WO2013125595A1 - Composition, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides - Google Patents

Composition, 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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WO2013125595A1
WO2013125595A1 PCT/JP2013/054218 JP2013054218W WO2013125595A1 WO 2013125595 A1 WO2013125595 A1 WO 2013125595A1 JP 2013054218 W JP2013054218 W JP 2013054218W WO 2013125595 A1 WO2013125595 A1 WO 2013125595A1
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liquid crystal
composition
group
carbon atoms
formula
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PCT/JP2013/054218
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English (en)
Japanese (ja)
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徳俊 三木
雅章 片山
幸司 園山
保坂　和義
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日産化学工業株式会社
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Priority to KR1020147026175A priority Critical patent/KR102035366B1/ko
Priority to CN201380010188.1A priority patent/CN104136542B/zh
Publication of WO2013125595A1 publication Critical patent/WO2013125595A1/fr

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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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation

Definitions

  • the present invention relates to a composition used for forming a polyimide film, a liquid crystal alignment treatment agent used in the production of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film. .
  • Polyimide-based organic films are widely used as interlayer insulating films, protective films, liquid crystal alignment films in liquid crystal display elements, and the like in the electronic device field because of their ease of formation and insulating performance.
  • the substrate used and the unevenness of the level difference of the substrate have increased. In such a situation, a uniform liquid crystal alignment film is required even for a large substrate, even if there are large uneven steps.
  • liquid crystal alignment treatment agent containing a polyamic acid or a solvent-soluble polyimide also referred to as a resin
  • a liquid crystal alignment treatment agent containing a polyamic acid or a solvent-soluble polyimide also referred to as a resin
  • it is generally performed industrially by a flexographic printing method or an ink jet coating method. Is.
  • the coating property of the liquid crystal aligning agent is poor, repelling and pinholes are generated, and that portion becomes a display defect when the liquid crystal display element is formed.
  • a coating film for a liquid crystal alignment film in addition to N-methyl-2-pyrrolidone and ⁇ -butyrolactone, which are solvents having excellent resin solubility (also referred to as good solvents), a coating film for a liquid crystal alignment film In order to enhance the properties, ethylene glycol monobutyl ether or the like, which is a solvent having low resin solubility (also referred to as a poor solvent), is mixed (for example, see Patent Document 1).
  • liquid crystal display elements for mobile use such as smartphones and mobile phones that have been used in recent years
  • a sealing agent used for bonding between substrates of liquid crystal display elements is used to secure as many display surfaces as possible. It exists at a position close to the end of the alignment film.
  • the object of the present invention is made in view of the above circumstances, and is to provide a composition having excellent coating properties in order to form a polyimide film.
  • a liquid crystal alignment film having a high wettability and a uniform coating property of the coating solution to the substrate and excellent in the coating property of the end portion can be obtained. Is to get.
  • the inventor has a composition containing a solvent having a specific structure and a polyimide precursor and at least one polymer selected from the group consisting of polyimides obtained by imidizing polyimide precursors.
  • the inventors have found that the present invention is extremely effective for achieving the above object, and have completed the present invention. That is, the present invention has the following gist.
  • (1) A composition containing the following component (A) and component (B).
  • X 1 represents an alkyl group having 1 to 3 carbon atoms.
  • the component (B) is selected from the group consisting of a polyimide precursor using a diamine compound having a side chain represented by the following formula [2] as a part of the raw material and a polyimide obtained by imidizing the polyimide precursor.
  • Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—.
  • Y 2 is a single bond or — (CH 2 ) b — (b is an integer of 1 to 15.)
  • Y 3 is a single bond, — (CH 2 ) c — (c is 1 to 15)
  • Y 4 is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, or —O—, —CH 2 O—, —COO—, or —OCO—, or A divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, wherein an arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or 1 carbon atom Or a fluorine-containing alkyl group having 3 to 3, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom
  • Y 5 is a benzene ring, a divalent cyclic group selected from the group consisting of cyclohexane ring and heterocyclic, any of hydrogen atoms on these cyclic groups, an alkyl group having 1 to 3 carbon atoms, carbon atoms It may be substituted with an alkoxyl group having 1 to 3, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, n is an integer of 0 to 4.
  • Y 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
  • composition according to (2) above, wherein the diamine compound having a side chain represented by the formula [2] is a diamine compound represented by the following formula [2a].
  • Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—.
  • Y 2 is a single bond or — (CH 2 ) b — (b is an integer of 1 to 15.)
  • Y 3 is a single bond, — (CH 2 ) c — (c is 1 to 15) of an integer), -.
  • Y 4 is a divalent cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic, Or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, and an arbitrary hydrogen atom on the cyclic group includes an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, and a carbon number Substituted with 1 to 3 fluorine-containing alkyl groups, 1 to 3 fluorine-containing alkoxyl groups or fluorine atoms Which may .
  • Y 5 is a benzene ring, a divalent cyclic group selected from the group consisting of cyclohexane ring and heterocyclic, any of hydrogen atoms on these cyclic groups, an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with
  • Y 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms, and m is 1 to 4 Integer.
  • the diamine compound having a side chain represented by the formula [2] or the diamine compound represented by the formula [2a] is 5 to 80 mol% in the diamine component, as described in the above (2) or (3) Composition.
  • the above component (B) is a polymer using a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula [3]: The composition in any one of.
  • Z 1 is at least one structure selected from the group consisting of the following formulas [3a] to [3j].)
  • Z 2 to Z 5 are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.
  • Z 6 and Z 7 Are hydrogen atoms or methyl groups, which may be the same or different.
  • the component (C) contains at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and ⁇ -butyrolactone.
  • component (D) 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, Any one of the above (1) to (6) containing at least one solvent selected from the group consisting of diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monobutyl ether Composition.
  • a liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates.
  • a liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates.
  • the composition containing a solvent having a specific structure and at least one polymer selected from the group consisting of a polyimide precursor and a polyimide according to the present invention is a composition for forming a polyimide film having excellent coating properties. Can be provided as a thing.
  • the composition of the present invention as a liquid crystal alignment treatment agent, the coating solution having high wettability and spreading property of the coating solution to the substrate can be obtained, and furthermore, the coating property at the end of the liquid crystal alignment film.
  • the liquid crystal aligning film which is excellent in these characteristics can be provided.
  • the liquid crystal display element which has said liquid crystal aligning film, and the liquid-crystal aligning agent which can provide said liquid crystal aligning film can be provided.
  • the present invention includes a composition containing the following component (A) and component (B), a liquid crystal alignment treatment agent, a liquid crystal alignment film obtained using the liquid crystal alignment treatment agent, and a liquid crystal having the liquid crystal alignment film. It is a display element.
  • Component (A) A solvent represented by the following formula [1] (also referred to as a specific solvent). (In the formula [1], X 1 represents an alkyl group having 1 to 3 carbon atoms).
  • the specific solvent of this invention can be used as a poor solvent used in order to improve the coating property of a polyimide film or a liquid crystal aligning film.
  • the specific solvent of the present invention usually has a lower surface tension as a solvent than ethylene glycol monobutyl ether (also referred to as butyl cellosolve or BCS) used as a poor solvent. Therefore, compared to a coating solution that does not use a specific solvent, the coating solution using a specific solvent has higher wettability of the coating solution on the substrate, and even without using many poor solvents with low resin solubility, A polyimide film or a liquid crystal alignment film having excellent coating properties can be obtained.
  • the specific solvent of the present invention has a higher boiling point than ethylene glycol monobutyl ether, which is usually used as a poor solvent. Therefore, the coating solution using the specific solvent can suppress the rise of the end portion of the polyimide film when the polyimide film or the liquid crystal alignment film is used.
  • the component (B) of the present invention is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by imidizing the polyimide precursor.
  • the polyimide precursor and polyimide precursor which have a side chain (it is also called a specific side chain structure) shown by following formula [2] It is preferable to use at least one polymer (also referred to as a specific polymer) selected from the group consisting of polyimides obtained by imidizing the above.
  • Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—.
