WO2010050523A1 - Diamine, polyimide, liquid crystal aligning agent, and liquid crystal alignment film - Google Patents
Diamine, polyimide, liquid crystal aligning agent, and liquid crystal alignment film Download PDFInfo
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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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- 0 CCC(C1)C1(C)C1(C)C(Cc2c(C)ccc(C)c2)=C(CC*2)C2CC1CC Chemical compound CCC(C1)C1(C)C1(C)C(Cc2c(C)ccc(C)c2)=C(CC*2)C2CC1CC 0.000 description 3
- DSPYCWLYGXGJNJ-UHFFFAOYSA-N CC(C)(C)OC(NCC#C)=O Chemical compound CC(C)(C)OC(NCC#C)=O DSPYCWLYGXGJNJ-UHFFFAOYSA-N 0.000 description 1
- XNBHGYQYSLXHEX-UHFFFAOYSA-N CC(C)(C)OC(NCC#Cc1cc([N+]([O-])=O)cc(C#CCNC(OC(C)(C)C)=O)c1N)=O Chemical compound CC(C)(C)OC(NCC#Cc1cc([N+]([O-])=O)cc(C#CCNC(OC(C)(C)C)=O)c1N)=O XNBHGYQYSLXHEX-UHFFFAOYSA-N 0.000 description 1
- YPVYMWQYENWFAT-UHFFFAOYSA-O [NH3+]c(c(I)cc([N+]([O-])=O)c1)c1I Chemical compound [NH3+]c(c(I)cc([N+]([O-])=O)c1)c1I YPVYMWQYENWFAT-UHFFFAOYSA-O 0.000 description 1
Classifications
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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
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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
- 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
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- 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
Description
1.下記式(1)で表される構造の置換基を有するポリイミド前駆体又は該ポリイミド前駆体のイミド化重合体を含有することを特徴とする液晶配向剤。 That is, 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.
2.ポリイミド前駆体又は該ポリイミド前駆体のイミド化重合体が、式(1)で表される置換基を有するジアミン化合物及び式(1)で表される置換基を有するテトラカルボン酸誘導体からなる群から選ばれる少なくとも1つを用いて得られる上記1に記載の液晶配向剤。
3.式(1)で表される置換基を有するジアミン化合物及び/又は式(1)で表される置換基を有するテトラカルボン酸誘導体を、全ジアミン化合物及びテトラカルボン酸誘導体の2~100モル%を用いて得られるポリイミド前駆体又は該ポリイミド前駆体のイミド化重合体である上記2に記載の液晶配向剤。
4.ポリイミド前駆体が、下記式(2)の構造単位を含有する構造である上記1~3のいずれかに記載の液晶配向剤。
2. 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. 3. 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).
5.ポリイミド前駆体が、下記式(3)の構造単位を含有する構造である上記1~3のいずれかに記載の液晶配向剤。
5). 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 of the following formula (3).
6.ポリイミド前駆体が、下記式(4)で表される構造単位を含有する構造である上記1~3のいずれかに記載の液晶配向剤。
6). 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 (4).
7.ポリイミド前駆体が、下記式(5)で表される構造単位を含有する構造である上記1~3のいずれかに記載の液晶配向剤。
7). 4. The liquid crystal aligning agent according to any one of 1 to 3, wherein the polyimide precursor has a structure containing a structural unit represented by the following formula (5).
8.上記1~7のいずれかに記載の液晶配向剤を150~300℃にて焼成して得られる液晶配向膜。
9.下記式(6)で表される構造単位を含有するポリイミド前駆体。
8). 8. 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.
9. The polyimide precursor containing the structural unit represented by following formula (6).
10.下記式(7)で表される構造単位を含有するポリイミド。
10. Polyimide containing a structural unit represented by the following formula (7).
11.下記式(8)で表される構造単位を含有するポリイミド前駆体。
11. The polyimide precursor containing the structural unit represented by following formula (8).
12.下記式(9)で表される構造単位を含有するポリイミド。
12 The polyimide containing the structural unit represented by following formula (9).
13.下記式(10)で表される構造単位を含有するポリイミド前駆体。
13. The polyimide precursor containing the structural unit represented by following formula (10).
14.下記式(11)で表される構造単位を含有するポリイミド。
14 A polyimide containing a structural unit represented by the following formula (11).
15.下記式(A)~(F)で表されるジアミン化合物。
15. Diamine compounds represented by the following formulas (A) to (F).
さらに、シクロブタン環の光分解反応により生成したマレイミドは、加熱により生成した1級又は2級の脂肪族アミノ基と反応することができる(下記式(xiv))。このような架橋反応においても、低分子量成分の液晶中への溶出を抑制することが可能である。これらの架橋反応の進行により、光配向法により液晶配向能を付与した液晶配向膜を液晶表示素子に用いた場合でも、高温時においても電圧保持率が高く、イオン密度が低い、表示特性に優れた液晶表示素子が得られると考えられる。 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. Due to the progress of these cross-linking reactions, even when a liquid crystal alignment film provided with liquid crystal alignment ability by a photo-alignment method is used for a liquid crystal display element, the voltage holding ratio is high even at high temperatures, the ion density is low, and the display characteristics are excellent It is considered that a liquid crystal display element can be obtained.
a.[ポリイミド前駆体及びポリイミド]
本発明におけるポリイミド前駆体とは、加熱又は触媒の作用によりポリイミドとなる重合体であり、例えば、ポリアミック酸、ポリアミック酸エステル、ポリアミック酸シリルエステル、ポリイソイミドが挙げられる。製造の容易さ及びイミド化の反応効率からポリイミド前駆体としては、ポリアミック酸、又はポリアミック酸エステルが特に好ましい。また、本発明におけるポリイミドとは、ポリイミド前駆体をイミド化することで得られる重合体である。 Hereinafter, the present invention will be described in more detail.
a. [Polyimide precursor and polyimide]
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. As the polyimide precursor, 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.
なお、これらの1価の炭化水素基の水素原子の一部又は全部は、ハロゲン原子、水酸基、チオール基、リン酸エステル基、エステル基、カルボキシル基、リン酸基、チオエステル基、アミド基、ニトロ基、オルガノオキシ基、オルガノシリル基、オルガノチオ基、アシル基、アルキル基、シクロアルキル基、ビシクロアルキル基、アルケニル基、アリール基、アラルキル基、ピロール基、イミダゾール基、ピラゾール基、アルコキシカルボニルアミノ基などで置換されていてもよい。また、これらは環状構造であってもよい。その中でも、ピロール基、イミダゾール基、ピラゾール基が好ましく、ピロール基、イミダゾール基、ピラゾール基の窒素原子上の水素原子がBoc基で置換されている場合がより好ましい。 In the formula, 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 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. Specific examples of the monovalent hydrocarbon group 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. Among them, 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.
R3が、嵩高い構造であると架橋反応の反応効率が低下するため、R3としてはメチル基、エチル基、プロピル基、ブチル基などのアルキル基、又は水素原子が好ましく、水素原子がより好ましい。
Aが2価の有機基である場合、その構造は例えば、下記式(12)で表される。 When 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.
When 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.
When A is a divalent organic group, the structure is represented by the following formula (12), for example.
以上より、式(1)で表されるBoc基で保護された1級又は2級の脂肪族アミンを含有する置換基の具体的な例としては、下記式(13)~(18)の構造が特に好ましい。 If 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.
From the above, 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.
上記式(2)のポリイミド前駆体及びそのイミド化重合体を製造する方法としては、ポリイミド前駆体の原料であるテトラカルボン酸誘導体及びジアミン化合物に、上記式(1)で表される置換基を導入した原料を用いることが好ましい。具体的には、下記式(19)~(21)で表されるテトラカルボン酸誘導体及び下記式(22)で表されるジアミン化合物を用いることが好ましい。
As a method for producing the polyimide precursor of the above formula (2) and the imidized polymer thereof, 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. Specifically, it is preferable to use a tetracarboxylic acid derivative represented by the following formulas (19) to (21) and a diamine compound represented by the following formula (22).
上記式(19)~(21)及び上記式(23)~(25)において、X及びX1の構造は特に限定されるものではない。その具体例を挙げるならば、下記X-1~X-46で表される構造が挙げられる。また、これらのテトラカルボン酸誘導体は2種類以上使用してもよい。
ただし、上記式(19)~(21)においては、Zの置換数であるaによって、X1の価数が変化する。すなわち、Zの置換数だけ、下記X-1~X-46で表される構造の任意の位置から水素原子を取り除いた構造がX1の構造である。
In the above formulas (19) to (21) and the above formulas (23) to (25), 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.
However, in the above formulas (19) to (21), 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.
ただし、上記式(22)においては、Zの置換数b(b=0~4)によって、Y1の価数が変化する。すなわち、Zの置換数だけ、下記Y-1~Y-100で表される構造の任意の位置から水素原子を取り除いた構造がY1の構造である。 In the above formula (22) and the above formula (26), 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.
