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WO2014192922A1 - 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 - Google Patents

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 Download PDF

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WO2014192922A1
WO2014192922A1 PCT/JP2014/064428 JP2014064428W WO2014192922A1 WO 2014192922 A1 WO2014192922 A1 WO 2014192922A1 JP 2014064428 W JP2014064428 W JP 2014064428W WO 2014192922 A1 WO2014192922 A1 WO 2014192922A1
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group
ring
liquid crystal
carbon atoms
side chain
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PCT/JP2014/064428
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English (en)
French (fr)
Japanese (ja)
Inventor
雅章 片山
隆之 根木
喜弘 川月
瑞穂 近藤
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日産化学工業株式会社
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Priority to KR1020157036850A priority Critical patent/KR102191954B1/ko
Priority to JP2015519962A priority patent/JPWO2014192922A1/ja
Priority to CN201480043238.0A priority patent/CN105431770B/zh
Publication of WO2014192922A1 publication Critical patent/WO2014192922A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • 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
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133715—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films by first depositing a monomer
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133726—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films made of a mesogenic material
    • 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
    • G02F1/133742—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers for homeotropic alignment

Definitions

  • the present invention relates to a method for manufacturing a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element. Specifically, the present invention relates to a novel method for manufacturing a liquid crystal display element having a liquid crystal alignment film that has excellent image sticking characteristics, high end linearity, and small end bulge.
  • 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 wrinkle 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 dependency of the ultraviolet ray 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 orthogonal to the polarization direction (see, for example, Non-Patent Document 1).
  • Non-Patent Document 2 when a side chain polymer having azo benzene in the side chain is used, polarized ultraviolet light is irradiated to cause an isomerization reaction in the azobenzene portion of the side chain parallel to the polarized light, and the liquid crystal is perpendicular to the polarization direction.
  • polarized ultraviolet light is irradiated to cause an isomerization reaction in the azobenzene portion of the side chain parallel to the polarized light, and the liquid crystal is perpendicular to the polarization direction.
  • polarized ultraviolet light is irradiated to cause an isomerization reaction in the azobenzene portion of the side chain parallel to the polarized light, and the liquid crystal is perpendicular to the polarization direction.
  • 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.
  • a liquid crystal aligning agent also referred to as “coating solution” used for forming a liquid crystal alignment film
  • the solvent of the coating solution is usually N-methyl-2-pyrrolidone or ⁇ -butyrolactone, which is a solvent excellent in resin solubility (also referred to as “good solvent”), or the like.
  • butyl cellosolve which is a solvent with low resin solubility (also referred to as “poor solvent”), is used in combination (for example, see Patent Document 2).
  • the photo-alignment method has a great advantage because the rubbing process itself is not necessary as compared with the rubbing method that has been industrially used as an alignment treatment method for liquid crystal display elements. 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. However, the photo-alignment method may require a large amount of polarized light irradiation to achieve the same degree of alignment control ability as the rubbing method, and stable liquid crystal alignment cannot be realized. There is.
  • liquid crystal display elements have been used for mobile applications such as smartphones and mobile phones.
  • a sealant used for bonding the substrates of the liquid crystal display elements is present at a position close to the end of the liquid crystal alignment film. For this reason, when the coating property of the edge part of a liquid crystal aligning film falls, ie, when the edge part of a liquid crystal aligning film is not a straight line, or the edge part is in the state which has risen, it is between the board
  • the adhesive effect may be reduced, and the display characteristics and reliability of the liquid crystal display element may be reduced.
  • the present invention provides a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element, which has high efficiency and orientation control ability, is excellent in image sticking characteristics, has high end linearity, and has low end bulge, and the substrate It is an object of the present invention to provide a lateral electric field drive type liquid crystal display device having
  • the component (A) preferably has a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofleece transition.
  • the specific good solvent in the component (B) is N-ethyl-2-pyrrolidone (NEP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide It may be one or more selected from the group consisting of (DMAc), 1,3-dimethyl-imidazolidinone (DMI), and propylene glycol monomethyl ether (PGME).
  • NEP N-ethyl-2-pyrrolidone
  • DMF N-dimethylformamide
  • PGME propylene glycol monomethyl ether
  • the specific good solvent in the component (B) is preferably N-ethyl-2-pyrrolidone (NEP).
