WO2015046374A1 - Agent d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant - Google Patents

Agent d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant Download PDF

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Publication number
WO2015046374A1
WO2015046374A1 PCT/JP2014/075516 JP2014075516W WO2015046374A1 WO 2015046374 A1 WO2015046374 A1 WO 2015046374A1 JP 2014075516 W JP2014075516 W JP 2014075516W WO 2015046374 A1 WO2015046374 A1 WO 2015046374A1
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Prior art keywords
liquid crystal
group
carbon atoms
formula
aligning agent
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PCT/JP2014/075516
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English (en)
Japanese (ja)
Inventor
尚士 鉄谷
宏之 桜井
保坂　和義
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日産化学工業株式会社
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Priority to CN201480064518.XA priority Critical patent/CN105765453B/zh
Priority to JP2015539350A priority patent/JP6501073B2/ja
Priority to KR1020167010702A priority patent/KR102255769B1/ko
Publication of WO2015046374A1 publication Critical patent/WO2015046374A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Definitions

  • the present invention relates to a liquid crystal alignment treatment agent used in the production of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film.
  • Liquid crystal display elements are now widely used as display devices that are thin and light.
  • a liquid crystal alignment film is used to determine the alignment state of the liquid crystal.
  • the pretilt angle of the liquid crystal As one of the characteristics required for the liquid crystal alignment film, there is control of the so-called pretilt angle of the liquid crystal, which maintains the alignment tilt angle of the liquid crystal molecules with respect to the substrate surface at an arbitrary value. It is known that the magnitude of the pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film.
  • the method using a diamine having a side chain as a part of the polyimide raw material can control the pretilt angle in accordance with the proportion of the diamine used, so that the desired pretilt angle is obtained. This is relatively easy and is useful as a means for increasing the pretilt angle (see, for example, Patent Document 1).
  • the diamine component for increasing the pretilt angle of the liquid crystal has been studied for improving the stability and process dependency of the pretilt angle
  • the side chain structure used here is phenyl. Those containing a ring structure such as a group or a cyclohexyl group have been proposed (see, for example, Patent Document 2).
  • liquid crystal alignment films used in the liquid crystal alignment films used in the liquid crystal display elements have a high voltage holding ratio and a direct current voltage from the viewpoint of suppressing contrast reduction and afterimage phenomenon.
  • the characteristic that the accumulated charge when applied is small or the charge accumulated by the DC voltage is quickly relaxed has become increasingly important.
  • a liquid crystal alignment treatment agent containing a tertiary amine with a specific structure in addition to polyamic acid or imide group-containing polyamic acid is used as a short time until the afterimage generated by direct current voltage disappears.
  • a liquid crystal alignment treatment agent containing a soluble polyimide using a specific diamine having a pyridine skeleton or the like as a raw material for example, see Patent Document 4.
  • a compound containing one carboxylic acid group in the molecule In addition to polyamic acid and its imidized polymer, a compound containing one carboxylic acid group in the molecule, assuming that the voltage holding ratio is high and the time until the afterimage generated by direct current voltage disappears is short , Using a liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing one carboxylic anhydride group in the molecule and a compound containing one tertiary amino group in the molecule (for example, Patent Document 5) is known.
  • the liquid crystal alignment film is also used for controlling the angle of the liquid crystal with respect to the substrate, that is, the pretilt angle of the liquid crystal.
  • the liquid crystal needs to be aligned vertically, so the liquid crystal alignment film has the ability to align the liquid crystal vertically (vertical alignment and high pretilt). Called corners).
  • the liquid crystal alignment film has become important not only for high vertical alignment but also for its stability.
  • liquid crystal display elements that use a backlight that generates a large amount of heat and has a large amount of light to obtain high brightness, such as car navigation systems and large televisions, are exposed to high temperatures and light for a long time. There are cases where it is used or left in a dark environment. Under such severe conditions, when the vertical alignment property is deteriorated, problems such as inability to obtain initial display characteristics or occurrence of unevenness in display occur.
  • the voltage holding ratio which is one of the electrical characteristics of the liquid crystal display element
  • high stability under the above severe conditions is also required. That is, if the voltage holding ratio is reduced by light irradiation from the backlight, a burn-in defect (also referred to as line burn-in), which is one of display defects of the liquid crystal display element, is likely to occur. A high liquid crystal display element cannot be obtained. Therefore, in the liquid crystal alignment film, in addition to good initial characteristics, for example, it is required that the voltage holding ratio does not easily decrease even after being exposed to light irradiation for a long time. Furthermore, there is a need for a liquid crystal alignment film that can quickly relieve residual charges accumulated by a direct current voltage by light irradiation from a backlight, even for another surface burn-in that is a poor image burn-in.
  • an object of the present invention is to provide a liquid crystal aligning agent having the above characteristics. That is, an object of the present invention is to provide a liquid crystal alignment film that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. In addition, an object of the present invention is to provide a liquid crystal alignment film that suppresses a decrease in the voltage holding ratio even after being exposed to light irradiation for a long time and quickly relaxes residual charges accumulated by a DC voltage.
  • another object of the present invention is to provide a liquid crystal display element having the above liquid crystal alignment film and a liquid crystal alignment treatment agent that can provide the above liquid crystal alignment film.
  • an object of the present invention is to provide a liquid crystal display element provided with a liquid crystal alignment film that meets the above-mentioned requirements.
  • the present invention has the following gist.
  • Liquid crystal aligning agent containing the following (A) component and (B) component.
  • A) Component A polymer containing at least one selected from a polyimide precursor having a structure containing a nitrogen atom and polyimide.
  • B) Component A polymer containing at least one selected from a polyimide precursor having a structure represented by the following formula [2] and a polyimide.
  • at least one of the polymer of the component (A) and the component (B) contains a structure represented by the following formula [3].
  • Y 1 and Y 7 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —N (R 1 ) — (R 1 is a hydrogen atom or carbon number) 1 to 3 alkylene group), —CON (R 2 ) — (R 2 represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), —N (R 3 ) CO— (R 3 represents a hydrogen atom) Or an alkylene group having 1 to 3 carbon atoms), at least one organic group selected from —CH 2 O—, —COO— and —OCO—, wherein Y 2 and Y 6 are each independently carbon An alkylene group having 1 to 10 carbon atoms, Y 3 and Y 5 each independently represents a hydrogen atom or an alkylene group having 1 to 10 carbon atoms, and Y 4 represents an oxygen atom or a sulfur atom).
  • B 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—.
  • B 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15)
  • B 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15) ), —O—, —CH 2 O—, —COO— or —OCO—
  • B 4 is a carbon having a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a steroid skeleton
  • X 1 represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring
  • X 2 represents a hydrogen atom or a disubstituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms
  • X 3 and X 7 each independently represents an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings
  • X 4 and X 6 are each independently Represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms
  • X 5 represents an alkylene group or biphenyl group having 2 to 5 carbon atoms
  • m represents an integer of 0 or 1
  • X 8 And X 10 each independently represents at least one structure selected from the structures represented by the following formulas [1c-a] and [1c-b]
  • X 9 represents an alkylene group having 1 to 5 carbon atoms. Or a benzene ring).
  • the polymer of the component (A) is a polymer obtained by using a diamine compound represented by the following formula [1-1] as a part of the raw material.
  • the liquid crystal aligning agent of description is a polymer obtained by using a diamine compound represented by the following formula [1-1] as a part of the raw material.
  • X A represents an organic group having at least one structure selected from the structures represented by Formula [1a] to Formula [1c], and A 1 and A 2 are each independently selected.
  • X 1 represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring
  • X 2 represents a hydrogen atom or a disubstituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms
  • X 3 and X 7 each independently represents an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings
  • X 4 and X 6 are Each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms
  • X 5 represents an alkylene group or biphenyl group having 2 to 5 carbon atoms
  • m represents an integer of 0 or 1
  • X 8 and X 10 each independently represent at least one structure selected from the structures represented by the formulas [1c-a] and [1c-b]
  • X 9 has 1 carbon atom Represents an alkylene group or a benzene ring represented by formulas [1a
  • R 1 represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.
  • n represents an integer of 1 to 10
  • a 1 to A 8 each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.
  • Y A represents an organic group having the structure represented by Formula [2], and A 1 and A 2 are each independently a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. Showing).
