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WO2018159733A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

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

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WO2018159733A1
WO2018159733A1 PCT/JP2018/007686 JP2018007686W WO2018159733A1 WO 2018159733 A1 WO2018159733 A1 WO 2018159733A1 JP 2018007686 W JP2018007686 W JP 2018007686W WO 2018159733 A1 WO2018159733 A1 WO 2018159733A1
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liquid crystal
group
ppm
formula
carbon atoms
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PCT/JP2018/007686
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English (en)
Japanese (ja)
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司 藤枝
一平 福田
美希 豊田
雄介 山本
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日産化学株式会社
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Priority to CN202210301600.6A priority Critical patent/CN114609830B/zh
Priority to JP2019503096A priority patent/JP7096534B2/ja
Priority to CN201880028793.4A priority patent/CN110573952B/zh
Priority to KR1020197027969A priority patent/KR102588036B1/ko
Publication of WO2018159733A1 publication Critical patent/WO2018159733A1/fr
Priority to JP2022090434A priority patent/JP7409431B2/ja

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/76—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and etherified hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/90—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. amino-diphenylethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/32—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and esterified hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C229/62—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino groups and at least two carboxyl groups bound to carbon atoms of the same six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
    • C07C237/40—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having the nitrogen atom of the carboxamide group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J41/00—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring
    • C07J41/0033—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring not covered by C07J41/0005
    • C07J41/0088—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring not covered by C07J41/0005 containing unsubstituted amino radicals
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element, which are excellent in the ability to align liquid crystal vertically.
  • a liquid crystal display element of a method in which liquid crystal molecules aligned perpendicular to the substrate respond by an electric field also referred to as a vertical alignment (VA) method
  • VA vertical alignment
  • a photopolymerizable compound is previously added to the liquid crystal composition, and a polyimide-based vertical alignment film is used, and ultraviolet rays are applied while applying a voltage to the liquid crystal cell. Therefore, a technique for increasing the response speed of liquid crystal (PSA (Polymer Sustained Alignment) type element, for example, see Patent Document 1 and Non-Patent Document 1) is known.
  • PSA Polymer Sustained Alignment
  • the alignment film has a problem in that the ability to align the liquid crystal vertically decreases, and as a result, the obtained liquid crystal display element partially causes a display defect.
  • the liquid crystal alignment film and the column spacer come into contact with each other, and the liquid crystal alignment film is damaged, so that an alignment defect (bright spot) is generated in that portion.
  • a liquid crystal aligning agent having the following constitution, and completed the present invention. That is, the configuration of the present invention is as follows. 1. A liquid crystal containing at least one polymer selected from a polyimide precursor which is a reaction product of a diamine component containing a diamine represented by the following formula [1] and a tetracarboxylic acid component and a polyimide which is an imidized product thereof. Alignment agent.
  • X represents a single bond, —O—, —C (CH 3 ) 2 —, —NH—, —CO—, —NHCO—, —COO—, — (CH 2 ) m —, — It represents a divalent organic group composed of SO 2 — and any combination thereof, and m represents an integer of 1 to 8.
  • Y independently represents a structure of the following formula [1-1].
  • Y 1 and Y 3 each independently represent a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O— , -CONH-, -NHCO-, -COO-, and -OCO-.
  • Y 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15) (provided that Y 1 or Y 3 is a single bond, — (CH 2 ) a — 2 is a single bond, and Y 1 is at least one selected from the group consisting of —O—, —CH 2 O—, —CONH—, —NHCO—, —COO—, and —OCO—, and / or Or when Y 3 is at least one selected from the group consisting of —O—, —CH 2 O—, —CONH—, —NHCO—, —COO— and —OCO—, Y 2 is a single bond or — ( CH 2 ) b — (provided that when Y 1 is —CONH—, they are Y 2 and Y 3 single bonds)).
  • Y 4 represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton and a tocophenol skeleton
  • the optional hydrogen atom on the cyclic group includes an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkoxy group having 1 to 3 carbon atoms. Alternatively, it may be substituted with a fluorine atom.
  • Y 5 represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, a carbon number of 1 It may be substituted with 1 to 3 alkoxy groups, 1 to 3 fluorine-containing alkyl groups, 1 to 3 fluorine-containing alkoxy groups or fluorine atoms.
  • Y 6 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and 1 to 18 carbon atoms. And at least one selected from the group consisting of fluorine-containing alkoxy groups.
  • n represents an integer of 0 to 4.
  • a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film that does not deteriorate the ability to align liquid crystals vertically even when exposed to excessive heating.
  • a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film that does not deteriorate the ability to align liquid crystal vertically even when some foreign matter comes into contact with the film and is damaged.
  • a liquid crystal alignment film obtained from the liquid crystal alignment agent and a method for obtaining a liquid crystal alignment film using the liquid crystal alignment agent can be provided.
  • the liquid crystal aligning agent of the present invention contains a diamine represented by the above formula [1] (hereinafter, the “diamine represented by the above formula [1]” may be abbreviated as “specific diamine”). And at least one polymer selected from a polyimide precursor that is a reaction product with a tetracarboxylic acid component and a polyimide that is an imidized product thereof (hereinafter sometimes abbreviated as “specific polymer”).
  • the specific polymer contains a specific diamine, but may have a diamine other than the specific diamine.
  • the amount of the specific diamine and other diamines is such that the specific diamine is 5 mol% to 70 mol%, preferably 10 mol% to 50 mol%, more preferably 10 mol% to 40 mol% in the specific polymer. It is good.
  • the liquid crystal aligning agent of this invention may contain "polyimide which is a polyimide precursor and / or its imidized substance" other than a specific polymer.
  • specific diamine will be described, and then diamines other than “specific diamine” will be described.