  • the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6). Good.
  • 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 component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (7) to (10): Good.
  • the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (11) to (13): Good.
  • A, X, l, m, m1 and R have the same definition as above.
  • the component (A) 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 component (A) preferably has a photosensitive side chain represented by the following formula (16) or (17).
  • A, X, l and m have the same definition as above.
  • the component (A) preferably has 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.
  • R 1 represents a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group.
  • the component (A) 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 component (A) has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31). Good.
  • A, B, q1 and q2 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; 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, and formulas (25) to (26 ), The sum of all m is 1
  • ⁇ 16> a step of preparing the substrate (first substrate) of ⁇ 14>above; [I ′] on the second substrate (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) both good and poor solvents of the side chain polymer
  • A a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range
  • B both good and poor solvents of the side chain polymer
  • the good solvent contains one or more specific good solvents having a boiling point of 100 to 230 ° C.
  • the component (A) preferably has a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofleece transition.
  • the specific good solvent in the component (B) is N-ethyl-2-pyrrolidone (NEP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide It may be one or more selected from the group consisting of (DMAc), 1,3-dimethyl-imidazolidinone (DMI), and propylene glycol monomethyl ether (PGME).
  • NEP N-ethyl-2-pyrrolidone
  • DMF N-dimethylformamide
  • PGME propylene glycol monomethyl ether
  • the specific good solvent in the component (B) is preferably N-ethyl-2-pyrrolidone (NEP).
  • the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6). Good.
  • 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 ⁇ .
  • 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 a single bond, a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, or a combination thereof.
  • I is a group selected from However, when X is —CH ⁇ CH—CO—O— or —O—CO—CH ⁇ CH—, P or Q on the side to which —CH ⁇ CH— is bonded is an aromatic ring; 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 component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (7) to (10): Good.
  • the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (11) to (13). Good.
  • A, X, l, m and R have the same definition as above.
  • the component (A) may have a photosensitive side chain represented by the following formula (14) or (15).
  • A, Y 1 , X, 1, m1, and m2 have the same definition as above.
  • the component (A) preferably has a photosensitive side chain represented by the following formula (16) or (17).
  • A, X, l and m have the same definition as above.
  • the component (A) 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.
  • R 1 represents a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group.
  • the component (A) 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 component (A) has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31). Good.
  • A, B, q1 and q2 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; l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in the formulas (25) to (26), the sum of all m is 2 or more, and the formulas (27) to (28 ), The sum of all m
  • ⁇ P13> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device manufactured by any of the above ⁇ P1> to ⁇ P12>.
  • ⁇ P14> A lateral electric field drive type liquid crystal display device having the substrate of ⁇ P13> above.
  • ⁇ P15> Step of preparing a substrate (first substrate) of ⁇ P13>above; [I ′] on the second substrate (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) both good and poor solvents of the side chain polymer
  • A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range
  • the good solvent contains one or more specific good solvents having a boiling point of 100 to 230 ° C.
  • ⁇ P16> A lateral electric field drive type liquid crystal display device manufactured according to the above ⁇ P15>.
  • ⁇ P17> (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range; and (B) both a good solvent and a poor solvent of the side-chain polymer, and a boiling point An organic solvent having a good solvent of 180 ° C. or higher per 10 parts by mass of a good solvent, The good solvent contains one or more specific good solvents having a boiling point of 100 to 230 ° C.
  • composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element which contains an organic solvent, which contains propylene glycol monobutyl ether.
  • the specific good solvent in the component (B) is N-ethyl-2-pyrrolidone (NEP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), It may be one or more selected from the group consisting of 1,3-dimethyl-imidazolidinone (DMI) and propylene glycol monomethyl ether (PGME).
  • NEP N-ethyl-2-pyrrolidone
  • DMF N-dimethylformamide
  • DMAc N-dimethylacetamide
  • DMAc N-dimethylacetamide
  • DMAc N-dimethylacetamide
  • DMAc N-dimethylacetamide
  • DMAc N-dimethylacetamide
  • DMAc N-dimethylacetamide
  • DMAc N-dimethylacetamide
  • DMAc N-dimethylacetamide
  • PGME propylene glycol monomethyl ether
  • 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. Moreover, the liquid crystal aligning agent of this invention can obtain the liquid crystal aligning film with the high linearity of the edge part of a liquid crystal aligning film, and a small rise
  • 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 (B) a boiling point that has both a good solvent and a poor solvent of the side chain polymer.
