WO2022168722A1 - 液晶配向剤、液晶配向膜、液晶表示素子の製造方法及び液晶表示素子 - Google Patents

液晶配向剤、液晶配向膜、液晶表示素子の製造方法及び液晶表示素子 Download PDF

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WO2022168722A1
WO2022168722A1 PCT/JP2022/003033 JP2022003033W WO2022168722A1 WO 2022168722 A1 WO2022168722 A1 WO 2022168722A1 JP 2022003033 W JP2022003033 W JP 2022003033W WO 2022168722 A1 WO2022168722 A1 WO 2022168722A1
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liquid crystal
group
component
formula
aligning agent
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PCT/JP2022/003033
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English (en)
French (fr)
Japanese (ja)
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直史 長谷川
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日産化学株式会社
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Priority to KR1020237028678A priority Critical patent/KR20230136633A/ko
Priority to CN202280013462.XA priority patent/CN116868114A/zh
Priority to JP2022579491A priority patent/JPWO2022168722A1/ja
Publication of WO2022168722A1 publication Critical patent/WO2022168722A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

  • the present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, a method for manufacturing a liquid crystal display element, and a liquid crystal display element.
  • Liquid crystal display elements used in liquid crystal televisions, navigators, smartphones, etc. are usually provided with a liquid crystal alignment film for controlling the alignment state of liquid crystals.
  • a liquid crystal alignment film has a function of controlling the alignment of liquid crystal molecules in a certain direction in a liquid crystal display element.
  • a liquid crystal display element has a structure in which liquid crystal molecules forming a liquid crystal layer are sandwiched between liquid crystal alignment films formed on respective surfaces of a pair of substrates. There, the liquid crystal molecules are aligned in a certain direction by the liquid crystal alignment film and respond by applying a voltage to the electrodes provided between the substrate and the liquid crystal alignment film. As a result, the liquid crystal display element displays a desired image by utilizing the alignment change due to the response of the liquid crystal molecules.
  • liquid crystal alignment films have mainly been polyimide-based liquid crystal alignment films, which are obtained by applying a liquid crystal alignment agent whose main component is a polyimide precursor such as polyamic acid (polyamic acid) or a solution of soluble polyimide to a glass substrate or the like and baking it. used.
  • a liquid crystal alignment agent whose main component is a polyimide precursor such as polyamic acid (polyamic acid) or a solution of soluble polyimide
  • a liquid crystal alignment agent whose main component is a polyimide precursor such as polyamic acid (polyamic acid) or a solution of soluble polyimide
  • in-vehicle applications e.g., car navigation systems and meter panels
  • monitoring cameras and medical camera monitors etc.
  • horizontal electric field systems such as IPS (In Plane Switching) and FFS (Fringe Field Switching) are being studied (Patent Documents 1 and 2). ).
  • Liquid crystal alignment films used in liquid crystal display elements of the IPS driving method and the FFS driving method require an alignment regulating force for suppressing afterimages (hereinafter also referred to as AC afterimages) generated by long-term AC driving.
  • AC afterimages an alignment regulating force for suppressing afterimages
  • liquid crystal display elements used for the above applications are required to have a pretilt angle lower than that of the conventional ones due to the demand for viewing angle characteristics.
  • Patent Document 1 after obtaining polyimide from polyamic acid, a liquid crystal alignment film is produced using a liquid crystal alignment agent containing the polyimide. has the disadvantage of being high.
  • Patent Document 2 describes that a liquid crystal alignment film obtained from a liquid crystal alignment agent containing two types of polyamic acids has high resistance to AC afterimages. It became clear that the effect of reducing the pretilt angle was not sufficient with the film.
  • the present invention provides a liquid crystal aligning agent excellent in cost performance that provides a liquid crystal alignment film having excellent resistance to AC afterimage and low pretilt angle characteristics, and a liquid crystal formed using the liquid crystal aligning agent.
  • An object of the present invention is to provide an alignment film and a liquid crystal display device having the liquid crystal alignment film.
  • the present inventors by forming a liquid crystal aligning film using a liquid crystal aligning agent containing a specific polymer component, to achieve the above objects It was found to be effective, and the present invention was completed.
  • a liquid crystal aligning agent characterized by containing the following (A) component and (B) component.
  • Product polyamic acid (A) Reaction of a tetracarboxylic acid derivative component containing 100 mol % of all tetracarboxylic acid derivative components of an aromatic tetracarboxylic dianhydride with a diamine component containing a diamine represented by the following formula (d AL ).
  • A is a group “* 11 —(CH 2 ) n —O—* 12 ” (* 11 is a bond bonding to an oxygen atom or a bond bonding to a carbon atom constituting a benzene ring represents a bond, * 12 represents a bond, n is an integer from 1 to 5.) Any hydrogen atom of the benzene ring bonded to the NH2 group is a monovalent may be replaced on the basis of (In formula (d n ), Y is a nitrogen atom-containing heterocyclic ring and a group “* 21 —NR-* 22 ” (* 21 and * 22 are bonds that bind to carbon atoms constituting an aromatic ring.
  • R represents a hydrogen atom or a monovalent organic group
  • the monovalent organic group is a carbon atom other than carbonyl carbon and a nitrogen atom. bond.
  • the liquid crystal aligning agent of this invention excellent in resistance to an AC afterimage and the liquid crystal aligning film which has a low pretilt-angle characteristic is obtained, and is excellent in cost performance can be obtained. Moreover, the liquid crystal display element which has a liquid crystal aligning film formed using this liquid crystal aligning agent is excellent in the viewing angle characteristic, and has a high display quality.
  • FIG. 1 is a schematic cross-sectional view showing an example of a lateral electric field liquid crystal display element of the present invention
  • FIG. 4 is a schematic cross-sectional view showing another example of the horizontal electric field liquid crystal display device of the present invention
  • the diamine component used for producing the polyamic acid (A) contained in the liquid crystal aligning agent of the present invention contains a diamine represented by the following formula (d AL ).
  • the diamines represented by the formula (d AL ) may be used singly or in combination of two or more.