  • X represents a single bond, —O—, —C (CH 3 ) 2 —, —NH—, —CO—, —NHCO—, —COO—, — (CH 2 ) m —, — It represents a divalent organic group composed of SO 2 — and any combination thereof, and m represents an integer of 1 to 8.
  • X is preferably a single bond, —O—, —NH—, —O— (CH 2 ) m —O—.
  • Y may be in the meta position or in the ortho position from the position of X, but is preferably in the ortho position. That is, the formula [1] is preferably the following formula [1 ′].
  • the position of “—NH 2 ” in the above formula [1] may be any position as shown in formula [1], but preferably the following formula [1] -a1, [1] -a2, [ 1] -a3 is preferable, and [1] -a1 is more preferable.
  • the above formula [1] may be any structure selected from the following formulas, preferably the formula [1] ] -A1-1 is preferable.
  • Y independently represents the structure of the following formula [1-1].
  • Y 1 and Y 3 each independently represent a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O— , -CONH-, -NHCO-, -COO-, and -OCO-.
  • Y 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15) (provided that Y 1 or Y 3 is a single bond, — (CH 2 ) a — 2 is a single bond, and Y 1 is at least one selected from the group consisting of —O—, —CH 2 O—, —CONH—, —NHCO—, —COO—, and —OCO—, and / or Or when Y 3 is at least one selected from the group consisting of —O—, —CH 2 O—, —CONH—, —NHCO—, —COO— and —OCO—, Y 2 is a single bond or — ( CH 2 ) b — (provided that when Y 1 is —CONH—, they are Y 2 and Y 3 single bonds)).
  • Y 4 represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton and a tocophenol skeleton
  • the optional hydrogen atom on the cyclic group includes an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkoxy group having 1 to 3 carbon atoms. Alternatively, it may be substituted with a fluorine atom.
  • Y 5 represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, a carbon number of 1 It may be substituted with 1 to 3 alkoxy groups, 1 to 3 fluorine-containing alkyl groups, 1 to 3 fluorine-containing alkoxy groups or fluorine atoms.
  • Y 6 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and 1 to 18 carbon atoms. And at least one selected from the group consisting of fluorine-containing alkoxy groups.
  • n represents an integer of 0 to 4.
  • Examples of the group represented by the above formula [1-1] include, but are not limited to, the following groups [1-1] -1 to [1-1] -22. Of these, [1-1] -1 to [1-1] -4, [1-1] -8, and [1-1] -10 are preferable. Note that * indicates the position of bonding with the phenyl group in the above formula [1], the above formula [1 '], the above formula [1] -a1 to the above formula [1] -a3. m represents an integer of 1 to 15, and n represents an integer of 0 to 18.
  • the polymer contained in the liquid crystal aligning agent of the present invention may have a photoreactive side chain.
  • the photoreactive side chain is possessed by “polyimide precursor and / or imidized product thereof” which is a polymer other than “specific polymer”, even if “specific polymer” has. May be.
  • ⁇ Diamine containing photoreactive side chain> In order to introduce a photoreactive side chain into a polymer other than the “specific polymer” and / or “specific polymer”, a diamine having a photoreactive side chain is used as a part of the diamine component. Good. Examples of the diamine having a photoreactive side chain include, but are not limited to, a diamine having a side chain represented by Formula [VIII] or Formula [IX].
  • the bonding positions of the two amino groups (—NH 2 ) in Formula [VIII] and Formula [IX] are not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.
  • R 8 , R 9 and R 10 in formula [VIII] are as follows. That is, R 8 is a single bond, —CH 2 —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ). —, —CON (CH 3 ) —, or —N (CH 3 ) CO— is represented.
  • R 8 is preferably a single bond, —O—, —COO—, —NHCO—, or —CONH—.
  • R 9 represents a single bond or an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, and —CH 2 — in the alkylene group is optionally substituted with —CF 2 — or —CH ⁇ CH—. If any of the following groups are not adjacent to each other, these groups may be substituted; —O—, —COO—, —OCO—, —NHCO—, —CONH—, — NH-, divalent carbocyclic or heterocyclic ring. Specific examples of the divalent carbocycle or heterocycle include, but are not limited to, the following.
  • R 9 can be formed by a general organic synthetic method, but a single bond or an alkylene group having 1 to 12 carbon atoms is preferable from the viewpoint of ease of synthesis.
  • R 10 represents a photoreactive group selected from the following formulae.
  • R 10 is preferably a methacryl group, an acryl group or a vinyl group from the viewpoint of photoreactivity.
  • Y 1 represents —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, or —CO—.
  • Y 2 is an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are fluorine atoms or organic It may be substituted with a group.
  • Y 2 when the following groups are not adjacent to each other, —CH 2 — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—.
  • Y 3 represents —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—, or a single bond.
  • Y 4 represents a cinnamoyl group.
  • Y 5 is a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are fluorine atoms Alternatively, it may be substituted with an organic group.
  • —CH 2 — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—.
  • Y 6 represents a photopolymerizable group which is an acrylic group or a methacryl group.
  • X 9 and X 10 are each independently a single bond, a bonding group that is —O—, —COO—, —NHCO—, or —NH—, and Y may be substituted with a fluorine atom Represents an alkylene group having 1 to 20 carbon atoms.
  • examples of the diamine having a photoreactive side chain include a diamine having a group causing a photodimerization reaction and a group causing a photopolymerization reaction represented by the following formula in the side chain.
  • Y 1 to Y 6 are the same as defined above.
  • the diamine having a photoreactive side chain depends on the liquid crystal alignment property when it is used as a liquid crystal alignment film, the pretilt angle, the voltage holding property, the characteristics such as accumulated charge, the response speed of the liquid crystal when it is used as a liquid crystal display device, etc. 1 type or 2 types or more can be mixed and used.
  • the diamine having a photoreactive side chain is preferably used in an amount of 10 to 70 mol%, more preferably 20 to 60 mol%, particularly preferably 30 to 50 mol% of the diamine component used for the synthesis of the polyamic acid. It is.
