WO2010050523A1 - Diamine, polyimide, agent d’alignement de cristaux liquides et film d’alignement de cristaux liquides - Google Patents

Diamine, polyimide, agent d’alignement de cristaux liquides et film d’alignement de cristaux liquides Download PDF

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WO2010050523A1
WO2010050523A1 PCT/JP2009/068523 JP2009068523W WO2010050523A1 WO 2010050523 A1 WO2010050523 A1 WO 2010050523A1 JP 2009068523 W JP2009068523 W JP 2009068523W WO 2010050523 A1 WO2010050523 A1 WO 2010050523A1
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liquid crystal
group
organic group
formula
aligning agent
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PCT/JP2009/068523
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English (en)
Japanese (ja)
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直樹 作本
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日産化学工業株式会社
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Priority to CN200980148012.6A priority Critical patent/CN102224452B/zh
Priority to KR1020157033438A priority patent/KR101649839B1/ko
Priority to JP2010535825A priority patent/JP5614284B2/ja
Publication of WO2010050523A1 publication Critical patent/WO2010050523A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/16—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/24—Anthracenes; Hydrogenated anthracenes
    • 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 aligning agent for producing a liquid crystal aligning film, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a polymer (polymer) and a monomer (monomer) for obtaining the liquid crystal aligning agent. More specifically, a liquid crystal alignment film with excellent mechanical strength that is resistant to rubbing scratches even after rubbing treatment, high voltage retention at high temperature, low ion density, and excellent reliability It is related with the liquid crystal aligning agent from which an element is obtained, and the polymer and monomer for obtaining this liquid crystal aligning agent.
  • Liquid crystal display elements used for liquid crystal televisions, liquid crystal displays, and the like are usually provided with a liquid crystal alignment film for controlling the alignment state of the liquid crystals.
  • the liquid crystal alignment film is imparted with liquid crystal alignment by subjecting the surface of the film to various alignment treatments.
  • the liquid crystal alignment film is a so-called rubbing process in which the surface of the resin film formed on the electrode substrate is rubbed in one direction with a cloth such as cotton, nylon or polyester. It is produced by doing.
  • a polyimide film obtained by applying and baking a polyimide precursor such as polyamic acid or a polyimide solution is widely used.
  • the method of rubbing the polyimide film is an industrially useful method that is simple and excellent in productivity. However, when the adhesion and mechanical strength of the polyimide film formed on the electrode substrate are insufficient, the film is peeled or scratched by rubbing due to the rubbing treatment.
  • the mechanical strength of the polyimide film is improved by adding a crosslinking agent containing a reactive group such as an epoxy group to the polyimide precursor or polyimide.
  • a crosslinking agent containing a reactive group such as an epoxy group
  • JP-A-9-146100 JP 10-333153 A Japanese Patent Laid-Open No. 10-46151 Japanese Patent Laid-Open No. 2007-11221
  • a compound used as a crosslinking agent is a low molecular compound. Therefore, it sublimes during firing, and the effect cannot be sufficiently obtained unless an excessive amount is added. Moreover, when it adds excessively, an unreacted crosslinking agent remains in a film
  • the present invention has been made in view of such circumstances, and a liquid crystal alignment film excellent in mechanical strength that is difficult to be subjected to rubbing scratches even by rubbing treatment without the addition of a crosslinking agent can be obtained, and at a high temperature.
  • a liquid crystal aligning agent capable of obtaining a highly reliable liquid crystal alignment film having a high voltage holding ratio of a liquid crystal display element and a low ion density, and a polymer and a monomer for obtaining the liquid crystal aligning agent.
  • a diamine compound and / or tetracarboxylic acid derivative having a t-butoxycarbonyl group (hereinafter also referred to as a Boc group) that is eliminated by heating. It has been found that the above object can be achieved by a polyimide precursor obtained by using a liquid crystal or a liquid crystal aligning agent containing polyimide. Specifically, the Boc group is eliminated by heating, and a highly reactive aliphatic amine is formed. This aliphatic amine becomes a cross-linking point, and the liquid crystal has excellent mechanical properties that do not cause film peeling or scratching due to rubbing. An alignment film was obtained, and a liquid crystal display device using this liquid crystal alignment film was found to have a high voltage holding ratio and a low ion density even at high temperatures, and the present invention was completed.
  • the gist of the present invention is as follows. 1.
  • the liquid crystal aligning agent characterized by containing the polyimide precursor which has a substituent of the structure represented by following formula (1), or the imidation polymer of this polyimide precursor.
  • A is a single bond or a divalent organic group, and R 1 , R 2 , and R 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • the polyimide precursor or the imidized polymer of the polyimide precursor is selected from the group consisting of a diamine compound having a substituent represented by the formula (1) and a tetracarboxylic acid derivative having a substituent represented by the formula (1). 2.
  • the liquid crystal aligning agent according to 1 above which is obtained using at least one selected. 3.
  • a diamine compound having a substituent represented by the formula (1) and / or a tetracarboxylic acid derivative having a substituent represented by the formula (1) is used in an amount of 2 to 100 mol% of the total diamine compound and tetracarboxylic acid derivative.
  • the liquid crystal aligning agent according to 2 above which is a polyimide precursor obtained by use or an imidized polymer of the polyimide precursor. 4). 4. The liquid crystal aligning agent according to any one of 1 to 3 above, wherein the polyimide precursor has a structure containing a structural unit represented by the following formula (2).
  • X 1 is a (4 + a) valent organic group
  • Y 1 is a (2 + b) valent organic group
  • R 4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • Z is the above (It is a structure represented by the formula (1).
  • a and b are each an integer of 0 to 4, and a + b> 0.) 5).
  • X is a tetravalent organic group
  • R 4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 5 is a single bond or a divalent organic group having 1 to 20 carbon atoms.
  • Z is a structure represented by the above formula (1), and c is an integer of 1 to 4.) 7).
  • a liquid crystal alignment film obtained by baking the liquid crystal aligning agent according to any one of the above 1 to 7 at 150 to 300 ° C.
  • X is a tetravalent organic group
  • Y 2 is a (2 + c) valent organic group
  • Z is a structure represented by the following formula (1)
  • R 4 is a hydrogen atom or a carbon number.
  • c is an integer of 1 to 4.
  • A is a single bond or a divalent organic group, and R 1 , R 2 , and R 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • R 1 , R 2 , and R 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • A is a single bond or a divalent organic group, and R 1 , R 2 , and R 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • X is a tetravalent organic group
  • Z is a structure represented by the following formula (1)
  • R 4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 5 is carbon.
