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WO2016080458A1 - Agent d'alignement de cristaux liquides contenant un acide polyamide ou un dérivé de celui-ci, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

Agent d'alignement de cristaux liquides contenant un acide polyamide ou un dérivé de celui-ci, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides Download PDF

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Publication number
WO2016080458A1
WO2016080458A1 PCT/JP2015/082443 JP2015082443W WO2016080458A1 WO 2016080458 A1 WO2016080458 A1 WO 2016080458A1 JP 2015082443 W JP2015082443 W JP 2015082443W WO 2016080458 A1 WO2016080458 A1 WO 2016080458A1
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Prior art keywords
formula
liquid crystal
ring
group
alkyl
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PCT/JP2015/082443
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English (en)
Japanese (ja)
Inventor
隆浩 森
智章 清水
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JNC Corp
JNC Petrochemical Corp
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JNC Corp
JNC Petrochemical Corp
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Priority to JP2016560275A priority Critical patent/JP6575528B2/ja
Priority to KR1020167036427A priority patent/KR20170089760A/ko
Priority to CN201580056596.XA priority patent/CN107077031B/zh
Publication of WO2016080458A1 publication Critical patent/WO2016080458A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

  • the present invention relates to a polyamic acid obtained using tetracarboxylic dianhydride or a derivative thereof, a liquid crystal aligning agent containing a specific solvent, a liquid crystal aligning film formed using this liquid crystal aligning agent, and further this liquid crystal aligning film
  • the present invention relates to a liquid crystal display element having
  • liquid crystal alignment agent in the present invention means a polymer-containing composition used for forming a liquid crystal alignment film.
  • liquid crystal display elements are display elements using nematic liquid crystals.
  • a TN (Twisted Nematic) mode and an STN (Super Twisted Nematic) mode are well known.
  • a TN liquid crystal display device using an optical compensation film MVA (Multi -domain (vertical alignment) mode, IPS (in-plane switching) mode of lateral electric field method, and FFS (fringe field switching) mode have been proposed and put into practical use.
  • MVA Multi -domain (vertical alignment) mode
  • IPS in-plane switching
  • FFS far field switching
  • the development of the technology of the liquid crystal display element has been achieved not only by improving these driving methods and element structures but also by improving the components used in the elements.
  • the liquid crystal alignment film is one of important materials related to display quality, and the performance of the alignment film can be improved with the improvement in quality of the liquid crystal display element. It is becoming important.
  • the liquid crystal alignment film is formed using a liquid crystal aligning agent.
  • liquid crystal aligning agents mainly used are resins such as polyamic acid, polyimide, polyamide, polyimide amide, and polyamic acid ester, and are solutions (varnishes) in which these resins are dissolved in an organic solvent. . After this solution is applied to the substrate, it is formed by means such as heating to form a polyimide-based liquid crystal alignment film.
  • the rubbing method is a process of rubbing the surface of the liquid crystal alignment film in one direction using a cloth in which fibers of nylon, rayon, polyester, or the like are planted, and this makes it possible to obtain uniform alignment of liquid crystal molecules.
  • the rubbing process has problems such as dust generated by scraping the liquid crystal alignment film, scratches on the liquid crystal alignment film degrading display quality, and generation of static electricity. Development of an alignment treatment method that replaces this has been activated.
  • an alignment treatment method that replaces the rubbing method is a photo-alignment treatment method in which alignment treatment is performed by irradiating light.
  • Many alignment mechanisms such as a photodecomposition method, a photoisomerization method, a photodimerization method, and a photocrosslinking method have been proposed for the photoalignment treatment method (see, for example, Non-Patent Document 1, Patent Documents 1 and 2).
  • the photo-alignment method has higher uniformity of alignment than the rubbing method, and it is a non-contact alignment method, so the film is not damaged and causes the display defects of liquid crystal display elements such as dust generation and static electricity. There are advantages such as reduction.
  • examples of the alignment film printing method include spin coating, flexographic printing, and inkjet printing.
  • a technique suitable for pattern printing is flexographic printing. This method is a method of transferring the varnish on the APR plate to the substrate, and causes film thickness unevenness and disorder of the linearity of the edge portion of the printed alignment film (hereinafter, sometimes referred to as “backlash”). It is hard to do.
  • inkjet printing is more suitable for printing on a large-area substrate of the sixth generation or higher.
  • An object of the present invention is to provide a liquid crystal aligning agent capable of preventing the coating film from being uneven when printing a coating film for a liquid crystal alignment film by an ink jet method and not causing film shrinkage or edge backlash.
  • Another object of the present invention is to provide a liquid crystal alignment film formed using the liquid crystal alignment agent, and further a liquid crystal display element having the liquid crystal alignment film.
  • the present inventors have found a solvent that can simultaneously solve the problem of preventing uneven stripes, shrinking of the film, and preventing rattling of the edge by using a solvent of a plurality of components for the resin forming the alignment film described later. Completed the invention.
  • a liquid crystal aligning agent comprising at least one polymer selected from the group consisting of polyamic acid and derivatives thereof and a solvent;
  • the solvent is at least one selected from the group consisting of N-methyl-2-pyrrolidone, ⁇ -butyrolactone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone as the first solvent,
  • the second solvent at least one selected from the group consisting of butyl cellosolve, 1-butoxy-2-propanol, diethylene glycol ethyl methyl ether, diethylene glycol propyl methyl ether,
  • As the third solvent at least one selected from the group consisting of diisobutyl ketone and dipentyl ether, and
  • R 1 is alkyl having 2 carbons
  • R 2 is alkyl
  • the proportion of the first solvent is 20 to 89% by weight with respect to the total solvent weight
  • the proportion of the second solvent is 10 to 60% by weight with respect to the total solvent weight
  • the proportion of the third solvent is 0.1 to 15% by weight with respect to the total solvent weight
  • the liquid crystal aligning agent according to item [1] wherein the proportion of the fourth solvent is 0.1 to 20% by weight based on the total solvent weight.
  • the tetracarboxylic dianhydride used for the synthesis of the polymer contains at least one selected from the group of compounds represented by the following formulas (AN-I) to (AN-VII); Diamine does not have a side chain represented by the following formulas (DI-1) to (DI-16), and does not have a side chain represented by any of the following formulas (DIH-1) to (DIH-3)
  • X is independently a single bond or —CH 2 —.
  • G is a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO 2 —, —C (CH 3 ) 2 —, or —C (CF 3 ) 2 —.
  • Y is independently one selected from the group of the following trivalent groups, and the bond is connected to any carbon.
  • At least one hydrogen may be replaced by methyl, ethyl or phenyl;
  • the ring A 10 is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, At least one hydrogen of the group may be replaced by methyl, ethyl or phenyl, and the bond on the ring is connected to any carbon constituting the ring, and the two bonds are the same carbon You may connect to.
  • X 10 is alkylene having 2 to 6 carbon atoms, Me represents methyl, Ph represents phenyl;
  • G 10 is independently —O—, —COO— or —OCO—, and r is independently 0 or 1;
  • G 20 is —CH 2 —, at least one —CH 2 — may be replaced by —NH—, —O—, and m is an integer of 1 to 12 And at least one hydrogen of the alkylene may be replaced by —OH;
  • G 21 is independently a single bond, —NH—, —NCH 3 —, —O—, —S—, —S.
  • At least one hydrogen of the cyclohexane ring and the benzene ring in formula (DI-2) to formula (DI-7) is —F, —Cl, alkyl having 1 to 3 carbon atoms, —OCH 3 , —OH, —CF 3 , —CO 2 H, —CONH 2 , —NHC 6 H 5 , phenyl, or benzyl, and in Formula (DI-4), at least one hydrogen of the benzene ring is represented by the following formula ( DI-4-a) to (DI-4-e) may be substituted with one selected from the group of groups represented by formula (DI-4-e); the bonding position is fixed to the carbon atom constituting the ring in the above formula An unlabeled group indicates that the position of attachment in the ring is arbitrary; The bonding position of —NH 2 to the cyclohexane ring or the benzene ring is any position except the bonding position of G 21 or G 22
  • R 21 and R 22 are independently alkyl or phenyl having 1 to 3 carbon atoms
  • G 23 is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms.
  • R 23 is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or —Cl, p is independently an integer from 0 to 3, and q is An integer from 0 to 4;
  • ring B is a monocyclic heteroaromatic group, R 24 is hydrogen, —F, —Cl, C 1-6 alkyl, alkoxy, vinyl, alkynyl, q is independently an integer of 0 to 4.
  • ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group
  • G 24 is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, and r is 0 or 1; A group whose bonding position is not fixed to the carbon atom constituting the ring in the above formula indicates that the bonding position in the ring is arbitrary;
  • the bonding position of —NH 2 bonded to the ring is an arbitrary position;
  • G 25 represents a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO 2 —, —C (CH 3 ) 2 —, or — C (CF 3 ) 2 —;
  • ring D is a cyclohexane ring, a benzene ring
  • R 25 is an alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a).
  • this alkyl at least one hydrogen is —F.
  • At least one —CH 2 — may be replaced by —O—, —CH ⁇ CH— or —C ⁇ C—, and the hydrogen of the phenyl is —F, —CH 3 , —OCH 3 , —OCH 2 F, —OCHF 2, —OCF 3, alkyl having 3 to 30 carbon atoms, or alkoxy having 3 to 30 carbon atoms, and —NH 2 bonded to the benzene ring
  • the bond position is any position in the ring;
  • G 27 , G 28 and G 29 are bonding groups, and these are each independently a single bond or alkylene having 1 to 12 carbon atoms, and one or more — CH 2 — may be replaced by —O—, —COO—, —OCO—, —CONH—, —CH ⁇ CH—, and ring B 21 , ring B 22 , ring B 23 and ring B 24 are independent.
  • t and u are each independently an integer of 0 to 2, and their sum is 1 to 5, and when s, t or u is 2, two bonds in each parenthesis
  • the groups may be the same or different, and the two rings may be the same or different, and R 26 is hydrogen, —F, —OH, alkyl having 1 to 30 carbons, carbon number 1 to 30 fluorine-substituted alkyl, 1 to 30 carbon alk
  • R 31 is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one —CH 2 — of the alkyl may be replaced by —O—, —CH ⁇ CH— or —C ⁇ C—
  • R 32 is alkyl having 6 to 22 carbon atoms
  • R 33 is hydrogen or alkyl having 1 to 22 carbon atoms
  • ring B 25 is 1,4-phenylene or 1,4-cyclohexylene
  • r is 0
  • —NH 2 bonded to a benzene ring indicates that the bonding position in the ring is arbitrary.
  • the tetracarboxylic dianhydride used for the synthesis of the polymer contains at least one selected from the group of compounds represented by the following formulas (2) to (13);
  • X and Y are each independently a single bond, —O—, —NH—, —S—, or alkylene having 1 to 6 carbon atoms;
  • a is an integer of 1 to 8;
  • Ra is alkyl having 1 to 3 carbons; and At least one hydrogen of the benzene ring in the above formula may be replaced by —CH 3 .
  • the polyamic acid and its derivative are polymers (a) obtained by reacting a raw material monomer in which at least one of tetracarboxylic dianhydride and diamine has a photoreactive structure, [1] to [4 ]
  • the tetracarboxylic dianhydride used for the synthesis of the polymer (b) contains at least one selected from the group of compounds represented by the following formulas (2) to (13);
  • X and Y are each independently a single bond, —O—, —NH—, —S—, or alkylene having 1 to 6 carbon atoms;
  • a is an integer of 1 to 8;
  • Ra is alkyl having 1 to 3 carbons; and At least one hydrogen of the benzene ring in the above formula may be replaced by —CH 3 .
  • liquid crystal alignment according to any one of [1] to [8], further containing at least one selected from the group consisting of an oxazine compound, an oxazoline compound, an epoxy compound, and a silane coupling agent. Agent.
  • the liquid crystal aligning agent of the present invention in which a polymer obtained from tetracarboxylic dianhydride and diamine is dissolved in a solvent obtained by mixing the first solvent to the fourth solvent is a coating film for a liquid crystal aligning film by an inkjet method.
  • a liquid crystal aligning agent prepared by blending two or more polymers exhibits the same effect.
  • 6 is an image obtained by photographing a discharge pattern in an ink jet discharge experiment (Example 1) performed using the polyamic acid solution PC-1.
  • 6 is an image obtained by photographing a discharge pattern in an ink jet discharge experiment (Comparative Example 1) performed using a polyamic acid solution PC-27.