  • A is a group “* 11 —(CH 2 ) n —O—* 12 ” (* 11 is a bond bonding to an oxygen atom or a bond bonding to a carbon atom constituting a benzene ring represents a bond, * 12 represents a bond, n is an integer from 1 to 5.) Any hydrogen atom of the benzene ring bonded to the NH2 group is a monovalent may be replaced on the basis of
  • a in the above formula (d AL ) By setting A in the above formula (d AL ) to the above aspect, the resistance to AC afterimage is improved, and when two types of polyamic acids are used, they are appropriately compatible, and low pretilt angle characteristics are obtained. be done.
  • * 11 is preferably a bond that bonds to an oxygen atom.
  • n in the group “* 11 —(CH 2 ) n —O—* 12 ” is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and an integer of 1 to 2. is more preferable.
  • the two amino groups in the above formula (d AL ) are preferably para-positions with respect to A from the viewpoint of obtaining high liquid crystal orientation.
  • a in the above formula (d AL ) is preferably a divalent organic group having 10 or less carbon atoms from the viewpoint of favorably obtaining the effects of the present invention.
  • the monovalent group includes a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms.
  • fluoroalkyl group fluoroalkenyl group having 2 to 10 carbon atoms, fluoroalkoxy group having 1 to 10 carbon atoms, carboxy group, hydroxy group, alkyloxycarbonyl group having 1 to 10 carbon atoms, cyano group, nitro group and the like. be done.
  • diamine represented by the above formula (d AL ) diamines represented by the following formulas (d AL -1) to (d AL -9) are preferable from the viewpoint of suitably obtaining the effects of the present invention.
  • n is more preferably 1 to 4 from the viewpoint of obtaining low pretilt angle characteristics, and 1 ⁇ 3 is more preferred, and 1-2 is even more preferred.
  • m and n in the above formula (d AL -3) are each independently more preferably 1 to 4, still more preferably 1 to 3, and even more preferably 1 to 2, from the viewpoint of obtaining low pretilt angle characteristics.
  • n in the above formula (d AL -6) is more preferably 1-3, and even more preferably 1-2.
  • m1 and m2 in the above formula (d AL -6) are each independently more preferably 1 to 3, and even more preferably 1 to 2.
  • the sum of m1, m2 and n is preferably 10 or less.
  • n in the above formulas (d AL -7) and (d AL -9) is more preferably 1 to 3, even more preferably 1 to 2, from the viewpoint of obtaining low pretilt angle characteristics.
  • n in the above formula (d AL -8) is more preferably 1 to 4, still more preferably 1 to 3, and even more preferably 1 to 2.
  • m1 and m2 in the above formula (d AL -8) are each independently more preferably 1 to 4, still more preferably 1 to 3, and even more preferably 1 to 2.
  • the sum of m1, m2 and n is preferably 10 or less.
  • the two amino groups in the above formulas (d AL -1) to (d AL -9) are at the para position with respect to the divalent organic group connecting the two benzene rings from the viewpoint of obtaining high liquid crystal orientation. Preferably.
  • the content of the diamine represented by the above formula (d AL ) in the component of the polyamic acid (A) is not particularly limited, but is 10 mol% or more of the total diamine component used in the production of the polyamic acid (A). It is preferably 20 mol % or more, more preferably 50 mol % or more. When other diamines described later are used in combination, the content of the diamine represented by the above formula (d AL ) is preferably 95 mol% or less, more preferably 90 mol% or less, and 85 mol% or less. is more preferable.
  • the diamine component used in the production of the polyamic acid (A) contained in the liquid crystal aligning agent of the present invention in addition to the diamine represented by the above formula (d AL ), varies depending on the desired properties of the liquid crystal aligning agent.
  • diamine hereinafter also referred to as other diamine
  • the other diamines the following can be used.
  • the diamines may be used singly or in combination of two or more.
  • diamines represented by the formula (d n ) (excluding diamines represented by the formula (d n )); diamines having a siloxane bond such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane; meta-xylylenediamine , 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4′-methylenebis(cyclohexylamine), international A diamine or the like in which two amino groups are bonded to a group represented by any one of formulas (Y-1) to (Y-167) described in Publication No.
  • diamines having a siloxane bond such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane; meta-xylylenediamine ,
  • Ar represents a divalent benzene ring, a biphenyl structure, or a naphthalene ring. However, when p is 1, at least one of Ar is a biphenyl structure or a naphthalene ring In the above case, when one of the two Ars is a biphenyl structure, the other represents a biphenyl structure or a naphthalene ring.
  • the two Ars may be the same or different, and any hydrogen in the ring in the above Ar
  • the atom may be replaced by a monovalent group
  • Specific examples of the monovalent group are: Examples include the structures exemp
  • the two or more m may be the same or different.
  • One or more hydrogen atoms on the benzene ring may be substituted with a monovalent group.
  • An example of formula (d 0 ) will be described later.
  • a 1 is a single bond, —CH 2 —, —C 2 H 4 —, —C(CH 3 ) 2 —, —CF 2 —, —C(CF 3 ) 2 —, -O-, -CO-, -NH-, -N(CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CON( CH 3 )— or —N(CH 3 )CO—, m1 and m2 are each independently an integer of 0-4, and m1+m2 is an integer of 1-4.
  • m3 and m4 are each independently an integer of 1-5.
  • A2 represents a linear or branched alkyl group having 1-5 carbon atoms, and m5 is an integer of 1-5.
  • a 3 and A 4 are each independently a single bond, —CH 2 —, —C 2 H 4 —, —C(CH 3 ) 2 —, —CF 2 —, —C (CF 3 ) 2 -, -O-, -CO-, -NH-, -N(CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CON(CH 3 )- or -N(CH 3 )CO-, where m6 is an integer of 1-4. )
  • X v1 to X v4 and X p1 to X p2 are each independently —(CH 2 ) a — (a is an integer of 1 to 15 ), -CONH-, -NHCO-, -CON(CH 3 )-, -NH-, -O-, -CH 2 O-, -CH 2 OCO-, -COO-, or -OCO-, X v5 represents -O-, -CH 2 O-, -CH 2 OCO-, -COO- or -OCO- X a is a single bond, -O-, -NH- or -O-( CH 2 ) m —O— (m represents an integer of 1 to 6), and R v1 to R v4 and R 1a to R 1b each independently represent an alkyl group having 1 to 20 carbon atoms, a carbon represents an alkoxy group with a number of 1 to 20
  • the monovalent group in the above formula (d o ) include the structures exemplified for the monovalent group in the above formula (d AL ).