  • It is a divalent organic group having a number of 1 to 20.
  • c is an integer of 1 to 4.
  • A is a single bond or a divalent organic group, and R 1 , R 2 , and R 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • R 1 , R 2 , and R 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • X is a tetravalent organic group
  • Z is a structure represented by the following formula (1)
  • R 5 is a divalent organic group having 1 to 20 carbon atoms
  • c is 1 It is an integer of ⁇ 4.
  • A is a single bond or a divalent organic group, and R 1 , R 2 , and R 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • X is a tetravalent organic group
  • Z is a structure represented by the following formula (1)
  • R 4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • C is 1 It is an integer of ⁇ 4.
  • A is a single bond or a divalent organic group, and R 1 , R 2 , and R 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • R 1 , R 2 , and R 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • X is a tetravalent organic group
  • Z is a structure represented by the following formula (1)
  • c is an integer of 1 to 4.
  • A is a single bond or a divalent organic group, and R 1 , R 2 , and R 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • liquid crystal aligning agent of the present invention it is possible to obtain a liquid crystal aligning film excellent in mechanical strength that hardly causes peeling or scratches due to rubbing without adding a crosslinking agent.
  • this liquid crystal alignment film even when liquid crystal alignment ability is imparted by irradiating polarized radiation, the liquid crystal display has excellent display characteristics because of high voltage retention at low temperatures and low ion density. An element is obtained.
  • the liquid crystal aligning agent of the present invention has a high storage stability in a varnish state because a highly reactive primary or secondary aliphatic amine is protected with a Boc group. Moreover, since the polyimide precursor and polyimide contained in the liquid crystal aligning agent of this invention have a Boc group which is a bulky substituent, they show high solubility with respect to various organic solvents, and also are reactive by heating. High-grade primary or secondary aliphatic amines are produced, and intermolecular crosslinking reaction is advanced to form a polyimide film having excellent mechanical strength.
  • the diamine compound protected with a Boc group in the present invention is easily produced by reacting with a tetracarboxylic acid derivative to produce a polyimide precursor or polyimide having a primary or secondary amino group protected with a Boc group. can do.
  • the liquid crystal aligning agent of the present invention is characterized by containing a polyimide precursor having a primary or secondary aliphatic amino group protected with a Boc group or an imidized polymer thereof.
  • the primary or secondary aliphatic amino group protected by the Boc group means an aliphatic amino group having —NR 3 Boc (R 3 is defined by the above formula (1)).
  • a polyimide precursor having a primary or secondary aliphatic amino group protected with a Boc group or an imidized polymer thereof is heated at 150 ° C. or more, whereby the Boc group is released and the protection of the Boc group is lost. Reactive primary or secondary aliphatic amino groups are formed.
  • the generated primary or secondary aliphatic amino group reacts with a functional group present in the polyimide precursor or its imidized polymer to form intermolecular crosslinks. Examples of crosslinking reactions include reactions with carboxylic acids or esters (following formula (i)), reactions with acid dianhydrides generated by the reverse reaction of polyamic acids (following formula (ii)), and reactions with imides. (The following formula (iii)).
  • the above cross-linking reaction proceeds in the process of forming a liquid crystal alignment film from the liquid crystal aligning agent of the present invention, so that the liquid crystal alignment film obtained in the present invention has improved mechanical strength, It is considered that a polyimide film that does not cause scratches is obtained.
  • a method for imparting liquid crystal alignment ability to the liquid crystal alignment film in addition to the rubbing method, there is known an optical alignment method for imparting liquid crystal alignment ability by irradiating a polyimide film with polarized radiation.
  • an optical alignment method for imparting liquid crystal alignment ability by irradiating a polyimide film with polarized radiation As the photo-alignment method, a method using a photoisomerization reaction, a method using a photocrosslinking reaction, a method using a photolysis reaction, and the like have been proposed.
  • the liquid crystal aligning agent and the liquid crystal alignment film of the present invention are useful for the photo-alignment method, and are particularly useful for the photo-alignment method using a photodecomposition reaction.
  • a low molecular weight component is generated by light irradiation.
  • a photo-alignment method using a photodecomposition reaction of a polyimide having a cyclobutane ring in the main chain a low molecular weight component having a maleimide moiety is generated by performing an alignment treatment (the following formula (xiii)).
  • liquid crystal alignment film containing a low molecular weight component When such a liquid crystal alignment film containing a low molecular weight component is used in a liquid crystal display device, the low molecular weight component is eluted into the liquid crystal, causing a decrease in the voltage holding ratio and an increase in ion density of the liquid crystal display device. There is a possibility of deteriorating the display characteristics of the element.
  • the liquid crystal aligning agent and the liquid crystal alignment film of the present invention suppress the lowering of the molecular weight of the polyimide precursor and polyimide by intermolecular three-dimensional crosslinking formed by the reactions of the above formulas (i) to (iii), and into the liquid crystal. It is possible to suppress elution of low molecular weight components. Furthermore, the maleimide produced by the photolysis reaction of the cyclobutane ring can react with a primary or secondary aliphatic amino group produced by heating (the following formula (xiv)). Even in such a crosslinking reaction, it is possible to suppress elution of low molecular weight components into the liquid crystal.
  • the crosslinking reaction as described above proceeds to form intermolecular crosslinking.
  • a primary or secondary aliphatic amine is added to a polyimide precursor or polyimide solution, salt formation with carboxylic acid, progress of imidization reaction, ring-opening reaction of imide ring, etc. proceed, and polymer Gelation, precipitation, and molecular weight reduction occur, and it is difficult to stably store the polymer solution for a long period of time.
  • the functional group in the polymer is stored when the liquid crystal aligning agent is stored in a solution state.
  • the liquid crystal aligning agent excellent in storage stability is obtained.
  • the low molecular crosslinking agent sublimes during firing in the process of forming the liquid crystal alignment film, and the effect may not be sufficiently obtained unless an excessive amount is added. is there.
  • an unreacted crosslinking agent remains in a film
  • the sublimated crosslinking agent may contaminate the firing furnace.
  • the liquid crystal aligning agent of the present invention since the aliphatic amine serving as a crosslinking point is incorporated in the polymer, the low-molecular compound remains in the film without being reacted, or the sublimation product is a firing furnace. Will not contaminate.