  • Y 2 is a single bond or — (CH 2 ) b — (b is an integer of 1 to 15.)
  • Y 3 is a single bond, — (CH 2 ) c — (c is 1 to 15)
  • Y 4 is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, or —O—, —CH 2 O—, —COO—, or —OCO—, or A divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, wherein an arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to
  • Y 5 is a benzene ring, a divalent cyclic group selected from the group consisting of cyclohexane ring and heterocyclic, any of hydrogen atoms on these cyclic groups, an alkyl group having 1 to 3 carbon atoms, carbon atoms It may be substituted with an alkoxyl group having 1 to 3, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, n is an integer of 0 to 4.
  • Y 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
  • the specific side chain structure of the present invention has a divalent organic group having 12 to 25 carbon atoms having a benzene ring, a cyclohexyl ring or a heterocyclic ring, or a steroid skeleton in the side chain portion.
  • These divalent organic groups having 12 to 25 carbon atoms and having a benzene ring, a cyclohexyl ring or a heterocyclic ring, or a steroid skeleton have a rigid structure as compared with the conventional long-chain alkyl group.
  • the stability of the side chain site to heat and ultraviolet light is improved, and a liquid crystal alignment film having a stable pretilt angle against heat and light can be obtained.
  • the composition containing at least one polymer selected from the group consisting of the specific solvent of the present invention, a polyimide precursor, and a polyimide obtained by imidizing the polyimide precursor is a polyimide film having excellent coating properties. Or it becomes a composition or liquid crystal aligning agent for forming a liquid crystal aligning film.
  • the specific solvent of this invention, the polyimide precursor which has the specific side chain structure shown by said Formula [2], and the at least 1 sort (s) of polymer chosen from the group which consists of the polyimide which imidated the polyimide precursor are contained.
  • the liquid crystal aligning agent obtained from the composition becomes a liquid crystal alignment film whose pretilt angle does not change even when exposed to high temperature and light irradiation for a long time. Further, by using this liquid crystal alignment film, a highly reliable liquid crystal display element having excellent display characteristics can be provided.
  • the specific solvent of the present invention is represented by the following formula [1].
  • X 1 represents an alkyl group having 1 to 3 carbon atoms.
  • the specific solvent of the present invention is preferably 5 to 70% by mass based on the total amount of the solvent contained in the liquid crystal aligning agent in order to enhance the effect of increasing the wet spreading property of the coating solution onto the substrate.
  • 5 to 65% by mass is preferable.
  • a more preferred range is 5 to 60% by mass, and a further more preferred range is 10 to 55% by mass.
  • the more the amount of the specific solvent of the present invention in the whole solvent in the composition the higher the effect of the present invention, that is, the wet spreading property of the coating solution to the substrate, and the polyimide film having excellent coating properties or A liquid crystal alignment film can be obtained.
  • the polymer of the present invention has the effect of increasing the hydrophobicity of the polyimide film when formed into a polyimide film and the effect of increasing the stability of the pretilt angle when formed into a liquid crystal alignment film. It is preferable to use a specific polymer having the specific side chain structure shown.
  • Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—. is there.
  • a single bond, — (CH 2 ) a — (wherein a is an integer of 1 to 15), —O—, —CH 2 O— or —COO— is preferable because the side chain structure can be easily synthesized. . More preferably, they are a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
  • Y 2 is a single bond or — (CH 2 ) b — (b is an integer of 1 to 15).
  • a single bond or — (CH 2 ) b — (b is an integer of 1 to 10) is preferable.
  • Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—. is there.
  • a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO— is preferable because they are easy to synthesize.
  • Y 4 is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms.
  • Y 4 is a divalent organic group selected from the group consisting of organic groups having 12 to 25 carbon atoms having a steroid skeleton. Among these, an organic group having 12 to 25 carbon atoms having a benzene ring, a cyclohexane ring, or a steroid skeleton is preferable.
  • Y 5 is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl having 1 to 3 carbon atoms.
  • n is an integer of 0-4.
  • it is an integer of 0-2.
  • Y 6 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. .
  • an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable.
  • it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
  • Preferred combinations of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 and n in the formula [2] are those described in Items 13 to 34 of International Publication No. WO2011 / 132751 (published 2011.10.27). Examples include the same combinations as (2-1) to (2-629) listed in Tables 6 to 47. In each table of the International Publication, Y 1 to Y 6 in the present invention are shown as Y 1 to Y 6 , but Y 1 to Y 6 are read as Y 1 to Y 6 .
  • Specific side chain diamine compound As a specific polymer of the present invention, that is, a method for introducing a specific side chain structure represented by the formula [2] into at least one selected from the group consisting of a polyimide precursor and a polyimide obtained by imidizing a polyimide precursor, It is preferable to use a diamine compound having a side chain structure as a part of the raw material. In particular, it is preferable to use a diamine compound represented by the following formula [2a] (also referred to as a specific side chain diamine compound).
  • Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—. is there.
  • a single bond, — (CH 2 ) a — (wherein a is an integer of 1 to 15), —O—, —CH 2 O— or —COO— is preferable because the side chain structure can be easily synthesized.
  • they are a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
  • Y 2 is a single bond or — (CH 2 ) b — (b is an integer of 1 to 15).
  • a single bond or — (CH 2 ) b — (b is an integer of 1 to 10) is preferable.
  • Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—. is there.
  • a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO— is preferable because they are easily synthesized. More preferably, they are a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O—, —COO— or —OCO—.
  • Y 4 is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl having 1 to 3 carbon atoms Group, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
  • Y 4 is a divalent organic group selected from organic compounds having 12 to 25 carbon atoms and having a steroid skeleton.
  • Y 5 is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms.
  • an alkoxyl group having 1 to 3 carbon atoms an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
  • n is an integer of 0 to 4. Preferably, it is an integer of 0-2.
  • Y 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. .
  • an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable.
  • it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
  • a preferred combination of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 and n in the formula [2a] is the same as that in the formula [2].
  • more preferred combinations are 2-25 to 2-96, 2-145 to 2-168, 2-217 to 2- 240, 2-268 to 2-315, 2-364 to 2-387, 2-436 to 2-483, 2-603 to 2-615, etc., and particularly preferred combinations are 1-49 to 1-96, 1-145 to 1-168, 1-217 to 1-240, 2-603 to 2-606, and the like.
  • m is an integer of 1 to 4.
  • R 1 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 — or —CH 2 OCO—.
  • R 2 represents A linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, or the number of carbon atoms 1 to 22 fluorine-containing alkoxyl groups.
  • R 3 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 — or —CH 2 —, wherein R 4 is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, carbon number A linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 22 carbon atoms.
  • R 5 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 —, —O— or —NH—, wherein R 6 is fluorine, cyano, trifluoromethane, nitro, azo, formyl, acetyl, acetoxy Or a hydroxyl group.
  • R 7 is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is Trans isomer.
  • R 8 is a linear or branched alkyl group having 3 to 12 carbon atoms, and cis-trans isomerism of 1,4-cyclohexylene is Trans isomer.
  • a 4 is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom.
  • a 3 is a 1,4-cyclohexylene group or
  • a 2 is an oxygen atom or COO- * (where a bond marked with “*” is bonded to A 3 )
  • a 1 is an oxygen atom or COO— * (wherein , A bond marked with “*” binds to (CH 2 ) a 2 ).
  • a 1 is an integer of 0 or 1
  • a 2 is an integer of 2 to 10
  • a 3 is an integer of 0 or 1.
  • diamine compounds have the structures [2-1] to [2-6], [2-9] to [2-13]. ] Or formula [2-22] to formula [2-31].
  • the specific side chain diamine compound is soluble in a solvent when used as a polymer of the present invention, hydrophobicity of a polyimide film when used in a polyimide film, and liquid crystal alignment when used as a liquid crystal alignment film. Depending on the characteristics such as the property, voltage holding ratio, and accumulated charge, one kind or a mixture of two or more kinds can be used.
  • the diamine compound which has an alkyl group or a fluorine-containing alkyl group in a diamine side chain can be used.