  • diamine represented by the above formula (d o ) diamines represented by the following formulas (d o -1) to (d o -6), 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl ether are preferred.
  • any hydrogen atom in the benzene ring, biphenyl structure or naphthalene ring may be replaced with a monovalent group.
  • Specific examples of the monovalent group include the structures exemplified for the monovalent group in the formula (d AL ).
  • diamines represented by the above formula (O) diamines represented by the following formulas (o-1) to (o-8) are preferable from the viewpoint of enhancing the liquid crystal orientation.
  • the tetracarboxylic acid derivative component used for producing the polyamic acid (A) contained in the liquid crystal aligning agent of the present invention contains 100 mol % of the total tetracarboxylic acid derivative component of the aromatic tetracarboxylic dianhydride.
  • An aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to an aromatic ring.
  • the aromatic tetracarboxylic dianhydride is preferably a tetracarboxylic dianhydride represented by the following formula (t R ).
  • X R is a structure selected from the following formulas (X R -1) to (X R -2).
  • j and k are integers of 0 or 1
  • a 1 and A 2 are each independently a single bond, —O—, —CO -, -COO-, a phenylene group, a sulfonyl group, or an amide group.
  • a plurality of A 2 may be the same or different. * represents a bond.
  • X R is preferably (X R -3) to (X R -10), and (X R -3), (X R -6) to (X R -8). , and (X R ⁇ 10) are more preferred.
  • the diamine component used for producing the polyamic acid (B) contained in the liquid crystal aligning agent of the present invention contains the diamine represented by the above formula (d AL ) and the diamine represented by the above formula (d n ). .
  • the diamine represented by the above formula (d AL ) and the diamine represented by the above formula (d n ) may be used singly or in combination of two or more.
  • a preferred embodiment of the diamine represented by the above formula (d AL ) used in the production of the polyamic acid (B) is a preferred embodiment of the diamine represented by the above formula (d AL ) used in the production of the polyamic acid (A). is similar to
  • the content of the diamine represented by the above formula (d AL ) in the constituent component of the polyamic acid (B) is not particularly limited, but is 5 to 80 mol% of the total diamine component used in the synthesis of the polyamic acid (B). is preferred, 10 to 70 mol% is more preferred, and 40 to 60 mol% is even more preferred.
  • Examples of the nitrogen atom-containing heterocyclic ring in the above formula ( dn ) include pyrrole ring, imidazole ring, pyrazole ring, triazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, indole ring, benzimidazole ring and purine ring.
  • quinoline ring isoquinoline ring, naphthyridine ring, quinoxaline ring, phthalazine ring, triazine ring, carbazole ring, acridine ring, piperidine ring, piperazine ring, pyrrolidine ring, hexamethyleneimine ring and the like.
  • a pyridine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a quinoline ring, a carbazole ring and an acridine ring are preferred.
  • the monovalent organic group represented by R in the above formula (d n ) includes, for example, alkyl groups such as methyl group, ethyl group and propyl group; alkenyl groups such as vinyl group; cycloalkyl groups such as cyclohexyl group; , an aryl group such as a methylphenyl group, an alkoxy group (eg, a methoxy group, an ethoxy group), and the like.
  • R is preferably a hydrogen atom or a methyl group.
  • diamine represented by the formula (d n ) examples include 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl -3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diamino Examples include carbazole and diamines represented by the following formulas (d n -1) to (d n -3).
  • n1 and m1′ are each independently an integer of 1 to 2.
  • n1 is an integer of 1-3.
  • R 1 has the same definition as R in the amino group represented by "* 21 -NR-* 22 ".
  • the plurality of R1 and m1' may be the same or different.
  • X 2 represents a monovalent nitrogen atom-containing heterocyclic group, and specific examples of the nitrogen atom-containing heterocyclic ring in the monovalent nitrogen atom-containing heterocyclic group are the above formulas (d n ) and the structures exemplified for the nitrogen atom-containing heterocycle in ).
  • n1 is an integer of 1 to 2
  • L 1 and L 2 are each independently a single bond, —CO—, an alkylene group having 1 to 6 carbon atoms, or —O— or —CO— between the carbon-carbon bonds of the alkylene group or at the terminal is a divalent organic group in which is inserted, and represents a divalent organic group bonded to a nitrogen atom via a carbon atom.
  • R represents a hydrogen atom or a methyl group.
  • X 3 represents a divalent group having a nitrogen atom-containing heterocyclic ring. Examples include the structures illustrated.
  • Ar 3 represents a divalent aromatic ring group or a divalent saturated nitrogen atom-containing heterocyclic group.
  • aromatic ring in the divalent aromatic ring group examples include benzene ring, naphthalene ring, anthracene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, pyrrole ring, imidazole ring, pyrazole ring, quinoline ring, isoquinoline ring, carbazole ring, benzimidazole ring, indole ring, quinoxaline ring and acridine ring.
  • saturated nitrogen atom-containing heterocyclic ring in the divalent saturated nitrogen atom-containing heterocyclic group include a piperidine ring and a piperazine ring.
  • Arbitrary hydrogen atoms of aromatic ring groups and saturated nitrogen atom-containing heterocyclic groups may be replaced with monovalent groups.
  • Examples of the monovalent group include the structures exemplified for the monovalent group in the above formula (d AL ).
  • L 3 is a single bond, -(CH 2 ) n - (n is an integer of 1 to 6), -NR'-, -(CH 2 ) n -NR'- (n is an integer of 1 to 6 ), -O-, -NR'-CO-, -CO-NR'-, -O-CO-, or -CO-O-, and R' is a hydrogen atom, a methyl group, or tert- represents a butoxycarbonyl group.
  • m3 and m3' are each independently an integer of 0 to 2, and either m3 or m3' is an integer of 1 or more.
  • the plurality of Ar 3 and L 3 may be the same or different.
  • all NH 2 groups in formula (d n -3) are bonded to carbon atoms constituting an aromatic ring.
  • diamines represented by the above formulas (d n -1) to (d n -3) include the diamines represented by the following formulas (Dp-1) to (Dp-6), the following formulas (z- 1) to diamines represented by formulas (z-14).
  • the content of the diamine represented by the above formula (d n ) in the constituent component of the polyamic acid (B) is not particularly limited, but is 20 to 95 mol% of the total diamine component used in the production of the polyamic acid (B). is preferred, 30 to 90 mol% is more preferred, and 40 to 60 mol% is even more preferred.