However, in the above formula (22), the valence of Y 1 varies depending on the substitution number b (b = 0 to 4) of Z. That is, the substitution number of Z by a structure structure obtained by removing a hydrogen atom from an arbitrary position of Y 1 in the structure represented by the following Y-1 ~ Y-100.
製造の容易さ及び単量体の扱いやすさの観点から上記式(22)で表されるジアミン化合物を用いることが好ましい。本発明のポリイミド前駆体及びポリイミドとしては、下記式(3)で表される構造単位を含有するポリイミド前駆体、及び下記式(7)で表される構造単位を含有するポリイミドが好ましい。
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).
上記式(3)及び(7)の構造単位を含有するポリイミド前駆体又はポリイミドは、上記式(23)~(25)で表されるテトラカルボン酸誘導体及び下記式(27)で表されるジアミン化合物と上記式(26)で表されるジアミン化合物を任意の割合で混合し、反応することで製造される。
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.
ただし、上記式(27)においては、Zの置換数cによって、Y2の価数が変化する。すなわち、Zの置換数だけ、Y-1~Y-100で表される構造の任意の位置から水素原子を取り除いた構造がY2の構造である。
However, in the above formula (27), 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.
本発明においては、得られる重合体の直線性が高いほどより良好な液晶配向性を有する液晶配向膜が得られるので、置換基Zを含有するジアミン化合物としては、下記式(28)~(44)及び下記式(58)~(61)で表されるジアミン化合物がより好ましい。これらの式において、Zは上記式(1)で表される構造であり、cは、1~4の整数であり、d及びeは、1~2の整数である。
In the present invention, the higher the linearity of the polymer obtained, the more liquid crystal alignment film having better liquid crystal alignment can be obtained. As the diamine compound containing the substituent Z, the following formulas (28) to (44) And diamine compounds represented by the following formulas (58) to (61) are more preferable. In these formulas, Z is a structure represented by the above formula (1), c is an integer of 1 to 4, and d and e are integers of 1 to 2.
b.[特定ジアミン化合物]
本発明では、ポリイミド前駆体を製造するための原料として、特に好ましいジアミン化合物として、下記式(A)~(F)のジアミン化合物が挙げられる。
b. [Specific diamine compound]
In the present invention, particularly preferred diamine compounds as raw materials for producing the polyimide precursor include diamine compounds of the following formulas (A) to (F).
上記式(A)~(E)で表される特定ジアミン化合物の製造法について以下に説明するが、本発明はこれらに限定されるものはない。
まず、上記式(A)のジアミン化合物は、例えば、下記式(45)の2-シアノ-4-ニトロアニリンを出発原料として用いて、下記式(iv)に示す中間体を経て、製造される。 b1. [Production of specific diamine compound]
The method for producing the specific diamine compound represented by the above formulas (A) to (E) will be described below, but the present invention is not limited thereto.
First, the diamine compound of the above formula (A) is produced through an intermediate represented by the following formula (iv) using, for example, 2-cyano-4-nitroaniline of the following formula (45) as a starting material. .
次に、上記式(47)で表される化合物から下記式(A)で表されるジアミン化合物を製造する方法について説明する。 First, 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. . Moreover, in order to advance reaction more efficiently, you may add 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). After completion of the reaction, 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. 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. As long as 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.
Next, a method for producing a diamine compound represented by the following formula (A) from the compound represented by the above formula (47) will be described.
次いで、上記式(51)で表される化合物を用いて、下記式(52)で表される化合物を製造する方法について説明する。 Dissolve propargylamine in organic solvent and add organic base. Here, the organic solvent used for the reaction is not limited as long as it dissolves propargylamine and does not react with di-tert-butyl dicarbonate to be added later, but dichloromethane is preferable. The organic base is added for the purpose of improving the nucleophilicity of the amino group, and triethylamine or pyridine is more preferable. The reaction solution is -5 ° C to 40 ° C, preferably 0 ° C to 20 ° C, and di-tert-butyl dicarbonate is added dropwise to the reaction solution. If the dropping speed is too high, the reaction proceeds rapidly, so the dropping time is preferably 10 minutes to 1 hour. The dropping rate can be changed depending on the amount of di-tert-butyl dicarbonate added. After completion of the dropwise addition, the mixture is stirred for 1 to 10 hours, preferably 2 to 4 hours, and then the reaction solution is extracted by adding water, saturated brine or an organic solvent. The organic solvent used for extraction is not limited as long as it is not mixed with water, but it is preferable to use the same organic solvent as used for the reaction. The organic layer obtained by extraction is dried with a desiccant. As the desiccant, sodium sulfate or magnesium sulfate is preferable. The resulting organic layer is dried for 4 to 24 hours, preferably 12 to 24 hours. When the desiccant is removed and the solvent is distilled off from the obtained filtrate, the compound represented by the above formula (51) can be obtained. The obtained compound can be used for the next reaction without purification, but is preferably 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. As long as the organic solvent used for recrystallization is an organic solvent which can recrystallize following formula (51), the kind may be chosen and it may recrystallize with 2 or more types of mixed solvents.
Next, a method for producing a compound represented by the following formula (52) using the compound represented by the above formula (51) will be described.
上記式(49)で表されるヨウ化アリール、パラジウム触媒、銅触媒、及び塩基を加え、有機溶剤に溶解させる。パラジウム触媒としては、ビス(トリフェニルホスフィン)パラジウム(II)ジクロリドが好ましく、添加量は、ヨウ化アリールのヨード基に対して、0.05~1.0モル%、好ましくは、0.1~0.5モル%がより好ましい。銅触媒としては、ヨウ化銅が好ましく、その添加量は、ハロゲン化アリールのヨード基に対して、0.05~1.0モル%、好ましくは、0.1~0.5モル%がより好ましい。塩基としては、トリエチルアミン、ジエチルアミンが好ましく、その添加量は、ヨウ化アリールのヨード基に対して、1~3モル等量が好ましく、1~2モル等量がより好ましい。反応に使用する有機溶剤としては、ヨウ化アリールを溶解し、かつ、後に加える種々の試薬と反応しないものであれば、その種類を選ばないが、N,N-ジメチルホルムアミドが好ましい。
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. As 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. As the copper catalyst, copper iodide is preferable, and the addition amount thereof is 0.05 to 1.0 mol%, preferably 0.1 to 0.5 mol%, based on the iodo group of the aryl halide. preferable. As the base, triethylamine and diethylamine are preferable, and the addition amount thereof is preferably 1 to 3 molar equivalents, more preferably 1 to 2 molar equivalents with respect to the iodo group of aryl iodide. The organic solvent used in the reaction is not particularly limited as long as it dissolves aryl iodide and does not react with various reagents to be added later. N, N-dimethylformamide is preferred.
下記式(B)で表される本発明のジアミン化合物は、上記式(52)で表される化合物の水添反応により製造することができる。 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 obtained organic layer is washed several times with an acidic aqueous solution and then dried with a desiccant. 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. When the desiccant is removed and the solvent is distilled off from the obtained filtrate, the compound represented by the formula (52) can be obtained. The obtained compound can be used for the next reaction without purification, but is preferably 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. As long as the organic solvent used for recrystallization is an organic solvent which can recrystallize said Formula (52), the kind may be chosen and it may recrystallize with 2 or more types of mixed solvents.
The diamine compound of the present invention represented by the following formula (B) can be produced by a hydrogenation reaction of the compound represented by the above formula (52).
以下、上記式(D)及び(E)のジアミン化合物の製造方法を示すが、これに限定されない。 The compound represented by the above formula (52) is dissolved in an organic solvent. Here, the organic solvent to be used is not particularly limited as long as it is a known one, but methanol, ethanol, 2-propanol, tetrahydrofuran, and 1,4-dioxane are preferable in order to promote the reaction more efficiently. More preferred are methanol and ethanol. After dissolving the compound represented by the formula (52) in an organic solvent, 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. Examples of the catalyst include palladium carbon, platinum carbon, platinum oxide and the like, and palladium carbon is more preferable from the viewpoint of reaction efficiency. The reaction mixture is stirred at 0 ° C. to 100 ° C., preferably 10 to 60 ° C., for 15 to 72 hours, preferably 24 to 48 hours. After completion of the reaction, the diamine compound of the present invention represented by the above formula (B) can be obtained by removing the catalyst and distilling off the organic solvent. 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. As long as the organic solvent used for recrystallization is an organic solvent that can recrystallize the diamine represented by the above formula (B), the kind thereof may be selected and recrystallization may be performed with two or more kinds of mixed solvents.
Hereinafter, although the manufacturing method of the diamine compound of the said Formula (D) and (E) is shown, it is not limited to this.
反応に使用する塩基としては、3級アミンが好ましく、ピリジン、トリエチルアミン、ジメチルアミノピリジン、N―メチルモルホルリンがより好ましい。塩基の添加量は、多すぎると除去が難しいため、2-アミノ-4-ニトロアニリンに対して2~4倍モルであることが好ましい。 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.
