WO2021200291A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides - Google Patents

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

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WO2021200291A1
WO2021200291A1 PCT/JP2021/011521 JP2021011521W WO2021200291A1 WO 2021200291 A1 WO2021200291 A1 WO 2021200291A1 JP 2021011521 W JP2021011521 W JP 2021011521W WO 2021200291 A1 WO2021200291 A1 WO 2021200291A1
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liquid crystal
group
formula
repeating unit
crystal alignment
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PCT/JP2021/011521
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English (en)
Japanese (ja)
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美希 豊田
里枝 軍司
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日産化学株式会社
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Priority to KR1020227028415A priority Critical patent/KR20220159955A/ko
Priority to JP2022511931A priority patent/JPWO2021200291A1/ja
Priority to CN202180026171.XA priority patent/CN115380244A/zh
Publication of WO2021200291A1 publication Critical patent/WO2021200291A1/fr

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    • 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
    • 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Definitions

  • the present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.
  • liquid crystal display element various drive methods having different electrode structures and physical properties of liquid crystal molecules to be used have been developed.
  • TN Transmission Nematic
  • STN Super Twisted Nematic
  • VA Very Organic
  • IPS In Plane Switching
  • FFS Frringe Field Switching
  • liquid crystal display elements have a liquid crystal alignment film for orienting liquid crystal molecules.
  • a material for the liquid crystal alignment film for example, polyamic acid, polyamic acid ester, polyimide, polyamide and the like are known.
  • the VA type liquid crystal display element which is one of the driving methods of the liquid crystal display element
  • a photopolymerizable compound is added to the liquid crystal composition in advance, and a vertically oriented film such as a polyimide-based film is used to apply a voltage to the liquid crystal cell.
  • a technique for increasing the response speed of the liquid crystal display PSA (Polymer Sustained Alignment) type element) (see, for example, Patent Document 1 and Non-Patent Document 1) is known.
  • PSA Polymer Sustained Alignment
  • Patent Document 2 proposes a polyimide-based liquid crystal alignment film having a pyrrole structure.
  • large-screen, high-definition liquid crystal televisions have been widely put into practical use, and liquid crystal display elements in such applications have an afterimage as compared with conventional display applications that mainly display characters and still images.
  • Patent Document 3 proposes a polyimide-based liquid crystal alignment film having a diphenylamine structure.
  • an object of the present invention is a liquid crystal display orientation having a high voltage retention rate even after being exposed to high temperature and high humidity for a long time, quick relaxation of accumulated charges, and excellent afterimage characteristics.
  • An object of the present invention is to provide a liquid crystal alignment agent capable of obtaining a film, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element using the same.
  • a further object of the present invention is to provide a liquid crystal alignment agent capable of obtaining a liquid crystal alignment film having a high light transmittance, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element using the same.
  • the present invention is based on such findings, and the gist of the present invention is as follows.
  • the first repeating unit (a1) selected from the group consisting of the repeating unit represented by the following formula (1-a) and the repeating unit represented by the following formula (1-i), and Contains a polymer component having a second repeating unit (a2) selected from the group consisting of a repeating unit represented by the following formula (2-a) and a repeating unit represented by the following formula (2-i).
  • (X 1 and X 2 represent a tetravalent organic group.
  • Y 1 represents a divalent organic group having any of the structures represented by the following formulas (S1) to (S3).
  • Y 2 represents the following formula.
  • Two R 1 and R 2 independently represent a hydrogen atom or a monovalent organic group.
  • Two Z 1 and Z 2 represent a hydrogen atom or a monovalent organic group.
  • (X 1 and X 2 are independent, single bond,-(CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH 3 ).
  • a1 is an integer of 1 to 15, and A 1 is.
  • m 1 is an integer of 1 to 2.
  • G 1 and G 2 are independently divalent aromatic groups having 6 to 12 carbon atoms and 3 carbon atoms. Represents a divalent cyclic group selected from the group consisting of divalent alicyclic groups of 8 to 8. Any hydrogen atom on the cyclic group may be substituted.
  • M and n are independent of each other. It is an integer of 0 to 3, and m + n is 1 to 6, preferably 1 to 4.
  • R 1 is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 2 to 20 carbon atoms.
  • Any hydrogen atom representing an alkoxyalkyl group and forming R 1 may be substituted with a fluorine atom.
  • a plurality of X 1 , X 2 , G 1 , G 2 , a 1, m 1 and A 1 are present.
  • X 1 , X 2 , G 1 , G 2 , a1, m 1 and A 1 which exist in a plurality of each have the above definitions independently.
  • (X 3 represents a single bond, -CONH-, -NHCO-, -CO-N (CH 3 )-, -NH-, -O-, -CH 2 O-, -COO- or -OCO-.
  • R 2 represents an alkyl group having 1 to 20 carbon atoms or an alkoxy alkyl group having 2 to 20 carbon atoms, and any hydrogen atom forming R 2 may be substituted with a fluorine atom.
  • X 4 represents -CONH-, -NHCO-, -O-, -CH 2 O-, -COO- or -OCO-.
  • R 3 represents a structure having a steroid skeleton.
  • R represents a hydrogen atom or a monovalent organic group. * Represents a bond.
  • Boc represents the tert-butoxycarbonyl group.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the carbamate-based protecting group include a tert-butoxycarbonyl group and a 9-fluorenylmethoxycarbonyl group.
  • liquid crystal alignment agent of the present invention a liquid crystal alignment film having a high voltage retention rate even after being exposed to high temperature and high humidity for a long time, quickly relaxing accumulated charges, and having excellent afterimage characteristics can be obtained. Obtainable. Furthermore, according to the liquid crystal alignment agent of the present invention, a liquid crystal alignment film having a high light transmittance can be obtained.