  • diamine compounds represented by the following formulas [DA1] to [DA12] can be exemplified.
  • a 1 is a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms. ).
  • a 2 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO— or —NH—.
  • a 3 represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.
  • diamine compounds represented by the following formulas [DA13] to [DA20] can also be used.
  • m is an integer of 0 to 3
  • n is an integer of 1 to 5.
  • a diamine compound having a carboxyl group in the molecule represented by the following formulas [DA21] to [DA25] can also be used as long as the effects of the present invention are not impaired.
  • m 1 is an integer of 1 to 4.
  • a 4 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —. , —CF 2 —, —C (CF 3 ) —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 -, - COO -, - OCO -, - CON (CH 3) - or -N (CH 3) a CO- .m 2, and m 3 is an integer of 0 to 4, and m 2 + m 3 Is an integer of 1 to 4.
  • m 4 and m 5 are each an integer of 1 to 5.
  • a 5 is linear or branched having 1 to 5 carbon atoms.
  • the .m 6 is Jo alkyl group is an integer of 1 to 5 formula in [DA25], a 6 represents a single bond, -CH 2 -., - C 2 H 4 -, - C (CH 3 ) 2 —, —CF 2 —, —C (CF 3 ) —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O— , —OCH 2 —, —COO—, —OCO—, —CON (CH 3 ) — or —N (CH 3 ) CO—, where m 7 is an integer of 1 to 4.
  • a diamine compound represented by the following formula [DA26] can also be used as long as the effects of the present invention are not impaired.
  • a 1 is —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCO—, —CON (CH 3 ).
  • a 3 is a single bond, —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH 3 ).
  • a 4 is a nitrogen-containing aromatic heterocycle, n is 1 to It is an integer of 4.
  • a diamine compound having a steroid skeleton represented by the following formula [DA27] or [DA28] can also be used.
  • the above other diamine compounds are soluble in a solvent when used as a polymer of the present invention, hydrophobicity of a polyimide film when used in a polyimide film, and liquid crystal alignment and voltage when used as a liquid crystal alignment film.
  • One type or a mixture of two or more types can be used according to characteristics such as retention rate and accumulated charge.
  • tetracarboxylic dianhydride also referred to as a specific tetracarboxylic dianhydride
  • Z 1 is a tetravalent group represented by the following formulas [3a] to [3j].
  • Z 2 to Z 5 are groups selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom and a benzene ring, and may be the same or different
  • the formula [3g] Z 6 and Z 7 are a hydrogen atom or a methyl group, and may be the same or different.
  • particularly preferred structure of Z 1 is the formula [3a], the formula [3c], the formula [3d], the formula [3e], the formula [3f] or the formula from the viewpoint of polymerization reactivity and ease of synthesis. [3 g].
  • the formula [3a], the formula [3e], the formula [3f], or the formula [3g] is preferable.
  • tetracarboxylic dianhydrides other tetracarboxylic dianhydrides other than the specific tetracarboxylic dianhydride (also referred to as other tetracarboxylic dianhydrides) can be used as long as the effects of the present invention are not impaired.
  • examples of other tetracarboxylic dianhydrides include tetracarboxylic dianhydrides of the following tetracarboxylic acids.
  • Said specific tetracarboxylic dianhydride and other tetracarboxylic dianhydrides are soluble in a solvent when used as a polymer of the present invention, hydrophobicity of a polyimide film when used in a polyimide film, One type or a mixture of two or more types can be used according to the characteristics such as the liquid crystal alignment property, voltage holding ratio, and accumulated charge when the liquid crystal alignment film is formed.
  • the polymer which is the component (B) of the present invention is at least one polymer selected from a polyimide precursor or a polyimide.
  • the polyimide precursor has a structure represented by the following formula [A].
  • R 1 is a tetravalent organic group
  • R 2 is a divalent organic group
  • a 1 and A 2 are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, (It may be the same or different, and n represents a positive integer.)
  • the polymer of the present invention can be obtained relatively easily by using a diamine component represented by the following formula [B] and a tetracarboxylic dianhydride represented by the following formula [C] as raw materials.
  • Polyamic acid having a structural formula of a repeating unit represented by the following formula [D] or polyimide obtained by imidizing the polyamic acid is preferable.
  • R 1 and R 2 are the same as defined in formula [A].
  • R 1 and R 2 have the same meaning as defined in formula [A].
  • the method for synthesizing the polymer is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acids and derivatives thereof is reacted with a diamine component consisting of one or more diamine compounds to obtain a polyamic acid.
  • a method of obtaining polyamic acid by polycondensation of tetracarboxylic dianhydride and a diamine component a method of obtaining polyamic acid by dehydration polycondensation reaction of tetracarboxylic acid and a diamine component, or tetracarboxylic acid dihalide
  • a method is used in which a polyamic acid is obtained by polycondensation of a diamine component and diamine component.
  • Polyamide acid alkyl ester can be obtained by polycondensation of carboxylic acid group with dialkyl esterified tetracarboxylic acid and diamine component, tetracarboxylic acid dihalide with carboxylic acid group dialkylesterified and diamine component.
  • a method or a method of converting a carboxyl group of a polyamic acid into an ester is used.
  • the specific polymer of the present invention is at least one polymer selected from a polyimide precursor having a side chain represented by the formula [2] or a polyimide.
  • the liquid crystal alignment film obtained using the specific polymer of the present invention is more hydrophobic when the liquid crystal alignment film is used as the content of the specific side chain structure represented by the formula [2] in the diamine component increases. And the pretilt angle of the liquid crystal can be increased. In that case, it is preferable to use the specific side chain type diamine compound shown by said Formula [2a] for a diamine component.
  • the specific side chain represented by formula [2-1] to formula [2-6], formula [2-9] to formula [2-12] or formula [2-22] to formula [2-31] It is preferable to use a type diamine compound.
  • 5 mol% or more and 80 mol% or less of the diamine component is the specific side chain diamine compound.
  • 5 mol% or more and 60 mol% or less of a diamine component are a specific side chain type diamine compound from the viewpoint of the applicability
  • a tetracarboxylic dianhydride in which Z 1 in the formula [3] is a group having a structure represented by the formulas [3a] to [3j].
  • 1 mol% or more of a tetracarboxylic acid component is a specific tetracarboxylic dianhydride, More preferably, it is 5 mol% or more, More preferably, it is 10 mol% or more.
  • 100 mol% of the tetracarboxylic acid component may be a specific tetracarboxylic dianhydride.
  • the reaction of the diamine component and the tetracarboxylic acid component is usually performed in an organic solvent with the diamine component and the tetracarboxylic acid component.
  • the organic solvent used in that case is not particularly limited as long as the generated polyimide precursor is dissolved. Specific examples are given below. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, ⁇ -butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4 -Hydroxy-4-methyl-2-pentanone and the like.
  • the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic acid component is dispersed or dissolved in the organic solvent as it is.
  • a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent a method of alternately adding a tetracarboxylic acid component and a diamine component, etc. Any of these methods may be used.
  • the polymerization temperature 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 is difficult. It becomes. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
  • the 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 produced increases as the molar ratio approaches 1.0.
  • the polyimide of the present invention is a polyimide obtained by ring-closing the above polyimide precursor, and is useful as a polymer for obtaining a polyimide film or a liquid crystal alignment film.
  • the cyclization rate (also referred to as imidization rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.
  • Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalyst imidization in which a catalyst is added to the polyimide precursor solution.
  • the temperature is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidization reaction from the system.
  • 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 of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
  • the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • 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 collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating.
  • the molecular weight of the polymer of the present invention is the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method in consideration of the strength of the polyimide film obtained therefrom, workability at the time of forming the polyimide film, and the coating property of the polyimide film. It is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.
  • composition of the present invention or a liquid crystal alignment treatment agent using the same is a coating solution for forming a polyimide film or a liquid crystal alignment film (also collectively referred to as a resin film), and contains a specific solvent and a polymer.