  • the diamine component used in the production of the polyamic acid (B) contained in the liquid crystal aligning agent of the present invention includes, in addition to the above diamines, various diamines (hereinafter referred to as other diamines ( Also referred to as b).) can be used.
  • diamines (b) include, for example, the compounds exemplified for the diamines used in the production of the polyamic acid (A). Each of the other diamines (b) may be used alone or in combination of two or more.
  • the tetracarboxylic acid derivative component used for producing the polyamic acid (B) contained in the liquid crystal aligning agent of the present invention consists of an acyclic aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride. At least one tetracarboxylic dianhydride selected from the group is contained in an amount of 5 mol % or more of all tetracarboxylic acid derivative components.
  • the total amount of the acyclic aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride is the total amount of tetracarboxylic acid used in the production of the polyamic acid (B). 10 mol % or more of the derivative component is more preferable, and 20 mol % or more is even more preferable.
  • the acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure.
  • An alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to an alicyclic structure. However, none of these four carboxy groups are bonded to the aromatic ring. Moreover, it is not necessary to consist only of an alicyclic structure, and a part thereof may have a chain hydrocarbon structure or an aromatic ring structure.
  • the acyclic aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride may be used alone or in combination of two or more.
  • a polyamic acid (B) having a composition different from that of the polyamic acid (A) can be obtained.
  • the acyclic aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride in the component (B) are, among others, a cyclobutane ring structure, a cyclopentane ring structure, and cyclohexane from the viewpoint of enhancing the liquid crystal orientation. It is preferably a tetracarboxylic dianhydride having at least one partial structure selected from the group consisting of ring structures.
  • the acyclic aliphatic tetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydride is preferably a tetracarboxylic dianhydride represented by the following formula (t).
  • X 1 is a structure selected from the following formulas (X1-1) to (X1-23).
  • R 1 to R 21 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, It represents an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group. * represents a bond.
  • R 1 to R 21 are preferably a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, more preferably a hydrogen atom or a methyl group, from the viewpoint of enhancing liquid crystal orientation.
  • formula (X1-1) include the following formulas (1-1) to (1-6).
  • Formula (1-1) is particularly preferred from the viewpoint of enhancing liquid crystal orientation. * has the same meaning as above.
  • X 1 in the above formula (t) is preferably the above formulas (X1-1) to (X1-10) and (X1-18) to (X1-23) from the viewpoint of improving the liquid crystal alignment, and the above formula ( X1-1) to (X1-2), (X1-5), (X1-7) to (X1-10), (X1-21) or (X1-23) are more preferred, and the above formula (1-1 ), (1-2), (X1-2) or (X1-7) to (X1-10) are more preferred.
  • the tetracarboxylic acid derivative component used for producing the polyamic acid (B) contained in the liquid crystal aligning agent of the present invention is the above-mentioned acyclic aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride.
  • aromatic tetracarboxylic dianhydrides or other tetracarboxylic dianhydrides may be used.
  • Preferred specific examples of the aromatic tetracarboxylic dianhydride used for producing the polyamic acid (B) are the same as the aromatic tetracarboxylic dianhydride used for producing the polyamic acid (A).
  • the tetracarboxylic acid derivative component used for producing the polyamic acid (B) contained in the liquid crystal aligning agent of the present invention contains other tetracarboxylic dianhydride (b), other tetracarboxylic dianhydride
  • the content of (b) is preferably 5 to 95 mol%, more preferably 10 to 90 mol%, more preferably 20 to 95 mol% of the total tetracarboxylic acid derivative component used in the production of polyamic acid (B). More preferably 80 mol %.
  • the total amount of the acyclic aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride is preferably 5 to 95 mol% of the total tetracarboxylic acid derivative component. , more preferably 10 to 90 mol %, more preferably 20 to 80 mol %.
  • the content ratio of the above components (A) and (B) is such that the content ratio of the components (A) and (B) is [(A) component] / [(B) component ] may be from 10/90 to 90/10, from 20/80 to 90/10, or from 20/80 to 80/20.
  • Polyamic acid can be produced, for example, by the following method. Specifically, the tetracarboxylic acid derivative component containing the tetracarboxylic dianhydride and the diamine component containing the diamine are heated in the presence of an organic solvent at ⁇ 20 to 150° C., preferably 0 to 50° C., for 30 minutes. It can be synthesized by reacting for up to 24 hours, preferably 1 to 12 hours (polycondensation).
  • organic solvent used in the above reaction examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone and the like.
  • the polymer has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3] Any of the indicated solvents can be used. These may be used in combination of two or more.
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • D 3 represents an alkyl group having 1 to 4 carbon atoms.
  • the reaction can be carried out at any concentration, preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial stage of the reaction may be carried out at a high concentration, and then the solvent may be added.
  • the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the closer this molar ratio is to 1.0, the greater the molecular weight of the polyamic acid produced.
  • the polyamic acid obtained in the above reaction can be recovered by precipitating the polyamic acid by injecting the reaction solution into a poor solvent while stirring well. Further, a purified polyamic acid powder can be obtained by performing precipitation several times, washing with a poor solvent, and drying at room temperature or by heating. Poor solvents include, but are not limited to, water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.
  • Terminal blocking agent When synthesizing the polyamic acids (A) and (B) in the present invention, a terminal-blocking polymer is added using an appropriate terminal blocking agent together with a tetracarboxylic acid derivative component containing a tetracarboxylic dianhydride and a diamine component. It is good also as synthesize
  • Terminal blockers include, for example, acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-( 3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynylphthalic anhydride, etc.
  • the proportion of the end blocking agent used is preferably 20 mol parts or less, and preferably 10 mol parts or less, with respect to a total of 100 mol parts of the diamine component used and the organic diol component used as necessary. is more preferred.
  • the reaction solution may be added to the solvent to precipitate.
  • Solvents used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water.
  • the polyamic acid precipitated by putting it into a solvent can be filtered and recovered, and then dried at room temperature or under heat under normal pressure or reduced pressure.
  • the impurities in the polymer can be reduced by redissolving the precipitated and recovered polymer in an organic solvent and repeating the operation of reprecipitating and recovering 2 to 10 times.