  • the mechanism by which the above effects of the present invention are obtained is not always clear, but it is considered that the following is one of the causes. That is, it is considered that by using a liquid crystal alignment agent containing the above polymer, hydrolysis of the polymer is unlikely to occur even under high temperature and high humidity, so that a liquid crystal alignment film having a high voltage retention rate can be obtained.
  • the absorbance of the polymer oxide which is one of the factors for lowering the light transmittance
  • the absorbance of the polymer composed of the above polymer was extremely small, so that the light transmittance was high. It is considered that a liquid crystal alignment film having a ratio can be obtained.
  • the liquid crystal alignment agent of the present invention includes a first repeating unit (a1) selected from the group consisting of a repeating unit represented by the above formula (1-a) and a repeating unit represented by the above formula (1-i). , Contains a polymer component having a second repeating unit (a2) selected from the group consisting of a repeating unit represented by the above formula (2-a) and a repeating unit represented by the above formula (2-i). do.
  • the polymer component include (i) a polyimide precursor having the first repeating unit (a1) and the second repeating unit (a2) in the same molecule, and imidization thereof. At least one polymer (P-a1 + a2) (hereinafter, also referred to as a copolymer) selected from the group consisting of polymers, (ii) a polyimide precursor having the first repeating unit (a1) and an imide thereof. At least one selected from the group consisting of at least one polymer (P-a1) selected from the group consisting of chemical polymers, a polyimide precursor having the second repeating unit (a2), and an imidized polymer thereof.
  • a mixture with a polymer of the seed (P-a2) (hereinafter, also referred to as a polymer blend) can be mentioned.
  • the above-mentioned copolymer or the above-mentioned polymer blend may be used alone or in combination.
  • the polymer component is at least one selected from the group consisting of a polyimide precursor and an imidized polymer thereof, which does not have either a first repeating unit (a1) or a second repeating unit (a2). May further contain the polymer of.
  • the total of the first repeating unit (a1) and the second repeating unit (a2) is 5 to 100 of all the repeating units constituting the copolymer. It is preferably mol%, more preferably 10 to 100 mol%.
  • the content ratio of the repeating unit (a1) is preferably 1 to 90 mol%, more preferably 1 to 85 mol% of the total number of repeating units constituting the copolymer.
  • the content ratio of the repeating unit (a1) is 1 mol of the entire repeating unit constituting the polymer (P-a1) in terms of enhancing the liquid crystal orientation. % Or more and 99 mol% or less is preferable, 2 mol% or more and 95 mol% or less is more preferable, and 5 mol% or more and 90 mol% or less is further preferable. Further, the content ratio of the repeating unit (a2) is 5 mol% or more and 90 mol% or less of the entire repeating unit constituting the polymer (P-a2) from the viewpoint of efficiently obtaining the effect of the present invention. Preferably, it is 10 mol% or more and 80 mol% or less, more preferably.
  • the mass ratio of the content of the polymer (P-a2) to the content of the polymer (P-a1) is preferably 5/95 to 95/5, more preferably 10/90 to It is 90/10.
  • Y 1 represents a divalent organic group having a structure represented by the above formulas (S1) to (S3).
  • Y 1 is preferably a divalent organic group derived from a diamine having a structure represented by the above formulas (S1) to (S3).
  • a divalent organic group having a structure represented by the above formulas (S1) to (S3) an aromatic diamine having a structure represented by the above formulas (S1) to (S3) in a side chain ( Examples thereof include a divalent organic group derived from d).
  • the divalent organic group having the structure represented by the above formulas (S1) to (S3) is preferably a group obtained by removing two amino groups from the above aromatic diamine (d).
  • examples of the substituent on the cyclic group include a halogen atom, a halogen atom-containing alkyl group, a halogen atom-containing alkoxy group, an alkyl group having 1 to 10 carbon atoms, and carbon.
  • Carbon-carbon contained in an alkoxy group having a number of 1 to 10 an alkenyl group having 1 to 10 carbon atoms, and any methylene group of the halogen atom-containing alkyl group, halogen atom-containing alkoxy group, alkyl group, alkoxy group, and alkenyl group.
  • Examples include substituents selected from the group consisting of heteroatomic groups whose bond is interrupted by an oxygen atom.
  • Preferred specific examples of the structure represented by the above formula (S1) include structures represented by the following formulas (S1-1) to (S1-7).
  • a preferable specific example of the structure represented by the above formula (S3) is a structure represented by (S3-a).
  • X represents the formula (X1), the formula (X2), or -CH 2 O-
  • Col is the formula (Col-1), the formula (Col-2), or the formula.
  • (Col-3) is represented
  • G represents the formula (G1), the formula (G2), the formula (G3) or the formula (G4).
  • R 1 represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms.
  • X p is-(CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N (CH 3 )-, -NH-, -O-,- Represents CH 2 O-, -CH 2- OCO-, -COO-, or -OCO-.
  • a 1 is an oxygen atom or -COO- * (however, the bond with "*” binds to (CH 2 ) a2 ), and A 2 is an oxygen atom or * -COO- (however, "*").
  • bond marked with represents a (CH 2) binds to a2)
  • a 1, a 3 are each independently an integer of 0 or 1
  • a 2 represents an integer of 1 ⁇ 10
  • X 3 from the viewpoint of enhancing the liquid crystal alignment property, -CONH -, - NHCO -, - O -, - CH 2 O -, - COO- or -OCO- are preferred.
  • R 2 from the viewpoint of liquid crystal alignment property, preferably an alkoxyalkyl group alkyl or C 2-20 having 3 to 20 carbon atoms. Any hydrogen atom forming R 2 may be substituted with a fluorine atom.
  • the aromatic diamine (d) preferably has at least one benzene ring.
