WO2016080033A1 - 液晶配向剤、液晶配向膜、液晶配向膜の製造方法、液晶表示素子、重合体及び化合物 - Google Patents

液晶配向剤、液晶配向膜、液晶配向膜の製造方法、液晶表示素子、重合体及び化合物 Download PDF

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WO2016080033A1
WO2016080033A1 PCT/JP2015/073157 JP2015073157W WO2016080033A1 WO 2016080033 A1 WO2016080033 A1 WO 2016080033A1 JP 2015073157 W JP2015073157 W JP 2015073157W WO 2016080033 A1 WO2016080033 A1 WO 2016080033A1
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group
formula
following formula
represented
liquid crystal
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PCT/JP2015/073157
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English (en)
French (fr)
Japanese (ja)
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伸夫 安池
利之 秋池
洋平 野辺
尚基 菅野
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Jsr株式会社
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Priority to CN202011089406.3A priority Critical patent/CN112210390B/zh
Priority to KR1020177013059A priority patent/KR102282111B1/ko
Priority to CN201580061347.XA priority patent/CN107111191B/zh
Priority to JP2016560082A priority patent/JP6579114B2/ja
Publication of WO2016080033A1 publication Critical patent/WO2016080033A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/30—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings
    • C07C57/42—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the rings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/40—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino groups bound to carbon atoms of at least one six-membered aromatic ring and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/44—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino groups bound to carbon atoms of at least one six-membered aromatic ring and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton with carboxyl groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by unsaturated carbon chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/20—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
    • 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
    • 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 aligning agent, a liquid crystal aligning film, a method for producing a liquid crystal aligning film, a liquid crystal display element, a polymer and a compound.
  • Liquid crystal display elements are widely used in televisions, mobile devices, various monitors and the like.
  • a liquid crystal alignment film is used to control the alignment of liquid crystal molecules in the liquid crystal cell.
  • Conventional methods for obtaining an organic film having a liquid crystal alignment regulating force include a method of rubbing an organic film, a method of obliquely depositing silicon oxide, a method of forming a monomolecular film having a long chain alkyl group, and a photosensitive organic film.
  • a method of irradiating a film with light photo-alignment method
  • Patent Document 1 discloses that a liquid crystal alignment film is formed using a liquid crystal alignment agent containing a polyimide precursor having a cinnamoyl group in the main chain, polyimide or polyamide.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal display element having good afterimage characteristics and contrast characteristics.
  • liquid crystal aligning agent As a result of intensive studies to achieve the above-described problems of the prior art, the present inventors have found that the above problems can be solved by including a compound having a specific structure in the liquid crystal aligning agent.
  • the invention has been completed. Specifically, the following liquid crystal aligning agent, liquid crystal alignment film, liquid crystal alignment film manufacturing method, liquid crystal display element, polymer, and compound are provided.
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a cyano group, or a monovalent organic group
  • R 3 is a substituent, provided that R 1 and R 2 At least one is a halogen atom, a cyano group or a monovalent organic group
  • X 1 is an oxygen atom or —NR 4 — (wherein R 4 is a hydrogen atom, a hydroxyl group or a monovalent organic group, and R 4 is It may be bonded to another group to form a ring structure together with the nitrogen atom.)
  • R 3 may be bonded to another group to constitute at least a part of the ring, and n is 0. (It is an integer of ⁇ 4. When n is 2 or more, a plurality of R 3 may be the same or different. “*” Represents a bond.)
  • a method for producing a liquid crystal alignment film comprising: a step of applying the liquid crystal aligning agent of [1] above on a substrate to form a coating film; and a step of irradiating the coating film with light.
  • a liquid crystal display device comprising the liquid crystal alignment film according to [3].
  • a 1 is a group represented by the following formula (1-1) or a group represented by the following formula (1-2)
  • a 2 is a single bond, the following formula (1 -1) or a group represented by the following formula (1-2):
  • R 5 is a divalent organic compound when A 1 is a group represented by the following formula (1-1).
  • a group, .R 7 a 1 is a single bond or a divalent organic group in the case of a group represented by the following formula (1-2)
  • a 2 is represented by the following formula (1-1)
  • R 6 is a divalent organic group, and when A 2 is a group represented by the following formula (1-2) or a single bond, it is a single bond or a divalent organic group.
  • R 8 is 1 when A 1 is a group represented by the following formula (1-1). the valence of the organic radical, a hydrogen atom or a monovalent organic group when the group a 1 is represented by the following formula (1-2).
  • R 8 is a hydrogen atom
  • a 1 is diamino a phenyl group
  • R 8 is a monovalent organic group
  • R 10 R 8 is having a diamino phenyl group
  • group a 2 is represented by the following formula (1-1)
  • a 2 is a group represented by the following formula (1-2) or a single bond
  • R 9 is a divalent organic group. “* 1” in formula (1-1) and formula (1-2) is bonded to R 9.
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a cyano group, or a monovalent organic group
  • R 3 is a substituent.
  • R 1 and R 2 is a halogen atom, a cyano group or a monovalent organic group
  • X 1 is an oxygen atom or —NR 4 — (where R 4 is a hydrogen atom, a hydroxyl group or a monovalent group)
  • R 4 may be bonded to another group to form a ring structure together with the nitrogen atom.
  • N is an integer of 0 to 4.
  • n is 2 or more, a plurality of The R 3 groups may be the same or different. “* 1” represents a bond.)
  • a 3 is a group represented by the above formula (1-1) or a group represented by the above formula (1-2)
  • a 4 is a single bond
  • R 15 and R 17 are each independently an aromatic ring group, an alicyclic group or a heterocyclic group
  • R 16 is a divalent organic group
  • X 3 and X 4 are each independently a single bond or a divalent linking group, provided that in the above formulas (1-1) and (1-2), “* 1” is bonded to R 16.
  • R 18 is a divalent organic group
  • R 19 is an aromatic ring group, an alicyclic group, or a heterocyclic group.
  • R 1 , R 2, and X 1 are the above-mentioned groups. (It is synonymous with the formula (5-1).)
  • a 1 is a group represented by the above formula (1-1) or a group represented by the above formula (1-2)
  • a 2 is a single bond
  • R 11 is a monovalent organic group when A 1 is a group represented by the above formula (1-1).
  • a 1 is a group represented by the above formula (1-2)
  • R 12 is a divalent organic group
  • R 13 is A 2 A divalent organic group when the group is represented by the formula (1-1), and a single bond or a divalent organic group when A 2 is a group represented by the formula (1-2).
  • S and r are each independently 0 or 1.
  • it has one carboxyl group, and “*” in the above formulas (1-1) and (1-2). 1 "is attached to R 12.)
  • liquid crystal aligning agent containing the compound (X) it is possible to obtain a liquid crystal display element in which an afterimage (particularly an afterimage due to an AC voltage) hardly occurs and a good contrast.
  • the schematic block diagram of a FFS type liquid crystal display element The plane schematic diagram of the top electrode used for manufacture of the liquid crystal display element by a photo-alignment process.
  • A is a top view of a top electrode
  • (b) is the elements on larger scale of a top electrode.
  • the liquid crystal aligning agent of this indication contains the compound (henceforth "compound (X)" which has the partial structure represented by following formula (1).
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a cyano group, or a monovalent organic group
  • R 3 is a substituent, provided that R 1 and R 2 At least one is a halogen atom, a cyano group or a monovalent organic group
  • X 1 is an oxygen atom or —NR 4 — (wherein R 4 is a hydrogen atom, a hydroxyl group or a monovalent organic group, and R 4 is It may be bonded to another group to form a ring structure together with the nitrogen atom.)
  • R 3 may be bonded to another group to constitute at least a part of the ring, and n is 0.
  • It is an integer of ⁇ 4. When n is 2 or more, a plurality of R 3 may be the same or different.
  • examples of the monovalent organic group represented by R 1 and R 2 include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, Examples thereof include a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an epoxy group, an alkylsilyl group, and an alkoxysilyl group.
  • the alkyl group having 1 to 20 carbon atoms may be linear or branched.
  • Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group;
  • examples of the fluoroalkyl group having 1 to 20 carbon atoms include a perfluoromethyl group, A fluoroethyl group, a 2,2,2-trifluoroethyl group and the like;
  • examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group and a methylcyclohexyl group; an aryl group having 6 to 20 carbon atoms Examples thereof include a phenyl group and a tolyl group, and examples of the aralkyl group having 6 to 20 carbon atoms include a benzyl group.
  • halogen atom of R ⁇ 1 > and R ⁇ 2 > a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, A fluorine atom is preferable.
  • At least one of R 1 and R 2 is a halogen atom, a cyano group, or a monovalent organic group. From the viewpoint of sufficiently expressing the alignment regulating power of liquid crystal by light irradiation, at least R 2 is a halogen atom. An atom, a cyano group or a monovalent organic group is preferred.
  • R 1 is preferably a hydrogen atom, a fluorine atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a fluorine atom or a methyl group. Further preferred.
  • R 2 is preferably a fluorine atom or an alkyl group having 1 to 10 carbon atoms, more preferably a fluorine atom or an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group.
  • R 1 is a hydrogen atom and R 2 is a methyl group is particularly preferable.
  • R 4 in —NR 4 — is preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or a protecting group.
  • the protecting group include carbamate protecting groups, amide protecting groups, imide protecting groups, sulfonamide protecting groups, and the like.
  • carbamate protecting groups Preferred are carbamate protecting groups, and specific examples thereof include, for example, t-butoxycarbonyl group, benzyloxycarbonyl group, 1,1-dimethyl-2-haloethyloxycarbonyl group, 1,1-dimethyl-2- A cyanoethyloxycarbonyl group, a 9-fluorenylmethylcarbonyl group, an allyloxycarbonyl group, a 2- (trimethylsilyl) ethoxycarbonyl group, and the like can be given.
  • a t-butoxycarbonyl group is preferable in that it can be easily deprotected by heat and can be easily discharged from the membrane as a gas.
  • R 4 is preferably a hydrogen atom, a methyl group, a hydroxyl group or a t-butoxycarbonyl group, and more preferably a hydrogen atom or a methyl group.
  • R 4 may combine with other groups to form a ring structure together with the nitrogen atom. Examples of such a ring structure include piperidine and piperazine.
  • X 1 is preferably an oxygen atom.
  • Examples of the substituent for R 3 include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, an alkylsilyl group, an alkoxysilyl group, and an ester. Groups and the like.
  • Examples of the ring formed by bonding R 3 to another group include an imide ring.
  • n is preferably 0 to 2, more preferably 0 or 1.
