least one nitrogen atom-containing structure (hereinafter also referred to as specific nitrogen atom-containing structure) selected from the group consisting of a nitrogen atom-containing heterocycle, a secondary amino group, and a tertiary amino group (however, they do not have an amino group bonded with a protecting group that is eliminated by heating and replaced with a hydrogen atom in the molecule, and also excluding the specific diamine (p) above); 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6 -diaminoresorcinol; 4,4'-diamino-3,3'-dihydroxybiphenyl; 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-
  • m and n are each independently an integer of 0 to 3, and satisfy 1 ⁇ m+n ⁇ 4.
  • j is an integer of 0 or 1.
  • X 1 represents -(CH 2 ) a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH 3 )-, -NH-, -O-, -CH 2 O-, -CH 2 -OCO-, -COO-, or -OCO-.
  • R 1 represents a monovalent group such as a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkoxyalkyl group having 2 to 10 carbon atoms.
  • X 2 represents —O—, —CH 2 O—, —CH 2 —OCO—, —COO—, or —OCO—, and when there are two of m, n, X 1 and R 1 , each independently has the above definition.
  • Examples of the nitrogen atom-containing heterocycle that may be contained in the diamine having the nitrogen atom-containing structure include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzimidazole, purine, quinoline, isoquinoline, naphthyridine, quinoxaline, phthalazine, triazine, carbazole, acridine, piperidine, piperazine, pyrrolidine, and hexamethyleneimine.
  • pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole, and acridine are preferred.
  • the other diamines may be diamines selected from the group consisting of the first diamine, diamines having an amide bond, diamines having a urea bond, diamines having the group "-N(D)-", diamines having a specific nitrogen atom-containing structure, and diamines having a carboxy group, from the viewpoint of improving the liquid crystal alignment.
  • the liquid crystal aligning agent of the present invention is a liquid composition obtained by dispersing or dissolving the polymer (P) and other components used as necessary, preferably in a suitable solvent.
  • the liquid crystal alignment agent of the present invention may contain other polymers in addition to the polymer (P).
  • other polymers include, in addition to the above polymer (P), at least one polymer selected from the group consisting of a polyimide precursor obtained using a diamine component that does not contain the above specific diamine (p) and a polyimide that is an imidized product of the polyimide precursor (also referred to as polymer (B) in the present invention), polysiloxane, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-maleic anhydride) copolymer, poly(isobutylene-maleic anhydride) copolymer, poly(vinyl ether-maleic anhydride) copolymer, poly(styrene-phenylmaleimide) derivative, and a polymer selected from the group consisting of poly(meth)acrylate.
  • poly(styrene-maleic anhydride) copolymers include SMA1000, SMA2000, SMA3000 (manufactured by Cray Valley Corporation) and GSM301 (manufactured by Gifu Ceramics Manufacturing Co., Ltd.), and a specific example of poly(isobutylene-maleic anhydride) copolymers includes ISOBAM-600 (manufactured by Kuraray Co., Ltd.).
  • a specific example of poly(vinyl ether-maleic anhydride) copolymers includes Gantrez AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by Ashland Corporation).
  • the polymer (B) is more preferred from the viewpoint of improving the display quality of the liquid crystal display element.
  • the other polymers may be used alone or in combination of two or more.
  • the content of the other polymers is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, and even more preferably 20 to 80 parts by mass, based on 100 parts by mass of the total of the polymers contained in the liquid crystal alignment agent.
  • tetracarboxylic acid component used in the production of the polymer (B) include the same compounds as those exemplified for the polymer (P), including preferred specific examples.
  • the tetracarboxylic acid component used in the production of the polymer (B) more preferably contains a tetracarboxylic acid dianhydride having at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring, or a derivative thereof (hereinafter, these are also referred to as specific tetracarboxylic acid component (B)).
  • the amount of the specific tetracarboxylic acid component (B) used is preferably 10 mol % or more, more preferably 20 mol % or more, and even more preferably 50 mol % or more, based on 1 mol of the total tetracarboxylic acid components used in the production of the polymer (B).
  • Examples of the diamine component for obtaining the polymer (B) include the diamines exemplified for the polymer (P) above. Among them, it is preferable to include at least one diamine selected from the group consisting of the first diamine, a diamine having a urea bond, a diamine having an amide bond, and a diamine having a group "-N(D)-" (these are also referred to as specific diamine (b) in the present invention).
  • the diamine component may be a single diamine or a combination of two or more diamines.
  • the amount of the specific diamine (b) is preferably 10 mol % or more, more preferably 20 mol % or more, based on the total diamine components used in the production of the polymer (B).
  • the amount of the specific diamine (b) is preferably 90 mol % or less, more preferably 80 mol % or less, based on 1 mole of the total diamine components used in the production of the polymer (B).
  • the polyamic acid is produced by reacting a diamine component with a tetracarboxylic acid component in an organic solvent.
  • the ratio of the tetracarboxylic acid component and the diamine component used in the reaction for producing the polyamic acid is preferably such that the acid anhydride group of the tetracarboxylic acid component is 0.5 to 2 equivalents, more preferably 0.8 to 1.2 equivalents, per equivalent of the amino group of the diamine component.
  • the closer the equivalent of the acid anhydride group of the tetracarboxylic acid component is to 1 equivalent the higher the molecular weight of the polyamic acid produced.
  • the reaction temperature in the production of polyamic acid is preferably ⁇ 20 to 150° C., more preferably 0 to 100° C.
  • the reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.
  • the production of polyamic acid can be carried out at any concentration, but the concentration of polyamic acid is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the reaction can be carried out at a high concentration in the early stage of the reaction, and then a solvent can be added.
  • organic solvent examples include cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide (hereinafter also referred to as DMAc), dimethylsulfoxide, and 1,3-dimethyl-2-imidazolidinone.
  • solvents such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether can be used.
  • the polyamic acid ester can be obtained by a known method such as, for example, [I] a method of reacting the polyamic acid obtained by the above method with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, or [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine.
  • Polyimide can be obtained by ring-closing (imidizing) a polyimide precursor such as the polyamic acid or polyamic acid ester.
  • the imidization ratio in this specification refers to the ratio of imide groups to the total amount of imide groups derived from tetracarboxylic dianhydride or its derivatives and carboxyl groups (or their derivatives).
  • the imidization ratio does not necessarily need to be 100% and can be adjusted as desired depending on the application or purpose.
  • Methods for imidizing the polyimide precursor include thermal imidization, in which a solution of the polyimide precursor is heated as is, and catalytic imidization, in which a catalyst is added to a solution of the polyimide precursor.
  • the temperature when thermally imidizing the polyimide precursor in a solution is preferably 100 to 400° C., more preferably 120 to 250° C., and it is preferable to carry out the imidization while removing water generated by the imidization reaction from the system.