  • Specific examples of the aromatic diamine (d) include diamines represented by the following formula (d1) or formula (d2).
  • (X is a single bond, -O-, -C (CH 3 ) 2- , -NH-, -CO-,-(CH 2 ) m- , -SO 2- , -O- (CH 2 ) m- O -, - O-C ( CH 3) 2 -, - CO- (CH 2) m -, - NH- (CH 2) m -, - SO 2 - (CH 2) m -, - CONH- (CH 2) m -, - CONH- ( CH 2) m -NHCO-, or -COO- (CH 2) .m representing a divalent organic group m -OCO- is an integer of 1 ⁇ 8 .
  • Y is , Represents the structure of any of the above formulas (
  • Preferred examples of the diamine represented by the above formula (d1) include the following formulas (d1-1) to (d1-7).
  • Preferred examples of the diamine represented by the above formula (d2) include the following formulas (d2-1) to (d2-6).
  • (X v1 to X v4 and X p1 to X p8 are independently- (CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, and -CO-N ( CH 3 )-, -NH-, -O-, -CH 2 O-, -CH 2- OCO-, -COO-, or -OCO-, where X V5 to X V6 and X s1 to X s4 are They independently represent -O-, -CH 2 O-, -COO- or -OCO-.
  • X v7 is a single bond, -CONH-, -NHCO-, -CO-N (CH 3 )-,-. NH -, - O -, - CH 2 O -, - COO- or .
  • X represents an -OCO- a ⁇
  • X f is a single bond, -O -, - NH-, or -O- (CH 2) m -O- (m represents an integer of 1 to 8), R v1 to R v4 , and R 1a to R 1h independently represent -C n H 2n + 1 (n represents an integer of 1 to 20). ), Or -OC n H 2n + 1 (n represents an integer of 2 to 20).
  • X 1 represents a tetravalent organic group.
  • X 1 preferably represents a tetravalent organic group derived from tetracarboxylic dianhydride or a derivative thereof.
  • the tetravalent organic group include a tetravalent organic group derived from an acyclic aliphatic tetcarboxylic acid dianhydride or a derivative thereof, and a tetravalent organic derived from an alicyclic tetracarboxylic acid dianhydride or a derivative thereof.
  • Examples thereof include a tetravalent organic group derived from a group or aromatic tetracarboxylic acid dianhydride or a derivative thereof, preferably derived from a tetracarboxylic acid dianhydride represented by the following formula (3) or a derivative thereof 4 It is a valent organic group.
  • X represents a structure selected from any of the following formulas (x-1) to (x-13).
  • R 1 to R 4 each independently contain a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, and a fluorine atom.
  • R 5 and R 6 independently represent a hydrogen atom or a methyl group.
  • J and k are integers of 0 or 1.
  • a 1 and A 2 independently represent a single bond, -O-, -CO-, -COO-, phenylene, sulfonyl group, or amide group.
  • * 1 is one of the acid anhydride groups. It is a bond that binds, and * 2 is a bond that binds to the other acid anhydride group.
  • two A 2s may be the same or different from each other. good.
  • X is the above formulas (x-1) to (x-7), (x-11) to (x-13).
  • the tetracarboxylic dianhydride represented by the formula (3) or a derivative thereof can be mentioned.
  • 2 pieces of R 1 each independently represent a hydrogen atom or a monovalent organic group.
  • the monovalent organic group include a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • Two R 1 are each independently preferably represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • 2 pieces of Z 1 each independently represents a hydrogen atom or a monovalent organic group.
  • the monovalent organic group include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, and a substituent.
  • each of X 1 , Y 1 , R 1 , and Z 1 may be one type or two or more types.
  • Y 2 represents a divalent organic group represented by the following formula (2c).
  • Examples of the monovalent organic group of R in the above formula (2c) include an alkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group, and a phenyl group.
  • Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group and the like.
  • R is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group, or a phenyl group from the viewpoint of preferably obtaining the effects of the present invention.
  • Y 2 More preferred specific examples of Y 2 are 3,6-diaminocarbazole, 9-methyl-3,6-diaminocarbazole, 9-ethyl-3,6-diaminocarbazole, and 9-phenyl-3,6-diamino.
  • a group obtained by removing two amino groups from carbazole selected from the group consisting of carbazole can be mentioned.
  • X 2 in the formula (2-a) and the formula (2-i) the same thing can be mentioned as X 1 in the above formula (1-a) and the formula (1-i).
  • the R 2 in the above formula (2-a) is the same as the R 1 in the above formula (1-a).
  • the Z 2 in the above formula (2-a) is the same as the Z 1 in the above formula (1-a).
  • the formula (2-a) and the formula (2-i), X 2 , Y 2, R 2, Z 2 may each be a single type, or may be two or more types.
  • the polymer component further has a third repeating unit (a3) selected from the group consisting of a repeating unit represented by the following formula (3-a) and a repeating unit represented by the following formula (3-i).
  • a3 selected from the group consisting of a repeating unit represented by the following formula (3-a) and a repeating unit represented by the following formula (3-i).
  • Y 3 represents a divalent organic group, which is a divalent organic group having a structure represented by the above formulas (S1) to (S3) and the above formula (2c). in .2 one R 3 representing a divalent organic group other than a divalent organic group represented, two Z 3 has the same meaning as R 1, Z 1, respectively formula (1-a).)
  • polymer component further having the third repeating unit (a3) include copolymers and polymer blends.
  • a polyimide precursor having the first repeating unit (a1), the second repeating unit (a2), and the third repeating unit (a3) in the same molecule.
  • At least one polymer selected from the group consisting of the polymer and the imidized polymer thereof can be mentioned.
