[go: up one dir, main page]

WO2015012341A1 - Polymère, composition polymère, et film d'alignement de cristaux liquides pour élément d'affichage à cristaux liquides du type à attaque à champ électrique horizontal - Google Patents

Polymère, composition polymère, et film d'alignement de cristaux liquides pour élément d'affichage à cristaux liquides du type à attaque à champ électrique horizontal Download PDF

Info

Publication number
WO2015012341A1
WO2015012341A1 PCT/JP2014/069529 JP2014069529W WO2015012341A1 WO 2015012341 A1 WO2015012341 A1 WO 2015012341A1 JP 2014069529 W JP2014069529 W JP 2014069529W WO 2015012341 A1 WO2015012341 A1 WO 2015012341A1
Authority
WO
WIPO (PCT)
Prior art keywords
ring
group
carbon atoms
side chain
liquid crystal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2014/069529
Other languages
English (en)
Japanese (ja)
Inventor
隆之 根木
勇太 川野
喜弘 川月
瑞穂 近藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
Original Assignee
Nissan Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Priority to CN201480052684.8A priority Critical patent/CN105593751B/zh
Priority to JP2015528326A priority patent/JP6523169B2/ja
Priority to KR1020167004558A priority patent/KR102290811B1/ko
Publication of WO2015012341A1 publication Critical patent/WO2015012341A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • G02F1/1343—Electrodes
    • G02F1/134309—Electrodes characterised by their geometrical arrangement
    • G02F1/134363—Electrodes characterised by their geometrical arrangement for applying an electric field parallel to the substrate, i.e. in-plane switching [IPS]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • G02F1/133703—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by introducing organic surfactant additives into the liquid crystal material