  • 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] a polymer composition containing a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range and an organic solvent is applied onto a substrate having a conductive film for driving a lateral electric field. 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 contains (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range; and (B) an organic solvent.
  • the component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity within a predetermined temperature range.
  • 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 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.
  • the structure of the photosensitive side chain polymer film capable of exhibiting liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, It has a main chain composed of at least one selected from the group consisting of radically polymerizable groups such as vinyl, maleimide, norbornene and siloxane, and a side chain composed of at least one of the following formulas (1) to (6) A structure 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.
  • R 1 represents a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group.
  • 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, B, q1 and q2 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; 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, and formulas (25) to (26 ), The sum of all m is 1
  • 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 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.
  • 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.
  • the side chain has a mesogenic group such as biphenyl or phenylbenzoate that has a mesogenic structure alone, or a group that has a mesogenic 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 other monomers include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound.
  • the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
  • the acrylic ester compound 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, and tert-butyl.
  • (Meth) acrylate compounds having a cyclic ether group such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, and (3-ethyl-3-oxetanyl) methyl (meth) acrylate are also used. be able to.
  • Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
  • Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.
  • Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
  • 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-diethylthio ⁇ xanthone, 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- [
  • 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 soot 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 which has been 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 100,000.
  • 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.
  • Organic solvent used in the polymer composition used in the present invention (that is, the organic solvent of the component (B)) is also referred to as an organic solvent (here, “good solvent”) that dissolves the side chain polymer of the component (A). ) And a solvent that improves the uniformity of film thickness and surface smoothness (herein also referred to as “poor solvent” of the side chain polymer of component (A)), and has a boiling point of 180 ° C. or higher Is an organic solvent having 10% by mass or more per 100 parts by mass of the good solvent.
  • the good solvent in the organic solvent of component (B) is one or more specific good solvents (here, selected from those having a boiling point of 100 to 230 ° C.
  • the poor solvent in the organic solvent of component (B) includes propylene glycol monobutyl ether, which is a specific poor solvent (herein referred to as “specific poor solvent”). It is a waste.
  • the organic solvent of the component (B) includes both the good solvent and the poor solvent of the side chain polymer of the component (A), and the good solvent having a boiling point of 180 ° C. or higher is 10 per 100 parts by mass of the good solvent.
  • the good solvent contains the specific good solvent
  • the poor solvent contains the specific poor solvent
  • the good solvent contains the specific good solvent
  • the poor solvent contains the specific good solvent
  • the poor solvent is It contains a specific poor solvent. That is, in the present invention, the organic solvent of the component (B) contains at least 10% by mass of a good solvent having a boiling point of 180 ° C. or more per 100 parts by mass of the good solvent and at least one of the specified good solvent and the specified poor solvent. It is a waste.
  • the good solvent preferably contains 10 to 100% by mass of a good solvent having a boiling point of 180 ° C. or higher per 100 parts by mass of the good solvent so that the good solvent remains at the end in the heat drying step. Of these, 20 to 100% by mass is preferable, and 30 to 100% by mass is more preferable.
  • the “good solvent having a boiling point of 180 ° C. or higher” can be appropriately selected by referring to known literature such as “Solvent Handbook” (Kodansha) mentioned above.
  • the good solvent is preferably 5 to 90% by mass of the whole organic solvent contained in the liquid crystal aligning agent in order to enhance the solubility of the polymer. Of these, 10 to 80% by mass is preferable. More preferred is 30 to 70% by mass.
  • the specific good solvent that can be contained in the organic solvent of the component (B) is a good solvent that is excellent in solubility of polyamic acid or soluble polyimide, and usually used N-methyl-2-pyrrolidone (NMP).
  • NMP N-methyl-2-pyrrolidone
  • ⁇ -butyrolactone ( ⁇ BL) have a lower surface tension as a solvent and a boiling point within a predetermined range. More specifically, as described above, the boiling point is 100 to 230 ° C. and the surface tension is less than 41.0 dyn / cm.