  • “*” In formula (1) may be bonded to a hydrogen atom, may be bonded to an organic group, or may be bonded to R 3 to form a ring structure (eg, an imide ring). May be.
  • the compound (X) may be a polymer component that can be a main component of the liquid crystal alignment film, or may be an additive component that is blended separately from the polymer component.
  • the “main chain” of the polymer in the present specification refers to a “trunk” portion composed of the longest chain of atoms in the polymer. It is allowed that the “trunk” portion includes a ring structure.
  • “having the partial structure represented by the above formula (1) in the main chain of the polymer” means that the partial structure constitutes a part of the main chain. However, it does not exclude that the partial structure represented by the above formula (1) exists also in a portion other than the main chain, for example, a side chain (a portion branched from the “trunk” of the polymer).
  • “Organic group” means a group containing a hydrocarbon group, and the structure may contain a hetero atom.
  • the main skeleton when the compound (X) is a polymer is not particularly limited.
  • polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenyl) Main skeletons such as maleimide) derivatives and poly (meth) acrylates are particularly limited.
  • polyamic acid, polyimide, polyamic acid ester, polyamide, polyorganosiloxane, and poly (meth) acrylate from the viewpoint of heat resistance, mechanical strength, affinity with liquid crystal, and the like.
  • polymer (A) a polymer
  • polymer (A) a polymer
  • the polymer is more preferably at least one polymer selected from the group consisting of polyamic acid, polyimide and polyamic acid ester.
  • the polymer used for preparation of a liquid crystal aligning agent may be only 1 type, and 2 or more types may be sufficient as it.
  • (Meth) acrylate is meant to include acrylate and methacrylate.
  • the polyamic acid as the compound (X) is a polyamic acid having a partial structure represented by the above formula (1), and can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine.
  • [1] a method of polymerizing a monomer containing a tetracarboxylic dianhydride having a partial structure represented by the above formula (1) (hereinafter also referred to as “specific acid non-hydrate”)
  • [ 2] A method of polymerizing a monomer containing a diamine having a partial structure represented by the above formula (1) (hereinafter also referred to as “specific diamine”)
  • [3] including the above-mentioned specific acid dihydrate and the above-mentioned specific diamine.
  • a method of polymerizing monomers it is preferable to use a specific diamine because the synthesis of the monomer is relatively easy.
  • the method [2] is preferable.
  • the specific acid dianhydride used for the synthesis of the polyamic acid is not particularly limited as long as it has the partial structure represented by the above formula (1), but preferred specific examples include the following formula (5-1 ) And a compound represented by the following formula (5-2).
  • a 3 is a group represented by the following formula (1-1) or a group represented by the following formula (1-2)
  • a 4 is a single bond, the following formula (1 -1) or a group represented by the following formula (1-2):
  • R 15 and R 17 are each independently an aromatic ring group, an alicyclic group, or a heterocyclic group
  • R 16 is a divalent organic group
  • X 3 and X 4 are each independently a single bond or a divalent linking group, provided that in the following formulas (1-1) and (1-2) “* 1” is bonded to R 16.
  • R 1 , R 2 , R 3 , X 1 and n are as defined in formula (1) above.
  • R 18 is a divalent organic group
  • R 19 is an aromatic ring group, an alicyclic group, or a heterocyclic group.
  • R 1 , R 2, and X 1 are the above-mentioned groups. (It is synonymous with Formula (1).)
  • R 15 and R 17 are groups in which three hydrogen atoms have been removed from the ring portion of the aromatic ring, aliphatic ring or heterocyclic ring.
  • An aromatic ring group or an alicyclic group is preferable, and a group obtained by removing three hydrogen atoms from a ring portion of a benzene ring, naphthalene ring, cyclopentane ring or cyclohexane ring is more preferable.
  • a group obtained by removing three hydrogen atoms from the ring portion of the cyclohexane ring is more preferable.
  • the description of R 5 to R 7 in the following formula (2-1) can be applied.
  • a substituted or unsubstituted aromatic ring group or an alicyclic group preferably a substituted or unsubstituted aromatic ring group.
  • the divalent linking group for X 3 and X 4 include —O—, —CO—, —COO—, —CONR 4 — (R 4 has the same meaning as the above formula (1)), and the following formula (2 And divalent organic groups exemplified for R 5 to R 7 in 1).
  • the description of the above formula (1) can be applied to R 1 , R 2 , R 3 and X 1 in the above formulas (1-1) and (1-2).
  • the compound represented by the above formula (5-1) is preferably a compound in which A 3 is represented by the above formula (1-2), and A 4 is a single bond. More preferably.
  • the description of R 5 to R 7 in the following formula (2-1) can be applied to the divalent organic group of R 18 .
  • R 19 the illustrations of R 15 and R 17 in the above formula (5-1) and the description of preferred specific examples can be applied.
  • a partial structure represented by the above formula (1) may be further formed by a structure in which at least a part of R 18 and R 19 are bonded. Good.
  • specific acid dianhydride examples include, for example, compounds represented by the following formulas (t-1) to (t-31).
  • specific acid dianhydride may be used individually by 1 type, and may be used in combination of 2 or more type.
  • R is an alkyl group having 1 to 5 carbon atoms
  • k and j are each independently It is an integer from 0 to 2.
  • the position of R bonded to the ring portion of the 1,4-phenylene group is particularly limited. Not. Specifically, in the case of monosubstitution, it can be in the 2-position, 3-position, 5-position or 6-position, and in the case of disubstitution, the 2,4-position or 3,5-position. Is preferred. R is preferably a methyl group.
  • the specific acid dianhydride can be synthesized by appropriately combining conventional methods of organic chemistry. For example, a compound having “—C (R 1 ) ⁇ C (R 2 ) —CO—X 1 —” is reacted with a phthalic acid derivative to form a tetra-structure having a partial structure represented by the above formula (1). It can be obtained by synthesizing a carboxylic acid and then acidifying the resulting tetracarboxylic acid.
  • the method for synthesizing the specific acid dianhydride is not limited to the above.
  • the tetracarboxylic dianhydride used for the synthesis of the polyamic acid as the compound (X) may be only the specific acid dianhydride, A tetracarboxylic dianhydride having no partial structure represented by 1) (hereinafter also referred to as “other acid dianhydrides”) may be used in combination.
  • a tetracarboxylic dianhydride having no partial structure represented by 1) hereinafter also referred to as “other acid dianhydrides”
  • combination of the polyamic acid as a compound (X) another acid dianhydride is used as a tetracarboxylic dianhydride.
  • Examples of other acid dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and the like. Specific examples thereof include aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride, the following formula (AN-2) or formula (AN-3): (In the formula (AN-2), X 13 and X 14 are each independently a group obtained by removing one hydrogen atom from a methylene group or a nitrogen atom, and R 41 is an alkanediyl group having 1 to 10 carbon atoms.
  • X 15 and X 16 are each independently a group obtained by removing one hydrogen atom from a methylene group or a nitrogen atom, and B 1 and B 2 are each independently a phenylene group. Or a pyridinylene group, R 42 is an alkanediyl group having 1 to 10 carbon atoms, and m is an integer of 1 to 3. However, when m is 2 or 3, a plurality of R 42 may be the same or different from each other.
  • a compound represented by: Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1 , 3-dione, 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydro
  • aromatic tetracarboxylic dianhydride examples include pyromellitic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, and the following formula (AN-1)
  • X 11 and X 12 are each independently a single bond, an oxygen atom, a sulfur atom, —CO—, * —COO—, * —OCO—, * —CO—NR 21 —, * —NR 21 —CO— (wherein R 21 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. “*” Represents a bond to R 20 ).
  • examples of the alkanediyl group having 1 to 10 carbon atoms of R 41 and R 42 include a methylene group, an ethylene group, a propylene group, a butanediyl group, a pentanediyl group, a hexanediyl group, a heptanediyl group, An octanediyl group, a nonanediyl group, a decanediyl group, etc. are mentioned, These may be linear or branched.
  • B 1 and B 2 are preferably a 1,4-phenylene group or a 2,5-pyridinylene group.
  • AN-2 Specific examples of the compound represented by the above formula (AN-2) include, for example, a compound represented by the following formula (a-2) and the like, and specific examples of the compound represented by the above formula (AN-3) Examples include compounds represented by the following formulas (AN-3-1) to (AN-3-28), for example.
  • divalent hydrocarbon group having 1 to 20 carbon atoms of R 20 in the above formula (AN-1) include, for example, a methylene group, an ethylene group, a propylene group, a butanediyl group, a pentanediyl group, a hexanediyl group, and a heptanediyl.
  • alkanediyl group such as octanediyl group, nonanediyl group and decandiyl group
  • divalent alicyclic hydrocarbon group such as cyclohexylene group
  • divalent aromatic hydrocarbon group such as phenylene group and biphenylene group
  • the number of oxygen atoms that may be introduced between the carbon-carbon bonds of the hydrocarbon group may be one or may be two or more.
  • R 20 is a divalent group having a nitrogen-containing heterocyclic ring
  • examples of the nitrogen-containing heterocyclic ring include a pyrrole ring, an imidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a piperidine ring, a piperazine ring, and a pyrrolidine ring.
  • AN-1 examples include, for example, compounds represented by the following formulas (AN-1-1) to (AN-1-27), examples thereof include a compound represented by 1) and a compound represented by the following formula (a-3).
  • a polyamic acid examples include 1,3-bis(trimethoxyphenyl)-2,3-bis(trimethoxyphenyl)-2,3-bis(trimethoxyphenyl)-2,3-bis(trimethoxyphenyl)-2-organic acid, tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.
  • Other acid dianhydrides preferably include at least one selected from the group consisting of an aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride from the viewpoint of electrical characteristics.
  • a-2 bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-dianhydride, , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride , 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- (2,5-dione Oxotetrahydrofuran
  • the amount of these preferred compounds used is preferably 10 mol% or more based on the total amount of other acid dianhydrides used for the synthesis of the polyamic acid. More preferably, it is 20 mol% or more, more preferably 50 mol% or more.
  • the specific acid dianhydride used in the above method [1] is used based on the total amount of tetracarboxylic dianhydride used for the synthesis of polyamic acid from the viewpoint of sufficiently obtaining the effect of improving the afterimage characteristics and contrast characteristics of the liquid crystal display device. On the other hand, it is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more.
  • the specific diamine used for the synthesis of the polyamic acid is not particularly limited as long as it has the partial structure represented by the above formula (1).
  • it is represented by the following formula (2-1):
  • a 1 is a group represented by the following formula (1-1) or a group represented by the following formula (1-2)
  • a 2 is a single bond, the following formula (1 -1) or a group represented by the following formula (1-2):
  • R 5 is a divalent organic compound when A 1 is a group represented by the following formula (1-1).