  • 6 is a photomicrograph of edge roughness measured in edge linearity evaluation (Example 1) performed using the polyamic acid solution PC-1.
  • 4 is a photomicrograph of edge roughness measured in edge linearity evaluation (Comparative Example 1) performed using the polyamic acid solution PC-27.
  • 6 is a photograph showing in-plane uneven stripes in an in-plane stripe unevenness evaluation (Example 1) performed using the polyamic acid solution PC-1.
  • 6 is a photograph showing in-plane uneven stripes in an in-plane stripe unevenness evaluation (Comparative Example 1) performed using a polyamic acid solution PC-27.
  • the subject of the present invention is a liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyamic acid and derivatives thereof and a solvent.
  • the solvent used for the liquid crystal aligning agent of this invention is divided into the following four groups.
  • the first solvent is selected from the group of polar organic solvents that have good solubility in the polymer forming the alignment film.
  • polar organic solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N, N-dimethylacetamide, Lactones such as dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide, and ⁇ -butyrolactone.
  • preferred solvents from the boiling point are N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylimidazolidinone, and ⁇ -butyrolactone.
  • the boiling point of the first solvent is preferably in the range of 190 ° C to 250 ° C.
  • the second solvent is characterized by a relatively small surface energy of less than 30 mN / m and good paintability to the substrate.
  • Specific examples include alcohols and ethers.
  • alcohols include butyl cellosolve (ethylene glycol monobutyl ether), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, 1- Butoxy-2-propanol, ethyl lactate, methyl lactate, propyl lactate.
  • butyl cellosolve ethylene glycol monobutyl ether
  • ethylene glycol monomethyl ether ethylene glycol monoethyl ether
  • propylene glycol monomethyl ether propylene glycol monomethyl ether
  • propylene glycol monobutyl ether propylene glycol monopropyl ether
  • 1- Butoxy-2-propanol ethyl lactate, methyl lactate, propyl lactate.
  • ethers are ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol propyl methyl ether, propylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl.
  • preferred solvents from the boiling point are butyl cellosolve (ethylene glycol monobutyl ether), 1-butoxy-2-propanol, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and diethylene glycol propyl methyl ether.
  • More preferred solvents are butyl cellosolve, 1-butoxy-2-propanol, diethylene glycol ethyl methyl ether, and diethylene glycol propyl methyl ether.
  • the boiling point of the second solvent is preferably in the range of 120 ° C. to 200 ° C.
  • the third solvent is a solvent that improves the spread of the solution. Mixing this solvent can prevent the coating film from becoming uneven.
  • Such solvents specifically include ketones such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, methyl-3-methoxypropionate, and the like.
  • dipentyl ether preferred solvents are methyl isobutyl ketone, diisobutyl ketone and dipentyl ether. More preferred solvents are diisobutyl ketone and dipentyl ether.
  • the fourth solvent has an effect of suppressing film shrinkage and preventing backlash of the coating film. This effect is considered to be due to the fact that the fourth solvent has a boiling point in a temperature range close to that of the first solvent and is higher than the boiling points of the second solvent and the third solvent. That is, it seems that the drying rate when the discharged liquid spreads by the fourth solvent having a high boiling point becomes slow, and in particular, evaporation of the solvent at the edge portion is suppressed.
  • the preferred fourth solvent are diethylene glycol ethyl propyl ether, diethylene glycol butyl methyl ether and diethylene glycol butyl ethyl ether.
  • the ratio of the first solvent to the total solvent weight is 20 to 89% by weight, preferably 30 to 84% by weight, and more preferably 45 to 75% by weight.
  • the first solvent has a ratio of 20% by weight or more with respect to the total solvent weight in order to prevent the precipitation of the polymer in the solution, the clogging of the nozzles and heads of the ink jet apparatus, and the occurrence of in-plane unevenness of the coating film. Used.
  • the amount of the second solvent which is a poor solvent, is reduced and does not deteriorate printability, so that it is used in a proportion of 89% by weight or less based on the total solvent weight.
  • the ratio of the second solvent to the total solvent weight is 10 to 60% by weight, preferably 15 to 50% by weight, and more preferably 20 to 45% by weight.
  • the second solvent is used in a ratio of 10% by weight or more based on the total solvent weight in order to prevent the occurrence of liquid shrinkage due to printing failure or evaporation from the edge portion. On the contrary, the ratio of good solvent is reduced, so that precipitation of the polymer in the solution, clogging of the nozzles and heads of the ink jet device, and in-plane unevenness of the coating film are prevented. And 60% by weight or less.
  • the ratio of the third solvent to the total solvent weight is 0.1 to 15% by weight, preferably 0.1 to 10% by weight, and more preferably 0.1 to 5% by weight.
  • the third solvent is used at a ratio of 0.1% by weight or more with respect to the total solvent weight in order to prevent deterioration of the liquid spreading property and generation of unevenness in the head running direction.
  • it is used at a ratio of 15 wt% or less based on the total solvent weight.
  • the ratio of the fourth solvent to the total solvent weight is 0.1 to 20% by weight, preferably 0.1 to 15% by weight, and more preferably 0.1 to 10% by weight.
  • the fourth solvent is used at a ratio of 0.1% by weight or more with respect to the total solvent weight in order to exhibit the effect of maintaining the linearity of the edge and the effect of good liquid spreading. On the contrary, in order to prevent the coating film from being poorly dried, causing in-plane unevenness and deterioration of uniformity, it is used at a ratio of 20% by weight or less with respect to the total solvent weight.
  • the polyamic acid and derivatives thereof of the present invention will be described.
  • the polyamic acid and derivatives thereof of the present invention are reaction products of tetracarboxylic dianhydride and diamine.
  • the polyamic acid derivative is a component that dissolves in a solvent when the liquid crystal aligning agent described later containing a solvent is used.
  • the liquid crystal aligning agent is used as a liquid crystal aligning film, the liquid crystal alignment is mainly composed of polyimide. It is a component that can form a film. Examples of such a derivative of polyamic acid include soluble polyimide, polyamic acid ester, polyamic acid amide, and the like.
  • polyimide in which all amino acids and carboxyl of polyamic acid are subjected to a dehydration ring-closing reaction
  • Partially dehydrated ring-closing partial polyimide 3) Polyamic acid ester in which carboxyl of polyamic acid is converted to ester
  • Part of acid dianhydride contained in tetracarboxylic dianhydride compound is organic dicarboxylic Examples thereof include polyamic acid-polyamide copolymers obtained by reacting with an acid, and 5) polyamideimide obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closing reaction.
  • the polyamic acid and its derivative may be a compound having a structure of a reaction product of tetracarboxylic dianhydride and diamine, and other raw materials may be used except for the reaction of tetracarboxylic dianhydride and diamine. It may contain reaction products from other reactions.
  • the tetracarboxylic dianhydride used for producing the polyamic acid and its derivative contained in the liquid crystal aligning agent of the present invention will be described.
  • the tetracarboxylic dianhydride used in the present invention can be selected without limitation from known tetracarboxylic dianhydrides.
  • Such tetracarboxylic dianhydrides include aromatic systems (including heteroaromatic ring systems) in which dicarboxylic acid anhydrides are directly bonded to aromatic rings, and aliphatic groups in which dicarboxylic acid anhydrides are not directly bonded to aromatic rings. It may belong to any group of systems (including heterocyclic ring systems).
  • Tetracarboxylic dianhydride may react one compound with diamine, or may mix two or more compounds and react with diamine.
  • “tetracarboxylic dianhydride” refers not only to one compound, but may also include a mixture of two or more compounds in its meaning.
  • tetracarboxylic dianhydrides include those represented by the formulas (AN-I) to (AN-VII) from the viewpoint of easy availability of raw materials, ease of polymer polymerization, and electrical characteristics of the film.
  • the tetracarboxylic dianhydride represented is mentioned.
  • X is independently a single bond or —CH 2 —.
  • G is a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO 2 —, —C (CH 3 ) 2 —, or —C (CF 3 ) 2 —.
  • Y is independently one selected from the group of the following trivalent groups, and the bond is connected to any carbon. At least one hydrogen may be replaced with methyl, ethyl or phenyl.
  • the ring A 10 is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, At least one hydrogen of the group may be replaced by methyl, ethyl or phenyl, and the bond on the ring is connected to any carbon constituting the ring, and the two bonds are the same carbon You may connect to.
  • X 10 is alkylene having 2 to 6 carbon atoms, Me represents methyl, and Ph represents phenyl.
  • G 10 is independently —O—, —COO— or —OCO—, and r is independently 0 or 1.
  • tetracarboxylic dianhydrides represented by the following formulas (AN-1) to (AN-16-14) can be mentioned.
  • G 11 is a single bond, alkylene having 1 to 12 carbons, 1,4-phenylene, or 1,4-cyclohexylene.
  • X 11 is independently a single bond or —CH 2 —.
  • G 12 is independently one of the following trivalent groups. When G 12 is> CH—, the hydrogen of> CH— may be replaced with —CH 3 . When G 12 is> N—, G 11 is not a single bond and —CH 2 —, and X 11 is not a single bond.
  • R 11 is hydrogen or —CH 3 .
  • Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formula. In the formulas (AN-1-2) and (AN-1-14), m is an integer of 1 to 12.
  • R 12 is independently hydrogen, —CH 3 , —CH 2 CH 3 , or phenyl.
  • Examples of the tetracarboxylic dianhydride represented by the formula (AN-2) include compounds represented by the following formula.
  • ring A 11 is a cyclohexane ring or a benzene ring.
  • Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include compounds represented by the following formula.
  • G 13 is a single bond, — (CH 2 ) m —, —O—, —S—, —C (CH 3 ) 2 —, —SO 2 —, —CO—, —C (CF 3 ) 2 — or a divalent group represented by the following formula (G13-1), and m is an integer of 1 to 12.
  • Each ring A 11 is independently a cyclohexane ring or a benzene ring.
  • G 13 may be bonded to any position of ring A 11 .
  • G 13a and G 13b each independently represent a single bond, a divalent group represented by —O— or —NHCO—.
  • the phenylene is preferably 1,4-phenylene and 1,3-phenylene.
  • Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formula.
  • m is an integer of 1 to 12.
  • R 11 is hydrogen or —CH 3 .
  • R 11 whose bond position is not fixed to the carbon atom constituting the benzene ring indicates that the bond position in the benzene ring is arbitrary.
  • Examples of the tetracarboxylic dianhydride represented by the formula (AN-5) include compounds represented by the following formula.
  • X 11 is independently a single bond or —CH 2 —.
  • n is 1 or 2.
  • Examples of the tetracarboxylic dianhydride represented by the formula (AN-6) include compounds represented by the following formula.
  • Examples of the tetracarboxylic dianhydride represented by the formula (AN-7) include compounds represented by the following formula.
  • X 11 is a single bond or —CH 2 —.
  • R 12 is hydrogen, —CH 3 , —CH 2 CH 3 , or phenyl, and ring A 12 is a cyclohexane ring or a cyclohexene ring.
  • Examples of the tetracarboxylic dianhydride represented by the formula (AN-8) include compounds represented by the following formula.
  • Examples of the tetracarboxylic dianhydride represented by the formula (AN-9) include compounds represented by the following formula.
  • ring A 11 is independently a cyclohexane ring or a benzene ring.
  • Examples of the tetracarboxylic dianhydride represented by the formula (AN-11) include compounds represented by the following formula.
  • each ring A 11 is independently a cyclohexane ring or a benzene ring.
  • Examples of the tetracarboxylic dianhydride represented by the formula (AN-12) include compounds represented by the following formula.
  • Examples of the tetracarboxylic dianhydride represented by the formula (AN-13) include compounds represented by the following formula.
  • Ph represents phenyl.
  • Examples of the tetracarboxylic dianhydride represented by the formula (AN-14) include compounds represented by the following formula.
  • Examples of the tetracarboxylic dianhydride represented by the formula (AN-15) include compounds represented by the following formula.
  • Examples of tetracarboxylic dianhydrides other than the above include the following compounds.
  • the tetracarboxylic dianhydride more preferably used as a raw material for the polymer contained in the liquid crystal aligning agent of the present invention is at least one selected from the group of compounds represented by the following formulas (2) to (13). It is. At least one of the hydrogens in the above formula may be replaced with —CH 3 , —CH 2 CH 3 or phenyl.