  • Catalytic imidization of polyimide precursors can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring the solution at preferably -20 to 250°C, more preferably 0 to 180°C.
  • the amount of the basic catalyst is preferably 0.5 to 30 molar times, more preferably 2 to 20 molar times
  • the amount of the acid anhydride is preferably 1 to 50 molar times, more preferably 3 to 30 molar times, the amount of the amic acid group.
  • Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine, and among these, pyridine is preferred because it has a suitable basicity for promoting the reaction.
  • acid anhydrides examples include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride, and among these, acetic anhydride is preferred because it facilitates purification after the reaction.
  • the imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the reaction solution may be poured into a solvent to cause precipitation.
  • solvents used for precipitation include methanol, ethanol, isopropyl alcohol (hereinafter also referred to as IPA), acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water.
  • the polymer precipitated by pouring into the solvent can be recovered by filtration, and then dried at room temperature or by heating under normal or reduced pressure.
  • the recovered polymer can be redissolved in an organic solvent and the reprecipitation recovery operation repeated 2 to 10 times to reduce impurities in the polymer.
  • the solvent used in this case include alcohol, ketone, and hydrocarbon, and it is preferable to use three or more solvents selected from these because this further increases the efficiency of purification.
  • a terminal-capping polymer may be produced by using a tetracarboxylic acid component containing a tetracarboxylic dianhydride or a derivative thereof, and a diamine component containing a diamine, together with a suitable terminal-capping agent.
  • the terminal-capping polymer has the effect of improving the film hardness of the liquid crystal alignment film obtained by coating, and improving the adhesion property between the sealant and the liquid crystal alignment film.
  • the terminals of the polyimide precursor or polyimide in the present invention include an amino group, a carboxy group, an acid anhydride group, or a group derived from a terminal blocking agent described below.
  • the amino group, the carboxy group, and the acid anhydride group can be obtained by a normal condensation reaction or by blocking the terminals with the terminal blocking agent described below.
  • end-capping agents include acid anhydrides such as acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, and 4-ethynylphthalic anhydride; dicarbonate diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride, and nicotinic acid chloride; Examples of the monoamine compounds include aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid
  • the proportion of the end-capping agent used is preferably 0.01 to 20 molar parts, and more preferably 0.01 to 10 molar parts, per 100 molar parts of the total diamine components used.
  • the polystyrene-equivalent weight average molecular weight (Mw) of the polyimide precursor and polyimide measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000.
  • the molecular weight distribution (Mw/Mn), expressed as the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC, is preferably 15 or less, and more preferably 10 or less. Having the molecular weight within this range ensures good liquid crystal alignment in the liquid crystal display element.
  • the organic solvent contained in the liquid crystal alignment agent according to the present invention is not particularly limited as long as it can uniformly dissolve the polymer (P) and other polymers added as necessary.
  • N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, N,N-diethylacetamide, N,N-dimethylpropionamide tetramethylurea
  • N,N-diethylformamide N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, ⁇ -butyrolactone, ⁇ -valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylacet ...acetamide, tetramethylurea, N,N-diethylacetamide, tetramethylurea, N
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and ⁇ -butyrolactone are preferred.
  • the content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass, of the total solvent contained in the liquid crystal alignment agent.
  • the organic solvent contained in the liquid crystal alignment agent is preferably a mixed solvent that uses, in addition to the above-mentioned solvent, a solvent (also called a poor solvent) that improves the applicability when applying the liquid crystal alignment agent and the surface smoothness of the coating film.
  • a solvent also called a poor solvent
  • Specific examples of poor solvents are listed below, but are not limited to these.
  • the content of the poor solvent is preferably 1 to 80 mass % of the total solvent contained in the liquid crystal alignment agent, more preferably 10 to 80 mass %, and particularly preferably 20 to 70 mass %.
  • the type and content of the poor solvent are appropriately selected depending on the application device, application conditions, application environment, etc. of the liquid crystal alignment agent.
  • Examples of poor solvents include diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, and 3-ethoxybutyl ether.
  • diisobutyl carbinol propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, and diisobutyl ketone are preferred.
  • Preferred solvent combinations of good and poor solvents include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, ⁇ -butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, ⁇ -butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, N-ethyl-2-pyrrolidone and propylene glycol diacetate, N,N-dimethyl lactamide and diisobutyl ketone, and N-methyl-2-pyrrolidone.
  • N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate
  • N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate and dipropylene glycol monomethyl ether N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate and propylene glycol monobutyl ether
  • N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate and diethylene glycol monopropyl ether N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate and diethylene glycol monopropyl ether
  • N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate ether N-ethyl-2-pyrrolidone and dipropylene glycol dimethyl ether, N,
  • the liquid crystal aligning agent of the present invention contains the above polymer (P), and, if necessary, the above other polymers and the above organic solvent.
  • the total content of the polymers contained in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the thickness of the coating film to be formed, but it is preferably 1% by mass or more from the viewpoint of forming a uniform and defect-free coating film, and is preferably 10% by mass or less from the viewpoint of storage stability of the solution.
  • the particularly preferred total content of the polymers is 2 to 8% by mass.
  • the content of the polymer (P) used in the present invention is preferably 1 to 100 mass %, more preferably 10 to 100 mass %, particularly preferably 20 to 100 mass %, based on the total amount of the polymer contained in the liquid crystal alignment agent.
  • the liquid crystal alignment agent of the present invention may contain other components (hereinafter also referred to as additive components) in addition to the above polymer (P), the other polymers, and the organic solvent.
  • additive components include at least one crosslinking compound selected from the group consisting of crosslinking compounds having at least one substituent selected from an oxiranyl group, an oxetanyl group, a blocked isocyanate group, an oxazoline group, a cyclocarbonate group, a hydroxyl group, and an alkoxy group, and crosslinking compounds having a polymerizable unsaturated group, a functional silane compound, a metal chelate compound, a curing accelerator, a surfactant, an antioxidant, a sensitizer, a preservative, and a compound for adjusting the dielectric constant and electrical resistance of the resulting liquid crystal alignment film.
  • crosslinkable compound examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, bisphenol A type epoxy resins such as Epicoat (registered trademark) 828 (manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resins such as Epicoat 807 (manufactured by Mitsubishi Chemical Corporation), hydrogenated bisphenol A type epoxy resins such as YX-8000 (manufactured by Mitsubishi Chemical Corporation), and biphenyl ske
  • the compound for adjusting the dielectric constant and electrical resistance may be a monoamine having a nitrogen atom-containing aromatic heterocycle, such as 3-picolylamine.