  • the spreading property of the coating solution to the substrate is increased, and a poor solvent having a low resin solubility is not often used.
  • the liquid crystal aligning film excellent in the coating-film uniformity can be obtained.
  • the wetting and spreading property of the coating solution (liquid crystal aligning agent) is increased, the linearity of the end portion when the liquid crystal alignment film is formed is increased.
  • the specific good solvent in the present invention has a boiling point of preferably 100 to 230 ° C., more preferably 110 to 230 ° C., and further preferably 180 to 220 ° C.
  • the specific good solvent in the present invention has a surface tension of less than 41.0 dyn / cm, more preferably less than 39.0 dyn / cm, and further preferably 36.0 dyn / cm or less.
  • the specific good solvent preferably has a boiling point of 100 to 230 ° C. and a surface tension of less than 41.0 dyn / cm, more preferably a boiling point of 110 to 230 ° C. and a surface tension of 39.
  • the specific good solvent in the present invention is one or more selected from organic solvents that satisfy these boiling point and surface tension conditions.
  • the specific specific good solvent satisfies the above-described boiling point and surface tension, and can be appropriately selected by referring to known literature values relating to the boiling point and surface tension relating to the organic solvent.
  • N-ethyl-2-pyrrolidone N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), 1,3-dimethyl-imidazolidinone (DMI), propylene glycol monomethyl ether
  • PGME boiling point and surface tension
  • NMP N-methyl-2-pyrrolidone
  • ⁇ BL ⁇ -butyrolactone
  • the specific good solvent in the present invention is N-ethyl-2-pyrrolidone (NEP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), 1, 3-dimethyl-imidazolidinone (DMI), propylene glycol monomethyl ether (PGME), and solvents represented by the following formulas [D-1] to [D-3], wherein the boiling point and surface tension conditions are What is satisfied is included.
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • D 3 represents an alkyl group having 1 to 4 carbon atoms
  • the specific good solvent in the present invention is N-ethyl-2-pyrrolidone (NEP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), 1 , 3-dimethyl-imidazolidinone (DMI), propylene glycol monomethyl ether (PGME), one or more selected from the group consisting of: More preferably, it is selected from the group consisting of N-ethyl-2-pyrrolidone (NEP) and 1,3-dimethyl-imidazolidinone (DMI), Particularly preferred is N-ethyl-2-pyrrolidone (NEP).
  • the specific good solvent when the good solvent contains a specific good solvent and contains a good solvent having a boiling point of 180 ° C. or higher in addition to the specific good solvent, the specific good solvent is a good solvent in the organic solvent used.
  • the total content is preferably 10 to 90% by mass. More preferred is 30 to 80% by mass.
  • the good solvent when the good solvent includes a specific good solvent and the specific good solvent is a good solvent having a boiling point of 180 ° C. or higher, the specific good solvent is 10% of all the good solvents in the organic solvent used. It is preferably from ⁇ 100% by mass. More preferred is 30 to 100% by mass.
  • the specific good solvent is the total organic solvent contained in the liquid crystal aligning agent. It is preferably 5 to 80% by mass. Among these, 10 to 70% by mass is preferable. More preferred is 20 to 60% by mass.
  • the good solvent when the good solvent includes a specific good solvent and the specific good solvent is a good solvent having a boiling point of 180 ° C. or higher, the specific good solvent is 5 to 5% of the total organic solvent contained in the liquid crystal aligning agent. It is preferably 90% by mass. Of these, 10 to 80% by mass is preferable. More preferred is 20 to 70% by mass.
  • the specific poor solvent that can be contained in the organic solvent of the component (B) is propylene glycol monobutyl ether.
  • the specific poor solvent is preferably 30 to 100% by mass of the whole poor solvent in the organic solvent to be used. More preferred is 50 to 100% by mass.
  • the propylene glycol monobutyl ether is 5% of the total organic solvent contained in the liquid crystal aligning agent in order to improve the wet spreadability of the coating solution on the substrate. It is preferable that the amount be ⁇ 70% by mass. Among these, 10 to 70% by mass is preferable. More preferred is 10 to 60% by mass.