上記式(55)で表される化合物の水添反応により、下記式(56)で表されるジアミン化合物を製造することができる。 The obtained organic layer is washed several times with the acidic aqueous solution or the basic aqueous solution and then dried with a desiccant. 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. When the desiccant is removed and the solvent is distilled off from the obtained filtrate, the compound represented by the formula (55) can be obtained. The obtained compound can be used for the next reaction without purification, but is preferably 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. As long as the 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).
本発明のポリイミド前駆体及びポリイミドは、式(1)で表される置換基を有するジアミン化合物及び式(1)で表される置換基を有するテトラカルボン酸誘導体からなる群から選ばれる少なくとも1つの化合物(以下、特定モノマーともいう。)を用いて製造される。詳細には、上記した式(19)~式(21)で表わされるテトラカルボン酸誘導体及び/又は式(22)で表わされるジアミン化合物を用いて製造される。なかでも、特定モノマーは、上記式(1)で表わされる置換基を有するジアミン化合物であるのが好ましい。
本発明のポリイミド前駆体及びポリイミドを製造する際、原料モノマーとしては、特定のモノマー以外のテトラカルボン酸誘導体(例えば、上記した式(23)~式(25)で表わされるテトラカルボン酸誘導体)及び/又は特定のモノマー以外のジアミン化合物(例えば、上記した式(26)で表わされるジアミン化合物)を併用してもよい。この場合、原料モノマー中における特定モノマーの使用量は好ましくは2~100モル%、より好ましくは2~60モル%、さらに好ましくは2~50モル%、特に好ましくは2~30モル%である。 c. [Production of polyimide precursor and polyimide]
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).
When producing the polyimide precursor and polyimide of the present invention, as raw material monomers, tetracarboxylic acid derivatives other than specific monomers (for example, tetracarboxylic acid derivatives represented by the above formulas (23) to (25)) and A diamine compound other than the specific monomer (for example, a diamine compound represented by the above formula (26)) may be used in combination. In this case, 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%.
ポリイミド前駆体であるポリアミック酸は、テトラカルボン酸二無水物とジアミン化合物から製造することができる(下記式(viii))が、このテトラカルボン酸二無水物及び/又はジアミン化合物には、特定モノマーが含有される。 c1. (Production of polyamic acid)
The polyamic acid which is a polyimide precursor can be produced from a tetracarboxylic dianhydride and a diamine compound (the following formula (viii)), but the tetracarboxylic dianhydride and / or diamine compound includes a specific monomer. Is contained.
上記のようにして得られたポリアミック酸は、その反応溶液を本発明の液晶配向剤とすることができるが、重合に用いた溶媒を液晶配向剤中に含有させたくない場合等は、重合体として固体で回収した後、本発明のポリアミック酸として使用することができる。 When producing a polyimide precursor, 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 γ-butyrolactone from the solubility of the monomer and polymer. Or you may use it in mixture of 2 or more types. If the concentration at the time of production is too high, polymer precipitation is likely to occur, and if it is too low, the molecular weight does not increase. Therefore, 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.
前記貧溶媒は、特に限定されないが、水、メタノール、エタノール、ヘキサン、ブチルセロソルブ、アセトン、トルエン等が挙げられる。 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.
Although the said poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
ポリアミック酸エステルは、公知の製造方法により製造することができ、具体的には以下の(a)~(c)の方法が挙げられるが、これに限定されない。
(a)ポリアミック酸からポリアミック酸エステルを製造する場合 c2. (Production of polyamic acid ester)
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
上記式(ix)のポリアミック酸エステルの製造に用いる溶媒は、単量体及び重合体の溶解性からN,N-ジメチルホルムアミド、N-メチル-2-ピロリドン、γ-ブチロラクトンが好ましく、これらは1種又は2種以上を混合して用いてもよい。製造時の濃度は、高すぎると重合体の析出が起こりやすく、低すぎると分子量が上がらないので、ポリアミック酸とエステル化剤の反応液中の合計量が1~30質量%が好ましく、5~20質量%がより好ましい。 The esterifying agent is preferably one that can be easily removed by purification. N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethyl Formamide dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3- Examples include p-tolyltriazene. 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 γ-butyrolactone from the solubility of the monomer and polymer. You may mix and use seed | species or 2 or more types. If the concentration at the time of production is too high, precipitation of the polymer tends to occur, and if it is too low, the molecular weight does not increase. Therefore, the total amount of the polyamic acid and the esterifying agent in the reaction solution is preferably 1 to 30% by mass. 20 mass% is more preferable.
具体的には、酸クロライドとジアミン化合物とを塩基と有機溶剤の存在下で-20℃~140℃、好ましくは0℃~50℃において、30分~24時間、好ましくは1~4時間反応させることによって製造することができる。前記塩基には、ピリジン、トリエチルアミン、4-ジメチルアミノピリジンが使用できるが、反応が穏和に進行するためにピリジンが好ましい。塩基の添加量は、多すぎると除去が難しく、少なすぎると分子量が小さくなるため、酸クロライドに対して、2~4倍モルであることが好ましい。
Specifically, 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. Can be manufactured. As the 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.
具体的には、ジアルキルエステルジカルボン酸とジアミン化合物を縮合剤、塩基、及び有機溶剤の存在下で0℃~140℃、好ましくは0℃~100℃において、30分~24時間、好ましくは3~15時間反応させることによって製造することができる。
Specifically, a dialkyl ester dicarboxylic acid and a diamine compound in the presence of a condensing agent, a base, and an organic solvent at 0 ° C. to 140 ° C., preferably 0 ° C. to 100 ° C., for 30 minutes to 24 hours, preferably 3 to It can be produced by reacting for 15 hours.
また、上記反応において、ルイス酸を添加剤として加えることで反応が効率的に進行する。ルイス酸としては、塩化リチウム、臭化リチウムなどのハロゲン化リチウムが好ましい。ルイス酸の添加量はジアミン成分に対して0~1.0倍モルであることが好ましい。 As 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 moles relative to the diamine component.
In the above reaction, the reaction proceeds efficiently by adding Lewis acid as an additive. As the 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 mole per mole of the diamine component.
前記貧溶媒は、特に限定されないが、水、メタノール、エタノール、ヘキサン、ブチルセロソルブ、アセトン、トルエン等が挙げられる。 The polyamic acid ester solution obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
Although the said poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
重合反応に用いるジアミン成分とテトラカルボン酸誘導体(テトラカルボン酸二無水物、酸クロライド及びジアルキルエステルジカルボン酸)の比率は分子量制御の観点からモル比で1:0.7~1:1.2であることが好ましい。このモル比が1:1に近いほど得られるポリイミド前駆体の分子量は大きくなる。ポリイミド前駆体の分子量は、ワニスの粘度や、ポリイミド膜の物理的な強度に影響を与え、ポリイミド前駆体の分子量が大きすぎるとワニスの塗布作業性や塗膜均一性が悪くなる場合があり、分子量が小さすぎると得られるポリイミド膜の強度が不十分となる場合がある。従って、本発明のポリイミド前駆体組成物に用いるポリアミック酸エステルの分子量は、重量平均分子量で2,000~500,000が好ましく、より好ましくは5,000~300,000であり、さらに好ましくは、10,000~100,000である。 c3. [Molecular weight]
The ratio of the diamine component used in the polymerization reaction to the tetracarboxylic acid derivative (tetracarboxylic dianhydride, acid chloride and dialkyl ester dicarboxylic acid) is 1: 0.7 to 1: 1.2 in terms of molecular weight control. Preferably there is. The closer the molar ratio is to 1: 1, the higher the molecular weight of the resulting polyimide precursor. The molecular weight of the polyimide precursor affects the viscosity of the varnish and the physical strength of the polyimide film, and if the molecular weight of the polyimide precursor is too large, the coating workability and coating film uniformity of the varnish may deteriorate. If the molecular weight is too small, the strength of the resulting polyimide film may be insufficient. Therefore, 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.
本発明のポリイミドは、前記ポリイミド前駆体をイミド化することにより製造することができる。ポリイミド前駆体からポリイミドを製造する場合、ジアミン成分とテトラカルボン酸二無水物との反応で得られた前記ポリアミック酸の溶液に触媒を添加する化学的イミド化が簡便である。化学的イミド化は、比較的低温でイミド化反応が進行し、イミド化の課程で重合体の分子量低下が起こりにくいので好ましい。 d. [Production of polyimide]
The polyimide of the present invention can be produced by imidizing the polyimide precursor. When manufacturing a polyimide from a 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.
以上のようにして得られるポリイミドの溶液は、よく撹拌させながら貧溶媒に注入することで、重合体を析出させることができる。析出を数回行い、貧溶媒で洗浄後、常温あるいは加熱乾燥して精製されたポリアミック酸エステルの粉末を得ることができる。
前記貧溶媒は、特に限定されないが、メタノール、アセトン、ヘキサン、ブチルセルソルブ、ヘプタン、メチルエチルケトン、メチルイソブチルケトン、エタノール、トルエン、ベンゼン等が挙げられる。 The temperature for carrying out the imidization reaction is −20 ° C. to 140 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amic acid group. Is double. The imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. Since the added catalyst or the like remains in the solution after the imidation reaction, the obtained imidized polymer is recovered by the means described below, redissolved in an organic solvent, and the liquid crystal alignment according to the present invention. It is preferable to use an agent.