  • the content of the monoamine having a nitrogen atom-containing aromatic heterocycle is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the polymer component contained in the liquid crystal alignment agent.
  • Preferred specific examples of the functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, Examples of the functional silane include silane, 3-glycidoxypropy
  • the solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of the components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., and is preferably 1 to 10 mass %.
  • a particularly preferred range of solid content concentration varies depending on the method used when applying the liquid crystal alignment agent to the substrate. For example, when using a spin coating method, it is particularly preferred that the solid content concentration is 1.5 to 4.5 mass%. When using a printing method, it is particularly preferred that the solid content concentration is 3 to 9 mass%, thereby making the solution viscosity 12 to 50 mPa ⁇ s.
  • the solid content concentration is 1 to 5 mass%, thereby making the solution viscosity 3 to 15 mPa ⁇ s.
  • the temperature when preparing the polymer composition is preferably 10 to 50°C, more preferably 20 to 30°C.
  • a liquid crystal alignment film can be produced by using the liquid crystal alignment agent.
  • the liquid crystal display element of the present invention is provided with the liquid crystal alignment film.
  • the operation mode of the liquid crystal display element according to the present invention is not particularly limited, and it can be applied to various operation modes such as TN type, STN (Super Twisted Nematic) type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, optical compensation bend type (OCB type), etc.
  • the liquid crystal alignment film of the present invention is a liquid crystal alignment film suitable for a horizontal alignment type liquid crystal display element such as an IPS type or FFS type.
  • the liquid crystal display element of the present invention can be manufactured, for example, by a method including the following steps (1) to (4), a method including steps (1) to (2) and (4), a method including steps (1) to (3), (4) and (5), or a method including steps (1) to (3), (4) and (6).
  • Step (1) is a step of applying the liquid crystal aligning agent of the present invention onto a substrate.
  • step (1) is a step of applying the liquid crystal aligning agent of the present invention onto a substrate.
  • the liquid crystal alignment agent of the present invention is applied to one side of a substrate on which a patterned transparent conductive film is provided by an appropriate application method such as a roll coater method, a spin coat method, a printing method, or an inkjet method.
  • the substrate is not particularly limited as long as it is a highly transparent substrate, and plastic substrates such as acrylic substrates and polycarbonate substrates can be used in addition to glass substrates and silicon nitride substrates.
  • an opaque material such as a silicon wafer can be used for only one substrate, and in this case, a material that reflects light such as aluminum can be used for the electrode.
  • a substrate on which an electrode made of a transparent conductive film or a metal film patterned into a comb tooth shape is provided and an opposing substrate on which no electrode is provided are used.
  • Methods for applying the liquid crystal alignment agent to a substrate and forming a film include screen printing, offset printing, flexographic printing, the inkjet method, and the spray method.
  • the inkjet method is the most suitable for application and film formation.
  • Step (2) Step of baking the applied liquid crystal alignment agent>
  • the liquid crystal alignment agent applied on the substrate is baked to form a film.
  • Specific examples of the step (2) are as follows. After the liquid crystal alignment agent is applied to the substrate in step (1), the solvent can be evaporated or the polyamic acid or polyamic acid ester can be thermally imidized by a heating means such as a hot plate, a hot air circulation oven, or an IR (infrared) oven.
  • the drying and baking steps after the application of the liquid crystal alignment agent of the present invention can be performed at any temperature and time, and may be performed multiple times.
  • the temperature at which the solvent of the liquid crystal alignment agent is reduced can be, for example, 40 to 180°C.
  • the baking can be performed at 40 to 150°C.
  • the baking time is not particularly limited, but may be 1 to 10 minutes or 1 to 5 minutes.
  • a baking step may be added after the above step, for example, at a temperature range of 150 to 300°C or 150 to 250°C.
  • the baking time is not particularly limited, but may be 5 to 40 minutes or 5 to 30 minutes. If the film-like material after firing is too thin, the reliability of the liquid crystal display device may decrease, so the film thickness is preferably 5 to 300 nm, and more preferably 10 to 200 nm.
  • Step (3) is a step of subjecting the film obtained in step (2) to an alignment treatment, if necessary. That is, in the case of a horizontal alignment type liquid crystal display element such as an IPS type or FFS type, an alignment ability imparting treatment is performed on the coating film. On the other hand, in the case of a vertical alignment type liquid crystal display element such as a VA type or PSA type, the formed coating film can be used as a liquid crystal alignment film as it is, but the coating film may be subjected to an alignment ability imparting treatment. Examples of the alignment treatment method for the liquid crystal alignment film include a rubbing treatment method and a photo-alignment treatment method.
  • Examples of the photo-alignment treatment method include a method in which the surface of the above-mentioned film-like material is irradiated with polarized radiation in a certain direction, and, if necessary, a heat treatment is performed at a temperature of preferably 150 to 250° C. to impart liquid crystal alignment (also called liquid crystal alignment ability).
  • a heat treatment is performed at a temperature of preferably 150 to 250° C. to impart liquid crystal alignment (also called liquid crystal alignment ability).
  • the radiation ultraviolet rays or visible light having a wavelength of 100 to 800 nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and more preferably 200 to 400 nm are more preferable.
  • the rubbing treatment may be carried out by rubbing the coating film in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, or cotton.
  • the radiation when the radiation is polarized, it may be linearly polarized or partially polarized.
  • the radiation when the radiation used is linearly polarized or partially polarized, the radiation may be irradiated from a direction perpendicular to the substrate surface, from an oblique direction, or a combination of these.
  • the irradiation direction is preferably an oblique direction.
  • Step (4) Step of Producing a Liquid Crystal Cell> Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and liquid crystal is disposed between the two substrates arranged opposite to each other. Specifically, the following two methods can be mentioned.
  • the first method first, two substrates are arranged facing each other with a gap (cell gap) between them so that the liquid crystal alignment films face each other, and then the peripheries of the two substrates are bonded together using a sealant, and a liquid crystal composition is injected into the substrate surfaces and the cell gap defined by the sealant so that the liquid crystal composition comes into contact with the film surface, and then the injection hole is sealed.
  • the second method is a method called ODF (One Drop Fill) method.
  • ODF One Drop Fill
  • a UV-curable sealant is applied to a predetermined location on one of the two substrates on which a liquid crystal alignment film is formed, and a liquid crystal composition is dropped at a predetermined number of locations on the liquid crystal alignment film surface.
  • the other substrate is bonded so that the liquid crystal alignment film faces the other substrate, and the liquid crystal composition is spread over the entire surface of the substrate to contact the film surface.
  • the entire surface of the substrate is irradiated with UV light to cure the sealant.
  • it is preferable to further remove the flow alignment during liquid crystal filling by heating to a temperature at which the liquid crystal composition used has an isotropic phase and then slowly cooling to room temperature.
