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WO2015060358A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

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

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Publication number
WO2015060358A1
WO2015060358A1 PCT/JP2014/078137 JP2014078137W WO2015060358A1 WO 2015060358 A1 WO2015060358 A1 WO 2015060358A1 JP 2014078137 W JP2014078137 W JP 2014078137W WO 2015060358 A1 WO2015060358 A1 WO 2015060358A1
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Prior art keywords
liquid crystal
group
formula
carbon atoms
hydrogen atom
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English (en)
Japanese (ja)
Inventor
勇歩 野口
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Nissan Chemical Corp
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Nissan Chemical Corp
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Priority to CN201480070728.XA priority Critical patent/CN105849631B/zh
Priority to KR1020167013223A priority patent/KR102291426B1/ko
Priority to JP2015543890A priority patent/JPWO2015060358A1/ja
Publication of WO2015060358A1 publication Critical patent/WO2015060358A1/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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133397—Constructional arrangements; Manufacturing methods for suppressing after-image or image-sticking
    • 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
    • G02F1/133784—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 rubbing

Definitions

  • the present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display element using the liquid crystal aligning film.
  • a liquid crystal display element used for a liquid crystal television, a liquid crystal display, or the like is usually provided with a liquid crystal alignment film for controlling the alignment (also referred to as alignment) state of liquid crystals.
  • a liquid crystal alignment film for controlling the alignment (also referred to as alignment) state of liquid crystals.
  • the most widely used liquid crystal alignment film in the industry is a polyimide precursor formed on an electrode substrate, for example, a polyamic acid or a resin coating made of polyimide obtained by imidizing this with cotton, nylon, polyester. It is produced by performing a so-called rubbing treatment method in which a cloth such as a cloth is rubbed in one direction.
  • the method of rubbing the surface of the resin coating is an industrially useful method that is simple and excellent in productivity.
  • the demand for higher performance, higher definition, and larger size of liquid crystal display elements is increasing, and the surface of the liquid crystal alignment film generated by rubbing treatment, dust generation, the influence of mechanical force and static electricity,
  • various problems such as in-plane non-uniformity of the orientation treatment have been revealed.
  • Patent Document 1 proposes that a resin film made of a polyimide resin having an alicyclic structure such as a cyclobutane ring in the main chain is used for the photo-alignment treatment.
  • a polyimide resin is used for a liquid crystal alignment film of a photo-alignment method, its usefulness is expected because it has higher heat resistance than that of other resins.
  • the photo-alignment treatment as described above has an advantage that it can be produced by an industrially simple manufacturing process as a rubbing-less liquid crystal alignment treatment. Further, in a liquid crystal display element of an IPS (In-Plane Switching) driving method or an FFS (Fringe Field Switching) driving method, the liquid crystal alignment film obtained by the above-described photo-alignment treatment can be used to obtain the rubbing treatment method. Compared with the liquid crystal alignment film, it is possible to improve the performance of the liquid crystal display element, such as an improvement in contrast and viewing angle characteristics of the liquid crystal display element. For this reason, the photo-alignment treatment method is particularly attracting attention as a future liquid crystal alignment treatment method.
  • liquid crystal alignment film used for a liquid crystal display element of an IPS driving method or an FFS driving method in addition to basic properties such as excellent liquid crystal alignment (also referred to as liquid crystal alignment property or liquid crystal alignment regulating force) and electrical properties.
  • liquid crystal alignment property or liquid crystal alignment regulating force also referred to as liquid crystal alignment property or liquid crystal alignment regulating force
  • the liquid crystal alignment film obtained by the photo-alignment treatment method has insufficient liquid crystal orientation, electrical characteristics as a liquid crystal display element, and stability of these characteristics, and it is difficult to satisfy the above characteristics. It was.
  • the present inventor has developed a liquid crystal alignment method as a method for obtaining a liquid crystal alignment film that suppresses an afterimage due to alternating current drive generated in a liquid crystal display element of an IPS drive method or an FFS drive method and has high adhesion to a sealant. Attention was focused on a liquid crystal aligning agent obtained by blending an excellent component (hereinafter referred to as a liquid crystal aligning component) having a strong alignment regulating force for liquid crystal and a component excellent in adhesiveness between the sealing agent and the base substrate (hereinafter referred to as an adhesive component).
  • a liquid crystal aligning agent does not necessarily solve the above-described problems particularly in the photo-alignment treatment method.
  • the liquid crystal alignment film obtained from the liquid crystal alignment agent containing the above two components has improved adhesion to the sealing agent and the base substrate due to the presence of the adhesion component, but it inhibits the alignment regulating force of the liquid crystal. As a result, an afterimage generated by AC driving occurs, and the two characteristics cannot always be achieved.
  • the present invention suppresses afterimages caused by AC driving in a liquid crystal aligning agent blended with a liquid crystal aligning component, that is, a liquid crystal aligning component having a strong liquid crystal alignment regulating force, and an adhesive component excellent in adhesiveness with a sealing agent and a base substrate.
  • a liquid crystal aligning component that is, a liquid crystal aligning component having a strong liquid crystal alignment regulating force, and an adhesive component excellent in adhesiveness with a sealing agent and a base substrate.
  • an object of the present invention is to provide a liquid crystal alignment film that achieves both adhesion with a sealing agent and a base substrate.
  • it is providing 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.
  • liquid crystal aligning agent having a polymer containing a specific structure is extremely effective for achieving the above object, and has completed the present invention. That is, the present invention has the following gist.
  • Liquid crystal aligning agent containing the following (A) component and (B) component.
  • Component (A) having at least one structure selected from structures represented by the following formula [1A] (also referred to as specific structure (1A)) and formula [1B] (also referred to as specific structure (1B)).
  • At least one kind of polymer selected from a polyimide precursor and polyimide also referred to as a specific polymer (A)).
  • Component (B) At least one kind of polymer selected from a polyimide precursor and a polyimide having a structure represented by the following formula [2] (also referred to as a specific structure (2)) (also referred to as a specific polymer (B)) Say).
  • X A and X C each independently represents a protecting group which is replaced with a hydrogen atom by heat
  • X B represents a single bond or a carbon number of 1 to 40 organic groups, in which the atom to which the ester group (—COO— group) is bonded is a carbon atom).
  • Y 1 and Y 7 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —N (R 1 ) —, —CON (R 2 ) —, At least one selected from —N (R 3 ) CO—, —CH 2 O—, —COO—, and OCO—, wherein R 1 , R 2 , and R 3 are each independently a hydrogen atom or carbon Represents an alkyl group having 1 to 3, Y 2 and Y 6 each independently represent an alkylene group having 1 to 10 carbon atoms, and Y 3 and Y 5 each independently represent a hydrogen atom or a carbon number 1 to 10 alkyl groups, and Y 4 represents an oxygen atom or a sulfur atom).
  • the structure represented by the formula [1A] and the formula [1B] is at least one structure selected from the structures represented by the following formula [1a], formula [1b] and formula [1c]
  • the liquid crystal aligning agent as described in (1) In the formula [1a], Xa represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, Xb represents a protecting group which is replaced by a hydrogen atom by heat, and m represents an integer of 1 or 2, , without the substituent of X a when m in the formula [1a] is 2, the formula [1b], X c represents a protecting group to replace a hydrogen atom by heat, wherein [1c], X d is A single bond or an organic group having 1 to 20 carbon atoms, Xe represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, Xf represents a protecting group that is replaced with a hydrogen atom by heat, and n represents 1 to 4 Indicates an integer).
  • the diamine component containing a diamine having at least one structure selected from the structures represented by the formula [1a], formula [1b] and formula [1c] is used as the polymer of the component (A).
  • the liquid crystal aligning agent of Claim 2 which is a polymer containing at least 1 type chosen from the polyimide precursor and polyimide which are obtained by this.