The polyimide solution obtained as described above can be polymerized by pouring into a poor solvent while thoroughly stirring. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
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.
本発明の液晶配向剤は、上記のように得られたポリイミド前駆体又はポリイミドが有機溶剤に均一に溶解している液晶配向剤形成用の塗布液である。 e. [Liquid crystal aligning agent]
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.
本発明の液晶配向剤に使用される溶剤としては、ポリイミド前駆体又はポリイミドを溶解させることができる溶剤(以下、良溶媒)と液晶配向剤を基板へ塗布する際の塗膜均一性を向上させるための溶剤(以下、貧溶媒)の2種類が挙げられる。良溶媒としては、ポリイミド前駆体又はポリイミドを溶解させるものであれば特に限定されない。あえて、その具体例を挙げるならば、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン、N-エチル-2-ピロリドン、N-メチルカプロラクタム、2-ピロリドン、N-エチルピロリドン、N-ビニルピロリドン、ジメチルスルホキシド、ジメチルスルホン、ヘキサメチルスルホキシド、γ-ブチロラクトン、1,3-ジメチル-イミダゾリジノン、3-メトキシ-N,N-ジメチルプロパンアミド等を挙げることができる。これらは1種又は2種以上を混合して用いてもよい。また、単独では重合体を溶解させない溶媒であっても、重合体が析出しない範囲であれば、混合してもよい。
貧溶媒としては、低表面張力で、塗膜均一性を向上させるものであれば、特に限定されない。あえて、その具体例を挙げるならば、エチルセロソルブ、ブチルセロソルブ、エチルカルビトール、ブチルカルビトール、エチルカルビトールアセテート、エチレングリコール、1-メトキシ-2-プロパノール、1-エトキシ-2-プロパノール、1-ブトキシ-2-プロパノール、1-フェノキシ-2-プロパノール、プロピレングリコールモノアセテート、プロピレングリコールジアセテート、プロピレングリコール-1-モノメチルエーテル-2-アセテート、プロピレングリコール-1-モノエチルエーテル-2-アセテート、ジプロピレングリコール、2-(2-エトキシプロポキシ)プロパノール、乳酸メチルエステル、乳酸エチルエステル、乳酸n-プロピルエステル、乳酸n-ブチルエステル、乳酸イソアミルエステル等が挙げられる。これらの溶媒は2種類上を併用してもよい。 e1. [solvent]
As a solvent used for the liquid crystal aligning agent of the present invention, a polyimide precursor or a solvent capable of dissolving the polyimide (hereinafter referred to as a good solvent) and a coating film uniformity when applying the liquid crystal aligning agent to the substrate are improved. Two types of solvents (hereinafter referred to as poor solvents). The good solvent is not particularly limited as long as it dissolves the polyimide precursor or the polyimide. Specific examples are N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl. Caprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N, N-dimethylpropane Examples include amides. You may use these 1 type or in mixture of 2 or more types. Even if the solvent alone does not dissolve the polymer, it may be mixed as long as the polymer does not precipitate.
The poor solvent is not particularly limited as long as it has low surface tension and improves coating film uniformity. Specific examples include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy. -2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene Glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester, etc. And the like. Two types of these solvents may be used in combination.
シランカップリング剤は分子中に有機材料と化学結合する有機官能基、及び無機材料と反応性を有する加水分解基の両方を有する有機ケイ素化合物で、その構造は一般的に下記式(57)で表される。 [Silane coupling agent]
A silane coupling agent is an organosilicon compound having both an organic functional group chemically bonded to an organic material in a molecule and a hydrolyzable group reactive with an inorganic material, and its structure is generally represented by the following formula (57). expressed.
シランカップリング剤は、電子デバイスの基板として用いられる各種無機材料と重合体との密着性を向上される目的で添加される。シランカップリング剤は、加水分解基であるアルコキシシランが加熱により加水分解してシラノールとなり、基板表面に存在する極性基と水素結合又は共有結合を形成し、密着性が付与される。
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. In the silane coupling agent, 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.
3-アミノプロピルトリエトキシシラン、3-(2-アミノエチル)アミノプロピルトリメトキシシラン、3-(2-アミノエチル)アミノプロピルメチルジメトキシシラン、3-アミノプロピルトリメトキシシラン、3-フェニルアミノプロピルトリメトキシシラン、3-トリエトキシシリル-N-(1,3-ジメチル-ブチリデン)プロピルアミン、3-アミノプロピルジエトキシメチルシランなどのアミン系シランカップリング剤;ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(2-メトキシエトキシ)シラン、ビニルメチルジメトキシシラン、ビニルトリアセトキシシラン、ビニルトリイソプロポキシシラン、アリルトリメトキシシラン、p-スチリルトリメトキシシランなどのビニル系シランカップリング剤;3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランなどのエポキシ系シランカップリング剤;3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-メタクリロキシプロピルトリエトキシシランなどのメタクリル系シランカップリング剤;3-アクリロキシプロピルトリメトキシシランなどのアクリル系シランカップリング剤;3-ウレイドプロピルトリエトキシシランなどのウレイド系シランカップリング剤;ビス(3-(トリエトキシシリル)プロピル)ジスルフィド、ビス(3-(トリエトキシシリル)プロピル)テトラスルフィドなどのスルフィド系シランカップリング剤;3-メルカプトプロピルメチルジメトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-オクタノイルチオ-1-プロピルトリエトキシシランなどのメルカプト系シランカップリング剤;3-イソシアネートプロピルトリエトキシシラン、3-イソシアネートプロピルトリメトキシシランなどのイソシアネート系シランカップリング剤;トリエトキシシリルブチルアルデヒドなどのアルデヒド系シランカップリング剤;トリエトキシシリルプロピルメチルカルバメート、(3-トリエトキシシリルプロピル)-t-ブチルカルバメートなどのカルバメート系シランカップリング剤などが挙げられる。 Although the specific example of the silane coupling agent used for this invention is put together below, it is not limited to this.
3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-phenylaminopropyltri Amine-based silane coupling agents such as methoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-aminopropyldiethoxymethylsilane; vinyltrimethoxysilane, vinyltriethoxysilane, Vinyl-based silane couplings such as vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane Agents: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4- Epoxy cyclohexyl) Epoxy silane coupling agent such as ethyltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri Methacrylic silane coupling agents such as ethoxysilane; Acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; Ureido silane cups such as 3-ureidopropyltriethoxysilane Sulfide silane coupling agents such as bis (3- (triethoxysilyl) propyl) disulfide and bis (3- (triethoxysilyl) propyl) tetrasulfide; 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl Mercapto silane coupling agents such as trimethoxysilane and 3-octanoylthio-1-propyltriethoxysilane; Isocyanate silane coupling agents such as 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane; triethoxysilyl Aldehyde-based silane coupling agents such as butyraldehyde; carbamates such as triethoxysilylpropylmethylcarbamate and (3-triethoxysilylpropyl) -t-butylcarbamate Examples include mate-based silane coupling agents.
また、公知の官能性化合物で重合体の末端を修飾することにより、任意の官能基を重合体に導入することができる。このような場合は、導入した官能基と反応する有機官能基Qを有するシランカップリング剤を添加するのが好ましい。
前記カップリング剤を配合する場合は、カップリング剤の添加後に加熱し重合体と反応させることで、密着性が向上させることができる。カップリング剤の添加後、20~80℃で、より好ましくは40~60℃で、1~24時間反応させると良い。 When a polyimide film is used in an electronic device such as a liquid crystal display element, it is preferable to introduce a silane coupling agent into the polymer terminal in order to improve adhesion without impairing its characteristics. 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. Therefore, 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. From the viewpoint of properties, amine-based silane coupling agents and epoxy-based silane coupling agents are particularly preferable.
Moreover, 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.
When the coupling agent is blended, 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.
本発明の液晶配向剤に、さらに架橋剤などの各種添加剤を使用しても構わないことは言うまでもない。また、本発明のポリイミド前駆体又はポリイミド組成物に含有される重合体は2種類以上であってもよい。 e3. [Other additives]
It goes without saying that various additives such as a crosslinking agent may be further used in the liquid crystal aligning agent of the present invention. Two or more kinds of polymers may be contained in the polyimide precursor or polyimide composition of the present invention.