  • liquid crystal aligning agent of the present invention by using the liquid crystal aligning agent of the present invention, a liquid crystal aligning film excellent in mechanical strength that does not cause peeling or scratching of the film due to rubbing can be obtained. Regardless of the treatment method, a liquid crystal display element having a high voltage holding ratio and a low ion density even at high temperatures can be obtained. Furthermore, the present inventors have found that a liquid crystal aligning agent having excellent storage stability can be obtained by protecting a primary or secondary aliphatic amino group serving as a crosslinking point with a Boc group.
  • the polyimide precursor in the present invention is a polymer that becomes a polyimide by heating or the action of a catalyst, and examples thereof include polyamic acid, polyamic acid ester, polyamic acid silyl ester, and polyisoimide.
  • polyamic acid or polyamic acid ester is particularly preferable from the viewpoint of ease of production and imidization reaction efficiency.
  • the polyimide in the present invention is a polymer obtained by imidizing a polyimide precursor.
  • the liquid crystal aligning agent of the present invention contains a polyimide precursor having a substituent represented by the following formula (1) or an imidized polymer thereof.
  • A is a single bond or a divalent organic group
  • R 1 , R 2 , and R 3 are each independently a hydrogen atom or a carbon number of 1 to 20, preferably 1 to 10, more preferably 1 to 6 is a monovalent organic group.
  • Monovalent organic groups include monovalent hydrocarbon groups, hydroxyl groups, thiol groups, phosphate ester groups, ester groups, carboxyl groups, phosphate groups, thioester groups, amide groups, nitro groups, organooxy groups, organosilyl groups. Group, organothio group, acyl group and the like.
  • the monovalent organic group is preferably a monovalent hydrocarbon group from the viewpoint of the reactivity of the aliphatic amine.
  • the monovalent hydrocarbon group examples include methyl groups, ethyl groups, propyl groups, butyl groups, t-butyl groups, hexyl groups, octyl groups, decyl groups and other alkyl groups; cyclopentyl groups, cyclohexyl groups, etc.
  • a bicycloalkyl group such as a bicyclohexyl group; a vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-methyl-2-propenyl group, 1 or 2 or 3-butenyl group, hexenyl
  • An alkenyl group such as a group; an aryl group such as a phenyl group, a xylyl group, a tolyl group, a biphenyl group and a naphthyl group; and an aralkyl group such as a benzyl group, a phenylethyl group and a phenylcyclohexyl group.
  • Some or all of the hydrogen atoms of these monovalent hydrocarbon groups are halogen atoms, hydroxyl groups, thiol groups, phosphate ester groups, ester groups, carboxyl groups, phosphate groups, thioester groups, amide groups, nitro groups, Group, organooxy group, organosilyl group, organothio group, acyl group, alkyl group, cycloalkyl group, bicycloalkyl group, alkenyl group, aryl group, aralkyl group, pyrrole group, imidazole group, pyrazole group, alkoxycarbonylamino group, etc. May be substituted. In addition, these may have a ring structure.
  • a pyrrole group, an imidazole group, and a pyrazole group are preferable, and a case where the hydrogen atom on the nitrogen atom of the pyrrole group, the imidazole group, and the pyrazole group is substituted with a Boc group is more preferable.
  • R 1 and R 2 have a bulky structure, the reaction efficiency of the crosslinking reaction is lowered. Therefore, as R 1 and R 2 , an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or a hydrogen atom Preferably, a hydrogen atom is more preferable.
  • R 3 has a bulky structure, the reaction efficiency of the cross-linking reaction decreases. Therefore, R 3 is preferably an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a hydrogen atom, preferable.
  • A is a divalent organic group, the structure is represented by the following formula (12), for example.
  • B is a divalent linking group
  • R 6 and R 16 are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.
  • Specific examples of B include the following B-1 to B-14, but are not limited thereto.
  • R 6 and R 16 in formula (12) are shown below, but are not limited thereto.
  • Methylene group 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, 1,2-butylene group, 1,2-pentylene Group, 1,2-hexylene group, 1,2-nonylene group, 1,2-dodecylene group, 2,3-butylene group, alkylene group such as 2,4-pentylene group; 1,2-cyclopropylene group, Cycloalkylene such as 1,2-cyclobutylene group, 1,3-cyclobutylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group, 1,2-cyclononylene group, 1,2-cyclododecylene, etc.
  • some or all of the hydrogen atoms of the above divalent hydrocarbon group are halogen atoms, hydroxyl groups, thiol groups, phosphate ester groups, ester groups, carboxyl groups, phosphate groups, thioester groups, amide groups, nitro groups.
  • R 6 and R 16 have a structure containing an aromatic ring or an alicyclic structure, the liquid crystal orientation may be lowered. Therefore, R 6 and R 16 are a single bond or an alkylene group having 1 to 10 carbon atoms, an alkenyl group. Group or an alkynyl group is preferable, and an alkylene group having 1 to 10 carbon atoms is more preferable. Moreover, it is preferable that both or one of R 6 and R 16 is a single bond.
  • R 7 , R 8 , R 9 , R 10 , and R 11 are each independently a hydrogen atom or a monovalent hydrocarbon having 1 to 20 carbon atoms. It is a group.
  • the monovalent hydrocarbon group is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group or a decyl group; a cycloalkyl such as a cyclopentyl group or a cyclohexyl group.
  • bicycloalkyl groups such as bicyclohexyl groups
  • vinyl groups 1-propenyl groups, 2-propenyl groups, isopropenyl groups, 1-methyl-2-propenyl groups, 1 or 2 or 3-butenyl groups, hexenyl groups, etc.
  • alkenyl groups aryl groups such as phenyl, xylyl, tolyl, biphenyl, and naphthyl groups
  • aralkyl groups such as benzyl, phenylethyl, and phenylcyclohexyl.
  • Some or all of the hydrogen atoms of these monovalent hydrocarbon groups are halogen atoms, hydroxyl groups, thiol groups, phosphate ester groups, ester groups, carboxyl groups, phosphate groups, thioester groups, amide groups, nitro groups, Group, organooxy group, organosilyl group, organothio group, acyl group, alkyl group, cycloalkyl group, bicycloalkyl group, alkenyl group, aryl group, aralkyl group and the like may be substituted. In addition, these may have a ring structure.