  • a coating solution for forming a film All of the polymer components in the composition of the present invention or the liquid crystal liquid crystal aligning agent using the same may be the polymer of the present invention.
  • the coalescence may be mixed.
  • the content of the other polymer in the polymer is 0.5 to 15% by mass, preferably 1 to 10% by mass.
  • the other polymer include a polyimide precursor and a polymer other than polyimide, specifically, an acrylic polymer, a methacrylic polymer, polystyrene, polyamide, or a siloxane polymer.
  • a specific polymer As the polymer.
  • all the polymer components may all be the specific polymer of the present invention, and other polymers may be mixed with the specific polymer of the present invention.
  • the content of the other polymer in the specific polymer is 0.5 to 15% by mass, preferably 1 to 10% by mass.
  • Other polymers include polyimide precursors or polyimides obtained from a diamine component not containing a specific side chain diamine compound and a tetracarboxylic acid component not containing a specific tetracarboxylic dianhydride.
  • a polyimide precursor and a polymer other than polyimide specifically, an acrylic polymer, a methacrylic polymer, polystyrene, polyamide, or a siloxane-based polymer can be used.
  • the organic solvent in the composition of the present invention or the liquid crystal aligning agent using the same may contain 70 to 99.9% by mass of the organic solvent from the viewpoint of forming a uniform resin film by coating. 70 to 98% by mass is more preferable. This content can be appropriately changed depending on the film thickness of the target polyimide film or liquid crystal alignment film.
  • the organic solvent in that case will not be specifically limited if it is an organic solvent in which the polymer of this invention is dissolved. Specific examples are given below.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyllactone (hereinafter also referred to as component (C)) is preferably used.
  • components (C) are preferably 20 to 90% by mass of the whole organic solvent contained in the composition or the liquid crystal aligning agent using the composition. Of these, 30 to 80% by mass is preferable. More preferred is 40 to 80% by mass, and still more preferred is 40 to 70% by mass.
  • the coating properties and surface smoothness of the resin film when the composition or the liquid crystal aligning agent using the composition does not impair the effects of the present invention.
  • An organic solvent that improves the property that is, a poor solvent can be used. Specific examples of the poor solvent for improving the coating properties and surface smoothness of the resin coating 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-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Etanji 1,2-propanediol, 1,3-propaned
  • component (D) propylene glycol monobutyl ether
  • These poor solvents are preferably 1 to 60% by mass of the total organic solvent contained in the composition or the liquid crystal aligning agent using the composition. Among these, 1 to 50% by mass is preferable. More preferred is 5 to 45% by mass.
  • the composition of the present invention or the liquid crystal alignment treatment agent using the same is a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, and a hydroxyalkyl group.
  • a crosslinkable compound having at least one substituent selected from the group consisting of lower alkoxyalkyl groups, or a crosslinkable compound having a polymerizable unsaturated bond may be introduced. It is necessary to have two or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.
  • crosslinkable compound having an epoxy group or an isocyanate group examples include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl, Liglycidyl-p-a
  • the crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4]. Specific examples include crosslinkable compounds represented by formulas [4a] to [4k] described in paragraphs 58 to 59 of International Publication No. WO2011 / 132751 (published 2011.10.27).
  • the crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5]. Specifically, crosslinkable compounds represented by the formulas [5-1] to [5-42] described in the paragraphs 76 to 82 of International Publication No. WO2012 / 014898 (published in 2012.2.2) are listed. It is done.
  • Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril.
  • a melamine derivative, a benzoguanamine derivative, or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both can be used.
  • the melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol
  • Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring.
  • Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p-tert-butylphenol. More specifically, crosslinkable compounds represented by the formulas [6-1] to [6-48] described on pages 62 to 66 of International Publication No. WO2011 / 132751 (published 2011.10.27) can be mentioned. .
  • crosslinkable compound having a polymerizable unsaturated bond examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxytrimethylol.
  • Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as propane, glycerin polyglycidyl ether poly (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin Di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl
  • E 1 is a cyclohexane ring, bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, a group selected from the group consisting of an anthracene ring and phenanthrene ring
  • E 2 Is a group selected from the group consisting of the following formulas [7a] and [7b]
  • n is an integer of 1 to 4.
  • the said compound is an example of a crosslinkable compound, It is not limited to these.
  • the crosslinkable compound used for the composition of this invention or a liquid-crystal aligning agent using the same may be one type, and may combine two or more types.
  • the content of the crosslinkable compound in the composition of the present invention or the liquid crystal aligning agent using the same is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all polymer components.
  • the amount is more preferably 0.1 to 100 parts by weight, and most preferably 1 to 50 parts by weight, based on 100 parts by weight of all polymer components.
  • a liquid crystal alignment film using the liquid crystal alignment agent using the composition of the present invention as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge release of a liquid crystal cell using the liquid crystal alignment film, examples thereof include nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156], which are listed on pages 69 to 73 of International Publication No. WO2011 / 132751 (published 2011.10.27).
  • the formula [M1], the formula [M7], the formula [M16] to the formula [20], the formula [M24], the formula [M35], the formula [M36], the formula [M40], the formula [M49], the formula [ M50], Formula [M52], Formula [M60] to Formula [M62], Formula [M68], Formula [M69], Formula [M76], Formula [M77], Formula [M82], Formula [M100], Formula [M M101], Formula [M108], Formula [M109], Formula [M118] to Formula [M121], Formula [M128], Formula [M134] to Formula [136], or Formula [M140] are preferable.
  • amine compounds may be added directly to the composition, but they should be added after a solution having a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass with an appropriate solvent.
  • the solvent is not particularly limited as long as it is an organic solvent that dissolves the above-described polymer.
  • the uniformity of the film thickness of the resin film when the composition or the liquid crystal aligning agent using the composition is applied A compound that improves the surface smoothness can be used. Furthermore, a compound that improves the adhesion between the resin coating and the substrate can also be used. Examples of the compound that improves the film thickness uniformity and surface smoothness of the resin coating include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
  • F-top EF301, EF303, EF352 manufactured by Tochem Products
  • MegaFuck F171, F173, R-30 manufactured by Dainippon Ink
  • Florard FC430, FC431 manufactured by Sumitomo 3M
  • Asahi Guard AG710 Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) and the like.
  • the content of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of all the polymer components contained in the composition or liquid crystal aligning agent. 1 part by mass.
  • the compound that improves the adhesion between the resin coating and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
  • the content thereof is 0.1 to 30 parts by mass with respect to 100 parts by mass of all polymer components contained in the composition or the liquid crystal aligning agent using the composition.
  • the amount is preferably 1 to 20 parts by mass. If the amount is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the storage stability of the composition or the liquid crystal alignment treatment agent using the composition may be deteriorated.
  • the composition of the present invention or the liquid crystal aligning agent using the composition includes the above poor solvent, crosslinkable compound, compound that improves the film thickness uniformity and surface smoothness of the resin film, and compound that adheres to the substrate.
  • a dielectric material or a conductive material for the purpose of changing electrical characteristics such as dielectric constant or conductivity of the polyimide film or the liquid crystal alignment film may be added.
  • the composition of the present invention can be used as a polyimide film after coating and baking on a substrate.
  • a substrate used in this case a glass substrate, a silicon wafer, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used depending on a target device.
  • the coating method of the composition is not particularly limited, but industrially, there are methods such as a dipping method, a roll coater method, a slit coater method, a spinner method, a spray method, screen printing, offset printing, flexographic printing, or an inkjet method. It is common. You may use these according to the objective.
  • the solvent is evaporated at 50 to 300 ° C., preferably 80 to 250 ° C. by a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven, and the resin coating is formed. can do.
  • the thickness of the resin film after firing can be adjusted to 0.01 to 50 ⁇ m depending on the purpose.
  • the liquid crystal alignment treatment agent using the composition of the present invention can be used as a liquid crystal alignment film by applying alignment treatment by rubbing treatment or light irradiation after coating and baking on a substrate. In the case of vertical alignment, etc., it can be used as a liquid crystal alignment film without alignment treatment.
  • the substrate used at this time is not particularly limited as long as it is a highly transparent substrate.