  • the unsubstituted compound in formula (2) is the compound of formula (AN-3-2), the unsubstituted compound in formula (3) is the compound of formula (AN-2-1),
  • the unsubstituted compound in 4) is the compound of formula (AN-1-1), the unsubstituted compound in formula (5) is the compound of formula (AN-3-1), and the
  • the substituted compound is the compound of the formula (AN-1-13), the unsubstituted compound in the formula (7) is the compound of the formula (AN-16-1), and the unsubstituted compound in the formula (8) is
  • the diamine and dihydrazide used for producing the polyamic acid and its derivative contained in the liquid crystal aligning agent of the present invention will be described.
  • the diamine and dihydrazide used in the present invention can be selected without limitation from known diamines and dihydrazides.
  • Diamine may react one compound with tetracarboxylic dianhydride, or may mix two or more compounds and react with tetracarboxylic dianhydride.
  • diamine refers not only to one compound but also to a mixture of two or more compounds. In the present specification, dihydrazide is also handled as “diamine”.
  • Diamines can be divided into two types according to their structure. That is, when a skeleton connecting two amino groups is viewed as a main chain, a group branched from the main chain, that is, a diamine having a side chain group and a diamine having no side chain group.
  • This side chain group is a group having an effect of increasing the pretilt angle.
  • the side chain group having such an effect needs to be a group having 3 or more carbon atoms. Specific examples include alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms, alkoxyalkyl having 3 or more carbon atoms, and A group having a steroid skeleton can be exemplified.
  • a diamine having such a side chain group may be referred to as a side chain diamine.
  • Such a diamine having no side chain group may be referred to as a non-side chain diamine.
  • the side chain diamine is preferably used in combination so as not to impair the properties of the present invention.
  • the side chain diamine and the non-side chain diamine are preferably selected and used for the purpose of improving the vertical alignment with respect to the liquid crystal, the voltage holding ratio, the image sticking property, and the alignment.
  • the non-side chain diamine will be described.
  • diamines having no known side chain include diamines of the following formulas (DI-1) to (DI-16).
  • G 20 is —CH 2 —, at least one —CH 2 — may be replaced by —NH—, —O—, and m is an integer of 1 to 12 And at least one hydrogen of the alkylene may be replaced by —OH.
  • G 21 is independently a single bond, —NH—, —NCH 3 —, —O—, —S—, —S.
  • s is independently an integer of 0 to 2.
  • G 22 is independently a single bond, —O—, —S—, —CO—, —C (CH 3 ) 2 —, —C (CF 3 2 ), -NH-, or alkylene having 1 to 10 carbon atoms.
  • Formula (DI-2) at least one hydrogen of cyclohexane ring and benzene ring in ⁇ formula (DI-7) is, -F, -Cl, alkyl having 1 to 3 carbon atoms, -OCH 3, -OH, -CF 3 , —CO 2 H, —CONH 2 , —NHC 6 H 5 , phenyl, or benzyl, and in Formula (DI-4), at least one hydrogen of the benzene ring is represented by the following formula ( DI-4-a) to one selected from the group of groups represented by formula (DI-4-e) may be substituted.
  • a group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary.
  • the bonding position of —NH 2 to the cyclohexane ring or benzene ring is an arbitrary position excluding the bonding position of G 21 or G 22 .
  • R 20 is independently hydrogen or —CH 3 .
  • R 21 and R 22 are independently alkyl or phenyl having 1 to 3 carbon atoms
  • G 23 is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms.
  • w is an integer of 1 to 10.
  • R 23 is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or —Cl
  • p is independently an integer from 0 to 3
  • q is It is an integer from 0 to 4.
  • ring B is a monocyclic heteroaromatic group
  • R 24 is hydrogen, —F, —Cl, C 1-6 alkyl, alkoxy, vinyl, alkynyl
  • q is independently an integer of 0 to 4.
  • ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group.
  • G 24 is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, and r is 0 or 1.
  • a group whose bond position is not fixed to the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary.
  • the bonding position of —NH 2 bonded to the ring is an arbitrary position.
  • diamine represented by the formula (DI-1) examples are shown below.
  • k is each independently an integer of 1 to 3.
  • diamines represented by formula (DI-2) and formula (DI-3) are shown below.
  • Examples of the diamine represented by the formula (DI-4) are shown below.
  • Examples of the diamine represented by the formula (DI-5) are shown below.
  • m is an integer of 1 to 12.
  • m is an integer of 1 to 12.
  • v is an integer of 1 to 6.
  • k is an integer of 1 to 5.
  • m is an integer of 1 to 12, and the formula (DI-5-38) and the formula (DI In DI-5-39), k is an integer of 1 to 5, and in Formula (DI-5-40), n is an integer of 1 or 2.
  • Examples of the diamine represented by the formula (DI-7) are shown below.
  • m is an integer of 1 to 12
  • n is independently 1 or 2.
  • Examples of the diamine represented by the formula (DI-12) are shown below.
  • Examples of the diamine represented by the formula (DI-13) are shown below.
  • dihydrazide Describes dihydrazide.
  • dihydrazide having no known side chain include the following formulas (DIH-1) to (DIH-3).
  • G 25 represents a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO 2 —, —C (CH 3 ) 2 —, or — C (CF 3 ) 2 —.
  • ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of this group may be replaced with methyl, ethyl or phenyl.
  • each ring E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of this group may be replaced with methyl, ethyl, or phenyl, and Y is a single bond, It is alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO 2 —, —C (CH 3 ) 2 —, or —C (CF 3 ) 2 —.
  • the bonding position of —CONHNH 2 bonded to the ring is an arbitrary position.
  • non-side chain diamines and hydrazides have the effect of improving electrical properties, such as reducing the ion density of liquid crystal display elements.
  • the proportion of the diamine and dihydrazide in the total amount is 0 to 90 mol. %, Preferably 0 to 50 mol%.
  • the side chain type diamine will be described.
  • Examples of the side chain group of the side chain type diamine include the following groups.
  • alkyl, alkyloxy, alkyloxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkenylcarbonyloxy, alkenyloxycarbonyl, alkenylaminocarbonyl, Alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylaminocarbonyl and the like can be mentioned.
  • Alkyl, alkenyl and alkynyl in these groups are all groups having 3 or more carbon atoms. However, in alkyloxyalkyl, it is sufficient if the entire group has 3 or more carbon atoms. These groups may be linear or branched.
  • phenyl, phenylalkyl, phenylalkyloxy, phenyloxy provided that the terminal ring has alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms or alkoxyalkyl having 2 or more carbon atoms as a substituent.
  • a ring assembly group having an alkoxy of several or more or an alkoxyalkyl having two or more carbons can be given.
  • a group having a steroid skeleton is also effective as a side chain group.
  • Examples of the diamine having a side chain include compounds represented by the following formulas (DI-31) to (DI-35).
  • G 26 represents a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —CH 2 O—, —OCH 2 —, —CF 2 O—. , —OCF 2 —, or — (CH 2 ) m ′ —, and m ′ is an integer of 1 to 12.
  • G 26 are a single bond, —O—, —COO—, —OCO—, —CH 2 O—, and alkylene having 1 to 3 carbon atoms, and particularly preferred examples are a single bond, —O—, — COO -, - OCO -, - CH 2 O -, - CH 2 - and -CH 2 CH 2 -.
  • R 25 is an alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a).
  • At least one hydrogen may be replaced with —F, and at least one —CH 2 — may be replaced with —O—, —CH ⁇ CH— or —C ⁇ C—.
  • the hydrogen of this phenyl is replaced by —F, —CH 3 , —OCH 3 , —OCH 2 F, —OCHF 2, —OCF 3, alkyl having 3 to 30 carbon atoms or alkoxy having 3 to 30 carbon atoms. Also good.
  • the bonding position of —NH 2 bonded to the benzene ring indicates an arbitrary position in the ring, but the bonding position is preferably meta or para.
  • G 27 , G 28 and G 29 are bonding groups, and these are each independently a single bond or alkylene having 1 to 12 carbon atoms, and one or more — CH 2 — may be replaced by —O—, —COO—, —OCO—, —CONH—, —CH ⁇ CH—.
  • Ring B 21 , Ring B 22 , Ring B 23 and Ring B 24 are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5 -Diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, ring B 21 , ring B 22 , ring B 23 and ring in B 24, at least one hydrogen may be replaced by -F, or -CH 3, s, t and u is an integer of 0 to 2 independently, the total is 1 to 5, When s, t or u is 2, the two linking groups in each parenthesis may be the same or different, and the two rings may be the same or different.
  • R 26 is hydrogen, —F, —OH, alkyl having 1 to 30 carbons, fluorine-substituted alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —CN, —OCH 2 F, —OCHF 2 , or —OCF 3 and at least one —CH 2 — of the alkyl having 1 to 30 carbon atoms may be replaced with a divalent group represented by the following formula (DI-31-b).
  • R 27 and R 28 are independently alkyl having 1 to 3 carbon atoms, and v is an integer of 1 to 6.
  • Preferred examples of R 26 are alkyl having 1 to 30 carbons and alkoxy having 1 to 30 carbons.
  • G 30 is independently a single bond, —CO— or —CH 2 —, R 29 is independently hydrogen or —CH 3 , R 30 30 is hydrogen, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons. At least one hydrogen of the benzene ring in the formula (DI-33) may be replaced with alkyl having 1 to 20 carbons or phenyl. A group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary.
  • One of the two groups “-phenylene-G 30 —O—” in the formula (DI-32) is preferably bonded to the 3-position of the steroid nucleus and the other is bonded to the 6-position of the steroid nucleus.
  • the bonding position of the two groups “-phenylene-G 30 —O—” in the formula (DI-33) to the benzene ring is preferably a meta position or a para position, respectively, with respect to the bonding position of the steroid nucleus.
  • —NH 2 bonded to the benzene ring indicates that the bonding position in the ring is arbitrary.
  • G 31 is independently —O— or alkylene having 1 to 6 carbons, and G 32 is a single bond or alkylene having 1 to 3 carbons.
  • R 31 is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one —CH 2 — of the alkyl may be replaced by —O—, —CH ⁇ CH— or —C ⁇ C—.
  • R 32 is alkyl having 6 to 22 carbon atoms, and R 33 is hydrogen or alkyl having 1 to 22 carbon atoms.
  • Ring B 25 is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1.
  • —NH 2 bonded to the benzene ring indicates that the bonding position in the ring is arbitrary, but it is preferably independently of the meta position or the para position with respect to the bonding position of G 31 .
  • side chain diamines are illustrated below.
  • Examples of the diamine having a side chain of the formula (DI-31) to the formula (DI-35) include compounds represented by the following formulas (DI-31-1) to (DI-35-3). it can.
  • R 34 is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl having 5 to 25 carbons or Alkoxy having 5 to 25 carbon atoms.
  • R 35 is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl having 3 to 25 carbons or alkoxy having 3 to 25 carbons.
  • R 36 is alkyl having 4 to 30 carbons, and preferably alkyl having 6 to 25 carbons.
  • R 37 is alkyl having 6 to 30 carbon atoms, preferably alkyl having 8 to 25 carbon atoms.
  • R 38 is alkyl having 1 to 20 carbons or alkoxy having 1 to 20 carbons, preferably alkyl having 3 to 20 carbons or Alkoxy having 3 to 20 carbon atoms.
  • R 39 is hydrogen, —F, alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —CN, —OCH 2 F, —OCHF 2 or —OCF 3 , preferably having 3 to 25 carbons. Alkyl or alkoxy having 3 to 25 carbon atoms.
  • G 33 is alkylene having 1 to 20 carbon atoms.
  • R 40 is hydrogen or alkyl having 1 to 20 carbons, preferably hydrogen or alkyl having 1 to 10 carbons, and R 41 is Hydrogen or alkyl having 1 to 12 carbons.
  • R 37 is alkyl having 6 to 30 carbons
  • R 41 is hydrogen or alkyl having 1 to 12 carbons.
  • Examples of the diamine in the present invention include formulas (DI-1-1) to (DI-16-1), formulas (DIH-1-1) to (DIH-3-6), and formula (DI-31-1). ) To diamines other than those represented by the formula (DI-35-3) can also be used. Examples of such diamines include compounds represented by the following formulas (DI-36-1) to (DI-36-13). In the formulas (DI-36-1) to (DI-36-8), R 42 each independently represents an alkyl group having 3 to 30 carbon atoms.
  • R 43 each independently represents hydrogen, —NHBoc Or —N (Boc) 2 , at least one of R 43 is —NHBoc or —N (Boc) 2 , and in formula (DI-36-13), R 44 is —NHBoc or —N (Boc) 2 and m is an integer from 1 to 12.