  • the two substrates are disposed opposite each other so that the rubbing directions of the coating films are at a predetermined angle, for example, perpendicular or anti-parallel to each other.
  • the sealing agent for example, an epoxy resin containing a hardener and aluminum oxide spheres as spacers can be used.
  • the liquid crystal composition is not particularly limited, and any liquid crystal composition containing at least one type of liquid crystal compound (liquid crystal molecule) and having a positive or negative dielectric anisotropy can be used.
  • a liquid crystal composition with a positive dielectric anisotropy is also called a positive liquid crystal
  • a liquid crystal composition with a negative dielectric anisotropy is also called a negative liquid crystal.
  • the liquid crystal composition may contain a liquid crystal compound having a fluorine atom, a hydroxy group, an amino group, a fluorine atom-containing group (e.g., a trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocycle, a cycloalkane, a cycloalkene, a steroid skeleton, a benzene ring, or a naphthalene ring, and may contain a compound having two or more rigid moieties (mesogenic skeletons) that exhibit liquid crystallinity within the molecule (e.g., a bimesogenic compound in which two rigid biphenyl structures or terphenyl structures are linked by an alkylene group).
  • the liquid crystal composition may be a liquid crystal composition exhibiting a nematic phase, a liquid crystal composition exhibiting a smectic phase, or
  • the liquid crystal composition may further contain an additive from the viewpoint of improving the liquid crystal alignment property.
  • additives include a photopolymerizable monomer such as a compound having a polymerizable group, an optically active compound (e.g., S-811 manufactured by Merck Ltd.), an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerization initiator, or a polymerization inhibitor.
  • examples of the positive type liquid crystal include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, and MLC-7081 manufactured by Merck Co., Ltd., and PA-1492 manufactured by DIC Corporation.
  • Examples of negative type liquid crystals include MLC-6608, MLC-6609, MLC-6610, and MLC-7026-100 manufactured by Merck. Furthermore, an example of a liquid crystal containing a compound having a polymerizable group is MLC-3023 manufactured by Merck.
  • the liquid crystal aligning agent of the present invention is also preferably used for a liquid crystal display element (PSA type liquid crystal display element) which has a liquid crystal layer between a pair of substrates provided with electrodes, and is produced through a step of disposing a liquid crystal composition containing a polymerizable compound which is polymerized by at least one of active energy rays and heat between the pair of substrates, and polymerizing the polymerizable compound by at least one of irradiation with active energy rays and heating while applying a voltage between the electrodes (hereinafter, this step is also referred to as step (5)).
  • PSA type liquid crystal display element which has a liquid crystal layer between a pair of substrates provided with electrodes, and is produced through a step of disposing a liquid crystal composition containing a polymerizable compound which is polymerized by at least one of active energy rays and heat between the pair of substrates, and polymerizing the polymerizable compound by at least one of irradiation with active energy rays
  • the liquid crystal aligning agent of the present invention is also preferably used for a liquid crystal display element (SC-PVA type liquid crystal display element) which has a liquid crystal layer between a pair of substrates provided with electrodes, and is produced through a step of disposing a liquid crystal alignment film between the pair of substrates, the liquid crystal alignment film including a polymerizable group which is polymerized by at least one of active energy rays and heat, and applying a voltage between the electrodes (hereinafter, this step is also referred to as step (6)).
  • SC-PVA type liquid crystal display element which has a liquid crystal layer between a pair of substrates provided with electrodes, and is produced through a step of disposing a liquid crystal alignment film between the pair of substrates, the liquid crystal alignment film including a polymerizable group which is polymerized by at least one of active energy rays and heat, and applying a voltage between the electrodes (hereinafter, this step is also referred to as step (6)).
  • a polarizing plate can be attached to the outer surface of the liquid crystal cell to obtain a liquid crystal display element.
  • polarizing plates that can be attached to the outer surface of the liquid crystal cell include a polarizing film called an "H film” made by stretching and aligning polyvinyl alcohol and absorbing iodine, sandwiched between cellulose acetate protective films, and a polarizing plate made of the H film itself.
  • An IPS substrate which is a comb-tooth electrode substrate used in the IPS mode, has a base material, a plurality of linear electrodes formed on the base material and arranged in a comb-tooth shape, and a liquid crystal alignment film formed on the base material so as to cover the linear electrodes.
  • the FFS substrate which is a comb-tooth electrode substrate used in the FFS method, has a base material, a surface electrode formed on the base material, an insulating film formed on the surface electrode, a plurality of linear electrodes formed on the insulating film and arranged in a comb-tooth shape, and a liquid crystal alignment film formed on the insulating film so as to cover the linear electrodes.
  • FIG. 1 is a schematic cross-sectional view showing an example of a horizontal electric field liquid crystal display element of the present invention, which is an example of an IPS mode liquid crystal display element.
  • liquid crystal 3 is sandwiched between a comb-tooth electrode substrate 2 having a liquid crystal alignment film 2c and a counter substrate 4 having a liquid crystal alignment film 4a.
  • the comb-tooth electrode substrate 2 has a base material 2a, a plurality of linear electrodes 2b formed on the base material 2a and arranged in a comb-tooth shape, and a liquid crystal alignment film 2c formed on the base material 2a so as to cover the linear electrodes 2b.
  • the counter substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b.
  • the liquid crystal alignment film 2c is, for example, the liquid crystal alignment film of the present invention.
  • the liquid crystal alignment film 4c is also the liquid crystal alignment film of the present invention.
  • this IPS LCD element 1 when a voltage is applied to the linear electrodes 2b, an electric field is generated between the linear electrodes 2b as indicated by electric force lines L.
  • FIG. 2 is a schematic cross-sectional view showing another example of the in-plane switching liquid crystal display element of the present invention, which is an example of an FFS mode liquid crystal display element.
  • liquid crystal 3 is sandwiched between a comb-tooth electrode substrate 2 having a liquid crystal alignment film 2h and a counter substrate 4 having a liquid crystal alignment film 4a.
  • the comb-tooth electrode substrate 2 has a base material 2d, a plane electrode 2e formed on the base material 2d, an insulating film 2f formed on the plane electrode 2e, a plurality of linear electrodes 2g formed on the insulating film 2f and arranged in a comb-tooth shape, and a liquid crystal alignment film 2h formed on the insulating film 2f so as to cover the linear electrodes 2g.
  • the counter substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b.
  • the liquid crystal alignment film 2h is, for example, the liquid crystal alignment film of the present invention.
  • the liquid crystal alignment film 4a is also the liquid crystal alignment film of the present invention.