  • R 7 , R 8 , R 9 , R 10 , and R 11 have a bulky structure such as an aromatic ring or an alicyclic structure, the liquid crystal orientation may be lowered or the solubility of the polymer may be lowered. Therefore, an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a hydrogen atom is preferable, and a hydrogen atom is more preferable.
  • specific examples of the substituent containing the primary or secondary aliphatic amine protected by the Boc group represented by the formula (1) include the structures of the following formulas (13) to (18): Is particularly preferred.
  • the liquid crystal aligning agent of the present invention contains a polyimide precursor or an imidized polymer thereof having the substituent represented by the above formula (1) at the end of the polymer or the side chain of the polymer.
  • X 1 is a (4 + a) valent organic group
  • Y 1 is a (2 + b) valent organic group
  • R 4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • Z is the above (It is a structure represented by the formula (1).
  • a and b are each an integer of 0 to 4, preferably 0 to 2, and a + b> 0.)
  • the substituent represented by the above formula (1) is added to the tetracarboxylic acid derivative and the diamine compound which are raw materials of the polyimide precursor. It is preferable to use the introduced raw material.
  • R 4 is an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, a 2-propyl group, a butyl group, and a t-butyl group.
  • the polyamic acid ester has a higher temperature at which imidization proceeds as the number of carbon atoms in the alkyl group increases. Therefore, R 4 is preferably a methyl group or an ethyl group from the viewpoint of easiness of imidization by heat. Is particularly preferred.
  • Z is a substituent having a structure represented by the above formula (1), and a is an integer of 0-4.
  • X 1 is a (4 + a) valent organic group.
  • Z is a substituent having a structure represented by the above formula (1), and b is an integer of 0-4.
  • Y 1 is a (2 + b) -valent organic group.
  • a tetracarboxylic acid derivative represented by the above formulas (19) to (21) and a diamine compound represented by the above formula (22) are used together with tetra compounds represented by the following formulas (23) to (25).
  • a carboxylic acid derivative and a diamine compound represented by the following formula (26) mixing these at an arbitrary ratio, and producing a polyimide precursor, containing a structural unit represented by the above formula (2)
  • the polyimide precursor to be manufactured can be manufactured.
  • Y is a divalent organic group.
  • the structures of X and X 1 are not particularly limited. Specific examples thereof include the structures represented by the following X-1 to X-46. Two or more of these tetracarboxylic acid derivatives may be used.
  • the valence of X 1 varies depending on a which is the number of substitution of Z. That is, the substitution number of Z by a structure structure obtained by removing a hydrogen atom from an arbitrary position of X 1 of the structures represented by the following X-1 ⁇ X-46.
  • the structures of Y and Y 1 are not particularly limited. Specific examples thereof include the structures represented by the following Y-1 to Y-100. Two or more diamine compounds may be used.
  • the substituent Z may be present in one or more of either the tetracarboxylic acid derivative or the diamine moiety. It is preferable to use the diamine compound represented by the above formula (22) from the viewpoint of ease of production and ease of handling of the monomer.
  • the polyimide precursor and polyimide of the present invention are preferably a polyimide precursor containing a structural unit represented by the following formula (3) and a polyimide containing a structural unit represented by the following formula (7).
  • X is a tetravalent organic group
  • Y 2 is a (2 + c) valent organic group
  • R 4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • Z is a structure represented by the above formula (1).
  • c is an integer of 1 to 4, preferably 1 to 2.
  • X, Y 2, Z, and c have the same meaning as in the above formula (3).
  • the polyimide precursor or polyimide containing the structural units of the above formulas (3) and (7) is a tetracarboxylic acid derivative represented by the above formulas (23) to (25) and a diamine represented by the following formula (27).
  • the compound and the diamine compound represented by the above formula (26) are mixed at an arbitrary ratio and reacted.
  • Y 2 , Z, and c have the same meanings as in the above formulas (3) and (7).
  • Specific examples of the structure represented by Y 2 include the structures represented by Y-1 to Y-100. Two or more diamine compounds may be used.
  • the valence of Y 2 changes depending on the substitution number c of Z. That is, the substitution number of Z only structure obtained by removing a hydrogen atom from any position of the structure represented by Y-1 ⁇ Y-100 has the structure of Y 2.
  • a liquid crystal alignment film having good liquid crystal alignment properties and excellent mechanical properties can be obtained.
  • a liquid crystal aligning agent of invention it is preferable to contain the polyimide precursor containing the structural unit represented by following formula (4), or the polyimide containing the structural unit represented by following formula (9).
  • the polyimide precursor and polyimide of the present invention contain a structural unit represented by the following formula (5).
  • the polyimide precursor which performs and the polyimide containing the structural unit represented by following formula (11) are more preferable.
  • particularly preferred diamine compounds as raw materials for producing the polyimide precursor include diamine compounds of the following formulas (A) to (F).
  • 2-cyano-4-nitroaniline of the above formula (45) is dissolved in an organic solvent.
  • the organic solvent to be used is not particularly limited as long as it is an organic solvent in which 2-cyano-4-nitroaniline is dissolved and is not decomposed by a reducing agent added later, but dehydrated tetrahydrofuran (THF) Is preferred.
  • THF dehydrated tetrahydrofuran
  • a reducing agent is added while stirring the reaction solution.
  • the reducing agent is powder, it is preferably added to the reaction solution as it is, and when the reducing agent is a solution, it is preferably added dropwise.
  • Examples of the reducing agent include borane, borane complex, sodium borohydride, lithium aluminum hydride and the like, and borane-THF complex is preferable.
  • the reaction solution is stirred for 30 minutes to 4 hours, preferably 1 to 2 hours while cooling. Thereafter, the mixture is stirred at room temperature for 12 to 72 hours, preferably 24 to 48 hours.
  • 1-2M inorganic acid is added to make the reaction solution acidic.
  • inorganic acids include hydrochloric acid, hydrogen fluoride, hydrobromic acid, hydroiodic acid, phosphoric acid, nitric acid, sulfuric acid, boric acid and the like, with hydrochloric acid being more preferred.
  • the reaction solution After adding the inorganic acid, the mixture is stirred at room temperature for 1-2 hours, the reaction solution is cooled to 0-10 ° C., and 1-2 M aqueous inorganic alkali solution is added to make the reaction solution alkaline.
  • the inorganic alkaline aqueous solution include aqueous solutions of sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like, but an aqueous sodium hydroxide solution is more preferable.
  • an organic solvent is added for extraction.