Definitions

  • the present invention relates to a novel polymer, a composition containing the polymer, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element using the same, and a method for producing a substrate having the alignment film. Furthermore, the present invention relates to a novel method for producing a liquid crystal display device having excellent image sticking characteristics.
  • the liquid crystal display element is known as a light, thin, and low power consumption display device and has been remarkably developed in recent years.
  • the liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes.
  • an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates.
  • the liquid crystal alignment film is a component of the liquid crystal display element, and is formed on the surface of the substrate that holds the liquid crystal in contact with the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates.
  • the liquid crystal alignment film may be required to play a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate.
  • alignment control ability is given by performing an alignment treatment on the organic film constituting the liquid crystal alignment film.
  • the rubbing method is a method of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide or polyimide on a substrate with a cloth such as cotton, nylon or polyester in the rubbing direction (rubbing direction).
  • This is a method of aligning liquid crystals. Since this rubbing method can easily realize a relatively stable alignment state of liquid crystals, it has been used in the manufacturing process of conventional liquid crystal display elements.
  • an organic film used for the liquid crystal alignment film a polyimide-based organic film excellent in reliability such as heat resistance and electrical characteristics has been mainly selected.
  • Anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy.
  • a decomposition type photo-alignment method is known as a main photo-alignment method.
  • the polyimide film is irradiated with polarized ultraviolet rays, and anisotropic decomposition is caused by utilizing the polarization direction dependence of the ultraviolet absorption of the molecular structure. Then, the liquid crystal is aligned by the polyimide remaining without being decomposed (see, for example, Patent Document 1).
  • photocrosslinking type and photoisomerization type photo-alignment methods are also known.
  • polyvinyl cinnamate is used and irradiated with polarized ultraviolet rays to cause a dimerization reaction (crosslinking reaction) at the double bond portion of two side chains parallel to the polarized light. Then, the liquid crystal is aligned in a direction perpendicular to the polarization direction (see, for example, Non-Patent Document 1).
  • the liquid crystal alignment film alignment treatment method by the photo alignment method does not require rubbing, and there is no fear of generation of dust or static electricity.
  • An alignment process can be performed even on a substrate of a liquid crystal display element having an uneven surface, which is a method for aligning a liquid crystal alignment film suitable for an industrial production process.
  • the photo-alignment method eliminates the rubbing process itself as compared with the rubbing method that has been used industrially as an alignment treatment method for liquid crystal display elements, and thus has a great advantage. And compared with the rubbing method in which the alignment control ability becomes almost constant by rubbing, the photo alignment method can control the alignment control ability by changing the irradiation amount of polarized light.
  • the photo-alignment method in order to achieve the same degree of alignment control ability as in the rubbing method, a large amount of polarized light irradiation may be required or stable liquid crystal alignment may not be realized. .
  • the present invention provides a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element which is provided with high efficiency and orientation control ability and has excellent image sticking characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate.
  • an object of the present invention is to provide a lateral electric field drive type liquid crystal element having an improved voltage holding ratio and a liquid crystal alignment film for the element.
  • a photosensitive side-chain polymer that exhibits liquid crystallinity within a predetermined temperature range which is represented by the following formula (0):
  • a and B are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—O
  • S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group
  • T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group
  • X is a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, —CH ⁇ CH—CO—O—, or —O—CO—CH ⁇ .
  • X may be the same or different;
  • P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof.
  • R 50 represents a group selected from a hydrogen atom, a halogen atom, an alkyl group, a phenyl group having 1 to 3 carbon atoms, if R 50 is more mutually the same or different T is an integer of 1 to 7, J represents O, S, NH or NR 51 , and R 51 represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group)
  • T is an integer of 1 to 7
  • J represents O, S, NH or NR 51
  • R 51 represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group
  • the side chain polymer preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofleece transition.
  • the side chain polymer may have any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6).
  • A, B, and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—.
  • S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
  • T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
  • Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents.
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof
  • the hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a
  • R May be substituted with an alkyloxy group of R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
  • X is a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, —CH ⁇ CH—CO—O—, or —O—CO—CH ⁇ .
  • X may be the same or different;
  • Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH— May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof.
  • P or Q on the side to which —CH ⁇ CH— is bonded is an aromatic ring;
  • the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
  • l1 is 0 or 1;
  • l2 is an integer from 0 to 2; when l1 and l2 are both 0,
  • A represents a single bond when T is a single bond; when l1 is 1, B represents a single bond when T is a single bond;
  • H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.
  • the side chain polymer preferably has any one type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
  • the side chain polymer may have any one photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
  • A, X, l, m, m1 and R have the same definition as above.
  • the side chain polymer preferably has a photosensitive side chain represented by the following formula (14) or (15).
  • A, Y 1 , l, m1 and m2 have the same definition as above.
  • the side chain polymer may have a photosensitive side chain represented by the following formula (16) or (17).
  • A, X, l and m have the same definition as above.
  • the side chain polymer may have a photosensitive side chain represented by the following formula (18) or (19).
  • A, B, Y 1 , q1, q2, m1, and m2 have the same definition as above.
  • the side chain polymer preferably has a photosensitive side chain represented by the following formula (20).
  • A, Y 1 , X, l and m have the same definition as above.
  • the side chain polymer has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31): Is good.
  • a and B have the same definition as above;
  • Y 3 is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof.
  • each hydrogen atom bonded thereto may be independently substituted with —NO 2 , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
  • R 3 is a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms; one of q1 and q2 is 1 and the other is 0; l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more,
  • a polymer composition comprising (A) the side chain polymer according to any one of ⁇ 1> to ⁇ 10> above and (B) an organic solvent.
  • the polymer composition further includes (C) one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is aliphatic carbonized. It is preferable to contain an amine compound bonded to a hydrogen group or a non-aromatic cyclic hydrocarbon group.
  • the component (C) is represented by the following formula A- [1] (wherein Y 11 is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group) And Y 12 is a nitrogen-containing aromatic heterocyclic ring).
  • ⁇ 14> A step of applying a composition according to any one of the above ⁇ 11> to ⁇ 13> onto a substrate having a conductive film for driving a lateral electric field to form a coating film; [II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
  • substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements by which orientation control ability was provided by having.
  • ⁇ 15> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device produced by the method of ⁇ 14>.
  • ⁇ 16> A lateral electric field drive type liquid crystal display device having the substrate of ⁇ 15> above.
  • ⁇ 17> a step of preparing a substrate (first substrate) of ⁇ 15>above;
  • [I ′] A step of applying a polymer composition according to any one of the above ⁇ 11> to ⁇ 13> on the second substrate to form a coating film;
  • [II ′] a step of irradiating the coating film obtained in [I ′] with polarized ultraviolet rays; and
  • [III ′] a step of heating the coating film obtained in [II ′];
  • the liquid crystal display element is obtained by disposing the first and second substrates so as to face each other;
  • a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element which is provided with high efficiency and orientation control ability and has excellent image sticking characteristics
  • a horizontal electric field drive type liquid crystal display element having the substrate can do. Since the lateral electric field drive type liquid crystal display device manufactured by the method of the present invention is provided with the alignment control ability with high efficiency, the display characteristics are not impaired even when continuously driven for a long time. Further, according to the present invention, in addition to the above effects, a lateral electric field drive type liquid crystal element having improved voltage holding ratio by adsorbing ionic impurities in the liquid crystal at the liquid crystal alignment film interface and a liquid crystal alignment film for the element are provided. Can be provided.
  • the polymer composition used in the production method of the present invention has a photosensitive side chain polymer that can exhibit liquid crystallinity (hereinafter, also simply referred to as a side chain polymer), and the polymer composition
  • the coating film obtained by using the product is a film having a photosensitive side chain polymer that can exhibit liquid crystallinity.
  • This coating film is subjected to orientation treatment by irradiation with polarized light without being rubbed. And after polarized light irradiation, it will become the coating film (henceforth a liquid crystal aligning film) to which the orientation control ability was provided through the process of heating the side chain type polymer film.
  • the method for producing a substrate having the liquid crystal alignment film of the present invention is [I] (A) A photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and further having a side chain represented by the above formula (0), and B) The process of apply
  • a lateral electric field drive type liquid crystal display element can be obtained.
  • the second substrate instead of using a substrate having no lateral electric field driving conductive film instead of a substrate having a lateral electric field driving conductive film, the above steps [I] to [III] (for lateral electric field driving) Since a substrate having no conductive film is used, for the sake of convenience, in this application, the steps [I ′] to [III ′] may be abbreviated as steps), thereby providing a first liquid crystal alignment film having alignment controllability. Two substrates can be obtained.
  • the manufacturing method of the horizontal electric field drive type liquid crystal display element is: [IV] A step of obtaining a liquid crystal display element by arranging the first and second substrates obtained above so that the liquid crystal alignment films of the first and second substrates face each other with liquid crystal interposed therebetween; Have Thereby, a horizontal electric field drive type liquid crystal display element can be obtained.
  • Step [I] is a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range on a substrate having a conductive film for driving a lateral electric field, and is represented by the above formula (0).
  • a side chain polymer further having a side chain, an organic solvent, and optionally, one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is aliphatic carbonized
  • a polymer composition containing an amine compound bonded to a hydrogen group or a non-aromatic cyclic hydrocarbon group is applied to form a coating film.
  • ⁇ Board> Although it does not specifically limit about a board
  • the substrate has a conductive film for driving a lateral electric field.
  • the conductive film include, but are not limited to, ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide) when the liquid crystal display element is a transmission type.
  • examples of the conductive film include a material that reflects light such as aluminum, but are not limited thereto.
  • a method for forming a conductive film on a substrate a conventionally known method can be used.
  • a polymer composition is applied on a substrate having a conductive film for driving a lateral electric field, particularly on the conductive film.
  • the polymer composition used in the production method of the present invention comprises: (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range; (B) an organic solvent; and, if desired, (C) a molecule having one primary amino group and a nitrogen-containing aromatic heterocyclic ring, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group; Containing amine compounds.
  • the component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and further has a side chain represented by the above formula (0).
  • the (A) side chain polymer preferably reacts with light in the wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in the temperature range of 100 ° C. to 300 ° C.
  • the (A) side chain polymer preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 nm to 400 nm.
  • the (A) side chain polymer preferably has a mesogenic group in order to exhibit liquid crystallinity in the temperature range of 100 ° C to 300 ° C.