  • this IPS LCD element 1 when a voltage is applied to the plane electrodes 2e and the linear electrodes 2g, an electric field is generated between the plane electrodes 2e and the linear electrodes 2g as indicated by electric field lines L.
  • the liquid crystal alignment film of the present invention can be used for various purposes other than the above-mentioned uses, such as a liquid crystal alignment film for a phase difference film, a liquid crystal alignment film for a scanning antenna or a liquid crystal array antenna, or a liquid crystal alignment film for a transparent scattering type liquid crystal dimming element. Furthermore, it can be used for purposes other than liquid crystal alignment film, such as a protective film (e.g., a protective film for a color filter), a spacer film, an interlayer insulating film, an anti-reflection film, a wiring covering film, an antistatic film, and an insulating film for an electric motor (a gate insulating film for a flexible display).
  • a protective film e.g., a protective film for a color filter
  • spacer film e.g., an interlayer insulating film, an anti-reflection film, a wiring covering film, an antistatic film, and an insulating film for an electric motor (a gate insulating film for a flexible
  • the liquid crystal display element of the present invention can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions, and information displays.
  • AD-1 to AD-4 Compounds represented by the following formulas (AD-1) to (AD-4), respectively.
  • GPC device GPC-101 (manufactured by Showa Denko K.K.), Column: GPC KD-803 and GPC KD-805 (Showa Denko K.K.) in series; Column temperature: 50 ° C.
  • DA-1 to DA-3, DA-6 to DA-8, and DA-11 were synthesized by the methods described below.
  • DA-5 was purchased as a commercial product (Tokyo Chemical Industry Co., Ltd.) and used.
  • DA-4, DA-9, DA-10, DA-12, and DA-13 are new compounds that have not been disclosed in the literature, and their synthesis methods are described in detail below.
  • the products described in the following Monomer Synthesis Examples 1 to 13 were identified by 1 H-NMR analysis (analysis conditions are as follows).
  • ⁇ Monomer Synthesis Example 1 Synthesis of DA-1> In a 500 mL four-neck flask, terephthalaldehyde (8.0 g, 59.6 mmol), MeOH (80 g) and isopropylamine (8.8 g, 149 mmol) were added and stirred at room temperature (25 ° C.) for 2 hours. Sodium borohydride (2.48 g, 65.6 mmol) was then added while cooling with ice and stirred at room temperature for 2 hours. After the reaction was completed, the solution was diluted with acetone and filtered. 12 N hydrochloric acid was added and the resulting solid was filtered off.
  • ⁇ Monomer Synthesis Example 8 Synthesis of DA-9> In a 500 mL four-neck flask, terephthalaldehyde (6.00 g, 44.7 mmol), MeOH (60 g), and pyrazin-2-ylmethanamine (10.7 g, 98.4 mmol) were added and stirred at room temperature for 2 hours. Sodium borohydride (1.86 g, 49.2 mmol) was then added while cooling with ice, and stirred at room temperature for 2 hours. After the reaction was completed, the solution was diluted with acetone and filtered. 12 N hydrochloric acid was added, and the resulting solid was filtered off.
  • DA-2 (2.53 g, 8.00 mmol) and NMP (22.8 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while feeding nitrogen. Thereafter, CA-1 (2.33 g, 7.92 mmol) and NMP (12.9 g) were added, and the mixture was stirred at 50° C. for 18 hours to obtain a solution of polyamic acid (A-2) with a solid content concentration of 12% by mass (viscosity: 17 mPa ⁇ s). The Mn of this polyamic acid was 2,867, and the Mw was 8,933.
  • the polyamic acid (A-2) has the following partial structure (a0-A-2) and is included in the scope of the polymer (P0).
  • DA-3 (2.55 g, 8.00 mmol) and NMP (22.9 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while feeding nitrogen. Thereafter, CA-1 (2.33 g, 7.92 mmol) and NMP (12.8 g) were added, and the mixture was stirred at 50° C. for 18 hours to obtain a solution of polyamic acid (A-3) with a solid content concentration of 12% by mass (viscosity: 13 mPa ⁇ s). The Mn of this polyamic acid was 2,048 and the Mw was 5,041.
  • the polyamic acid (A-3) has the following partial structure (a0-A-3) and is included in the scope of the polymer (P0).
  • DA-4 (1.97 g, 6.00 mmol) and NMP (17.7 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while feeding nitrogen. Thereafter, CA-1 (1.75 g, 5.94 mmol) and NMP (9.50 g) were added, and the mixture was stirred at 50° C. for 18 hours to obtain a solution of polyamic acid (A-4) with a solid content concentration of 12% by mass (viscosity: 19 mPa ⁇ s). The Mn of this polyamic acid was 3,618, and the Mw was 11,403.
  • the polyamic acid (A-4) has the following partial structure (a0-A-4) and is included in the scope of the polymer (P0).
  • DA-5 (2.40 g, 10.00 mmol) and NMP (27.6 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while feeding nitrogen. Then, CA-1 (2.91 g, 9.90 mmol) and NMP (11.30 g) were added, and the mixture was stirred at 50° C. for 18 hours to obtain a solution of polyamic acid (A-5) with a solid content concentration of 12% by mass (viscosity: 18 mPa ⁇ s). The Mn of this polyamic acid was 3,823 and the Mw was 9,215.
  • the polyamic acid (A-5) has the following partial structure (a0-A-5) and is included in the scope of the polymer (P0).
  • DA-6 (2.23 g, 7.00 mmol) and NMP (20.1 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while feeding nitrogen. Thereafter, CA-1 (2.04 g, 6.93 mmol) and NMP (11.20 g) were added, and the mixture was stirred at 50° C. for 18 hours to obtain a solution of polyamic acid (A-6) with a solid content concentration of 12% by mass (viscosity: 47 mPa ⁇ s). The Mn of this polyamic acid was 7,095, and the Mw was 22,170.
  • the polyamic acid (A-6) has the following partial structure (a0-A-6) and is included in the scope of the polymer (P0).
  • DA-7 (2.06 g, 7.00 mmol) and NMP (18.5 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while feeding nitrogen. Then, CA-1 (2.04 g, 6.93 mmol) and NMP (11.50 g) were added, and the mixture was stirred at 50° C. for 18 hours to obtain a solution of polyamic acid (A-7) with a solid content concentration of 12% by mass (viscosity: 21 mPa ⁇ s). The Mn of this polyamic acid was 4,711, and the Mw was 11,526.
  • the polyamic acid (A-7) has the following partial structure (a0-A-7) and is included in the scope of the polymer (P0).