  • a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode for driving a liquid crystal is formed.
  • an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.
  • a method for applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, a method of performing screen printing, offset printing, flexographic printing, an inkjet method, or the like is common. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, or a spray method, and these may be used depending on the purpose.
  • the solvent is evaporated at 50 to 300 ° C., preferably 80 to 250 ° C. by a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven, and the liquid crystal.
  • An alignment film can be formed. If the thickness of the liquid crystal alignment film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 10 to 100 nm.
  • the fired liquid crystal alignment film is treated by rubbing or irradiation with polarized ultraviolet rays.
  • the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
  • a pair of substrates on which a liquid crystal alignment film is formed are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside, so that the other Examples include a method in which substrates are bonded together and liquid crystal is injected under reduced pressure, or a method in which liquid crystal is dropped onto a liquid crystal alignment film surface on which spacers are dispersed and then a substrate is bonded and sealed.
  • the liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board
  • the liquid crystal composition is also preferably used for a liquid crystal display element produced through a step of polymerizing a polymerizable compound by at least one of irradiation with active energy rays and heating while applying a voltage between electrodes.
  • ultraviolet rays are suitable as the active energy ray.
  • the wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.
  • the liquid crystal display element controls a pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method.
  • a PSA method a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, a predetermined voltage is applied to the liquid crystal layer and the photopolymerizable compound is irradiated with ultraviolet light.
  • the pretilt of the liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer.
  • the PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by the rubbing process. That is, in the liquid crystal display element of the present invention, a liquid crystal cell is prepared after obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the above-described method, and a polymerizable compound is obtained by at least one of ultraviolet irradiation and heating. The orientation of the liquid crystal molecules can be controlled by polymerizing.
  • a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded and the liquid crystal is injected under reduced pressure and sealed, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed and then the substrate is bonded and sealed.
  • the liquid crystal is mixed with a polymerizable compound that is polymerized by heat or ultraviolet irradiation.
  • the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule.
  • the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component.
  • the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the liquid crystal alignment cannot be controlled.
  • the polymerizable compound exceeds 10 parts by mass, the amount of the unreacted polymerizable compound increases and the liquid crystal display element. The seizure characteristics of the steel deteriorate.
  • the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.
  • the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display device manufactured through a step of disposing a liquid crystal alignment film containing a group and applying a voltage between the electrodes.
  • ultraviolet rays are suitable as the active energy ray.
  • the wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm.
  • the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C.
  • a method of adding a compound containing this polymerizable group to a liquid crystal aligning agent examples thereof include a method containing a coalescing component.
  • the liquid crystal aligning agent of the present invention contains a specific compound having a double bond site that reacts by irradiation with heat or ultraviolet rays
  • the alignment of liquid crystal molecules can be controlled by at least one of ultraviolet irradiation and heating. it can. If an example of liquid crystal cell production is given, prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside, Examples include a method in which the other substrate is attached and liquid crystal is injected under reduced pressure and sealing is performed, or a method in which the substrate is attached and sealed after the liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed.
  • the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.
  • the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen, high-definition liquid crystal television.
  • TCA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • TDA tetracarboxylic dianhydride represented by the following formula
  • 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 that appear in the vicinity of 9.5 ppm 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.
  • This reaction solution was poured into methanol (900 ml), and the resulting precipitate was separated by filtration. This deposit was wash
  • the imidation ratio of this polyimide was 55%, the number average molecular weight was 22,200, and the weight average molecular weight was 57,900.
  • Examples 1-34 and Comparative Examples 1-8 are preparation examples of the composition. Moreover, the obtained composition was used also for each characteristic evaluation of a liquid-crystal aligning agent. Tables 2 to 4 collectively show the compositions obtained in Examples and Comparative Examples, the liquid crystal aligning agents, and each component used for the preparation.
  • compositions or liquid crystal alignment treatment agents obtained in Examples and Comparative Examples, “Evaluation of printability of compositions and liquid crystal alignment treatment agents”, “Evaluation of ink jet coatability of liquid crystal alignment treatment agents”, “Preparation of liquid crystal cell” (Normal cell), “Evaluation of liquid crystal alignment (normal cell)”, “Evaluation of pretilt angle (normal cell)”, “Preparation of liquid crystal cell (PSA cell)”, and “Evaluation of liquid crystal alignment (PSA cell) ) ”.
  • the conditions are as follows.
  • Printability evaluation was performed using the compositions obtained in Examples and Comparative Examples.
  • a simple printer S15 type manufactured by Nissha Printing Co., Ltd.
  • the printing area is 80 mm x 80 mm
  • the printing pressure is 0.2 mm
  • five discarded substrates the time from printing to temporary drying is 90 seconds
  • temporary drying is a hot plate The above was carried out at 70 ° C. for 5 minutes. Evaluation of the pinhole of the obtained polyimide film, evaluation of the linearity of the end part of the polyimide film, and evaluation of the bulge of the end part of the polyimide film were performed.
  • Evaluation of the pinhole of the polyimide film was performed by visually observing the polyimide film under a sodium lamp. Specifically, the number of pinholes confirmed on the polyimide film was counted, and the smaller the number of pinholes, the better the evaluation.
  • Evaluation of the linearity of the end portion of the polyimide film was performed by observing the polyimide film at the right end portion with respect to the printing direction with an optical microscope. Specifically, the difference between (1) and (2) in FIG. 1 of the polyimide film image obtained by observing with an optical microscope magnification of 25 times, that is, the length of A in FIG. It was measured. All polyimide film images were obtained at the same magnification. The shorter the length of A, the better the linearity of the end of the polyimide film. Evaluation of the rising of the end portion of the polyimide film was performed by observing the polyimide film at the right end portion with respect to the printing direction with an optical microscope. Specifically, the length of B in FIG.
  • the printability evaluation result of the polyimide film obtained by the Example and the comparative example is the liquid crystal alignment film.
  • Tables 5 to 7 show the number of pinholes, the length of A, and the length of B of the polyimide films (liquid crystal alignment films) obtained in the examples and comparative examples.
  • the pretilt angle was evaluated using the obtained liquid crystal cell.
  • the pretilt angle was measured after injecting liquid crystal, after heat treatment at 95 ° C. for 5 minutes, and after heat treatment at 120 ° C. for 5 hours. Furthermore, after injecting the liquid crystal, the measurement was performed after irradiating the liquid crystal cell heated at 95 ° C. for 5 minutes with ultraviolet rays of 10 J / cm 2 in terms of 365 nm. The smaller the change in the pretilt angle after the heat treatment at 120 ° C for 5 hours or the ultraviolet irradiation after the heat treatment at 95 ° C for 5 minutes, the more stable the pretilt angle against heat or ultraviolet light. Was high.
  • the pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON). Furthermore, ultraviolet irradiation was performed using a desktop UV curing apparatus (HCT3B28HEX-1, manufactured by Senlite). Tables 8 to 10 show the evaluation results of the pretilt angles obtained in the examples and comparative examples.
  • the coating surface was washed with pure water, and then heat-treated at 100 ° C. for 15 minutes in a heat-circulating clean oven to obtain a substrate with a liquid crystal alignment film.
  • This substrate with a liquid crystal alignment film was combined with a liquid crystal alignment film surface inside, with a 6 ⁇ m spacer in between, and the periphery was adhered with a sealant to produce an empty cell.
  • the polymerizable compound (1) represented by the following formula was added to MLC-6608 (manufactured by Merck Japan) by 0.3% by mass with respect to 100% by mass of MLC-6608 by vacuum injection into this empty cell. The mixed liquid crystal was injected and the injection port was sealed to obtain a liquid crystal cell.
  • the response speed of the liquid crystal cell after the ultraviolet irradiation was higher than that of the liquid crystal cell before the ultraviolet irradiation, so that it was confirmed that the alignment direction of the liquid crystal was controlled.
  • any liquid crystal cell it was confirmed that the liquid crystal was uniformly aligned by observation with a polarizing microscope.