  • Y 1 and Y 7 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —N (R 1 ) — (R 1 is a hydrogen atom or carbon number) 1 to 3 alkylene group), —CON (R 2 ) — (R 2 represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), —N (R 3 ) CO— (R 3 represents a hydrogen atom) Or an alkylene group having 1 to 3 carbon atoms), at least one organic group selected from —CH 2 O—, —COO— and —OCO—, wherein Y 2 and Y 6 are each independently carbon An alkylene group having 1 to 10 carbon atoms, Y 3 and Y 5 each independently represents a hydrogen atom or an alkylene group having 1 to 10 carbon atoms, Y 4 represents an oxygen atom or a sulfur atom, and A 1 and A 5 2 each independently represent a hydrogen atom or
  • a 1 to A 6 each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms).
  • B represents the above formula [3]
  • a 1 and A 2 each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms, and m represents an integer of 1 to 4. Show).
  • 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 structures represented by the following formulas [4a] to [4k]).
  • Z 1 to Z 4 represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, which may be the same or different
  • Z 5 and Z 6 each represent a hydrogen atom or a methyl group, and may be the same or different.
  • the tetracarboxylic acid component is a tetracarboxylic acid having at least one structure selected from the structures represented by the formulas [4a] and [4e] to [4g], wherein Z in the formula [4]
  • the liquid-crystal aligning agent as described in said (10) which is a component.
  • the diamine compounds represented by the formulas [1a-1] to [1c-1] are 5 mol% to 95 mol% in 100 mol% of all diamine components.
  • the diamine compound represented by the formula [2a] is 5 mol% to 95 mol% in 100 mol% of all diamine components. 12)
  • the liquid-crystal aligning agent in any one of.
  • the solvent for the liquid crystal aligning agent is at least 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 (1) to (15) above, which contains one kind of solvent.
  • liquid crystal aligning agent comprising at least one crosslinkable compound selected from a crosslinkable compound having a group and a crosslinkable compound having a polymerizable unsaturated bond.
  • a liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and comprising a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates.
  • a liquid crystal display element comprising the liquid crystal alignment film according to (21).
  • a liquid crystal alignment film having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates.
  • a liquid crystal display device comprising the liquid crystal alignment film according to (23).
  • the liquid crystal aligning agent containing at least one polymer selected from polyimide precursors or polyimides having a specific structure of the present invention has a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time.
  • a liquid crystal alignment film that can be expressed can be obtained.
  • a liquid crystal alignment film that suppresses a decrease in the voltage holding ratio and quickly relaxes the residual charges accumulated by a DC voltage is obtained. 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 can be suitably used for a large-screen high-definition liquid crystal television.
  • the present invention relates to a liquid crystal alignment treatment agent containing the following components (A) and (B), a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent, and a liquid crystal display element having the liquid crystal alignment film. is there.
  • Liquid crystal aligning agent containing the following (A) component and (B) component.
  • A) Component A polymer (also referred to as a specific polymer (A)) containing at least one selected from a polyimide precursor having a structure containing a nitrogen atom and polyimide.
  • At least one of the polymers of the component (A) and the component (B) contains a structure represented by the following formula [3] (also referred to as a specific side chain structure).
  • Y 1 and Y 7 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —N (R 1 ) — (R 1 is a hydrogen atom or carbon number) 1 to 3 alkylene group), —CON (R 2 ) — (R 2 represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), —N (R 3 ) CO— (R 3 represents a hydrogen atom) Or an alkylene group having 1 to 3 carbon atoms), at least one organic group selected from —CH 2 O—, —COO— and —OCO—, wherein Y 2 and Y 6 are each independently carbon An alkylene group having 1 to 10 carbon atoms, Y 3 and Y 5 each independently represents a hydrogen atom or an alkylene group having 1 to 10 carbon atoms, and Y 4 represents an oxygen atom or a sulfur atom).
  • B 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—.
  • B 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15)
  • B 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15) ), —O—, —CH 2 O—, —COO— or —OCO—
  • B 4 is a carbon having a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a steroid skeleton
  • the specific side chain structure represented by the formula [3] contained in at least one of the specific polymer (A) and the specific polymer (B) of the present invention has a benzene ring or a cyclohexyl ring at the side chain site. Or a divalent organic group having 17 to 51 carbon atoms having a heterocyclic ring or a steroid skeleton.
  • the side chain structure of these rings and organic groups shows a rigid structure as compared with the side chain structure of long-chain alkyl groups, which is a conventional technique for vertically aligning liquid crystals.
  • the liquid crystal alignment film obtained from the liquid crystal aligning agent having a specific side chain structure of the present invention has higher and more stable vertical alignment of liquid crystals than the conventional long chain alkyl group side chain structure. Obtainable.
  • the specific side chain structure of the present invention is more stable to light such as ultraviolet rays than the conventional side chain structure of long-chain alkyl groups. Therefore, the specific side chain structure of the present invention can reduce the voltage holding ratio and suppress the decomposition product of the side chain component that accumulates residual charges due to DC voltage even when exposed to light irradiation for a long time. .
  • the interaction between the nitrogen atom in the structure containing the nitrogen atom contained in the specific polymer (A) of the present invention and the carboxyl group (COOH group) in the specific polymer (B), and the specific polymer It is considered that charge transfer occurs between the nitrogen atom in the formula [2] in B) and the carboxyl group in the specific polymer (A). Accordingly, the accumulated residual charge can be efficiently transferred within or between the molecules of the polymer. That is, it is considered that the residual charge loss due to the DC voltage can be promoted.
  • the structure having a nitrogen atom in the specific polymer (A) of the present invention can trap an ionic impurity component that is a factor that lowers the voltage holding ratio. That is, the liquid crystal display element can trap ionic impurities that are generated by exposure to light for a long time, and accordingly, a decrease in voltage holding ratio can be suppressed.
  • the liquid crystal aligning agent containing at least one polymer selected from polyimide precursors or polyimides having a specific structure of the present invention after being exposed to high temperature and light irradiation for a long time, A liquid crystal alignment film capable of exhibiting a stable pretilt angle can be obtained.
  • a liquid crystal alignment film that suppresses a decrease in the voltage holding ratio and quickly relaxes the residual charges accumulated by a DC voltage is obtained.
  • the specific polymer (A) of the present invention is a polymer containing at least one selected from a polyimide precursor having a structure containing a nitrogen atom and a polyimide.
  • X 1 represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring.
  • X 2 represents a hydrogen atom or a disubstituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms.
  • X 1 represents a nitrogen-containing aromatic heterocyclic ring
  • X 2 is a disubstituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms.
  • X 1 represents a benzene ring.
  • X 3 and X 7 each independently represents an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings.
  • X 4 and X 6 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.
  • X 5 represents an alkylene group having 2 to 5 carbon atoms or a biphenyl group.
  • m represents an integer of 0 or 1.
  • X 8 and X 10 each independently represent at least one structure selected from structures represented by the following formulas [1c-a] and [1c-b].
  • X 9 represents an alkylene group having 1 to 5 carbon atoms or a benzene ring.
  • the specific polymer (B) of the present invention is a polymer containing at least one selected from a polyimide precursor having a specific structure 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 ) — (R 1 is a hydrogen atom Or an alkylene group having 1 to 3 carbon atoms), —CON (R 2 ) — (wherein R 2 represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), —N (R 3 ) CO— (R 3 Represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), and represents at least one organic group selected from —CH 2 O—, —COO— and —OCO—.
  • 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 alignment properties 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 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.
  • the specific side chain structure represented by the formula [3] contained in at least one of the specific polymer (A) and the specific polymer (B) of the present invention is a structure represented by the following formula [3]. is there.
  • B 1 represents a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—. .
  • a single bond — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O— or —COO -Is preferred.
  • More preferred is a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
  • B 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15). Among these, a single bond or — (CH 2 ) b — (b is an integer of 1 to 10) is preferable.
  • B 3 represents a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—. .
  • a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O— or —COO— is preferable from the viewpoint of ease of synthesis. More preferred is a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
  • B 4 is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
  • B 4 may be a divalent organic group selected from organic groups having 17 to 51 carbon atoms having a steroid skeleton. Among these, an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton is preferable from the viewpoint of ease of synthesis.
  • B 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
  • a benzene ring or a cyclohexane ring is preferable.
  • n represents an integer of 0 to 4.
  • 0 to 3 are preferable from the viewpoint of availability of raw materials and ease of synthesis. More preferred is 0-2.