  • X D represents an organic group having 5 to 50 carbon atoms having at least one structure selected from the structures represented by Formula [1a], Formula [1b] and Formula [1c].
  • a 1 and A 2 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).
  • X 1 is a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —N (R 1 ) —, —CON (R 2 ) —, —N (R 3 ) Represents at least one organic group selected from CO—, —CH 2 O—, —COO— and OCO—, wherein R 1 , R 2 and R 3 each independently represents a hydrogen atom or a carbon number of 1 to X 2 represents a single bond, an alkylene group having 1 to 10 carbon atoms, X a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and X b is replaced with a hydrogen atom by heat.
  • X 3 and X 7 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —N (R 1 ) —, —CON (R 2 ) —. , —N (R 3 ) CO—, —CH 2 O—, —COO— and OCO—.
  • R 1 , R 2 and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • X 4 and X 6 each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms
  • X 5 represents a single bond or an alkylene group having 1 to 10 carbon atoms
  • X c represents a hydrogen atom by heat.
  • a protecting group to be substituted is represented, and r represents an integer of 1 to 4.
  • X 8 represents a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —N (R 1 ) —, —CON (R 2 ) —, —N (R 3 ) CO And at least one organic group selected from —, —CH 2 O—, —COO—, and OCO—.
  • R 1 , R 2 and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • X 9 represents a single bond or an alkylene group having 1 to 10 carbon atoms
  • X d represents a single bond or an organic group having 1 to 20 carbon atoms
  • X e represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.
  • X f represents a protecting group which is replaced by a hydrogen atom by heat
  • n represents an integer of 1 to 4
  • s represents an integer of 1 to 4
  • t represents an integer of 1 to 4, and the formula [1a-1 In formula [1c-1],
  • a 1 to A 6 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).
  • R 1 to R 7 are each independently at least selected from structures represented by the following formulas [a-1] to [a-6].
  • 1 represents a structure, and in formulas [1d-1] to [1d-5], A 1 to A 10 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R 1 represents an alkylene group having 1 to 5 carbon atoms.
  • a polymer containing at least one selected from a polyimide precursor and a polyimide obtained by using a diamine component containing a diamine having a structure represented by the formula [2], wherein the polymer of the component (B) The liquid crystal aligning agent according to any one of the above (1) to (6).
  • the liquid crystal aligning agent according to the above (7), wherein the diamine is a diamine represented by the following formula [2-1].
  • Y A represents an organic group having 10 to 50 carbon atoms having the structure represented by Formula [2], and A 1 and A 2 are each independently a hydrogen atom or a carbon number. 1 to 5 alkyl groups).
  • Y 1 and Y 7 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —N (R 1 ) —, —CON (R 2 ) —, At least one selected from —N (R 3 ) CO—, —CH 2 O—, —COO—, and OCO—, wherein R 1 , R 2 , and R 3 are each independently a hydrogen atom or carbon Represents an alkyl group having 1 to 3.
  • Y 2 and Y 6 each independently represent an alkylene group having 1 to 10 carbon atoms, and Y 3 and Y 5 each independently represent a hydrogen atom or 1 to 3 carbon atoms.
  • a 1 to A 6 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • the polymer of the component (A) is a polymer containing at least one selected from a polyimide precursor and a polyimide obtained by using a diamine represented by the following formula [3-1] as a diamine component.
  • the liquid crystal aligning agent according to any one of the above (1) to (10).
  • X E represents at least one structure selected from the structures represented by the following formulas [3a-1] to [3a-9], and A 1 and A 2 each represents Independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).
  • n represents an integer of 1 to 5.
  • the polymer of the component (A) and the polymer of the component (B) are at least one selected from a polyimide precursor obtained by using a tetracarboxylic acid component represented by the following formula [4] and a polyimide.
  • Z represents at least one structure selected from Formula [4a] to Formula [4q] below).
  • Z 1 to Z 4 each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring.
  • Z 5 and Z 6 are Each independently represents a hydrogen atom or a methyl group.
  • Z in the formula [4] is represented by the formula [4a], the formula [4e] to the formula [4g], the formula [4l], the formula [4m], or the formula [4p].
  • the liquid crystal aligning agent as described in said (12) which is a tetracarboxylic-acid component of the at least 1 sort (s) structure chosen from the structure shown.
  • the diamines represented by the formulas [1a-1], [1b-1], and [1c-1] are 5% in 100 mol% of all diamine components.
  • the diamine represented by the formula [2a] is 20 to 100 mol% in 100 mol% of all the diamine components.
  • the liquid crystal according to any one of (1) to (15), wherein the polymer of the component (B) is 40 to 250 parts by mass with respect to 100 parts by mass of the polymer of the component (A). Alignment agent.
  • the liquid crystal aligning agent according to any one of (1) to (16), wherein at least one of the polymers of the component (A) and the component (B) is a polyamic acid alkyl ester.
  • the solvent for the liquid crystal aligning agent is at least one selected from 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, and dipropylene glycol dimethyl ether.
  • the liquid crystal aligning agent according to any one of the above (1) to (18), which contains a seed solvent.
  • liquid crystal aligning agent at least one substituent selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group or a lower alkoxyalkyl group
  • a crosslinkable compound having an epoxy group an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group or a lower alkoxyalkyl group
  • the liquid crystal aligning agent according to any one of the above (1) to (19) comprising at least one kind of crosslinkable compound selected from a crosslinkable compound having a crosslinkable compound and a crosslinkable compound having a polymerizable unsaturated bond.
  • (23) A liquid crystal alignment film obtained by irradiating the liquid crystal alignment film according to (21) or (22) with polarized radiation.
  • (24) A liquid crystal display device having the liquid crystal alignment film according to any one of (21) to (23).
  • a liquid crystal aligning agent comprising at least one polymer selected from polyimide precursors or polyimides having a specific structure suppresses afterimages caused by alternating current driving, and achieves both adhesion with a sealing agent and a base substrate.
  • An alignment film can be obtained.
  • it is useful for a liquid crystal alignment film for photo-alignment treatment obtained by irradiating polarized radiation. Therefore, the liquid crystal display element having the 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, a small and medium-sized car navigation system, a smartphone, and the like. Can be used.
  • the specific structure (1A) and the specific structure (1B) are structures that can increase liquid crystal alignment. Therefore, the liquid crystal alignment film obtained from the liquid crystal aligning agent containing the polymer which has these structures turns into a liquid crystal aligning film excellent in liquid crystal alignability, and can suppress the afterimage by alternating current drive in a liquid crystal display element. Further, the specific structure (1A) and the specific structure (1B) also have an effect of improving the adhesion with the sealant.
  • the specific structure (2) can improve the adhesion with a base substrate, for example, an ITO (Indium Tin Oxide) substrate. Therefore, the liquid crystal aligning film obtained from the liquid crystal aligning agent containing the polymer which has these structures turns into a liquid crystal aligning film excellent in adhesiveness with a base substrate.
  • the effect of each specific structure cannot be obtained depending on the position of the liquid crystal alignment film. That is, the specific structure (1A) and the specific structure (1B) are required to be present near the interface of the liquid crystal alignment film, and the specific structure (2) is present inside the liquid crystal alignment film and at the interface of the base substrate. It will be necessary.
  • the specific weight The coalescence (A) is unevenly distributed in the vicinity of the interface of the liquid crystal alignment film, whereas the specific polymer (B) is considered to be unevenly distributed in the liquid crystal alignment film and at the interface with the substrate.
  • the specific structure (1A) and the specific structure (1B) and the specific structure (2) are used, the specific polymers are likely to be unevenly distributed as described above. Accordingly, it is considered that the liquid crystal alignment film of the present invention can achieve both the above-described liquid crystal alignment, adhesion with the sealing agent, and the base substrate.