  • DA-8 (2.22 g, 7.00 mmol) and NMP (20.0 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while feeding nitrogen. Then, CA-1 (2.04 g, 6.93 mmol) and NMP (11.20 g) were added, and the mixture was stirred at 50° C. for 18 hours to obtain a solution of polyamic acid (A-8) with a solid content concentration of 12% by mass (viscosity: 17 mPa ⁇ s). The Mn of this polyamic acid was 3,590 and the Mw was 11,228.
  • the polyamic acid (A-8) has the following partial structure (a0-A-8) and is included in the scope of the polymer (P0).
  • DA-9 (2.24 g, 7.00 mmol) and NMP (20.2 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while feeding nitrogen. Then, CA-1 (2.04 g, 6.93 mmol) and NMP (11.20 g) were added, and the mixture was stirred at 50° C. for 18 hours to obtain a solution of polyamic acid (A-9) with a solid content concentration of 12% by mass (viscosity: 17 mPa ⁇ s). The Mn of this polyamic acid was 3,602 and the Mw was 15,171.
  • the polyamic acid (A-9) has the following partial structure (a0-A-9) and is included in the scope of the polymer (P0).
  • DA-10 (1.46 g, 3.20 mmol) and NMP (13.1 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while feeding nitrogen. Thereafter, CA-1 (0.93 g, 3.17 mmol) and NMP (4.40 g) were added, and the mixture was stirred at 50° C. for 18 hours to obtain a solution of polyamic acid (A-10) with a solid content concentration of 12% by mass (viscosity: 38 mPa ⁇ s). The Mn of this polyamic acid was 4,052, and the Mw was 10,352.
  • the polyamic acid (A-10) has the following partial structure (a0-A-10) and is included in the scope of the polymer (P0).
  • DA-11 (1.36 g, 3.00 mmol) and NMP (12.3 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while feeding nitrogen. Thereafter, CA-1 (0.87 g, 2.97 mmol) and NMP (4.10 g) were added, and the mixture was stirred at 50° C. for 18 hours to obtain a solution of polyamic acid (A-4) with a solid content concentration of 12% by mass (viscosity: 17 mPa ⁇ s). The Mn of this polyamic acid was 3,202, and the Mw was 10,745.
  • the polyamic acid (A-11) has the following partial structure (a0-A-11) and is included in the scope of the polymer (P0).
  • DA-2 (2.06 g, 6.50 mmol) and NMP (18.5 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while feeding nitrogen. Thereafter, CA-2 (1.40 g, 6.44 mmol) and NMP (6.90 g) were added, and the mixture was stirred at 50° C. for 18 hours to obtain a solution of polyamic acid (A-14) with a solid content concentration of 12% by mass (viscosity: 21 mPa ⁇ s). The Mn of this polyamic acid was 4,281, and the Mw was 10,905.
  • the polyamic acid (A-14) has the following partial structure (a0-A-14) and is included in the scope of the polymer (P0).
  • DA-3 (2.23 g, 7.00 mmol) and NMP (20.1 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while feeding nitrogen. Thereafter, CA-2 (1.51 g, 6.93 mmol) and NMP (7.4 g) were added, and the mixture was stirred at 50° C. for 18 hours to obtain a solution of polyamic acid (A-15) with a solid content concentration of 12% by mass (viscosity: 11 mPa ⁇ s). The Mn of this polyamic acid was 2,820 and the Mw was 4,900.
  • the polyamic acid (A-15) has the following partial structure (a0-A-15) and is included in the scope of the polymer (P0).
  • DA-2 (1.74 g, 5.5 mmol) and NMP (20.0 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while feeding nitrogen. Thereafter, CA-3 (1.76 g, 5.45 mmol) and NMP (5.60 g) were added, and the mixture was stirred at 50° C. for 18 hours to obtain a solution of polyamic acid (A-16) with a solid content concentration of 12% by mass (viscosity: 15 mPa ⁇ s). The Mn of this polyamic acid was 2,073, and the Mw was 8,932.
  • the polyamic acid (A-16) has the following partial structure (a0-A-16) and is included in the scope of the polymer (P0).
  • DA-2 (1.74 g, 5.50 mmol) and NMP (20.0 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while feeding nitrogen. Thereafter, CA-4 (1.69 g, 5.45 mmol) and NMP (5.10 g) were added, and the mixture was stirred at 50° C. for 18 hours to obtain a solution of polyamic acid (A-17) with a solid content concentration of 12% by mass (viscosity: 12 mPa ⁇ s). The Mn of this polyamic acid was 1,513, and the Mw was 5,675.
  • the polyamic acid (A-17) has the following partial structure (a0-A-17) and is included in the scope of the polymer (P0).
  • DA-14 (1.80 g, 12.0 mmol) and NMP (20.7 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while feeding nitrogen. Thereafter, CA-1 (3.49 g, 11.9 mmol) and NMP (18.1 g) were added, and the mixture was stirred at 50° C. for 18 hours to obtain a solution of polyamic acid (A-18) with a solid content concentration of 12% by mass (viscosity: 187 mPa ⁇ s). The Mn of this polyamic acid was 4,753, and the Mw was 9,682.
  • the polyamic acid (A-18) has the following partial structure (c-A-18).
  • DA-15 (0.64 g, 3.0 mmol), DA-16 (2.22 g, 5.0 mmol), DA-17 (0.80 g, 2.0 mmol), and NMP (32.9 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while feeding nitrogen. Thereafter, CA-5 (2.13 g, 9.5 mmol) and NMP (9.5 g) were added, and the mixture was stirred at 40° C. for 18 hours to obtain a solution of polyamic acid (A-19) with a solid content concentration of 12% by mass (viscosity: 246 mPa ⁇ s). The Mn of this polyamic acid was 10,028, and the Mw was 24,122.
  • DA-18 (0.81 g, 7.5 mmol), DA-19 (9.16 g, 7.5 mmol), DA-17 (3.98 g, 10.0 mmol), DA-20 (3.66 g, 15.0 mmol), DA-21 (2.72 g, 10.0 mmol), and NMP (139.1 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature while feeding nitrogen to dissolve. Thereafter, CA-5 (10.70 g, 47.8 mmol) and NMP (28.1 g) were added, and the mixture was stirred at 40 ° C.
  • polyamic acid (A-20) with a solid content concentration of 12% by mass (viscosity: 233 mPa s).
  • the Mn of this polyamic acid was 9,546 and the Mw was 23,698.
  • the washed solid was dried under reduced pressure to obtain a polyamic acid powder in which the carboxylic acid was protected with a tertiary butyl group (yield: 0.87 g, carboxylic acid protection rate: 67%).
  • NMP 4.4 g was added to this polyamic acid powder (0.6 g), and the mixture was stirred at room temperature for 24 hours to dissolve the polyamic acid (A-21) in a solid content concentration of 12 mass% (viscosity: 12 mPa ⁇ s).