  • An example of the polymer blend is selected from the group consisting of a polyimide precursor having the first repeating unit (a1) and the second repeating unit (a2) in the same molecule and an imidized polymer thereof.
  • Examples thereof include a mixture with at least one polymer (P-a1 + a3) selected from the group consisting of.
  • the polymer (P-a1 + a3) does not have to have the second repeating unit (a2).
  • the above-mentioned copolymer or the above-mentioned polymer blend may be used alone or in combination.
  • the content ratio of the above-mentioned repeating unit (a3) is preferably 5 to 90 mol%, more preferably 10 to 80 mol% of the total of the repeating units constituting the above-mentioned copolymer.
  • the total of the first repeating unit (a1) and the second repeating unit (a2) is preferably 10 to 95 mol%, preferably 20 to 90 mol% of the total of the repeating units constituting the copolymer. Is more preferable.
  • the mass ratio of the content of the polymer (P-a1 + a3) to the content of the polymer (P-a1 + a2) is 5/95 to 95/5. It is preferable, more preferably 10/90 to 90/10.
  • Y 3 preferably represents a divalent organic group derived from a diamine.
  • the divalent organic group Y 3 p-phenylenediamine, m- phenylenediamine, 4- (2- (methylamino) ethyl) aniline, 2,4-diaminobenzoic acid, 2,5-diamino Diamines having a carboxy group such as benzoic acid, 3,5-diaminobenzoic acid, and diamine compounds represented by the following formulas (3b-1) to (3b-4), 4,4'-diaminodiphenylmethane, 3,3.
  • Diamines having a heterocycle such as 18 diamines having a diphenylamine skeleton such as the following formulas (Dp-1) to (Dp-9), groups such as the following formulas (5-1) to (5-10) "-N" (D)-”(D represents a protective group that is desorbed by heating and replaced with a hydrogen atom, and is preferably a tert-butoxycarbonyl group.
  • Diamines such as diamines having an oxazoline structure such as the following formulas (Ox-1) to (Ox-2) (hereinafter, also referred to as other diamines), and organic groups obtained by removing two amino groups.
  • Ox-1 oxazoline structure
  • Ox-2 organic groups obtained by removing two amino groups
  • 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 independently represent integers 0-4, and m1 + m2 represent integers 1-4. Equation (3b-2).
  • a 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms
  • m5 represents 1 to 5 in the whole
  • m3 and m4 independently represent integers of 1 to 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 -, - CO-N (CH 3) - or -N (CH 3) CO- indicates, m6 is an integer of 1 to 4). (In equations (R3) to (R5), n is an integer of 1 to 6.)
  • the above 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, the diamine having a photopolymerizable group at the end, the diamine represented by the above formulas (R1) to (R5), the above formula (z-1) to The diamine represented by (z-18) may be used alone or in combination of two or more when producing the above-mentioned polymer component from the viewpoint of accelerating the response speed of the liquid crystal display element using the PSA method or the SC-PVA mode. good.
  • diamines among the above, from the viewpoint of preferably obtaining the effects of the present invention, p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone , 2,2'-dimethyl-4,4'-diaminobiphenyl, 2- (2,4-diaminophenyloxy) ethyl methacrylate, 2,4-diamino-N, N-diallylaniline, the above formulas (R1) to ( The diamine represented by R5), the diamine represented by the above formulas (z-1) to (z-18), the diamine represented by the above formulas (Dp-1) to (Dp-9), and the above formula (Ox).
  • the diamine represented by -1) to (Ox-2) is preferable.
  • each of X 3 , Y 3 , R 3 , and Z 3 may be one type or two or more types.
  • Examples of the polyimide precursor used in the present invention include polyamic acid and polyamic acid ester.
  • the polyimide precursor used in the present invention can be synthesized, for example, by a known method as described in WO2013 / 157586. Specifically, it is synthesized by reacting a diamine component and a tetracarboxylic acid derivative component in a solvent (polycondensation).
  • Examples of the tetracarboxylic acid derivative component include tetracarboxylic acid dianhydride or a derivative thereof (tetracarboxylic acid dihalide, tetracarboxylic acid diester, or tetracarboxylic acid diester dihalide).
  • a polymer having an amic acid structure can be obtained by reacting a tetracarboxylic dianhydride component with a diamine component.
  • the solvent is not particularly limited as long as the produced polymer dissolves.
  • the diamine component is -N (Z 1 ) -Y 1- N (Z).
  • the polyimide can be obtained by ring-closing (imidizing) the polyimide precursor.
  • the imidization rate as used herein is the ratio of the imide group to the total amount of the imide group derived from the tetracarboxylic acid dianhydride or its derivative and the carboxy group (or its derivative).
  • the imidization ratio does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose.
  • the imidization ratio of the polyimide contained in the liquid crystal alignment agent of the present invention is 10 to 95%, preferably 20 to 95%, and more preferably 30 to 90% from the viewpoint of ensuring solubility.
  • Examples of the method for imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as it is or catalytic imidization in which a catalyst is added to the solution of the polyimide precursor.
  • the temperature at which the polyimide precursor is thermally imidized in the solution is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to remove the water generated by the imidization reaction from the outside of the system.
  • the catalytic imidization of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor and stirring at ⁇ 20 to 250 ° C., preferably 0 to 180 ° C.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times, the amount of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amic acid group. It is double.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine and trioctylamine, and among them, pyridine is preferable because it has an appropriate basicity for advancing the reaction.
  • the acid anhydride examples include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Among them, acetic anhydride is preferable because it facilitates purification after completion of the reaction.
  • the imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, the reaction temperature, and the reaction time.
  • the reaction solution may be added to a solvent to precipitate.
  • the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like.
  • the polymer which has been put into a solvent and precipitated can be collected by filtration and then dried at normal temperature or by heating under normal pressure or reduced pressure.