  • the specific polymer (A) of the present invention contains at least one selected from polyimide precursors and polyimides having at least one structure selected from the structures represented by the following formulas [1A] and [1B]. It is a polymer.
  • X A represents a protecting group that is replaced by a hydrogen atom by heat.
  • This group is called a protective group because it binds to a nitrogen atom, is eliminated by heat, and is replaced with a hydrogen atom to form an amino group.
  • the temperature at which the protective group is desorbed by heat and replaced with hydrogen atoms is the firing temperature for producing the liquid crystal alignment film, preferably 150 to 300 ° C., more preferably 200 to 270.
  • Such a protecting group is not particularly limited as long as it is eliminated by heat and replaced with a hydrogen atom.
  • R 1 represents an alkylene group having 1 to 5 carbon atoms.
  • R 1 represents an alkylene group having 1 to 5 carbon atoms.
  • the formula [1A] is preferably a structure represented by the following formula [1a] and formula [1b].
  • Xa represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. Of these, a hydrogen atom or an organic group having 1 to 10 carbon atoms is preferable.
  • Xb is a protecting group for a carboxy group and represents a group that is replaced with a hydrogen atom by heat. It is the same as X A described above, also, and preferred examples thereof are also the same.
  • m represents an integer of 1 or 2, in which, when m is 2, the substituents X a are not. Of these, 1 is preferable.
  • Xc is a protecting group for a carboxy group and represents a group that can be replaced by a hydrogen atom by heat.
  • the definition of X A and X b is the same as described above, and preferred examples thereof are also the same.
  • Specific structures represented by the formulas [1a] and [1b] include the following formulas [XA-1] to [XA-12].
  • a 1 to A 6 are each independently at least one selected from the structures represented by the formulas [a-1] to [a-6].
  • n1 represents an integer of 0 to 10
  • n2 to n6 represent an integer of 1 to 10.
  • a 7 to A 18 are each independently at least one selected from the structures represented by the formulas [a-1] to [a-6].
  • n7 represents an integer of 0 to 10
  • n8 to n12 represents an integer of 1 to 10.
  • X B represents a single bond or an organic group having 1 to 40 carbon atoms.
  • the organic group having 1 to 40 carbon atoms include an ether bond (—O—), an amide bond (—CONH— or NHCO—), an ester bond (—COO— or OCO—), a thioether bond (—S—).
  • a thioester bond (—S ( ⁇ O) 2 —), an alkylene group, an arylene group, or a combination thereof.
  • the atom to which the ester group (—COO—) in the formula [1B] is bonded is a carbon atom.
  • X C is a protecting group for a carboxy group and represents a group that can be replaced by a hydrogen atom by heat. This group is the same as X A described above, and preferred examples thereof are also the same.
  • the structure represented by the formula [1B] is preferably a structure having a structure represented by the following formula [1c].
  • X d represents a single bond or an organic group having 1 to 20 carbon atoms. In this case, when X d is a single bond, there is no substituent for X e . Of these, a single bond or an organic group having 1 to 10 carbon atoms is preferable.
  • Xe represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. Of these, a hydrogen atom or an organic group having 1 to 10 carbon atoms is preferable.
  • X f is a protecting group for a carboxy group and represents a group that can be replaced with a hydrogen atom by heat. This group is the same as X A described above, and preferred examples thereof are also the same.
  • n represents an integer of 1 to 4. Of these, 1 or 2 is preferred.
  • Specific examples of the structure represented by the formula [1c] include structures represented by the following formulas [XC-1] to [XC-12].
  • B 1 to B 6 are each independently at least one selected from the structures represented by the formulas [a-1] to [a-6].
  • n1 represents an integer of 0 to 10
  • n2 to n6 represent an integer of 1 to 10.
  • B 7 to B 18 are each independently at least one selected from the structures represented by the formulas [a-1] to [a-6].
  • n7 represents an integer of 0 to 10
  • n8 to n12 represents an integer of 1 to 10.
  • the specific polymer (B) of the present invention is a polymer containing at least one selected from a polyimide precursor having a specific structure (2) represented by the following formula [2] and a polyimide.
  • Y 1 and Y 7 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —S—, —N (R 1 ) —, —CON (R 2 ) —, —N (R 3 ) CO—, —CH 2 O—, —COO— and OCO—.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • a single bond, —O—, —S—, —OCO— or COO— is preferable. More preferred is a single bond, —O— or S— from the viewpoint of liquid crystal orientation and film hardness of the liquid crystal alignment film.
  • Y 2 and Y 6 each independently represent an alkylene group having 1 to 10 carbon atoms.
  • an alkylene group having 1 to 3 carbon atoms is preferable, and the structure thereof may be either linear or branched.
  • a methylene group (—CH 2 —), ethylene group (—CH 2 CH 2 ) having a structure with free rotation and small steric hindrance.
  • a propylene group (-(CH 2 ) 3- ) or an isopropyl group (-C (CH 2 ) 2- ) is preferred.
  • Y 3 and Y 5 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. Particularly preferred is a hydrogen atom.
  • Y 4 represents an oxygen atom or a sulfur atom. Of these, oxygen atoms are preferred from the viewpoint of the film hardness of the liquid crystal alignment film.
  • the specific polymer (A) and the specific polymer (B) are at least one polymer selected from a polyimide precursor and a polyimide (also collectively referred to as a polyimide polymer).
  • the polyimide-type polymer of this invention is a polyimide precursor or a polyimide obtained by making a diamine component and a tetracarboxylic acid component react.
  • 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 each independently a hydrogen atom or an alkyl having 1 to 5 carbon atoms.
  • a 3 and A 4 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acetyl group, and n represents a positive integer).
  • the diamine component include diamines having two primary or secondary amino groups in the molecule.
  • tetracarboxylic acid component examples include tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds, and tetracarboxylic acid dialkyl ester dihalide compounds.
  • a diamine having two primary or secondary amino groups in the molecule a tetracarboxylic acid compound or a tetracarboxylic acid It can be obtained by reacting with an acid anhydride.
  • the diamine, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or a tetra It can be obtained by reacting a carboxylic acid dialkyl ester dihalide compound.
  • an alkylene group having 1 to 5 carbon atoms of A 1 and A 2 represented by the formula [A] can be introduced into the polyamic acid obtained by the above method.
  • the specific polymer (A) is a polymer having at least one structure selected from the specific structure (1A) and the specific structure (1B).
  • the method for introducing the specific structure (1A) or the specific structure (1B) into the specific polymer (A) is not particularly limited, but a diamine having the specific structure (1A) or the specific structure (1B) is used as the diamine component. It is preferable. It is particularly preferable to use a diamine having a structure represented by the formula [1a], formula [1b] or formula [1c].
  • a diamine represented by the following formula [1-1] (also referred to as a specific diamine (1)).
  • X D represents an organic group having 5 to 50 carbon atoms having at least one structure selected from the structures represented by Formula [1a], Formula [1b] and Formula [1c].
  • a 1 and A 2 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • diamines represented by the following formulas [1a-1] to [1c-1] are preferably used.
  • X 1 is a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —N (R 1 ) —, —CON (R 2 ) —, —N (R 3 ) CO At least one selected from —, —CH 2 O—, —COO— and OCO— is shown.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • X 2 represents a single bond or an alkylene group having 1 to 10 carbon atoms. Of these, a single bond or an alkylene group having 1 to 5 carbon atoms is preferable.
  • X a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an organic group having 1 to 10 carbon atoms.
  • the organic group having 1 to 10 carbon atoms is preferably — (CH 2 ) n —COO-tBu (wherein n represents an integer of 1 to 5 and tBu represents a tert-butyl group).