  • Example 1 NMP (19.2 g) and [1a] (12.5 g) were added to the polyamic acid solution (1) (10.0 g) with a resin solid content concentration of 25.0 mass% obtained by the synthesis method of Synthesis Example 1. The mixture was stirred at 25 ° C. for 2 hours to obtain a composition (1). In this composition, no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (1) was used for evaluation also as a liquid-crystal aligning agent (1). Using the obtained composition (1) or liquid crystal aligning agent (1), production of cells and various evaluations were performed under the above-described conditions.
  • NMP (22.5 g) was added to the polyimide powder (2) (2.50 g) obtained by the synthesis method of Synthesis Example 2 and dissolved by stirring at 70 ° C. for 24 hours.
  • [1a] (8.30 g) and BCS (8.30 g) were added to this solution, and the mixture was stirred at 50 ° C. for 10 hours to obtain a composition (2).
  • this composition no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (2) was used for evaluation also as a liquid-crystal aligning agent (2). Using the obtained composition (2) or liquid crystal aligning agent (2), production of cells and various evaluations were performed under the above-described conditions.
  • NEP (20.4 g) was added to the polyimide powder (2) (2.50 g) obtained by the synthesis method of Synthesis Example 2 and dissolved by stirring at 70 ° C. for 24 hours.
  • [1a] (14.6 g) and BCS (4.20 g) were added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (3).
  • this composition (3) was used for evaluation also as a liquid-crystal aligning agent (3). Using the obtained composition (3) or liquid crystal aligning agent (3), cell preparation and various evaluations were performed under the above-described conditions.
  • NEP (22.8 g) was added to the polyimide powder (2) (1.55 g) obtained by the synthesis method of Synthesis Example 2, and dissolved by stirring at 70 ° C. for 24 hours.
  • [1a] (15.5 g) and BCS (4.40 g) were added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (4).
  • this composition no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (4) was used for evaluation as a liquid-crystal aligning agent (4). Using the obtained liquid crystal aligning agent (4), “evaluation of ink jet coatability of liquid crystal aligning agent” was performed under the above-described conditions.
  • Example 5 NMP (17.9 g) and [1a] (15.3 g) were added to the polyamic acid solution (3) (10.5 g) with a resin solid content concentration of 25.0 mass% obtained by the synthesis method of Synthesis Example 3. The mixture was stirred at 25 ° C. for 2 hours to obtain a composition (5). In this composition, no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (5) was used for evaluation also as a liquid-crystal aligning agent (5). Using the obtained composition (5) or liquid crystal aligning agent (5), production of cells and various evaluations were performed under the above-described conditions.
  • NMP (20.7 g) was added to the polyimide powder (4) (2.54 g) obtained by the synthesis method of Synthesis Example 4, and dissolved by stirring at 70 ° C. for 24 hours.
  • [1a] (19.1 g) was added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (6).
  • this composition (6) was used for evaluation also as a liquid-crystal aligning agent (6). Using the obtained composition (6) or liquid crystal aligning agent (6), production of cells and various evaluations were performed under the above-described conditions.
  • NMP (16.3 g) was added to the polyimide powder (4) (2.50 g) obtained by the synthesis method of Synthesis Example 4, and dissolved by stirring at 70 ° C. for 24 hours.
  • [1a] (8.30 g) and BCS (14.6 g) were added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (7).
  • this composition no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (7) was used for evaluation also as a liquid-crystal aligning agent (7). Using the obtained composition (7) or liquid crystal aligning agent (7), production of cells and various evaluations were performed under the above-described conditions.
  • NEP (16.6 g) was added to the polyimide powder (4) (2.55 g) obtained by the synthesis method of Synthesis Example 4, and dissolved by stirring at 70 ° C. for 24 hours.
  • [1a] (6.40 g) and BCS (17.0 g) were added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (8).
  • this composition no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (8) was used for evaluation also as a liquid-crystal aligning agent (8). Using the obtained composition (8) or liquid crystal aligning agent (8), cell preparation and various evaluations were performed under the above-described conditions.
  • Example 9 NMP (4.90 g) and NEP (12.9 g) were added to the polyimide powder (4) (1.50 g) obtained by the synthesis method of Synthesis Example 4, and dissolved by stirring at 70 ° C. for 24 hours. . [1a] (6.40 g) and BCS (17.1 g) were added to this solution, and the mixture was stirred at 50 ° C. for 10 hours to obtain a composition (9). In this composition, no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (9) was used for evaluation as a liquid-crystal aligning agent (9). Using the obtained liquid crystal aligning agent (9), “evaluation of ink jet coatability of liquid crystal aligning agent” was performed under the above-described conditions.
  • NMP (20.8 g) was added to the polyimide powder (5) (2.55 g) obtained by the synthesis method of Synthesis Example 5 and dissolved by stirring at 70 ° C. for 24 hours.
  • this composition no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (10) was used for evaluation also as a liquid-crystal aligning agent (10). Using the obtained composition (10) or liquid crystal aligning agent (10), production of cells and various evaluations were performed under the above-described conditions.
  • Example 11 NMP (14.5 g) and NEP (8.50 g) were added to the polyimide powder (5) (2.55 g) obtained by the synthesis method of Synthesis Example 5, and dissolved by stirring at 70 ° C. for 24 hours. . [1a] (12.8 g) and BCS (4.30 g) were added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (11). In this composition, no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (11) was used for evaluation also as a liquid-crystal aligning agent (11). Using the obtained composition (11) or liquid crystal aligning agent (11), production of cells and various evaluations were performed under the above-described conditions.
  • Example 12 NMP (16.2 g) and NEP (8.90 g) were added to the polyimide powder (5) (1.55 g) obtained by the synthesis method of Synthesis Example 5 and dissolved by stirring at 70 ° C. for 24 hours. . [1a] (13.3 g) and BCS (4.40 g) were added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (12). In this composition, no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (12) was used for evaluation as a liquid-crystal aligning agent (12). Using the obtained liquid crystal aligning agent (12), “evaluation of inkjet applicability of liquid crystal aligning agent” was performed under the above-described conditions.
  • NMP (20.8 g) was added to the polyimide powder (5) (2.55 g) obtained by the synthesis method of Synthesis Example 5 and dissolved by stirring at 70 ° C. for 24 hours.
  • [1a] (8.50 g), BCS (8.50 g) and MC (2.10 g) were added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (13).
  • this composition no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (13) was used for evaluation also as a liquid-crystal aligning agent (13). Using the obtained composition (13) or liquid crystal aligning agent (13), production of cells and various evaluations were performed under the above-described conditions.
  • NMP 23.0 g was added to the polyimide powder (5) (2.55 g) obtained by the synthesis method of Synthesis Example 5, and dissolved by stirring at 70 ° C. for 24 hours.
  • this composition no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (14) was used for evaluation also as a liquid-crystal aligning agent (14). Using the obtained composition (14) or liquid crystal aligning agent (14), production of cells and various evaluations were performed under the above-described conditions.
  • Example 15 NMP (21.0 g) was added to the polyimide powder (6) (2.57 g) obtained by the synthesis method of Synthesis Example 6, and dissolved by stirring at 70 ° C. for 24 hours. [1a] (12.9 g) and BCS (6.40 g) were added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (15). In this composition, no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (15) was used for evaluation also as a liquid-crystal aligning agent (15). Using the obtained composition (15) or liquid crystal aligning agent (15), cell preparation and various evaluations were performed under the above-described conditions.
  • NEP (16.4 g) was added to the polyimide powder (6) (2.53 g) obtained by the synthesis method of Synthesis Example 6 and dissolved by stirring at 70 ° C. for 24 hours.
  • [1a] (4.20 g) and BCS (19.0 g) were added to this solution, and the mixture was stirred at 50 ° C. for 10 hours to obtain a composition (16).
  • this composition (16) was used for evaluation also as a liquid-crystal aligning agent (16). Using the obtained composition (16) or liquid crystal aligning agent (16), cell preparation and various evaluations were performed under the above-described conditions.