  • B 6 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. .
  • an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable.
  • it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
  • B 1 to B 6 and n in Formula [3] are listed in Tables 6 to 47 on pages 13 to 34 of International Publication No. WO2011 / 132751 (published 2011.10.27) (2 -1) to (2-629) are the same combinations.
  • B 1 to B 6 in the present invention are indicated as Y 1 to Y 6, but Y 1 to Y 6 should be read as B 1 to B 6 .
  • the organic group having 17 to 51 carbon atoms having a steroid skeleton in the present invention has 12 to 20 carbon atoms having a steroid skeleton.
  • An organic group having 12 to 25 carbon atoms having a steroid skeleton is to be read as an organic group having 17 to 51 carbon atoms having a steroid skeleton.
  • the specific polymer (A) and the specific polymer (B) of the present invention 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 is 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 alkylene having 1 to 5 carbon atoms
  • a 3 and A 4 each independently represents a hydrogen atom, an alkylene group having 1 to 5 carbon atoms or an acetyl group
  • n represents a positive integer
  • diamine component examples include diamine compounds having two primary or secondary amino groups in the molecule.
  • examples of the tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, and a tetracarboxylic acid dialkyl ester dihalide compound.
  • a diamine compound having two primary or secondary amino groups in the molecule a tetracarboxylic acid compound or tetra It can be obtained by reacting with a carboxylic anhydride.
  • the diamine compound, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or It can be obtained by reacting with a tetracarboxylic 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) of the present invention is a polymer having a structure containing a nitrogen atom.
  • the structure represented by the formula [1a] to the formula [1c] is preferable.
  • the method for introducing a structure containing a nitrogen atom into the specific polymer (A) is not particularly limited, but a diamine compound having a structure represented by the above formulas [1a] to [1c] is used as a part of the raw material. It is preferable.
  • a diamine compound represented by the following formula [1-1] also referred to as a specific diamine compound (1).
  • X A represents an organic group having 5 to 50 carbon atoms having at least one structure selected from the structures represented by the formulas [1a] to [1c].
  • a 1 and A 2 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.
  • diamine compounds represented by the following formulas [1a-1] to [1c-1] are preferably used.
  • X 1 represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring.
  • X 2 represents a hydrogen atom or a disubstituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms.
  • X 1 represents a nitrogen-containing aromatic heterocyclic ring
  • X 2 is a disubstituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms.
  • X 1 represents a benzene ring.
  • X 3 and X 7 each independently represents an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings.
  • X 4 and X 6 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.
  • X 5 represents an alkylene group having 2 to 5 carbon atoms or a biphenyl group.
  • m represents an integer of 0 or 1.
  • X 8 and X 10 each independently represent at least one structure selected from structures represented by the following formulas [1c-a] and [1c-b].
  • X 9 represents an alkylene group having 1 to 5 carbon atoms or a benzene ring.
  • diamine compound (1) of the present invention include diamine compounds represented by the following formulas [1-1a] to [1-4a].
  • R 1 represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.
  • n represents an integer of 1 to 10.
  • a 1 to A 8 each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.
  • the specific diamine compound (1) in the specific polymer (A) of the present invention is preferably 1 mol% to 95 mol% in 100 mol% of all diamine components. Of these, 5 mol% to 95 mol% is preferable. More preferred is 20 mol% to 80 mol%.
  • the specific diamine compound (1) of the present invention includes the solubility of the specific polymer (A) of the present invention in the solvent, the coating property of the liquid crystal alignment treatment agent, the liquid crystal alignment property when the liquid crystal alignment film is formed, the voltage holding ratio, One type or a mixture of two or more types can be used depending on characteristics such as accumulated charge.
  • the specific polymer (B) of the present invention is a polymer having a specific structure (2).
  • the method for introducing the specific structure (2) of the present invention into the specific polymer (B) is not particularly limited, but a diamine compound having the specific structure (2) is preferably used as the diamine component. It is particularly preferable to use a diamine compound having a structure represented by the formula [2].
  • a diamine compound represented by the following formula [2-1] also referred to as a specific diamine compound (2).
  • Y A represents an organic group having a structure represented by Formula [2].
  • a 1 and A 2 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.
  • 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 ) — (R 1 is a hydrogen atom Or an alkylene group having 1 to 3 carbon atoms), —CON (R 2 ) — (wherein R 2 represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), —N (R 3 ) CO— (R 3 Represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), and represents at least one organic group selected from —CH 2 O—, —COO— and —OCO—.
  • a single bond, —O—, —S—, —OCO— or —COO— is preferable. More preferred is a single bond, —O— or —S—, which is a structure that is as flexible as possible and has as little steric hindrance in terms of liquid crystal orientation and film hardness.
  • 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 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.
  • a 1 and A 2 each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.
  • diamine compound (2) of the present invention include diamine compounds represented by the following formulas [2-1a] to [2-3a].
  • a 1 to A 6 each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms).
  • the specific diamine compound (2) in the specific polymer (B) of the present invention is preferably 1 mol% to 95 mol% in 100 mol% of all diamine components. Of these, 5 mol% to 95 mol% is preferable. More preferred is 20 mol% to 80 mol%.
  • the specific diamine compound (2) of the present invention has the solubility in the solvent of the specific polymer (B) of the present invention, the coating property of the liquid crystal alignment treatment agent, the liquid crystal alignment property when it is used as a liquid crystal alignment film, the voltage holding ratio, One type or a mixture of two or more types can be used depending on characteristics such as accumulated charge.
  • At least one of the specific polymer (A) and the specific polymer (B) of the present invention contains a specific side chain structure.
  • the method for introducing the specific side chain structure of the present invention into the specific polymer (A) or the specific polymer (B) is not particularly limited, but a diamine compound having a specific side chain structure is preferably used as the diamine component. .
  • a diamine compound represented by the following formula [3a] also referred to as a specific side chain diamine compound.
  • B represents the formula [3].
  • the preferred combinations of B 1 to B 6 and n in the formula [3] are as described above.
  • a 1 and A 2 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. Of these, a hydrogen atom or an alkylene group having 1 or 2 carbon atoms is preferable.
  • m represents an integer of 1 to 4. Of these, 1 is preferable.
  • Specific examples of the specific side chain diamine compound of the present invention include, for example, diamine compounds represented by the following formulas [3a-1] to [3a-31], and these amino groups are secondary amino groups. A certain diamine compound is mentioned.
  • R 1 , R 3 and R 5 are each independently —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 — or —CH 2 OCO—, wherein R 2 , R 4 and R 6 are each independently a linear or branched alkylene having 1 to 22 carbon atoms in the formulas [3a-1] to [3a-3] Group, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkylene group or fluorine-containing alkoxyl group having 1 to 22 carbon atoms).
  • R 1 , R 3 and R 5 are each independently —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 — , -CH 2 OCO -, - CH 2 O -, - OCH 2 - or -CH 2 - indicates, wherein [3a-4] ⁇ formula [3a-6], R 2 , R 4 and R 6 each Independently, a linear or branched alkylene group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms Or a fluorine-containing alkoxyl group).
  • R 1 and R 3 are each independently —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 —, —O— or —NH—, wherein R 2 and R 4 are each independently a fluorine group, a cyano group, a trifluoromethane group Nitro group, azo group, formyl group, acetyl group, acetoxy group or hydroxyl group).
  • R 1 and R 2 each independently represents a linear or branched alkylene group having 3 to 12 carbon atoms, and 1,4-cyclohexylene.
  • the cis-trans isomerism of each is the trans isomer).
  • R 1 and R 2 each independently represents a linear or branched alkylene group having 3 to 12 carbon atoms, and 1,4-cyclohexylene.
  • the cis-trans isomerism of each is the trans isomer).
  • a 4 is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom
  • a 3 is a 1,4-cyclohexylene group or A 2 -phenylene group
  • a 2 is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A 3 )
  • a 1 is an oxygen atom or —COO— * (However, the bond marked with “*” binds to (CH 2 ) a 2 )).
  • a 1 is an integer of 0 or 1
  • a 2 is an integer of 2 to 10
  • a 3 is an integer of 0 or 1.
  • the specific side chain diamine compound of the present invention may be used in at least one of the specific polymer (A) and the specific polymer (B), or may be used in both specific polymers. Especially, it is preferable to use for a specific polymer (A).