  • the diamine having a photoreactive side chain include a diamine having a side chain having a site having a radical generating structure that is decomposed by ultraviolet irradiation to generate radicals.
  • Ar, R 1 , R 2 , T 1 , T 2 , S and Q in the above formula (1) have the following definitions. That is, Ar represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, in which an organic group may be substituted, and a hydrogen atom may be substituted with a halogen atom.
  • R 1 and R 2 are each independently an alkyl or alkoxy group having 1 to 10 carbon atoms.
  • T1 and T2 are each independently a single bond or —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ) —, It is a bonding group of —CON (CH 3 ) — and —N (CH 3 ) CO—.
  • S is a single bond, unsubstituted or an alkylene group having 1 to 20 carbon atoms substituted by a fluorine atom.
  • the alkylene group —CH 2 — or —CF 2 — may be optionally replaced with —CH ⁇ CH—, and when any of the following groups is not adjacent to each other, these groups are replaced with these groups: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocycle, and a divalent heterocycle.
  • Q is a structure selected from the following (in the structural formula, R represents water, an elementary atom, or an alkyl group having 1 to 4 carbon atoms, and R 3 represents —CH 2 —, —NR—, —O—, or —S Represents-).
  • Ar to which carbonyl is bonded is involved in the absorption wavelength of ultraviolet rays. Therefore, when the wavelength is increased, a structure having a long conjugate length such as naphthylene or biphenylene is preferable.
  • Ar may be substituted with a substituent, and the substituent is preferably an electron-donating organic group such as an alkyl group, a hydroxyl group, an alkoxy group, and an amino group.
  • R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group, or a phenethyl group. In the case of an alkyl group or an alkoxy group, R 1 and R 2 are May be formed.
  • Q is preferably an electron donating organic group, and the above group is preferable.
  • Q is an amino derivative
  • the diaminobenzene in the formula (1) may have any structure of o-phenylenediamine, m-phenylenediamine, or p-phenylenediamine. However, in terms of reactivity with acid dianhydride, m-phenylenediamine, or p-Phenylenediamine is preferred.
  • n is an integer of 2 to 8.
  • a diamine other than the specific diamine represented by the formula [1] (hereinafter also referred to as other diamine) may be contained.
  • Such a diamine is represented by the following general formula [2].
  • Other diamines may be used alone or in combination of two or more.
  • a 1 and A 2 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms. It is. From the viewpoint of monomer reactivity, A 1 and A 2 are preferably a hydrogen atom or a methyl group.
  • An example of the structure of Y 1 is as follows.
  • n is an integer of 1 to 6 unless otherwise specified.
  • Boc represents a tert-butoxycarbonyl group.
  • diamine components used in the liquid crystal aligning agent of the present invention are not particularly limited, but (Y-7), (Y-8), from the viewpoints of coatability, voltage holding ratio characteristics, residual DC voltage characteristics, and the like.
  • (Y-16), (Y-17), (Y-21), (Y-22), (Y-28), (Y-37), (Y-38), (Y-60), (Y -67), (Y-68), (Y-71) to (Y-73), and (Y-160) to (Y-180) are particularly preferably selected and used in combination.
  • tetracarboxylic acid component examples include tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, and tetracarboxylic acid dialkyl ester dihalide. Then, these are also collectively referred to as a tetracarboxylic acid component.
  • tetracarboxylic acid component examples include tetracarboxylic dianhydride and its derivatives, tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, and tetracarboxylic acid dialkyl ester dihalide (collectively, 1 tetracarboxylic acid component).
  • tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides. Specific examples of these include the following groups [1] to [5].
  • aliphatic tetracarboxylic dianhydride for example, 1,2,3,4-butanetetracarboxylic dianhydride;
  • Examples of alicyclic tetracarboxylic dianhydrides include acid dianhydrides such as the following formulas (X1-1) to (X1-13),
  • R 3 to R 23 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, carbon An alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, which may be the same or different,
  • R M represents a hydrogen atom or a methyl group
  • Xa is a tetravalent organic group represented by the following formulas (Xa-1) to (Xa-7).
  • aromatic tetracarboxylic dianhydrides for example, pyromellitic anhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic Acid dianhydrides, acid dianhydrides represented by the following formulas (Xb-1) to (Xb-10), and the like, and
  • the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.
  • the tetracarboxylic dianhydride component used in the liquid crystal aligning agent of the present invention is not particularly limited, but from the viewpoints of coatability, voltage holding ratio characteristics, residual DC voltage characteristics, etc., (X1-1), (X1- 2), (X1-3), (X1-6), (X1-7), (X1-8), (X1-9), (Xa-2), pyromellitic anhydride, 3,3 ′, It is preferable to select and use a tetracarboxylic dianhydride selected from 4,4′-diphenylsulfonetetracarboxylic dianhydride, (Xb-6) and (Xb-9).
  • the method for producing these polymers is usually obtained by reacting a diamine component and a tetracarboxylic acid component.
  • a polyamic acid is obtained by reacting at least one tetracarboxylic acid component selected from the group consisting of a tetracarboxylic dianhydride and a derivative of the tetracarboxylic acid and a diamine component composed of one or more diamines.
  • a method is mentioned. Specifically, a method is used in which polycarboxylic acid is obtained by polycondensation of tetracarboxylic dianhydride and primary or secondary diamine.
  • a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group with a primary or secondary diamine, a tetracarboxylic acid dihalide obtained by halogenating a carboxylic acid group and a primary a method of polycondensation with a secondary diamine or a method of converting a carboxy group of a polyamic acid into an ester is used.
  • polyimide a method is used in which the polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.
  • the reaction of the diamine component and the tetracarboxylic acid component is usually performed in a solvent.
  • the solvent used at that time is not particularly limited as long as the produced polyimide precursor is soluble. Although the specific example of the solvent used for reaction below is given, it is not limited to these examples. Examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolidinone. It is done.