  • Example 17 NMP (14.5 g) and NEP (8.50 g) were added to the polyimide powder (6) (2.55 g) obtained by the synthesis method of Synthesis Example 6 and dissolved by stirring at 70 ° C. for 24 hours. . [1a] (4.30 g) and BCS (12.8 g) were added to this solution, and the mixture was stirred at 50 ° C. for 10 hours to obtain a composition (17). In this composition, no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (17) was used for evaluation also as a liquid-crystal aligning agent (17). Using the obtained composition (17) or liquid crystal aligning agent (17), cell preparation and various evaluations were performed under the above-described conditions.
  • Example 18 NMP (13.5 g) and NEP (8.60 g) were added to the polyimide powder (6) (1.50 g) obtained by the synthesis method of Synthesis Example 6, and dissolved by stirring at 70 ° C. for 24 hours. . [1a] (10.7 g) and BCS (8.60 g) were added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (18). In this composition, no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (18) was used for evaluation as a liquid-crystal aligning agent (18). Using the obtained liquid crystal aligning agent (18), “evaluation of ink jet coatability of liquid crystal aligning agent” was performed under the above-described conditions.
  • ⁇ -BL (16.6 g) was added to the polyimide powder (7) (2.55 g) obtained by the synthesis method of Synthesis Example 7, and dissolved by stirring at 70 ° C. for 24 hours.
  • [1a] (8.50 g) and BCS (14.9 g) were added to this solution, and the mixture was stirred at 50 ° C. for 10 hours to obtain a composition (19).
  • this composition (19) was used for evaluation also as a liquid-crystal aligning agent (19). Using the obtained composition (19) or liquid crystal aligning agent (19), production of cells and various evaluations were performed under the above-described conditions.
  • Example 20 NMP (14.5 g) and ⁇ -BL (2.10 g) were added to the polyimide powder (7) (2.56 g) obtained by the synthesis method of Synthesis Example 7, and dissolved by stirring at 70 ° C. for 24 hours. I let you. [1a] (6.40 g) and BCS (17.1 g) were added to this solution, and the mixture was stirred at 50 ° C. for 10 hours to obtain a composition (20). In this composition, no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (20) was used for evaluation also as a liquid-crystal aligning agent (20). Using the obtained composition (20) or liquid crystal aligning agent (20), production of cells and various evaluations were performed under the above-described conditions.
  • NMP (20.8 g) was added to the polyimide powder (7) (2.55 g) obtained by the synthesis method of Synthesis Example 7, and dissolved by stirring at 70 ° C. for 24 hours.
  • [1a] (12.8 g) and BCS (6.40 g) were added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (21).
  • this composition no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (21) was used for evaluation also as a liquid-crystal aligning agent (21). Using the obtained composition (21) or liquid crystal aligning agent (21), production of cells and various evaluations were performed under the above-described conditions.
  • NMP (20.8 g) was added to the polyimide powder (7) (2.55 g) obtained by the synthesis method of Synthesis Example 7, and dissolved by stirring at 70 ° C. for 24 hours. [1a] (19.1 g) was added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (22). In this composition, no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (22) was used for evaluation also as a liquid-crystal aligning agent (22). Using the obtained composition (22) or liquid crystal aligning agent (22), production of cells and various evaluations were performed under the above-described conditions.
  • NMP (22.5 g) was added to the polyimide powder (8) (2.50 g) obtained by the synthesis method of Synthesis Example 8, and the mixture was dissolved by stirring at 70 ° C. for 24 hours.
  • [1a] (8.30 g) and BCS (8.30 g) were added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (23).
  • this composition no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (23) was used for evaluation also as a liquid-crystal aligning agent (23). Using the obtained composition (23) or liquid crystal aligning agent (23), production of cells and various evaluations were performed under the above-described conditions.
  • Example 24 NMP (12.2 g) and NEP (8.40 g) were added to the polyimide powder (8) (2.52 g) obtained by the synthesis method of Synthesis Example 8, and dissolved by stirring at 70 ° C. for 24 hours. . [1a] (10.5 g) and BCS (8.40 g) were added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (24). In this composition, no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (24) was used for evaluation also as a liquid-crystal aligning agent (24). Using the obtained composition (24) or liquid crystal aligning agent (24), production of cells and various evaluations were performed under the above-described conditions.
  • NMP (20.7 g) was added to the polyimide powder (9) (2.54 g) obtained by the synthesis method of Synthesis Example 9 and dissolved by stirring at 70 ° C. for 24 hours.
  • [1a] (10.6 g) and BCS (8.50 g) were added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (25).
  • this composition no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (25) was used for evaluation also as a liquid-crystal aligning agent (25). Using the obtained composition (25) or liquid crystal aligning agent (25), production of cells and various evaluations were performed under the above-described conditions.
  • Example 26 NMP (5.90 g) and NEP (12.8 g) were added to the polyimide powder (9) (2.55 g) obtained by the synthesis method of Synthesis Example 9, and dissolved by stirring at 70 ° C. for 24 hours. . [1a] (10.6 g) and BCS (10.6 g) were added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (26). In this composition, no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (26) was used for evaluation also as a liquid-crystal aligning agent (26). Using the obtained composition (26) or liquid crystal aligning agent (26), a cell was prepared and various evaluations were performed under the above-described conditions.
  • Example 27 NMP (11.4 g) and NEP (12.9 g) were added to the polyimide powder (9) (1.50 g) obtained by the synthesis method of Synthesis Example 9, and dissolved by stirring at 70 ° C. for 24 hours. . [1a] (8.60 g) and BCS (8.60 g) were added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (27). In this composition, no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (27) was used for evaluation as a liquid-crystal aligning agent (27). Using the obtained liquid crystal aligning agent (27), “evaluation of ink jet coatability of liquid crystal aligning agent” was performed under the above-described conditions.
  • NEP (16.3 g) was added to the polyimide powder (10) (2.50 g) obtained by the synthesis method of Synthesis Example 10, and the mixture was dissolved by stirring at 70 ° C. for 24 hours.
  • [1a] (6.30 g) and BCS (16.7 g) were added to this solution, and the mixture was stirred at 50 ° C. for 10 hours to obtain a composition (28).
  • this composition no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (28) was used for evaluation also as a liquid-crystal aligning agent (28). Using the obtained composition (28) or liquid crystal aligning agent (28), cell preparation and various evaluations were performed under the above-described conditions.
  • NMP (18.7 g) was added to the polyimide powder (10) (2.55 g) obtained by the synthesis method of Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours.
  • this composition no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (29) was used for evaluation also as a liquid-crystal aligning agent (29). Using the obtained composition (29) or liquid crystal aligning agent (29), a cell was prepared and various evaluations were performed under the above-described conditions.
  • NMP 23.0 g was added to the polyimide powder (11) (2.56 g) obtained by the synthesis method of Synthesis Example 11 and dissolved by stirring at 70 ° C. for 24 hours.
  • this composition no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (30) was used for evaluation also as a liquid-crystal aligning agent (30). Using the obtained composition (30) or liquid crystal aligning agent (30), cell preparation and various evaluations were performed under the above-described conditions.
  • NEP (16.6 g) was added to the polyimide powder (11) (2.55 g) obtained by the synthesis method of Synthesis Example 11 and dissolved by stirring at 70 ° C. for 24 hours.
  • [1a] (17.0 g) and BCS (6.40 g) were added to this solution, and the mixture was stirred at 50 ° C. for 10 hours to obtain a composition (31).
  • this composition no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (31) was used for evaluation also as a liquid-crystal aligning agent (31). Using the obtained composition (31) or liquid crystal aligning agent (31), production of cells and various evaluations were performed under the above-described conditions.
  • NEP (16.6 g) and ⁇ -BL (2.10 g) are added to the polyimide powder (11) (2.55 g) obtained by the synthesis method of Synthesis Example 11, and dissolved by stirring at 70 ° C. for 24 hours.
  • [1a] (12.8 g) and BCS (8.50 g) were added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (32).