  • the specific side chain type diamine compound in the specific polymer (A) and / or the specific polymer (B) of the present invention is preferably 10 mol% or more and 80 mol% or less of the entire diamine component. Particularly preferred is 10 mol% or more and 70 mol% or less.
  • the specific side chain type diamine compound of the present invention is a liquid crystal in the case where the specific polymer (A) and the specific polymer (B) of the present invention are soluble in a solvent, coating property of a liquid crystal aligning agent, and a liquid crystal alignment film.
  • a liquid crystal aligning agent e.g., a liquid crystal aligning agent for polymer (A) and the specific polymer (B) of the present invention are soluble in a solvent, coating property of a liquid crystal aligning agent, and a liquid crystal alignment film.
  • One kind or a mixture of two or more kinds can be used depending on the orientation, voltage holding ratio, accumulated charge and the like.
  • the specific diamine compound (1), the specific diamine compound (2) and the specific side chain type are used as long as the effects of the present invention are not impaired.
  • Other diamine compounds other than the diamine compound also referred to as other diamine compounds can be used.
  • a diamine compound having a carboxyl group (COOH group) or a hydroxyl group (OH group) can also be used in the diamine compound.
  • 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid Mention may be made of 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid. Of these, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid is preferable.
  • diamine compounds represented by the following formulas [3b-1] to [3b-4] and diamine compounds in which these amino groups are secondary amino groups can also be used.
  • a 1 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —CF 2 —, —C (CF 3 ) 2 —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CON ( CH 3 ) — or —N (CH 3 ) CO—, each of m 1 and m 2 independently represents an integer of 0 to 4, and m 1 + m 2 represents an integer of 1 to 4, In [3b-2], m 3 and m 4 each independently represents an integer of 1 to 5, and in formula [3b-3], A 2 represents a linear or branched alkylene group having 1 to 5 carbon atoms.
  • m 5 represents an integer of 1 to 5, wherein [3b-4], a 3 and a 4 are each independently a single bond, -CH 2 -, - C 2 H 4 - -C (CH 3) 2 -, - CF 2 -, - C (CF 3) 2 -, - O -, - CO -, - NH -, - N (CH 3) -, - CONH -, - NHCO- , -CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CON (CH 3) - or -N (CH 3) CO- indicates, m 6 is an integer of 1 to 4) .
  • a diamine compound having a nitrogen-containing heterocyclic ring represented by the following formula [3c] and a diamine compound in which these amino groups are secondary amino groups can also be used in the diamine compound.
  • D 1 represents —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCO—, —CON (CH 3 ) —. Or —N (CH 3 ) CO—.
  • —O—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCO—, —CON (CH 3 ) — or —N (CH 3 ) CO— represents a diamine compound. It is preferable because it is easy to synthesize.
  • Particularly preferred is —O—, —CONH— or —CH 2 O—.
  • D 2 represents a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group.
  • the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear or branched. Moreover, you may have an unsaturated bond. Of these, an alkylene group having 1 to 10 carbon atoms is preferable.
  • non-aromatic hydrocarbon group examples include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring.
  • a cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring or adamantane ring is preferred.
  • aromatic hydrocarbon group examples include a benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring or phenalene ring.
  • a benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring or anthracene ring is preferred.
  • Preferred D 2 in the formula [3c] is a single bond, an alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, A naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring or an anthracene ring; Of these, a single bond, an alkylene group having 1 to 5 carbon atoms, a cyclohexane ring or a benzene ring is preferable.
  • D 3 represents a single bond, —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH 3 ).
  • — Or —N (CH 3 ) CO—, —O (CH 2 ) m — (m is an integer of 1 to 5) is shown.
  • a single bond, —O—, —COO—, —OCO— or —O (CH 2 ) m — (m is an integer of 1 to 5) is preferable. More preferred is a single bond, —O—, —OCO— or —O (CH 2 ) m — (m is an integer of 1 to 5).
  • D 4 is a nitrogen-containing aromatic heterocyclic ring, which is an aromatic heterocyclic ring containing at least one structure selected from the following formulas [a], [b] and [c]. is there.
  • Z represents an alkylene group having 1 to 5 carbon atoms.
  • a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring or benzimidazole ring are preferable. More preferred are a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring.
  • D 3 in the formula [3c] can expressions included in the D 4 [a], is preferably bonded with a substituent nonadjacent the formula [b] and the formula [c].
  • n is an integer of 1 to 4, and is preferably 1 or 2 from the viewpoint of reactivity with the tetracarboxylic acid component.
  • D 1 to D 4 and n in the formula [3c] are as follows: D 1 represents —CONH—, D 2 represents an alkyl group having 1 to 5 carbon atoms, D 3 represents a single bond, 4 is a diamine compound in which 4 represents an imidazole ring or a pyridine ring and n represents 1.
  • the bonding position of the two amino groups (—NH 2 ) in the formula [3c] is not limited. Specifically, with respect to the linking group (B 1 ) of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring Position or 3, 5 positions. Among these, from the viewpoint of reactivity when synthesizing the polyamic acid, the 2,4 position, the 2,5 position, or the 3,5 position is preferable. Considering the ease in synthesizing the diamine compound, the positions 2, 4 or 2, 5 are more preferable.
  • diamine compounds represented by the following formulas [3d-1] to [3d-13] and diamine compounds in which these amino groups are secondary amino groups can also be used.
  • a 1 to A 4 each independently represents an alkylene group having 1 to 22 carbon atoms or a fluorine-containing alkylene group).
  • a 1 and A 3 are each independently —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO— or — indicates NH-
  • a 2 represents a linear or straight-chain or branched fluorine-containing alkylene group having branched alkylene group or a C 1-22 of 1 to 22 carbon atoms
  • the formula [3d-6] in, and each a 4 and a 6 are independently, -COO -, - OCO -, - CONH -, - NHCO -, - CH 2 -, - O -, - CO- or -NH- are shown
  • a 5 Represents a linear or branched alkylene group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms).
  • a 1 and A 3 are each independently —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO— or — NH— represents
  • a 2 represents a linear or branched alkylene group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms, and represented by the formula [3d-8] in, and each a 4 and a 6 are independently, -COO -, - OCO -, - CONH -, - NHCO -, - CH 2 -, - O -, - CO- or -NH- are shown, a 5 Represents a linear or branched alkylene group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms).
  • a 1 and A 3 are each independently —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO— or — indicates NH-
  • a 2 represents a linear or straight-chain or branched fluorine-containing alkylene group having branched alkylene group or a C 1-22 of 1 to 22 carbon atoms
  • the formula [3d-10] in, and each a 4 and a 6 are independently, -COO -, - OCO -, - CONH -, - NHCO -, - CH 2 -, - O -, - CO- or -NH- are shown
  • a 5 Represents a linear or branched alkylene group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms).
  • p represents an integer of 1 to 10).
  • diamine compounds of the present invention include the solubility of the specific polymer (A) and the specific polymer (B) of the present invention in a solvent, the coating property of a liquid crystal aligning agent, and the liquid crystal alignment properties when used as a liquid crystal alignment film.
  • One type or a mixture of two or more types can be used depending on characteristics such as voltage holding ratio and accumulated charge.
  • specific polymer (A) and specific polymer (B) of the present invention that is, the tetracarboxylic acid component for producing these polyimide polymers, tetracarboxylic dianhydride represented by the following formula [4] It is preferable to use a product.
  • Z represents at least one structure selected from structures represented by the following formulas [4a] to [4k]).
  • Z 1 to Z 4 represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, and may be the same or different.
  • Z 5 and Z 6 each represent a hydrogen atom or a methyl group, and may be the same or different.
  • formula [4a], formula [4c] to formula [4g] or formula [4k] The tetracarboxylic dianhydride of the structure shown by these and its tetracarboxylic acid derivative are preferable. More preferable is the structure represented by the formula [4a] or the formula [4e] to the formula [4g]. Particularly preferred are tetracarboxylic dianhydrides and their tetracarboxylic acid derivatives having the structure represented by [4a], formula [4e] or formula [4f].
  • the specific tetracarboxylic acid component in the specific polymer (A) and the specific polymer (B) of the present invention is preferably 1 mol% to 100 mol% in 100 mol% of all tetracarboxylic acid components. Of these, 5 mol% to 95 mol% is preferable. More preferred is 20 mol% to 80 mol%.