  • the organic solvent used for extraction is preferably a halogen-based organic solvent, more preferably dichloromethane.
  • the obtained organic layer is washed with pure water or saturated saline and dried with a desiccant.
  • a desiccant sodium sulfate and magnesium sulfate are preferable.
  • the resulting organic layer is dried for 4 to 24 hours, preferably 12 to 24 hours.
  • a compound represented by the following formula (46) can be obtained.
  • the obtained compound can be used for the next reaction without purification, but may be purified by various methods. Examples of the purification method include silica gel column chromatography, recrystallization, washing with an organic solvent, and the like.
  • Recrystallization is more preferable from the viewpoint of ease of operation and high purification efficiency.
  • the organic solvent used for recrystallization is an organic solvent which can recrystallize following formula (46), the kind may be chosen and it may recrystallize with 2 or more types of mixed solvents.
  • the compound represented by the above formula (46) is dissolved in an organic solvent, di-tert-butyl dicarbonate is added, and the reaction temperature is ⁇ 10 ° C. to 40 ° C., preferably 0 ° C. to 20 ° C.
  • the reaction is allowed to stir for ⁇ 48 hours, preferably 20 to 40 hours.
  • the organic solvent used in the reaction is not particularly limited as long as it can dissolve the compound of the above formula (46) and does not react with di-tert-butyl dicarbonate, but dichloromethane and tetrahydrofuran are more preferable. .
  • organic bases such as a triethylamine and a pyridine.
  • the addition amount is preferably 1 to 2 molar equivalents relative to the compound of the above formula (46).
  • an organic solvent, pure water or saturated saline is added and extracted, and a drying agent is added to the obtained organic layer and dried.
  • the organic solvent used for the extraction is not limited as long as it is not mixed with water, but dichloromethane is preferred. Moreover, you may extract by adding water or a saturated salt solution to a reaction solution.
  • As the desiccant sodium sulfate and magnesium sulfate are preferable.
  • the resulting organic layer is dried for 4 to 24 hours, preferably 12 to 24 hours.
  • the compound represented by the above formula (47) can be obtained by removing the desiccant and distilling off the solvent from the obtained filtrate.
  • the obtained compound can be used for the next reaction without purification, but is preferably purified by various methods.
  • the purification method include silica gel column chromatography, recrystallization, washing with an organic solvent, and the like. Recrystallization is more preferable from the viewpoint of ease of operation and high purification efficiency.
  • the organic solvent used for recrystallization is an organic solvent which can recrystallize following formula (47), the kind may be chosen and it may recrystallize with 2 or more types of mixed solvents.
  • the compound represented by the above formula (47) is dissolved in an organic solvent.
  • the organic solvent to be used is a well-known thing, the kind will not be chosen.
  • methanol, ethanol, 2-propanol, tetrahydrofuran and 1,4-dioxane are preferred, and methanol and ethanol are more preferred.
  • the inside of the reaction vessel is replaced with nitrogen, a catalyst is added, and the inside of the reaction vessel is substituted with hydrogen.
  • the catalyst include palladium carbon, platinum carbon, platinum oxide, and the like, and platinum oxide is more preferable in order to suppress the decomposition reaction at the benzyl position.
  • the reaction mixture is stirred at 0-100 ° C., preferably 10-60 ° C., for 10-48 hours, preferably 15-30 hours.
  • the diamine compound of the present invention represented by the above formula (A) can be obtained by removing the catalyst and distilling off the organic solvent. If the obtained compound is not purified, the polymerization reaction does not proceed and a high molecular weight polymer cannot be obtained. Therefore, it is preferable to purify by various methods. Examples of the purification method include silica gel column chromatography, recrystallization, washing with an organic solvent, and the like. Recrystallization is more preferable from the viewpoint of ease of operation and high purification efficiency.
  • the organic solvent used for recrystallization is an organic solvent which can recrystallize the diamine of a following formula (A)
  • the kind may be chosen and it may recrystallize with 2 or more types of mixed solvents.
  • diamine compound of the said Formula (B) and (C) is shown, it is not limited to this.
  • the diamine compounds of the above formulas (B) and (C) are produced, for example, through the intermediates shown in the following formulas (v) and (vi) using propargylamine of the following formula (48) as a starting material. .
  • the diamines (B) and (C) can be produced in the same manner except that they are produced using aryl iodides of the following formulas (49) and (50), respectively.
  • aryl iodides of the following formulas (49) and (50)
  • a compound in which a chloro group, a bromo group, or a trifluoromethylsulfonyl group is substituted at the substitution position of the iodo group in the following formulas (49) and (50) may be used, but aryl iodide is preferable from the viewpoint of reactivity. .
  • the compound represented by the above formula (52) is produced by reacting Boc-propargylamine of the above formula (51) with the aryl halide represented by the above formula (49) by Sonogashira coupling reaction. can do.
  • the aryl iodide represented by the above formula (49), a palladium catalyst, a copper catalyst, and a base are added and dissolved in an organic solvent.
  • the palladium catalyst bis (triphenylphosphine) palladium (II) dichloride is preferable, and the addition amount is 0.05 to 1.0 mol%, preferably 0.1 to 0.1 mol% with respect to the iodo group of aryl iodide. 0.5 mol% is more preferable.
  • the reaction solution is stirred at 0 ° C. to 30 ° C., preferably 0 ° C. to 20 ° C. for 5 to 30 minutes, and then added with Boc-propargylamine of the above formula (51) for 2 to 12 hours, preferably Stir for 4-10 hours.
  • the amount of Boc-propargylamine added is preferably 1 to 2 molar equivalents, more preferably 1.20 to 1.50 molar equivalents with respect to the iodo group of aryl iodide.
  • An organic solvent and an acidic aqueous solution are added to the reaction solution for extraction.
  • the organic solvent used for extraction is not limited as long as it is not mixed with water, but ethyl acetate, dichloromethane, chloroform, and 1,2-dichloroethane are more preferable.
  • As the acidic aqueous solution an aqueous solution of ammonium chloride, hydrochloric acid, acetic acid, or formic acid is preferable. If the acidity is too high, Boc may be detached, so an aqueous ammonium chloride solution is more preferable.
  • the concentration of the acidic solution is preferably 0.5 to 2 mol / L, more preferably 1 to 1.5 mol / L.
  • the amino group at position 1 of 2-amino-4-nitroaniline is reduced in nucleophilicity due to the influence of the nitro group present at position 4. Therefore, since the amino group at the 2-position reacts preferentially with the carboxylic acid of the amino acid compound, the compound represented by the above formula (55) can be produced.