  • the side chain type polymer has a photosensitive side chain bonded to the main chain, and can cause a crosslinking reaction, an isomerization reaction, or a light fleece rearrangement in response to light.
  • the structure of the side chain having photosensitivity is not particularly limited, but a structure that undergoes a crosslinking reaction or photofleece rearrangement in response to light is desirable, and a structure that causes a crosslinking reaction is more desirable. In this case, even if exposed to external stress such as heat, the achieved orientation control ability can be stably maintained for a long period of time.
  • the structure of the photosensitive side chain polymer film capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable to have a rigid mesogenic component in the side chain structure. In this case, stable liquid crystal alignment can be obtained when the side chain polymer is used as a liquid crystal alignment film.
  • the side chain type polymer has a group represented by the above formula (0), thereby giving a highly reliable liquid crystal alignment film such as a voltage holding ratio (VHR).
  • VHR voltage holding ratio
  • the polymer structure has, for example, a main chain and a side chain bonded to the main chain, and the side chain includes a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group, and a tip.
  • a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group, and a tip.
  • More specific examples of the structure of the photosensitive side chain polymer film capable of exhibiting liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, A main chain composed of at least one selected from the group consisting of radically polymerizable groups such as vinyl, maleimide, norbornene and siloxane, a group represented by the above formula (0), and the following formula (1) ( The structure having a side chain comprising at least one kind of 6) is preferred.
  • A, B, and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—.
  • S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
  • T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
  • Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents.
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
  • Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof
  • the hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a
  • R May be substituted with an alkyloxy group of R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
  • X is a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, —CH ⁇ CH—CO—O—, or —O—CO—CH ⁇ .
  • X may be the same or different;
  • Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH— May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof.
  • P or Q on the side to which —CH ⁇ CH— is bonded is an aromatic ring;
  • the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
  • l1 is 0 or 1;
  • l2 is an integer from 0 to 2; when l1 and l2 are both 0,
  • A represents a single bond when T is a single bond; when l1 is 1, B represents a single bond when T is a single bond;
  • H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.
  • the side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
  • the side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
  • A, X, l, m, m1 and R have the same definition as above.
  • the side chain may be a photosensitive side chain represented by the following formula (14) or (15).
  • A, Y 1 , l, m1 and m2 have the same definition as above.
  • the side chain may be a photosensitive side chain represented by the following formula (16) or (17).
  • A, X, l and m have the same definition as above.
  • the side chain is preferably a photosensitive side chain represented by the following formula (18) or (19).
  • A, B, Y 1 , q1, q2, m1, and m2 have the same definition as above.
  • the side chain is preferably a photosensitive side chain represented by the following formula (20).
  • A, Y 1 , X, l and m have the same definition as above.
  • the (A) side chain polymer preferably has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).
  • a and B have the same definition as above;
  • Y 3 is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof.
  • each hydrogen atom bonded thereto may be independently substituted with —NO 2 , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
  • R 3 is a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms; one of q1 and q2 is 1 and the other is 0; l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more,
  • the photosensitive side chain polymer capable of exhibiting the above liquid crystallinity can be obtained by polymerizing the photoreactive side chain monomer having the above photosensitive side chain and the liquid crystalline side chain monomer.
  • the monomer having a side chain represented by the formula (0) include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, and maleimide. It is preferably a structure having a polymerizable group composed of at least one selected from the group consisting of radical polymerizable groups such as norbornene and siloxane, and a side chain represented by the above formula (0).
  • monomers having an epoxy group include compounds such as glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and allyl glycidyl ether.
  • the monomer having thiirane include those in which the epoxy structure of the monomer having the epoxy group is replaced with thiirane.
  • the monomer having aziridine include those in which the epoxy structure of the monomer having the epoxy group is replaced with aziridine or 1-methylaziridine.
  • Examples of the monomer having an oxetane group include (meth) acrylic acid ester having an oxetane group.
  • monomers 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3- Ethyl-oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxetane, 3- (Acryloyloxymethyl) -2-phenyl-oxetane, 2- (methacryloyloxymethyl) oxetane, 2- (acryloyloxymethyl)
  • the monomer having a thietane group for example, a monomer in which the oxetane group of the monomer having an oxetane group is replaced with a thietane group is preferable.
  • the monomer having an azetan group for example, a monomer in which an oxetane group of a monomer having an oxetane group is replaced with an azetan group is preferable.
  • a monomer having an epoxy group and a monomer having an oxetane group are preferable from the viewpoint of availability and the like, and a monomer having an epoxy group is more preferable.
  • glycidyl (meth) acrylate is preferable from the viewpoint of availability.
  • the photoreactive side chain monomer is a monomer capable of forming a polymer having a photosensitive side chain at the side chain portion of the polymer when the polymer is formed.
  • the photoreactive group possessed by the side chain the following structures and derivatives thereof are preferred.
  • photoreactive side chain monomer examples include radical polymerizable groups such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, norbornene, etc.
  • a polymerizable side group composed of at least one selected from the group consisting of siloxane and a photosensitive side chain consisting of at least one of the above formulas (1) to (6), preferably, for example, the above formula (7 ) To (10), a photosensitive side chain comprising at least one of the above formulas (11) to (13), and a photosensitivity represented by the above formula (14) or (15).
  • a photosensitive side chain a photosensitive side chain represented by the above formula (16) or (17), a photosensitive side chain represented by the above formula (18) or (19), and a photosensitivity represented by the above formula (20).
  • Sex side chain It is preferable that it has a structure.
  • the present application relates to novel compounds (1) to (11) represented by the following formulas (1) to (11), and the following formulas (12) to (17) as photoreactive and / or liquid crystalline side chain monomers. (12) to (17) are provided.
  • R represents a hydrogen atom or a methyl group
  • S represents an alkylene group having 2 to 10 carbon atoms
  • R 10 represents Br or CN
  • S represents an alkylene group having 2 to 10 carbon atoms
  • u represents Represents 0 or 1
  • Py represents a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group.
  • V represents 1 or 2.
  • the liquid crystalline side chain monomer is a monomer in which a polymer derived from the monomer exhibits liquid crystallinity and the polymer can form a mesogenic group at a side chain site.
  • a mesogenic group having a side chain even if it is a group having a mesogen structure alone such as biphenyl or phenylbenzoate, or a group having a mesogen structure by hydrogen bonding between side chains such as benzoic acid Good.
  • the mesogenic group possessed by the side chain the following structure is preferable.
  • liquid crystalline side chain monomers include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, norbornene and other radical polymerizable groups
  • a structure having a polymerizable group composed of at least one selected from the group consisting of siloxanes and a side chain composed of at least one of the above formulas (21) to (31) is preferable.
  • the side chain polymer can be obtained by the polymerization reaction of the above-described photoreactive side chain monomer that exhibits liquid crystallinity. Further, it can be obtained by copolymerization of a photoreactive side chain monomer that does not exhibit liquid crystallinity and a liquid crystalline side chain monomer, or by copolymerization of a photoreactive side chain monomer that exhibits liquid crystallinity and a liquid crystalline side chain monomer. it can. Furthermore, it can be copolymerized with other monomers as long as the liquid crystallinity is not impaired.
  • Examples of other monomers include industrially available monomers capable of radical polymerization reaction. Specific examples of the other monomer include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound.
  • unsaturated carboxylic acid examples include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
  • acrylic ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl.
  • methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl.
  • vinyl compound examples include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
  • styrene compound examples include styrene, methyl styrene, chlorostyrene, bromostyrene, and the like.
  • maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. *
  • the content of the side chain represented by the formula (0) in the side chain polymer of the present invention is preferably from 0.1 mol% to 20 mol% from the viewpoint of improving reliability and affecting liquid crystal orientation. 0.5 mol% to 10 mol% is more preferable, and 1 mol% to 5 mol% is still more preferable.
  • the content of the photoreactive side chain in the side chain polymer of the present invention is preferably 20 mol% to 99.9 mol%, more preferably 30 mol% to 95 mol%, from the viewpoint of liquid crystal alignment. More preferred is mol% to 90 mol%.
  • the content of the liquid crystalline side chain in the side chain type polymer of the present invention is preferably 80 mol% or less, more preferably 10 mol% to 70 mol%, more preferably 20 mol% to 60 mol% from the viewpoint of liquid crystal alignment. Is more preferable.
  • the side chain polymer of the present invention may contain other side chains other than the side chain represented by the above formula (0), the photoreactive side chain, and the liquid crystalline side chain.
  • the content is the remaining portion when the total content of the side chain, photoreactive side chain and liquid crystalline side chain represented by the above formula (0) is less than 100%.
  • the production method of the side chain polymer of the present embodiment is not particularly limited, and a general-purpose method that is handled industrially can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a liquid crystalline side chain monomer or photoreactive side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.
  • RAFT reversible addition-cleavage chain transfer
  • the radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher.
  • radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxidation).
  • the radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation.
  • examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (
  • the radical polymerization method is not particularly limited, and an emulsion polymerization method, suspension polymerization method, dispersion polymerization method, precipitation polymerization method, bulk polymerization method, solution polymerization method and the like can be used.
  • the organic solvent used for the polymerization reaction of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the generated polymer is soluble. Specific examples are given below.
  • organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the polymer
  • the polymerization temperature at the time of radical polymerization can be selected from any temperature of 30 ° C. to 150 ° C., but is preferably in the range of 50 ° C. to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass.
  • the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
  • the molecular weight of the obtained polymer is decreased when the ratio of the radical polymerization initiator is large relative to the monomer, and the molecular weight of the obtained polymer is increased when the ratio is small, the ratio of the radical initiator is
  • the content is preferably 0.1 mol% to 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added during the polymerization.
  • the polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating.
  • impurities in the polymer can be reduced.
  • the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
  • the molecular weight of the (A) side chain polymer of the present invention is measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, workability during coating film formation, and uniformity of the coating film.
  • the weight average molecular weight is preferably 2,000 to 1,000,000, more preferably 5,000 to 200,000.
  • the polymer composition used in the present invention is preferably prepared as a coating solution so as to be suitable for forming a liquid crystal alignment film. That is, the polymer composition used in the present invention is preferably prepared as a solution in which a resin component for forming a resin film is dissolved in an organic solvent.
  • the resin component is a resin component containing a photosensitive side chain polymer capable of exhibiting the liquid crystallinity already described.
  • the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
  • the resin component described above may be a photosensitive side chain polymer that can all exhibit the above-described liquid crystallinity, but does not impair the liquid crystal developing ability and the photosensitive performance.