  • Solvents in this case include, for example, alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more kinds of solvents selected from these, because the purification efficiency is further improved.
  • the molecular weights of the polyamic acid (A) and polyamic acid (B) used in the present invention are determined by GPC (Gel Permeation Chromatography) when considering the strength of the liquid crystal alignment film obtained therefrom, workability during film formation, and coating film properties. ), the weight average molecular weight is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.
  • the liquid crystal aligning agent of the present invention may contain polymers other than polyamic acid (A) and polyamic acid (B).
  • polymers other than polyamic acid (A) and polyamic acid (B) include polyamic acid esters, polyimides, polysiloxanes, polyesters, polyamides, polyureas, polyurethanes, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, and poly(styrene-maleic anhydride) copolymers.
  • polymers selected from the group consisting of polymers, poly(isobutylene-maleic anhydride) copolymers, poly(vinyl ether-maleic anhydride) copolymers, poly(styrene-phenylmaleimide) derivatives, and poly(meth)acrylates
  • polymers poly(isobutylene-maleic anhydride) copolymers, poly(vinyl ether-maleic anhydride) copolymers, poly(styrene-phenylmaleimide) derivatives, and poly(meth)acrylates
  • poly(styrene-maleic anhydride) copolymers include SMA1000, 2000, 3000 (manufactured by Cray Valley), GSM301 (manufactured by Gifu Shellac Co., Ltd.), etc.
  • Poly(isobutylene-maleic anhydride) ) copolymers include Isoban-600 (manufactured by Kuraray Co., Ltd.), and specific examples of poly(vinyl ether-maleic anhydride) copolymers include GANTREZ AN-139 (methyl vinyl ether maleic anhydride resin , manufactured by ISP Japan). Other polymers may be used singly or in combination of two or more.
  • the content of the other polymer is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, and further 20 to 80 parts by mass with respect to the total 100 parts by mass of the polymer contained in the liquid crystal aligning agent. preferable.
  • the liquid crystal aligning agent according to the present invention is preferably a liquid composition in which the polyamic acid (A) and the polyamic acid (B) are dissolved or dispersed in an organic solvent.
  • the organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as it uniformly dissolves the polyamic acid, but N,N-dimethylformamide, N,N-dimethylacetamide, N,N -dimethyllactamide, N,N-dimethylpropionamide, tetramethylurea, N,N-diethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, ⁇ -butyrolactone, ⁇ -valero lactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide and ⁇ -butyrolactone are mentioned.
  • the content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass of the total solvent contained in the liquid crystal aligning agent.
  • the organic solvent contained in the liquid crystal aligning agent is a mixture of the above solvents and a solvent (also referred to as a poor solvent) that improves the coatability and the surface smoothness of the coating film when applying the liquid crystal aligning agent.
  • a solvent also referred to as a poor solvent
  • the use of solvents is preferred. Specific examples of the poor solvent used in combination are shown below, but are not limited to these.
  • the content of the poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, particularly preferably 20 to 70% by mass, of the total solvent contained in the liquid crystal aligning agent.
  • the type and content of the poor solvent are appropriately selected according to the liquid crystal aligning agent coating device, coating conditions, coating environment, and the like.
  • poor solvents examples include diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, and diethylene glycol.
  • diisobutyl carbinol propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene Glycol monobutyl ether acetate or diisobutyl ketone are preferred.
  • Preferred solvent combinations of a good solvent and a poor solvent include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, ⁇ -butyrolactone and ethylene glycol monobutyl ether, N-methyl-2- Pyrrolidone and ⁇ -butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, N-ethyl-2- pyrrolidone and propylene glycol diacetate, N,N-dimethyllactamide and diisobutyl ketone, N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N- Methy
  • the liquid crystal aligning agent of the present invention may additionally contain components other than the components (A), (B), and organic solvent (hereinafter also referred to as additive components).
  • additive components include, for example, a crosslinkable compound having at least one substituent selected from an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group and an alkoxy group;
  • crosslinkable compound examples include compounds represented by any one of the following formulas (CL-1) to (CL-11).
  • Examples of compounds for adjusting the dielectric constant and electrical resistance of the resin film include monoamines having a nitrogen atom-containing aromatic heterocycle such as 3-picolylamine.
  • the content is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent, more preferably is 0.1 to 20 parts by mass.
  • Preferred specific examples of functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane.
  • Silane N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy silane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxysilane sidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane,
  • the solid content concentration in the liquid crystal aligning agent (ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., but preferably It is in the range of 1 to 10% by mass.
  • a particularly preferable solid content concentration range varies depending on the method used to apply the liquid crystal aligning agent to the substrate.
  • the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass.
  • the printing method it is particularly preferable to set the solid content concentration in the range of 3 to 9% by mass, thereby setting the solution viscosity in the range of 12 to 50 mPa ⁇ s.
  • the ink jet method it is particularly preferable to set the solid content concentration in the range of 1 to 5% by mass, thereby setting the solution viscosity in the range of 3 to 15 mPa ⁇ s.
  • the temperature in preparing the polymer composition is preferably 10-50°C, more preferably 20-30°C.
  • liquid crystal aligning agent can be effectively applied to various technical applications.
  • type liquid crystal alignment film for liquid crystal light control element protective film (e.g. protective film for color filter), spacer film, interlayer insulation film, antireflection film, wiring coating film, antistatic film, motor insulation film ( It can also be applied to gate insulating films of flexible displays, etc.
  • a liquid crystal aligning film can be manufactured by using the said liquid crystal aligning agent.
  • 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 such as type (IPS type, FFS type) and optically compensated bend type (OCB type).
  • the liquid crystal display element of the present invention includes, for example, the following steps (1) to (3).
  • the liquid crystal display element of the present invention can be produced, for example, by a method including the following steps (1) to (4), a method including steps (1) to (2) and (4), steps (1) to (3), and (4). -2) and (4-4), or by a method including steps (1) to (3), (4-3) and (4-4).
  • a process (1) is a process of apply
  • a specific example of step (1) is as follows.
  • the liquid crystal aligning agent of the present invention is applied to one surface of the substrate provided with the patterned transparent conductive film by an appropriate coating method such as a roll coater method, a spin coat method, a printing method, an inkjet method, or the like.
  • the substrate is not particularly limited as long as it is highly transparent, and in addition to a glass substrate and a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used.