  • the amino acid compound is added excessively, an amino group at the 4-position is formed with an amide bond, so that the amount of the amino acid compound added is 0.9 to 1.2 times the mole of 2-amino-4-nitroaniline. Preferably there is.
  • the compound represented by the above formula (55) can be produced by a condensation reaction between the amino group at the 2-position of 2-amino-4-nitroaniline and the carboxylic acid of the amino acid compound of the above formula (54). If the condensation of an amino group and carboxylic acid is a well-known method, the kind will not be limited, but when manufacturing the diamine compound of this invention, the method using a mixed acid anhydride and the method using a condensing agent are more preferable.
  • the organic solvent used in the reaction is not limited as long as it dissolves the amino acid compound represented by the above formula (54) and does not react with each reagent used in the reaction. Chloroform, dichloromethane and tetrahydrofuran are preferred, and tetrahydrofuran is more preferred because of its solubility in amino acid compounds.
  • the base used in the reaction is preferably a tertiary amine, more preferably pyridine, triethylamine, dimethylaminopyridine, or N-methylmorpholine. Since it is difficult to remove the base when the amount is too large, it is preferably 2 to 4 moles relative to 2-amino-4-nitroaniline.
  • the acid halide and acid derivative are preferably pivaloyl chloride, tosyl chloride, mesyl chloride, ethyl chloroformate, and isobutyl chloroformate.
  • the addition amount of the acid halide and the acid derivative is preferably 1.5 to 2 times mol of 2-amino-4-nitroaniline.
  • Nylmethylmorpholinium O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like.
  • the amount of the condensing agent added is preferably 2 to 3 moles compared to the amino acid compound.
  • the base tertiary amines such as pyridine and triethylamine can be used. If the amount of the base added is too large, removal is difficult, and if it is too small, the molecular weight becomes small. Therefore, the amount is preferably 2 to 4 times the mole of 2-amino-4-nitroaniline.
  • the reaction proceeds efficiently by adding Lewis acid as an additive.
  • Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
  • the addition amount of the Lewis acid is preferably 0 to 1.0-fold mol with respect to 2-amino-4-nitroaniline.
  • the precipitate it is preferable to remove the precipitate from the obtained reaction solution, and then add an acid or basic aqueous solution and an organic solvent to remove the acid halide or acid derivative, the condensing agent and the base by extraction.
  • an acidic aqueous solution an aqueous solution of hydrochloric acid, acetic acid, formic acid, or ammonium chloride is preferable.
  • an aqueous base solution an aqueous solution of sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, or potassium carbonate is preferable.
  • the organic solvent used for the extraction is not limited as long as it does not cause precipitation of the contents even when added to the reaction solution and does not mix with water. Ethyl acetate, dichloromethane, chloroform, 1,2- Dichloroethane is more preferred.
  • organic solvent used for recrystallization is an organic solvent which can recrystallize the compound represented by said Formula (55), it may select the kind and may recrystallize with 2 or more types of mixed solvents.
  • a diamine compound represented by the following formula (56) can be produced by a hydrogenation reaction of the compound represented by the above formula (55).
  • the reaction mixture is stirred at 0-100 ° C., preferably 10-60 ° C., for 15-72 hours, preferably 24-48 hours.
  • the catalyst is removed and the organic solvent is distilled off to obtain the diamine compound of the present invention represented by the above formula (56).
  • the obtained compound is preferably purified by various methods because the polymerization reaction does not proceed and a high molecular weight polymer cannot be obtained unless the compound is highly purified. Examples of the purification method include silica gel column chromatography, recrystallization, washing with an organic solvent, and the like. Recrystallization is more preferable from the viewpoint of ease of operation and high purification efficiency.
  • the organic solvent used for recrystallization is an organic solvent that can recrystallize the diamine represented by the following formula (56), the kind thereof may be selected and recrystallization may be performed with two or more kinds of mixed solvents.
  • the polyimide precursor and polyimide of the present invention are at least one selected from the group consisting of a diamine compound having a substituent represented by formula (1) and a tetracarboxylic acid derivative having a substituent represented by formula (1). It is produced using a compound (hereinafter also referred to as a specific monomer). Specifically, it is produced using the tetracarboxylic acid derivative represented by the above formulas (19) to (21) and / or the diamine compound represented by the formula (22). Especially, it is preferable that a specific monomer is a diamine compound which has a substituent represented by the said Formula (1).
  • the amount of the specific monomer used in the raw material monomer is preferably 2 to 100 mol%, more preferably 2 to 60 mol%, still more preferably 2 to 50 mol%, and particularly preferably 2 to 30 mol%.
  • the tetracarboxylic dianhydride and the diamine compound are preferably in the presence of an organic solvent at ⁇ 20 ° C. to 140 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably Can be produced by reacting for 1 to 12 hours.
  • the solvent used for the production of the polyamic acid of the above formula (viii) is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or ⁇ -butyrolactone from the solubility of the monomer and polymer. Or you may use it in mixture of 2 or more types.
  • the total amount of tetracarboxylic dianhydride and diamine compound in the reaction solution is preferably 1 to 30% by mass. 5 to 20% by mass is more preferable.
  • the polyamic acid obtained as described above can use the reaction solution as the liquid crystal aligning agent of the present invention, but if it is not desired to include the solvent used in the polymerization in the liquid crystal aligning agent, the polymer After being recovered as a solid, it can be used as the polyamic acid of the present invention.
  • the polymer By injecting the polymer into a poor solvent while thoroughly stirring the reaction solution, the polymer can be precipitated and recovered. Precipitation is performed several times, washed with a poor solvent, and then dried at room temperature or by heating to obtain a purified polyamic acid powder.
  • the said poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
  • the polyamic acid ester can be produced by a known production method, and specific examples thereof include, but are not limited to, the following methods (a) to (c). (A) When producing polyamic acid ester from polyamic acid
  • the addition amount of the esterifying agent is preferably 2 to 6 molar equivalents per 1 mol of the polyamic acid repeating unit.
  • the solvent used for the production of the polyamic acid ester of the above formula (ix) is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or ⁇ -butyrolactone from the solubility of the monomer and polymer. You may mix and use seed
  • the polyamic acid ester can be produced from an acid chloride and a diamine compound (the above formula (x)).
  • the acid chloride and / or diamine compound includes a specific monomer.