本発明の液晶配向剤の重合体濃度は、形成させようとするポリイミド膜の厚みの設定によって適宜変更することができるが、1~10質量%とすることが好ましく、2~8質量%がより好ましい。1質量%未満では均一で欠陥のない塗膜を形成させることが困難となり、10質量%よりも多いと溶液の保存安定性が悪くなる場合がある。 e4. [Polymer concentration]
The polymer concentration of the liquid crystal aligning agent of the present invention can be appropriately changed depending on the thickness of the polyimide film to be formed, but is preferably 1 to 10% by mass, more preferably 2 to 8% by mass. preferable. If it is less than 1% by mass, it is difficult to form a uniform and defect-free coating film, and if it exceeds 10% by mass, the storage stability of the solution may be deteriorated.
本発明の液晶配向剤は、以下の方法で製造することができる。
使用する重合体が粉末の場合、前記溶剤に溶解させて、重合体溶液とする。この時、重合体濃度は10~30質量%が好ましく、10~15質量%が特に好ましい。また、重合体の粉末を溶解する際に加熱してもよい。加熱温度は、20~140℃が好ましく、20~80℃が特に好ましい。
重合体の反応溶液、又は重合体を再溶解して得られた重合体溶液に前記溶剤及び前記塗膜均一性向上のための溶剤を加え、所定の重合体濃度になるように希釈することで本発明の液晶配向剤が得られる。シランカップリング剤を添加する場合は、重合体の析出を防ぐため、前記塗膜均一性向上のための溶剤を加える前に添加するのが好ましい。
シランカップリング剤の添加量は、多すぎると未反応のものが液晶配向性に悪影響を及ぼすことがあり、少なすぎると密着性への効果が現れないため、重合体粉末に対して0.01~5.0質量%が好ましく、0.1~1.0質量%がより好ましい。 f. [Method for producing liquid crystal aligning agent]
The liquid crystal aligning agent of this invention can be manufactured with the following method.
When the polymer to be used is powder, it is dissolved in the solvent to obtain a polymer solution. At this time, the polymer concentration is preferably 10 to 30% by mass, particularly preferably 10 to 15% by mass. Further, heating may be performed when the polymer powder is dissolved. The heating temperature is preferably 20 to 140 ° C, particularly preferably 20 to 80 ° C.
By adding the solvent and the solvent for improving the coating film uniformity to the polymer reaction solution or the polymer solution obtained by re-dissolving the polymer, and diluting to a predetermined polymer concentration. The liquid crystal aligning agent of this invention is obtained. When adding a silane coupling agent, it is preferable to add before adding the solvent for improving the uniformity of the coating film in order to prevent precipitation of the polymer.
If the addition amount of the silane coupling agent is too large, the unreacted material may adversely affect the liquid crystal alignment, and if it is too small, the effect on the adhesion does not appear. -5.0 mass% is preferable, and 0.1-1.0 mass% is more preferable.
本発明の液晶配向膜は次のようにして得られる。すなわち、本発明の液晶配向剤を、好ましくはろ過した後、基板に塗布し、乾燥、焼成して塗膜とすることができる。本発明の液晶配向剤を塗布する基板としては透明性の高い基板であれば特に限定されず、ガラス基板、窒化珪素基板、アクリル基板やポリカーボネート基板等のプラスチック基板等を用いることができ、液晶駆動のためのITO電極等が形成された基板を用いることがプロセスの簡素化の観点から好ましい。また、反射型の液晶表示素子では片側の基板のみにならばシリコンウエハー等の不透明な物でも使用でき、この場合の電極はアルミ等の光を反射する材料も使用できる。
本発明の液晶配向剤の塗布方法としては、スピンコート法、印刷法、インクジェット法などが挙げられる。本発明の液晶配向剤を塗布した後、好ましくは乾燥し、焼成される。液晶配向剤に含有されていた有機溶媒を十分に除去するため、好ましくは50~120℃で好ましくは1~10分乾燥させる。次いで、好ましくは150~300℃、より好ましくは150~250℃で焼成される。焼成時間は、焼成温度によっても異なるが、好ましくは5~120分、より好ましくは5~60分で行われる。 g. [Liquid crystal alignment film]
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. Further, in the reflection type liquid crystal display element, 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.
Examples of 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.
本発明の液晶配向膜を配向処理する方法としては、ラビング法、光配向処理法などが挙げられる。 The thickness of the liquid crystal alignment film of the present invention is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be lowered, so it is 5 to 300 nm, preferably 10 to 200 nm. By subjecting the coating surface to an orientation treatment such as rubbing, it can be used as a liquid crystal orientation film.
Examples of the method for aligning the liquid crystal alignment film of the present invention include a rubbing method and a photo-alignment processing method.
以下に実施例を挙げ、本発明を更に詳しく説明するが、本発明はこれらに限定されるものではない。 As a specific example of the photo-alignment treatment method, 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. Is mentioned. As 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. Further, in order to improve the liquid crystal orientation, radiation may be irradiated while heating the coated substrate at 50 to 250 ° C. Dose of the radiation is preferably in the range of 1 ~ 10,000mJ / cm 2, and particularly preferably in the range of 100 ~ 5,000mJ / cm 2.
The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
CBDA:シクロブタンテトラカルボン酸二無水物
1,3DMCBDE-Cl:ジメチル 1,3-ビス(クロロカルボニル)-1,3-ジ メチルシクロブタン-2,4-ジカルボキシレート
p-PDA:p-フェニレンジアミン
DA-A:上記式(A)のジアミン
DA-B:上記式(B)のジアミン
DA-D:上記式(D)のジアミン
DA-E:上記式(E)のジアミン
DA-F:上記式(F)のジアミン
DA-H:下記式(H)のジアミン The abbreviations and structures of the compounds used in the examples and comparative examples are shown below.
CBDA: cyclobutane tetracarboxylic dianhydride 1,3DMCBDE-Cl: dimethyl 1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate p-PDA: p-phenylenediamine DA -A: diamine of the above formula (A) DA-B: diamine of the above formula (B) DA-D: diamine of the above formula (D) DA-E: diamine of the above formula (E) DA-F: above formula ( F) Diamine DA-H: Diamine of Formula (H)
NMP:N-メチル-2-ピロリドン
BCS:ブチルセロソルブ
DMF:N,N-ジエチルホルムアミド
THF:テトラヒドロフラン
γ-BL:γ-ブチロラクトン
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve DMF: N, N-diethylformamide THF: Tetrahydrofuran γ-BL: γ-butyrolactone
[1H-NMR]
装置:フーリエ変換型超伝導核磁気共鳴装置(FT-NMR)INOVA-400(Varian社製)400MHz
溶媒:重水素化ジメチルスルホキシド(DMSO-d6)又は重水素クロロホルム(CDCl3)
標準物質:テトラメチルシラン(TMS)
[粘度]
合成例において、ポリアミック酸エステル及びポリアミック酸溶液の粘度は、E型粘度計TVE-22H(東機産業社製)を用い、サンプル量1.1mL、コーンロータTE-1(1°34’、R24)、温度25℃で測定した。
[分子量]
また、ポリアミック酸エステルの分子量はGPC(常温ゲル浸透クロマトグラフィー)装置によって測定し、ポリエチレングリコール、ポリエチレンオキシド換算値として数平均分子量(以下、Mnとも言う。)と重量平均分子量(以下、Mwとも言う。)を算出した。
GPC装置:Shodex社製(GPC-101)
カラム:Shodex社製(KD803、KD805の直列)
カラム温度:50℃
溶離液:N,N-ジメチルホルムアミド(添加剤として、臭化リチウム-水和物(LiBr・H2O)が30mmol/L、リン酸・無水結晶(o-リン酸)が30mmol/L、テトラヒドロフラン(THF)が10ml/L)
流速:1.0ml/分 The measurement methods for 1 H-NMR, viscosity, molecular weight, and rubbing resistance are shown below.
[ 1 H-NMR]
Apparatus: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (manufactured by Varian) 400 MHz
Solvent: deuterated dimethyl sulfoxide (DMSO-d 6 ) or deuterated chloroform (CDCl 3 )
Standard substance: Tetramethylsilane (TMS)
[viscosity]
In the synthesis examples, the viscosity of the polyamic acid ester and the polyamic acid solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), a sample amount of 1.1 mL, and cone rotor TE-1 (1 ° 34 ′, R24 ), Measured at a temperature of 25 ° C.
[Molecular weight]
The molecular weight of the polyamic acid ester is measured by a GPC (normal temperature gel permeation chromatography) apparatus, and is a number average molecular weight (hereinafter also referred to as Mn) and a weight average molecular weight (hereinafter also referred to as Mw) as polyethylene glycol and polyethylene oxide equivalent values. ) Was calculated.
GPC device: manufactured by Shodex (GPC-101)
Column: manufactured by Shodex (series of KD803 and KD805)
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystals (o-phosphoric acid) 30 mmol / L, tetrahydrofuran) (THF) is 10 ml / L)
Flow rate: 1.0 ml / min
透明電極付きガラス基板上に液晶配向剤をスピンコートし、温度80℃のホットプレート上で5分間の乾燥、温度230℃で20分間又は60分間の焼成をし、膜厚100nmのポリイミド膜を形成した。このポリイミド膜にラビング処理を施した後、ポリイミド膜の表面状態を観察して、ラビング傷の有無、ポリイミド膜の削れカスの有無、及びポリイミド膜の剥離の有無を評価した。 [Rubbing resistance of polyimide film]
A liquid crystal aligning agent is spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 80 ° C. for 5 minutes, and baked at a temperature of 230 ° C. for 20 minutes or 60 minutes to form a polyimide film having a thickness of 100 nm. did. After this polyimide film was rubbed, the surface state of the polyimide film was observed to evaluate the presence or absence of rubbing scratches, the presence or absence of chipping residue of the polyimide film, and the presence or absence of peeling of the polyimide film.