  • the operation of redistributing the polymer recovered by precipitation in an organic solvent and repeating the operation of recovering the precipitate by reprecipitation is repeated 2 to 10 times, impurities in the polymer can be reduced.
  • the solvent at this time include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more kinds of solvents selected from these, because the purification efficiency is further increased.
  • the molecular weight of the polymer used in the present invention is a weight average molecular weight measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the liquid crystal alignment film obtained from the polymer, the workability at the time of film formation, and the coating film property. It is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.
  • the blending ratio of the polymer component used in the method for producing the liquid crystal alignment film of the present invention is not particularly limited, but for example, the total amount of the polymer component contained in the liquid crystal alignment agent is 0.1 to 30% by mass, preferably 0.1 to 30% by mass. It is 3 to 10% by mass. Further, for example, the content of the above-mentioned copolymer (polymer (P-a1 + a2)) contained in the liquid crystal alignment agent is 1.5 to 9% by mass, preferably 2.5 to 9% by mass. Further, for example, the total content of the polymer blend (mixture of the polymer (P-a1) and the polymer (P-a2)) contained in the liquid crystal aligning agent is 1.5 to 9% by mass, preferably 1.5 to 9% by mass. , 2.5-9% by mass.
  • the liquid crystal alignment agent used for producing the liquid crystal alignment film may be mixed with the above-mentioned copolymer and other polymers other than the above-mentioned polymer blend.
  • the content of the other polymer is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass, based on the total amount of the polymer components.
  • other polymers include polyimide precursors other than the above-mentioned copolymers and the above-mentioned polymer blends or imidized polymers thereof, acrylic polymers, methacrylic polymers, polystyrene, polyamides, polysiloxanes and the like.
  • the solvent contained in the liquid crystal aligning agent is not particularly limited as long as it can dissolve the polymer, and is, for example, a lactone solvent such as ⁇ -valerolactone and ⁇ -butyrolactone; ⁇ -butyrolactam and N-methyl.
  • N-Pyrrolidone N-ethyl-2-pyrrolidone, N- (n-propyl) -2-pyrrolidone, N-isopropyl-2-pyrrolidone, N- (n-butyl) -2-pyrrolidone, N- (tert- Butyl) -2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N-cyclohexyl- Lactam solvents such as 2-pyrrolidone; N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethyllactoamide, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N- Amido solvents such as dimethylpropanamide;
  • Preferred solvent combinations include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and ⁇ -butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and ⁇ -butyrolactone and propylene.
  • the liquid crystal alignment agent of the present invention may contain other components other than the above, such as a crosslinkable compound, a functional silane compound, a surfactant, and a compound having a photopolymerizable group.
  • the crosslinkable compound can be used for the purpose of increasing the strength of the liquid crystal alignment film.
  • the crosslinkable compound is at least selected from the group consisting of a compound having an isocyanate group or a cyclocarbonate group, or a lower alkoxyalkyl group described in paragraphs [0109] to [0113] of WO2016 / 047771.
  • the compound having a blocked isocyanate group and the like can be mentioned.
  • Blocked isocyanate compounds are available as commercial products, for example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (all manufactured by Tosoh Corporation), Takenate B-830, B. -815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all manufactured by Mitsui Chemicals, Inc.) and the like can be preferably used.
  • preferable crosslinkable compound examples include compounds represented by the following formulas (CL-1) to (CL-11).
  • crosslinkable compound used in the liquid crystal alignment agent of the present invention may be one kind or a combination of two or more kinds.
  • the content of the other crosslinkable compound in the liquid crystal aligning agent of the present invention is 0.1 to 150 parts by mass, 0.1 to 100 parts by mass, or 1 to 1 to 100 parts by mass with respect to 100 parts by mass of all the polymer components. It is 50 parts by mass.
  • the functional silane compound can be used for the purpose of improving the adhesion between the liquid crystal alignment film and the underlying substrate.
  • the silane compound described in paragraph [0019] of International Publication 2014/119682 can be mentioned.
  • the content of the functional silane compound is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of all the polymer components.
  • the surfactant can be used for the purpose of improving the uniformity of the film thickness and the surface smoothness of the liquid crystal alignment film.
  • the compound include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant. Specific examples of these include the surfactants described in paragraph [0117] of WO2016 / 047771.
  • the amount of the surfactant used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent.
  • the compound having a photopolymerizable group is a compound having one or more polymerizable unsaturated groups such as an acrylate group and a methacrylate group in the molecule, for example, as represented by the following formulas (M-1) to (M-7). Compounds can be mentioned.
  • the liquid crystal aligning agent of the present invention is a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge loss of the element, as described in Paragraph of International Publication No. WO2011 / 132751 (Published 2011.10.27)
  • the nitrogen atom-containing heterocyclic amine compounds represented by the formulas [M1] to [M156], which are listed in 0194] to [0200], more preferably 3-picorylamine and 4-picorylamine can be added.
  • This amine compound may be added directly to the liquid crystal alignment agent, but it is preferably added after making a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass.
  • This solvent is not particularly limited as long as it dissolves the polymer.
  • the liquid crystal alignment agent of the present invention may be added with an imidization accelerator or the like for the purpose of efficiently advancing imidization by heating when firing the coating film.
  • the solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of the components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., but is preferable. It is in the range of 0.5 to 15% by mass, more preferably 1 to 10% by mass.
  • the range of particularly preferable solid content concentration depends on the method used when applying the liquid crystal alignment agent to the substrate. For example, in the case of the spin coating method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass.
  • the solid content concentration is in the range of 3 to 9% by mass, and the solution viscosity is in the range of 12 to 50 mPa ⁇ s.