  • Other polymers may be mixed within the range.
  • the content of the other polymer in the resin component is 0.5 to 80% by mass, preferably 1 to 50% by mass.
  • examples of such other polymers include polymers that are made of poly (meth) acrylate, polyamic acid, polyimide, and the like and are not a photosensitive side chain polymer that can exhibit liquid crystallinity.
  • the polymer composition used in the present invention has a specific amine compound, specifically, one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is a fatty acid. It is preferable to have an amine compound bonded to an aromatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. By including such an amine compound, it is possible to reduce elution of ionic impurities and promote the crosslinking reaction of the group represented by the above formula (0) or more durable when it is used as a liquid crystal alignment film. A liquid crystal alignment film having a high thickness can be obtained.
  • the specific amine compound is not particularly limited as long as it exhibits the following effects i) and / or ii) when the polymer composition used in the present invention forms a liquid crystal alignment film. i) Adsorbs ionic impurities in the liquid crystal at the liquid crystal alignment film interface and / or ii) exhibits improved voltage holding ratio.
  • the amount of the specific amine compound is not particularly limited as long as the above effect is obtained, but is 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass in 100 parts by mass of the polymer composition used in the present invention. It is good that it is a mass part.
  • aliphatic hydrocarbon group examples include a linear alkylene group, an alkylene group having a branched structure, and a divalent hydrocarbon group having an unsaturated bond.
  • the aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • divalent non-aromatic cyclic hydrocarbon group examples include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane Ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosan ring, tricyclodecosan ring, bicycloheptane ring, Examples include a decahydronaphthalene ring, a norbornene ring
  • it is a ring having 3 to 20 carbon atoms, more preferably a ring having 3 to 15 carbon atoms, and even more preferably a non-aromatic cyclic hydrocarbon group having a ring having 3 to 10 carbon atoms. It is.
  • the nitrogen-containing aromatic heterocyclic ring contained in the amine compound has the following formula [20a], formula [20b] and formula [20c] (wherein Z 2 is a linear or branched alkyl group having 1 to 5 carbon atoms) And an aromatic cyclic hydrocarbon containing at least 1, preferably 1 to 4 structures selected from the group consisting of:
  • More preferred amine compounds are those represented by the following formula A- [1] (wherein Y 11 is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y 12 is a nitrogen-containing group. It is preferable that the amine compound be an aromatic heterocyclic ring.
  • Y 12 is not particularly limited as long as Y 12 is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.
  • Preferred Y 11 in formula A- [1] is a divalent organic group having one kind selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. It is good to be.
  • Examples of the non-aromatic cyclic hydrocarbon group include the above-described structures.
  • Y 11 is more preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring. , Cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring, adamantane ring and the like. Y 11 is particularly preferably a linear or branched alkylene group having 1 to 10 carbon atoms.
  • —CH 2 — in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in Y 11 is —O—, —NH—, —CO—O—.
  • —O—CO—, —CO—NH—, —NH—CO—, —CO—, —S—, —S (O) 2 —, —CF 2 —, —C (CF 3 ) 2 —, — C (CH 3 ) 2 —, —Si (CH 3 ) 2 —, —O—Si (CH 3 ) 2 —, —Si (CH 3 ) 2 —O—, —O—Si (CH 3 ) 2 —O -It may be replaced by a divalent cyclic hydrocarbon group or a heterocyclic ring.
  • a hydrogen atom bonded to an arbitrary carbon atom includes a linear or branched alkylene group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, It may be replaced with a hydroxyl group.
  • divalent cyclic hydrocarbon group examples include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, cyclopropane ring, cyclobutane ring, cyclopentane ring , Cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring Ring, cyclon
  • divalent heterocyclic ring examples include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring.
  • Y 12 in the formula A- [1] is a nitrogen-containing aromatic heterocyclic ring, and as described above, at least one selected from the group consisting of the formula [20a], the formula [20b], and the formula [20c]
  • An aromatic cyclic hydrocarbon containing the structure Specific examples thereof include the structure described above.
  • pyrrole ring imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring
  • a phenazine ring and a phthalazine ring are preferable.
  • Y 11 is a formula [20a], a formula included in Y 12 It is preferably bonded to a substituent not adjacent to [20b] and formula [20c].
  • the carbon atom of the nitrogen-containing aromatic heterocyclic ring which is Y 12 in formula A- [1] may have a halogen atom and / or a substituent of an organic group, and the organic group is an oxygen atom, sulfur You may contain hetero atoms, such as an atom and a nitrogen atom.
  • a preferred combination of Y 11 and Y 12 in the formula A- [1] is a group in which Y 11 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms.
  • Y 12 is a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, A benzimidazole ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, or a phthalazine ring.
  • the carbon atom of the nitrogen-containing aromatic heterocycle of Y 12 may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
  • Y 13 is a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms
  • Y 14 Is a single bond, or —O—, —NH—, —S—, —SO 2 — or a divalent organic group having 1 to 19 carbon atoms
  • the total of carbon atoms of Y 13 and Y 14 Is an amine compound represented by:
  • Y 15 is a nitrogen-containing aromatic heterocyclic ring.
  • Y 13 in the formula A- [2] is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a non-aromatic cyclic hydrocarbon group. Specific examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclo Octane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cycloo
  • a linear or branched alkylene group having 1 to 10 carbon atoms cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane And a ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring, and an adamantane ring.
  • Particularly preferred is a linear or branched alkylene group having 1 to 10 carbon atoms.
  • —CH 2 — in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in Y 13 is —O—, —NH—, —CO—O—, — O—CO—, —CO—NH—, —NH—CO—, —CO—, —S—, —S (O) 2 —, —CF 2 —, —C (CF 3 ) 2 —, —C ( CH 3 ) 2 —, —Si (CH 3 ) 2 —, —O—Si (CH 3 ) 2 —, —Si (CH 3 ) 2 —O—, —O—Si (CH 3 ) 2 —O—, It may be replaced with a divalent cyclic hydrocarbon group or a heterocyclic ring.
  • a hydrogen atom bonded to an arbitrary carbon atom includes a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, It may be replaced with a hydroxyl group.
  • the cyclic hydrocarbon group and the heterocyclic ring mentioned here have the same meaning as defined for Y 11 in the formula A- [1].
  • Y 14 in the formula A- [2] is a single bond, —O—, —NH—, —S—, —SO 2 — or a divalent organic group having 1 to 19 carbon atoms.
  • the divalent organic group having 1 to 19 carbon atoms is a divalent organic group having 1 to 19 carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or the like. Specific examples of such Y 14 are given below.
  • Y 15 in the formula A- [2] is a nitrogen-containing aromatic heterocyclic ring, and has the same definition as Y 12 in the formula A- [1]. Specific examples may include the same structure as Y 12 described above. Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring , A phenazine ring, or a phthalazine ring is preferable.
  • Y 14 is a formula [20a] or formula included in Y 15. It is preferably bonded to a carbon atom that is not adjacent to [20b] or formula [20c]. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring which is Y 15 in the formula A- [2] may have a halogen atom and / or a substituent of an organic group, and the organic group is an oxygen atom or a sulfur atom. And may contain a hetero atom such as a nitrogen atom.
  • Y 13 is a linear or branched alkylene group having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring , Cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring or adamantane ring, and Y 14 is a single bond, having 1 carbon atom To 10 linear or branched alkylene groups, —O—, —NH—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —CO—, —, —CO—, —
  • the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15 may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
  • Y 13 is a linear or branched alkylene group having 1 to 5 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane A ring, a cycloheptane ring, a norbornene ring, or an adamantane ring
  • Y 14 is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —NH—, —CO—O—, — O—CO—, —CO—NH—, —NH—CO—, —CO—, —S—, —S (O) 2 —, —CH (OH) —, —NH—CH 2 —, —S— CH 2 —, —O—CH 2 —, —O—C 2 H 4
  • the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15 may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
  • Y 13 is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, or A cyclohexane ring
  • Y 14 is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —NH—, —CO—O—, —O—CO—, —CO—NH—.
  • the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15 may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
  • a particularly preferred combination of Y 13 , Y 14 and Y 15 in the formula A- [2] is that Y 13 is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclobutane ring, or a cyclohexane ring, and Y 14 is , Single bond, —O—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —CH (OH) —, benzene ring, naphthalene ring, fluorene ring, or anthracene Y 15 is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring.
  • the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15 may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
  • Specific examples of the specific amine compound of the component (B) of the present invention include compounds M1 to M156.
  • More preferable compounds include M6 to M8, M10, M16 to M21, M31 to M36, M40 to M45, M47 to M57, M59 to M63, M68, M69, M72 to M82, M95 to M98, M100 to M103, M108 to M125, M128 to M137, M139 to M143, and M149 to M156.
  • M6 to M8 M16 to M20, M32 to M36, M40, M41, M44, M49 to M54, M59 to M62, M68, M69, M75 to M82, M100 to M103, M108 to M112, M114 to M116 M118 to M121, M125, M134 to M136, M139, M140, M143, M150, and M152 to M156.
  • the organic solvent used for the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone,
  • the polymer composition used in the present invention may contain components other than the above components (A), (B) and (C). Examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when the polymer composition is applied, and compounds that improve the adhesion between the liquid crystal alignment film and the substrate.
  • the present invention is not limited to this.
  • solvent poor solvent which improves the uniformity of film thickness and surface smoothness.
  • solvents may be used alone or in combination.
  • it is preferably 5% by mass to 80% by mass of the total solvent, more preferably so as not to significantly reduce the solubility of the entire solvent contained in the polymer composition. Is 20% by mass to 60% by mass.
  • Examples of the compound that improves film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Company), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) It is done.
  • the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the polymer
  • the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds.
  • phenoplasts and epoxy group-containing compounds for the purpose of preventing the deterioration of electrical characteristics due to the backlight when the liquid crystal display element is constructed
  • An agent may be contained in the polymer composition. Specific phenoplast additives are shown below, but are not limited to this structure.
  • Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′,-tetraglycidyl- , 4'-diaminodip
  • the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the polymer composition. More preferably, it is 1 to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
  • a photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.
  • photosensitizers aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxyketones, and amino-substituted Aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl- ⁇ -naphthothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-b
  • Aromatic 2-hydroxy ketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal are preferred.
  • a dielectric, a conductive substance, or the like for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film, as long as the effects of the present invention are not impaired.
  • a crosslinkable compound may be added for the purpose of increasing the hardness and density of the liquid crystal alignment film.
  • the method for applying the polymer composition described above onto a substrate having a conductive film for driving a lateral electric field is not particularly limited.
  • the application method is generally performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like.
  • Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (rotary coating method), or a spray method, and these may be used depending on the purpose.
  • the polymer composition After the polymer composition is applied on a substrate having a conductive film for driving a horizontal electric field, it is 50 to 200 ° C., preferably 50 to 200 ° C. by a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven.
  • the solvent can be evaporated at 150 ° C. to obtain a coating film.
  • the drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain polymer. If the thickness of the coating film is too thick, it will be disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered.
  • it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is. In addition, it is also possible to provide the process of cooling the board
  • step [II] the coating film obtained in step [I] is irradiated with polarized ultraviolet rays.
  • the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction.
  • ultraviolet rays to be used ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used.
  • the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used.
  • ultraviolet light having a wavelength in the range of 290 nm to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced.
  • the ultraviolet light for example, light emitted from a high-pressure mercury lamp can be used.