  • R 7 is a group a 2 is represented by the following formula (1-1) In this case, it is a divalent organic group, and in the case of a group represented by the following formula (1-2) or a single bond, it is a single bond or a divalent organic group, and R 6 is a divalent organic group.
  • a 1 and A 2 have the same meanings as the above formula (2-1).
  • R 8 is 1 when A 1 is a group represented by the following formula (1-1).
  • R 8 is a hydrogen atom or a monovalent organic group, provided that when R 8 is a hydrogen atom, A 1 represents a diaminophenyl group.
  • R 8 is a monovalent organic group, R 8 has a diaminophenyl group, and R 10 is a monovalent organic group when A 2 is a group represented by the following formula (1-1):
  • a 2 is a group represented by the following formula (1-1):
  • R 9 is a divalent organic group.
  • examples of the divalent organic group represented by R 5 to R 7 include a divalent hydrocarbon group having 1 to 20 carbon atoms and a part of the methylene group of the hydrocarbon group.
  • the “hydrocarbon group” in this specification means a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
  • the “chain hydrocarbon group” means a linear hydrocarbon group and a branched hydrocarbon group which are composed only of a chain structure without including a cyclic structure in the main chain. However, it may be saturated or unsaturated.
  • the “alicyclic hydrocarbon group” means a hydrocarbon group that includes only an alicyclic hydrocarbon structure as a ring structure and does not include an aromatic ring structure. However, it is not necessary to be comprised only by the structure of an alicyclic hydrocarbon, The thing which has a chain structure in the part is also included.
  • “Aromatic hydrocarbon group” means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic hydrocarbon structure.
  • divalent hydrocarbon group having 1 to 20 carbon atoms in R 5 to R 7 include a chain hydrocarbon group such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a pentanediyl group, and a hexanediyl group.
  • Cyclohexylene xylene group and the like; may be mentioned, respectively.
  • Examples of the divalent heterocyclic group in R 5 to R 7 include groups in which two hydrogen atoms have been removed from a nitrogen-containing heterocyclic ring such as pyridine, piperazine, piperidine and the like.
  • Examples of the substituent that R 5 to R 7 may have include a halogen atom, an alkoxy group, a hydroxyl group, a carboxyl group, and a cyano group.
  • the divalent organic group of R 5 and R 7 includes, among the above, a substituted or unsubstituted phenylene group, biphenylene group, naphthylene group, cyclohexylene group, pyridinylene group, or — Ar 4 —COO— * 3 (Ar 4 represents a substituted or unsubstituted phenylene group, biphenylene group, naphthylene group, or cyclohexylene group, and “* 3 ” represents a bond with a benzene ring. ) Is preferable.
  • R 6 is preferably an alkanediyl group having 1 to 6 carbon atoms, a cyclohexylene group, a phenylene group, a biphenylene group or a naphthylene group.
  • examples of the monovalent organic group represented by R 8 and R 10 include a monovalent hydrocarbon group having 1 to 20 carbon atoms and a part of a methylene group possessed by the hydrocarbon group.
  • a monovalent group, a monovalent heterocyclic group, and the like obtained by replacing with O—, —CO—, —COO—, or —NR 33 — (R 33 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and the like. These may have a substituent.
  • R 8 and R 10 include, for example, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a cyclohexyl group, phenyl Group, tolyl group, benzyl group, biphenyl group, naphthyl group, pyridyl group, piperidyl group and the like.
  • R 9 the description of R 6 in the above formula (2-1) can be applied.
  • the two amino groups are preferably in the 2,4-position or 3,5-position with respect to the other groups. Note that the description of the above formula (1) can be applied to the description of R 1 , R 2 , R 3 and X 1 in the above formulas (1-1) and (1-2).
  • the specific diamine is preferably a compound having a partial structure represented by the following formula (4) in the molecule.
  • the partial structure represented by the following formula (4) it is preferable in that the effect of reducing the afterimage (AC afterimage) due to the AC voltage can be enhanced in the liquid crystal display element.
  • Ar 1 and Ar 2 are each independently a substituted or unsubstituted phenylene group or cyclohexylene group, X 2 is a single bond, —COO— or —CONR 20 — (R 20 is A hydrogen atom or a monovalent organic group.)
  • Ar 1 may constitute a benzene ring in the above formula (1), where t is 1 or 2.
  • t 2
  • Ar 2 and X 2 each independently have the above definition, “*” represents a bond.
  • examples of the monovalent organic group represented by R 20 include an alkyl group having 1 to 6 carbon atoms and a protecting group.
  • the protecting group include t-butoxycarbonyl group, benzyloxycarbonyl group, 1,1-dimethyl-2-haloethyloxycarbonyl group, allyloxycarbonyl group and the like.
  • X 2 is preferably a single bond or —COO—.
  • the substituent of the ring portion of Ar 1 and Ar 2 is preferably an alkyl group having 1 to 5 carbon atoms or a halogen atom, more preferably a methyl group or a fluorine atom.
  • the partial structure represented by the above formula (4) include, for example, 4,4′-biphenylene group, 4,4′-bicyclohexylene group, and the following formulas (4-1) to (4- And groups represented by each of 4) and groups having a methyl group or a fluorine atom in the ring portion of these groups. (In the formula, “*” indicates a bond.)
  • the above formula (2) is used as the specific diamine in that the effect of reducing the AC afterimage and improving the contrast of the liquid crystal display element is high. It is preferable to use the compound represented by -1).
  • the compound represented by the above formula (2-1) as the specific diamine, a polymer having a partial structure represented by the above formula (1) in the main chain can be obtained.
  • Specific examples of the specific diamine include compounds represented by the above formula (2-1), such as the following formula (b-1) to formula (b-17), formula (b-26) to formula (b-56). ); As the compound represented by the above formula (2-2), for example, compounds represented by the following formulas (b-18) to (b-59), Can be mentioned.
  • the specific diamine can be used alone or in combination of two or more.
  • the formulas (b-1) to (b-59), the formulas (b-1), (b-3), (b-5) to (b-7), (b-11), b-18), formula (b-20), formula (b-22) to (b-26), formula (b-28), formula (b-41) to formula (b-45), formula (b- 47), formula (b-54), formula (b-56) and formula (b-57) correspond to the compound having the partial structure represented by the formula (4).
  • the specific diamine can be synthesized by appropriately combining organic chemistry methods.
  • a dinitro intermediate having a nitro group in place of the primary amino group of the compound represented by the above formula (2-1) or (2-2) was synthesized, and then the obtained dinitro intermediate was synthesized.
  • a method of aminating the nitro group of the body using an appropriate reduction system is mentioned.
  • the method for synthesizing the dinitro intermediate can be appropriately selected according to the target compound. Specifically, for example, a compound represented by “O 2 N—R 5 —A 1 —H” and a compound represented by “HO—R 6 —A 2 —R 7 —NO 2 ” are preferably used.
  • the reduction reaction of the dinitro intermediate can be preferably carried out in an organic solvent using a catalyst such as palladium carbon, platinum oxide, zinc, iron, tin, nickel or the like.
  • a catalyst such as palladium carbon, platinum oxide, zinc, iron, tin, nickel or the like.
  • the organic solvent used here include ethyl acetate, toluene, tetrahydrofuran, and alcohols.
  • the synthesis procedure of the specific diamine is not limited to the above method.
  • a specific diamine may be used alone, or a diamine having no partial structure represented by the above formula (1) (other diamine) is used in combination. May be.
  • other diamines include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes.
  • aliphatic diamines such as m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1 , 2-bis (2-aminoethoxy) ethane and the like;
  • alicyclic diamines include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine) and the like;
  • aromatic diamines examples include dodecanoxydiaminobenzene, tetradecanoxydiaminobenzene, pentadecanoxydiaminobenzene, hexadecanoxydiaminobenzene, octadecanoxydiaminobenzene, cholestanyloxydiaminobenzene, and cholesteryloxydiaminobenzene.
  • the divalent group represented by “—X I — (R I —X II ) d —” in the above formula (E-1) is an alkanediyl group having 1 to 3 carbon atoms, * —O—, * It is preferably —COO— or * —O—C 2 H 4 —O— (where a bond marked with “*” binds to a diaminophenyl group).
  • the group “—C c H 2c + 1 ” includes, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group Group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and the like, and these are preferably linear.
  • the two amino groups in the diaminophenyl group are preferably in the 2,4-position or 3,5-position with respect to the other groups.
  • E-1 Specific examples of the compound represented by the above formula (E-1) include compounds represented by the following formulas (E-1-1) to (E-1-4).
  • combination of a polyamic acid 1 type of these compounds can be used individually or in combination of 2 or more types as appropriate.
  • a functional group capable of exhibiting liquid crystal alignment regulating power without depending on light irradiation on the side chain of the polyamic acid.
  • a functional group capable of exhibiting liquid crystal alignment regulating power without depending on light irradiation on the side chain of the polyamic acid.
  • Examples of such liquid crystal aligning groups include alkyl groups having 4 to 20 carbon atoms, fluoroalkyl groups having 4 to 20 carbon atoms, alkoxy groups having 4 to 20 carbon atoms, groups having a steroid skeleton having 17 to 51 carbon atoms, And a group having a ring structure (for example, a group having a partial structure represented by the above formula (4)).
  • the polyamic acid having a liquid crystal aligning group can be obtained, for example, by polymerization containing the above aligning group-containing diamine in the monomer composition.
  • the orientation group-containing diamine is used, the blending ratio is preferably 3 mol% or more with respect to the total diamine used in the synthesis, from the viewpoint of improving the liquid crystal orientation. More preferably.
  • the specific diamine is used in a total amount of the diamine used for the synthesis of the polyamic acid from the viewpoint of sufficiently obtaining the effect of improving the afterimage characteristics and contrast characteristics of the liquid crystal display element.
  • it is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more.
  • the total amount of the specific acid dianhydride and the specific diamine is 10 mol% with respect to the total amount of the tetracarboxylic dianhydride and diamine used in the synthesis.
  • the content is 20 mol% or more, and more preferably 30 mol% or more.
  • the polyamic acid can be obtained by reacting the above tetracarboxylic dianhydride and diamine together with a molecular weight adjusting agent as necessary.
  • the ratio of tetracarboxylic dianhydride and diamine used in the polyamic acid synthesis reaction is 0.2 to 2 for the acid anhydride group of tetracarboxylic dianhydride to 1 equivalent of amino group of diamine. A ratio of equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.