  • a reflective liquid crystal display element if only one substrate is used, an opaque material such as a silicon wafer can be used, and in this case, a light-reflecting material such as aluminum can be used for the electrodes.
  • a substrate provided with electrodes made of a transparent conductive film or a metal film patterned in a comb shape and a counter substrate provided with no electrodes are used.
  • Screen printing, offset printing, flexographic printing, inkjet method, spray method, etc. can be used as methods for applying the liquid crystal aligning agent to the substrate and forming a film.
  • the coating method and the film-forming method by the inkjet method can be preferably used.
  • a process (2) is a process of baking the liquid crystal aligning agent apply
  • a specific example of step (2) is as follows. After the liquid crystal aligning agent is applied onto the substrate in step (1), the solvent is evaporated or the polyamic acid is thermally imidized by heating means such as a hot plate, a thermal circulation oven, or an IR (infrared) oven. you can go
  • the drying and baking steps after applying the liquid crystal aligning agent of the present invention can be performed at any desired temperature and time, and may be performed multiple times.
  • the temperature for baking the liquid crystal aligning agent can be, for example, 40 to 180.degree.
  • the firing time is not particularly limited, but may be 1 to 10 minutes or 1 to 5 minutes.
  • a step of firing at a temperature range of 150 to 300° C. or 150 to 250° C. may be added after the above step.
  • the firing time is not particularly limited, but may be 5 to 40 minutes or 5 to 30 minutes.
  • the thickness of the film after baking is preferably 5 to 300 nm, more preferably 10 to 200 nm, because if it is too thin, the reliability of the liquid crystal display element may deteriorate.
  • Step (3) is a step of subjecting the film obtained in step (2) to an orientation treatment. That is, in a horizontally aligned liquid crystal display element such as an IPS system or an FFS system, the coating film is subjected to an alignment ability-imparting treatment. On the other hand, in a vertical alignment type liquid crystal display element such as VA mode or PSA mode, the formed coating film can be used as a liquid crystal alignment film as it is, but the coating film may be subjected to an alignment ability imparting treatment. Examples of the alignment treatment method for the liquid crystal alignment film include a rubbing treatment method and a photo-alignment treatment method.
  • the surface of the film is irradiated with radiation polarized in a certain direction, and optionally, preferably, heat treatment is performed at a temperature of 150 to 250 ° C. to improve liquid crystal alignment (liquid crystal alignment (also referred to as ability).
  • radiation ultraviolet light or visible light having a wavelength of 100 to 800 nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400 nm, more preferably 200 to 400 nm are preferred.
  • the irradiation dose of the radiation is preferably 1 to 10,000 mJ/cm 2 . Among them, 100 to 5,000 mJ/cm 2 is preferable.
  • the substrate having the film-like material may be irradiated with heating at 50 to 250° C. in order to improve liquid crystal orientation.
  • the liquid crystal alignment film thus produced can stably orient liquid crystal molecules in a certain direction.
  • the liquid crystal alignment film irradiated with polarized radiation can be subjected to contact treatment using water or a solvent, or the liquid crystal alignment film irradiated with radiation can be heat-treated.
  • the solvent used in the contact treatment is not particularly limited as long as it dissolves the decomposed product produced from the film-like material by irradiation with radiation.
  • Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3- methyl methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate and the like.
  • Solvents may be used singly or in combination of two or more.
  • the temperature of the heat treatment for the above radiation-irradiated coating film is more preferably 50 to 300°C, more preferably 120 to 250°C.
  • the heat treatment time is preferably 1 to 30 minutes.
  • Step (4) Step of producing a liquid crystal cell>
  • two substrates on which liquid crystal alignment films are formed as described above are prepared, and liquid crystal is arranged between the two substrates facing each other.
  • the following two methods are mentioned.
  • the first method first, two substrates are arranged to face each other with a gap (cell gap) interposed therebetween so that the respective liquid crystal alignment films face each other.
  • the peripheries of the two substrates are bonded together using a sealing agent, and a liquid crystal composition is injected and filled into the cell gap defined by the substrate surface and the sealing agent to contact the film surface, and then the injection hole is sealed. stop.
  • the second method is a method called ODF (One Drop Fill) method.
  • ODF One Drop Fill
  • a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed is coated with, for example, an ultraviolet light-curing sealant, and a liquid crystal composition is applied to several predetermined places on the surface of the liquid crystal alignment film. drip.
  • the other substrate is attached so that the liquid crystal alignment films face each other, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface.
  • the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant.
  • the two substrates are arranged opposite to each other so that the rubbing directions of the respective coating films are at a predetermined angle, for example, orthogonal or antiparallel.
  • the sealant for example, an epoxy resin or the like containing a curing agent and aluminum oxide spheres as spacers can be used.
  • the liquid crystal composition is not particularly limited, and various liquid crystal compositions containing at least one liquid crystal compound (liquid crystal molecule) and having positive or negative dielectric anisotropy can be used.
  • a liquid crystal composition with a positive dielectric anisotropy is also referred to as a positive liquid crystal
  • a liquid crystal composition with a negative dielectric anisotropy is also referred to as a negative liquid crystal.
  • the above liquid crystal composition contains a fluorine atom, a hydroxy group, an amino group, a fluorine atom-containing group (e.g., trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocyclic ring, a cycloalkane,
  • a liquid crystal compound having a cycloalkene, a steroid skeleton, a benzene ring, or a naphthalene ring may be included, and a compound having two or more rigid sites (mesogenic skeleton) exhibiting liquid crystallinity in the molecule (for example, two rigid biphenyl structures or terphenyl structures linked by alkyl groups).
  • liquid crystal compositions include liquid crystal compositions exhibiting a nematic phase, liquid crystal compositions exhibiting a smectic phase, and liquid crystal compositions exhibiting a cholesteric phase. Among them, liquid crystal compositions exhibiting a nematic phase are preferred. Furthermore, the liquid crystal composition may further contain an additive from the viewpoint of improving liquid crystal orientation. Examples of such additives include photopolymerizable monomers such as compounds having a polymerizable group; optically active compounds (eg, S-811 manufactured by Merck Co., Ltd.); antioxidants; UV absorbers; antifoaming agents; polymerization initiators; or polymerization inhibitors.