  • the solid content concentration is in the range of 1 to 5% by mass and the solution viscosity is in the range of 3 to 15 mPa ⁇ s.
  • the liquid crystal alignment film of the present invention is obtained from the above liquid crystal alignment agent.
  • the liquid crystal alignment film of the present invention can be used for a horizontally oriented type or a vertically oriented type liquid crystal alignment film, and is particularly suitable for a vertically oriented type liquid crystal display element such as a VA method or a PSA mode.
  • the liquid crystal display element of the present invention includes the liquid crystal alignment film.
  • the liquid crystal display element of the present invention can be manufactured, for example, by a method including the following steps (1) to (3) or steps (1) to (4).
  • the liquid crystal alignment film of the present invention is applied onto a pair of substrates having a conductive film to form a coating film, and the liquid crystal cells are arranged so as to face each other via a layer of liquid crystal molecules so that the liquid crystal cells are arranged.
  • a liquid crystal display element obtained by a method for manufacturing a liquid crystal display element which is formed and irradiates the liquid crystal cell with light in a state where a voltage is applied between the conductive films of the pair of substrates. More specifically, it is a PSA type liquid crystal display element or a liquid crystal display element for SC-PVA mode, which will be described later.
  • the liquid crystal alignment agent of the present invention is applied to one surface of a substrate provided with a patterned transparent conductive film, for example, by a roll coater method, a spin coating method, a printing method, or an inkjet. Apply by an appropriate coating method such as the method.
  • the substrate is not particularly limited as long as it is a highly transparent substrate, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used together with the glass substrate and the silicon nitride substrate.
  • 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. Then, it is preferable that a heating (post-baking) step is further carried out.
  • the post-bake temperature 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 film thickness of the film thus formed is preferably 5 to 300 nm, more preferably 10 to 200 nm.
  • the coating film formed in the above step (1) can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to an alignment ability imparting treatment.
  • the alignment ability-imparting treatment includes a rubbing treatment in which the coating film is rubbed in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, and cotton, and photoalignment in which the coating film is irradiated with polarized or unpolarized radiation. Processing etc. can be mentioned.
  • the radiation to irradiate the coating film for example, ultraviolet rays including light having a wavelength of 150 to 800 nm and visible light can be used.
  • the radiation when the radiation is polarized, it may be linearly polarized or partially polarized.
  • the irradiation may be performed from a direction perpendicular to the substrate surface, may be performed from an oblique direction, or may be performed in combination thereof.
  • the direction of irradiation is diagonal.
  • Step of forming a liquid crystal layer (3-1) In the case of a VA type liquid crystal display element Two substrates on which a liquid crystal alignment film is formed as described above are prepared, and a liquid crystal is formed between the two substrates arranged opposite to each other. To place. Specifically, the following two methods can be mentioned.
  • the first method is a conventionally known method. First, two substrates are arranged facing each other through a gap (cell gap) so that the liquid crystal alignment films face each other. Next, the peripheral portions of the two substrates are bonded together using a sealant, and the liquid crystal composition is injected and filled into the surface of the substrate and the cell gap partitioned by the sealant to contact the film surface, and then the injection holes are sealed. Stop.
  • the second method is a method called the ODF (One Drop Fill) method.
  • ODF One Drop Fill
  • an ultraviolet light-curable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and the liquid crystal composition is further applied to a predetermined number of places on the liquid crystal alignment film surface. Is dropped.
  • 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.
  • it is desirable to remove the flow orientation at the time of filling the liquid crystal by further heating the liquid crystal composition used to a temperature at which it takes an isotropic phase and then slowly cooling it to room temperature.
  • the compound having a polymerizable group is a compound having one or more polymerizable unsaturated groups in the molecule such as an acrylate group and a methacrylate group as represented by the above formulas (M-1) to (M-7).
  • the content thereof is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of all the polymer components.
  • the above-mentioned polymerizable group may be contained in the polymer used for the liquid crystal aligning agent, and as such a polymer, for example, a diamine component containing a diamine having the above-mentioned photopolymerizable group at the terminal is used in the reaction. Examples thereof include the obtained polymer.
  • the liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates obtained in (3-2) or (3-3) above.
  • the voltage applied here can be, for example, a direct current or an alternating current of 5 to 50 V.
  • the light to be irradiated for example, ultraviolet rays containing light having a wavelength of 150 to 800 nm and visible light can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable.
  • the light source of the 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 excima laser, or the like can be used.
  • the irradiation amount of light is preferably 1,000 to 200,000 J / m 2 , and more preferably 1,000 to 100,000 J / m 2 .
  • a liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell.
  • a polarizing plate attached to the outer surface of the liquid crystal cell a polarizing plate called "H film” in which polyvinyl alcohol is stretch-oriented and iodine is absorbed is sandwiched between cellulose acetate protective films or the H film itself.
  • a polarizing plate made of the above can be mentioned.
  • the liquid crystal display element of the present invention can be effectively applied to various devices, for example, a clock, a portable game, a word processor, a notebook computer, a car navigation system, a cam coder, a PDA, a digital camera, a mobile phone, a smartphone, and the like. It can be used for various display devices such as various monitors, liquid crystal televisions, and information displays.
  • AD-1 Compound represented by the following formula (AD-1) (solvent) NMP: N-methyl-2-pyrrolidone, BCS: Butyl cellosolve ⁇ Molecular weight measurement> Measuring device: Room temperature gel permeation chromatography (GPC) (SSC-7200) manufactured by Senshu Kagaku Co., Ltd., Column: Column manufactured by Shodex (in series with KD-803 and KD-805), Column temperature: 50 ° C., Eluent: N, N-Dimethylformamide (as an additive, lithium bromide monohydrate (LiBr ⁇ H2O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphate) is 30 mmol / L, tetrahydrofuran (THF) is 10 mL / L.