  • the irradiation amount of polarized ultraviolet rays depends on the coating film used.
  • the amount of irradiation is polarized ultraviolet light that realizes the maximum value of ⁇ A (hereinafter also referred to as ⁇ Amax), which is the difference between the ultraviolet light absorbance in a direction parallel to the polarization direction of polarized ultraviolet light and the ultraviolet light absorbance in a direction perpendicular to the polarization direction of the polarized ultraviolet light.
  • the amount is preferably in the range of 1% to 70%, more preferably in the range of 1% to 50%.
  • step [III] the ultraviolet-irradiated coating film polarized in step [II] is heated.
  • An orientation control ability can be imparted to the coating film by heating.
  • a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven can be used.
  • the heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film used is developed.
  • the heating temperature is preferably within the temperature range of the temperature at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal expression temperature).
  • the liquid crystal expression temperature on the coating film surface is expected to be lower than the liquid crystal expression temperature when a photosensitive side chain polymer that can exhibit liquid crystallinity is observed in bulk.
  • the heating temperature is more preferably within the temperature range of the liquid crystal expression temperature on the coating film surface. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C. lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain polymer used, and 10 ° C.
  • the liquid crystal expression temperature is not less than the glass transition temperature (Tg) at which the side chain polymer or coating film surface undergoes a phase transition from the solid phase to the liquid crystal phase, and from the liquid crystal phase to the isotropic phase (isotropic phase). It means a temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition.
  • the thickness of the coating film formed after heating is preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm, for the same reason described in the step [I].
  • the production method of the present invention can realize highly efficient introduction of anisotropy into the coating film. And a board
  • the step [IV] is performed in the same manner as in the above [I ′] to [III ′], similarly to the substrate (first substrate) obtained in [III] and having the liquid crystal alignment film on the conductive film for lateral electric field driving.
  • the obtained liquid crystal alignment film-attached substrate (second substrate) having no conductive film is placed oppositely so that both liquid crystal alignment films face each other through liquid crystal, and a liquid crystal cell is formed by a known method.
  • This is a step of manufacturing a lateral electric field drive type liquid crystal display element.
  • a substrate having no lateral electric field driving conductive film was used in place of the substrate having the lateral electric field driving conductive film in the step [I].
  • steps [I] to [III] It can be carried out in the same manner as in steps [I] to [III]. Since the difference between the steps [I] to [III] and the steps [I ′] to [III ′] is only the presence or absence of the conductive film, the description of the steps [I ′] to [III ′] is omitted. To do.
  • the first and second substrates described above are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside.
  • the other substrate is bonded and the liquid crystal is injected under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed.
  • Etc. can be illustrated.
  • the diameter of the spacer at this time is preferably 1 ⁇ m to 30 ⁇ m, more preferably 2 ⁇ m to 10 ⁇ m. This spacer diameter determines the distance between the pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.
  • substrate with a coating film of this invention irradiates the polarized ultraviolet-ray, after apply
  • the coating film used in the present invention realizes the introduction of highly efficient anisotropy into the coating film by utilizing the principle of molecular reorientation induced by the side chain photoreaction and liquid crystallinity. .
  • an embodiment using a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group is the first embodiment, a structure having a photofleece rearrangement group or a group causing isomerization as a photoreactive group
  • An embodiment using the side chain type polymer will be referred to as a second embodiment.
  • FIG. 1 schematically shows an anisotropic introduction process in a method for producing a liquid crystal alignment film using a side chain polymer having a structure having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. It is a figure of one example demonstrated to.
  • FIG. 1 (a) is a diagram schematically showing the state of the side chain polymer film before irradiation with polarized light
  • FIG. 1 (b) is a schematic diagram showing the state of the side chain polymer film after irradiation with polarized light
  • FIG. 1 (c) is a diagram schematically showing the state of the side-chain polymer film after heating, and particularly when the introduced anisotropy is small, that is, the first aspect of the present invention.
  • 1 is a schematic diagram when the ultraviolet ray irradiation amount in the step [II] is within a range of 1% to 15% of the ultraviolet ray irradiation amount that maximizes ⁇ A.
  • FIG. 2 is a schematic illustration of anisotropy introduction treatment in a method for producing a liquid crystal alignment film using a side chain polymer having a structure having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. It is a figure of one example demonstrated to.
  • FIG. 2A is a diagram schematically showing the state of the side chain polymer film before irradiation with polarized light
  • FIG. 2B is a schematic diagram showing the state of the side chain polymer film after irradiation with polarized light.
  • FIG. 2 (c) is a diagram schematically showing the state of the side-chain polymer film after heating, and particularly when the introduced anisotropy is large, that is, the first aspect of the present invention.
  • 1 is a schematic diagram when the ultraviolet ray irradiation amount in the step [II] is within a range of 15% to 70% of the ultraviolet ray irradiation amount that maximizes ⁇ A.
  • FIG. 3 shows a side chain polymer having a structure having a photo-isomerizable group as a photoreactive group or a photo-Fleece rearrangement group represented by the above formula (18) in the second embodiment of the present invention. It is a figure of one example which illustrates typically the introduction process of anisotropy in the manufacturing method of the used liquid crystal aligning film.
  • FIG. 3A is a diagram schematically showing the state of the side chain polymer film before polarized light irradiation
  • FIG. 3B is a schematic diagram of the state of the side chain polymer film after polarized light irradiation.
  • 3 (c) is a diagram schematically showing the state of the side-chain polymer film after heating, and particularly when the introduced anisotropy is small, that is, the first aspect of the present invention.
  • 2 is a schematic diagram when the ultraviolet irradiation amount in the step [II] is within a range of 1% to 70% of the ultraviolet irradiation amount that maximizes ⁇ A.
  • FIG. 4 shows the production of a liquid crystal alignment film using a side chain polymer having a structure having a photo-Fleece rearrangement group represented by the above formula (19) as a photoreactive group in the second embodiment of the present invention. It is a figure of one example which illustrates typically the introduction processing of anisotropy in a method.
  • FIG. 4A is a diagram schematically showing the state of the side chain polymer film before irradiation with polarized light
  • FIG. 4B is a schematic diagram of the state of the side chain polymer film after irradiation with polarized light.
  • FIG. 4 (c) is a diagram schematically showing the state of the side-chain polymer film after heating.
  • 2 is a schematic diagram when the ultraviolet irradiation amount in the step [II] is within a range of 1% to 70% of the ultraviolet irradiation amount that maximizes ⁇ A.
  • the ultraviolet irradiation amount in the step [II] is in the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ⁇ A.
  • the coating film 1 is formed on the substrate.
  • Fig.1 (a) in the coating film 1 formed on the board
  • the ultraviolet irradiation amount in the step [II] is in the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ⁇ A.
  • the coating film 3 is formed on the substrate. As shown in FIG. 2A, the coating film 3 formed on the substrate has a structure in which the side chains 4 are randomly arranged. According to the random arrangement of the side chains 4 of the coating film 3, the mesogenic components and the photosensitive groups of the side chains 4 are also randomly oriented, and the coating film 2 is isotropic.
  • a side chain type having a structure having a photo-isomerizable group or a photo-Fleece rearrangement group represented by the above formula (18) in the treatment for introducing anisotropy into the coating film In the case of using a liquid crystal alignment film using a polymer, when the ultraviolet irradiation amount in the step [II] is in the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ⁇ A, first, The coating film 5 is formed. As shown in FIG. 3A, the coating film 5 formed on the substrate has a structure in which the side chains 6 are randomly arranged. According to the random arrangement of the side chain 6 of the coating film 5, the mesogenic component and the photosensitive group of the side chain 6 are also randomly oriented, and the side chain type polymer film 5 is isotropic.
  • liquid crystal alignment using a side chain type polymer having a structure having a light Fleece rearrangement group represented by the above formula (19) in the treatment for introducing anisotropy into the coating film In the case of using a film, when the ultraviolet irradiation amount in the step [II] is within the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ⁇ A, first, the coating film 7 is formed on the substrate. . As shown in FIG. 4A, the coating film 7 formed on the substrate has a structure in which the side chains 8 are arranged at random. According to the random arrangement of the side chains 8 of the coating film 7, the mesogenic components and the photosensitive groups of the side chains 8 are also randomly oriented, and the coating film 7 is isotropic.
  • the ultraviolet irradiation amount in the step [II] is within the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ⁇ A
  • polarized ultraviolet rays are irradiated.
  • the photosensitive group of the side chain 2a having the photosensitive group among the side chains 2 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to dimerization reaction or the like.
  • Dimerization reaction or the like causes a photoreaction.
  • the density of the side chain 2a that has undergone photoreaction becomes slightly higher in the polarization direction of the irradiated ultraviolet light, and as a result, very small anisotropy is imparted to the coating film 1.
  • the ultraviolet irradiation amount in the step [II] is within the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ⁇ A
  • polarized ultraviolet rays are irradiated.
  • the photosensitive group of the side chain 4a having the photosensitive group among the side chains 4 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to dimerization reaction or the like.
  • the density of the side chain 4a that has undergone photoreaction increases in the polarization direction of the irradiated ultraviolet light, and as a result, a small anisotropy is imparted to the coating film 3.
  • the isotropic coating film 5 is irradiated with polarized ultraviolet rays.
  • the photosensitive group of the side chain 6a having the photosensitive group among the side chains 6 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to light fleece rearrangement or the like.
  • the density of the side chain 6a subjected to photoreaction becomes slightly higher in the polarization direction of the irradiated ultraviolet rays, and as a result, very small anisotropy is imparted to the coating film 5.
  • the amount of ultraviolet irradiation in the step [II] is obtained using a coating film using a side chain polymer having a structure having a photo-Fleece rearrangement group represented by the above formula (19). Is within the range of 1% to 70% of the amount of UV irradiation that maximizes ⁇ A, the isotropic coating film 7 is irradiated with polarized UV light. Then, as shown in FIG. 4 (b), the photosensitive group of the side chain 8a having the photosensitive group among the side chains 8 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to light fleece rearrangement or the like. Causes a photoreaction. As a result, the density of the side chain 8a that has undergone photoreaction increases in the polarization direction of the irradiated ultraviolet light, and as a result, small anisotropy is imparted to the coating film 7.
  • the coating film 1 after the polarized light irradiation 1 Is heated to a liquid crystal state. Then, as shown in FIG.1 (c), in the coating film 1, the amount of the generated crosslinking reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular thereto. In this case, since the amount of the crosslinking reaction generated in the direction parallel to the polarization direction of the irradiated ultraviolet ray is very small, this crosslinking reaction site functions as a plasticizer.
  • the liquid crystallinity in the direction perpendicular to the polarization direction of the irradiated ultraviolet light is higher than the liquid crystallinity in the parallel direction, and the side chain 2 containing the mesogenic component is reoriented by self-organizing in the direction parallel to the polarization direction of the irradiated ultraviolet light.
  • the very small anisotropy of the coating film 1 induced by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 1.
  • the coating film after polarized light irradiation 3 is heated to a liquid crystal state.
  • the amount of the generated crosslinking reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular thereto. Therefore, the side chain 4 containing the mesogenic component is reoriented by self-organizing in a direction parallel to the polarization direction of the irradiated ultraviolet light.
  • the small anisotropy of the coating film 3 induced by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 3.
  • a coating film using a side-chain polymer having a structure having a photo-isomerizable group or a photo-Fleece rearrangement group represented by the above formula (18) is used.