  • Xb is a group that is eliminated by heating and replaced with a hydrogen atom, and is a protecting group for a carboxyl group. Specific examples of this group are the same as those of X A described above, and preferred examples thereof are also the same as those of X A described above.
  • m represents an integer of 1 or 2, in which the substituents X a when m in the formula [1a] is 2 no.
  • p represents an integer of 1 to 4.
  • 1 to 3 are preferable from the viewpoint of availability of raw materials and ease of synthesis. More preferred is 1 to 2.
  • q represents an integer of 1 to 4.
  • 1 to 3 are preferable from the viewpoint of availability of raw materials and ease of synthesis. More preferred is 1 to 2.
  • X 3 and X 7 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —N (R 1 ) —, —CON (R 2 ) —.
  • —N (R 3 ) CO—, —CH 2 O—, —COO—, or OCO— represents at least one organic group.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Of these, a single bond, —O—, —CONH—, —NHCO—, —COO— or OCO— is preferable.
  • X 4 and X 6 each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms. In particular, a single bond or an alkyl group having 1 to 5 carbon atoms is preferable.
  • X 5 represents a single bond or an alkylene group having 1 to 10 carbon atoms. Of these, a single bond or an alkylene group having 1 to 5 carbon atoms is preferable.
  • Xc is a protecting group for a carboxy group, and is the same as Xb described above, and preferred examples thereof are also the same.
  • r represents an integer of 1 to 4. Among these, 1 to 3 are preferable from the viewpoint of availability of raw materials and ease of synthesis. More preferred is 1 to 2.
  • X 8 represents a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —N (R 1 ) —, —CON (R 2 ) —, —N (R 3 ) CO It represents at least one organic group selected from —, —CH 2 O—, —COO— or OCO—.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • a single bond, —O—, —CONH—, —NHCO—, —COO— or OCO— is preferable.
  • X 9 represents a single bond or an alkylene group having 1 to 10 carbon atoms, preferably a single bond or an alkylene group having 1 to 5 carbon atoms.
  • X d represents a single bond or an organic group having 1 to 20 carbon atoms. Of these, a single bond or an organic group having 1 to 10 carbon atoms is preferable. More preferably, it is a single bond or a carbon atom (> CH—).
  • Xe represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. At that time, X e is not when X d is a single bond.
  • a hydrogen atom or NH—COO-tBu (tBu represents a tert-butyl group) is preferable.
  • Xf is a protecting group for a carboxyl group, and is the same as Xb and Xb described above, and preferred examples thereof are also the same.
  • n represents an integer of 1 to 4.
  • 1 to 3 is preferable, and 1 to 2 is more preferable from the viewpoint of availability of raw materials and ease of synthesis.
  • s represents an integer of 1 to 4, and among these, 1 to 3 is preferable and 1 to 2 is more preferable in view of availability of raw materials and ease of synthesis.
  • t represents an integer of 1 to 4, and among these, 1 to 3 is preferable and 1 to 2 is more preferable in view of availability of raw materials and ease of synthesis.
  • a 1 to A 6 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • Specific diamines of the specific diamine (1) of the present invention include diamines represented by the following formula [1d].
  • D represents at least one structure selected from the structures represented by Formula [XA-1] to Formula [XA-12] and Formula [XC-1] to Formula [XC-12].
  • N represents an integer of 1 to 4).
  • diamines represented by the following formulas [1d-1] to [1d-11].
  • R 1 to R 7 each independently represents at least one structure selected from the formulas [a-1] to [a-6].
  • a 1 to A 10 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R 8 to R 14 are each independently at least one selected from the structures represented by the formulas [a-1] to [a-6].
  • a structure of a seed is shown, and in the formulas [1d-6] to [1d-9], A 11 to A 18 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).
  • the specific diamine (1) of the present invention it is preferable to use diamines represented by the above formulas [1d-1] to [1d-5].
  • diamines represented by the following formulas [1d-10] and [1d-11] can also be used.
  • R 15 to R 18 are each independently at least one selected from the structures represented by Formula [a-1] to Formula [a-6].
  • a 19 and A 20 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms in the formula [1d-11].
  • the specific diamine (1) in the specific polymer (A) is preferably 5 to 40 mol% in 100 mol% of all diamine components. Of these, 5 to 30 mol% is preferable. More preferred is 5 to 20 mol%.
  • the specific diamine (1) of the present invention has characteristics such as solubility of the specific polymer (A) in a solvent, applicability of a liquid crystal aligning agent, liquid crystal alignment in a liquid crystal alignment film, voltage holding ratio, accumulated charge, and the like. Depending on the above, one kind or a mixture of two or more kinds may be used.
  • the specific polymer (B) is a polymer having a specific structure (2).
  • a diamine represented by the following formula [2-1] (also referred to as a specific diamine (2)).
  • Y A represents an organic group having 10 to 50 carbon atoms and having the structure represented by Formula [2].
  • a 1 and A 2 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. More specifically, it is preferable to use a diamine represented by the following formula [2a].
  • Y 1 and Y 7 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —S—, —N (R 1 ) —, —CON (R 2 ) —, —N (R 3 ) CO—, —CH 2 O—, —COO— and OCO—.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • a single bond, —O—, —S—, —OCO— or COO— is preferable.
  • a single bond —O— or S—, which is a structure that is as flexible as possible and has as little steric hindrance from the viewpoint of liquid crystal orientation and film hardness.
  • Y 2 and Y 6 each independently represent an alkylene group having 1 to 10 carbon atoms. Among these, an alkylene group having 1 to 3 carbon atoms is preferable, and the structure thereof may be either linear or branched. Specifically, from the viewpoint of liquid crystal alignment properties and film hardness of the liquid crystal alignment film, a methylene group (—CH 2 —), ethylene group (—CH 2 CH 2 ) having a structure having a free rotation portion and small steric hindrance. -), A propylene group (-(CH 2 ) 3- ) or an isopropyl group (-C (CH 2 ) 2- ) is preferred.
  • Y 3 and Y 5 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. Particularly preferred is a hydrogen atom.
  • Y 4 represents an oxygen atom or a sulfur atom. Of these, oxygen atoms are preferred from the viewpoint of the film hardness of the liquid crystal alignment film. Preferred combinations of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 and Y 7 in the formula [2a] are as shown in Table 1 below.
  • A1 and A2 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • Specific diamines of the specific diamine (2) include diamines represented by the following formulas [2a-1] to [2a-3]. (In the formulas [2a-1] to [2a-3], A 1 to A 6 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).
  • the specific diamine (2) in the specific polymer (B) is preferably 10 to 100 mol% in 100 mol% of all diamine components. Of these, 20 to 100 mol% is preferable. More preferred is 30 to 100 mol%.
  • the specific diamine (2) depends on the properties such as the solubility of the specific polymer (B) in the solvent, the coating property of the liquid crystal aligning agent, the liquid crystal aligning property in the case of the liquid crystal aligning film, the voltage holding ratio, and the accumulated charge.
  • One kind or a mixture of two or more kinds may be used.
  • Y A represents at least one structure selected from structures represented by the following formulas [3a-1] to [3a-9].
  • n represents an integer of 1 to 5).
  • a 1 and A 2 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • a diamine represented by the formula [3a-1] to the formula [3a-4], the formula [3a-6], the formula [3a-8] or the formula [3a-9] is used. preferable. More preferred are formula [3a-1] to formula [3a-3], formula [3a-8] or formula [3a-9]. Particularly preferred is the formula [3a-1], the formula [3a-2] or the formula [3a-9].
  • the specific second diamine in the specific polymer (A) is preferably 50 to 95 mol% in 100 mol% of all diamine components. More preferably, it is 60 to 95 mol%. Particularly preferred is 80 to 95 mol%.