  • JNW-ECA500 an NMR measuring instrument manufactured by JEOL Datum.
  • the chemical imidization rate is determined by using a proton derived from a structure that does not change before and after imidization as a reference proton, and the peak integrated value of this proton and the proton derived from the NH group of the amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It was calculated by the following formula using the peak integrated value.
  • x is the integrated proton peak value derived from the NH group of the amic acid
  • y is the integrated peak value of the reference proton
  • ⁇ is the integrated value of the amic acid in the case of polyamic acid (imidization rate is 0%). It is the ratio of the number of reference protons to one proton of NH group.
  • Imidization rate (%) (1- ⁇ ⁇ x / y) ⁇ 100
  • NMP was added to the polyamic acid solution (5-a) (20.0 g) obtained in Synthesis Example 5 to dilute it to 6.5% by mass, and then acetic anhydride (4.27 g) and pyridine (1) were used as imidization catalysts. .33 g) was added and reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (270 mL), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C. to obtain a polyimide powder. The imidization ratio of this polyimide powder was 37%, Mn was 10,980, and Mw was 34,300. NMP (22.0 g) was added to the obtained polyimide powder (3.0 g), and the mixture was stirred and dissolved at 70 ° C. for 12 hours to obtain a polyimide solution (1).
  • NMP was added to the polyamic acid solution (6-a) (20.0 g) obtained in Synthesis Example 7 to dilute it to 6.5% by mass, and then acetic anhydride (4.23 g) and pyridine (1) were used as imidization catalysts. .31 g) was added and reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (270 mL), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C. to obtain a polyimide powder. The imidization ratio of this polyimide powder was 53%, Mn was 9,920, and Mw was 32,300. NMP (22.0 g) was added to the obtained polyimide powder (3.0 g), and the mixture was stirred and dissolved at 70 ° C. for 12 hours to obtain a polyimide solution (2).
  • NMP was added to the polyamic acid solution (7-a) (20.0 g) obtained in Synthesis Example 9 to dilute it to 6.5% by mass, and then acetic anhydride (4.27 g) and pyridine (1) were used as imidization catalysts. .32 g) was added and reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (270 mL), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C. to obtain a polyimide powder. The imidization ratio of this polyimide powder was 58%, Mn was 10,490, and Mw was 31,280. NMP (22.0 g) was added to the obtained polyimide powder (3.0 g), and the mixture was stirred and dissolved at 70 ° C. for 12 hours to obtain a polyimide solution (3).
  • NMP NMP was added to dilute it to 6.5% by mass, acetic anhydride (6.66 g) and pyridine (1.29 g) were added as imidization catalysts, and the temperature was 100 ° C. It was allowed to react for 2 hours. This reaction solution was put into methanol (243 mL), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C. to obtain a polyimide powder. The imidization ratio of this polyimide powder was 73%, Mn was 10,500, and Mw was 40,300. NMP (22.0 g) was added to the obtained polyimide powder (3.0 g), and the mixture was stirred and dissolved at 70 ° C. for 12 hours to obtain a polyimide solution (6).
  • NMP (22.0 g) is added to the obtained polyimide powder (3.0 g), and the mixture is dissolved by stirring at 70 ° C. for 12 hours, then NMP (5.0 g) and BCS (20.0 g) are added at room temperature.
  • the polyimide solution (8) was obtained by stirring for 2 hours.
  • NMP (22.0 g) is added to the obtained polyimide powder (3.0 g), and the mixture is dissolved by stirring at 70 ° C. for 12 hours, then NMP (5.0 g) and BCS (20.0 g) are added at room temperature.
  • the polyimide solution (9) was obtained by stirring for 2 hours.
  • Example 1 The liquid crystal alignment agent (A-1) was obtained by adding NMP (6.0 g) and BCS (8.0 g) to the polyamic acid solution (1) (6.0 g) obtained in Synthesis Example 1 and stirring at room temperature for 2 hours. Got
  • Example 2 Liquid crystal orientations of Examples 2, Comparative Examples 1 and 2 in the same manner as in Example 1 except that the polyamic acid solutions (2), (3) and (4) were used instead of the polyamic acid solution (1), respectively.
  • Agents (A-2), (B-1) and (B-2) were obtained.
  • Example 3 The liquid crystal alignment agent (A-3) was added to the polyimide solution (1) (10.0 g) obtained in Synthesis Example 6 by adding NMP (2.0 g) and BCS (8.0 g) and stirring at room temperature for 2 hours. Obtained.
  • Example 4 and 5 Comparative Examples 3 to 6
  • Examples were the same as in Example 3 except that the polyimide solutions (2), (5), (3), (4), (6), and (7) were used instead of the polyimide solution (1), respectively.
  • Liquid crystal alignment agents (A-4), (A-5), (B-3) to (B-6) of Comparative Examples 3 to 6 were obtained.
  • Example 6 The polyamic acid solution (5) (7.0 g) obtained in Synthesis Example 5, the polyimide solution (8) (3.0 g) and AD-1 (0.06 g) obtained in Synthesis Example 15 are mixed and liquid crystal displays are mixed. An alignment agent (C-1) was obtained.
  • Example 7 Liquid crystal alignment agents (C-2) of Example 7 and Comparative Example 7 in the same manner as in Example 6 except that the polymic acid solutions (6) and (7) were used instead of the polyamic acid solution (5), respectively. , (C-3) was obtained.
  • the liquid crystal alignment agents (A-1) to (A-5), (B-1) to (B-6), and (C-1) to (C-4) obtained as described above are turbid or precipitated. No abnormalities such as these were observed, and it was confirmed that the solution was uniform.