  • the acid chloride and diamine compound are reacted in the presence of a base and an organic solvent at ⁇ 20 ° C. to 140 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours.
  • a base pyridine, triethylamine, and 4-dimethylaminopyridine can be used, but pyridine is preferable because the reaction proceeds gently. If the amount of the base added is too large, removal is difficult, and if it is too small, the molecular weight is small. Therefore, the amount is preferably 2 to 4 moles relative to the acid chloride.
  • the solvent used for the production of the polyamic acid ester of the above formula (x) is preferably N-methyl-2-pyrrolidone or ⁇ -butyrolactone from the solubility of the monomer and the polymer, and these may be used alone or in combination of two or more. May be used. If the concentration at the time of production is too high, the polymer tends to precipitate, and if it is too low, the molecular weight does not increase. Therefore, the total amount of acid chloride and diamine compound in the reaction solution is preferably 1 to 30% by mass, and preferably 5 to 20%. The mass% is more preferable. In addition, in order to prevent hydrolysis of acid chloride, the solvent used for the production of the polyamic acid ester should be dehydrated as much as possible, and it is better to prevent external air from being mixed in a nitrogen atmosphere.
  • condensing agent examples include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazide.
  • Nylmethylmorpholinium O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like.
  • the amount of the condensing agent added is preferably 2 to 3 moles relative to the dialkyl ester dicarboxylic acid.
  • the molecular weight of the polyamic acid ester used in the polyimide precursor composition of the present invention is preferably 2,000 to 500,000 in terms of weight average molecular weight, more preferably 5,000 to 300,000, still more preferably, 10,000 to 100,000.
  • the polyimide of the present invention can be produced by imidizing the polyimide precursor.
  • the chemical imidation which adds a catalyst to the solution of the said polyamic acid obtained by reaction of a diamine component and tetracarboxylic dianhydride is simple.
  • Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer does not easily decrease during the imidization process.
  • the poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.
  • the liquid crystal aligning agent of the present invention is a coating liquid for forming a liquid crystal aligning agent in which the polyimide precursor or polyimide obtained as described above is uniformly dissolved in an organic solvent.
  • ethyl cellosolve ethyl cellosolve
  • butyl cellosolve ethyl carbitol
  • butyl carbitol ethyl carbitol acetate
  • ethylene glycol 1-methoxy-2-propanol
  • 1-ethoxy-2-propanol 1-butoxy.
  • Q represents an organic functional group
  • R 14 represents a divalent organic group
  • R represents an alkyl group
  • W represents an alkoxy group represented by OR 15 (where R 15 represents an alkyl group).
  • N is an integer of 1 to 3.
  • the silane coupling agent is added for the purpose of improving the adhesion between various inorganic materials used as substrates for electronic devices and the polymer.
  • alkoxysilane which is a hydrolyzable group, is hydrolyzed by heating to form silanol, and forms a hydrogen bond or a covalent bond with a polar group present on the substrate surface, thereby imparting adhesion.
  • silane coupling agent used for this invention is not limited to this.
  • the silane coupling agent can exert its effect more when the organic functional group Q is bonded to the functional group in the polymer and introduced into the polymer. That is, the silane coupling agent is preferably used depending on the composition of the polyimide precursor or polyimide used.
  • polyimide precursor and its imidized polymer polyimide are polymer terminal by adjusting the molar ratio of tetracarboxylic acid derivatives such as tetracarboxylic dianhydride, acid chloride, and dialkyl ester dicarboxylic acid and diamine compound. These functional groups can be amines, carboxylic acids or esters.
  • epoxy-based silane coupling agents isocyanate-based silane coupling agents, aldehyde-based silane coupling agents, carbamate-based silane coupling agents, and amine-based silane coupling agents that are highly reactive with these functional groups are preferable.
  • amine-based silane coupling agents and epoxy-based silane coupling agents are particularly preferable.
  • arbitrary functional groups can be introduced into the polymer by modifying the terminal of the polymer with a known functional compound. In such a case, it is preferable to add a silane coupling agent having an organic functional group Q that reacts with the introduced functional group.
  • the adhesion can be improved by heating after the coupling agent is added and reacting with the polymer. After the coupling agent is added, the reaction may be performed at 20 to 80 ° C., more preferably at 40 to 60 ° C. for 1 to 24 hours.
  • the liquid crystal alignment film of the present invention is obtained as follows. That is, the liquid crystal aligning agent of the present invention is preferably filtered, then applied to a substrate, dried and fired to form a coating film.
  • the substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like is formed.
  • an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
  • the method for applying the liquid crystal aligning agent of the present invention include a spin coating method, a printing method, and an ink jet method. After applying the liquid crystal aligning agent of the present invention, it is preferably dried and baked. In order to sufficiently remove the organic solvent contained in the liquid crystal aligning agent, it is preferably dried at 50 to 120 ° C., preferably for 1 to 10 minutes. Next, baking is preferably performed at 150 to 300 ° C., more preferably 150 to 250 ° C. The firing time varies depending on the firing temperature, but is preferably 5 to 120 minutes, more preferably 5 to 60 minutes.
  • the liquid crystal aligning agent of the present invention has 150 primary or secondary aliphatic amino groups protected by the Boc group of the polyimide precursor or its imidized polymer in the baking process of the coating film.
  • the Boc group By heating to a temperature higher than or equal to ° C., the Boc group is eliminated, and a reactive primary or secondary aliphatic amino group in which the protection of the Boc group is lost is generated.
  • the generated primary or secondary aliphatic amino group reacts with a functional group present in the polyimide precursor or its imidized polymer to form an intermolecular crosslink, and the liquid crystal obtained in the present invention through such a crosslink reaction.
  • the alignment film has improved mechanical strength, and a polyimide film that does not cause peeling or scratching due to rubbing can be obtained.
  • the surface of the coating film is irradiated with radiation polarized in a certain direction, and in some cases, a heat treatment is further performed at a temperature of 150 to 250 ° C. to impart liquid crystal alignment ability.
  • a heat treatment is further performed at a temperature of 150 to 250 ° C. to impart liquid crystal alignment ability.
  • the radiation ultraviolet rays and visible rays having a wavelength of 100 to 800 nm can be used. Of these, ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and ultraviolet rays having a wavelength of 200 to 400 nm are particularly preferable.
  • radiation may be irradiated while heating the coated substrate at 50 to 250 ° C.