  • additives include photopolymerizable monomers such as compounds having a polymerizable group; optically active compounds (eg, S-811 manufactured by Merck Co., Ltd.); antioxidants; UV absorbers; antifoaming agents; polymerization initiators; or polymerization inhibitors.
  • positive liquid crystal examples include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019 and MLC-7081 manufactured by Merck.
  • Negative liquid crystals include, for example, MLC-6608, MLC-6609, MLC-6610, and MLC-7026-100 manufactured by Merck.
  • MLC-3023 manufactured by Merck Co., Ltd. can be mentioned as a liquid crystal containing a polymerizable compound. From the viewpoint of suitably obtaining the effects of the present invention, the liquid crystal aligning agent of the present invention is preferably used for positive liquid crystals.
  • the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat between the pair of substrates.
  • a liquid crystal display element (PSA type liquid crystal display element) manufactured through a process of polymerizing a polymerizable compound by at least one of irradiating an active energy ray and heating while placing an object and applying a voltage between electrodes. It is preferably used.
  • the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group polymerized by at least one of active energy rays and heat is placed between the pair of substrates. It is also preferably used in a liquid crystal display element (SC-PVA mode type liquid crystal display element) manufactured through a process of arranging a liquid crystal alignment film containing a liquid crystal and applying a voltage between electrodes.
  • SC-PVA mode type liquid crystal display element manufactured through a process of arranging a liquid crystal alignment film containing a liquid crystal and applying a voltage between electrodes.
  • Step (4-2) is the same as step (4) above, except that a liquid crystal composition containing a polymerizable compound is injected or dropped.
  • the polymerizable compound include polymerizable compounds having one or more polymerizable unsaturated groups such as acrylate groups and methacrylate groups in the molecule.
  • Step (4-3) For SC-PVA mode liquid crystal display element>
  • a method of manufacturing a liquid crystal display element may be adopted by carrying out the same as the above step (4), followed by a step of irradiating ultraviolet rays, which will be described later. According to this method, a liquid crystal display device excellent in response speed can be obtained with a small amount of light irradiation, as in the case of manufacturing the PSA type liquid crystal display device.
  • the compound having a polymerizable group may be a compound having one or more polymerizable unsaturated groups in the molecule, and its content is 0.1 to 30 per 100 parts by mass of all polymer components. It is preferably parts by mass, more preferably 1 to 20 parts by mass.
  • the polymerizable group may be present in the polymer used for the liquid crystal alignment agent, and such a polymer includes, for example, a diamine component containing a diamine having a photopolymerizable group at the end thereof, which is used in the reaction.
  • a diamine component containing a diamine having a photopolymerizable group at the end thereof which is used in the reaction.
  • the polymer obtained is mentioned.
  • Step (4-4) Step of irradiating with ultraviolet rays>
  • the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates obtained in step (4-2) or (4-3).
  • the voltage applied here can be, for example, 5 to 50 V direct current or alternating current.
  • the light for irradiation for example, ultraviolet light containing light with a wavelength of 150 to 800 nm and visible light can be used, but ultraviolet light containing light with a wavelength of 300 to 400 nm is preferable.
  • 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 as the light source for the irradiation light.
  • the irradiation amount of light is preferably 1,000 to 200,000 J/m 2 , more preferably 1,000 to 100,000 J/m 2 .
  • a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell as necessary.
  • a polarizing plate to be attached to the outer surface of the liquid crystal cell, a polarizing film called "H film” in which polyvinyl alcohol is stretched and oriented while absorbing iodine is sandwiched between cellulose acetate protective films, or the H film itself.
  • a polarizing plate consisting of
  • a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell as necessary.
  • a polarizing plate to be attached to the outer surface of the liquid crystal cell, a polarizing film called "H film” in which polyvinyl alcohol is stretched and oriented while absorbing iodine is sandwiched between cellulose acetate protective films, or the H film itself.
  • a polarizing plate consisting of
  • the IPS substrate which is a comb-teeth electrode substrate used in the IPS mode, includes a base material, a plurality of linear electrodes formed on the base material and arranged in a comb-like shape, and the base material covering the linear electrodes. and a liquid crystal alignment film formed as follows.
  • the FFS substrate which is a comb-teeth electrode substrate used in the FFS mode, includes a substrate, a plane electrode formed on the substrate, an insulating film formed on the plane electrode, and an insulating film formed on the insulating film. , a plurality of linear electrodes arranged in a comb shape, and a liquid crystal alignment film formed on an insulating film so as to cover the linear electrodes.
  • FIG. 1 is a schematic cross-sectional view showing an example of the lateral electric field liquid crystal display device of the present invention, which is an example of an IPS mode liquid crystal display device.
  • the liquid crystal 3 is sandwiched between the comb-teeth electrode substrate 2 having the liquid crystal alignment film 2c and the opposing substrate 4 having the liquid crystal alignment film 4a.
  • the comb-shaped electrode substrate 2 includes a substrate 2a, a plurality of linear electrodes 2b formed on the substrate 2a and arranged in a comb-like shape, and formed on the substrate 2a so as to cover the linear electrodes 2b. and a liquid crystal alignment film 2c.
  • the counter substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b.
  • the liquid crystal alignment film 2c is, for example, the liquid crystal alignment film of the present invention.
  • the liquid crystal alignment film 4c is also the liquid crystal alignment film of the present invention.
  • the lateral electric field liquid crystal display element 1 when a voltage is applied to the linear electrodes 2b, an electric field is generated between the linear electrodes 2b as indicated by the lines of electric force L.
  • FIG. 2 is a schematic sectional view showing another example of the horizontal electric field liquid crystal display device of the present invention, which is an example of the FFS mode liquid crystal display device.
  • the liquid crystal 3 is sandwiched between the comb-teeth electrode substrate 2 having the liquid crystal alignment film 2h and the opposing substrate 4 having the liquid crystal alignment film 4a.
  • the comb-teeth electrode substrate 2 includes a base material 2d, a plane electrode 2e formed on the base material 2d, an insulating film 2f formed on the plane electrode 2e, and formed on the insulating film 2f to form a comb-like shape.
  • the counter substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b.
  • the liquid crystal alignment film 2h is, for example, the liquid crystal alignment film of the present invention.
  • the liquid crystal alignment film 4a is also the liquid crystal alignment film of the present invention.