  • a liquid crystal alignment film having a small bulge at the end of the film can be obtained.
  • the effect increases by including both the specific good solvent and the specific poor solvent of the present invention.
  • 30 to 100% of the good solvent is a specific good solvent having a boiling point of 180 ° C. or higher, and / or 30 to 30% of the poor solvent. 100% is preferably a specific poor solvent.
  • organic solvent used in the polymer composition used in the present invention can be used in addition to the above-mentioned specific good solvent and specific poor solvent.
  • a solvent is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below.
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • D 3 represents an alkyl group having 1 to 4 carbon atoms
  • N-methyl-2-pyrrolidone and ⁇ -butyrolactone are preferably used.
  • the solubility of the specific polymer in the solvent is high, it is also preferable to use the solvents represented by the above formulas [D-1] to [D-3].
  • organic solvents include the following as specific examples of solvents (other poor solvents) that improve film thickness uniformity and surface smoothness.
  • solvents other poor solvents
  • These other poor solvents are preferably 1 to 60% by mass of the whole organic solvent contained in the liquid crystal aligning agent. Among these, 1 to 50% by mass is preferable. More preferred is 5 to 40% by mass.
  • the polymer composition used in the present invention may contain components other than the above components (A) and (B). Examples thereof include, but are not limited to, compounds that improve the adhesion between the liquid crystal alignment film and the substrate when the polymer composition is applied.
  • Examples of the compound that improves the film thickness uniformity and the 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), 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 poly
  • 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 such as 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-dibromoneopentylglycol 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 Such as 4,4'-diamino
  • 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-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonylbiscoumarin, 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 coating method is generally performed by screen printing, offset printing, flexographic printing, or an inkjet method.
  • 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 the substrate having a conductive film for driving a transverse electric field, it is 50 to 200 ° C., preferably by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared ray) oven.
  • the coating film can be obtained by evaporating the solvent at 50 to 150 ° C.
  • 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. Therefore, it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is.
  • 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) that is the difference between the ultraviolet light absorbance in the direction parallel to the polarization direction of polarized ultraviolet light and the ultraviolet light absorbance in the 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 Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal expression temperature on the coating film surface.
  • 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 chain polymer used, and 10 ° C lower than the upper limit of the liquid crystal temperature range. It is preferable that it is the temperature of the range made into an upper limit. If the heating temperature is lower than the above temperature range, the anisotropic amplification effect due to heat in the coating film tends to be insufficient, and if the heating temperature is too higher than the above temperature range, the state of the coating film Tends to be close to an isotropic liquid state (isotropic phase), and in this case, self-organization may make it difficult to reorient in one direction.
  • 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 the liquid crystal phase changes 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 within the range of 1% to 15% of the ultraviolet ray irradiation amount that maximizes ⁇ A.
  • the coating film 1 is formed on the substrate. As shown in FIG. 1A, the coating film 1 formed on the substrate has a structure in which the side chains 2 are randomly arranged. According to the random arrangement of the side chain 2 of the coating film 1, the mesogenic component and the photosensitive group of the side chain 2 are also randomly oriented, and the coating film 1 is isotropic.
  • the ultraviolet irradiation amount in the step [II] is within the range of 15% to 70% of the ultraviolet ray 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 UV irradiation amount in the step [II] is within the range of 1% to 15% of the UV irradiation amount that maximizes ⁇ A
  • polarized ultraviolet rays are irradiated.
  • the photosensitive group of the side chain 2a having the photosensitive group in the side chain 2 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to a dimerization reaction or the like.
  • a photoreaction 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, the coating film 1 is provided with very small wrinkle anisotropy.
  • 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 in the side chain 4 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to a dimerization reaction or the like.
  • a photoreaction causes a photoreaction.
  • 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.
  • a liquid crystal film alignment film using a photoisomerizable group or a side chain polymer having a structure having a photo-Fleece rearrangement group represented by the above formula (18) is used.
  • the ultraviolet ray irradiation amount in the step is in the range of 1% to 70% of the ultraviolet ray irradiation amount that maximizes ⁇ A
  • the isotropic coating film 5 is irradiated with polarized blue ultraviolet rays. Then, as shown in FIG.