  • the molecular weight modifier examples include maleic anhydride, phthalic anhydride, itaconic anhydride, and the following formulas (F-1) to (F-4) And acid monoanhydrides such as compounds represented by each of these, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate.
  • a monoamine compound and acid monoanhydride can be preferably used. Specifically, for example, compounds represented by the following formulas (ma-1) to (ma-15), compounds represented by the following formulas (mt-1) to (mt-10), etc. Is mentioned.
  • the use ratio of the molecular weight modifier is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less with respect to 100 parts by weight of the total of the tetracarboxylic dianhydride and diamine used.
  • a molecular weight modifier can be used individually by 1 type or in combination of 2 or more types.
  • the polyamic acid synthesis reaction is preferably carried out in an organic solvent.
  • the reaction temperature at this time is preferably ⁇ 20 ° C. 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 organic solvent used in the reaction include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like.
  • organic solvents one or more selected from the group consisting of an aprotic polar solvent and a phenolic solvent (first group organic solvent), or one or more selected from the first group of organic solvents And a mixture of at least one selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (second-group organic solvent).
  • first group organic solvent one or more selected from the group consisting of an aprotic polar solvent and a phenolic solvent
  • second-group organic solvent a mixture of at least one selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons
  • the proportion of the second group organic solvent used is preferably 50% by weight or less, more preferably 40% by weight, based on the total amount of the first group organic solvent and the second group organic solvent. Or less, more preferably 30% by weight or less.
  • organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol. And at least one selected from the group consisting of halogenated phenols is used as a solvent, or a mixture of one or more of these and another organic solvent is preferably used in the above range.
  • the amount of organic solvent used (a) should be such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1 to 50% by weight based on the total amount (a + b) of the reaction solution. Is preferred.
  • a reaction solution obtained by dissolving polyamic acid is obtained.
  • This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent.
  • the above reaction solution may be directly subjected to dehydration and cyclization reaction, or may be subjected to dehydration and cyclization reaction after isolating the polyamic acid contained in the reaction solution.
  • the isolated polyamic acid may be purified and then subjected to a dehydration ring closure reaction. Isolation and purification of the polyamic acid can be performed according to known methods.
  • the polyamic acid ester as the compound (X) is, for example, [I] a method of reacting a polyamic acid having a partial structure represented by the above formula (1) with an esterifying agent, [II] a tetracarboxylic acid diester, It can be obtained by a method of reacting diamine, a method of reacting [III] tetracarboxylic acid diester dihalide and diamine, or the like.
  • tetracarboxylic acid diester means a compound in which two of the four carboxyl groups of tetracarboxylic acid are esterified and the remaining two are carboxyl groups.
  • Tetracarboxylic acid diester dihalide means a compound in which two of the four carboxyl groups of tetracarboxylic acid are esterified and the remaining two are halogenated.
  • esterifying agent used in Method [I] examples include a hydroxyl group-containing compound, an acetal compound, a halide, an epoxy group-containing compound, and the like.
  • hydroxyl group-containing compounds such as alcohols such as methanol, ethanol and propanol; phenols such as phenol and cresol; and acetal compounds such as N, N-dimethylformamide diethyl acetal, N, N-diethylformamide diethyl acetal and the like; halides such as methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane, chloromethyl methyl ether, 2-chloromethoxy-1,1,1-trifluoroethane, chloromethyl isopropyl carbonate, chloromethyl pivalate, chloromethyl acetate, chloromethyl butyrate, chloromethyl methyl methyl methyl
  • the tetracarboxylic acid diester used in Method [II] can be obtained, for example, by ring-opening the tetracarboxylic dianhydride exemplified in the above synthesis of polyamic acid using alcohols such as methanol and ethanol.
  • the diamine used include the diamines exemplified in the synthesis of polyamic acid.
  • the reaction of Method [II] is preferably carried out in an organic solvent in the presence of a suitable dehydration catalyst.
  • an organic solvent the organic solvent illustrated as what is used for the synthesis
  • Examples of the dehydration catalyst include 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium halide, carbonylimidazole, and phosphorus condensing agent.
  • the reaction temperature at this time 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 tetracarboxylic acid diester dihalide used in Method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride.
  • the diamine used include the diamines exemplified in the synthesis of polyamic acid.
  • the reaction of Method [III] is preferably carried out in an organic solvent in the presence of a suitable base.
  • an organic solvent the organic solvent illustrated as what is used for the synthesis
  • tertiary amines such as pyridine and triethylamine
  • alkali metals such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium and potassium
  • the reaction temperature at this time 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 polyamic acid ester contained in the liquid crystal aligning agent may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist.
  • the reaction solution formed by dissolving the polyamic acid ester may be used for the preparation of the liquid crystal aligning agent as it is, or may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid ester contained in the reaction solution.
  • the isolated polyamic acid ester may be purified and then used for the preparation of the liquid crystal aligning agent. Isolation and purification of the polyamic acid ester can be performed according to a known method.
  • polyimide as the compound (X) can be obtained, for example, by dehydrating and ring-closing the polyamic acid as the compound (X) synthesized as described above to imidize.
  • the polyimide may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure possessed by the polyamic acid that is the precursor, and only a part of the amic acid structure may be dehydrated and cyclized. It may be a partially imidized product in which a ring structure coexists.
  • the polyimide used for the reaction preferably has an imidization ratio of 20% or more, more preferably 30 to 99%, and still more preferably 40 to 99%. This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of polyimide amic acid structures and the number of imide ring structures in percentage.
  • a part of the imide ring may be an isoimide ring.
  • the polyamic acid is preferably dehydrated and closed by heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and heating the solution as necessary. . Of these, the latter method is preferred.
  • an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride
  • the amount of the dehydrating agent used is preferably 0.01 to 20 mol with respect to 1 mol of the amic acid structure of the polyamic acid.
  • the dehydration ring closure catalyst for example, tertiary amines such as pyridine, collidine, lutidine, triethylamine and the like can be used.
  • the amount of the dehydration ring closure catalyst used is preferably 0.01 to 10 moles per mole of the dehydrating agent used.
  • Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid.
  • the reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C.
  • the reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.
  • reaction solution containing polyimide is obtained.
  • This reaction solution may be used for the preparation of the liquid crystal aligning agent as it is, may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, and the liquid crystal after isolating the polyimide.
  • polyimide can also be obtained by imidation of polyamic acid ester.
  • the polyamic acid, polyamic acid ester and polyimide as the compound (X) obtained as described above are selected from the group consisting of partial structures represented by the following formulas (6-1) to (6-10), respectively. It is preferable to have at least one kind.
  • R 20 and R 21 are each independently a hydrogen atom or a monovalent organic group.
  • R 1 , R 2 and X 1 are respectively synonymous with the above formula (1)
  • R 18 and R 19 are each represented by the above formula (5- And R 20 and R 21 each independently represents a hydrogen atom or a monovalent organic group.
  • a 1 , A 2 , R 5 , R 6 and R 7 are respectively synonymous with the above formula (2-1).
  • R 20 and R 21 are each independently a hydrogen atom or a monovalent organic group, and R 22 and R 23 are each independently a trivalent organic group.)
  • a 1 , A 2 , R 9 and R 10 are respectively synonymous with the above formula (2-2).
  • R 20 and R 21 are respectively Independently, it is a hydrogen atom or a monovalent organic group, and R 22 and R 23 are each independently a trivalent organic group.
  • examples of the monovalent organic group represented by R 20 and R 21 include a monovalent hydrocarbon group having 1 to 10 carbon atoms and a cinnamic acid structure. Group and the like.
  • examples of the trivalent organic group for R 22 and R 23 include a chain hydrocarbon group, an alicyclic group, an aromatic ring group, and a heterocyclic group. Preferably, it is an alicyclic group or an aromatic ring group, and the description of R 15 and R 17 in the above formula (5-1) can be applied to specific examples thereof.
  • the polyamic acid, polyamic acid ester, and polyimide as the compound (X) preferably have a solution viscosity of 10 to 800 mPa ⁇ s, when this is a 10% by weight solution, and 15 to 500 mPa ⁇ s. More preferably, it has a solution viscosity of s.
  • the solution viscosity (mPa ⁇ s) of the above polymer is based on a polymer solution having a concentration of 10% by weight prepared using a good solvent for the polymer (eg, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, etc.). These are values measured at 25 ° C. using an E-type rotational viscometer (the same applies to the following polymers).
  • the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of polyamic acid, polyamic acid ester and polyimide is preferably 1,000 to 500,000, more preferably 2,000 to 300,000.
  • the molecular weight distribution (Mw / Mn) represented by the ratio between Mw and the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less.
  • polyamide The polyamide as the compound (X) can be obtained by, for example, a method of reacting dicarboxylic acid and diamine.
  • the dicarboxylic acid is preferably subjected to a reaction with a diamine after acid chloride using an appropriate chlorinating agent such as thionyl chloride.
  • the dicarboxylic acid used for the synthesis of the polyamide is not particularly limited.
  • oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid 2 Aliphatic dicarboxylic acids such as 1,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid, fumaric acid, muconic acid; Dicarboxylic acids having an alicyclic structure such as cyclobutanedicarboxylic acid, 1-cyclobutenedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid; Phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 2,5-dimethylterephthalic acid
  • the diamine used when synthesizing the polyamide as the compound (X) includes a specific diamine. Moreover, you may use other diamine together as needed.
  • the use ratio of the specific diamine is preferably 10 mol% or more, more preferably 20 mol% or more, and more preferably 30 mol% or more, based on the total amount of diamine used for the synthesis of the polyamide. preferable.
  • a diamine can be used individually by 1 type or in combination of 2 or more types.
  • the proportion of dicarboxylic acid and diamine used in the polyamide synthesis reaction is preferably such that the carboxyl group of dicarboxylic acid is 0.2 to 2 equivalents relative to 1 equivalent of amino group of diamine, and 0.3 to A ratio of 1.2 equivalent is more preferable.
  • the reaction between a dicarboxylic acid (preferably an acid-chloride dicarboxylic acid) and a diamine is preferably carried out in an organic solvent in the presence of a base.
  • the reaction temperature at this time is preferably 0 to 200 ° C., more preferably 10 to 100 ° C.
  • the reaction time is preferably 0.5 to 48 hours, more preferably 1 to 36 hours.
  • the organic solvent used in the reaction for example, tetrahydrofuran, dioxane, toluene, chloroform, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and the like can be preferably used.
  • the amount of the organic solvent used is preferably 400 to 900 parts by weight, and more preferably 500 to 700 parts by weight with respect to 100 parts by weight of the total amount of dicarboxylic acid and diamine.