  • Boc is a t-butoxycarbonyl group.
  • the formula (DI-1-3), the formula (DI-5-1), the formula (DI-5-5), Formula (DI-5-9), Formula (DI-5-12), Formula (DI-5-13), Formula (DI-5-29), Formula (DI-6-7), Formula (DI-7 -3) and a diamine represented by the formula (DI-11-2) are preferred.
  • the formula (DI-1-3), the formula (DI-2-1), the formula (DI-5-1), the formula ( It is preferred to use diamines represented by DI-5-5), formula (DI-5-24), and formula (DI-7-3), and diamines represented by (DI-2-1) are particularly preferred.
  • a part of the diamine may be replaced with a monoamine in a range where the ratio of the monoamine to the diamine is 40 mol% or less.
  • Such replacement can cause termination of the polymerization reaction when the polyamic acid is produced, and further progress of the polymerization reaction can be suppressed.
  • the molecular weight of the obtained polymer (polyamic acid or a derivative thereof) can be easily controlled by such replacement, and for example, the coating characteristics of the liquid crystal aligning agent are improved without impairing the effects of the present invention. be able to.
  • one or more diamines may be substituted for the monoamine.
  • Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n- Undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-eicosylamine Is mentioned.
  • the polyamic acid or derivative thereof of the present invention may further contain a monoisocyanate compound in the monomer.
  • a monoisocyanate compound in the monomer, the terminal of the resulting polyamic acid or derivative thereof is modified, and the molecular weight is adjusted.
  • the coating properties of the liquid crystal aligning agent can be improved without impairing the effects of the present invention.
  • the content of the monoisocyanate compound in the monomer is preferably 1 to 10 mol% based on the total amount of diamine and tetracarboxylic dianhydride in the monomer from the above viewpoint.
  • the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
  • the diamine more preferably used as a raw material for the polymer contained in the liquid crystal aligning agent of the present invention is at least one selected from the group of compounds represented by the following formulas (D-1) to (D-5). is there.
  • formula (D-2) and formula (D-4) X and Y are each independently a single bond, —O—, —NH—, —S—, or alkylene having 1 to 6 carbon atoms.
  • a is an integer of 1 to 8.
  • Ra is alkyl having 1 to 3 carbon atoms.
  • at least one hydrogen of the benzene ring in the above formula may be replaced with —CH 3 .
  • the unsubstituted compound in formula (D-1) is the compound of formula (DI-4-1), and the unsubstituted compound in formula (D-3) is the compound of formula (DI-13-1). Respectively. Further, the compound represented by the formula (D-2) or the formula (D-5) falls within the category of the formula (DI-5), and the compound represented by the formula (D-4) represents the formula (DI It is included in the category of -7).
  • diamines that are more preferably used among the above diamines include the following formulas (D-1), (D-2-1) to (D-2-9), (D-3), (D- 4-1) to (D-4-72) and (D-5-1) to (D-5-3).
  • a photoreactive structure In order to give the polymer contained in the liquid crystal aligning agent of the present invention a photoreactive structure, it is preferable to use a diamine having a photoreactive structure or a tetracarboxylic dianhydride having a photoreactive structure as a raw material. .
  • a diamine having a photoreactive structure and a tetracarboxylic dianhydride having a photoreactive structure may be used in combination.
  • Preferred examples of the monomer having these photoreactive structures are compounds represented by the following formulas (I-1) to (I-4).
  • the compound represented by the formula (I-3) is more preferable because it exhibits greater anisotropy when the alignment film is formed.
  • the polymer contained in the liquid crystal aligning agent of the present invention can be obtained by reacting the above tetracarboxylic dianhydride and diamine in a solvent. In this synthesis reaction, no special conditions other than the selection of the raw materials are required, and the conditions for normal polyamic acid synthesis can be applied as they are.
  • the polymer contained in the liquid crystal aligning agent of the present invention may be one, or a blend of two or more may be used.
  • at least one of the polymers is a polymer obtained by reacting a raw material monomer in which at least one of tetracarboxylic dianhydride and diamine has a photoreactive structure (a
  • at least one of the other polymers is a polyamic acid obtained by reacting a tetracarboxylic dianhydride having no photoreactive structure and a diamine not having a photoreactive structure, and a derivative thereof.
  • the case of at least one polymer (b) selected is included.
  • the polymer (a) changes its structure when the photoreactive structure is isomerized, decomposed or dimerized by the irradiation of ultraviolet energy energy rays, and the liquid crystal molecules in contact with the polymer film are moved in a specific direction. It has the ability to align (photo-alignment).
  • Such polymers may be used in blends with other polymers that do not contain photoreactive structures.
  • the liquid crystal aligning agent of the present invention may further contain other components other than polyamic acid or derivatives thereof.
  • the other component may be one type or two or more types. Examples of other components include other polymers and compounds described below.
  • the structure and molecular weight of each polymer are controlled, and applied to a substrate and pre-dried as described later, for example,
  • the polymer (a) having the photo-alignment function can be separated into the upper layer of the coating film, and the other polymer (b) can be separated into the lower layer of the coating film.
  • This can be controlled by using a phenomenon in which a polymer having a small surface energy is separated into an upper layer and a polymer having a large surface energy is separated into a lower layer in a mixed polymer. Confirmation of the layer separation can be confirmed by confirming that the surface energy of the formed alignment film is the same as or close to the surface energy of the alignment film formed by the liquid crystal aligning agent containing only the polymer (a).
  • tetracarboxylic dianhydride used for synthesizing the polymer (b) tetracarboxylic dianhydride used for synthesizing polyamic acid or a derivative thereof which is an essential component of the liquid crystal aligning agent of the present invention. It can select without limitation from well-known tetracarboxylic dianhydride as a thing, and can mention the same thing illustrated above.
  • the tetracarboxylic dianhydride used to synthesize the polymer (b) preferably contains 10% by mole or more of the aromatic tetracarboxylic dianhydride with respect to the total tetracarboxylic dianhydride. 30% or more is more preferable.
  • Examples of the diamine and hydrazide used for synthesizing the polymer (b) are the above as other diamines that can be used for synthesizing the polyamic acid or its derivative, which is an essential component of the liquid crystal aligning agent of the present invention. You can list the same ones.
  • the formula (DI-1-2), the formula (DI-2-1), the formula (DI-5-1), and the formula The diamine represented by (DI-7-3) is preferably used, and the diamine represented by the formula (DI-2-1) is particularly preferred.
  • the formula (DI-4-1), the formula (DI-5-1), and the formula (DI- The diamine represented by 5-12) is particularly preferred.
  • the diamine used for synthesizing the polymer (b) preferably contains 30% by mole or more, more preferably 50% or more of the aromatic diamine with respect to the total diamine.
  • the ratio of the polymer (a) to the total amount of the polymer (a) and the polymer (b) is preferably 10% by weight to 100% by weight, and 20% by weight to 100% by weight. % Is more preferable.
  • polysiloxane examples include JP2009-036966, JP2010-185001, JP2011-109633, JP2011-253175, JP2012-159825, International Publication 2008/044644, International Publication 2009/148099, International Publication. 2010/074261, International Publication 2010/074264, International Publication 2010/126108, International Publication 2011/068123, International Publication 2011/068127, International Publication 2011/068128, International Publication 2012/115157, International Publication 2012/165354, etc.
  • the polysiloxane may be further contained.
  • the liquid crystal aligning agent of the present invention may further contain various additives.
  • the various additives include oxazine compounds, oxazoline compounds, epoxy compounds, high molecular compounds other than polyamic acid and its derivatives, and other low molecular compounds, which can be selected and used according to their respective purposes. it can.
  • the liquid crystal aligning agent of the present invention may further contain an oxazine compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time.
  • the oxazine compound may be one type of compound or two or more types of compounds.
  • the content of the oxazine compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the polyamic acid or derivative thereof. More preferably.
  • the oxazine compound will be specifically described below.
  • the oxazine compound is soluble in a solvent that dissolves polyamic acid or a derivative thereof, and in addition, an oxazine compound having ring-opening polymerizability is preferable. Further, the number of oxazine structures in the oxazine compound is not particularly limited.
  • oxazine compounds Various structures are known for oxazine compounds.
  • the structure of oxazine is not particularly limited, but examples of the oxazine structure in the oxazine compound include an oxazine structure having an aromatic group containing a condensed polycyclic aromatic group such as benzoxazine and naphthoxazine.
  • Examples of the oxazine compound include compounds represented by the following formulas (OX-1) to (OX-6).
  • the bond displayed toward the center of the ring indicates that it is bonded to any carbon that forms the ring and can be bonded to a substituent.
  • L 3 and L 4 are organic groups having 1 to 30 carbon atoms.
  • L 5 to L 8 is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms
  • Q 1 is a single bond, —O—, — S—, —S—S—, —SO 2 —, —CO—, —CONH—, —NHCO—, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, — (CH 2 ) v -, -O- (CH 2 ) v -O-, -S- (CH 2 ) v -S-, where v is an integer of 1 to 6, and is represented by formula (OX-5) and formula (OX In ⁇ 6), Q 2 is independently a single bond, —O—, —S—, —CO—, —C (CH 3 ) 2 —, —C (CF 3 ) 2 — or a carbon
  • Is alkylene The hydrogen bonded to the benzene ring and naphthalene ring in Q 2 may be independently replaced with —F, —CH 3 , —OH, —COOH, —SO 3 H, —PO 3 H 2. .
  • the oxazine compound includes an oligomer or polymer having an oxazine structure in the side chain, and an oligomer or polymer having an oxazine structure in the main chain.
  • Examples of the oxazine compound represented by the formula (OX-1) include the following oxazine compounds.
  • L 3 is preferably alkyl having 1 to 30 carbons, more preferably alkyl having 1 to 20 carbons.
  • Examples of the oxazine compound represented by the formula (OX-2) include the following oxazine compounds.
  • L 3 is preferably alkyl having 1 to 30 carbons, more preferably alkyl having 1 to 20 carbons.
  • Examples of the oxazine compound represented by the formula (OX-3) include an oxazine compound represented by the following formula (OX-3-I).
  • L 3 and L 4 are organic groups having 1 to 30 carbon atoms
  • L 5 to L 8 are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms
  • Q 1 is A single bond, —CH 2 —, —C (CH 3 ) 2 —, —CO—, —O—, —SO 2 —, —C (CH 3 ) 2 —, or —C (CF 3 ) 2 —.
  • Examples of the oxazine compound represented by the formula (OX-3-I) include the following oxazine compounds.
  • L 3 and L 4 are preferably alkyl having 1 to 30 carbon atoms, more preferably alkyl having 1 to 20 carbon atoms.
  • Examples of the oxazine compound represented by the formula (OX-4) include the following oxazine compounds.
  • Examples of the oxazine compound represented by the formula (OX-5) include the following oxazine compounds.
  • Examples of the oxazine compound represented by the formula (OX-6) include the following oxazine compounds.
  • the formula (OX-2-1), the formula (OX-3-1), the formula (OX-3-3), the formula (OX-3-5), and the formula (OX-3- 7), Formula (OX-3-9), Formula (OX-4-1) to Formula (OX-4-6), Formula (OX-5-3), Formula (OX-5-4), and Formula Oxazine compounds represented by (OX-6-2) to (OX-6-4) are listed.
  • the oxazine compound can be produced by the same method as described in International Publication No. 2004/009708, JP-A-11-12258, and JP-A-2004-352670.
  • the oxazine compound represented by the formula (OX-1) can be obtained by reacting a phenol compound, a primary amine, and an aldehyde (see International Publication 2004/009708).
  • the oxazine compound represented by the formula (OX-2) is obtained by reacting by a method in which a primary amine is gradually added to formaldehyde, and then reacting by adding a compound having a naphthol-based hydroxyl group (International Publication 2004 / (See 009708.)
  • the oxazine compound represented by the formula (OX-3) is a secondary aliphatic compound in which an organic solvent contains 1 mol of a phenol compound, at least 2 mol or more of an aldehyde per 1 phenolic hydroxyl group, and 1 mol of a primary amine. It can be obtained by reacting in the presence of an amine, a tertiary aliphatic amine, or a basic nitrogen-containing heterocyclic compound (see International Publication No. 2004/009708 and JP-A-11-12258).