  • the specific tetracarboxylic acid component of the present invention includes the solubility of the specific polymer (A) and the specific polymer (B) of the present invention in a solvent, the coating property of a liquid crystal aligning agent, and the liquid crystal alignment film.
  • One type or a mixture of two or more types can be used depending on the properties such as orientation, voltage holding ratio, and accumulated charge.
  • tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds or 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
  • the other tetracarboxylic acid component of the present invention includes the solubility of the specific polymer (A) and the specific polymer (B) of the present invention in a solvent, the coating property of a liquid crystal aligning agent, and the liquid crystal alignment film.
  • One type or a mixture of two or more types can be used depending on the properties such as orientation, voltage holding ratio, and accumulated charge.
  • the specific polymer (A) and the specific polymer (B), that is, methods for producing these polyimide polymers are 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 their derivatives is reacted with a diamine component consisting of one or more diamine compounds. And a method of obtaining a polyamic acid.
  • a method of obtaining polyamic acid by polycondensation of tetracarboxylic dianhydride and primary or secondary diamine compound, dehydration polycondensation reaction of tetracarboxylic acid and primary or secondary diamine compound A method of obtaining polyamic acid by polycondensation of a tetracarboxylic acid dihalide and a primary or secondary diamine compound is used.
  • polyimide In order to obtain polyimide, a method is used in which the polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.
  • the reaction of the diamine component and the tetracarboxylic acid component is usually 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 alkylene group having 1 to 3 carbon atoms.
  • D 2 represents an alkylene group having 1 to 3 carbon atoms.
  • D 3 represents an alkylene group having 1 to 4 carbon atoms.
  • solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use it for the said solvent in the range which the produced
  • the polymerization temperature can be selected from -20 ° C to 150 ° C, but is preferably in the range of -5 ° C to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. It becomes. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial reaction can be carried out at a high concentration, and then a solvent can be added.
  • the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor 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.
  • Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalytic imidization in which a catalyst is added to the polyimide precursor solution.
  • the temperature is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.
  • the catalytic 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 ° C to 250 ° C, preferably 0 ° C to 180 ° C. it can.
  • the amount of the basic catalyst is 0.5 mol times to 30 mol times, preferably 2 mol times to 20 mol times of the amic acid groups, and the amount of the acid anhydride is 1 mol times to 50 mol times of the amic acid groups, The amount is preferably 3 mole times to 30 mole times.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine.
  • pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
  • the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like.
  • use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the reaction solution may be poured into a solvent and precipitated.
  • the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water.
  • the polymer precipitated in the solvent can be collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating.
  • the 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 increased.
  • the liquid crystal aligning agent of the present invention is a coating solution for forming a liquid crystal alignment film (also referred to as a resin film), and a liquid crystal alignment film containing a specific polymer (A), a specific polymer (B) and a solvent. It is a coating solution for forming.
  • the specific polymer (A) of the present invention may be any polyimide polymer such as polyamic acid, polyamic acid alkyl ester and polyimide. Of these, polyamic acid alkyl ester or polyimide is preferable. More preferably, it is a polyimide.
  • the specific polymer (B) of the present invention may be any polyimide polymer such as polyamic acid, polyamic acid alkyl ester and polyimide. Of these, polyamic acid or polyamic acid alkyl ester is preferable. More preferred is polyamic acid.
  • the ratio of the specific polymer (A) and the specific polymer (B) in the liquid crystal aligning agent of the present invention is 0.5 mass for the specific polymer (B) with respect to 100 mass parts of the specific polymer (A). Part to 950 parts by mass is preferable. Of these, 10 parts by weight to 900 parts by weight is preferable, and 10 parts by weight to 400 parts by weight is more preferable.
  • 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) of the present invention, and other polymers are mixed. May be.
  • examples of other polymers include the polyimide polymer having no tertiary nitrogen atom structure and the polyimide polymer having no 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 other than that is 0.5 parts by mass with respect to 100 parts by mass of the specific polymer (A) and the specific polymer (B) of the present invention. To 30 parts by mass. Of these, 1 to 20 parts by mass is preferable.
  • the content of the solvent in the liquid crystal aligning agent of the present invention is preferably 70% by mass 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 in the liquid crystal alignment treatment agent of the present invention is not particularly limited as long as it is a solvent (also referred to as a good solvent) that dissolves the specific polymer (A) and the specific polymer (B).
  • a solvent also referred to as a good solvent
  • the specific example of a good solvent is given to the following, it is not limited to these examples.
  • N-methyl-2-pyrrolidone N-ethyl-2-pyrrolidone, and ⁇ -butyrolactone are preferably used.
  • the good solvent in the liquid crystal aligning agent of the present invention is preferably 20% by mass to 99% by mass of the total solvent contained in the liquid crystal aligning agent. Of these, 20% by mass to 90% by mass is preferable. More preferred is 30% by mass 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 unless the effects of the present invention are impaired. be able to.
  • a solvent also referred to as a poor solvent
  • a poor solvent is given to the following, it is not limited to these examples.
  • 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- Ethane All, 1,2-propanediol, 1,3-propan
  • 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% by mass to 80% by mass of the total solvent contained in the liquid crystal aligning agent. Of these, 10% by mass to 80% by mass is preferable. More preferred is 20% by mass to 70% by mass.
  • the liquid crystal aligning agent of the present invention has at least one substituent selected from 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 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 , Triglycidyl-p-
  • the crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4A].
  • crosslinkable compounds represented by the formulas [4a] to [4k] published on pages 58 to 59 of International Publication No. WO2011 / 132751 (published 2011.10.27).
  • the crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5A].
  • 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 resin, a urea resin, a guanamine resin, and a glycoluril 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 or 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 groups or alkoxymethyl groups per
  • Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring.
  • Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( (sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p-tert-butylphenol.
  • 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 Cold di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin Di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether
  • E 1 represents at least one selected from a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, and a phenanthrene ring
  • E 2 represents And represents a group selected from the following formula [7a] or [7b], and n represents an integer of 1 to 4.
  • 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 is preferably 0.1 parts by mass to 150 parts by mass with respect to 100 parts by mass of all the polymer components.
  • the amount is preferably 0.1 parts by mass 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.
  • liquid crystal alignment treatment agent of the present invention a compound that improves the uniformity of the film thickness and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used as long as the effects of the present invention are not impaired.
  • Examples of compounds that improve the film thickness uniformity and surface smoothness of the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
  • 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) And Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.).
  • the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 parts by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent. ⁇ 1 part by mass.
  • liquid crystal alignment treatment agent of the present invention as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge loss of the element, page 69 of International Publication No. WO2011 / 132751 (published 2011.10.20). It is also possible to add nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156], which are listed on page 73.
  • This amine compound may be added directly to the liquid crystal aligning agent, but it is added after a solution having a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass with an appropriate solvent. It is preferable.
  • 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 alignment treatment agent of the present invention includes, in addition to the above poor solvent, crosslinkable compound, resin film or compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film, and a compound that promotes charge removal, As long as the effects of the present invention are not impaired, a dielectric or conductive material for changing the electrical characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film may be added.
  • the liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and then subjected to alignment treatment by rubbing treatment or light irradiation. In the case of vertical alignment, etc., it can be used as a liquid crystal alignment film without alignment treatment.
  • the substrate used at this time is not particularly limited as long as it is a highly transparent substrate.
  • a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode for driving a liquid crystal is formed.
  • an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.
  • the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, an inkjet method, or the like is generally used.
  • Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spray method, and these may be used depending on the purpose.
  • the liquid crystal aligning agent After applying the liquid crystal aligning agent on the substrate, it is preferably 30 to 300 ° C., depending on the solvent used for the liquid crystal aligning agent, by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven.
  • the liquid crystal alignment film can be obtained by evaporating the solvent at a temperature of 30 to 250 ° C. If the thickness of the liquid crystal alignment film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 10 to 100 nm.
  • the fired liquid crystal alignment film is treated by rubbing or irradiation with polarized ultraviolet rays.
  • the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method and then preparing a liquid crystal cell by a known method.
  • a method for manufacturing a liquid crystal cell prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and place the other side of the liquid crystal alignment film on the other side. And a method of sealing the substrate by injecting liquid crystal under reduced pressure, or a method of bonding the substrate after dropping the liquid crystal on the surface of the liquid crystal alignment film on which the spacers are dispersed, and the like.