  • the specific second diamine depends on properties such as the solubility of the specific polymer (A) in the solvent, the coating property of the liquid crystal aligning agent, the liquid crystal alignment property when the liquid crystal alignment film is used, the voltage holding ratio, and the accumulated charge. One kind or a mixture of two or more kinds may be used.
  • the specific diamine (1), the specific diamine (2), the specific second diamine, and other Diamine can be used as a diamine component of the specific polymer (A) and the specific polymer (B).
  • diamines include the solubility of the specific polymer (A) and the specific polymer (B) in the solvent, the coating property of the liquid crystal aligning agent, the liquid crystal alignment in the case of using the liquid crystal alignment film, voltage holding ratio, accumulated charge Depending on the characteristics, one kind or a mixture of two or more kinds may be used.
  • the tetracarboxylic acid component for producing the specific polymer (A) and the specific polymer (B) that is, these polyimide polymers
  • tetracarboxylic dianhydride represented by the following formula [4] is used. It is preferable to use it.
  • tetracarboxylic dianhydride represented by the formula [4] not only the tetracarboxylic dianhydride represented by the formula [4] but also the tetracarboxylic acid derivative tetracarboxylic acid, tetracarboxylic dihalide compound, tetracarboxylic dialkyl ester compound or tetracarboxylic dialkyl ester di Halide compounds can also be used (the tetracarboxylic dianhydride represented by the formula [4] and derivatives thereof are collectively referred to as a specific tetracarboxylic acid component).
  • Z represents at least one structure selected from Formula [4a] to Formula [4q] below).
  • Z 1 to Z 4 each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring.
  • Z 5 and Z 6 each independently represent a hydrogen atom or a methyl group.
  • Z 1 in the formula [4] from the viewpoint of easy synthesis and ease of polymerization reactivity when producing a polymer, the formula [4a], the formula [4c] to the formula [4g], the formula [4] 4k] to [4m] or a tetracarboxylic dianhydride having a structure represented by the formula [4p] and a tetracarboxylic acid derivative thereof are preferable.
  • Particularly preferred is a tetracarboxylic dianhydride having a structure represented by [4a], formula [4e], formula [4f], formula [4l], formula [4m] or formula [4p] and a tetracarboxylic acid derivative thereof. It is.
  • the specific tetracarboxylic acid component in the specific polymer (A) and the specific polymer (B) is preferably 50 to 100 mol% in 100 mol% of all tetracarboxylic acid components. Among these, 70 to 100 mol% is preferable. More preferred is 80 to 100 mol%.
  • the specific tetracarboxylic acid component is the solubility of the specific polymer (A) and the specific polymer (B) in the solvent, the coating property of the liquid crystal aligning agent, the orientation of the liquid crystal when the liquid crystal alignment film is used, the voltage holding ratio, One or a mixture of two or more can be used depending on the characteristics such as accumulated charge.
  • other tetracarboxylic acid components other than a specific tetracarboxylic acid component can also be used for the polyimide polymer of a specific polymer (A) and a specific polymer (B).
  • tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds, and tetracarboxylic acid dialkyl ester dihalide compounds.
  • tetracarboxylic acid components include 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4 ′ -Benzophenone tetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1, 1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane
  • tetracarboxylic acid components include the solubility of the specific polymer (A) and the specific polymer (B) in the solvent, the coating property of the liquid crystal aligning agent, the liquid crystal alignment property when the liquid crystal alignment film is used, the voltage holding ratio, One or a mixture of two or more can be used depending on the characteristics such as accumulated charge.
  • the specific polymer (A) and the specific polymer (B), that is, a method for producing these polyimide polymers is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. In general, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydrides and derivatives of the tetracarboxylic acid is reacted with a diamine component consisting of one or more diamines. And a method of obtaining a polyamic acid.
  • tetracarboxylic dianhydride and primary or secondary diamine are polycondensed to obtain polyamic acid
  • tetracarboxylic acid and primary or secondary diamine are subjected to dehydration polycondensation reaction.
  • a method of obtaining a polyamic acid or a method of polycondensing a tetracarboxylic acid dihalide and a primary or secondary diamine to obtain a polyamic acid is used.
  • a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group with a primary or secondary diamine, a tetracarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group and 1 A method of polycondensation with a secondary or secondary diamine or a method of converting a carboxyl group of a polyamic acid into an ester is used.
  • polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.
  • the reaction between the diamine component and the tetracarboxylic acid component is usually carried out in a solvent with the diamine component and the tetracarboxylic acid component.
  • the solvent used at that time is not particularly limited as long as the produced polyimide precursor is soluble. Although the specific example of the solvent used for reaction below is given, it is not limited to these examples.
  • Examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolidinone. It is done.
  • the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3]
  • the indicated solvents can be used.
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • the formula [D-3 represents an alkyl group having 1 to 4 carbon atoms.
  • These solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use it for the said solvent in the range which the produced
  • 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.
  • 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 closure of the polyimide precursor, and in this polyimide, the ring closure rate of the amic acid group (also referred to as imidization rate) is not necessarily 100%. It can be arbitrarily adjusted according to the purpose.
  • 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 at which the polyimide precursor is thermally imidized in the solution is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.
  • the catalyst imidation of the polyimide precursor can be performed 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.
  • Examples of 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.
  • polymer collected by precipitation is redissolved in a solvent and then re-precipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced.
  • the solvent at this time include alcohols, ketones, and hydrocarbons, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further improved.
  • Polyamide acid alkyl ester is preferably used for the specific polymer (A) and the specific polymer (B).
  • More specific methods for producing the polyamic acid alkyl ester of the present invention are shown in the following (1) to (3).
  • (1) Method of preparing by esterification reaction of polyamic acid Polyamic acid is prepared from a diamine component and a tetracarboxylic acid component, and a chemical reaction, that is, an esterification reaction is performed on the carboxyl group (COOH group).
  • the polyamic acid and the esterifying agent are present in the presence of a solvent at ⁇ 20 to 150 ° C. (preferably 0 to 50 ° C.) for 30 minutes to 24 hours (preferably 1 to 4 hours). This is a reaction method.
  • the esterifying agent is preferably one that can be easily removed after the esterification reaction.
  • N N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl -3-p-tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like.
  • the amount of the esterifying agent used is preferably 2 to 6 molar equivalents per 1 mol of the polyamic acid repeating unit. Of these, 2 to 4 molar equivalents are preferred.
  • the solvent used for the esterification reaction include a solvent used for the reaction of the diamine component and the tetracarboxylic acid component from the viewpoint of solubility of the polyamic acid in the solvent. Of these, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone is preferable. These solvents may be used alone or in combination of two or more.
  • the concentration of the polyamic acid in the solvent in the esterification reaction is preferably 1 to 30% by mass from the viewpoint that the polyamic acid does not easily precipitate. Among these, 5 to 20% by mass is preferable.
  • the amount of the base used is preferably an amount that can be easily removed after the reaction, and is preferably 2 to 4 times mol of tetracarboxylic acid diester dichloride. Of these, 2 moles to 3 moles are more preferred.
  • the solvent used in the reaction include a solvent used in the reaction of the diamine component and the tetracarboxylic acid component from the viewpoint of the solubility of the resulting polymer, that is, the polyamic acid alkyl ester, in the solvent. Of these, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone is preferable. These solvents may be used alone or in combination of two or more.
  • the concentration of the polyamic acid alkyl ester in the solvent in the reaction is preferably 1 to 30% by mass from the viewpoint that precipitation of the polyamic acid alkyl ester hardly occurs. Among these, 5 to 20% by mass is preferable.
  • the solvent used for preparing the polyamic acid alkyl ester is dehydrated as much as possible.
  • the reaction is preferably performed in a nitrogen atmosphere to prevent outside air from being mixed.