液晶セルの電圧保持率の測定は以下のようにして行った。
4Vの電圧を60μs間印加し、16.67ms後の電圧を測定することで、初期値からの変動を電圧保持率として計算した。測定の際、液晶セルの温度を23℃、60℃、及び90℃とし、それぞれの温度で測定を行った。
[イオン密度]
液晶セルのイオン密度の測定は以下のようにして行った。
東陽テクニカ社製の6254型液晶物性評価装置を用いて測定を行った。10V、0.01Hzの三角波を印加し、得られた波形のイオン密度に相当する面積を三角形近似法により算出し、イオン密度とした。測定の際、液晶セルの温度を23℃、及び60℃とし、それぞれの温度で測定を行った。 [Voltage holding ratio]
The voltage holding ratio of the liquid crystal cell was measured as follows.
By applying a voltage of 4 V for 60 μs and measuring the voltage after 16.67 ms, the fluctuation from the initial value was calculated as the voltage holding ratio. During the measurement, the temperature of the liquid crystal cell was set to 23 ° C., 60 ° C., and 90 ° C., and the measurement was performed at each temperature.
[Ion density]
The ion density of the liquid crystal cell was measured as follows.
Measurement was carried out using a 6254 type liquid crystal property evaluation apparatus manufactured by Toyo Technica. A triangular wave of 10 V and 0.01 Hz was applied, and an area corresponding to the ion density of the obtained waveform was calculated by a triangle approximation method to obtain an ion density. During the measurement, the temperature of the liquid crystal cell was set to 23 ° C. and 60 ° C., and the measurement was performed at each temperature.
(前駆体合成1) Example 1 Synthesis of DA-A (Precursor Synthesis 1)
得られた固体の1H-NMRを測定し、DA-Aであることを確認した。
1H-NMR(DMSO-d6,δppm):1.44(s,9H)、3.87(d,J=6.3Hz,2H)、4.10~4.30(m,4H)、6.27(dd,J=2.4Hz,8.1Hz1H)、6.31(d,J=2.4Hz,1H)、6.38(d,J=8.1Hz,1H)、7.14(t,J=6.3Hz,1H).
1 H-NMR of the obtained solid was measured and confirmed to be DA-A.
1 H-NMR (DMSO-d 6 , δppm): 1.44 (s, 9H), 3.87 (d, J = 6.3 Hz, 2H), 4.10-4.30 (m, 4H), 6.27 (dd, J = 2.4 Hz, 8.1Hz1H), 6.31 (d, J = 2.4Hz, 1H), 6.38 (d, J = 8.1Hz, 1H), 7.14 (t, J = 6.3Hz, 1H).
(N-Boc-プロパルギルアミンの合成) Example 2 Synthesis of DA-B (Synthesis of N-Boc-propargylamine)
1H-NMR(DMSO-d6,δppm):1.38(s,9H)、1.57(q,J=7.2Hz,2H)、2.30(t,J=7.2Hz,2H)、2.94(quin,J=6.0Hz,2H)、3.88~4.22(m,4H)、6.22(dd,J=2.1Hz,8.1Hz,1H)、6.25(d,J=2.1Hz,1H)、6.37(d,J=8.1Hz,1H)、6.84(t,J=6.0Hz,1H).
1 H-NMR (DMSO-d 6 , δ ppm): 1.38 (s, 9H), 1.57 (q, J = 7.2 Hz, 2H), 2.30 (t, J = 7.2 Hz, 2H), 2.94 (quin, J = 6.0Hz, 2H), 3.88-4.22 (m, 4H), 6.22 (dd, J = 2.1Hz, 8.1Hz, 1H), 6.25 (d, J = 2.1Hz, 1H), 6.37 (d, J = 8.1Hz , 1H), 6.84 (t, J = 6.0Hz, 1H).
(ニトロ体の合成) Example 3 Synthesis of DA-D (Synthesis of Nitro Compound)
1H-NMR(DMSO-d6,δppm):1.40(s,9H)、3.70(d,J=6.0Hz,2H)、4.04(bs,2H)、4.35(bs,2H)、6.23(dd,J=2.4Hz,8.0Hz,1H)、6.48(d,J=8.0Hz,1H)、6.61(d,J=2.4Hz,1H)、7.05(t,J=6.0Hz,1H)、8.94(s,1H). The nitro compound (9.85 g, 31.75 mmol) was added to an eggplant-shaped flask, and 150 ml of ethanol was added. After the reaction vessel was purged with nitrogen, palladium carbon (1.11 g, 10% by mass with respect to the mass of the nitro compound) was added, and the nitrogen was substituted again. Subsequently, the reaction vessel was replaced with hydrogen and stirred at 20 ° C. for 48 hours. After completion of the reaction, palladium carbon was removed by Celite filtration, and the solvent was distilled off from the filtrate. When 150 ml of toluene was added to the obtained concentrated liquid and heated to reflux, a solid was precipitated. The precipitated solid was filtered while hot to obtain a light purple solid. The yield was 8.05 g, and the yield was 90.4%. 1 H-NMR of the obtained solid was measured and confirmed to be DA-C.
1 H-NMR (DMSO-d 6 , δ ppm): 1.40 (s, 9H), 3.70 (d, J = 6.0 Hz, 2H), 4.04 (bs, 2H), 4.35 (bs, 2H), 6.23 (dd, J = 2.4Hz, 8.0Hz, 1H), 6.48 (d, J = 8.0Hz, 1H), 6.61 (d, J = 2.4Hz, 1H), 7.05 (t, J = 6.0Hz, 1H), 8.94 (s , 1H).
(ニトロ体の合成) Example 4 Synthesis of DA-E (Synthesis of nitro form)
1H-NMR(DMSO-d6,δppm):1.36(s,9H)、1.56(s,9H)、2.76~2.96(m,3H)、4.04(bs,2H)、4.35(bs,2H)、6.25(dd,J=2.4Hz,8.4Hz,1H)、6.48(d,J=8.4Hz,1H)、6.55(d,J=2.4Hz,1H)、7.02(d,J=8.0Hz,1H)、7.29(s,1H)、8.13(s,1H)、9.11(s,1H).
1 H-NMR (DMSO-d 6 , δ ppm): 1.36 (s, 9H), 1.56 (s, 9H), 2.76 to 2.96 (m, 3H), 4.04 (bs, 2H), 4.35 (bs, 2H), 6.25 (dd, J = 2.4Hz, 8.4Hz, 1H), 6.48 (d, J = 8.4Hz, 1H), 6.55 (d, J = 2.4Hz, 1H), 7.02 (d, J = 8.0Hz, 1H) 7.29 (s, 1H), 8.13 (s, 1H), 9.11 (s, 1H).
撹拌装置、及び窒素導入管付きの300mL四つ口フラスコに、p-PDAを1.125g(10.40mmol)、DA-Bを0.689g(2.596mmol)、及びNMP30.62gを入れ、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながら、CBDA2.424g(12.36mmol)を添加し、更に固形分濃度が10質量%になるようにNMPを加え、室温で24時間撹拌してポリアミック酸(A-1)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は138.6mPa・sであった。また、このポリアミック酸の分子量はMn=16,079、Mw=33,544であった。 <Example 5> Preparation of polyamic acid (A-1) solution In a 300 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 1.125 g (10.40 mmol) of p-PDA and 0 DA-B were added. 689 g (2.596 mmol) and NMP 30.62 g were added and stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 2.424 g (12.36 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-1). Solution was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 138.6 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 16,079 and Mw = 33,544.
撹拌装置、及び窒素導入管付きの300mL四つ口フラスコに、p-PDAを1.037g(9.589mmol)、DA-Dを0.671g(2.394mmol)、及びNMP28.37gを入れ、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながら、CBDA2.277g(11.61mmol)を添加し、更に固形分濃度が10質量%になるようにNMPを加え、室温で24時間撹拌してポリアミック酸(A-2)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は146.2mPa・sであった。また、このポリアミック酸の分子量はMn=17,260、Mw=34,532であった。 <Example 6> Preparation of polyamic acid (A-2) solution In a 300 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 1.037 g (9.589 mmol) of p-PDA and 0 of DA-D were added. .671 g (2.394 mmol) and NMP 28.37 g were added and dissolved while stirring while feeding nitrogen. While stirring this diamine solution, 2.277 g (11.61 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-2). Solution was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 146.2 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 17,260 and Mw = 34,532.