  • the oxazine compounds represented by the formulas (OX-4) to (OX-6) include diamines such as 4,4′-diaminodiphenylmethane and diamines having a plurality of benzene rings and organic groups connecting them, formalin and the like. It can be obtained by subjecting an aldehyde and phenol to a dehydration condensation reaction in n-butyl alcohol at a temperature of 90 ° C. or higher (see JP 2004-352670 A).
  • the liquid crystal aligning agent of this invention may further contain the oxazoline compound from the objective of stabilizing the electrical property in a liquid crystal display element for a long term.
  • An oxazoline compound is a compound having an oxazoline structure.
  • the oxazoline compound may be one type of compound or two or more types of compounds.
  • the content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the polyamic acid or derivative thereof.
  • the content of the oxazoline compound is preferably 0.1 to 40% by weight based on the polyamic acid or its derivative when the oxazoline structure in the oxazoline compound is converted to oxazoline.
  • the oxazoline compound will be specifically described below.
  • the oxazoline compound may have only one type of oxazoline structure in one compound, or may have two or more types. Further, the oxazoline compound may have one oxazoline structure in one compound, but preferably has two or more.
  • the oxazoline compound may be a polymer having an oxazoline structure in the side chain, or may be a copolymer.
  • the polymer having an oxazoline structure in the side chain may be a homopolymer of a monomer having an oxazoline structure in the side chain, or a copolymer of a monomer having an oxazoline structure in the side chain and a monomer having no oxazoline structure It may be.
  • the copolymer having an oxazoline structure in the side chain may be a copolymer of two or more monomers having an oxazoline structure in the side chain, or two or more monomers having an oxazoline structure in the side chain and an oxazoline structure. It may also be a copolymer with a monomer that does not have.
  • the oxazoline structure is preferably a structure present in the oxazoline compound so that one or both of oxygen and nitrogen in the oxazoline structure can react with the carbonyl group of the polyamic acid.
  • oxazoline compound examples include 2,2′-bis (2-oxazoline), 1,2,4-tris- (2-oxazolinyl-2) -benzene, 4-furan-2-ylmethylene-2-phenyl-4H— Oxazol-5-one, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, 1,3-bis (4,5-dihydro-2-oxazolyl) benzene, 2,3-bis (4- Isopropenyl-2-oxazolin-2-yl) butane, 2,2′-bis-4-benzyl-2-oxazoline, 2,6-bis (isopropyl-2-oxazolin-2-yl) pyridine, 2,2 ′ -Isopropylidenebis (4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis (4-phenyl-2-oxazoline), 2,2'-methylene Scan (4-ter
  • polymers and oligomers having oxazolyl such as Epocross (trade name, manufactured by Nippon Shokubai Co., Ltd.) are also included.
  • Epocross trade name, manufactured by Nippon Shokubai Co., Ltd.
  • 1,3-bis (4,5-dihydro-2-oxazolyl) benzene is more preferable.
  • the liquid crystal aligning agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time.
  • the epoxy compound may be one type of compound or two or more types of compounds.
  • the content of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, more preferably 1 to 20% by weight with respect to the polyamic acid or derivative thereof for the above purpose. More preferably.
  • the epoxy compound will be specifically described below.
  • Examples of the epoxy compound include various compounds having one or more epoxy rings in the molecule.
  • Examples of the compound having one epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, 3-glycidoxy Propyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-glycidylphthalimide, (nonafluoro-N-butyl) epoxide, perfluoroethylglycidyl ether, epichlorohydrin, epibromohydrin, N, N-diglycidylaniline, and 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane.
  • Examples of the compound having two epoxy rings in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl.
  • Examples of the compound having three epoxy rings in the molecule include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3- Epoxypropoxy] phenyl)] ethyl] phenyl] propane (trade name “Techmore VG3101L” (manufactured by Mitsui Chemicals, Inc.)).
  • Examples of the compound having four epoxy rings in the molecule include 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, and 3- (N-allyl-N-glycidyl) Aminopropyltrimethoxysilane is mentioned.
  • examples of compounds having an epoxy ring in the molecule include oligomers and polymers having an epoxy ring.
  • examples of the monomer having an epoxy ring include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.
  • monomers that copolymerize with monomers having an epoxy ring include, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, iso-butyl (Meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, chloromethyl Styrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide and N-phenylmaleimide.
  • the monomer polymer having an epoxy ring include polyglycidyl methacrylate.
  • Preferred examples of the copolymer of the monomer having an epoxy ring and another monomer include N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate.
  • examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic epoxy compound.
  • an epoxy compound means the compound which has an epoxy group
  • an epoxy resin means resin which has an epoxy group.
  • Examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic epoxy compound.
  • Examples of the glycidyl ether include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, bisphenol type epoxy compound, hydrogenated bisphenol-A type epoxy compound, hydrogenated bisphenol-F type epoxy compound, hydrogenated bisphenol.
  • glycidyl ester examples include a diglycidyl ester compound and a glycidyl ester epoxy compound.
  • glycidylamine examples include polyglycidylamine compounds and glycidylamine type epoxy resins.
  • epoxy group-containing acrylic compound examples include homopolymers and copolymers of monomers having oxiranyl.
  • glycidyl amide examples include glycidyl amide type epoxy compounds.
  • Examples of the chain aliphatic epoxy compound include compounds containing an epoxy group obtained by oxidizing a carbon-carbon double bond of an alkene compound.
  • Examples of the cycloaliphatic epoxy compound include compounds containing an epoxy group obtained by oxidizing a carbon-carbon double bond of a cycloalkene compound.
  • Examples of the bisphenol A type epoxy compound include jER828, jER1001, jER1002, jER1003, jER1004, jER1007, jER1010 (all trade names, manufactured by Mitsubishi Chemical Corporation), Epototo YD-128 (manufactured by Tohto Kasei Co., Ltd.), DER -331, DER-332, DER-324 (all manufactured by The Dow Chemical Company), Epicron 840, Epicron 850, Epicron 1050 (all trade names, manufactured by DIC Corporation), Epomic R-140, Epomic R-301 And Epomic R-304 (both trade names, manufactured by Mitsui Chemicals, Inc.).
  • Examples of the bisphenol F type epoxy compound include jER806, jER807, jER4004P (all trade names, manufactured by Mitsubishi Chemical Corporation), Epototo YDF-170, Epototo YDF-175S, Epototo YDF-2001 (all trade names, Toto Kasei) DER-354 (trade name, manufactured by Dow Chemical Company), Epicron 830, and Epicron 835 (all trade names, manufactured by DIC Corporation).
  • Examples of the bisphenol type epoxy compound include epoxidized products of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.
  • Examples of the hydrogenated bisphenol-A type epoxy compound include Santo Tote ST-3000 (trade name, manufactured by Toto Kasei Co., Ltd.), Jamaica Resin HBE-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), and Denacol EX-252. (Trade name, manufactured by Nagase ChemteX Corporation).
  • Examples of the hydrogenated bisphenol type epoxy compound include an epoxidized product of hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.
  • brominated bisphenol-A type epoxy compounds examples include jER5050, jER5051 (both trade names, manufactured by Mitsubishi Chemical Corporation), Epototo YDB-360, Epototo YDB-400 (both trade names, manufactured by Toto Kasei Co., Ltd.) ), DER-530, DER-538 (both trade names, manufactured by The Dow Chemical Company), Epicron 152, and Epicron 153 (all trade names, manufactured by DIC Corporation).
  • phenol novolac type epoxy compounds examples include jER152, jER154 (both trade names, manufactured by Mitsubishi Chemical Corporation), YDPN-638 (trade names, manufactured by Tohto Kasei Co., Ltd.), DEN431, DEN438 (both trade names, The Dow Chemical Company), Epicron N-770 (trade name, manufactured by DIC Corporation), EPPN-201, and EPPN-202 (all trade names, manufactured by Nippon Kayaku Co., Ltd.).
  • cresol novolac type epoxy compound examples include jER180S75 (trade name, manufactured by Mitsubishi Chemical Corporation), YDCN-701, YDCN-702 (all trade names, manufactured by Tohto Kasei Co., Ltd.), Epicron N-665, and Epicron N-695. (All trade names, manufactured by DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all trade names, manufactured by Nippon Kayaku Co., Ltd.) ).
  • Examples of the bisphenol A novolak type epoxy compound include jER157S70 (trade name, manufactured by Mitsubishi Chemical Corporation) and Epicron N-880 (trade name, manufactured by DIC Corporation).
  • naphthalene skeleton-containing epoxy compound examples include Epicron HP-4032, Epicron HP-4700, Epicron HP-4770 (all trade names, manufactured by DIC Corporation), and NC-7000 (trade names, manufactured by Nippon Kayaku Co., Ltd.). Is mentioned.
  • aromatic polyglycidyl ether compound examples include hydroquinone diglycidyl ether (following formula EP-1), catechol diglycidyl ether (following formula EP-2), resorcinol diglycidyl ether (following formula EP-3), 2- [4 -(2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane (formula EP-4 below) , Tris (4-glycidyloxyphenyl) methane (following formula EP-5), jER1031S, jER1032H60 (all trade names, manufactured by Mitsubishi Chemical Corporation), TACTIX-742 (trade name, manufactured by The Dow Chemical Company), Denacol EX-201 (trade name, manufactured by Nagase ChemteX Corporation), DPPN-503, DPPN-50 H, DPPN-501H, NC6000 (all trade names
  • Examples of the dicyclopentadiene phenol type epoxy compound include TACTIX-556 (trade name, manufactured by The Dow Chemical Company) and Epicron HP-7200 (trade name, manufactured by DIC Corporation).
  • Examples of the alicyclic diglycidyl ether compound include cyclohexane dimethanol diglycidyl ether compound and licarresin DME-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.).
  • Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (following formula EP-8), diethylene glycol diglycidyl ether (following formula EP-9), polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (following formula EP).
  • polysulfide-type diglycidyl ether compound examples include FLDP-50 and FLDP-60 (both trade names, manufactured by Toray Rethiocol Co., Ltd.).
  • biphenol type epoxy compound examples include YX-4000, YL-6121H (both trade names, manufactured by Mitsubishi Chemical Corporation), NC-3000P, and NC-3000S (all trade names, manufactured by Nippon Kayaku Co., Ltd.). ).
  • diglycidyl ester compound examples include diglycidyl terephthalate (following formula EP-17), diglycidyl phthalate (following formula EP-18), bis (2-methyloxiranylmethyl) phthalate (following formula EP-19), di Examples thereof include glycidyl hexahydrophthalate (following formula EP-20), a compound represented by the following formula EP-21, a compound represented by the following formula EP-22, and a compound represented by the following formula EP-23.
  • Examples of the glycidyl ester epoxy compound include jER871, jER872 (both trade names, manufactured by Mitsubishi Chemical Corporation), Epicron 200, Epicron 400 (all trade names, manufactured by DIC Corporation), Denacol EX-711, and Denacol. EX-721 (both trade names, manufactured by Nagase ChemteX Corporation) can be mentioned.
  • polyglycidylamine compound examples include N, N-diglycidylaniline (formula EP-24 below), N, N-diglycidyl-o-toluidine (formula EP-25 below), N, N-diglycidyl-m-toluidine (formula EP-25)
  • Examples of the homopolymer of the monomer having oxiranyl include polyglycidyl methacrylate.
  • Examples of the copolymer of monomers having oxiranyl include N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer.
  • Examples of the monomer having oxiranyl include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methylglycidyl (meth) acrylate.
  • Examples of the monomer other than the monomer having oxiranyl in the copolymer of the monomer having oxiranyl include, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth).
  • Examples of glycidyl isocyanurate include 1,3,5-triglycidyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (formula EP-50 below), 1,3 -Diglycidyl-5-allyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (formula EP-51 below) and glycidyl isocyanurate type epoxy resin.
  • chain aliphatic epoxy compound examples include epoxidized polybutadiene and epolide PB3600 (trade name, manufactured by Daicel Corporation).
  • cycloaliphatic epoxy compound examples include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (Celoxide 2021 (manufactured by Daicel Corporation), the following formula EP-52), 2-methyl -3,4-epoxycyclohexylmethyl-2'-methyl-3 ', 4'-epoxycyclohexylcarboxylate (formula EP-53 below), 2,3-epoxycyclopentane-2', 3'-epoxycyclopentane ether (Formula EP-54), ⁇ -caprolactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2: 8,9-diepoxy limonene (Celoxide 3000 (trade name, ( Manufactured by Daicel Corporation), the following formula EP-55), a compound represented by the following formula
  • the epoxy compound is preferably one or more of a polyglycidylamine compound, a bisphenol A novolac type epoxy compound, a cresol novolac type epoxy compound, and a cycloaliphatic type epoxy compound, and N, N, N ′, N′-tetraglycidyl -M-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, trade name “Techmore VG3101L” 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, N, N, O-triglycidyl-p-aminophenol, bisphenol A novolak type Epoxy compound And is preferably one or more
  • polymer compound examples include polymer compounds that are soluble in an organic solvent. It is preferable to add such a polymer compound to the liquid crystal aligning agent of the present invention from the viewpoint of controlling the electrical characteristics and orientation of the liquid crystal alignment film to be formed.