  • the ultraviolet irradiation amount in the step [II] is within the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ⁇ A
  • the coating film 5 after polarized irradiation is heated to be in a liquid crystal state.
  • generated light fleece rearrangement reaction differs between the direction parallel to the polarization direction of irradiation ultraviolet rays, and a perpendicular
  • the liquid crystal alignment force of the light fleece rearrangement generated in the direction perpendicular to the polarization direction of the irradiated ultraviolet light is stronger than the liquid crystal alignment force of the side chain before the reaction, it is self-organized in the direction perpendicular to the polarization direction of the irradiated ultraviolet light.
  • the side chain 6 containing the mesogenic component is reoriented.
  • the very small anisotropy of the coating film 5 induced by the photofleece rearrangement reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 5.
  • a coating film using a side chain type polymer having a structure having a photofleece rearrangement group represented by the above formula (19) is used.
  • the ultraviolet irradiation amount is in the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ⁇ A
  • the coated film 7 after polarized irradiation is heated to a liquid crystal state.
  • the amount of the generated light fleece rearrangement reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet light and the direction perpendicular thereto. .
  • the anchoring force of the optical fleece rearrangement 8 (a) is stronger than that of the side chain 8 before the rearrangement, when a certain amount or more of the optical fleece rearrangement occurs, it is self-assembled in a direction parallel to the polarization direction of the irradiated ultraviolet light.
  • the side chain 8 containing the mesogenic component is reoriented.
  • the small anisotropy of the coating film 7 induced by the photofleece rearrangement reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 7.
  • the coating film used in the method of the present invention is a liquid crystal alignment film having anisotropy introduced with high efficiency and excellent alignment control ability by sequentially performing irradiation of polarized ultraviolet rays on the coating film and heat treatment. can do.
  • the irradiation amount of polarized ultraviolet rays to the coating film and the heating temperature in the heat treatment are optimized. Thereby, introduction of anisotropy into the coating film with high efficiency can be realized.
  • the optimum irradiation amount of polarized ultraviolet rays for introducing highly efficient anisotropy into the coating film used in the present invention is such that the photosensitive group undergoes photocrosslinking reaction, photoisomerization reaction, or photofries rearrangement reaction in the coating film.
  • the photo-crosslinking reaction, photoisomerization reaction, or photo-fleece rearrangement reaction has few photosensitive groups in the side chain, the amount of photoreaction will not be sufficient. . In that case, sufficient self-organization does not proceed even after heating.
  • the crosslinking reaction between the side chains is caused when the photosensitive group of the side chain undergoing the crosslinking reaction becomes excessive. Too much progress. In that case, the resulting film may become rigid and hinder the progress of self-assembly by subsequent heating.
  • the coating film used in the present invention is irradiated with polarized ultraviolet rays to the structure having the light Fleece rearrangement group, if the photosensitive group of the side chain that undergoes the light Fleece rearrangement reaction becomes excessive, the liquid crystallinity of the coating film Will drop too much.
  • the liquid crystallinity of the obtained film is also lowered, which may hinder the progress of self-assembly by subsequent heating. Furthermore, when irradiating polarized ultraviolet light to a structure having a photo-fleece rearrangement group, if the amount of ultraviolet light irradiation is too large, the side-chain polymer is photodegraded, preventing the subsequent self-organization by heating. It may become.
  • the optimum amount of the photopolymerization reaction, photoisomerization reaction, or photofleece rearrangement reaction of the side chain photosensitive group by irradiation with polarized ultraviolet rays is the side chain polymer film. It is preferably 0.1 to 40 mol%, more preferably 0.1 to 20 mol% of the photosensitive group possessed by.
  • the coating film used in the method of the present invention by optimizing the irradiation amount of polarized ultraviolet rays, photocrosslinking reaction or photoisomerization reaction of photosensitive groups or photofleece rearrangement reaction in the side chain of the side chain polymer film Optimize the amount of. Then, in combination with the subsequent heat treatment, highly efficient introduction of anisotropy into the coating film used in the present invention is realized. In that case, a suitable amount of polarized ultraviolet rays can be determined based on the evaluation of ultraviolet absorption of the coating film used in the present invention.
  • the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorption in the vertical direction after the irradiation with the polarized ultraviolet ray are measured.
  • ⁇ A which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays.
  • the maximum value of ⁇ A ( ⁇ Amax) realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet light that realizes it are obtained.
  • a preferable amount of polarized ultraviolet rays to be irradiated in the production of the liquid crystal alignment film can be determined on the basis of the amount of polarized ultraviolet rays to realize this ⁇ Amax.
  • the amount of irradiation of polarized ultraviolet rays onto the coating film used in the present invention is preferably in the range of 1% to 70% of the amount of polarized ultraviolet rays that realizes ⁇ Amax. More preferably, it is within the range of 50%.
  • the irradiation amount of polarized ultraviolet light within the range of 1% to 50% of the amount of polarized ultraviolet light that realizes ⁇ Amax is 0. 0% of the entire photosensitive group of the side chain polymer film. 1 mol% to 20 mol% corresponds to the amount of polarized ultraviolet light that undergoes a photocrosslinking reaction.
  • a suitable heating temperature as described above is set based on the liquid crystal temperature range of the side chain polymer. It is good to decide. Therefore, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is 100 ° C. to 200 ° C., the heating temperature after irradiation with polarized ultraviolet light is desirably 90 ° C. to 190 ° C. By doing so, greater anisotropy is imparted to the coating film used in the present invention.
  • the liquid crystal display element provided by the present invention exhibits high reliability against external stresses such as light and heat.
  • the lateral electric field drive type liquid crystal display element substrate manufactured by the method of the present invention or the lateral electric field drive type liquid crystal display element having the substrate has excellent reliability, large screen and high definition. It can be suitably used for LCD TVs.
  • GMA, HBAGE, G1, and additive T1 are shown below as monomers having methacrylic monomers MA1 and MA2 and epoxy side chains used in the examples.
  • MA1 and M2 were synthesized as follows. That is, MA1 was synthesized by the synthesis method described in the patent document (WO2011-084546). MA2 was synthesized by the synthesis method described in the patent document (Japanese Patent Laid-Open No. 9-118717). G1 was synthesized by the synthesis method described in Synthesis Example 1 below. GMA (glycidyl methacrylate), HBAGE (hydroxybutyl acrylate glycidyl ether), and additive T1 (3-aminomethylpyridine) were commercially available.
  • Carboxylic acid derivative (MA2) (18.4 g, 60 mmol) in THF (tetrahydrofuran) solution (184 g) was mixed with (COCl) 2 (oxalyl chloride) (11.4 g, 90 mmol) and DMF (dimethylformamide). The solution was added dropwise and reacted at room temperature for 2 hours. The solid obtained by concentrating this solution was dissolved in THF (350 g). This solution was added dropwise to a THF solution (88 g) of glycidol (8.89 g, 120 mmol) and triethylamine (13.4 g, 132 mmol) over 1 hour and allowed to react for 18 hours.
  • THF tetrahydrofuran
  • Glycidyl derivative (G1) 1 H-NMR (CDCl 3 , ⁇ ppm): 8.01 (d, 2H), 7.01 (d, 2H), 6.01 (s, 1H), 5.56 (s, 1H), 4.65 -4.61 (m, 1H), 4.18-4.12 (m, 3H), 4.02 (t, 2H), 3.36-3.32 (m, 1H), 2.91-2 .89 (m, 1H), 2.74-2.72 (m, 1H), 1.95-1.94 (m, 3H), 1.86-1.79 (m, 2H), 1.76 -1.69 (m, 2H), 1.57-1.44 (m, 4H).
  • Carboxylic acid derivative (M2) (21.4 g, 70 mmol), dimethylaminopyridine (0.85 g, 7 mmol), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (14, 8 g, 77 mmol) in THF
  • 3-ethyl-3-oxetanemethanol (8.58 g, 73.5 mmol) was added and reacted at room temperature for 18 hours.
  • the precipitated insoluble matter was removed by filtration, ethyl acetate (500 g) was added, washed three times with water (200 g), and dried over magnesium sulfate.
  • Magnesium sulfate was removed by filtration and then concentrated to obtain G2 as a colorless liquid (yield 27.3 g, yield 96%).
  • Oxetane compound (G3) 1 H-NMR (CDCl 3 , ⁇ ppm): 7.98 (d, 2H), 6.90 (d, 2H), 6.10 (s, 1H), 5.55 (s, 1H), 4.45 (D, 2H), 4.39 (d, 2H), 4.31 (t, 2H), 4.16 (t, 2H), 4,01 (t, 2H), 4.01 (t, 2H) 3.54-3.50 (m, 4H), 1.87-1.66 (m, 10H) 1.56-1.44 (m, 4H), 0.89 (t, 3H).
  • NMP 54.0 g was added to the methacrylate polymer powder P1 (6.0 g) obtained in Polymer Synthesis 1, and dissolved by stirring for 5 hours at room temperature.
  • Polymer solution A1 was obtained by adding BC (40.0g) to this solution and stirring. This polymer solution was used as a liquid crystal aligning agent for forming a liquid crystal alignment film as it was.
  • Examples 2 to 12 The compositions shown in Table 2 were adjusted using the same method as in Example 1 to obtain liquid crystal aligning agents A2 to A12 of Examples 2 to 12.
  • Control polymer synthesis example 2> Using a method similar to Control 1 with the composition of MA1 (5.9 g, 18 mmol), MA2 (3.7 g, 12 mmol), THF (55.5 g), AIBN (0.15 g, 3 mmol), methacrylate polymer powder CP2 Got.
  • Control 1 liquid crystal aligning agent B1 was obtained in the same manner as in Example 1 using CP1. Similarly, Control 2 liquid crystal aligning agent B2 was obtained using CP2.
  • liquid crystal aligning agent A1 obtained in Example 1, a liquid crystal cell was prepared according to the procedure shown below.
  • the substrate used was a glass substrate having a size of 30 mm ⁇ 40 mm and a thickness of 0.7 mm, on which comb-like pixel electrodes formed by patterning an ITO film were arranged.
  • the pixel electrode had a comb-like shape configured by arranging a plurality of electrode elements having a dogleg shape with a bent central portion.
  • the width of each electrode element in the short direction was 10 ⁇ m, and the distance between the electrode elements was 20 ⁇ m. Since the pixel electrode forming each pixel is formed by arranging a plurality of bent-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but in the central portion like the electrode elements. It has a shape that bends and resembles a bold-faced koji.
  • Each pixel was divided up and down with the central bent portion as a boundary, and had a first region above the bent portion and a second region below.
  • the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel.
  • the electrode elements of the pixel electrode were formed so as to form an angle of ⁇ 15 ° (clockwise).
  • the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It was configured to be in the opposite direction.
  • the liquid crystal aligning agent A1 obtained in Example 1 was spin-coated on the prepared substrate with electrodes. Subsequently, it dried for 90 second with a 70 degreeC hotplate, and formed the liquid crystal aligning film with a film thickness of 100 nm. Next, the coating film surface was irradiated with 20 mJ / cm 2 of 313 nm ultraviolet rays via a polarizing plate and then heated on a hot plate at 150 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Further, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 ⁇ m on which no electrode was formed as a counter substrate, and an orientation treatment was performed.
  • a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one substrate. Next, the other substrate was bonded so that the liquid crystal alignment film faces each other and the alignment direction was 0 °, and then the sealing agent was thermally cured to produce an empty cell.
  • a liquid crystal cell having a configuration of an IPS (In-Plane Switching) mode liquid crystal display element was prepared by injecting liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) into the empty cell by a reduced pressure injection method, sealing the injection port. Obtained.
  • liquid crystal cells were similarly prepared.
  • VHR voltage holding ratio
  • VHR1 is improved by copolymerizing a monomer having an epoxy group as compared with Controls 1 and 2 which are not copolymerized. It can also be seen that the results of VHR2 are good by adding the additive T1 in Examples 5 to 8, 11 and 12.
  • the liquid crystal cell for IPS mode prepared in Examples 1 to 8 is installed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, and the backlight is turned on with no voltage applied.
  • the arrangement angle of the liquid crystal cell was adjusted so that the luminance of the liquid crystal cell became the smallest.
  • the rotation angle when the liquid crystal cell was rotated from the angle at which the second region of the pixel was darkest to the angle at which the first region was darkest was calculated as the initial orientation azimuth.
  • an alternating voltage of 16 V PP was applied in a 60 ° C. oven at a frequency of 30 Hz for 168 hours.
  • the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited and left as it was at room temperature for 1 hour.
  • the orientation azimuth was measured in the same manner, and the difference in orientation azimuth before and after AC driving was calculated as an angle ⁇ (deg.). The same measurement was performed in other examples.
  • the angle ⁇ was 0.1 or less.
  • the long-chain polymer film that exhibits liquid crystallinity is irradiated with ultraviolet rays and then heated in the liquid crystal expression temperature range, so that the liquid crystal alignment ability is imparted to the entire polymer by self-organization. Even after AC driving, the alignment azimuth was hardly observed.
  • FIG. 1 Side chain polymer membrane 2, 2a Side chain Fig. 2 3 Side chain polymer membrane 4, 4a Side chain Fig. 3 5 Side chain polymer membrane 6, 6a Side chain Fig. 4 7 Side chain polymer membrane 8, 8a Side chain