撹拌装置、及び窒素導入管付きの300mL四つ口フラスコに、p-PDAを0.951g(8.794mmol)、DA-Eを1.012g(2.197mmol)、及びNMP29.10gを入れ、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながら、CBDA2.095g(10.69mmol)を添加し、更に固形分濃度が10質量%になるようにNMPを加え、室温で24時間撹拌してポリアミック酸(A-3)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は157.3mPa・sであった。また、このポリアミック酸の分子量はMn=20,610、Mw=40,640であった。 Example 7 Preparation of Polyamic Acid (A-3) Solution In a 300 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 0.951 g (8.794 mmol) of p-PDA and 1 DA-E were added. .012 g (2.197 mmol) and NMP 29.10 g were added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 2.095 g (10.69 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-3). Solution was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 157.3 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 20,610 and Mw = 40,640.
撹拌装置、及び窒素導入管付きの300mL四つ口フラスコに、p-PDAを1.621g(14.99mmol)、及びNMP28.96gを入れ、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながら、CBDA2.87g(14.74mmol)を添加し、更に固形分濃度が10質量%になるようにNMPを加え、室温で24時間撹拌してポリアミック酸(B-1)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は152.7mPa・sであった。また、このポリアミック酸の分子量はMn=13,972、Mw=30,181であった。 <Comparative Synthesis Example 1> Preparation of polyamic acid (B-1) solution In a 300 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 1.621 g (14.99 mmol) of p-PDA and 28.96 g of NMP Was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 2.87 g (14.74 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 (B-1). Solution was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 152.7 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 13,972 and Mw = 30,181.
実施例5で得られたポリアミック酸(A-1)の溶液12.59gを撹拌子の入った50mL三角フラスコに分取し、NMP4.21g、及びBCS4.19gを加え、マグネチックスターラーで30分間撹拌して液晶配向剤(A-1)を得た。 <Example 8> Preparation of liquid crystal aligning agent (A-1) 12.59 g of the polyamic acid (A-1) solution obtained in Example 5 was dispensed into a 50 mL Erlenmeyer flask containing a stir bar, and NMP4. 21 g and 4.19 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-1).
実施例6で得られたポリアミック酸(A-2)の溶液11.37gを撹拌子の入った50mL三角フラスコに分取し、NMP3.80g、及びBCS3.79gを加え、マグネチックスターラーで30分間撹拌して液晶配向剤(A-2)を得た。 <Example 9> Preparation of liquid crystal aligning agent (A-2) 11.37 g of the solution of polyamic acid (A-2) obtained in Example 6 was dispensed into a 50 mL Erlenmeyer flask containing a stir bar, and NMP3. 80 g and 3.79 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-2).
実施例7で得られたポリアミック酸(A-3)の溶液11.17gを撹拌子の入った50mL三角フラスコに分取し、NMP3.74g、及びBCS3.76gを加え、マグネチックスターラーで30分間撹拌して液晶配向剤(A-3)を得た。 <Example 10> Preparation of liquid crystal aligning agent (A-3) 11.17 g of the solution of polyamic acid (A-3) obtained in Example 7 was dispensed into a 50 mL Erlenmeyer flask containing a stir bar, and NMP3. 74 g and 3.76 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-3).
比較合成例1得られたポリアミック酸(B-1)の溶液12.98gを撹拌子の入った50mL三角フラスコに分取し、NMP4.42g、及びBCS4.27gを加え、マグネチックスターラーで30分間撹拌して液晶配向剤(B-1)を得た。 Comparative Example 1 Preparation of Liquid Crystal Alignment Agent (B-1) Comparative Synthesis Example 1 12.98 g of the obtained polyamic acid (B-1) solution was fractionated into a 50 mL Erlenmeyer flask containing a stir bar, and NMP4. 42 g and 4.27 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (B-1).
実施例8で得られた液晶配向剤(A-1)を1.0μmのフィルターで濾過した後、透明電極付きガラス基板上にスピンコートし、温度80℃のホットプレート上で5分間の乾燥、温度230℃で20分間の焼成を経て、膜厚100nmのポリイミド膜を得た。このポリイミド膜をレーヨン布でラビング(ロール径120mm、回転数1000rpm、移動速度20mm/sec、押し込み量0.4mm)した後、ポリイミド膜の表面状態を観察したところ、ラビングによる傷、ポリイミド膜の削れカス、及びポリイミド膜の剥離は観察されなかった。 <Example 11>
The liquid crystal aligning agent (A-1) obtained in Example 8 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, and dried for 5 minutes on a hot plate at a temperature of 80 ° C. After baking for 20 minutes at a temperature of 230 ° C., a polyimide film having a thickness of 100 nm was obtained. This polyimide film was rubbed with a rayon cloth (roll diameter: 120 mm, rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation amount: 0.4 mm), and then the surface condition of the polyimide film was observed. No debris or peeling of the polyimide film was observed.
実施例9で得られた液晶配向剤(A-2)を用いた以外は、実施例11と同様の方法にポリイミド膜を作製し、ラビング処理を行った。ポリイミド膜の表面状態を観察したところ、ラビングによる傷、ポリイミド膜の削れカス、及びポリイミド膜の剥離は観察されなかった。 <Example 12>
A polyimide film was produced in the same manner as in Example 11 except that the liquid crystal aligning agent (A-2) obtained in Example 9 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were not observed.
実施例10で得られた液晶配向剤(A-3)を用いた以外は、実施例11と同様の方法にポリイミド膜を作製し、ラビング処理を行った。ポリイミド膜の表面状態を観察したところ、ラビングによる傷、ポリイミド膜の削れカス、及びポリイミド膜の剥離は観察されなかった。 <Example 13>
A polyimide film was produced in the same manner as in Example 11 except that the liquid crystal aligning agent (A-3) obtained in Example 10 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were not observed.
比較例1で得られた液晶配向剤(B-1)を用いた以外は、実施例11と同様の方法にポリイミド膜を作製し、ラビング処理を行った。ポリイミド膜の表面状態を観察したところ、ラビングによる傷やポリイミド膜の削れカスが観察された。 <Comparative 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.
実施例8で得られた液晶配向剤(A-1)を1.0μmのフィルターで濾過した後、透明電極付きガラス基板上にスピンコートし、温度80℃のホットプレート上で5分間の乾燥、温度230℃で20分間の焼成を経て、膜厚100nmのポリイミド膜を得た。このポリイミド膜をレーヨン布でラビング(ロール径120mm、回転数1000rpm、移動速度20mm/sec、押し込み量0.4mm)し、純水中にて1分間超音波照射をして洗浄を行い、エアーブローにて水滴を除去した後、80℃で10分間乾燥して液晶配向膜付き基板を得た。このような液晶配向膜付き基板を2枚用意し、一方の基板の液晶配向膜面に6μmのスペーサーを散布した後、2枚の基板のラビング方向が逆平行から85度捩れるように組み合わせ、液晶注入口を残して周囲をシールし、セルギャップが6μmの空セルを作製した。この空セルに液晶(MLC-2003、メルク社製)を真空注入し、注入口を封止してツイストネマチック液晶セルとした。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った結果、電圧保持率は温度23℃で99.3%、温度60℃で98.7%、温度90℃で94.1%であり、イオン密度は23℃で10pC/cm2であり、60℃で18pC/cm2であった。 <Example 14>
The liquid crystal aligning agent (A-1) obtained in Example 8 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, and dried for 5 minutes on a hot plate at a temperature of 80 ° C. After baking for 20 minutes at a temperature of 230 ° C., a polyimide film having a thickness of 100 nm was obtained. This polyimide film is rubbed with a rayon cloth (roll diameter: 120 mm, rotation speed: 1000 rpm, moving speed: 20 mm / sec, pushing amount: 0.4 mm), washed by irradiating with ultrasonic waves in pure water for 1 minute, and air blown After removing the water droplets at, the substrate was dried at 80 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Two such substrates with a liquid crystal alignment film are prepared, and after a 6 μm spacer is dispersed on the liquid crystal alignment film surface of one substrate, the rubbing directions of the two substrates are combined so that the rubbing direction can be twisted by 85 degrees from antiparallel, The periphery was sealed leaving the liquid crystal injection port, and an empty cell with a cell gap of 6 μm was produced. Liquid crystal (MLC-2003, manufactured by Merck & Co., Inc.) was vacuum-injected into the empty cell, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. 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., 98.7% 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..
実施例9で得られた液晶配向剤(A-2)を用いた以外は、実施例14と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。
この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った結果、電圧保持率は温度23℃で99.3%、温度60℃で98.8%、温度90℃で94.4%であり、イオン密度は23℃で5pC/cm2であり、60℃で11pC/cm2であった。 <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..