  • Method of making by reaction of diamine component and tetracarboxylic acid diester It is a method of making by polycondensation reaction of a diamine component and tetracarboxylic acid diester. Specifically, in the polycondensation reaction, the diamine component and the tetracarboxylic acid diester are mixed in the presence of a condensing agent, a base and a solvent at 0 to 150 ° C. (preferably 0 to 100 ° C.) for 30 minutes to 24 hours. It is a method of reacting (preferably 3 to 15 hours).
  • condensing agent examples include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazide.
  • Nylmethylmorpholinium O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like can be used.
  • the amount of the condensing agent used is preferably 2 to 3 moles, and more preferably 2 to 2.5 moles, based on the tetracarboxylic acid diester.
  • tertiary amines such as pyridine and triethylamine can be used.
  • the amount of the base used is preferably an amount that can be easily removed after the polycondensation reaction, preferably 2 to 4 times mol, particularly preferably 2 to 3 times mol, of the diamine component.
  • the solvent used for the polycondensation reaction examples include a solvent used for the reaction of the diamine component and the tetracarboxylic acid component from the viewpoint of the solubility of the resulting polymer, that is, the polyamic acid alkyl ester, in the solvent.
  • a solvent used for the reaction of the diamine component and the tetracarboxylic acid component from the viewpoint of the solubility of the resulting polymer, that is, the polyamic acid alkyl ester, in the solvent.
  • N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone is preferable.
  • These solvents may be used alone or in combination of two or more.
  • the reaction proceeds efficiently by adding a Lewis acid as an additive.
  • the Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
  • the amount of Lewis acid used is preferably 0.1 to 10 times the mole of the diamine component. In particular, 2.0 to 3.0 moles are more preferable.
  • the reaction solution may be poured into a solvent and precipitated.
  • the solvent used for precipitation include water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, and toluene.
  • the polymer precipitated in the solvent is preferably washed with the solvent several times for the purpose of removing the additives and catalysts used above.
  • the polyamic acid alkyl ester of the present invention is preferably produced by the method (1) or (2) among the methods for producing the polyamic acid alkyl ester represented by the above (1) to (3).
  • the liquid crystal alignment agent of the present invention is a coating solution for forming a liquid crystal alignment film (also referred to as a resin film), and forms a liquid crystal alignment film containing a specific polymer (A), a specific polymer (B) and a solvent. It is the coating solution for doing.
  • the ratio of the specific polymer (B) in the liquid crystal aligning agent is preferably 10 to 900 parts by mass, more preferably 25 to 400 parts by mass, and 40 to 250 parts by mass with respect to 100 parts by mass of the specific polymer (A). Particularly preferred is 60 to 160 parts by mass.
  • All of the polymer components in the liquid crystal aligning agent of the present invention may be the specific polymer (A) and the specific polymer (B), or other polymers may be mixed.
  • Other polymers include polyimide precursors and polyimides that do not have the specific structure (1A), specific structure (1B), and specific structure (2).
  • a cellulose polymer, an acrylic polymer, a methacrylic polymer, polystyrene, polyamide, or polysiloxane may be used.
  • the content of the other polymer is preferably 0.5 to 15 parts by mass, particularly 1 to 100 parts by mass in total with the specific polymer (A) and the specific polymer (B). ⁇ 10 parts by mass are preferred.
  • the content of the solvent in the liquid crystal aligning agent is preferably 70 to 99.9% by mass. This content can be appropriately changed depending on the application method of the liquid crystal aligning agent and the film thickness of the target liquid crystal alignment film.
  • the solvent used for the liquid crystal aligning agent of this invention will not be specifically limited if it is a solvent (it is also called a good solvent) in which a specific polymer (A) and a specific polymer (B) are dissolved.
  • a good solvent is also called to the following, it is not limited to these examples.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and ⁇ -butyrolactone are preferable.
  • the solvents represented by the formulas [D-1] to [D-3] are preferable.
  • the good solvent in the liquid crystal aligning agent is preferably 20 to 99% by mass of the total solvent contained in the liquid crystal aligning agent. Of these, 20 to 90% by mass is preferable. More preferred is 30 to 80% by mass.
  • the liquid crystal aligning agent of the present invention uses a solvent (also referred to as a poor solvent) that improves the coating properties and surface smoothness of the liquid crystal aligning film when the liquid crystal aligning agent is applied. it can.
  • a solvent also referred to as a poor solvent
  • 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
  • 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether is preferably used.
  • These poor solvents are preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass with respect to the total solvent contained in the liquid crystal aligning agent.
  • the liquid crystal aligning agent of the present invention includes at least one substituent selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. It is preferable to introduce a crosslinkable compound having a crosslinkable compound or a crosslinkable compound having a polymerizable unsaturated bond. 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 [4A].
  • Specific examples include crosslinkable compounds represented by the formulas [4a] to [4k] described in the paragraphs 58 to 59 of the international publication 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 [5A]. Specific examples include crosslinkable compounds represented by the formulas [5-1] to [5-42] published on pages 76 to 82 of International Publication No. WO2012 / 014898 (2012.2.2 publication). .
  • 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.
  • glycoluril examples include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powderlink 1174.
  • 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, International Publication WO2011 / 132751. (2011.10.27), pages 62 to 66, and crosslinkable compounds represented by formulas [6-1] to [6-48].
  • 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 or 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 Rudi (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
  • a compound represented by the following formula [7A] can also be used.
  • E 1 represents a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring or a phenanthrene ring
  • 2 represents a group selected from the following formula [7a] or [7b]
  • n represents 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 liquid crystal aligning agent of this invention may be 1 type, and may be combined 2 or more types.
  • the content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all the polymer components.
  • the amount is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of all the polymer components. More preferred is 1 to 50 parts by mass.
  • the liquid crystal aligning agent of the present invention can use a compound that improves the uniformity of the film thickness and surface smoothness of the liquid crystal aligning film when the liquid crystal aligning agent is applied.
  • Examples of the compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink), Florard FC430, FC431 (or more) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.) and the like.
  • fluorine-based surfactants silicone-based surfactants
  • nonionic surfactants More specifically, for example, F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink), Florard FC430, FC4
  • the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent. is there.
  • the liquid crystal aligning agent of the present invention includes compounds 69 to 73 of International Publication No. WO2011 / 132751 (published 2011.10.27) as a compound that promotes charge transfer in the liquid crystal aligning film and promotes charge loss of the device. Nitrogen-containing heterocyclic amines represented by the formulas [M1] to [M156] shown on the page can also be added.
  • the amine may be added directly to the liquid crystal aligning agent, but it is preferable to add the amine after making a solution with a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass with an appropriate solvent.
  • the solvent is not particularly limited as long as it is a solvent that dissolves the specific polymer (A) and the specific polymer (B) described above.
  • the liquid crystal aligning agent of the present invention includes, in addition to the above-mentioned poor solvent, crosslinkable compound, resin film or compound that improves the film thickness uniformity and surface smoothness of the liquid crystal aligning film, and a compound that promotes charge removal. As long as the effects of the invention are not impaired, a dielectric or conductive material for changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film may be added.
  • the liquid crystal alignment film of the present invention is a film obtained by applying the liquid crystal aligning agent to a substrate, drying and baking.
  • the substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used together with a glass substrate or a silicon nitride substrate. At that time, it is preferable to use a substrate on which an ITO electrode or the like for driving the liquid crystal is used from the viewpoint of simplification of the process.
  • an opaque material such as a silicon wafer can be used as long as it is only on one side of the substrate, and a material that reflects light such as aluminum can be used for the electrode in this case.
  • a method for applying the liquid crystal aligning 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 can be evaporated by a heating means such as a hot plate, a thermal circulation oven, or an IR (infrared) oven to form a liquid crystal alignment film.
  • a heating means such as a hot plate, a thermal circulation oven, or an IR (infrared) oven to form a liquid crystal alignment film.