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials Engineering (AREA)
  • Geometry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Crystal (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

En vue d'obtenir un élément d'affichage à cristaux liquides du type à attaque à champ électrique horizontal qui confère une fonctionnalité de commande d'alignement avec une efficacité élevée et présente des propriétés de fiabilisation supérieures, un polymère à chaîne latérale photosensible, qui exprime une cristallinité liquide dans une plage de températures prescrite, comprend, selon la présente invention, une chaîne latérale répondant à la formule (0). Dans la formule, G représente un groupe choisi parmi (G-1), (G-2), (G-3), et (G-4) de la formule (dans la formule : une ligne en pointillés représente un moyen de liaison ; R50 représente un groupe choisi parmi un atome d'hydrogène, un atome d'halogène, un groupe alkyle ayant de 1 à 3 atomes de carbone, et un groupe phényle, et peut être identique ou différent lorsqu'il est présent en une pluralité ; J représente O, S, NH, ou NR51 ; et R51 représente un groupe choisi parmi un groupe alkyle ayant de 1 à 3 atomes de carbone et un groupe phényle).
PCT/JP2014/069529 2013-07-24 2014-07-24 Polymère, composition polymère, et film d'alignement de cristaux liquides pour élément d'affichage à cristaux liquides du type à attaque à champ électrique horizontal Ceased WO2015012341A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201480052684.8A CN105593751B (zh) 2013-07-24 2014-07-24 聚合物、聚合物组合物和横向电场驱动型液晶表示元件用液晶取向膜
JP2015528326A JP6523169B2 (ja) 2013-07-24 2014-07-24 重合体、重合体組成物および横電界駆動型液晶表示素子用液晶配向膜
KR1020167004558A KR102290811B1 (ko) 2013-07-24 2014-07-24 중합체, 중합체 조성물 및 횡전계 구동형 액정 표시 소자용 액정 배향막