  • a tertiary amine such as pyridine, triethylamine, N-ethyl-N, N-diisopropylamine can be preferably used.
  • the amount of the base used is preferably 2 to 4 mol, more preferably 2 to 3 mol, relative to 1 mol of the diamine.
  • reaction solution obtained by dissolving polyamide is obtained.
  • This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, and may be used for the preparation of the liquid crystal aligning agent after isolating the polyamide contained in the reaction solution, or after purifying the isolated polyamide. You may use for preparation of a liquid crystal aligning agent.
  • the isolation and purification of the polyamide can be performed according to known methods.
  • the solution viscosity of the polyamide as the compound (X) preferably has a solution viscosity of 10 to 800 mPa ⁇ s, and a solution viscosity of 15 to 500 mPa ⁇ s, when this is a 10% by weight solution. It is more preferable that it has.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by GPC for polyamide is preferably 1,000 to 500,000, more preferably 5,000 to 300,000.
  • polymer (S) The polyorganosiloxane (hereinafter also referred to as “polymer (S)”) as the compound (X) can be obtained, for example, by hydrolyzing and condensing a hydrolyzable silane compound.
  • the method [1] is preferable because it is simple and can increase the introduction rate of the partial structure represented by the above formula (1) in the polymer (S).
  • a reaction product of a polyorganosiloxane having an epoxy group and a carboxylic acid is used as the compound (X).
  • hydrolyzable silane compound (ms-1) having an epoxy group examples include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxy.
  • Silane 3-glycidoxypropylmethyldiethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethyldimethylmethoxysilane, 2-glycidoxyethyldimethyl Ethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutylmethyldimethoxysilane, 4-glycidoxybutylmethyldiethoxysilane, 4-glycidoxybutyldimethylmethoxysilane, 4-glycidoxybutyl Dimethylethoxysila 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysi
  • silane compounds are not particularly limited as long as they are hydrolyzable silane compounds.
  • the hydrolysis / condensation reaction of the silane compound is carried out by reacting one or more of the above silane compounds with water, preferably in the presence of an appropriate catalyst and an organic solvent.
  • an appropriate catalyst and an organic solvent preferably in the presence of an appropriate catalyst and an organic solvent.
  • the epoxy equivalent of the epoxy group-containing polyorganosiloxane is preferably 100 to 10,000 g / mol, and more preferably 150 to 1,000 g / mol.
  • the amount of water used is preferably 0.5 to 100 mol, more preferably 1 to 30 mol, per 1 mol of the silane compound (total amount).
  • Examples of the catalyst used in the hydrolysis / condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds and the like.
  • Examples of the catalyst include alkali metal compounds or organic bases among them in that side reactions such as ring opening of epoxy groups can be suppressed, the rate of hydrolysis condensation can be increased, and the storage stability is excellent.
  • a tertiary or quaternary organic base is particularly preferable.
  • the amount of the organic base used varies depending on the reaction conditions such as the type of organic base and temperature, and should be set as appropriate, but is preferably 0.01 to 3 times the mole of the total silane compound, More preferably, it is 0.05 to 1 mole.
  • Examples of the organic solvent used in the hydrolysis / condensation reaction include hydrocarbons, ketones, esters, ethers, alcohols and the like. Specific examples thereof include hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone and cyclopentanone; esters such as ethyl acetate.
  • a water-insoluble organic solvent it is preferable to use a water-insoluble organic solvent.
  • these organic solvents can be used individually by 1 type or in mixture of 2 or more types.
  • the proportion of the organic solvent used in the hydrolysis condensation reaction is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, with respect to 100 parts by weight of the total silane compounds used in the reaction. .
  • the hydrolysis / condensation reaction is preferably carried out by dissolving the silane compound as described above in an organic solvent, mixing this solution with an organic base and water, and heating the solution with, for example, an oil bath.
  • the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C.
  • the heating time is preferably 0.5 to 12 hours, and more preferably 1 to 8 hours. During heating, the mixture may be stirred or placed under reflux.
  • the organic solvent layer separated from the reaction solution is preferably washed with water.
  • washing with water containing a small amount of salt (for example, an aqueous ammonium nitrate solution of about 0.2% by weight) is preferable in that the washing operation is facilitated. Washing is performed until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve as necessary, and then the polyorgano Siloxane can be obtained.
  • a desiccant such as anhydrous calcium sulfate or molecular sieve as necessary
  • the epoxy group-containing polyorganosiloxane obtained by the above reaction is then reacted with a specific carboxylic acid.
  • the epoxy group of the epoxy group-containing polyorganosiloxane reacts with the carboxylic acid to obtain a polymer (S) as a polyorganosiloxane having a partial structure represented by the above formula (1) in the side chain. be able to.
  • Specific examples of the specific carboxylic acid include a compound represented by the following formula (3).
  • a 1 and A 2 are respectively synonymous with the above formula (2-1), provided that “* 1” in the above formulas (1-1) and (1-2) is , R 11 represents a bond bonded to R 12.
  • R 11 is a monovalent organic group when A 1 is a group represented by the following formula (1-1), and A 1 is represented by the following formula (1-2): And a hydrogen atom or a monovalent organic group, R 12 is a divalent organic group, and R 13 is a group in which A 2 is represented by the following formula (1-1): Is a divalent organic group, and when A 2 is a group represented by the following formula (1-2), it is a single bond or a divalent organic group. 0 or 1. However, in formula (3), it has one carboxyl group.)
  • the description of R 8 and R 10 in the above formula (2-2) can be applied to the illustration of the monovalent organic group of R 11 .
  • the description of R 5 to R 7 in the above formula (2-1) can be applied to the examples of the divalent organic group of R 12 and R 13 .
  • the description of the above formula (1) can be applied to the description of R 1 , R 2 , R 3 and X 1 of A 1 and A 2 .
  • the specific carboxylic acid preferably further has a partial structure represented by the above formula (4) in the molecule together with the partial structure represented by the above formula (1) from the viewpoint of enhancing the effect of reducing the AC afterimage.
  • the description in the case of specific diamine is applicable to the preferable specific example of the partial structure represented by the said Formula (4).
  • the point that the structure represented by the said Formula (4) may be comprised by the benzene ring in the said Formula (1) is the same as specific diamine.
  • specific carboxylic acid examples include compounds represented by the following formulas (g-1) to (g-13).
  • combination of a polymer (S) specific carboxylic acid can be used individually by 1 type or in combination of 2 or more types.
  • formulas (g-1) to (g-13) formulas (g-1), (g-2), (g-4) to (g-8), and formulas (g-11) to Formula (g-13) corresponds to a compound having a partial structure represented by Formula (4) above.
  • the content ratio of the partial structure represented by the above formula (1) in one molecule of the polymer (S) is from the viewpoint of improving the sensitivity to light with respect to the silicon atom of the polymer (S). It is preferably 3 to 100 mol%, more preferably 5 to 95 mol%, still more preferably 10 to 90 mol%. Therefore, when synthesizing the polymer (S), it is preferable to select the use ratio of the specific carboxylic acid so that the content ratio of the partial structure represented by the formula (1) is in the above range.
  • the specific carboxylic acid can be synthesized by appropriately combining organic chemistry methods.
  • the compound represented by “R 11 -A 1 -H” and “HO—R 12 —A 2 —R 13 —COOM (where M is a protecting group for a carboxyl group)” are exemplified.
  • the compound is preferably reacted in an organic solvent in the presence of a catalyst, if necessary, and then deprotected, and the like.
  • the synthesis procedure of the specific carboxylic acid is not limited to the above method.
  • the carboxylic acid used for the reaction with the epoxy group-containing polyorganosiloxane may be only the specific carboxylic acid, but other carboxylic acids other than the specific carboxylic acid may be used in combination.
  • the other carboxylic acid is not particularly limited as long as it does not have the partial structure represented by the above formula (1), and examples thereof include carboxylic acid having the above liquid crystal alignment group.
  • carboxylic acids include, for example, fatty acids having 6 to 20 carbon atoms such as caproic acid, lauric acid, pentadecylic acid, palmitic acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, arachidic acid, Examples thereof include compounds represented by the following formulas (C-2-1) to (C-2-10). (In the formula, j is an integer from 0 to 12, and h is an integer from 1 to 10.) In addition, other carboxylic acid can be used individually by 1 type selected from these or in combination of 2 or more types.
  • the use ratio of the carboxylic acid to be reacted with the epoxy group-containing polyorganosiloxane is preferably 0.001 to 1.5 mol with respect to 1 mol of the total epoxy groups of the polyorganosiloxane, 0.01 to 1 More preferably, it is 0.0 mol.
  • the other carboxylic acid is preferably used in an amount of 80 mol% or less, based on the total amount of carboxylic acid to be reacted with the epoxy group-containing polyorganosiloxane. % Or less is more preferable.
  • the reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid can be preferably carried out in the presence of a catalyst and an organic solvent.
  • a catalyst used in the reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid for example, an organic base or a compound known as a so-called curing accelerator that accelerates the reaction of the epoxy compound can be used.
  • the organic base include primary and secondary organic amines such as ethylamine, piperazine and piperidine; tertiary organic amines such as triethylamine and pyridine; quaternary organic amines such as tetramethylammonium hydroxide; Can do.
  • tertiary organic amines or quaternary organic amines are preferred as the organic base.
  • the curing accelerator include tertiary amines, imidazole compounds, organic phosphorus compounds, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds such as tin octylate, quaternary ammonium salts, boron compounds, secondary chlorides.
  • organometallic compounds such as tin octylate, quaternary ammonium salts, boron compounds, secondary chlorides.
  • metal halide compounds such as tin.
  • quaternary ammonium salts are preferred, and specific examples include tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride and the like.
  • the catalyst is used in an amount of preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy group-containing polyorganosiloxane.
  • organic solvent used in the above reaction examples include hydrocarbons, ethers, esters, ketones, amides, alcohols and the like. Of these, ethers, esters, and ketones are preferred from the viewpoints of solubility of raw materials and products, and ease of purification of the products. Specific examples of particularly preferred solvents include 2-butanone, 2-hexanone, methyl Examples thereof include isobutyl ketone and butyl acetate.
  • the organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more, More preferably, it is used in a proportion of 5 to 50% by weight.
  • the reaction temperature in the above reaction is preferably 0 to 200 ° C, more preferably 50 to 150 ° C.
  • the reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.
  • finish of reaction it is preferable to wash
  • the method for synthesizing the polyorganosiloxane is not limited to the hydrolysis / condensation reaction as described above. For example, a method in which a hydrolyzable silane compound is reacted in the presence of oxalic acid and alcohol may be employed.