  • the liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board
  • the liquid crystal composition is also preferably used for a liquid crystal display device produced through a step of polymerizing a polymerizable compound by at least one of irradiation with active energy rays and heating while applying a voltage between electrodes.
  • ultraviolet rays are suitable as the active energy ray.
  • the wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.
  • the above liquid crystal display element controls the pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method.
  • a PSA method a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, a predetermined voltage is applied to the liquid crystal layer and an ultraviolet ray is applied to the photopolymerizable compound.
  • the pretilt of the liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer.
  • the PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by the rubbing process.
  • a liquid crystal cell is prepared after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method, and a polymerizable compound is produced by at least one of irradiation with ultraviolet rays and heating.
  • the orientation of the liquid crystal molecules can be controlled by polymerizing.
  • a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded and the liquid crystal is injected under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed.
  • the substrate is bonded and sealed.
  • a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed.
  • the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule.
  • the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component.
  • the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled. The seizure characteristics of the steel deteriorate.
  • the polymerizable compound After producing the liquid crystal cell, the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell. Thereby, the alignment of the liquid crystal molecules can be controlled.
  • the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferable to use it for a liquid crystal display element manufactured through a step of arranging a liquid crystal alignment film containing a group and applying a voltage between electrodes, that is, an SC-PVA mode.
  • ultraviolet rays are suitable as the active energy ray.
  • the wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C.
  • a pair of substrates on which the liquid crystal alignment film of the present invention is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is prepared.
  • the other substrate is bonded so that the inner side is on the inside and the liquid crystal is injected under reduced pressure to seal, or the liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed and then the substrate is bonded and sealed.
  • the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.
  • the liquid crystal aligning agent of the present invention can provide a liquid crystal alignment film that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time.
  • a liquid crystal alignment film that suppresses a decrease in the voltage holding ratio and quickly relaxes the residual charges accumulated by a DC voltage is obtained. Therefore, the liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and is used for a large-screen high-definition liquid crystal television, a small-sized car navigation system, a smartphone, and the like. It can be suitably used.
  • A1 Diamine compound represented by the following formula [A1]
  • A2 Diamine compound represented by the following formula [A2]
  • A3 Diamine compound represented by the following formula [A3]
  • C1 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene
  • C2 1,3-diamino-4- [4- (trans-4-n-heptylcyclo) Hexyl) phenoxymethyl] benzene
  • C3 1,3-diamino-4- ⁇ 4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy ⁇ benzene
  • E1 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • E2 bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride
  • E3 the following formula [E3
  • E4 tetracarboxylic dianhydride represented by the following formula [E4]
  • E5 tetracarboxylic dianhydride represented by the following formula [E5]
  • Crosslinkable compound used in the present invention K1: Crosslinkable compound represented by the following formula [K1]
  • NMP N-methyl-2-pyrrolidone
  • NEP N-ethyl-2-pyrrolidone
  • ⁇ -BL ⁇ -butyrolactone
  • BCS ethylene glycol monobutyl ether
  • PB propylene glycol monobutyl ether
  • EC diethylene glycol monoethyl ether
  • DME Dipropylene glycol dimethyl ether
  • the imidation ratio of polyimide of the present invention 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 imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid that appear in the vicinity of 9.5 ppm to 10.0 ppm. Using the integrated value, the following formula was used.
  • Imidation rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
  • x is a proton peak integrated value derived from NH group of amic acid
  • y is a peak integrated value of reference proton
  • ⁇ is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.
  • NEP was added to the polyamic acid solution (3) (30.0 g) obtained by the synthesis method of Synthesis Example 3 and diluted to 6% by mass, and then acetic anhydride (3.45 g) and pyridine (2. 50 g) was added and reacted at 60 ° C. for 2 hours.
  • This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration.
  • This deposit was wash
  • the imidation ratio of this polyimide was 55%, the number average molecular weight was 18,500, and the weight average molecular weight was 49,300.
  • NEP was added to the polyamic acid solution (9) (30.0 g) obtained by the synthesis method of Synthesis Example 9 and diluted to 6% by mass, and then acetic anhydride (3.40 g) and pyridine (2. 63 g) was added and reacted at 60 ° C. for 2 hours.
  • This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration.
  • This deposit was wash
  • the imidation ratio of this polyimide was 57%, the number average molecular weight was 18,200, and the weight average molecular weight was 48,300.
  • NEP was added to the polyamic acid solution (24) (30.0 g) obtained by the synthesis method of Synthesis Example 24 and diluted to 6% by mass, and then acetic anhydride (3.40 g) and pyridine (2. 65 g) was added and reacted at 60 ° C. for 2 hours.
  • This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration.
  • This deposit was wash
  • the imidation ratio of this polyimide was 57%, the number average molecular weight was 20,100, and the weight average molecular weight was 54,100.
  • Tables 2 to 4 show the polyimide polymers of the present invention.
  • Tables 5 to 7 show the liquid crystal aligning agents of the present invention.
  • liquid crystal aligning agents obtained in the examples and comparative examples of the present invention, “Evaluation of ink-jet coating properties of liquid crystal aligning agents", "Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)", “Voltage Evaluation of retention rate (normal cell), evaluation of relaxation of residual charge (normal cell), and production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell) were performed.
  • ITO Indium Tin Oxide
  • nozzle pitch is 0.423 mm
  • scan pitch is 0.5 mm
  • application speed is 40 mm / second, from application to temporary drying For 60 seconds, and temporary drying was performed on a hot plate at 70 ° C. for 5 minutes.
  • 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. As a result, in any of the liquid crystal alignment films obtained in any of the examples, no pinhole was found on the coating film, and a liquid crystal alignment film having excellent coating properties was obtained.
  • the liquid crystal aligning agent obtained in Examples and Comparative Examples of the present invention was pressure filtered through a membrane filter having a pore diameter of 1 ⁇ m to produce a liquid crystal cell (normal cell).
  • This solution was spin-coated on the ITO surface of a 40 ⁇ 30 mm ITO electrode substrate (40 mm long ⁇ 30 mm wide, 0.7 mm thick) washed with pure water and IPA, and heated on a hot plate at 100 ° C. for 5 minutes. Then, heat treatment was performed at 230 ° C. for 30 minutes in a heat circulation clean oven to obtain an ITO substrate with a polyimide liquid crystal alignment film having a film thickness of 100 nm.
  • liquid crystal aligning agent (4) obtained in Example 4 of the present invention the liquid crystal aligning agent (9) obtained in Example 9 and the liquid crystal aligning agent (15) obtained in Example 15 are: Then, under the same conditions as in the above-mentioned “Evaluation of Inkjet Applicability of Liquid Crystal Alignment Treatment Agent”, a substrate with a liquid crystal alignment film is prepared, and then heat-treated at 230 ° C. for 30 minutes in a thermal circulation clean oven, An ITO substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm was obtained.
  • the coated surface of this ITO substrate was rubbed using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.1 mm.
  • Two ITO substrates with a liquid crystal alignment film thus obtained were prepared, combined with a 6 ⁇ m spacer sandwiched with the liquid crystal alignment film surface on the inside, and the periphery was adhered with a sealant to produce an empty cell.
  • a nematic liquid crystal was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell (ordinary cell).
  • the pretilt angle of this liquid crystal cell was measured.
  • the pretilt angle was measured after the liquid crystal cell was subjected to isotropic treatment (heat treatment at 95 ° C. for 5 minutes) and then heat treatment (heat treatment at 120 ° C. for 5 hours).
  • the liquid crystal cell after being irradiated with ultraviolet rays of 10 J / cm 2 in terms of 365 nm was also measured.
  • the pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON).
  • ultraviolet irradiation was performed using a tabletop UV curing device (HCT3B28HEX-1) (manufactured by Senlite).
  • the evaluation is based on the pretilt angle after the liquid crystal isotropic treatment (also referred to after the Iso treatment) and after the heat treatment (also referred to as the high temperature treatment) and after the ultraviolet irradiation (also referred to as the ultraviolet irradiation).
  • the smaller the change in angle, the better. Tables 8 to 10 show pretilt angle values after Iso treatment, after high temperature treatment and after ultraviolet irradiation).
  • Tables 8 to 10 show the results obtained in the examples and comparative examples.
  • VHR-1 voltage holding ratio measuring device (manufactured by Toyo Technica Co., Ltd.) with settings of Voltage: ⁇ 1 V, Pulse Width: 60 ⁇ s, and Frame Period: 50 ms.