  • the solvent solubility of the polyimide precursor is high, it is represented by methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3]. Can be used.
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • D-3 represents an alkyl group having 1 to 4 carbon atoms.
  • solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use it for the said solvent in the range which the produced
  • diamine components or tetracarboxylic acid components when reacting using a plurality of diamine components or tetracarboxylic acid components, they may be reacted in a premixed state, individually or sequentially, or further individually reacted low molecular weight substances. May be mixed and reacted to form a polymer.
  • the temperature for polycondensation of the diamine component and the tetracarboxylic acid component can be selected from -20 to 150 ° C., but is preferably in the range of ⁇ 5 to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. . Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial reaction is carried out at a high concentration, and then a solvent can be added.
  • the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor formed increases as the molar ratio approaches 1.0.
  • Polyimide is a polyimide obtained by ring closure of the polyimide precursor, and in this polyimide, the ring closure rate (also referred to as imidation rate) of the amic acid group is not necessarily 100%. It can be adjusted as desired.
  • the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is, or catalytic imidization in which a catalyst is added to the polyimide precursor solution.
  • the temperature when the polyimide precursor is thermally imidized in a solution is 100 to 400 ° C., preferably 120 to 250 ° C., and a method of removing water generated by the imidation reaction from the system is preferable.
  • the catalytic imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amidic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amido group. 30 mole times.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has a basicity suitable for advancing the reaction.
  • the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. In particular, it is preferable to use acetic anhydride because purification after completion of the reaction is easy.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the reaction solution may be poured into a solvent and precipitated.
  • the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water.
  • the polymer precipitated in the solvent can be recovered by filtration, and then dried at normal temperature or under reduced pressure at room temperature or by heating.
  • the solvent at this time include alcohols, ketones, hydrocarbons and the like. It is preferable to use three or more kinds of solvents selected from these, since the purification efficiency is further increased.
  • More specific methods for producing the polyamic acid alkyl ester of the present invention are shown in the following (1) to (3).
  • (1) Method of producing by polyamic acid esterification reaction Polyamic acid is produced from a diamine component and a tetracarboxylic acid component, and the carboxy group (COOH group) is subjected to a chemical reaction, that is, an esterification reaction.
  • This is a method for producing an alkyl ester.
  • the esterification reaction is a method in which a polyamic acid and an esterifying agent are reacted at ⁇ 20 to 150 ° C. (preferably 0 to 50 ° C.) for 30 minutes to 24 hours (preferably 1 to 4 hours) in the presence of a solvent. is there.
  • the esterifying agent is preferably one that can be easily removed after the esterification reaction.
  • N N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl -3-p-tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like.
  • the amount of the esterifying agent used is preferably 2 to 6 molar equivalents per 1 mol of the polyamic acid repeating unit. Of these, 2 to 4 molar equivalents are preferred.
  • the solvent used for the esterification reaction examples include a solvent used for the reaction of the diamine component and the tetracarboxylic acid component from the viewpoint of solubility of the polyamic acid in the solvent.
  • a solvent used for the reaction of the diamine component and the tetracarboxylic acid component from the viewpoint of solubility of the polyamic acid in the solvent.
  • N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone is preferable.
  • These solvents may be used alone or in combination of two or more.
  • the concentration of the polyamic acid in the solvent in the esterification reaction is preferably 1 to 30% by mass from the viewpoint that the polyamic acid does not easily precipitate. Among these, 5 to 20% by mass is preferable.
  • the diamine component and tetracarboxylic acid diester dichloride are ⁇ 20 to 150 ° C. (preferably in the presence of a base and a solvent) (0 to 50 ° C.) for 30 minutes to 24 hours (preferably 1 to 4 hours).
  • a base pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used. Of these, pyridine is preferable because the reaction proceeds gently.
  • the amount of the base used is preferably an amount that can be easily removed after the reaction, and is preferably 2 to 4 moles relative to the tetracarboxylic acid diester dichloride. Of these, 2 to 3 moles are more preferred.
  • the solvent examples include a solvent used for the reaction of the diamine component and the tetracarboxylic acid component from the viewpoint of solubility of the obtained polymer, that is, the polyamic acid alkyl ester in the solvent.
  • a solvent used for the reaction of the diamine component and the tetracarboxylic acid component from the viewpoint of solubility of the obtained polymer, that is, the polyamic acid alkyl ester in the solvent.
  • N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone is preferable.
  • These solvents may be used alone or in combination of two or more.
  • the concentration of the polyamic acid alkyl ester in the solvent in the reaction is preferably 1 to 30% by mass from the viewpoint that precipitation of the polyamic acid alkyl ester hardly occurs. Among these, 5 to 20% by mass is preferable.
  • the solvent used for preparing the polyamic acid alkyl ester is dehydrated as much as possible. Furthermore, the reaction is preferably performed in a nitrogen atmosphere to prevent outside air from being mixed.
  • Condensation agents include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazinyl Methylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like can be used.
  • the amount of the condensing agent used is preferably 2 to 3 moles, and more preferably 2 to 2.5 moles, based on
  • tertiary amines such as pyridine and triethylamine can be used.
  • the amount of the base used is preferably an amount that can be easily removed after the polycondensation reaction, preferably 2 to 4 times by mole, more preferably 2 to 3 times by mole with respect to the diamine component.
  • the solvent used for the polycondensation reaction include a solvent used for the reaction of the diamine component and the tetracarboxylic acid component from the viewpoint of the solubility of the resulting polymer, that is, the polyamic acid alkyl ester, in the solvent.
  • N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone is preferable.
  • These solvents may be used alone or in combination of two or more.
  • the reaction proceeds efficiently by adding Lewis acid as an additive.
  • Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
  • the amount of Lewis acid used is preferably 0.1 to 10 times the mole of the diamine component. Among these, 2.0 to 3.0 moles are preferable.