  • this composition no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (32) was used for evaluation also as a liquid-crystal aligning agent (32). Using the obtained composition (32) or liquid crystal aligning agent (32), cell preparation and various evaluations were performed under the above-described conditions.
  • Example 33 NMP (22.5 g) was added to the polyimide powder (12) (2.50 g) obtained by the synthesis method of Synthesis Example 12, and dissolved by stirring at 70 ° C. for 24 hours. [1a] (14.6 g) and EC (2.10 g) were added to this solution, and the mixture was stirred at 50 ° C. for 10 hours to obtain a composition (33). In this composition, no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (33) was used for evaluation also as a liquid-crystal aligning agent (33). Using the obtained composition (33) and liquid crystal aligning agent (33), cell preparation and various evaluations were performed under the above-described conditions.
  • NEP (18.7 g) was added to the polyimide powder (12) (2.55 g) obtained by the synthesis method of Synthesis Example 12, and dissolved by stirring at 70 ° C. for 24 hours. [1a] (21.3 g) was added to this solution and stirred at 50 ° C. for 10 hours to obtain a composition (34). In this composition, no abnormality such as turbidity and precipitation was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (34) was used for evaluation also as a liquid-crystal aligning agent (34). Using the obtained composition (34) or liquid crystal aligning agent (34), production of cells and various evaluations were performed under the above-described conditions.
  • the polyimide film obtained from the composition of the example of the present invention has a uniform coating property that does not generate pinholes compared to the polyimide film obtained from the composition of the comparative example. Indicated. Further, the linearity of the end portion of the formed polyimide film was high, and the result that the rise of the end portion of the polyimide film was small was also obtained. Moreover, the same result was obtained also in the liquid crystal aligning film obtained from the liquid crystal aligning agent using the composition of this invention.
  • Example 1 and Comparative Example 1 Example 2 and Comparative Example 2, Example 5 and Comparative Example 3, Example 6 and Comparative Example 4, Example 10 and Comparative Example 5, and Example 15 were compared. This is a comparison between Example 6, Example 19 and Comparative Example 7, and Example 29 and Comparative Example 8.
  • Example 1 and Comparative Example 1 Example 2 and Comparative Example 2, Example 5 and Comparative Example 3, Example 6 and Comparative Example 4, Example 10 and Comparative Example 5, and Example 15 were compared. This is a comparison between Example 6, Example 19 and Comparative Example 7, and Example 29 and Comparative Example 8.
  • the liquid crystal containing the specific side chain structure of the present invention in the comparison between the liquid crystal alignment treatment agent containing the specific side chain structure of the present invention and the liquid crystal alignment treatment agent not containing the specific side chain structure, the liquid crystal containing no specific side chain structure
  • the alignment treatment agent has low stability of the pretilt angle, that is, changes with respect to heating and ultraviolet rays are large. Specifically, this is a comparison between Example 8 and Example 28.
  • the composition of the present invention can form a polyimide film having a uniform coating property with no occurrence of pinholes, a high linearity at the end, and a small bulge at the end, and the composition of the present invention.
  • a film can be formed.
  • a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has excellent reliability, and is suitable for a large-screen, high-definition liquid crystal television, etc., TN element, STN element It is useful as a TFT liquid crystal device, particularly a vertical alignment type liquid crystal display device. Furthermore, the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is also useful for a liquid crystal display element that needs to be irradiated with ultraviolet rays when producing a liquid crystal display element.

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  • Chemical & Material Sciences (AREA)
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  • Polymers & Plastics (AREA)
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  • Liquid Crystal (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

La présente invention concerne une composition qui présente d'excellentes propriétés de film de revêtement ; et un film d'alignement de cristaux liquides qui utilise la composition et possède une mouillabilité et une aptitude à étalement élevées d'une solution de revêtement sur un substrat et des propriétés de film de revêtement uniformes, tout en présentant d'excellentes propriétés de film de revêtement sur le bord. L'invention concerne spécifiquement un film d'alignement de cristaux liquides qui présente les caractéristiques mentionnées ci-dessus, même dans les cas où l'agent d'alignement de cristaux liquides utilise un acide polyamidique ou un polyimide soluble dans un solvant qui est obtenu en utilisant un composé diamine comprenant une chaîne latérale. La présente invention concerne une composition qui contient le composant (A) et le composant (B) décrits ci-après. Composant (A) : solvant qui est représenté par la formule (1). (Dans la formule (1), X1 représente un groupe alkyle comprenant de 1 à 3 atomes de carbone.) Composant (B) : au moins un polymère qui est choisi dans le groupe constitué par des précurseurs de polyimide et les polyimides obtenus par imidation des précurseurs de polyimide.
PCT/JP2013/054218 2012-02-22 2013-02-20 Composition, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides WO2013125595A1 (fr)

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CN201380010188.1A CN104136542B (zh) 2012-02-22 2013-02-20 组合物、液晶取向处理剂、液晶取向膜及液晶显示元件

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WO2014061780A1 (fr) * 2012-10-18 2014-04-24 日産化学工業株式会社 Composition, cristal liquide, agent d'alignement, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
WO2014061779A1 (fr) * 2012-10-18 2014-04-24 日産化学工業株式会社 Composition, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
JP2016138236A (ja) * 2014-12-26 2016-08-04 Jsr株式会社 組成物、液晶配向剤、液晶配向膜及び液晶表示素子
WO2017170940A1 (fr) * 2016-03-31 2017-10-05 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
CN110945416A (zh) * 2017-07-27 2020-03-31 日产化学株式会社 树脂组合物、树脂膜及液晶表示元件
WO2021065933A1 (fr) 2019-10-02 2021-04-08 日産化学株式会社 Élément de commande de lumière à cristaux liquides

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KR102611592B1 (ko) * 2017-05-22 2023-12-07 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
JP7375544B2 (ja) * 2017-11-21 2023-11-08 日産化学株式会社 液晶配向剤、液晶配向膜、液晶配向膜の製造方法、及び液晶表示素子
TWI799469B (zh) * 2017-11-21 2023-04-21 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
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WO2014061778A1 (fr) * 2012-10-18 2014-04-24 日産化学工業株式会社 Composition, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
WO2014061780A1 (fr) * 2012-10-18 2014-04-24 日産化学工業株式会社 Composition, cristal liquide, agent d'alignement, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
WO2014061779A1 (fr) * 2012-10-18 2014-04-24 日産化学工業株式会社 Composition, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
JP5930239B2 (ja) * 2012-10-18 2016-06-08 日産化学工業株式会社 組成物、液晶配向処理剤、液晶配向膜および液晶表示素子
JP5930238B2 (ja) * 2012-10-18 2016-06-08 日産化学工業株式会社 組成物、液晶配向処理剤、液晶配向膜および液晶表示素子
JP5930237B2 (ja) * 2012-10-18 2016-06-08 日産化学工業株式会社 組成物、液晶配向処理剤、液晶配向膜および液晶表示素子
JP5950137B2 (ja) * 2012-10-18 2016-07-13 日産化学工業株式会社 組成物、液晶配向処理剤、液晶配向膜および液晶表示素子
JP2016138236A (ja) * 2014-12-26 2016-08-04 Jsr株式会社 組成物、液晶配向剤、液晶配向膜及び液晶表示素子
WO2017170940A1 (fr) * 2016-03-31 2017-10-05 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
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JPWO2017170940A1 (ja) * 2016-03-31 2019-03-07 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
KR102275486B1 (ko) 2016-03-31 2021-07-08 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
CN110945416A (zh) * 2017-07-27 2020-03-31 日产化学株式会社 树脂组合物、树脂膜及液晶表示元件
JPWO2019022202A1 (ja) * 2017-07-27 2020-05-28 日産化学株式会社 樹脂組成物、樹脂膜及び液晶表示素子
CN110945416B (zh) * 2017-07-27 2022-08-26 日产化学株式会社 树脂组合物、树脂膜及液晶表示元件
WO2021065933A1 (fr) 2019-10-02 2021-04-08 日産化学株式会社 Élément de commande de lumière à cristaux liquides

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TW201343788A (zh) 2013-11-01
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