  • the polyamic acid had an Mn of 6,018 and an Mw of 9,992.
  • the polyamic acid (A-21) has the following partial structure (a0-A-21) and is included in the scope of the polymer (P0). is included in the range.
  • the washed solid was dried under reduced pressure to obtain a polyamic acid powder in which the carboxylic acid was protected with a tertiary butyl group (yield: 1.05 g, carboxylic acid protection rate: 94%).
  • NMP (4.4 g) was added to this polyamic acid powder (0.6 g), and the mixture was stirred at room temperature for 24 hours to dissolve the polyamic acid, and a solution of polyamic acid (A-22) with a solid content concentration of 12 mass% (viscosity: 12 mPa ⁇ s) was obtained.
  • the polyamic acid had an Mn of 5,707 and an Mw of 9,254.
  • the polyamic acid (A-22) has the following partial structure (a0-A-22) and is included in the scope of the polymer (P0). is included in the range.
  • Example 1 The polyamic acid solution (A-1) obtained in Synthesis Example 1 was diluted with NMP and BCS, and stirred at room temperature (25° C.) for 2 hours to obtain a liquid crystal alignment agent (AL-1) having a mass ratio of polyamic acid solid content to each solvent (polyamic acid solid content:NMP:BCS) of 5:75:20.
  • Examples 2 to 19 and Comparative Example 1 The polyamic acid solution used was changed as shown in Table 3, and the same operation as in Example 1 was performed to obtain liquid crystal alignment agents AL-2 to AL-19, which are Examples 2 to 19 of the present invention, and liquid crystal alignment agent AL-C1, which is Comparative Example 1.
  • Example 20 To the polyamic acid solution (A-2) obtained in Synthesis Example 2, NMP, BCS, AD-1 (1 mass% NMP solution), and AD-2 (10 mass% NMP solution) were added, and the mixture was stirred at room temperature (25°C) for 2 hours to obtain a liquid crystal alignment agent (AL-20) having a mass ratio of polyamic acid solid content to each solvent (polyamic acid solid content:NMP:BCS) of 5:75:20.
  • Examples 21 and 22 Except for changing the additives used as shown in Table 3, the same operation as in Example 20 was performed to obtain liquid crystal alignment agents AL-21 and AL-22, which are Examples 21 and 22 of the present invention.
  • Example 23 The polyamic acid solution (A-2) obtained in Synthesis Example 2 and the polyamic acid solution (A-19) obtained in Synthesis Example 19 were diluted with NMP and BCS so that the mass ratio of the two types of polymer solid contents became 50:50, and the mixture was stirred at room temperature (25° C.) for 2 hours to obtain a liquid crystal alignment agent (AL-23) in which the mass ratio of the polyamic acid solid content to each solvent (polyamic acid solid content:NMP:BCS) became 5:75:20.
  • A-3 liquid crystal alignment agent
  • Example 24 and Comparative Examples 2 and 3 The polyamic acid solution used was changed as shown in Table 3, and the same operation as in Example 23 was performed to obtain the liquid crystal alignment agent AL-24, which is Example 24 of the present invention, and the liquid crystal alignment agents AL-C2 and AL-C3, which are Comparative Examples 2 and 3.
  • Additive 1 and Additive 2 represent the ratio (parts by mass) of additive to 100 parts by mass of the polyamic acid component.
  • a liquid crystal cell having the structure of an FFS mode liquid crystal display element was prepared.
  • a substrate with electrodes was prepared.
  • the substrate was a rectangular glass substrate with dimensions of 30 mm x 35 mm and a thickness of 0.7 mm.
  • An ITO electrode with a solid pattern was formed on the substrate as a first layer, which constituted a common electrode.
  • a SiN (silicon nitride) film formed by CVD (chemical vapor deposition) was formed as a second layer on the first common electrode.
  • the thickness of the second SiN film was 300 nm, which was a thickness that functioned as an interlayer insulating film.
  • a comb-shaped pixel electrode formed by patterning an ITO film as a third layer was arranged on the second SiN film, and two pixels, a first pixel and a second pixel, were formed, and the size of each pixel was 10 mm long and 5 mm wide.
  • This substrate with electrodes had a structure in which the first common electrode and the third pixel electrode were insulated by the second SiN film.
  • the pixel electrode of the third layer had a comb-like shape with the central portion bent at an interior angle of 160° and multiple electrode lines, each 3 ⁇ m wide, arranged in parallel at intervals of 6 ⁇ m.
  • One pixel was formed by multiple electrode lines and had a first region and a second region separated by a line connecting the bent portions.
  • the liquid crystal alignment agents (AL-C1), (AL-1) to (AL-19) obtained in the above Comparative Example 1 and Examples 1 to 19 were each filtered with a filter having a pore size of 1.0 ⁇ m, and then applied by spin coating to the above-mentioned electrode-attached substrate (hereinafter referred to as the electrode substrate) and a glass substrate having a columnar spacer with a height of 3.3 ⁇ m and an ITO film formed on the back surface (hereinafter referred to as the counter substrate). After drying for 2 minutes on a hot plate at 80° C., the substrate was baked for 20 minutes in a hot air circulation oven at 230° C. to form a coating film with a thickness of 100 nm.
  • the coating film was subjected to a rubbing alignment treatment (roller diameter: 120 mm, roller rotation speed: 500 rpm, moving speed: 30 mm/sec, indentation length: 0.3 mm) with a rayon cloth (HY-5318 manufactured by Hyperflex). Thereafter, the substrate was cleaned by ultrasonic irradiation in pure water for 1 minute, water droplets were removed by air blowing, and then the substrate was dried in an oven at 80°C for 15 minutes to obtain a substrate with a liquid crystal alignment film.
  • a rubbing alignment treatment roller diameter: 120 mm, roller rotation speed: 500 rpm, moving speed: 30 mm/sec, indentation length: 0.3 mm
  • rayon cloth HY-5318 manufactured by Hyperflex
  • the liquid crystal alignment film formed on the electrode substrate was oriented so that the direction that equally divides the inner angle of the pixel bend portion and the alignment direction of the liquid crystal were orthogonal, and the alignment film formed on the counter substrate was oriented so that the alignment direction of the liquid crystal on the electrode substrate and the alignment direction of the liquid crystal on the counter substrate coincided when the liquid crystal cell was produced.
  • the above two substrates were combined into a set, and a sealant (Mitsui Chemicals XN-1500T) was printed on the substrate with a dispenser, and another substrate was laminated so that the alignment directions of the liquid crystal alignment films of each substrate were 0° and faced each other.
  • the laminated substrates were then pressed together and heated in a hot air circulating oven at 150°C for 60 minutes to harden the sealant, and an empty cell was produced.