  • the polymer (S) obtained as described above preferably has a partial structure formed by the reaction of a polyorganosiloxane having an epoxy group and a carboxylic acid, and specifically, the following formula (7) It is preferable that it has the partial structure represented by these.
  • a 1 , A 2 , R 11 , R 12 , R 13 , s, and r are respectively synonymous with the above formula (3).
  • Z 1 is a divalent organic group. * "Indicates a bond with a silicon atom.)
  • Examples of the divalent organic group for Z 1 include groups exemplified for R 5 to R 7 in the above formula (2-1).
  • the polymer (S) contained in the liquid crystal aligning agent of the present disclosure preferably has a solution viscosity of 1 to 500 mPa ⁇ s when it is made into a solution having a concentration of 10% by weight. More preferably, it has a solution viscosity of s.
  • the polymer (S) has a polystyrene equivalent weight average molecular weight (Mw) measured by GPC of preferably 1,000 to 200,000, more preferably 2,000 to 50,000. More preferably, it is from 20,000 to 20,000.
  • the poly (meth) acrylate as the compound (X) is, for example, a (meth) acrylic monomer (m-1) having an epoxy group, or the (meth) acrylic monomer (m-1) and other And a polymer obtained by polymerizing a mixture of the (meth) acrylic monomer in the presence of a polymerization initiator (hereinafter also referred to as “epoxy group-containing poly (meth) acrylate”), It can be obtained by a method of reacting with a specific carboxylic acid.
  • a polymerization initiator hereinafter also referred to as “epoxy group-containing poly (meth) acrylate”
  • Examples of the (meth) acrylic monomer (m-1) include an unsaturated carboxylic acid ester having an epoxy group. Specific examples thereof include, for example, glycidyl (meth) acrylate, glycidyl ⁇ -ethyl acrylate, glycidyl ⁇ -n-propyl acrylate, glycidyl ⁇ -n-butyl acrylate, 3,4-epoxybutyl (meth) acrylate.
  • the (meth) acrylic monomer (m-1) can be used alone or in combination of two or more.
  • Examples of other (meth) acrylic monomers include (meth) acrylic acid, (meth) acrylic acid ⁇ -carboxypolycaprolactone, crotonic acid, ⁇ -ethylacrylic acid, ⁇ -n-propylacrylic acid, ⁇ -Unsaturated carboxylic acids such as n-butylacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, vinylbenzoic acid; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, ( (Meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid lauryl, (meth) acrylic acid trimethoxysilylpropyl, (
  • (Meth) acrylic acid ester ⁇ -meth Shiakuriru methyl, alpha-ethoxy alpha-alkoxy acrylate ester of methyl acrylate: methyl crotonate, crotonic acid esters such as ethyl crotonate: unsaturated carboxylic acid esters and the like; And unsaturated polyvalent carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrahydrophthalic anhydride; and the like.
  • another (meth) acrylic-type monomer it can be used individually by 1 type or in combination of 2 or more types.
  • the total amount (number of moles) of epoxy groups per gram of epoxy group-containing poly (meth) acrylate is preferably 5.0 ⁇ 10 ⁇ 5 or more, and 1.0 ⁇ 10 -4 to 1.0 ⁇ 10 ⁇ 2 mol / g is more preferable, and 5.0 ⁇ 10 ⁇ 4 to 5.0 ⁇ 10 ⁇ 3 mol / g is still more preferable. Therefore, the use ratio of the (meth) acrylic monomer (m-1) is adjusted so that the total number of moles of epoxy groups per gram of the epoxy group-containing poly (meth) acrylate is within the above numerical range. It is preferable.
  • a monomer other than the (meth) acrylic monomer may be used.
  • examples of other monomers include conjugated diene compounds such as 1,3-butadiene and 2-methyl-1,3-butadiene; aromatic vinyl compounds such as styrene, methylstyrene, and divinylbenzene.
  • the proportion of other monomers used is preferably 30 mol% or less, more preferably 20 mol% or less, based on the total amount of monomers used for the synthesis of poly (meth) acrylate.
  • the polymerization reaction using the (meth) acrylic monomer is preferably performed by radical polymerization.
  • the polymerization initiator used in the polymerization reaction include initiators usually used in radical polymerization.
  • initiators usually used in radical polymerization For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4 -Dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like; benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis ( organic peroxides such as t-butylperoxy) cyclohexane; hydrogen peroxide; redox initiators composed of these peroxides and reducing agents.
  • azo compounds are preferable, and 2,2′-azobis (isobutyronitrile) is more preferable.
  • a polymerization initiator these can be used individually by 1 type or in combination of 2 or more types.
  • the use ratio of the polymerization initiator is preferably 0.01 to 50 parts by weight, and more preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of the total monomers used in the reaction.
  • the polymerization reaction of the (meth) acrylic monomer is preferably performed in an organic solvent.
  • the organic solvent used in the reaction include alcohols, ethers, ketones, amides, esters, hydrocarbon compounds, and the like. Among these, it is preferable to use at least one selected from the group consisting of alcohols and ethers, and it is more preferable to use partial ethers of polyhydric alcohols. Preferred examples thereof include diethylene glycol methyl ethyl ether and propylene glycol monomethyl ether acetate.
  • an organic solvent these can be used individually by 1 type or in combination of 2 or more types.
  • the reaction temperature is preferably 30 to 120 ° C., more preferably 60 to 110 ° C.
  • the reaction time is preferably 1 to 36 hours, more preferably 2 to 24 hours.
  • the amount of organic solvent used (a) is such that the total amount (b) of monomers used in the reaction is 0.1 to 50% by weight with respect to the total amount (a + b) of the reaction solution. It is preferable to do.
  • the epoxy group-containing poly (meth) acrylate obtained by the above reaction is then reacted with a specific carboxylic acid.
  • a specific carboxylic acid As specific examples of the specific carboxylic acid, the explanation of the polymer (S) can be applied.
  • the specific carboxylic acid may be used alone, or other carboxylic acid other than the specific carboxylic acid may be used in combination.
  • the proportion of the carboxylic acid to be reacted with the epoxy group-containing poly (meth) acrylate may be 0.001 to 0.95 mol with respect to a total of 1 mol of epoxy groups contained in the epoxy group-containing poly (meth) acrylate. preferable. More preferably, it is 0.01 to 0.9 mol, and more preferably 0.05 to 0.8 mol.
  • the reaction between the epoxy group-containing poly (meth) acrylate and the carboxylic acid can be preferably performed in the presence of a catalyst and an organic solvent.
  • a catalyst used for reaction the compound illustrated as a catalyst which can be used by the synthesis
  • a quaternary ammonium salt is preferable.
  • the amount of the catalyst used is preferably not more than 100 parts by weight, more preferably not more than 0.01 to 100 parts by weight, still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy group-containing poly (meth) acrylate. It is.
  • organic solvent used in the reaction examples of organic solvents that can be used in the polymerization of (meth) acrylic monomers can be applied, and among these, esters are preferable.
  • the organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more, More preferably, it is used in a proportion of 5 to 50% by weight.
  • the reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C.
  • the reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.
  • a solution containing poly (meth) acrylate as compound (X) can be obtained.
  • This reaction solution may be used for the preparation of the liquid crystal aligning agent as it is, may be used for the preparation of the liquid crystal aligning agent after isolating the poly (meth) acrylate contained in the reaction solution, or the isolated poly You may use for preparation of a liquid crystal aligning agent, after refine
  • combining method of poly (meth) acrylate as compound (X) is not limited to the said method.
  • a (meth) acrylic monomer having a partial structure represented by the above formula (1), or a mixture of the (meth) acrylic monomer and another (meth) acrylic monomer is polymerized. It can also be obtained by a method of polymerizing in the presence of an initiator.
  • the polystyrene-equivalent number average molecular weight (Mn) measured by GPC improves the liquid crystal alignment of the liquid crystal alignment film to be formed and ensures the stability of the liquid crystal alignment over time.
  • Mn number average molecular weight
  • the liquid crystal aligning agent which concerns on this invention contains the above compounds (X), it may contain the other component as needed.
  • Other components that may be added to the liquid crystal aligning agent include, for example, other polymers other than the compound (X), compounds having at least one epoxy group in the molecule (hereinafter referred to as “epoxy group-containing compound”).
  • epoxy group-containing compound compounds having at least one epoxy group in the molecule
  • a functional silane compound a compound having a photopolymerizable group (hereinafter referred to as “photopolymerizable group-containing compound”), a photosensitizer, and the like.
  • the above other polymers can be used for improving solution properties and electrical properties.
  • Such other polymer is a polymer having no partial structure represented by the above formula (1), and the main skeleton thereof is not particularly limited.
  • polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate and the like are used as the main skeleton. Can be mentioned.
  • the blending ratio is preferably 90 parts by weight or less with respect to 100 parts by weight in total of the polymers contained in the liquid crystal aligning agent, The amount is more preferably 80 parts by weight, and further preferably 0.1 to 70 parts by weight.
  • Epoxy group-containing compound can be used to improve the adhesion and electrical properties with the substrate surface in the liquid crystal alignment film.
  • examples of such epoxy group-containing compounds 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, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylylene Amine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N
  • an epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598 can be used as an example of the epoxy group-containing compound.
  • the blending ratio thereof is preferably 40 parts by weight or less with respect to a total of 100 parts by weight of the polymer contained in the liquid crystal aligning agent. More preferred are parts by weight.
  • the functional silane compound can be used for the purpose of improving the printability of the liquid crystal aligning agent.
  • Examples of such functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl).
  • the blending ratio is preferably 2 parts by weight or less with respect to a total of 100 parts by weight of the polymer contained in the liquid crystal aligning agent. More preferably, the content is set to ⁇ 0.2 parts by weight.
  • the photopolymerizable group-containing compound is used for the purpose of enhancing the alignment regulating force in the liquid crystal alignment film when the liquid crystal alignment ability is imparted by irradiating light to the coating film formed using the liquid crystal aligning agent.
  • examples of the photopolymerizable group include a group having a polymerizable unsaturated bond, and specific examples include (meth) acryloyloxy group, styryl group, (meth) acrylamide group, vinyl group, vinylidene. Group, vinyloxy group (CH 2 ⁇ CH—O—), maleimide group and the like.
  • a (meth) acrylate compound can be preferably used in terms of high photoreactivity, and specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl ( (Meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl Monofunctional (meth) acrylates such as (meth) acrylate; ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, polyether (meth) acrylate Over DOO, polyfunctional (meth) acrylate
  • the blending ratio is preferably 30 parts by weight or less with respect to 100 parts by weight of the total of the polymers contained in the liquid crystal aligning agent. More preferred is 20 parts by weight.