  • the reaction solution may be poured into a solvent and precipitated.
  • the solvent used for precipitation include water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, toluene and the like.
  • the polymer deposited in the solvent is preferably washed with the solvent several times for the purpose of removing the additives and catalysts used above. After washing, filtration and recovery, the polymer can be dried at normal temperature or reduced pressure at room temperature or with heating.
  • the impurities in the polymer can be reduced by re-dissolving the polymer recovered by precipitation in a solvent and repeating the operation of re-precipitation recovery 2 to 10 times.
  • the production method of (2) or (3) above is preferable for the polyamic acid alkyl ester.
  • the liquid crystal aligning agent of this invention contains the above-mentioned specific polymer, Preferably it is a solution for forming a liquid crystal aligning film.
  • the content of the polymer in the liquid crystal aligning agent is preferably 2 to 10% by mass and more preferably 3 to 8% by mass in the liquid crystal aligning agent.
  • All the polymer components in the liquid crystal aligning agent of the present invention may all be the specific polymer of the present invention, or other polymers may be mixed.
  • examples of other polymers include cellulose polymers, acrylic polymers, methacrylic polymers, polystyrenes, polyamides, polysiloxanes, etc., in addition to polyimides and polyimide precursors.
  • the content of the other polymer is preferably 1 to 90% by mass and more preferably 30 to 80% by mass in the resin component contained in the liquid crystal aligning agent.
  • the good solvent used for the liquid crystal aligning agent of this invention will not be specifically limited if the specific polymer of this invention melt
  • the specific example of the solvent used for a liquid crystal aligning agent below is given, it is not limited to these examples. Examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolidinone. It is done.
  • the solvent solubility of the polyimide precursor is high, it is represented by methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the above formula [D-1] to formula [D-3].
  • the solvent used can also be used.
  • the said good solvent may be used by 1 type, and may be used by the combination and ratio which are more suitable according to the application
  • the good solvent in the liquid crystal aligning agent of the present invention is preferably 20 to 99% by mass of the whole solvent contained in the liquid crystal aligning agent. Of these, 20 to 90% by mass is preferable. More preferred is 30 to 80% by mass.
  • the liquid crystal aligning agent of this invention can use the solvent (it is also called a poor solvent) which improves the coating property and surface smoothness of a liquid crystal aligning film at the time of apply
  • the solvent it is also called a poor solvent
  • Specific examples are given below.
  • ethanol isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octan
  • preferred solvent combinations include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, ⁇ -butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and ⁇ - Butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N- Methyl-2-pyrrolidone, ⁇ -butyrolactone, propylene glycol monobutyl ether, 2,6-dimethyl-4-heptanone, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, and propylene glycol Monobutyl ether and diisopropyl ether, N-methyl
  • These poor solvents are preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass with respect to the total solvent contained in the liquid crystal aligning agent.
  • the kind and content of such a solvent are appropriately selected according to the application device, application conditions, application environment, and the like of the liquid crystal aligning agent.
  • the liquid crystal aligning agent of the present invention includes a polymer other than the polymer described in the present invention, a dielectric for the purpose of changing electrical properties such as dielectric constant and conductivity of the liquid crystal aligning film, Silane coupling agent for the purpose of improving adhesion to the substrate, crosslinkable compound for the purpose of increasing the hardness and density of the liquid crystal alignment film, and heating of the polyimide precursor when the coating film is baked
  • a dielectric for the purpose of changing electrical properties such as dielectric constant and conductivity of the liquid crystal aligning film
  • Silane coupling agent for the purpose of improving adhesion to the substrate
  • crosslinkable compound for the purpose of increasing the hardness and density of the liquid crystal alignment film
  • An imidization accelerator for the purpose of efficiently proceeding imidization by the above may be contained.
  • Examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include a functional silane-containing compound and an epoxy group-containing compound, such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl- 3-aminopropyl
  • additives may be added to the liquid crystal aligning agent of the present invention in order to increase the mechanical strength of the liquid crystal aligning film.
  • the above-mentioned additive is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. If the amount is less than 0.1 parts by mass, the effect cannot be expected. If the amount exceeds 30 parts by mass, the orientation of the liquid crystal is lowered.
  • the liquid crystal alignment film of the present invention can be formed by applying the liquid crystal aligning agent of the present invention on a substrate and baking it.
  • the cured film obtained by baking can also be used as a liquid crystal aligning film as it is.
  • the cured film is rubbed, irradiated with polarized light or light of a specific wavelength, or treated with an ion beam, or a voltage is applied to the liquid crystal display element after filling the liquid crystal as a PSA alignment film It is also possible to irradiate with UV. In particular, it is useful to use as an alignment film for PSA.
  • the substrate to be used is not particularly limited as long as it is a highly transparent substrate.
  • Glass plate polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone ,
  • Plastic substrates such as trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose can be used.
  • a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplifying the process.
  • an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
  • the method for applying the liquid crystal aligning agent is not particularly limited, and examples thereof include printing methods such as screen printing, offset printing, flexographic printing, ink jet method, spray method, roll coating method, dip, roll coater, slit coater, and spinner. From the standpoint of productivity, the transfer printing method is widely used industrially, and is preferably used in the present invention.
  • the coating film formed by applying the liquid crystal aligning agent by the above method can be baked to obtain a cured film.
  • the drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, the drying process is performed. It is preferable.
  • the drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like. For example, a method of drying on a hot plate at a temperature of 40 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C., for 0.5 minutes to 30 minutes, preferably 1 minute to 5 minutes.
  • the baking temperature of the coating film formed by applying the liquid crystal aligning agent is not limited, and is, for example, 100 to 350 ° C, preferably 120 to 350 ° C, and more preferably 150 ° C to 330 ° C.