  • the polymer compound include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, and silicone-modified polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, and poly (styrene-phenylmaleimide).
  • Derivatives and poly (meth) acrylates 1 type or 2 types or more may be sufficient. Of these, polysiloxane is preferred.
  • low molecular weight compounds include, for example, 1) a surfactant in accordance with the purpose when improvement in coating properties is desired, 2) an antistatic agent when improvement in antistatic properties is required, and 3) adhesion to the substrate.
  • a silane coupling agent or a titanium-based coupling agent is desired when improvement of the above is desired, and 4) an imidization catalyst when imidization proceeds at a low temperature.
  • silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyltri Methoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxy Lan, 3-
  • imidization catalyst examples include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline, methyl-substituted aniline, and hydroxy-substituted aniline.
  • cyclic amines such as pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxy-substituted isoquinoline, imidazole, methyl-substituted imidazole, and hydroxy-substituted imidazole.
  • the imidation catalyst may be one or more selected from N, N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline. preferable.
  • the amount of the silane coupling agent added is usually 0 to 20% by weight, preferably 0.1 to 10% by weight, based on the total weight of the polyamic acid or its derivative.
  • the amount of the imidation catalyst added is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents, relative to the carbonyl group of the polyamic acid or derivative thereof.
  • the addition amount of other additives varies depending on the application, but is usually 0 to 100% by weight, preferably 0.1 to 50% by weight, based on the total weight of the polyamic acid or its derivative.
  • the polyamic acid or derivative thereof of the present invention can be produced in the same manner as a known polyamic acid or derivative thereof used for forming a polyimide film.
  • the total amount of tetracarboxylic dianhydride is preferably approximately equimolar to the total number of moles of diamine (molar ratio of about 0.9 to 1.1).
  • the molecular weight of the polyamic acid or derivative thereof contained in the liquid crystal aligning agent of the present invention is preferably 7,000 to 500,000 in terms of polystyrene-equivalent weight average molecular weight (Mw), and is 10,000 to 200,000. More preferably.
  • the molecular weight of the polyamic acid or derivative thereof can be determined from measurement by gel permeation chromatography (GPC).
  • the presence of the polyamic acid or derivative thereof of the present invention can be confirmed by analyzing the solid content obtained by precipitation with a large amount of poor solvent by IR or NMR.
  • the concentration of the polyamic acid in the aligning agent of the present invention is preferably 0.1 to 40% by weight.
  • an operation of diluting the contained polyamic acid with a solvent in advance may be required to adjust the film thickness.
  • the solid content concentration in the aligning agent of the present invention is not particularly limited, and an optimal value may be selected according to the following various coating methods.
  • the amount is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight based on the weight of the varnish in order to suppress unevenness and pinholes during coating.
  • the preferred range of the viscosity of the liquid crystal aligning agent of the present invention varies depending on the coating method, the concentration of the polyamic acid or its derivative, the type of polyamic acid or its derivative used, and the type and ratio of the solvent.
  • 5 to 50 mPa ⁇ s is suitable.
  • it is preferably 5 mPa ⁇ s or more, and in order not to cause printing unevenness, it is preferably 50 mPa ⁇ s or less. More preferably, it is in the range of 5 to 20 mPa ⁇ s.
  • the viscosity of the liquid crystal aligning agent is measured by a rotational viscosity measurement method, for example, using a rotational viscometer (TVE-20L type manufactured by Toki Sangyo Co., Ltd.) (measurement temperature: 25 ° C.).
  • the liquid crystal alignment film of the present invention is a film
  • the liquid crystal alignment film of the present invention can be obtained by an ordinary method for producing a liquid crystal alignment film from a liquid crystal aligning agent.
  • the liquid crystal alignment film of the present invention can be obtained through a step of forming a coating film of the liquid crystal alignment agent of the present invention, a step of drying by heating, and a step of baking by heating.
  • the coating film can be formed by applying the liquid crystal aligning agent of the present invention to the substrate in the liquid crystal display element in the same manner as the production of the normal liquid crystal aligning film.
  • the substrate include a glass substrate in which electrodes such as ITO (Indium Tin Oxide), IZO (In 2 O 3 —ZnO), and IGZO (In—Ga—ZnO 4 ) electrodes and a color filter may be provided. .
  • an ink jet method is preferable, but other generally known methods such as a spinner method, a printing method, a dipping method, and a dropping method are also applicable.
  • the heat drying step a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known.
  • the heat drying step is preferably performed at a temperature within a range where the solvent can be evaporated, and more preferably at a temperature relatively lower than the temperature in the heat baking step.
  • the heat drying temperature is preferably in the range of 30 ° C. to 150 ° C., and more preferably in the range of 50 ° C. to 120 ° C.
  • the heating and firing step can be performed under conditions necessary for the polyamic acid or derivative thereof to exhibit dehydration and ring closure reactions.
  • a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. These methods are equally applicable in the present invention. In general, it is preferably performed at a temperature of about 100 to 300 ° C. for 1 minute to 3 hours, more preferably 120 to 280 ° C., and still more preferably 150 to 250 ° C.
  • a rubbing method, a photo alignment method, or the like is known as a means for imparting anisotropy to the alignment film in order to align the liquid crystal in one direction with respect to the horizontal and / or vertical direction.
  • the forming method can be suitably used as a means for imparting anisotropy to the alignment film in order to align the liquid crystal in one direction with respect to the horizontal and / or vertical direction.
  • the liquid crystal alignment film of the present invention using the rubbing method includes a step of applying the liquid crystal alignment agent of the present invention to a substrate, a step of heating and drying the substrate coated with the alignment agent, a step of heating and baking the film, Can be formed through a rubbing process.
  • the rubbing treatment can be performed in the same manner as the rubbing treatment for the alignment treatment of a normal liquid crystal alignment film, and may be any conditions as long as sufficient retardation is obtained in the liquid crystal alignment film of the present invention.
  • the preferable conditions are a push-in amount of 0.2 to 0.8 mm, a stage moving speed of 5 to 250 mm / sec, and a roller rotation speed of 500 to 2,000 rpm.
  • the method for forming the liquid crystal alignment film of the present invention by the photo-alignment method will be described in detail.
  • the liquid crystal alignment film of the present invention using the photo-alignment method gives the coating film anisotropy by irradiating linearly polarized light or non-polarized light after the coating film is heated and dried, and the film is heated and fired. Can be formed.
  • the coating film can be formed by irradiating linearly polarized light or non-polarized light after the coating film is heated and dried and heated and fired. From the viewpoint of orientation, the radiation irradiation step is preferably performed before the heating and baking step.
  • the heating and drying temperature in this step is preferably in the range of 30 ° C. to 150 ° C., more preferably in the range of 50 ° C. to 120 ° C.
  • the heating and baking temperature in this step is preferably in the range of 30 ° C. to 300 ° C., more preferably in the range of 50 ° C. to 250 ° C.
  • ultraviolet rays including light having a wavelength of 150 to 800 nm or visible light can be used, but ultraviolet rays including light having a wavelength of 300 to 400 nm are preferable.
  • linearly polarized light or non-polarized light can be used. These lights are not particularly limited as long as they are capable of imparting liquid crystal alignment ability to the coating film, but linearly polarized light is preferable when it is desired to develop a strong alignment regulating force for liquid crystals.
  • the liquid crystal alignment film of the present invention can exhibit high liquid crystal alignment ability even with low energy light irradiation.
  • the irradiation amount of linearly polarized light in the radiation irradiation step is preferably 0.05 to 20 J / cm 2, and more preferably 0.5 to 10 J / cm 2.
  • the wavelength of linearly polarized light is preferably 200 to 400 nm, and more preferably 300 to 400 nm.
  • the irradiation angle with respect to the film surface of linearly polarized light is not particularly limited, it is preferable from the viewpoint of shortening the alignment processing time that it is as perpendicular as possible to the film surface in order to develop a strong alignment regulating force for the liquid crystal.
  • the liquid crystal alignment film of the present invention can align liquid crystal in a direction perpendicular to the polarization direction of linearly polarized light by irradiating linearly polarized light.
  • the light applied to the film may be linearly polarized light or non-polarized light as described above.
  • the amount of light irradiated to the film is preferably 0.05 to 20 J / cm 2, particularly preferably 0.5 to 10 J / cm 2, and its wavelength is 250 to 400 nm. It is preferable that the thickness is 300 to 380 nm.
  • the irradiation angle of the light applied to the film with respect to the film surface is not particularly limited, but is preferably 30 to 60 degrees from the viewpoint of shortening the alignment processing time.
  • the light source used in the process of irradiating linearly polarized light or non-polarized light is ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, deep UV lamp, halogen lamp, metal halide lamp, high power metal halide lamp, xenon lamp, mercury.
  • a xenon lamp, an excimer lamp, a KrF excimer laser, a fluorescent lamp, an LED lamp, a sodium lamp, a microwave excitation electrodeless lamp, and the like can be used without limitation.
  • the liquid crystal alignment film of the present invention can be suitably obtained by a method further including other steps than the steps described above.
  • the liquid crystal alignment film of the present invention does not require a process of cleaning the film after baking or radiation irradiation with a cleaning liquid, but a cleaning process can be provided for convenience of other processes.
  • the cleaning liquid is pure water, various alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, xylene, halogen solvents such as methylene chloride, and ketones such as acetone and methyl ethyl ketone. Although it can be used, it is not limited to these. Of course, these cleaning liquids are sufficiently purified and have few impurities. Such a cleaning method can also be applied to the cleaning step in the formation of the liquid crystal alignment film of the present invention.
  • annealing treatment with heat or light can be used before or after the heating and baking step, before or after the rubbing step, or before or after irradiation with polarized or non-polarized radiation.
  • the annealing temperature is 30 to 180 ° C., preferably 50 to 150 ° C., and the time is preferably 1 minute to 2 hours.
  • the annealing light used for the annealing treatment include a UV lamp, a fluorescent lamp, and an LED lamp.
  • the amount of light irradiation is preferably 0.3 to 10 J / cm 2 .
  • the thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 to 300 nm, and more preferably 30 to 150 nm.
  • the film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as a step meter or an ellipsometer.
  • the liquid crystal alignment film of the present invention is characterized by a particularly large alignment anisotropy.
  • the magnitude of such anisotropy can be evaluated by a method using polarized IR described in JP-A-2005-275364. Further, as shown in the following examples, evaluation can also be made by a method using ellipsometry.
  • the retardation value of the liquid crystal alignment film can be measured by a spectroscopic ellipsometer. The retardation value of the film increases in proportion to the degree of orientation of the polymer main chain. That is, those having a large retardation value have a large degree of alignment, and when used as a liquid crystal alignment film, an alignment film having a greater anisotropy is considered to have a large alignment regulating force on the liquid crystal composition.
  • the liquid crystal alignment film of the present invention can be used for alignment control of an optical compensation material and all other liquid crystal materials, in addition to the alignment use of a liquid crystal composition for liquid crystal displays. Further, since the alignment film of the present invention has large anisotropy, it can be used alone for an optical compensator application.
  • liquid crystal display element of the present invention will be described in detail.
  • a pair of substrates disposed opposite to each other, an electrode formed on one or both of the surfaces facing each of the pair of substrates, and a surface facing each of the pair of substrates are formed.
  • a liquid crystal display element having a liquid crystal alignment film formed and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the alignment film of the present invention.
  • the electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate.
  • Examples of such electrodes include ITO and metal vapor deposition films.
  • the electrode may be formed on the entire surface of one surface of the substrate, or may be formed in a desired shape that is patterned, for example. Examples of the desired shape of the electrode include a comb shape or a zigzag structure.
  • the electrode may be formed on one of the pair of substrates, or may be formed on both substrates.
  • the form of electrode formation varies depending on the type of liquid crystal display element. For example, in the case of an IPS liquid crystal display element, an electrode is disposed on one of the pair of substrates, and in the case of other liquid crystal display elements, the electrodes of the pair of substrates are arranged. Electrodes are arranged on both sides.