  • the photosensitizer various compounds having a photosensitizing function can be used.
  • the “photosensitization function” means that a singlet excited state is caused by light irradiation, and in some cases, further intersystem crossing occurs. A function that returns to the ground state.
  • Specific examples of the photosensitizer include compounds represented by the following formulas (H-1) to (H-6).
  • the blending ratio is preferably 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymer contained in the liquid crystal aligning agent. More preferably.
  • additives usually used for the preparation of liquid crystal aligning agents can be used.
  • additives other than the above include compounds having at least one oxetanyl group in the molecule, antioxidants, surfactants, and dispersants.
  • the liquid crystal aligning agent according to the present invention is prepared as a liquid composition in which the above specific compound and other components used as necessary are preferably dispersed or dissolved in an appropriate solvent.
  • organic solvent used examples include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ⁇ -butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, Ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether , Ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene Glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol
  • the liquid crystal aligning agent which concerns on this invention may contain only 1 type of polymer as a polymer component, and may contain 2 or more types of polymers.
  • Preferable embodiments in the case of containing two or more polymers include the following [1] to [3].
  • a polymer (hereinafter, also referred to as “specific polymer”) as the compound (X) and other polymers, and the specific polymer and other polymers are polyamic acid, polyamic acid ester, The aspect which is at least 1 type chosen from a polyimide and polyamide.
  • An embodiment containing a plurality of types of specific polymers, and the plurality of types of specific polymers being at least one selected from polyamic acid, polyamic acid ester, polyimide and polyamide.
  • [3] Contains a specific polymer and another polymer, the specific polymer is polyorganosiloxane, and the other polymer is at least one selected from polyamic acid, polyamic acid ester, polyimide and polyamide.
  • the specific polymer having a fluorine atom or a silicon atom is used as the specific polymer, so that the specific polymer having a fluorine atom or a silicon atom does not have a fluorine atom and a silicon atom in the upper layer. It is presumed that other polymers are unevenly distributed in the lower layer, and therefore, it is possible to cause uneven distribution of the polymer in the liquid crystal alignment film.
  • the reason why the afterimage characteristics and contrast characteristics of the liquid crystal display element are improved is not clear, but one hypothesis may be as follows. . That is, in the partial structure represented by the above formula (1), the compound (X) has a monovalent organic group introduced into at least one of the ⁇ carbon and ⁇ carbon of the carbonyl group, preferably the ⁇ carbon of the carbonyl group. Therefore, when light is irradiated, the photodimerization reaction is suppressed and light is reduced as compared with a compound having a partial structure (cinnamoyl group) in which R 1 and R 2 in the formula (1) are hydrogen atoms. It is considered that the isomerization reaction proceeds preferentially.
  • the alignment regulating power of the liquid crystal is improved, and as a result, the effect of improving the afterimage characteristics and contrast characteristics of the liquid crystal display element is obtained. It is guessed.
  • the solid content concentration in the liquid crystal aligning agent according to the present invention is appropriately selected in consideration of viscosity, volatility, and the like. Is preferably in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent which concerns on this invention is apply
  • the particularly preferable solid content concentration range varies depending on the method used when applying the liquid crystal aligning agent to the substrate.
  • the solid content concentration (the ratio of the total weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is in the range of 1.5 to 4.5% by weight. It is particularly preferred.
  • the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa ⁇ s.
  • the solid content concentration is particularly preferably in the range of 1 to 5% by weight, and thereby the solution viscosity is preferably in the range of 3 to 15 mPa ⁇ s.
  • the temperature at which the liquid crystal aligning agent according to the present invention is prepared is preferably 10 to 50 ° C., more preferably 20 to 30 ° C.
  • liquid crystal alignment film and liquid crystal display element By using the liquid crystal aligning agent according to the present invention described above, a liquid crystal alignment film can be produced. Moreover, the liquid crystal display element which concerns on this invention comprises the liquid crystal aligning film formed using the said liquid crystal aligning agent.
  • the operation mode of the liquid crystal display device according to the present invention is not particularly limited. It can be applied to various operation modes.
  • the liquid crystal display element according to the present invention can be manufactured, for example, by processes including the following processes (1-1) to (1-3).
  • step (1-1) the substrate to be used varies depending on the desired operation mode.
  • step (1-2) and step (1-3) are common to each operation mode.
  • the liquid crystal aligning agent of this invention is apply
  • (1-1A) For example, when manufacturing a TN type, STN type, or VA type liquid crystal display element, first, a pair of two substrates provided with a patterned transparent conductive film is formed, and each transparent conductive film is formed. On the surface, the liquid crystal aligning agent according to the present invention is preferably applied by an offset printing method, a spin coating method, a roll coater method or an ink jet printing method.
  • the substrate for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly (cycloaliphatic olefin) can be used.
  • a transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of US PPG) made of tin oxide (SnO 2 ), an ITO film made of indium oxide-tin oxide (In 2 O 3 -SnO 2 ), etc. Can be used.
  • a method of forming a pattern by photo-etching a method of using a mask having a desired pattern when forming a transparent conductive film; And so on.
  • a functional silane compound or a functional titanium compound is formed on the surface of the substrate surface on which the coating film is formed. It is also possible to perform a pretreatment to apply the above in advance.
  • preheating is preferably performed for the purpose of preventing dripping of the applied liquid crystal aligning agent.
  • the prebake temperature is preferably 30 to 200 ° C., more preferably 40 to 150 ° C., and particularly preferably 40 to 100 ° C.
  • the prebake time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes.
  • a baking (post-baking) process is implemented for the purpose of removing a solvent completely and heat imidating the amic acid structure which exists in a polymer as needed.
  • the firing temperature (post-bake temperature) at this time is preferably 80 to 300 ° C., more preferably 120 to 250 ° C.
  • the post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes.
  • the thickness of the film thus formed is preferably 0.001 to 1 ⁇ m, more preferably 0.005 to 0.5 ⁇ m.
  • an electrode forming surface of a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape, and an electrode are provided.
  • the liquid crystal aligning agent of this invention is each apply
  • the coating method, the heating conditions after coating, the patterning method for the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film thickness of the coating film to be formed The same as (1-1A).
  • the metal film for example, a film made of a metal such as chromium can be used.
  • the organic solvent is removed to form a liquid crystal alignment film or a liquid crystal alignment film.
  • the dehydration ring-closing reaction of the polyamic acid, polyamic acid ester and polyimide blended in the liquid crystal aligning agent of the present invention may be advanced to obtain a more imidized coating film.
  • a treatment for imparting liquid crystal alignment ability to the coating film formed in the step (1-1) is performed.
  • the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film.
  • the orientation imparting treatment include a rubbing treatment in which a coating film is rubbed in a fixed direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton, and photo-alignment in which the coating film is irradiated with polarized or non-polarized radiation. Processing.
  • the coating film formed in the above step (1-1) can be used as it is as a liquid crystal alignment film. May be.
  • the light irradiation in the photo-alignment treatment is [1] a method of irradiating the coating film after the post-baking process, [2] a method of irradiating the coating film after the pre-baking process and before the post-baking process, [3 ] It can carry out by the method of irradiating with respect to a coating film during the heating of a coating film in at least any one of a prebaking process and a post-baking process. Of these, the method [2] is preferable because the effect of improving the afterimage characteristics and contrast characteristics of the liquid crystal display element is high.
  • the radiation applied to the coating film for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used.
  • the radiation When the radiation is polarized light, it may be linearly polarized light or partially polarized light.
  • irradiation may be performed from a direction perpendicular to the substrate surface, an oblique direction, or a combination thereof.
  • the direction of irradiation is an oblique direction.
  • a light source to be used for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used.
  • Ultraviolet rays in a preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter or a diffraction grating.
  • the radiation dose is preferably 100 to 50,000 J / m 2 , more preferably 300 to 20,000 J / m 2 .
  • the temperature at the time of heating is usually 30 to 250 ° C, preferably 40 to 200 ° C, more preferably 50 to 150 ° C.
  • the liquid crystal alignment film after the rubbing treatment is further subjected to a process for changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet rays or a surface of the liquid crystal alignment film.
  • a resist film is formed on the part, and a rubbing process is performed in a direction different from the previous rubbing process, followed by a process of removing the resist film, so that the liquid crystal alignment film has different liquid crystal alignment capabilities for each region. .
  • a liquid crystal alignment film suitable for a VA liquid crystal display element can also be suitably used for a PSA (Polymer Sustained Alignment) type liquid crystal display element.
  • Step (1-3): Construction of liquid crystal cell (1-3A) Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal cell is manufactured by disposing a liquid crystal between the two substrates facing each other.
  • the first method is a conventionally known method. First, two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the substrate surface and the seal are bonded.
  • a liquid crystal cell is manufactured by injecting and filling liquid crystal into the cell gap partitioned by the agent and then sealing the injection hole.
  • the second method is a method called an ODF (One Drop Fill) method.
  • ODF One Drop Fill
  • an ultraviolet light curable sealant is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped at predetermined locations on the liquid crystal alignment film surface.
  • the other substrate is bonded so that the liquid crystal alignment films face each other and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal cell.
  • the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase and then gradually cooled to room temperature. It is desirable to remove.
  • an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
  • the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable.
  • Cyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used.
  • cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate and cholesteryl carbonate; chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck)
  • a ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be added and used.
  • a liquid crystal cell is constructed in the same manner as in the above (1-3A) except that a photopolymerizable compound is injected or dropped together with a liquid crystal. Thereafter, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.
  • the voltage applied here can be, for example, 5 to 50 V direct current or alternating current.
  • the light to be irradiated for example, ultraviolet rays including visible light having a wavelength of 150 to 800 nm and visible light can be used, but ultraviolet rays including light having a wavelength of 300 to 400 nm are preferable.
  • a light source of irradiation light for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used.
  • the ultraviolet rays in the above preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter diffraction grating.
  • the amount of light irradiation is preferably 1,000 J / m 2 or more and less than 200,000 J / m 2 , more preferably 1,000 to 100,000 J / m 2 .
  • a liquid crystal cell is prepared in the same manner as (1-3A) above. Then, a method of manufacturing a liquid crystal display element may be adopted by performing a step of irradiating light to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates. According to this method, the PSA mode can be realized with a small amount of light irradiation.
  • the description of (1-3B) above can be applied to the voltage to be applied and the conditions of light to be irradiated.
  • the liquid crystal display element of this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell.