  • the firing time is 5 minutes to 240 minutes, preferably 10 minutes to 90 minutes, and more preferably 10 minutes to 30 minutes. Heating can be performed by a generally known method such as a hot plate, a hot air circulating furnace, an infrared furnace, or the like.
  • the thickness of the liquid crystal alignment film obtained by firing is not particularly limited, but is preferably 5 to 300 nm, more preferably 20 to 200 nm.
  • the liquid crystal display element can produce a liquid crystal cell by a known method after forming a liquid crystal alignment film on a substrate by the above method.
  • the two substrates disposed so as to face each other, the liquid crystal layer provided between the substrates, and the liquid crystal alignment agent provided between the substrate and the liquid crystal layer are formed by the above-described liquid crystal display element.
  • the polymerizable compound contained in the liquid crystal is reacted by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer.
  • a PSA type liquid crystal display element having a remarkably excellent vertical alignment ability is obtained.
  • the substrate of the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate in which a transparent electrode for driving liquid crystal is formed on the substrate.
  • a substrate provided with a conventional electrode pattern or protrusion pattern may be used.
  • the liquid crystal aligning agent containing the polyimide polymer of the present invention is used. It is possible to operate even in a structure in which a line / slit electrode pattern of 1 to 10 ⁇ m is formed and no slit pattern or protrusion pattern is formed on the counter substrate.
  • the liquid crystal display element of this structure simplifies the manufacturing process. And high transmittance can be obtained.
  • a high-performance element such as a TFT type element
  • an element in which an element such as a transistor is formed between an electrode for driving a liquid crystal and a substrate is used.
  • a transmissive liquid crystal display element it is common to use a substrate as described above.
  • an opaque substrate such as a silicon wafer may be used. Is possible.
  • a material such as aluminum that reflects light may be used for the electrode formed on the substrate.
  • the liquid crystal material constituting the liquid crystal layer of the liquid crystal display element is not particularly limited, and the liquid crystal material used in the conventional vertical alignment method, for example, negative types such as MLC-6608, MLC-6609, MLC-3023 manufactured by Merck The liquid crystal can be used.
  • the PSA type liquid crystal display element for example, a polymerizable compound-containing liquid crystal represented by the following formula can be used.
  • a known method can be exemplified. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one substrate so that the surface on which the liquid crystal alignment film is formed is on the inside. Then, the other substrate is bonded, and liquid crystal is injected under reduced pressure to seal.
  • a liquid crystal cell can also be produced by a method in which the other substrate is bonded to each other so as to be inside, and sealing is performed.
  • the thickness of the spacer is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
  • the step of producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer includes, for example, applying an electric field between the electrodes installed on the substrate to apply an electric field to the liquid crystal alignment film and the liquid crystal layer. And applying ultraviolet rays while maintaining this electric field.
  • the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p.
  • the irradiation amount of ultraviolet rays is, for example, 1 to 60 J, preferably 40 J or less, and the smaller the irradiation amount of ultraviolet rays, the lowering of reliability caused by the destruction of the members constituting the liquid crystal display element can be suppressed, and the irradiation time of ultraviolet rays can be reduced. This is preferable because the manufacturing efficiency is increased.
  • the polymerizable compound when ultraviolet rays are irradiated while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, the polymerizable compound reacts to form a polymer, and the direction in which the liquid crystal molecules are tilted is stored by this polymer.
  • the response speed of the obtained liquid crystal display element can be increased.
  • a polyimide precursor having a side chain for vertically aligning liquid crystal and a photoreactive side chain when irradiated with ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, and the polyimide precursor as an imide Since the photoreactive side chains of at least one polymer selected from the polyimide obtained by the reaction or the photoreactive side chains of the polymer react with the polymerizable compound, the liquid crystal display element obtained The response speed can be increased.
  • W-A1 Compound W-A2 represented by the formula [W-A1]: Compound W-A3 represented by the formula [W-A2]: Compound W-A4 represented by the formula [W-A3]: Formula Compound W-A5 represented by [W-A4]: Compound W-A6 represented by formula [W-A5]: Compound W-A7 represented by formula [W-A6]: Formula [W-A7]
  • A1 Compound represented by Formula [A1]
  • A2 Compound represented by Formula [A2]
  • A3 Compound represented by Formula [A3]
  • (Tetracarboxylic acid component) D1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • D2 bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride
  • D3 pyromellitic dianhydride
  • D4 2,3,5-tricarboxycyclopentyl acetic acid dianhydride
  • D5 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride
  • the molecular weight of the polyimide precursor and polyimide is as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK) and a column (KD-803, KD-805) (manufactured by Shodex). It measured as follows.
  • the imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated
  • Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
  • x is a proton peak integrated value derived from NH group of amic acid
  • y is a peak integrated value of reference proton
  • ⁇ is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.
  • the viscosity of the polyimide polymer is an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), a sample amount of 1.1 mL, a cone rotor TE-1 (1 ° 34 ′, R24), measured at a temperature of 25 ° C.
  • W-A1 to W-A3 and W-A4 to W-A10 are novel compounds that have not been disclosed yet, and the synthesis method will be described in detail below.
  • the products described in Synthesis Examples 1 to 3 and Synthesis Examples 4 to 10 were identified by 1 H-NMR analysis (analysis conditions are as follows).
  • activated carbon brand: special white birch, 2.27 g
  • the obtained filtrate was concentrated under reduced pressure to obtain an oily compound.
  • the oily compound was dispersed in hexane (100 g), crystals were precipitated under dry ice / ethanol cooling conditions, filtered and dried to obtain compound [8] (yield: 27.5 g, 101 mmol, yield: 75%).
  • the obtained concentrate was crystallized from ethyl acetate (346 g) and hexane (395 g) and filtered to collect crystals. Further, the filtrate was concentrated, recrystallized and filtered again with chloroform (223 g) and hexane (434 g), and dried to obtain a crude product of compound [16] (crude yield: 21.3 g, crude yield). : 37%).