  • Dimroth and 100 mL dropping funnel were connected to a 1 L four-necked flask, 2-cyano-4-nitroaniline (15 g, 92 mmol) was added, and the system was purged with nitrogen, and then 400 mL of THF was added and cooled to 0 ° C. .
  • borane-THF complex (1M in THF, 100 mL, 100 mmol) was dropped from the dropping funnel over 30 minutes. Generation of gas was confirmed from the reaction system, and a yellow solid was precipitated.
  • the mixture was stirred at room temperature for 2 days.
  • an aqueous hydrochloric acid solution (2N, 200 mL) was added, and the mixture was stirred at room temperature for 2 hours.
  • the obtained organic layer was washed once with a 1M aqueous potassium dihydrogen phosphate solution, once with a saturated saline solution, twice with a saturated aqueous sodium bicarbonate solution, and once with a saturated saline solution.
  • the obtained organic layer was dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off from the filtrate to obtain an orange solid. This solid was suspended in 300 ml of toluene and heated and stirred for 30 minutes. The solid was filtered off with suction, and 1 H-NMR of the obtained solid was measured. As a result, it was confirmed that it was the target nitro compound (yield: 9.85 g, yield: 54.9%).
  • Example 2 A polyimide film was prepared in the same manner as in Example 11 except that the liquid crystal aligning agent (B-1) obtained in Comparative Example 1 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing and scraped scraps of the polyimide film were observed.
  • the voltage holding ratio was 99.3% at a temperature of 23 ° C., 98.7% at a temperature of 60 ° C., and 94 at a temperature of 90 ° C. a .1%
  • the ion density of 10pC / cm 2 at 23 ° C. was 18pC / cm 2 at 60 ° C..
  • Example 15 A twisted nematic liquid crystal cell was prepared in the same manner as in Example 14 except that the liquid crystal aligning agent (A-2) obtained in Example 9 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density were performed. Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. As a result of measuring the voltage holding ratio of the liquid crystal cell and then measuring the ion density, the voltage holding ratio was 99.3% at a temperature of 23 ° C., 98.8% at a temperature of 60 ° C., and 94 at a temperature of 90 ° C. a .4%, the ion density of 5 pC / cm 2 at 23 ° C., was 11pC / cm 2 at 60 ° C..
  • Example 3 A twisted nematic liquid crystal cell was prepared in the same manner as in Example 14 except that the liquid crystal aligning agent (B-1) obtained in Comparative Example 1 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, ion density was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. With respect to this cell, the voltage holding ratio was measured, and then the ion density was measured. As a result, the voltage holding ratio was 99.1% at a temperature of 23 ° C., 97.4% at a temperature of 60 ° C., and 86. 7%, ion density 50pc / cm 2 at 23 ° C., was 256pC / cm 2 at a temperature 60 ° C..
  • the nitro compound (47.07 g, 106 mmol) was placed in a 1 L four-necked flask and suspended in 560 ml of ethanol.
  • the system was degassed and purged with nitrogen, then palladium carbon (4.71 g) was added, purged with hydrogen, and heated and stirred at room temperature (50 ° C.) for 8 days.
  • the palladium carbon was removed by Celite filtration, and the solvent was distilled off.
  • the obtained solid was dissolved in 200 ml of 1,2-dichloroethane, and then 70 ml of hexane was added for recrystallization.
  • the obtained solid was dried under reduced pressure to obtain a gray solid.
  • the yield was 39.54 g, and the yield was 87.5%.
  • Example 20 Preparation of Polyamic Acid (A-5) Solution
  • 0.8665 g (8.013 mmol) of p-PDA and 0 of DA-H were added.
  • 8442 g (1.998 mmol) and NMP 25.31 g were added and dissolved while stirring while feeding nitrogen.
  • 1.90447 g (9.713 mmol) of CBDA was added, NMP was further added so that the solid content concentration was 10% by mass, and the mixture was stirred at room temperature for 24 hours to polyamic acid (A-5). ) was obtained.
  • Example 25 Preparation of polyamic acid ester resin (C-5) A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 1.420 g (13.13 mmol) of p-PDA and 1 DA-H were added. .3872 g (3.283 mmol), 59.54 g of NMP, and 2.87 g (36.24 mmol) of pyridine as a base were added and dissolved by stirring. Next, 4.999 g (15.10 mmol) of 1,3DM-CBDE-Cl was added while stirring the diamine solution, and the mixture was reacted for 4 hours under water cooling.
  • Example 46 A twisted nematic liquid crystal cell was prepared in the same manner as in Example 42 except that the liquid crystal aligning agent (C-5) obtained in Example 32 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density were performed. Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 described later.
  • Example 49 A twisted nematic liquid crystal cell was prepared in the same manner as in Example 47 except that the liquid crystal aligning agent (A-3) obtained in Example 10 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density were performed. Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.
  • the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention can be a liquid crystal alignment film excellent in mechanical strength that is not easily damaged by rubbing treatment without adding a crosslinking agent or the like. confirmed. Moreover, it was confirmed that the liquid crystal display element which has the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention turns into a liquid crystal display element excellent in the reliability with a high voltage holding rate and a low ion density even at high temperature.

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Abstract

L’invention concerne un agent d’alignement de cristaux liquides permettant d’obtenir, sans ajout d’un agent de réticulation, un film d’alignement de cristaux liquides qui présente une excellent résistance mécanique et qui n’est pas facile à rayer par frottement. L’agent d’alignement de cristaux liquides permet également d’obtenir un film d’alignement de cristaux liquides très fiable qui comprend un élément d’affichage à cristaux liquides à faible densité ionique et à taux de maintien de tension élevée même à des températures élevées. L’invention concerne également un polymère ou analogue permettant d’obtenir l’agent d’alignement de cristaux liquides. Ledit agent est caractérisé en ce qu’il contient un précurseur polyimide doté d’un constituant dont la structure est représentée par la formule (1), ou un polymère imidisé du précurseur polyimide. Dans la formule (1), A représente une liaison simple ou un groupe organique divalent ; et R1, R2 et R3 représentent chacun indépendamment un atome d’hydrogène ou un groupe organique divalent comprenant 1 à 10 atomes de carbone.
PCT/JP2009/068523 2008-10-29 2009-10-28 Diamine, polyimide, agent d’alignement de cristaux liquides et film d’alignement de cristaux liquides WO2010050523A1 (fr)

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JP5614284B2 (ja) 2014-10-29
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