  • a UV light of 50 J / cm 2 in terms of 365 nm was converted into a liquid crystal cell for which the measurement of the voltage holding ratio immediately after the liquid crystal cell was finished, using a desktop UV curing device (HCT3B28HEX-1) (manufactured by Senlite). Irradiation was performed, and the voltage holding ratio was measured under the same conditions as described above.
  • Tables 11 to 13 show the results obtained in the examples and comparative examples.
  • the residual charge immediately after the above liquid crystal cell was measured was irradiated with 30 J / cm 2 of UV converted to 365 nm using a desktop UV curing device (HCT3B28HEX-1) (manufactured by Senlite). Then, the residual charge was measured under the same conditions as described above.
  • Tables 11 to 13 show the results obtained in the examples and comparative examples.
  • This solution was washed with pure water and IPA at the center with a 10 ⁇ 10 mm ITO electrode substrate with a pattern spacing of 20 ⁇ m (vertical 40 mm ⁇ width 30 mm, thickness 0.7 mm) and at the center with a 10 ⁇ 40 mm ITO electrode substrate Spin coated on ITO surface (length 40mm x width 30mm, thickness 0.7mm), heat-treated on a hot plate at 100 ° C for 5 minutes, and heat-circulating clean oven at 230 ° C for 30 minutes to form a film A polyimide coating film having a thickness of 100 nm was obtained.
  • This substrate with a liquid crystal alignment film was combined with a 6 ⁇ m spacer sandwiched with the liquid crystal alignment film surface inside, and an empty cell was prepared by adhering the periphery with a sealant.
  • a nematic liquid crystal (MLC-6608) (manufactured by Merck Japan) was added to the empty cell by a reduced pressure injection method, and a polymerizable compound (1) represented by the following formula was added to 100% by mass of the nematic liquid crystal (MLC-6608). Liquid crystal mixed with 0.3% by mass of the polymerizable compound (1) was injected, and the injection port was sealed to obtain a liquid crystal cell.
  • the response speed of the liquid crystal before and after UV irradiation of this liquid crystal cell was measured.
  • T90 ⁇ T10 from 90% transmittance to 10% transmittance was measured.
  • the PSA cell obtained in any of the examples confirmed that the orientation direction of the liquid crystal was controlled because the response speed of the liquid crystal cell after ultraviolet irradiation was faster than that of the liquid crystal cell before ultraviolet irradiation. . Further, in any liquid crystal cell, it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) that the liquid crystal was uniformly aligned.
  • ECLIPSE E600WPOL polarizing microscope
  • Example 1 Polyamic acid solution (1) (5.00 g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 1 and polyamic acid having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 2 NMP (18.2 g) and BCS (8.16 g) were added to the solution (2) (3.33 g), and the mixture was stirred at 25 ° C. for 6 hours 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 or precipitation.
  • liquid crystal aligning agent (1) “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.
  • Example 2 Polyamic acid solution (3) (4.50 g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 3 and polyamic acid having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 5 NEP (14.4 g) and PB (14.1 g) were added to the solution (5) (4.50 g), and the mixture was stirred at 25 ° C. for 6 hours 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 or precipitation.
  • NEP (21.6 g) was added to polyimide powder (4) (1.15 g) obtained by the synthesis method of Synthesis Example 4 and polyimide powder (6) (1.15 g) obtained by the synthesis method of Synthesis Example 6. In addition, it was dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (14.4 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (3). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • NEP (14.9 g) is added to polyimide powder (4) (0.65 g) obtained by the synthesis method of Synthesis Example 4 and polyimide powder (6) (0.43 g) obtained by the synthesis method of Synthesis Example 6. In addition, it was dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (5.97 g), PB (8.96 g) and K1 (0.032 g) were added and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (4). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • NMP (20.3 g) is added to polyimide powder (7) (1.65 g) obtained by the synthesis method of Synthesis Example 7 and polyimide powder (8) (0.71 g) obtained by the synthesis method of Synthesis Example 8.
  • it was dissolved by stirring at 70 ° C. for 24 hours.
  • BCS (12.9 g) and DME (3.69 g) were added to this solution, and the mixture was stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (5).
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • NEP (15.0 g) was added to the polyimide powder (10) (1.75 g) obtained by the synthesis method of Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours.
  • PB (11.0 g) and DME (1.37 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
  • NEP (3.80 g) was added to polyimide powder (6) (0.44 g) obtained by the synthesis method of Synthesis Example 6 and dissolved by stirring at 70 ° C. for 24 hours.
  • PB (2.70 g) and DME (0.34 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
  • Example 8 To the polyimide powder (11) (0.75 g) obtained by the synthesis method of Synthesis Example 11 and the polyimide powder (8) (1.39 g) obtained by the synthesis method of Synthesis Example 8, NMP (6.71 g) and NEP (13.4 g) was added and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (13.4 g) and K1 (0.107 g) were added and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (8). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 9 NEP (15.2 g) and polyimide powder (11) (0.55 g) obtained by the synthesis method of Synthesis Example 11 and polyimide powder (8) (0.83 g) obtained by the synthesis method of Synthesis Example 8 ⁇ -BL (3.79 g) was added and dissolved by stirring at 70 ° C. for 24 hours. PB (15.2 g) and DME (3.79 g) were added to this solution, and the mixture was stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (9). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • NMP (1.73 g) and NEP (6.90 g) were added to the polyimide powder (4) (1.10 g) obtained by the synthesis method of Synthesis Example 4, and dissolved by stirring at 70 ° C. for 24 hours.
  • BCS (1.73 g) and PB (6.90 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
  • NMP (1.73 g) and NEP (6.90 g) were added to the polyimide powder (12) (1.10 g) obtained by the synthesis method of Synthesis Example 12, and dissolved by stirring at 70 ° C. for 24 hours. It was. To this solution, BCS (1.73 g) and PB (6.90 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
  • liquid crystal aligning agent 10
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • liquid crystal aligning agent (10) “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.
  • Example 11 To the polyimide powder (13) (1.25 g) obtained by the synthesis method of Synthesis Example 13 and the polyimide powder (8) (0.83 g) obtained by the synthesis method of Synthesis Example 8, NEP (13.1 g) and ⁇ -BL (3.26 g) was added and dissolved by stirring at 70 ° C. for 24 hours. BCS (13.1g) and EC (3.26g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (11). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • liquid crystal aligning agent (11) “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.
  • Example 12 To the polyimide powder (10) (0.65 g) obtained by the synthesis method of Synthesis Example 10 and the polyimide powder (8) (1.52 g) obtained by the synthesis method of Synthesis Example 8, NMP (17.0 g) and ⁇ -BL (1.70 g) was added and dissolved by stirring at 70 ° C. for 24 hours. BCS (6.79 g) and PB (8.49 g) were added to this solution, and the mixture was stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (12). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • liquid crystal aligning agent (13) “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.
  • NEP (15.9 g) is added to polyimide powder (7) (0.90 g) obtained by the synthesis method of Synthesis Example 7 and polyimide powder (17) (1.35 g) obtained by the synthesis method of Synthesis Example 17. In addition, it was dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (5.29 g) and PB (14.1 g) were added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (14). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • liquid crystal aligning agent (14) “production of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.
  • Example 15 To the polyimide powder (7) (0.55 g) obtained by the synthesis method of Synthesis Example 7 and the polyimide powder (17) (0.83 g) obtained by the synthesis method of Synthesis Example 17, NMP (3.79 g) and NEP (15.2 g) was added and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (19.0 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (15). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • liquid crystal aligning agent evaluation of inkjet coating property of liquid crystal aligning agent”, “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio ( Normal cell) ”and“ Evaluation of residual charge relaxation (normal cell) ”.
  • NMP (8.82 g) was added to the polyimide powder (18) (1.25 g) obtained by the synthesis method of Synthesis Example 18, and dissolved by stirring at 70 ° C. for 24 hours.
  • BCS (2.94 g) and PB (7.86 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
  • NMP (5.88 g) was added to the polyimide powder (17) (0.83 g) obtained by the synthesis method of Synthesis Example 17 and dissolved by stirring at 70 ° C. for 24 hours.
  • BCS (1.96 g) and PB (5.24 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
  • liquid crystal aligning agent (16).