  • Arbitrary temperature and time can be selected for the drying and baking steps after applying the liquid crystal aligning agent of the present invention.
  • a condition of baking at 50 to 120 ° C. for 1 to 10 minutes and then baking at 150 to 300 ° C. for 5 to 120 minutes in order to sufficiently remove the contained solvent may be mentioned.
  • the thickness of the liquid crystal alignment film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be lowered, and therefore it is preferably 5 nm to 300 nm. Among these, 10 nm to 200 nm is preferable.
  • Examples of the method for aligning the obtained liquid crystal alignment film include the rubbing method and the photo-alignment method.
  • the surface of the liquid crystal alignment film is irradiated with radiation deflected in a certain direction, and in some cases, heat treatment is performed at a temperature of 150 to 250 ° C. And a method of imparting the orientation ability).
  • the radiation ultraviolet rays or visible rays having a wavelength of 100 to 800 nm can be used. Among these, ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and ultraviolet rays having a wavelength of 200 to 400 nm are more preferable.
  • the substrate coated with the liquid crystal alignment film may be irradiated with radiation while heating at 50 to 250 ° C.
  • the radiation dose is preferably 1 to 10,000 mJ / cm 2 . Of these, 100 to 5,000 mJ / cm 2 is preferable.
  • the liquid crystal alignment film thus prepared can stably align liquid crystal molecules in a certain direction. Further, the liquid crystal alignment film irradiated with polarized radiation can be subjected to contact treatment using water or a solvent by the above method.
  • the solvent used for the contact treatment is not particularly limited as long as it is a solvent that dissolves a decomposition product generated from the liquid crystal alignment film by irradiation with radiation.
  • Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3- Examples thereof include methyl methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate or cyclohexyl acetate.
  • water, 2-propanol, 1-methoxy-2-propanol or ethyl lactate is preferable from the viewpoint of versatility and solvent safety. More preferred is water, 1-methoxy-2-propanol or ethyl lactate.
  • These solvents may be used alone or in combination of two or more.
  • Examples of the contact treatment in the present invention that is, treatment of water or solvent on the liquid crystal alignment film irradiated with polarized radiation include immersion treatment and spray treatment (also referred to as spray treatment).
  • the treatment time in these treatments is preferably 10 seconds to 1 hour from the viewpoint of efficiently dissolving the decomposition products generated from the liquid crystal alignment film by radiation.
  • the immersion treatment is preferably performed for 1 minute to 30 minutes.
  • the solvent used in the contact treatment may be warmed up at room temperature or preferably 10 to 80 ° C. Of these, 20 to 50 ° C. is preferable.
  • ultrasonic treatment or the like may be performed as necessary.
  • rinsing also referred to as rinsing
  • a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, or methyl ethyl ketone
  • baking of the liquid crystal alignment film is preferably performed.
  • a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, or methyl ethyl ketone
  • the firing temperature is preferably 150 to 300 ° C. Of these, 180 to 250 ° C. is preferable. More preferably, the temperature is 200 to 230 ° C.
  • the firing time is preferably 10 seconds to 30 minutes. Of these, 1 minute to 10 minutes is preferable.
  • the liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film of a horizontal electric field type liquid crystal display element such as an IPS mode or an FFS mode, and is particularly useful as a liquid crystal alignment film of an FFS mode liquid crystal display element.
  • a liquid crystal cell was prepared by a known method, and the liquid crystal cell was used as a liquid crystal display element. Is.
  • a liquid crystal display element having a passive matrix structure will be described as an example. Note that an active matrix liquid crystal display element in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion constituting the image display may be used.
  • TFT Thin Film Transistor
  • a transparent glass substrate is prepared, a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate.
  • These electrodes can be ITO electrodes, for example, and are patterned so as to display a desired image.
  • an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode.
  • the insulating film can be, for example, a film made of SiO 2 —TiO 2 formed by a sol-gel method.
  • a liquid crystal alignment film is formed on each substrate, the other substrate is overlapped with one substrate so that the liquid crystal alignment film faces each other, and the periphery is sealed with a sealant. Glue.
  • a spacer is usually mixed in the sealant. Further, it is preferable that spacers for controlling the gap between the substrates are also sprayed on the in-plane portion where no sealant is provided. A part of the sealant is provided with an opening that can be filled with liquid crystal from the outside. Thereafter, a liquid crystal material is injected into a space surrounded by the two substrates and the sealant through an opening provided in the sealant. Thereafter, the opening is sealed with an adhesive.
  • a vacuum injection method may be used, or a method utilizing capillary action in the atmosphere may be used.
  • the liquid crystal material either a positive liquid crystal material or a negative liquid crystal material may be used.
  • a polarizing plate is installed.
  • a pair of polarizing plates is attached to the surfaces of the two substrates opposite to the liquid crystal layer.
  • the liquid crystal aligning agent of the present invention it is possible to obtain a liquid crystal aligning film that suppresses afterimages due to AC driving and has both adhesiveness with the sealing agent and the base substrate.
  • (Other diamines) 4A p-phenylenediamine (Specific tetracarboxylic acid component)
  • C1 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • C2 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • C3 3,3 ′, 4,4 '-Biphenyltetracarboxylic dianhydride
  • C4 tetracarboxylic acid dialkyl ester dihalide compound represented by the following formula [C4]
  • the imidation ratio of polyimide was measured as follows. 20 mg of polyimide powder was put into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, ⁇ 5 (manufactured by Kusano Kagaku)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane)). (Mixed product) (0.53 ml) was added and completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Datum).
  • the viscosity of this polyamic acid solution at a temperature of 25 ° C. was 230 mPa ⁇ s.
  • the number average molecular weight (Mn) of this polyamic acid was 11,100, and the weight average molecular weight (Mw) was 30,000.
  • the obtained polyamic acid alkyl ester solution was poured into water (1230 g) with stirring, and the precipitated white precipitate was collected by filtration, washed 5 times with IPA (isopropyl alcohol) (1230 g), and dried.
  • White polyamic acid alkyl ester powder (10.2 g) was obtained. Mn of this polyamic acid alkyl ester was 20,800, and Mw was 41,000.
  • the coating film with a film thickness of 100 nm.
  • the coating surface was irradiated with UV light of 254 nm at 600 mJ / cm 2 through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Further, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 ⁇ m on which no electrode was formed as a counter substrate, and an orientation treatment was performed.
  • the two substrates are combined as a set, a sealant is printed on the substrate, and the other substrate is bonded so that the liquid crystal alignment film faces and the alignment direction is 0 °, and then the sealant is added.
  • An empty cell was produced by curing.
  • Liquid crystal MLC-2041 manufactured by Merck Japan Ltd.
  • an AC voltage of ⁇ 10 V was applied for 120 hours at a frequency of 60 Hz in a constant temperature environment of 60 ° C. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited and left as it was at room temperature for one day.
  • the liquid crystal cell After standing, the liquid crystal cell is placed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, and the backlight is turned on with no voltage applied, so that the liquid crystal has the lowest brightness.
  • the cell placement angle was adjusted. Then, the rotation angle when the liquid crystal cell was rotated from the angle at which the second region of the first pixel became darkest to the angle at which the first region became darkest was calculated as an angle ⁇ (°). Similarly, in the second pixel, the second region and the first region were compared, and a similar angle ⁇ (°) was calculated.
  • a 6 ⁇ m bead spacer is applied to one side of this substrate, and further a sealing agent (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) is printed on the liquid crystal alignment film of the other substrate, and the overlapping width of the substrates is 1 cm. Lamination was performed so that At that time, the amount of the sealing agent was adjusted so that the diameter of the sealing agent after bonding was 3 mm. The two bonded substrates were fixed with a clip and then thermally cured at 150 ° C. for 1 hour to produce a test sample substrate for this evaluation.