  • NMP (28.2 g) was added to the polyimide powder (1) (3.00 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 24 hours.
  • NMP (g) and BCS (18.8 g) were added to this solution, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (V-1).
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 2> and ⁇ Example 3> In Example 1, using the polyimide powders (2) and (3) in place of the polyimide powder (1), the liquid crystal aligning agents (V-2) and (V-3) were prepared in the same procedure as in Example 1. Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 1 In Example 1, using the polyimide powder (4) obtained in Control Synthesis Example 1 instead of the polyimide powder (1), the liquid crystal aligning agent (V-4) was obtained by the same procedure as in Example 1. It was. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 4 3.0 g of the liquid crystal aligning agent (V-1) obtained from Example 1 was mixed as the first component, and 7.0 g of the liquid crystal aligning agent (V-4) obtained in Control 1 was mixed as the second component.
  • the liquid crystal aligning agent (V-5) was obtained by stirring for 1 hour.
  • Example 4 using the liquid crystal aligning agent (V-2) or (V-3) instead of the liquid crystal aligning agent (V-1) as the first component, respectively, by the same procedure as in Example 4, respectively. Liquid crystal aligning agents (V-6) and (V-7) were obtained.
  • NMP (22.0 g) was added to the polyimide powder (5) (3.00 g) obtained in Synthesis Example 5, and dissolved by stirring at 70 ° C. for 24 hours.
  • 3.0 g of E2 (1 wt% NMP solution) and BCS (20.0 g) were added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (V-8).
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
  • NEP (22.0 g) was added to the polyimide powder (12) (3.00 g) obtained in Synthesis Example 12, and dissolved by stirring at 70 ° C. for 24 hours.
  • NEP (3.0 g) and BCS (20.0 g) were added to this solution, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (V-15).
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.
  • Example 18 For the polyimide powder (16) obtained in Synthesis Example 16, the same operation as in Example 14 was performed to obtain a liquid crystal alignment film treating agent (V-19).
  • Example 21 > 3.0 g of the liquid crystal aligning agent (V-15) obtained from Example 14 as the first component, 7.0 g of the liquid crystal aligning agent (V-19) obtained in Example 18 as the second component, The cross-linking agent E1 was mixed at 5% by weight with respect to the resin component in the liquid crystal alignment film agent, and stirred for 1 hour to obtain a liquid crystal aligning agent (W-2).
  • Example 22 to 24 Liquid crystal alignment agents (W-3) to (W-5) were obtained in the same manner as in Example 21 for the liquid crystal alignment agents (V-16) to (V-21) obtained in Examples 15 to 20. It was.
  • liquid crystal aligning agent obtained in the examples Using the liquid crystal aligning agent obtained in the examples and the liquid crystal aligning agent obtained in the comparative example, production of a liquid crystal display element, evaluation of vertical alignment, scratch test, evaluation of pretilt angle, evaluation of voltage holding ratio Afterimage characteristics were evaluated.
  • the liquid crystal aligning agent obtained in the examples and the liquid crystal aligning agent obtained in the comparative example were subjected to pressure filtration with a membrane filter having a pore diameter of 1 ⁇ m.
  • the obtained solution was spin-coated on an ITO surface of a 40 mm ⁇ 30 mm ITO electrode glass substrate (length: 40 mm, width: 30 mm, thickness: 1.1 mm) washed with pure water and IPA (isopropyl alcohol), Heat treatment was performed on a hot plate at 70 ° C. for 90 seconds and in a heat circulation type clean oven at 230 ° C. for 30 minutes to obtain an ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm.
  • Liquid crystal MLC-3023 (trade name, manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal cell. After that, in the state where a DC voltage of 15 V was applied to the obtained liquid crystal cell, ultraviolet light passing through a band pass filter with a wavelength of 365 nm was irradiated at 15 J / cm 2 using an ultraviolet irradiation device using a high pressure mercury lamp as a light source. Thus, a vertically aligned liquid crystal display element was obtained. The UV irradiation amount was measured by connecting a UV-35 light receiver to UV-M03A manufactured by ORC.
  • the liquid crystal aligning agent obtained in the examples was filtered under pressure through a membrane filter having a pore diameter of 1 ⁇ m.
  • the obtained solution was washed with pure water and IPA (isopropyl alcohol), and an ITO electrode substrate (vertical: 35 mm, horizontal: 30 mm) on which an ITO electrode pattern having a pixel size of 200 ⁇ m ⁇ 600 ⁇ m and a line / space of 3 ⁇ m was formed.
  • Thickness 0.7 mm
  • ITO electrode substrate on which the ITO electrode pattern is formed is divided into four in a cross checker (checkered) pattern, and can be driven separately for each of the four areas.
  • the periphery was coated with a sealant (XN-1500T manufactured by Mitsui Chemicals).
  • a sealant XN-1500T manufactured by Mitsui Chemicals.
  • Liquid crystal MLC-3023 (trade name, manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal cell. Thereafter, a DC voltage of 15 V was applied to the obtained liquid crystal cell, and all the pixel areas were driven and passed through a band-pass filter having a wavelength of 365 nm using an ultraviolet irradiation device using a high-pressure mercury lamp as a light source.
  • a vertical alignment type liquid crystal display device was obtained by irradiation with ultraviolet rays at 10 J / cm 2 .
  • a UV-35 light receiver was connected to UV-M03A manufactured by ORC for measurement of the amount of ultraviolet irradiation.
  • vertical alignment was performed under the same conditions as described above except that the liquid crystal alignment film was formed under severe conditions by heating at 230 ° C. for 120 minutes.
  • Type liquid crystal display element was prepared.