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013153738 2013-07-24
JP2013-153738 2013-07-24

Publications (1)

Publication Number Publication Date
WO2015012341A1 true WO2015012341A1 (fr) 2015-01-29

Family

ID=52393375

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/069529 Ceased WO2015012341A1 (fr) 2013-07-24 2014-07-24 Polymère, composition polymère, et film d'alignement de cristaux liquides pour élément d'affichage à cristaux liquides du type à attaque à champ électrique horizontal

Country Status (5)

Country Link
JP (1) JP6523169B2 (fr)
KR (1) KR102290811B1 (fr)
CN (1) CN105593751B (fr)
TW (1) TWI637044B (fr)
WO (1) WO2015012341A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016021570A1 (fr) * 2014-08-05 2016-02-11 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
WO2017018501A1 (fr) * 2015-07-30 2017-02-02 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
JP2017076045A (ja) * 2015-10-14 2017-04-20 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
JP2017082140A (ja) * 2015-10-29 2017-05-18 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
WO2019117082A1 (fr) * 2017-12-15 2019-06-20 富士フイルム株式会社 Copolymère à photo-alignement, film photo-aligné et produit stratifié optique
CN110546560A (zh) * 2017-02-27 2019-12-06 日产化学株式会社 液晶取向剂、液晶取向膜及液晶表示元件
JP2019214553A (ja) * 2018-06-07 2019-12-19 住友化学株式会社 化合物、樹脂、レジスト組成物及びレジストパターンの製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10506420A (ja) * 1994-09-29 1998-06-23 エフ・ホフマン−ラ ロシュ アーゲー 液晶配向層を製造するためのクマリン及びキノリノン誘導体
JP2008262074A (ja) * 2007-04-13 2008-10-30 Fujifilm Corp 液晶配向剤、配向膜、液晶セル及び液晶表示装置
JP2010174128A (ja) * 2009-01-29 2010-08-12 Nippon Oil Corp 液晶性組成物、液晶フィルム及びその製造方法並びに液晶表示素子
JP2012107198A (ja) * 2010-10-28 2012-06-07 Jnc Corp 光配向法に適した化合物および該化合物からなる感光性ポリマー
WO2013081066A1 (fr) * 2011-11-29 2013-06-06 日産化学工業株式会社 Procédé de fabrication d'un film d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2819157B2 (ja) * 1989-07-21 1998-10-30 大日本印刷株式会社 放射線重合可能な液晶性モノマー及びそのポリマー
JP3893659B2 (ja) 1996-03-05 2007-03-14 日産化学工業株式会社 液晶配向処理方法
DE59814236D1 (de) * 1997-02-24 2008-07-17 Rolic Ag Photovernetzbare Polymere
JP4368134B2 (ja) * 2003-03-24 2009-11-18 大日本印刷株式会社 着色レジスト用顔料分散液、感光性着色組成物、及び、カラーフィルター
JP2006321893A (ja) * 2005-05-18 2006-11-30 Nippon Oil Corp 側鎖型液晶性高分子化合物
JP2007009021A (ja) * 2005-06-29 2007-01-18 Nippon Oil Corp 液晶性高分子組成物および液晶性光学フィルム
US8123977B2 (en) * 2005-11-07 2012-02-28 Lg Chem, Ltd. Copolymer for liquid crystal alignment, liquid crystal aligning layer including copolymer for liquid crystal alignment, and liquid crystal display including liquid crystal aligning layer
CN103038704B (zh) * 2010-06-10 2015-07-29 日产化学工业株式会社 液晶取向处理剂、液晶取向膜及液晶显示元件

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10506420A (ja) * 1994-09-29 1998-06-23 エフ・ホフマン−ラ ロシュ アーゲー 液晶配向層を製造するためのクマリン及びキノリノン誘導体
JP2008262074A (ja) * 2007-04-13 2008-10-30 Fujifilm Corp 液晶配向剤、配向膜、液晶セル及び液晶表示装置
JP2010174128A (ja) * 2009-01-29 2010-08-12 Nippon Oil Corp 液晶性組成物、液晶フィルム及びその製造方法並びに液晶表示素子
JP2012107198A (ja) * 2010-10-28 2012-06-07 Jnc Corp 光配向法に適した化合物および該化合物からなる感光性ポリマー
WO2013081066A1 (fr) * 2011-11-29 2013-06-06 日産化学工業株式会社 Procédé de fabrication d'un film d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2016021570A1 (ja) * 2014-08-05 2017-05-18 日産化学工業株式会社 液晶配向剤、液晶配向膜および液晶表示素子
WO2016021570A1 (fr) * 2014-08-05 2016-02-11 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
KR20180037971A (ko) * 2015-07-30 2018-04-13 닛산 가가쿠 고교 가부시키 가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
CN107849365A (zh) * 2015-07-30 2018-03-27 日产化学工业株式会社 液晶取向剂、液晶取向膜和液晶表示元件
WO2017018501A1 (fr) * 2015-07-30 2017-02-02 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
US11111387B2 (en) 2015-07-30 2021-09-07 Nissan Chemical Industries, Ltd. Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
CN117186663A (zh) * 2015-07-30 2023-12-08 日产化学工业株式会社 液晶取向剂、液晶取向膜和液晶表示元件
KR102674352B1 (ko) * 2015-07-30 2024-06-11 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
JP2017076045A (ja) * 2015-10-14 2017-04-20 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
JP2017082140A (ja) * 2015-10-29 2017-05-18 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
CN110546560A (zh) * 2017-02-27 2019-12-06 日产化学株式会社 液晶取向剂、液晶取向膜及液晶表示元件
WO2019117082A1 (fr) * 2017-12-15 2019-06-20 富士フイルム株式会社 Copolymère à photo-alignement, film photo-aligné et produit stratifié optique
JPWO2019117082A1 (ja) * 2017-12-15 2020-11-26 富士フイルム株式会社 光配向性共重合体、光配向膜および光学積層体
JP2019214553A (ja) * 2018-06-07 2019-12-19 住友化学株式会社 化合物、樹脂、レジスト組成物及びレジストパターンの製造方法
JP7389567B2 (ja) 2018-06-07 2023-11-30 住友化学株式会社 化合物、樹脂、レジスト組成物及びレジストパターンの製造方法

Also Published As

Publication number Publication date
CN105593751B (zh) 2019-07-30
JP6523169B2 (ja) 2019-05-29
KR102290811B1 (ko) 2021-08-17
TWI637044B (zh) 2018-10-01
CN105593751A (zh) 2016-05-18
JPWO2015012341A1 (ja) 2017-03-02
KR20160035010A (ko) 2016-03-30
TW201522583A (zh) 2015-06-16

Similar Documents

Publication Publication Date Title
JP6992746B2 (ja) 液晶配向剤、液晶配向膜及び液晶表示素子
JP6784593B2 (ja) 液晶配向剤、液晶配向膜及び液晶表示素子
JP2015007702A (ja) 横電界駆動型液晶表示素子用液晶配向膜を有する基板の製造方法
JP6523169B2 (ja) 重合体、重合体組成物および横電界駆動型液晶表示素子用液晶配向膜
WO2015199052A1 (fr) Composition polymère et film d'alignement de cristaux liquides pour élément d'affichage à cristaux liquides à excitation par champ électrique transversal
JP2014206715A (ja) 横電界駆動型液晶表示素子用液晶配向膜を有する基板の製造方法
WO2015156314A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
KR102540422B1 (ko) 중합체 조성물, 액정 배향제, 액정 배향막, 그 액정 배향막을 갖는 기판 및 그 액정 배향막을 갖는 액정 표시 소자
JP2022036952A (ja) 液晶配向剤、液晶配向膜及び液晶表示素子
KR102165624B1 (ko) 횡전계 구동형 액정 표시 소자용 액정 배향막을 갖는 기판의 제조 방법
WO2015002292A1 (fr) Matériau anisotrope vis-à-vis de l'ultraviolet polarisé
WO2014196590A1 (fr) Procédé de production d'un substrat comprenant un film d'alignement de cristaux liquides pour commutation en plan d'éléments d'affichage à cristaux liquides
JP6872315B2 (ja) 重合体組成物および横電界駆動型液晶表示素子用液晶配向膜
JP6571524B2 (ja) 横電界駆動型液晶表示素子用液晶配向膜を有する基板の製造方法
JP6744717B2 (ja) 横電界駆動型液晶表示素子用液晶配向膜を有する基板の製造方法
WO2016113930A1 (fr) Agent d'alignement de cristaux liquides utilisant un cristal liquide polymère photoréactif à liaisons hydrogène, et pellicule d'alignement de cristaux liquides
JP6794257B2 (ja) 液晶配向剤、液晶配向膜および液晶表示素子
WO2016186189A1 (fr) Composition polymère, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, substrat comprenant ledit film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides comprenant ledit film d'alignement de cristaux liquides
KR102254609B1 (ko) 횡전계 구동형 액정 표시 소자용 액정 배향막을 갖는 기판의 제조 방법
WO2014192922A1 (fr) Procédé de production de substrat pourvu d'un film d'alignement de cristaux liquides pour élément d'afficheur à cristaux liquides à excitation par champ électrique horizontal
JP2018109788A (ja) 横電界駆動型液晶表示素子用液晶配向膜を有する基板の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14829913

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015528326

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20167004558

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 14829913

Country of ref document: EP

Kind code of ref document: A1