  • a polarizing plate to be bonded to the outer surface of the liquid crystal cell a polarizing film or an H film itself in which a polarizing film called an “H film” in which iodine is absorbed while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films
  • the polarizing plate which consists of can be mentioned.
  • the liquid crystal display device 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. It can be used in various display devices such as various monitors, liquid crystal televisions, and information displays.
  • the weight average molecular weight Mw and epoxy equivalent of the polymer were measured by the following methods.
  • the compound represented by Formula A may be simply referred to as “Compound A”.
  • Mw is a polystyrene equivalent value measured by GPC under the following conditions.
  • the epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.
  • Example 1-2 Synthesis of compound (b-2)] Synthesis was performed in the same manner as in Example 1-1 except that 4-hydroxy-4′-nitrobiphenyl was changed to 4-nitrophenol in the second stage of Scheme 1 in Example 1-1, and compound (b -2) was obtained.
  • Example 1-3 Synthesis of compound (b-3)] Synthesis was performed in the same manner as in Example 1-1 except that 4-hydroxy-4′-nitrobiphenyl was changed to 4-amino-4′-nitrobiphenyl in the second stage of Scheme 1 in Example 1-1. Compound (b-3) was obtained.
  • Example 1-4 Synthesis of compound (g-1)
  • the same operation as in the first stage of Scheme 1 was carried out except that 4-nitrobenzaldehyde was changed to 4-phenylbenzaldehyde in the first stage of Scheme 1 in Example 1-1, and compound (g-1) was obtained in one stage.
  • 4-nitrobenzaldehyde was changed to 4-phenylbenzaldehyde in the first stage of Scheme 1 in Example 1-1, and compound (g-1) was obtained in one stage.
  • Example 1-5 Synthesis of compound (b-27)] Synthesis was performed in the same manner as in Example 1-1 except that 4-hydroxy-4′-nitrobiphenyl was changed to 2-methyl-4-nitroaniline in the second stage of Scheme 1 in Example 1-1. Compound (b-27) was obtained.
  • Example 2-1 Synthesis of polymer (A-1)] 100 mol parts of the compound represented by the above formula (a-1) as tetracarboxylic dianhydride and 100 mol parts of the compound (b-1) as diamine were dissolved in N-methyl-2-pyrrolidone (NMP). The reaction was performed at 60 ° C. for 6 hours to obtain a solution containing 20% by weight of polyamic acid. The obtained polyamic acid (polymer (A-1)) had a weight average molecular weight Mw of 45,000.
  • Example 2-2 to 2-9 and Synthesis Examples 1 to 3 A polyamic acid (polymers (A-2) to (A-9)) was prepared in the same manner as in Example 2-1 except that the types and amounts of tetracarboxylic dianhydride and diamine used were changed as shown in Table 1 below. And polymers (B-1) to (B-3)) were synthesized.
  • ⁇ Tetracarboxylic dianhydride> a-1 Compound represented by the above formula (a-1) a-2: Compound represented by the above formula (a-2) a-3: 1,3-propylene glycol bis (anhydrotrimellitate) (Compound represented by the above formula (a-3)) a-4: 1,2,3,4-cyclobutanetetracarboxylic dianhydride a-5: 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride a-6: pyromellitic dianhydride t- 5: Compound represented by formula (t-5) ⁇ diamine> b-1: Compound represented by the above formula (b-1) b-2: Compound represented by the above formula (b-2) b-3: Compound represented by the above formula (b-3) b- 27: Compound represented by the above formula (b-27) c-1: Compound represented by the following formula (c-1) c-2: Compound represented by the following formula (
  • Example 2-10 Synthesis of polymer (S-1)] 9.3 g of an epoxy group-containing polyorganosiloxane (ES-1) obtained in Synthesis Example 4 above, 26 g of methyl isobutyl ketone, 3 g of Compound (g-1) obtained in Example 1-4 above, and UCAT 18X (product) Name, a quaternary amine salt manufactured by San Apro Co., Ltd.) 0.10 g was mixed and stirred at 80 ° C. for 12 hours. Thereafter, the precipitate formed by adding the reaction mixture to methanol is filtered, dissolved in ethyl acetate to form a solution, the solution is separated with pure water, and then concentrated to obtain compound (X). Of polyorganosiloxane (polymer (S-1)) was obtained as white powder. The weight average molecular weight Mw of the polymer (S-1) was 4,000.
  • Example 3-1 Preparation of Liquid Crystal Alignment Agent
  • NMP and butyl cellosolve (BC) are added to the solution containing the polymer (A-1) obtained in Example 2-1 above, and the mixture is sufficiently stirred.
  • BC 70: 30 (weight ratio), a solid content concentration of 3.0% by weight.
  • a liquid crystal aligning agent was prepared by filtering this solution using a filter having a pore diameter of 0.45 ⁇ m.
  • the FFS type liquid crystal display element 10 shown in FIG. 1 was produced. First, a glass substrate 11a having an electrode pair on one side of which a bottom electrode 15 having no pattern, a silicon nitride film as an insulating layer 14, and a top electrode 13 patterned in a comb shape are formed in this order, and an electrode The counter glass substrate 11b not provided with a pair of the glass substrate 11a and the surface of the glass substrate 11a having a transparent electrode and one surface of the counter glass substrate 11b are respectively 1.
  • the liquid crystal aligning agent prepared in (1) was applied using a spinner to form a coating film. A schematic plan view of the used top electrode 13 is shown in FIG.
  • FIG. 2A is a top view of the top electrode 13, and FIG. 2B is an enlarged view of a portion C1 surrounded by a broken line in FIG. 2A.
  • the line width d1 of the electrodes was 4 ⁇ m, and the distance d2 between the electrodes was 6 ⁇ m.
  • the bottom electrode 15 functions as a common electrode that acts on all of the four systems of drive electrodes, and each of the four systems of drive electrodes serves as a pixel area. After the coating film was formed by the spinner, the coating film was pre-baked for 1 minute on an 80 ° C. hot plate.
  • each surface of the coating film was irradiated with polarized ultraviolet rays of 5,000 J / m 2 using a Hg—Xe lamp and a Grand Taylor prism to obtain a pair of substrates having a liquid crystal alignment film.
  • the irradiation direction of the polarized ultraviolet rays is from the normal direction of the substrate, and the polarization plane direction is set so that the direction of the line segment in which the polarization plane of the polarized ultraviolet rays is projected onto the substrate is the direction of the double-headed arrow in FIG.
  • the light irradiation process was performed after setting. After light irradiation, the film was heated (post-baked) at 230 ° C. for 1 hour in an oven in which the inside of the chamber was replaced with nitrogen to form a coating film having an average film thickness of 0.1 ⁇ m.
  • an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 ⁇ m is applied to the outer periphery of the surface of the substrate having the liquid crystal alignment film by screen printing, and the liquid crystal alignment film surfaces of the pair of substrates are then applied. It was made to oppose and it piled up and crimped
  • an FFS type liquid crystal display element was manufactured by attaching polarizing plates to both outer surfaces of the substrate. At this time, one of the polarizing plates is stuck so that the polarization direction thereof is parallel to the direction of projection of the polarization plane of the polarized ultraviolet light of the liquid crystal alignment film onto the substrate surface, and the other one has the polarization direction first.
  • the polarizing plate was stuck so as to be orthogonal to the polarization direction of the polarizing plate.
  • liquid crystal display element 2 The following (1) was evaluated using the liquid crystal display device manufactured in (1). Further, the above 2. except that the polarizing plate was not bonded. A liquid crystal display element (a liquid crystal cell in which a polarizing plate was not bonded) was manufactured by performing the same operation as described above, and the following (2) was evaluated. In addition, about the evaluation result, the best result was selected from the 3 or more liquid crystal display elements from which ultraviolet irradiation amount differs, and it used for evaluation of the liquid crystal display element.
  • the FFS type liquid crystal display device manufactured in the above was placed in an environment of 25 ° C. and 1 atmosphere.
  • the bottom electrode was set as a common electrode for all four drive electrodes, and the potential of the bottom electrode was set to 0 V potential (ground potential). While the electrodes B and D were short-circuited with the common electrode to be in a 0 V application state, a composite voltage consisting of an AC voltage of 5 V was applied to the electrodes A and C for 100 hours. Immediately after 100 hours, an AC voltage of 1.5 V was applied to all of the electrodes A to D.
  • the time until the luminance difference from the pixel area) cannot be visually confirmed is measured, and this is defined as an afterimage erasing time Ts. Note that the shorter this time, the less likely an afterimage is generated.
  • the case where the afterimage erasing time Ts is less than 30 seconds is “good ( ⁇ )”, the case where it is 30 seconds or more and less than 120 seconds is “good ( ⁇ )”, and the case where it is 120 seconds or more is “bad” ( ⁇ ) ",
  • the liquid crystal display device of this example was evaluated as having good afterimage characteristics.
  • the liquid crystal display element is sandwiched between the analyzers, and this is the minimum light transmission amount.
  • the black level in the dark state is represented by the minimum relative transmittance of the liquid crystal display element, and the smaller the black level in the dark state, the better the contrast.
  • a sample with a minimum relative transmittance of less than 0.5% is defined as “Good ( ⁇ )”
  • a sample having a minimum relative transmittance of less than 0.5% and less than 1.0% is defined as “Yes”
  • the contrast evaluation of this liquid crystal display element was determined to be “good”.
  • Examples 3-2 to 3-10 and Comparative Example 1 Liquid crystal aligning agents were respectively prepared at the same solvent ratio and solid content concentration as in Example 3-1, except that the type of polymer used was changed as shown in Table 2 below.
  • a liquid crystal display device was produced using each liquid crystal aligning agent in the same manner as in Example 3-1, and various evaluations were performed using the obtained liquid crystal display device. The results are shown in Table 2 below.
  • Example 3-1 to Example 3-10 In the liquid crystal display device manufactured using the liquid crystal aligning agent containing the compound (X), the evaluation of the AC afterimage characteristics and the contrast characteristics was “good” or “good” in all the examples.
  • Example 3-1 to Example 3-10 In particular, in Examples 3-1 to 3-7 and Examples 3-9 to 3-10 having the partial structure represented by the above formula (1) in the main chain of the polymer, the partial structure As a result, a better result was obtained than in Example 3-8. It was also found that the effect of improving AC afterimage characteristics is enhanced by using a diamine having a polycyclic structure such as a biphenyl structure.
  • AC afterimage characteristics and contrast characteristics were inferior to those of the examples.

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KR102349617B1 (ko) * 2018-01-25 2022-01-10 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막, 액정 소자 및 액정 소자의 제조 방법
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