  • 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 photocathode 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 to the direction. 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
  • 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 photon fleece rearrangement 8 (a) is stronger than that of the side chain 8 before the rearrangement, when a certain amount or more of the light 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 wrinkle anisotropy of the coating film 7 induced by the light fleece 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, the photocrosslinking reaction or photoisomerization reaction of the photosensitive group or the photofleece rearrangement reaction in the side chain of the side chain type polymer film Optimize the amount. 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 150 ° C. to 250 ° C., the heating temperature after irradiation with polarized ultraviolet light is desirably 140 ° C. to 240 ° 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.
  • MA1 was synthesized by a synthesis method described in a patent document (WO2011 / 084546).
  • NEP 49.0 g was added to the resulting methacrylate polymer powder (A) (6.0 g), and dissolved by stirring at room temperature for 5 hours. By adding BCS (45.0 g) to this solution and stirring, a liquid crystal aligning agent (A1) was obtained.
  • NMP 49.0 g was added to the resulting methacrylate polymer powder (A) (6.0 g), and the mixture was dissolved by stirring at room temperature for 5 hours.
  • PB (45.0 g) was added to this solution and stirred to obtain a liquid crystal aligning agent (A2).
  • NEP 49.0 g was added to the resulting methacrylate polymer powder (A) (6.0 g), and dissolved by stirring at room temperature for 5 hours.
  • PB (45.0 g) was added to this solution and stirred to obtain a liquid crystal aligning agent (A3).
  • the ink-jet coating property of the liquid crystal aligning agent was evaluated.
  • the conditions are as follows.
  • liquid crystal aligning agent (A1) obtained in Example 1 of the present invention the liquid crystal aligning agent (A2) obtained in Example 2, the liquid crystal aligning agent (A3) obtained in Example 3, and the control 1.
  • the liquid crystal aligning agent (control 1) was filtered under pressure through a membrane filter having a pore diameter of 1 ⁇ m, and the ink jet coating property was evaluated.
  • HIS-200 manufactured by Hitachi Plant Technology
  • Application is on an ITO (indium tin oxide) vapor-deposited substrate cleaned with pure water and IPA (isopropyl alcohol), application area is 80 ⁇ 72 mm, nozzle pitch is 0.423 mm, scan pitch is 0.5 mm, application The speed was 40 mm / second, the time from coating to temporary drying was 30 seconds, and temporary drying was performed on a hot plate at 70 ° C. for 90 seconds.
  • ITO indium tin oxide
  • IPA isopropyl alcohol
  • Evaluation of the linearity of the edge part of a liquid crystal aligning film was performed by observing the liquid crystal aligning film of a right end part with respect to a printing direction with an optical microscope (Nikon Corporation ECLIPSE ME600). Specifically, the difference between (1) and (2) in FIG. 5 of the liquid crystal alignment film image obtained by observation with an optical microscope at a magnification of 25 times, that is, the length of A in FIG. 5 is measured. did. At this time, images of all liquid crystal alignment films were obtained at the same magnification. In the evaluation, the shorter the length of A, the better the linearity of the end portion of the liquid crystal alignment film.
  • Evaluation of the bulge of the end of the liquid crystal alignment film was performed by observing the liquid crystal alignment film at the right end with respect to the printing direction with an optical microscope. Specifically, the length of B in FIG. 6 of the liquid crystal alignment film image obtained by observation with an optical microscope at a magnification of 25 was measured. At that time, all liquid crystal alignment film images were obtained at the same magnification. In the evaluation, the shorter the length of B, the better the rise of the end of the liquid crystal alignment film.
  • the liquid crystal alignment film using the liquid crystal aligning agent of the example had a high linearity at the end of the liquid crystal alignment film and a small rise in the end of the liquid crystal alignment film.
  • 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 Fig. 5 9
  • Liquid crystal alignment film 10 ITO (indium tin oxide) deposition substrate 11
  • Liquid crystal alignment film 12 ITO (indium tin oxide) vapor deposition substrate

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PCT/JP2014/064428 2013-05-31 2014-05-30 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 WO2014192922A1 (ja)

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JP2015519962A JPWO2014192922A1 (ja) 2013-05-31 2014-05-30 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
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