  • a positive liquid crystal PA-1492 (DIC Corporation) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS drive liquid crystal cell.
  • the obtained liquid crystal cell was then heated at 120°C for 1 hour and allowed to stand overnight at 23°C before being used for evaluation.
  • liquid crystal alignment agents (AL-C2), (AL-C3), (AL-23), and (AL-24) obtained in the above Comparative Examples 2 and 3 and Examples 23 and 24 were each filtered through a filter with a pore size of 1.0 ⁇ m, and then applied by spin coating to the above electrode-attached substrate (hereinafter referred to as the electrode substrate) and a glass substrate (hereinafter referred to as the opposing substrate) having a columnar spacer with a height of 4 ⁇ m and an ITO film formed on the back surface. After drying for 2 minutes on a hot plate at 80 ° C., the substrate was baked for 30 minutes in an IR oven at 230 ° C.
  • the coating surface was irradiated with 300 mJ / cm 2 polarized ultraviolet light having a wavelength of 254 nm through a 240 nm low-cut filter and a polarizer, and further baked for 30 minutes in an IR oven at 230 ° C. to perform an alignment treatment, thereby obtaining a substrate with a liquid crystal alignment film.
  • the liquid crystal alignment film formed on the electrode substrate was subjected to an alignment treatment so that the direction that equally divides the inner angle of the pixel bend portion and the alignment direction of the liquid crystal were orthogonal, and the liquid crystal alignment film formed on the counter substrate was subjected to an alignment treatment so that the alignment direction of the liquid crystal on the electrode substrate and the alignment direction of the liquid crystal on the counter substrate coincided when the liquid crystal cell was produced.
  • the above two substrates were combined into a set, and a sealant (Mitsui Chemicals XN-1500T) was printed on the substrate using a dispenser, and another substrate was attached to the set so that the alignment directions of the liquid crystal alignment films of the substrates were 0° and faced each other.
  • the attached substrates were then pressed together and heated in a hot air circulation oven at 150° C. for 60 minutes to harden the sealant, producing an empty cell.
  • Positive liquid crystal PA-1492 (DIC) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS drive liquid crystal cell. Thereafter, the obtained FFS driving liquid crystal cell was heated at 120° C. for 1 hour and allowed to stand overnight at 23° C. before being used for evaluation.
  • the liquid crystal cell prepared above was placed between two polarizing plates arranged so that the polarization axes were perpendicular to each other, and in a state in which the pixel electrode and the common electrode were short-circuited to have the same potential, an LED backlight was irradiated from below the two polarizing plates, and the angle of the liquid crystal cell was adjusted so that the brightness of the LED backlight transmitted light measured above the two polarizing plates was minimized.
  • a VT curve voltage-transmittance curve
  • the liquid crystal cell was driven for 30 minutes by applying an AC voltage of 30 Hz at which the relative transmittance was 23%, while simultaneously applying a DC voltage of 1 V. Thereafter, the application of the DC voltage alone was stopped, and the cell was driven for another 10 minutes by the AC voltage alone, and the relative transmittance was measured.
  • the relative transmittance relaxed to 25% or less within 10 minutes from the point when the application of the DC voltage was stopped, it was defined as "O", and when it took 10 minutes or more for the relative transmittance to fall to 25% or less, it was defined as "X”.
  • the afterimage evaluation according to the above-mentioned method was carried out under a temperature condition in which the temperature of the liquid crystal cell was 23°C.
  • "-" in Comparative Example 1 indicates that the relaxation rate of the accumulated charge was not measured.
  • Flicker level (%) ⁇ flicker amplitude/(2 x z) ⁇ x 100
  • z is the luminance value read by the data acquisition/data logger switch unit 34970A when driven with an AC voltage of 30 Hz at which the relative transmittance is 23%.
  • the photoresponsiveness was evaluated as follows: if the flicker level at the time when the LED backlight was turned on and the AC voltage was applied was subtracted from the maximum flicker level reached until 30 minutes had elapsed, the evaluation was given a rating of "O"; if the difference between the maximum value and the flicker level at the start reached 0.6% or more, the evaluation was given a rating of "X.”
  • the evaluation of the flicker level according to the above-mentioned method was carried out under a temperature condition in which the temperature of the liquid crystal cell was 23°C.
  • Table 4 shows the evaluation results of the relaxation speed of the accumulated charge and the flicker of the liquid crystal cells using the liquid crystal alignment agents of Examples 1 to 19, 23, and 24 and Comparative Examples 1 to 3.
  • the liquid crystal display elements using the liquid crystal alignment agents of Examples 1 to 11, 14 to 19, and 24 had good relaxation speeds of accumulated charges and good photoresponsiveness.
  • the liquid crystal display elements using the liquid crystal alignment agents of Examples 12, 13, and 23 had good relaxation speeds of accumulated charges.

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Abstract

La présente invention concerne : un film d'alignement de cristaux liquides dans lequel une charge générée peut être réduite en un court laps de temps, tout en réduisant la valeur absolue de la charge accumulée ; et un agent d'alignement de cristaux liquides qui permet d'obtenir un film d'alignement de cristaux liquides dans lequel le papillotement et l'accumulation de charge attribuables à la lumière du rétroéclairage sont réduits.　Est divulgué un agent d'alignement de cristaux liquides qui est caractérisé en ce qu'il contient au moins un polymère (PO) qui est choisi dans le groupe constitué par : un précurseur de polyimide ayant une structure partielle (a0) représentée par la formule (0) ; et un polyimide qui est un produit imidisé du précurseur de polyimide. (Dans la formule, la définition de chaque symbole est telle que définie dans la description.)
PCT/JP2024/037751 2023-10-26 2024-10-23 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides Pending WO2025089307A1 (fr)

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JP2023183784 2023-10-26

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017090850A (ja) * 2015-11-17 2017-05-25 Jsr株式会社 液晶配向剤、液晶配向膜、液晶素子、重合体及び重合体の製造方法
JP2017102350A (ja) * 2015-12-03 2017-06-08 Jsr株式会社 液晶配向剤、液晶配向膜、液晶素子、重合体及び化合物
WO2019107533A1 (fr) * 2017-12-01 2019-06-06 サイエンスファーム株式会社 Dérivé de pyridine et de benzène

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017090850A (ja) * 2015-11-17 2017-05-25 Jsr株式会社 液晶配向剤、液晶配向膜、液晶素子、重合体及び重合体の製造方法
JP2017102350A (ja) * 2015-12-03 2017-06-08 Jsr株式会社 液晶配向剤、液晶配向膜、液晶素子、重合体及び化合物
WO2019107533A1 (fr) * 2017-12-01 2019-06-06 サイエンスファーム株式会社 Dérivé de pyridine et de benzène

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