  • the liquid crystal alignment film of the present invention can be applied to various uses other than the liquid crystal alignment film for the above uses. It can also be used for a liquid crystal alignment film for a transmission scattering type liquid crystal light control device. Furthermore, applications other than liquid crystal alignment films, such as protective films (e.g. protective films for color filters), spacer films, interlayer insulating films, antireflection films, wiring coating films, antistatic films, motor insulating films (flexible It can also be used for a gate insulating film of a display).
  • protective films e.g. protective films for color filters
  • spacer films e.g. protective films for color filters
  • interlayer insulating films e.g. antireflection films
  • wiring coating films e.g. antistatic films
  • motor insulating films flexible It can also be used for a gate insulating film of a display.
  • the liquid crystal display device of the present invention can be effectively applied to various devices such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smart phones, It can be used for various display devices such as various monitors, liquid crystal televisions, and information displays.
  • Table 1 summarizes the types and amounts of the diamine components and tetracarboxylic acid components used in Synthesis Examples 1-14.
  • Example 1 Using the polymer solution A-1 and the polymer solution B-1, polymer solution A-1 (7.5 g) and polymer solution B-1 ( 14.0 g) were mixed. For this mixed solution, NMP (12.1 g), BCS (12.5 g), NMP solution (3.0 g) containing 1% by mass of AD-1, and NMP solution (0 g) containing 10% by mass of AD-2 .9 g) was added while stirring, and the liquid crystal aligning agent AL-1 of the present invention was obtained by stirring at room temperature for 2 hours.
  • Example 2 (Examples 2 to 5 and Comparative Examples 1 to 10) With the composition shown in Table 2 below, the same operation as in Example 1 was performed, and the liquid crystal aligning agents AL-2 to AL-5 of Examples 2 to 5 of the present invention and the liquid crystals of Comparative Examples 1 to 10 were used. Aligning agents AL-C1 to AL-C10 were obtained.
  • the FFS mode liquid crystal cell includes a first glass substrate on which an FOP (Finger on Plate) electrode layer consisting of a planar common electrode, an insulating layer, and comb-shaped pixel electrodes is formed, and a high
  • FOP Finger on Plate
  • a second glass substrate having columnar spacers with a thickness of 4 ⁇ m and having an antistatic ITO film formed on its back surface was used as a set.
  • the pixel electrode has a comb shape in which a plurality of electrode elements each having a width of 3 ⁇ m and having a central portion bent at an internal angle of 160° are arranged in parallel with an interval of 6 ⁇ m. It had a first region and a second region bordering on a line connecting bends of a plurality of electrode elements.
  • the liquid crystal alignment film formed on the first glass substrate is aligned so that the direction of equally dividing the internal angle of the bent portion of the pixel and the alignment direction of the liquid crystal are orthogonal, and the liquid crystal alignment film formed on the second glass substrate is aligned.
  • the film was subjected to orientation treatment so that the orientation direction of the liquid crystal on the first glass substrate and the orientation direction of the liquid crystal on the second glass substrate coincided when the liquid crystal cell was produced.
  • the surface of the substrate with the liquid crystal alignment film was rubbed with a rayon cloth (manufactured by Yoshikawa Kako Co., Ltd., YA-20R) (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, pushing length: 0.4 mm). After that, the substrate was cleaned by irradiating ultrasonic waves in pure water for 1 minute, water droplets were removed by an air blow, and dried at 80° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film.
  • a rayon cloth manufactured by Yoshikawa Kako Co., Ltd., YA-20R
  • a sealing agent (XN-1500T manufactured by Mitsui Chemicals, Inc.) is applied around the liquid crystal injection port. ) was printed, and the other substrate was attached so that the liquid crystal alignment film surfaces faced each other and the rubbing directions thereof were antiparallel. After that, a heat treatment was performed at 150° C. for 60 minutes to cure the sealant to prepare an empty cell.
  • Liquid crystal MLC-3019 (manufactured by Merck Ltd., positive type liquid crystal) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell. After that, the obtained liquid crystal cell was heated at 120° C. for 1 hour, left overnight, and then subjected to various evaluations.
  • the pretilt angle of the liquid crystal cell was measured using "OPTIPRO-micro” manufactured by SHINTECH. It can be said that the smaller the pretilt angle, the better the viewing angle characteristics. Specifically, when the pretilt angle was 2.0 degrees or less, it was evaluated as “good”, and when it was greater than 2.0 degrees, it was evaluated as “poor”.
  • a liquid crystal cell is placed between two polarizing plates whose polarization axes are orthogonal to each other, a backlight is turned on, and the liquid crystal cell is arranged so that the transmitted light intensity in the first region of the pixel is minimized. was adjusted, and then the rotation angle ⁇ required when the liquid crystal cell was rotated so that the intensity of transmitted light in the second region of the pixel was minimized was obtained. It can be said that the smaller the value of this rotation angle ⁇ , the better the afterimage characteristics due to long-term AC drive. Specifically, when the rotation angle ⁇ was 0.05 degrees or less, it was evaluated as “Good”, and when it was greater than 0.05 degrees, it was evaluated as "Bad".
  • Table 3 shows the evaluation results of the liquid crystal cells using the liquid crystal aligning agents of the above Examples and Comparative Examples.
  • the liquid crystal display element using the liquid crystal aligning agent of the present invention has a small pretilt angle and good afterimage properties.

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WO2014189104A1 (ja) * 2013-05-22 2014-11-27 日産化学工業株式会社 液晶配向剤、液晶配向膜およびそれを用いた液晶表示素子
WO2015050133A1 (ja) * 2013-10-01 2015-04-09 日産化学工業株式会社 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子
WO2018043326A1 (ja) * 2016-08-30 2018-03-08 日産化学工業株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
WO2020158818A1 (ja) * 2019-01-30 2020-08-06 日産化学株式会社 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子

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WO2014189104A1 (ja) * 2013-05-22 2014-11-27 日産化学工業株式会社 液晶配向剤、液晶配向膜およびそれを用いた液晶表示素子
WO2015050133A1 (ja) * 2013-10-01 2015-04-09 日産化学工業株式会社 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子
WO2018043326A1 (ja) * 2016-08-30 2018-03-08 日産化学工業株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
WO2020158818A1 (ja) * 2019-01-30 2020-08-06 日産化学株式会社 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子

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