  • Afterimage characteristics Using the afterimage evaluation liquid crystal display element produced above, 60 Hz, 20 Vp-p AC voltage was applied to two diagonal areas of the four pixel areas, and the device was driven at a temperature of 23 ° C. for 168 hours. Thereafter, all four pixel areas were driven with an AC voltage of 5 Vp-p, and the luminance difference of the pixels was visually observed. A state in which almost no difference in luminance was confirmed was considered good.
  • the evaluation results are shown in Table 3.
  • a scratch test was performed on the alignment film surface of the substrate with the polyimide coating film obtained in the example using UMT-2 (Bruker AXS Co., Ltd.). FVL was selected as the UMT-2 sensor, and a 1.6 mm sapphire sphere was attached to the tip of the scratch part.
  • a scratch test was conducted by changing the load from 1 mN to 20 mN over 100 seconds in a range of 0.5 mm in width and 2.0 mm in length with the tip of the scratch part in contact with the surface of the liquid crystal alignment film at a load of 1 mN. At this time, the moving direction of the tip of the scratch part was reciprocating to the side, and the moving speed was 5.0 mm / sec.
  • the scratch area was moved in the vertical direction by moving the substrate with the liquid crystal alignment film in the vertical direction at 20 ⁇ m / second.
  • MLC-3022 (a negative type liquid crystal manufactured by Merck & Co., Inc.) was dropped onto the liquid crystal alignment film surface that had been scratch-tested.
  • another substrate with a liquid crystal alignment film obtained in Example 1 and a 4 ⁇ m spacer dispersed thereon was superimposed so that the liquid crystal alignment film surfaces face each other, and the dropped MLC-3022 was sandwiched.
  • the liquid crystal display element using the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is It was found that the pretilt angle was not changed even under severe conditions, and the liquid crystal orientation was good. Further, as shown in Table 5, it was found that in Example 4 to Example 6 in which the liquid crystal aligning agent (V-4) was mixed, the afterimage characteristics were satisfactory. Furthermore, from this example, it was found that the liquid crystal alignment film obtained using a specific side chain diamine was excellent in pretilt angle stability even when baked under severe conditions. It was also confirmed that even when there was physical contact with the liquid crystal alignment film as in the scratch test, good vertical alignment could be maintained with little damage to the alignment film.
  • a liquid crystal display element using a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention can be suitably used for a liquid crystal display element. These elements are also useful in liquid crystal displays for display purposes, and in light control windows and optical shutters for controlling transmission and blocking of light.

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Abstract

La présente invention concerne un agent d'alignement de cristaux liquides grâce auquel un film d'alignement de cristaux liquides est obtenu dans lequel sa capacité à aligner des cristaux liquides verticalement n'est pas réduite même lorsque le film d'alignement de cristaux liquides est exposé à un chauffage excessif, et fournit un agent d'alignement de cristaux liquides grâce auquel un film d'alignement de cristaux liquides est obtenu dans lequel la capacité de celui-ci à aligner des cristaux liquides verticalement n'est pas réduite même lorsque certaines matières étrangères touchent ou endommagent le film. La présente invention concerne un agent d'alignement de cristaux liquides contenant un composant diamine contenant une diamine représentée par la formule [1] (dans la formule [1], X représente une liaison simple ou – O- ou un autre groupe divalent, Y représente un groupe représenté par la formule [1-1], et Y 1 à Y 6 représentent des groupes spécifiques décrits dans la description.), et au moins une espèce de polymère choisie parmi un précurseur de polyimide et un polyimide qui est un produit d'imidisation du précurseur de polyimide, le précurseur de polyimide étant un produit de réaction avec un composant d'acide tétracarboxylique.
PCT/JP2018/007686 2017-03-02 2018-03-01 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides WO2018159733A1 (fr)

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WO2020105561A1 (fr) * 2018-11-19 2020-05-28 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et dispositif d'affichage à cristaux liquides
JPWO2020203110A1 (fr) * 2019-03-29 2020-10-08
WO2021261281A1 (fr) * 2020-06-26 2021-12-30 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
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WO2021177080A1 (fr) * 2020-03-06 2021-09-10 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
KR20230002334A (ko) * 2020-04-10 2023-01-05 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
CN116234857B (zh) * 2020-07-17 2024-04-26 日产化学株式会社 液晶取向剂、液晶取向膜以及液晶显示元件
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US12037304B2 (en) 2017-08-02 2024-07-16 Samsung Electronics Co., Ltd. Monomer and polymer, compensation film, optical film, and display device
JP2019026848A (ja) * 2017-08-02 2019-02-21 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． モノマー、重合体、補償フィルム、光学フィルムおよび表示装置
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JP7414006B2 (ja) 2018-11-19 2024-01-16 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
CN113168052A (zh) * 2018-11-19 2021-07-23 日产化学株式会社 液晶取向剂、液晶取向膜、及液晶表示元件
JPWO2020105561A1 (ja) * 2018-11-19 2021-10-07 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
KR20210092194A (ko) * 2018-11-19 2021-07-23 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
TWI816939B (zh) * 2018-11-19 2023-10-01 日商日產化學股份有限公司 液晶配向劑、液晶配向膜及液晶顯示元件
WO2020105561A1 (fr) * 2018-11-19 2020-05-28 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et dispositif d'affichage à cristaux liquides
KR102775262B1 (ko) 2018-11-19 2025-02-28 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
CN113711117A (zh) * 2019-03-29 2021-11-26 日产化学株式会社 液晶取向剂、液晶取向膜、液晶显示元件以及二胺
WO2020203110A1 (fr) * 2019-03-29 2020-10-08 日産化学株式会社 Agent et film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides et diamine
JPWO2020203110A1 (fr) * 2019-03-29 2020-10-08
JP7428177B2 (ja) 2019-03-29 2024-02-06 日産化学株式会社 液晶配向剤、液晶配向膜、液晶表示素子及びジアミン
WO2021261281A1 (fr) * 2020-06-26 2021-12-30 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
JP7622744B2 (ja) 2020-06-26 2025-01-28 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

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