  • the liquid crystal alignment film is formed on the substrate or electrode.
  • the liquid crystal layer is formed in such a manner that the liquid crystal composition is sandwiched between the pair of substrates facing each other on which the liquid crystal alignment film is formed.
  • a spacer such as fine particles or a resin sheet that is interposed between the pair of substrates to form an appropriate interval can be used as necessary.
  • the liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used.
  • Preferred liquid crystal compositions having a positive dielectric anisotropy include Japanese Patent No. 3086228, Japanese Patent No. 2635435, JP-A-5-501735, JP-A-8-157826, JP-A-8-231960, JP-A-9-241644 (EP8827272A1), Kaihei 9-302346 (EP806466A1); -204436, JP-A-10-231482, JP-A-2000-087040, JP-A-2001-48822, and the like.
  • a liquid crystal composition having a negative dielectric anisotropy will be described.
  • the negative dielectric anisotropy liquid crystal composition include a composition containing at least one liquid crystal compound selected from the group of liquid crystal compounds represented by the following formula (NL-1) as the first component.
  • R 1a and R 2a are independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or a carbon number in which at least one hydrogen is replaced by fluorine.
  • 2-12 alkenyl, ring A 2 and ring B 2 are independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1 , 4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-fluoro-3-chloro-1,4 - phenylene, a 2,3-difluoro-6-methyl-1,4-phenylene, 2,6-naphthalene-diyl or 7,8-difluoro-chroman-2,6-diyl, wherein the ring a 2 Contact At least one 2,3-difluoro-1,4-phenylene fine ring B 2, 2-fluoro-3-chloro-1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phen
  • Preferred ring A 2 and ring B 2 are each 2,3-difluoro-1,4-phenylene or tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and 1,2 for decreasing the viscosity. 4-cyclohexylene.
  • Desirable Z 1 is —CH 2 O— for increasing the dielectric anisotropy, and a single bond for decreasing the viscosity.
  • Preferred j is 1 for decreasing the lower limit temperature and 2 for increasing the upper limit temperature.
  • liquid crystal compound of the above formula (NL-1) include compounds represented by the following formulas (NL-1-1) to (NL-1-32).
  • R 1a and R 2a independently represent an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or a carbon number in which at least one hydrogen is replaced by fluorine.
  • 2-12 alkenyl, ring A 21 , ring A 22 , ring A 23 , ring B 21 , and ring B 22 are independently 1,4-cyclohexylene or 1,4-phenylene;
  • 11 and Z 12 are each independently a single bond, — (CH 2 ) 2 —, —CH 2 O—, or —COO—.
  • Desirable R 1a and R 2a are alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat, or alkoxy having 1 to 12 carbons for increasing the absolute value of dielectric anisotropy.
  • Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More desirable alkyl is ethyl, propyl, butyl, pentyl, or heptyl for decreasing the viscosity.
  • Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More desirable alkoxy is methoxy or ethoxy for decreasing the viscosity.
  • Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More desirable alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing the viscosity.
  • the preferred configuration of —CH ⁇ CH— in these alkenyls depends on the position of the double bond.
  • Trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity.
  • Cis is preferred for alkenyl such as 2-butenyl, 2-pentenyl, and 2-hexenyl.
  • linear alkenyl is preferable to branching.
  • alkenyl in which at least one hydrogen is replaced by fluorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro-4 -Pentenyl, and 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl and 4,4-difluoro-3-butenyl for decreasing the viscosity.
  • Desirable ring A 21 , ring A 22 , ring A 23 , ring B 21 , and ring B 22 are each 1,4-cyclohexylene for decreasing the viscosity.
  • Desirable Z 11 and Z 12 are —CH 2 O— for increasing the dielectric anisotropy, and a single bond for decreasing the viscosity.
  • a compound (NL-1) in which a liquid crystal composition having a negative dielectric anisotropy is preferably used as the first component is the compounds (NL-1-1), (NL-1-4), (NL-1-7). ) Or (NL-1-32).
  • liquid crystal composition having a negative dielectric anisotropy are disclosed in JP-A-57-114532, JP-A-2-4725, JP-A-4-224858, JP-A-8-40953, JP-A-8-104869, JP-A-8-104869.
  • JP-A-10-168453 JP-A-10-236989, JP-A-10-236990, JP-A-10-236992, JP-A-10-236993, JP-A-10-236994, JP-A-10-237000, JP-A-10- 237,004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075, JP-A-10-237076, JP-A-10-237448 (EP967261A1), JP-A-10-287874, JP-A-10-287875, JP-A-10-287875 -291945, JP-A-11-029581, JP 11-080049, JP 2000-256307, JP 2001-019965, JP 2001-072626, JP 2001-192657, JP 2010-037428, International Publication 2011/024666, International Publication 2010/072370, Special Table 2010. -537010, JP2012-0777
  • the liquid crystal composition used in the device of the present invention may further contain an additive from the viewpoint of improving the orientation, for example.
  • additives are photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerization initiators, polymerization inhibitors, and the like.
  • the photopolymerizable monomer or oligomer is desirably 0.01% by weight or more in order to exhibit the effect of determining the tilt direction of the liquid crystal after polymerization. Further, in order to make the orientation effect of the polymer after polymerization appropriate, or in order to avoid the unreacted monomer or oligomer from eluting into the liquid crystal after ultraviolet irradiation, the content is preferably 30% by weight or less.
  • An optically active compound is mixed with the composition for the purpose of inducing a helical structure of liquid crystal to give a twist angle.
  • examples of such compounds are from compound (PAC-1-1) to compound (PAC-1-4).
  • a desirable ratio of the optically active compound is 5% by weight or less. A more desirable ratio is in the range of 0.01% to 2% by weight.
  • an antioxidant is added to the liquid crystal composition. Mixed.
  • a preferred example of the antioxidant is a compound (AO-1) where w is an integer of 1 to 10.
  • preferred w is 1, 3, 5, 7, or 9. Further preferred w is 1 or 7.
  • the compound (AO-1) in which w is 1 has high volatility, it is effective in preventing a decrease in specific resistance due to heating in the atmosphere.
  • the compound (AO-1) in which w is 7 has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a high temperature after the device has been used for a long time.
  • a desirable ratio of the antioxidant is 50 ppm or more for achieving its effect, and is 600 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature.
  • a more desirable ratio is in the range of 100 ppm to 300 ppm.
  • the ultraviolet absorber examples include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines.
  • a desirable ratio in these absorbents and stabilizers is 50 ppm or more for obtaining the effect thereof, and 10,000 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of 100 ppm to 10,000 ppm.
  • a dichroic dye such as an azo dye or an anthraquinone dye is mixed with the composition so as to be adapted to a GH (Guest host) mode element.
  • a preferred ratio of the dye is in the range of 0.01% by weight to 10% by weight.
  • an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is mixed with the composition.
  • a desirable ratio of the antifoaming agent is 1 ppm or more for obtaining the effect thereof, and 1000 ppm or less for preventing a poor display.
  • a more desirable ratio is in the range of 1 ppm to 500 ppm.
  • a polymerizable compound can be mixed into the composition in order to adapt it to a PSA (polymer-sustained-alignment) mode device.
  • Preferred examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. Particularly preferred examples are acrylate or methacrylate derivatives. Examples of such compounds are compound (PM-2-1) to compound (PM-2-9).
  • a desirable ratio of the polymerizable compound is approximately 0.05% by weight or more for obtaining the effect thereof, and approximately 10% by weight or less for preventing a display defect. A more desirable ratio is in the range of approximately 0.1% by weight to approximately 2% by weight.
  • R 3a , R 4a , R 5a , and R 6a are independently acryloyl or methacryloyl
  • R 7a and R 8a are independently hydrogen, halogen, or alkyl having 1 to 10 carbons
  • Z 13 , Z 14 , Z 15 , and Z 16 are each independently a single bond or alkylene having 1 to 12 carbons, and at least one —CH 2 — is replaced by —O— or —CH ⁇ CH—.
  • S, t, and u are each independently 0, 1, or 2.
  • a polymerization initiator can be mixed as a substance necessary for easily generating radicals or ions and initiating a chain polymerization reaction.
  • Irgacure 651 registered trademark
  • Irgacure 184 registered trademark
  • Darocure 1173 registered trademark
  • the polymerizable compound preferably contains a photopolymerization initiator in the range of 0.1% to 5% by weight.
  • the photopolymerization initiator is contained in the range of 1% by weight to 3% by weight.
  • a polymerization inhibitor In a radical polymerization system, a polymerization inhibitor is mixed for the purpose of rapidly reacting with a radical generated from a polymerization initiator or monomer to change to a stable radical or neutral compound, and as a result, stop the polymerization reaction. Can do.
  • Polymerization inhibitors are classified into several structures. One is a radical that is itself stable, such as tri-p-nitrophenylmethyl, di-p-fluorophenylamine, and the other is a radical that is easily reacted with radicals present in the polymerization system. Typical examples include nitro, nitriso, amino, and polyhydroxy compounds. Representative examples of the latter include hydroquinone and dimethoxybenzene.
  • a desirable ratio of the polymerization inhibitor is 5 ppm or more for obtaining the effect thereof, and 1000 ppm or less for preventing a poor display. A more desirable ratio is in the range of 5 ppm to 500 ppm.
  • Contrast The contrast of the liquid crystal element described later was evaluated using a luminance meter (YOKOGAWA 3298F).
  • a liquid crystal display element was placed under a polarizing microscope in a crossed Nicol state, and the element was rotated and fixed at an angle at which transmitted light intensity, that is, luminance was minimized.
  • the luminance value in this state was defined as “black luminance”.
  • an arbitrary rectangular wave voltage was applied to the element, and the numerical value at which the luminance became maximum was defined as “white luminance”. This white luminance / black luminance value was defined as contrast. Contrast is less than 2500, poor, 2500 or more is good, and 3000 or more is judged to be the best.
  • DAAB 4,4′-diaminoazobenzene (compound of formula (I-3))
  • DDE 4,4′-diaminodiphenyl ether (unsubstituted compound in which X in formula (D-2) is —O—)
  • APDA 4,4′-N, N′-bis (4-aminophenyl) piperazine (unsubstituted compound of formula (D-3))
  • DDBU 4,4′-diaminodiphenylbutane (an unsubstituted compound in which X in formula (D-2) is — (CH 2 ) 4 —)
  • PDA 1,4-phenylenediamine (formula (D-1))
  • BABZP3 4,4 ′-((propane-1,3-diylbis (4,1-phenylene)) bis (methylene)) dianiline (formula (D-4-3))
  • NMP N-methyl-2-pyrrolidone
  • GBL ⁇ -butyrolactone
  • BC butyl cellosolve
  • BP 1-butoxy-2-propanol
  • EDM diethylene glycol ethyl methyl ether
  • DIBK diisobutyl ketone
  • DPE dipentyl ether
  • BDM diethylene glycol butyl methyl ether
  • EDP diethylene glycol ethyl Propyl ether
  • BDE Diethylene glycol butyl ethyl ether
  • PB-1 The weight average molecular weight of the polyamic acid contained in PB-1 was 50,000.
  • composition ratio (weight ratio) of the solvent used for dilution is NMP 0.067 g, BP 2.667 g, GBL 13.60 g, EDM 15.00 g, BDM 1.00 g, and DIBK 1.00 g.
  • Example 1 ⁇ Evaluation of ink jet discharge properties> Using a polyamic acid solution (PC-1) with a blended polymer solid concentration of 4% by weight as a liquid crystal aligning agent, an ink jet apparatus DMP-2831 manufactured by FUJIFILM Dimatix was used for a continuous discharge experiment for 60 minutes. Five nozzles were confirmed on the monitor, and nozzle clogging could not be confirmed for 60 minutes continuously (see FIG. 1).
  • this liquid crystal aligning agent was apply
  • Examples 2 to 28, Comparative Examples 1 to 8 Except that the polyamic acid solutions shown in Table 3 and Table 4 were used as the liquid crystal aligning agent, the ejection properties, in-plane unevenness and edge linearity were evaluated by the method according to Example 1. The results are shown in Table 5 together with Example 1.