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 17 ⁇ Example 17> K1 (0.06 g) was added to the liquid crystal aligning agent (16) (20.0 g) obtained by the adjustment method of Example 16, and the mixture was stirred at 40 ° C. for 6 hours to give the liquid crystal aligning agent (17). Obtained.
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • NEP (21.2 g) was added to polyimide powder (19) (0.45 g) obtained by the synthesis method of Synthesis Example 19 and polyimide powder (6) (1.80 g) obtained by the synthesis method of Synthesis Example 6. In addition, it was dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (3.53 g) and PB (10.6 g) were added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (18). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 19 Polyimide powder (19) (1.63 g) obtained by the synthesis method of Synthesis Example 19 and a polyamic acid solution (5) (6.50 g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 5 NEP (19.4 g) was added thereto and stirred at 70 ° C. for 24 hours for dissolution. To this solution, BCS (6.47 g) and PB (6.47 g) were added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (19). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • liquid crystal aligning agent (20) “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.
  • liquid crystal aligning agent (21) “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.
  • liquid crystal aligning agent (22) “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.
  • liquid crystal aligning agent (23) “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.
  • NEP (20.7 g) was added to polyimide powder (4) (1.10 g) obtained by the synthesis method of Synthesis Example 4 and polyimide powder (25) (1.10 g) obtained by the synthesis method of Synthesis Example 25. In addition, it was dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (13.8 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (24). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • liquid crystal aligning agent (24) “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.
  • NEP (20.7 g) was added to polyimide powder (23) (1.10 g) obtained by the synthesis method of Synthesis Example 23 and polyimide powder (6) (1.10 g) obtained by the synthesis method of Synthesis Example 6. In addition, it was dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (13.8 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (25). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • NEP (20.7 g) was added to polyimide powder (23) (1.10 g) obtained by the synthesis method of Synthesis Example 23 and polyimide powder (25) (1.10 g) obtained by the synthesis method of Synthesis Example 25. In addition, it was dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (13.8 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (26). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • liquid crystal aligning agent (26) “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.
  • NEP (20.7 g) was added to polyimide powder (26) (1.10 g) obtained by the synthesis method of Synthesis Example 26 and polyimide powder (27) (1.10 g) obtained by the synthesis method of Synthesis Example 27. In addition, it was dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (13.8 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (27). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • * 1 An introduction amount (parts by mass) of the specific polymer (A) with respect to 100 parts by mass of all polymers.
  • * 2 Indicates the introduction amount (parts by mass) of the specific polymer (B) with respect to 100 parts by mass of all polymers.
  • * 3 An introduction amount (parts by mass) of other polymer with respect to 100 parts by mass of all polymers.
  • * 4 An introduction amount (parts by mass) of a crosslinkable compound with respect to 100 parts by mass of all polymers.
  • * 5 An introduction amount (parts by mass) of each solvent with respect to 100 parts by mass of all the solvents.
  • * 6 Indicates the ratio of all the polymers in the liquid crystal aligning agent.
  • * 1 An introduction amount (parts by mass) of the specific polymer (A) with respect to 100 parts by mass of all polymers.
  • * 2 Indicates the introduction amount (parts by mass) of the specific polymer (B) with respect to 100 parts by mass of all polymers.
  • * 3 An introduction amount (parts by mass) of other polymer with respect to 100 parts by mass of all polymers.
  • * 4 An introduction amount (parts by mass) of a crosslinkable compound with respect to 100 parts by mass of all polymers.
  • * 5 An introduction amount (parts by mass) of each solvent with respect to 100 parts by mass of all the solvents.
  • * 6 Indicates the ratio of all the polymers in the liquid crystal aligning agent.
  • * 1 An introduction amount (parts by mass) of the specific polymer (A) with respect to 100 parts by mass of all polymers.
  • * 2 Indicates the introduction amount (parts by mass) of the specific polymer (B) with respect to 100 parts by mass of all polymers.
  • * 3 An introduction amount (parts by mass) of other polymer with respect to 100 parts by mass of all polymers.
  • * 4 An introduction amount (parts by mass) of a crosslinkable compound with respect to 100 parts by mass of all polymers.
  • * 5 An introduction amount (parts by mass) of each solvent with respect to 100 parts by mass of all the solvents.
  • * 6 Indicates the ratio of all the polymers in the liquid crystal aligning agent.
  • the liquid crystal aligning agent of the example of the present invention has a stable pretilt angle even when the liquid crystal cell is subjected to high temperature treatment and ultraviolet irradiation, as compared with the liquid crystal aligning agent of the comparative example. Indicated. Furthermore, even when UV irradiation was performed, the decrease in the voltage holding ratio was suppressed, and the residual charge accumulated by the DC voltage was quickly relaxed. That is, the liquid crystal composition treating agent of the present invention becomes a liquid crystal alignment film that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time, and in addition, has been exposed to light irradiation for a long time. Even after this, a liquid crystal alignment film is obtained in which the decrease in the voltage holding ratio is suppressed and the residual charge accumulated by the DC voltage is quickly relaxed.
  • Examples of the liquid crystal alignment treatment agent using the specific polymer (A) and the specific polymer (B) of the present invention and Examples of the liquid crystal alignment treatment agent using only one of them. That is, the comparison between Example 2 and Comparative Example 2 or Comparative Example 3, and the comparison between Example 3 and Comparative Example 5 or Comparative Example 6.
  • the comparative examples using only these specific polymers (A) or the comparative examples using only the specific polymers (B) are greatly reduced in voltage holding ratio, particularly with respect to ultraviolet irradiation, as compared with the corresponding examples. In addition, the residual charge value also increased.
  • Example of the liquid-crystal aligning agent using the specific polymer (A) and specific polymer (B) of this invention, the polymer which does not have the structure containing the tertiary nitrogen atom of this invention, and specific structure ( 2) A comparative example of a liquid crystal aligning agent using a polymer having no polymer, that is, a comparison between Example 1 and Comparative Example 1, a comparison between Example 2 and Comparative Example 4, and Example 3 and Comparative Example 7 is a comparison.
  • the voltage holding ratio was greatly reduced, and the value of the residual charge was also increased particularly with respect to ultraviolet irradiation.
  • the liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time.
  • the liquid crystal display element which has said liquid crystal aligning film, and the liquid-crystal aligning agent which can provide said liquid crystal aligning film can be provided.
  • the 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 can be suitably used for a large-screen, high-definition liquid crystal television, etc. It is useful for a device, a TFT liquid crystal device, particularly a vertical alignment type liquid crystal display device.
  • the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is also useful for a liquid crystal display element that needs to be irradiated with ultraviolet rays when producing a liquid crystal display element. That is, a liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes, and containing a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates, A liquid crystal display element manufactured through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes, and further comprising a liquid crystal layer between a pair of substrates provided with electrodes, A liquid crystal produced by placing a liquid crystal alignment film containing a polymerizable group that polymerizes at least one of active energy rays and heat between substrates and polymerizing the polymerizable group while applying a voltage between the electrodes. It is also useful for display elements.

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Abstract

La présente invention porte sur un agent d'alignement de cristaux liquides qui contient le composant (A) et le composant (B) décrits ci-dessous. Composant (A) : un polymère contenant au moins une matière sélectionnée parmi des polyimides et des précurseurs de polyimide ayant une structure ayant un atome d'azote Composant (B) : un polymère contenant au moins une matière sélectionnée parmi des polyimides et des précurseurs de polyimide ayant une structure d'urée ou une structure de thiourée. Dans cette relation, le polymère du composant (A) et/ou le polymère du composant (B) contient une structure de chaîne latérale spécifique.
PCT/JP2014/075516 2013-09-26 2014-09-25 Agent d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant WO2015046374A1 (fr)

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JP2021103205A (ja) * 2019-12-24 2021-07-15 Jsr株式会社 液晶配向剤、液晶配向膜及び液晶素子
JP7322694B2 (ja) 2019-12-24 2023-08-08 Jsr株式会社 液晶配向剤、液晶配向膜及び液晶素子
WO2022176713A1 (fr) * 2021-02-16 2022-08-25 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément à cristaux liquides dispersés dans un polymère

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TW201527846A (zh) 2015-07-16
KR102255769B1 (ko) 2021-05-27
CN105765453A (zh) 2016-07-13
KR20160060733A (ko) 2016-05-30
CN105765453B (zh) 2019-04-12
JPWO2015046374A1 (ja) 2017-03-09
JP6501073B2 (ja) 2019-04-17

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