  • the transmittance was evaluated, the liquid crystal cell was prepared, the voltage retention rate was evaluated, the residual DC voltage, and the afterimage characteristics were evaluated.
  • UV-3600 manufactured by Shimadzu Corporation
  • the temperature was 25 ° C. and the scan wavelength was 380 to 800 nm.
  • a reference was used in which a refracting liquid was sandwiched between two uncoated quartz substrates. The evaluation is based on the transmittance of the wavelength of 550 nm, and the values are shown in Table 3 below.
  • liquid crystal display element for evaluating voltage retention and residual DC characteristics
  • liquid crystal alignment agents (A-1) to (A-5), (B-1) to (B-6), and (C-1) to (C-4) obtained in Examples and Comparative Examples.
  • the liquid crystal cell was manufactured by the procedure shown below.
  • the liquid crystal alignment agent was spin-coated on a glass substrate with an ITO electrode, dried on a hot plate at 70 ° C. for 90 seconds, and then baked in an IR oven at 230 ° C. for 20 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. ..
  • thermosetting sealant thermosetting sealant (SW-D1))
  • a liquid crystal MLC-3023 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal cell.
  • UV was irradiated from the outside of the liquid crystal cell through a cut filter of 325 nm or less at 10 J / cm 2.
  • the illuminance of UV was measured using UV-MO3A manufactured by ORC.
  • UV UV lamp: FLR40SUV32 /
  • UV-FL irradiation device manufactured by Toshiba Lighting & Technology Corporation in a state where no voltage was applied.
  • A-1) was irradiated for 30 minutes.
  • the liquid crystal alignment agent has an ITO electrode substrate (length: 35 mm, width: 30 mm, thickness: 0.7 mm) in which an ITO electrode pattern having a pixel size of 200 ⁇ m ⁇ 600 ⁇ m and a line / space of 3 ⁇ m is formed, and a height of 3 .
  • ITO electrode Spin-coat each on the ITO surface of a glass substrate with ITO electrode (length: 35 mm, width: 30 mm, thickness: 0.7 mm) in which a 2 ⁇ m photo spacer is patterned, and 90 at 70 ° C. on a hot plate. After drying for 2 seconds, it was baked in an IR oven at 230 ° C. for 20 minutes to form a liquid crystal alignment film having a thickness of 100 nm.
  • the ITO electrode substrate on which this ITO electrode pattern is formed is divided into four parts in a cross checker (checkerboard) pattern so that each of the four areas can be driven separately.
  • a sealant (XN-1500T manufactured by Mitsui Chemicals, Inc.) was printed.
  • a liquid crystal MLC-3023 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a vacuum injection method to prepare a liquid crystal cell. With a DC voltage of 15 V applied to the liquid crystal cell, UV was irradiated from the outside of the liquid crystal cell through a cut filter of 325 nm or less at 10 J / cm 2. The illuminance of UV was measured using UV-MO3A manufactured by ORC.
  • UV UV lamp: FLR40SUV32 /
  • A-1 UV-FL irradiation device manufactured by Toshiba Lighting & Technology Corporation in a state where no voltage was applied. A-1) was irradiated for 30 minutes.
  • the liquid crystal alignment films obtained by using the liquid crystal alignment agents (A-1) to (A-4), (C-1), and (C-2) of 4, 6 and 7 are the corresponding liquid crystal alignment films of Comparative Examples 1 to 3, High transmittance was obtained as compared with the liquid crystal alignment films obtained by using the liquid crystal alignment agents (B-1) to (B-3), (C-3) and (C-4) of 7 and 8. The difference of 1% in the transmittance is a remarkable difference in the art.
  • liquid crystal alignment agent obtained in the examples when used, a liquid crystal alignment film having a high voltage retention rate can be obtained in the evaluation of the voltage retention rate and the aging. Further, it can be seen that a liquid crystal alignment film showing good characteristics can be obtained in the evaluation of the residual DC voltage and the evaluation of the afterimage characteristics.

Abstract

L'invention concerne : un agent d'alignement de cristaux liquides qui permet d'obtenir un film d'alignement de cristaux liquides ayant un rapport de maintien de tension élevé même après une exposition prolongée dans des conditions de température élevée et d'humidité élevée, et présente d'excellentes caractéristiques d'image résiduelle dues à un allègement rapide des charges cumulées ; un film d'alignement de cristaux liquides obtenu à partir de l'agent d'alignement de cristaux liquides ; et un élément d'affichage à cristaux liquides utilisant ledit film. L'invention concerne également : un agent d'alignement de cristaux liquides qui permet d'obtenir un film d'alignement de cristaux liquides présentant une transmittance de lumière élevée, un film d'alignement de cristaux liquides obtenu à partir de l'agent d'alignement de cristaux liquides ; et un élément d'affichage à cristaux liquides utilisant ledit film.　L'agent d'alignement de cristaux liquides contient un composant polymère ayant : une première unité de répétition (a1) sélectionnée dans le groupe constitué d'une unité de représentation représentée par la formule (1-a) et d'une unité de répétition représentée par la formule (1-i) ; et une seconde unité de répétition (a2) sélectionnée dans le groupe constitué d'une unité de répétition représentée par la formule (2-a) et d'une unité de répétition représentée par la formule (2-i). (La définition de chaque substituant est telle que décrite dans la description.)
PCT/JP2021/011521 2020-03-30 2021-03-19 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides WO2021200291A1 (fr)

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JP2009175684A (ja) * 2007-12-26 2009-08-06 Chisso Corp 液晶配向剤、液晶配向膜及び液晶表示素子
JP2011095696A (ja) * 2009-01-30 2011-05-12 Sony Corp 液晶表示装置及びその製造方法
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WO2023074569A1 (fr) * 2021-10-28 2023-05-04 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides

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