  • Example 29 A polyamic acid solution (PC-1) having a polymer solid content concentration of 4% by weight prepared as a blend was used as a liquid crystal aligning agent, and this liquid crystal aligning agent was applied to a substrate with SiNx / ITO comb-teeth electrodes with a spinner. It applied to the attached glass substrate (height of spacer: 4 micrometers) with the inkjet coating apparatus (inkjet apparatus EB100XY100 made from Konica Minolta). The liquid crystal alignment film was adjusted to the following film thickness by adjusting the droplet interval and the cartridge applied voltage.
  • PC-1 polyamic acid solution having a polymer solid content concentration of 4% by weight prepared as a blend was used as a liquid crystal aligning agent, and this liquid crystal aligning agent was applied to a substrate with SiNx / ITO comb-teeth electrodes with a spinner. It applied to the attached glass substrate (height of spacer: 4 micrometers) with the inkjet coating apparatus (inkjet apparatus EB
  • the substrate was irradiated with ultraviolet linearly polarized light from the vertical direction through the polarizing plate.
  • the exposure energy at this time is 1.0 ⁇ 0.1 J / cm 2 at a wavelength of 365 nm when the amount of light is measured using a UV integrated light meter UIT-150 (receiver UVD-S365) manufactured by USHIO INC.
  • the exposure time was adjusted.
  • heat treatment was performed at 230 ° C. for 15 minutes in a clean oven (Espec Corp., PVHC-231) to form a liquid crystal alignment film having a thickness of 100 ⁇ 10 nm.
  • the substrate was irradiated with ultraviolet linearly polarized light from the vertical direction through the polarizing plate.
  • the exposure energy at this time is 1.0 ⁇ 0.1 J / cm 2 at a wavelength of 365 nm when the amount of light is measured using a UV integrated light meter UIT-150 (receiver UVD-S365) manufactured by USHIO INC.
  • the exposure time was adjusted.
  • the film was heat-treated at 230 ° C. for 15 minutes in a clean oven (Espec Corp., PVHC-231) to form an alignment film having a thickness of 100 ⁇ 10 nm.
  • Example 30 A polyamic acid solution (PD-1) having a polymer solid concentration of 4% by weight prepared as a blend was used as a liquid crystal aligning agent, and this liquid crystal aligning agent was applied to a substrate with SiNx / ITO comb-teeth electrodes with a spinner. It applied to the attached glass substrate (height of spacer: 4 micrometers) with the inkjet coating apparatus (inkjet apparatus EB100XY100 made from Konica Minolta). The liquid crystal alignment film was adjusted to the following film thickness by adjusting the droplet interval and the cartridge applied voltage. After the application, it was heated and dried at 70 ° C.
  • the substrate was irradiated with ultraviolet linearly polarized light from the vertical direction through the polarizing plate.
  • the exposure energy at this time is 1.0 ⁇ 0.1 J / cm 2 at a wavelength of 365 nm when the amount of light is measured using a UV integrated light meter UIT-150 (receiver UVD-S365) manufactured by USHIO INC.
  • the exposure time was adjusted.
  • heat treatment was performed at 230 ° C. for 15 minutes in a clean oven (Espec Corp., PVHC-231) to form a liquid crystal alignment film having a thickness of 100 ⁇ 10 nm.
  • the substrate was irradiated with ultraviolet linearly polarized light from the vertical direction through the polarizing plate.
  • the exposure energy at this time is 1.0 ⁇ 0.1 J / cm 2 at a wavelength of 365 nm when the amount of light is measured using a UV integrated light meter UIT-150 (receiver UVD-S365) manufactured by USHIO INC.
  • the exposure time was adjusted.
  • the film was heat-treated at 230 ° C. for 15 minutes in a clean oven (Espec Corp., PVHC-231) to form an alignment film having a thickness of 100 ⁇ 10 nm.
  • the same liquid crystal aligning agent as the FFS liquid crystal display element having the liquid crystal aligning film formed by drying, irradiating with ultraviolet rays, and heat-treating the coating film obtained by printing the liquid crystal aligning agent of the present invention on the substrate by the inkjet method is spin
  • an FFS liquid crystal display element having a liquid crystal alignment film formed by coating, coating, drying, ultraviolet irradiation, and heat treatment was compared in terms of the presence / absence of flow alignment, contrast, and AC afterimage, it was determined by the inkjet method.
  • the performance of the photo-alignment film obtained from the coating film was no different from that of the photo-alignment film obtained from the spin-coating coating film, and showed good cell characteristics.
  • BP20.0g was added to this reaction solution, and the polyamic acid solution whose polymer solid content concentration is 6 weight% was obtained.
  • This polyamic acid solution is designated as PB-7.
  • the weight average molecular weight of the polyamic acid contained in PB-7 was 48,000.
  • Table 7 shows the composition of the raw materials and the solvent.
  • composition ratio (weight ratio) of the solvent used for dilution is NMP 0.067 g, BP 2.667 g, GBL 13.60 g, EDM 15.00 g, BDM 1.00 g, and DIBK 1.00 g.
  • polyamic acids (PC-37) to (PC-40) one polyamic acid solution selected from polyamic acids (PA-6) to (PA-9) is used, and the polymer solid content concentration is as shown in Table 8. Dilution was carried out with various solvents so as to achieve a weight% of 5%.
  • the composition ratio of the polyamic acid solution and the solvent is shown in Table 8 together with PC-33.
  • Example 31 ⁇ Evaluation of ink jet discharge properties> Using a polyamic acid solution (PC-33) having a blended polymer solid concentration of 4% by weight as a liquid crystal aligning agent, a continuous discharge experiment was conducted for 60 minutes using an inkjet apparatus DMP-2831 manufactured by FUJIFILM Dimatix. Five nozzles were confirmed on the monitor, and clogging of the nozzles could not be confirmed for 60 minutes continuously.
  • PC-33 polyamic acid solution having a blended polymer solid concentration of 4% by weight
  • this liquid crystal aligning agent was apply
  • Example 32-42 Except that the polyamic acid solutions shown in Table 8 and Table 9 were used as the liquid crystal aligning agent, the ejection properties, in-plane unevenness and edge linearity were evaluated by the method according to Example 29. The results are shown in Table 10 together with Example 31.
  • liquid crystal aligning agent of the present invention can form a liquid crystal aligning film having good ejection properties, in-plane unevenness and edge linearity.
  • the liquid crystal aligning agent of this invention can be applied suitably in the model which requires a narrow frame.

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Abstract

La présente invention concerne un agent d'alignement de cristaux liquides qui contient au moins un polymère, qui est choisi dans le groupe comprenant des acides polyamides et des dérivés de ceux-ci, un premier solvant, qui est choisi dans le groupe comprenant du N-méthyl-2-pyrrolidone, du γ-butyrolactone et autre, un deuxième solvant, qui est choisi dans le groupe comprenant du butyl cellosolve, du 1-butoxy-2-propanol, de l'éther d'éthyle et de méthyle de diéthylène glycol et autre, un troisième solvant, qui est choisi dans le groupe comprenant du diisobutylcétone et de l'éther dipentylique, et un quatrième solvant, qui est choisi dans le groupe comprenant des composés représentés par la formule (1). L'utilisation de cet agent d'alignement de cristaux liquides dans la formation d'un film de revêtement pour un film d'alignement de cristaux liquides au moyen d'une impression par un procédé à jet d'encre présente des avantages tels qu'il est possible d'empêcher une irrégularité de stries dans le film de revêtement et que le film ne présente ni retrait, ni irrégularité de bord. R1O-(CH2CH2O)2-R2 (1) dans la formule (1), dans les cas où R1 est un groupe alkyle ayant 2 atomes de carbone, R2 est un groupe alkyle ayant 3 atomes de carbone, tandis que dans les cas où R1 est un groupe alkyle ayant 4 atomes de carbone, R2 est un groupe alkyle ayant 1 ou 2 atomes de carbone.
PCT/JP2015/082443 2014-11-21 2015-11-18 Agent d'alignement de cristaux liquides contenant un acide polyamide ou un dérivé de celui-ci, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides Ceased WO2016080458A1 (fr)

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KR1020167036427A KR20170089760A (ko) 2014-11-21 2015-11-18 폴리아믹산 또는 그 유도체를 포함하는 액정 배향제, 액정 배향막 및 액정 표시 소자
CN201580056596.XA CN107077031B (zh) 2014-11-21 2015-11-18 包含聚酰胺酸或其衍生物的液晶取向剂、液晶取向膜和液晶显示元件

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WO2018062353A1 (fr) * 2016-09-29 2018-04-05 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et dispositif d'affichage à cristaux liquides
WO2018155355A1 (fr) * 2017-02-24 2018-08-30 シャープ株式会社 Agent d'alignement de cristaux liquides, film d'alignement, et dispositif d'affichage à cristaux liquides
KR20200058281A (ko) 2018-11-19 2020-05-27 제이엔씨 주식회사 액정 배향막을 형성하기 위한 액정 배향제, 액정 배향막 및 이것을 사용한 액정 표시 소자
KR20220066246A (ko) 2019-09-24 2022-05-24 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
JP2022104391A (ja) * 2020-12-28 2022-07-08 株式会社カネカ 特定の組成を有するアミド酸オリゴマー、ワニス、硬化物、複合材料
KR20220166817A (ko) 2020-04-10 2022-12-19 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110462501B (zh) * 2016-12-28 2022-10-28 日产化学株式会社 液晶取向剂、液晶取向膜和液晶表示元件
KR102619748B1 (ko) * 2017-03-31 2023-12-29 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
CN111868617B (zh) * 2018-03-23 2023-09-12 日产化学株式会社 液晶取向剂、用于得到该液晶取向剂的聚合物、液晶取向膜、以及使用其的液晶显示元件
CN112194793B (zh) * 2019-07-08 2024-04-26 Jnc株式会社 聚酰胺酸组合物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009063797A (ja) * 2007-09-06 2009-03-26 Seiko Epson Corp 配向膜形成用組成物、液晶装置の製造方法
JP2009080454A (ja) * 2007-09-06 2009-04-16 Seiko Epson Corp 配向膜形成用組成物、液晶装置の製造方法
JP2009080156A (ja) * 2007-09-25 2009-04-16 Seiko Epson Corp 液晶配向膜形成用組成物及び液晶表示装置の製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5273357B2 (ja) * 2007-07-06 2013-08-28 Ｊｓｒ株式会社 液晶配向剤および液晶表示素子
JP5177150B2 (ja) * 2008-01-25 2013-04-03 日産化学工業株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
JP6056187B2 (ja) * 2012-05-09 2017-01-11 Jnc株式会社 光配向用液晶配向膜を形成するための液晶配向剤、液晶配向膜およびこれを用いた液晶表示素子

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009063797A (ja) * 2007-09-06 2009-03-26 Seiko Epson Corp 配向膜形成用組成物、液晶装置の製造方法
JP2009080454A (ja) * 2007-09-06 2009-04-16 Seiko Epson Corp 配向膜形成用組成物、液晶装置の製造方法
JP2009080156A (ja) * 2007-09-25 2009-04-16 Seiko Epson Corp 液晶配向膜形成用組成物及び液晶表示装置の製造方法

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017149796A (ja) * 2016-02-22 2017-08-31 富士ゼロックス株式会社 ポリイミド前駆体組成物、及びポリイミド前駆体組成物の製造方法
WO2018062353A1 (fr) * 2016-09-29 2018-04-05 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et dispositif d'affichage à cristaux liquides
JPWO2018062353A1 (ja) * 2016-09-29 2019-07-25 日産化学株式会社 液晶配向剤、液晶配向膜、及び液晶表示素子
JP7063270B2 (ja) 2016-09-29 2022-05-09 日産化学株式会社 液晶配向剤、液晶配向膜、及び液晶表示素子
WO2018155355A1 (fr) * 2017-02-24 2018-08-30 シャープ株式会社 Agent d'alignement de cristaux liquides, film d'alignement, et dispositif d'affichage à cristaux liquides
KR20200058281A (ko) 2018-11-19 2020-05-27 제이엔씨 주식회사 액정 배향막을 형성하기 위한 액정 배향제, 액정 배향막 및 이것을 사용한 액정 표시 소자
KR20220066246A (ko) 2019-09-24 2022-05-24 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
KR20220166817A (ko) 2020-04-10 2022-12-19 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
JP2022104391A (ja) * 2020-12-28 2022-07-08 株式会社カネカ 特定の組成を有するアミド酸オリゴマー、ワニス、硬化物、複合材料
JP7679005B2 (ja) 2020-12-28 2025-05-19 株式会社カネカ 特定の組成を有するアミド酸オリゴマー、ワニス、硬化物、複合材料

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