  • a sealing agent XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.
  • this test sample substrate is fixed from the upper part of the center of the substrate after fixing the upper and lower substrate ends with a desktop precision universal testing machine (AGS-X 500N) (manufactured by Shimadzu Corporation)
  • AGS-X 500N desktop precision universal testing machine
  • the pressure (N) at the time of peeling that is, the peeling pressure (N) was measured.
  • the larger the value of the peeling stress (N), the better the adhesion with the sealing agent and the base substrate Tables 5 and 6 show the value of the peeling stress (N)). Tables 5 and 6 show the results obtained in the examples and comparative examples.
  • Example 1 The polyamic acid solution (1) (4.95 g) obtained by the synthesis method of Synthesis Example 1 and the polyamic acid solution (2) (2) (2) obtained by the synthesis method of Synthesis Example 2 were placed in a 20 ml sample tube containing a stir bar. .68 g), NMP (4.37 g) and BCS (3.00 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (1).
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
  • “evaluation of afterimage by alternating current driving (FFS type liquid crystal cell)” and “evaluation of adhesion between the sealing agent and the base substrate” were performed.
  • Example 2 The polyamic acid solution (1) (4.98 g) obtained by the synthesis method of Synthesis Example 1 and the polyamic acid solution (3) (3) (2) obtained by the synthesis method of Synthesis Example 3 were placed in a 20 ml sample tube containing a stirrer. .72 g), NEP (4.29 g) and BCS (3.00 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (2).
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
  • “evaluation of an afterimage by AC driving (FFS type liquid crystal cell)” and “evaluation of adhesion between a sealing agent and a base substrate” were performed.
  • Example 3 The polyamic acid solution (1) (3.50 g) obtained by the synthesis method of Synthesis Example 1 and the polyamic acid solution (2) (2) (2) obtained by the synthesis method of Synthesis Example 2 were added to a 50 ml sample tube containing a stirrer. .33 g), NMP (12.8 g) and PB (4.66 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (3).
  • the obtained liquid crystal aligning agent (3) was pressure-filtered with the membrane filter with a pore diameter of 1 micrometer, and inkjet coating property was evaluated.
  • As the ink jet coater HIS-200 (manufactured by Hitachi Plant Technology) was used.
  • Coating is performed on a substrate cleaned with pure water and IPA, the coating area is 70 ⁇ 70 mm, the nozzle pitch is 0.423 mm, the scan pitch is 0.5 mm, the coating speed is 40 mm / second, from coating to temporary drying. For 60 seconds, and temporary drying was performed on a hot plate at 70 ° C. for 5 minutes.
  • substrate of the conditions of "the evaluation of the afterimage by an alternating current drive (FFS system liquid crystal cell)" and the “evaluation of the adhesiveness with a sealing agent and a base substrate” was used for the board
  • substrate The coating properties of the obtained substrate with a liquid crystal alignment film were confirmed. Specifically, the coating film was visually observed under a sodium lamp to confirm the presence or absence of pinholes.
  • * 1 The ratio (parts by mass) of the specific polymer (A) to 100 parts by mass of the total polymer.
  • * 2 The ratio (part by mass) of the specific polymer (B) with respect to 100 parts by mass of the total polymer.
  • * 3 Indicates the ratio (parts by mass) of other polymers to 100 parts by mass of the total polymer.
  • * 4 Indicates the ratio (parts by mass) of each solvent to 100 parts by mass of the total solvent.
  • * 5 Indicates the ratio of the total polymer in the liquid crystal aligning agent.
  • the liquid crystal aligning agents of the examples are superior in the afterimage characteristics due to alternating current driving and higher adhesion to the sealant and the base substrate than the liquid crystal aligning agents of the comparative examples. It was. Specifically, this is a comparison between Example 1 and Comparative Example 1 or Comparative Example 2. Comparative Example 1 using only the specific polymer (A) resulted in poor adhesion to the sealant and the base substrate as compared to the corresponding Examples. Further, Comparative Example 2 using only the specific polymer (B) resulted in poor afterimage characteristics due to AC driving. In contrast, Example 1 was excellent in both of these characteristics.
  • Example 1 it is a comparison between Example 1 and Comparative Example 3 or Comparative Example 4.
  • Comparative Example 3 using the polymer not containing the specific diamine (1), the afterimage characteristics due to AC driving were worse than those in the corresponding Examples.
  • the comparative example 4 using the polymer which does not contain specific diamine (1) brought a result with bad adhesiveness with a sealing compound and a base substrate.
  • 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 suitably used for a large-screen high-definition liquid crystal television, a small-to-medium-sized car navigation system, a smartphone, and the like. To do.
  • the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2013-219841 filed on Oct. 23, 2013 are cited here as disclosure of the specification of the present invention. Incorporated.

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Abstract

L'invention concerne : un agent d'alignement de cristaux liquides capable de former un film d'alignement de cristaux liquides présentant une excellente adhérence à un agent d'étanchéité et un substrat de base, tout en supprimant les images rémanentes dues à la commande par courant alternatif ; un film d'alignement de cristaux liquides qui est formé à partir dudit agent d'alignement de cristaux liquides ; et un élément d'affichage à cristaux liquides qui comprend ledit film d'alignement de cristaux liquides. Un agent d'alignement de cristaux liquides contient le composant (A) et le composant (B) ci-dessous. Composant (A) : un polymère contenant au moins une substance choisie parmi des précurseurs de polyimide et des polyimides ayant un groupe protecteur qui est remplacé par un atome d'hydrogène au moyen de chaleur. Composant (B) : un polymère contenant au moins une substance choisie parmi des précurseurs de polyimide et des polyimides ayant un groupe urée et/ou un groupe thiourée.
PCT/JP2014/078137 2013-10-23 2014-10-22 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides Ceased WO2015060358A1 (fr)

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CN201480070728.XA CN105849631B (zh) 2013-10-23 2014-10-22 液晶取向剂、液晶取向膜和液晶表示元件
KR1020167013223A KR102291426B1 (ko) 2013-10-23 2014-10-22 액정 배향제, 액정 배향막 및 액정 표시 소자
JP2015543890A JPWO2015060358A1 (ja) 2013-10-23 2014-10-22 液晶配向剤、液晶配向膜及び液晶表示素子

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JP2021103250A (ja) * 2019-12-25 2021-07-15 株式会社ジャパンディスプレイ 光配向膜用ワニス及び光配向膜の製造方法
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TWI791526B (zh) * 2017-05-31 2023-02-11 日商日產化學工業股份有限公司 使用液晶的移相調變元件用機能性樹脂組成物
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CN107884995B (zh) * 2017-12-22 2021-06-22 苏州华星光电技术有限公司 显示面板
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JP2016118763A (ja) * 2014-12-23 2016-06-30 Jsr株式会社 液晶配向膜の製造方法、液晶素子の製造方法及び光配向用重合体組成物
WO2017094490A1 (fr) * 2015-12-01 2017-06-08 富士フイルム株式会社 Appareil d'affichage à cristaux liquides et procédé de fabrication d'appareil d'affichage à cristaux liquides
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CN107022358A (zh) * 2016-01-29 2017-08-08 Jsr株式会社 液晶取向剂、液晶取向膜、液晶元件、聚合物以及二胺
CN107022358B (zh) * 2016-01-29 2021-09-07 Jsr株式会社 液晶取向剂、液晶取向膜、液晶元件、聚合物以及二胺
CN114761866A (zh) * 2019-12-06 2022-07-15 日产化学株式会社 液晶取向剂、液晶取向膜、液晶显示元件以及液晶显示元件的制造方法
JP2021103250A (ja) * 2019-12-25 2021-07-15 株式会社ジャパンディスプレイ 光配向膜用ワニス及び光配向膜の製造方法

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