実施例10で得られた液晶配向剤(A-3)を用いた以外は、実施例14と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この空セルに液晶(MLC-2003、メルク社製)を常温で真空注入し、注入口を封止してツイストネマチック液晶セルとした。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った結果、電圧保持率は温度23℃で99.4%、温度60℃で99.1%、温度90℃で96.7%であり、イオン密度は23℃で3pC/cm2であり、60℃で4pC/cm2であった。 <Example 16>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 14 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. Liquid crystal (MLC-2003, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. 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 99.4% at a temperature of 23 ° C., 99.1% at a temperature of 60 ° C., and 96 at a temperature of 90 ° C. a .7%, the ion density is pC / cm 2 at 23 ° C., it was 4Pc / cm 2 at 60 ° C..
比較例1で得られた液晶配向剤(B-1)を用いた以外は、実施例14と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認、及び電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。このセルについて、電圧保持率を測定し、その後、イオン密度の測定を行った結果、電圧保持率は温度23℃で99.1%、温度60℃で97.4%、温度90℃で86.7%であり、イオン密度は23℃で50pC/cm2、温度60℃で256pC/cm2であった。 <Comparative 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..
(前駆体合成1) Example 17 Synthesis of DA-F (Precursor Synthesis 1)
1H NMR (400MHz, CDCl3,δppm):1.44(s, 9H), 2.05(quin, J=6.4Hz, 2H), 3.27(q, J=6.4Hz, 2H), 3.45(t, J=6.4Hz,2H), 4.69(bs, 1H).
1 H NMR (400MHz, CDCl 3 , δppm): 1.44 (s, 9H), 2.05 (quin, J = 6.4Hz, 2H), 3.27 (q, J = 6.4Hz, 2H), 3.45 (t, J = 6.4 Hz, 2H), 4.69 (bs, 1H).
1H NMR (400MHz, CDCl3,δppm):1.42(s, 18H), 2.13(quin, J=6.0Hz, 4H), 3.41(q, J=6.0Hz, 4H), 4.289(t, J=6.0Hz,4H), 5.28 (bs, 2H), 7.23(d, J=8.8Hz, 2H), 7.93(d, J=8.8Hz, 2H).
1 H NMR (400MHz, CDCl 3 , δppm): 1.42 (s, 18H), 2.13 (quin, J = 6.0Hz, 4H), 3.41 (q, J = 6.0Hz, 4H), 4.289 (t, J = 6.0 Hz, 4H), 5.28 (bs, 2H), 7.23 (d, J = 8.8Hz, 2H), 7.93 (d, J = 8.8Hz, 2H).
1H NMR (400MHz, CDCl3,δppm):1.49(s, 18H), 2.06(quin, J=5.6Hz, 4H), 3.48(q, J=5.6Hz, 4H), 4.12(t, J=5.6Hz,4H), 6.54 (bs,42H), 6.92(d, J=9.2Hz, 2H), 7.06(m,2H)7.16 (d, J=9.2Hz, 2H).
1 H NMR (400MHz, CDCl 3 , δppm): 1.49 (s, 18H), 2.06 (quin, J = 5.6Hz, 4H), 3.48 (q, J = 5.6Hz, 4H), 4.12 (t, J = 5.6 Hz, 4H), 6.54 (bs, 42H), 6.92 (d, J = 9.2Hz, 2H), 7.06 (m, 2H) 7.16 (d, J = 9.2Hz, 2H).
(前駆体合成1) Example 18 Synthesis of DA-H (Precursor Synthesis 1)
1H NMR (400MHz, CDCl3,δppm):1.48(s, 18H), 4.16(d, J=6.0Hz, 4H), 4.93 (bs, 2H), 5.78(bs, 2H), 8.09 (s, 2H).
1 H NMR (400 MHz, CDCl 3 , δ ppm): 1.48 (s, 18H), 4.16 (d, J = 6.0 Hz, 4H), 4.93 (bs, 2H), 5.78 (bs, 2H), 8.09 (s, 2H ).
1H NMR (400MHz, CDCl3,δppm):1.45(s, 18H), 1.78(quin, J=6.4Hz, 4H), 2.48(t, J=6.4Hz, 4H), 3.45(q, J=6.4Hz, 4H), 4.69(bs, 1H), 6.36(s, 1H).
1 H NMR (400MHz, CDCl 3 , δppm): 1.45 (s, 18H), 1.78 (quin, J = 6.4Hz, 4H), 2.48 (t, J = 6.4Hz, 4H), 3.45 (q, J = 6.4 Hz, 4H), 4.69 (bs, 1H), 6.36 (s, 1H).
撹拌装置、及び窒素導入管付きの100mL四つ口フラスコに、p-PDAを1.7281g(16.47mmol)、DA-Aを0.9509g(4.007mmol)、及びNMP46.12gを入れ、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながら、CBDAを3.8093g(19.43mmol)添加し、更に固形分濃度が10質量%になるようにNMPを加え、室温で24時間撹拌してポリアミック酸(A-4)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は149mPa・sであった。また、このポリアミック酸の分子量はMn=18,136、Mw=37,265であった。 Example 19 Preparation of Polyamic Acid (A-4) Solution In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 1.7281 g (16.47 mmol) of p-PDA and 0 DA-A were added. .9509 g (4.007 mmol) and 46.12 g of NMP were added and stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 3.893 g (19.43 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-4 ) Was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 149 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 18,136 and Mw = 37,265.
撹拌装置、及び窒素導入管付きの100mL四つ口フラスコに、p-PDAを0.8665g(8.013mmol)、DA-Hを0.8442g(1.998mmol)、及びNMP25.31gを入れ、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながら、CBDAを1.9047g(9.713mmol)添加し、更に固形分濃度が10質量%になるようにNMPを加え、室温で24時間撹拌してポリアミック酸(A-5)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は254.7mPa・sであった。また、このポリアミック酸の分子量はMn=27,447、Mw=59,038であった。 Example 20 Preparation of Polyamic Acid (A-5) Solution In a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 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. While stirring this diamine solution, 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. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 254.7 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 27,447 and Mw = 59,038.
撹拌装置付きの300mL四つ口フラスコ内を窒素雰囲気とし、p-PDAを2.00 g (18.50mmol)、DA-Dを1.2269g(4.624mmol)、NMPを167.67g、及び塩基としてピリジン 4.21g (53.26mmol) を入れ、撹拌して溶解させた。次に、このジアミン溶液を撹拌しながら、1,3DM-CBDE-Clを7.216g (22.19mmol)添加し、水冷下4時間反応させた。得られたポリアミック酸エステルの溶液を、882g の水に撹拌しながら投入し、析出した白色沈殿をろ取した。続いて、889g の水で1回、882g のエタノールで1回、221g のエタノールで3回洗浄し、乾燥して白色のポリアミック酸エステル樹脂粉末(C-1)7.22gを得た。収率は、81.8%であった。また、このポリアミック酸エステルの分子量はMn=20,469、Mw=40,025であった。 <Example 21> Preparation of polyamic acid ester resin (C-1) A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 2.00 g (18.50 mmol) of p-PDA, and DA-D of 1 2269 g (4.624 mmol), 167.67 g of NMP, and 4.21 g (53.26 mmol) of pyridine as a base were added and dissolved by stirring. Next, while stirring this diamine solution, 7.216 g (22.19 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. The obtained polyamic acid ester solution was poured into 882 g of water while stirring, and the precipitated white precipitate was collected by filtration. Subsequently, it was washed once with 889 g of water, once with 882 g of ethanol, three times with 221 g of ethanol, and dried to obtain 7.22 g of white polyamic acid ester resin powder (C-1). The yield was 81.8%. Moreover, the molecular weight of this polyamic acid ester was Mn = 20,469 and Mw = 40,025.
撹拌装置付きの300mL四つ口フラスコ内を窒素雰囲気とし、p-PDAを2.00 g (18.50mmol)、DA-Bを1.2961g(4.624mmol)、NMPを 168.98g、及び塩基としてピリジン 4.21g (53.26mmol) を入れ、撹拌して溶解させた。次に、このジアミン溶液を撹拌しながら、1,3DM-CBDE-Clを7.216g (22.19mmol)添加し、水冷下4時間反応させた。得られたポリアミック酸エステルの溶液を、889g の水に撹拌しながら投入し、析出した白色沈殿をろ取した。続いて、889g の水で1回、889g のエタノールで1回、222g のエタノールで3回洗浄し、乾燥して白色のポリアミック酸エステル樹脂粉末C-2)7.79gを得た。収率は、87.6%であった。また、このポリアミック酸エステルの分子量はMn=20,886、Mw=45,830であった。 <Example 22> Preparation of polyamic acid ester resin (C-2) The inside of a 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 2.00 g (18.50 mmol) of p-PDA, and 1 DA-B. 2961 g (4.624 mmol), 168.98 g of NMP and 4.21 g (53.26 mmol) of pyridine as a base were added and dissolved by stirring. Next, while stirring this diamine solution, 7.216 g (22.19 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. The obtained polyamic acid ester solution was poured into 889 g of water while stirring, and the precipitated white precipitate was collected by filtration. Subsequently, it was washed once with 889 g of water, once with 889 g of ethanol, three times with 222 g of ethanol, and dried to obtain 7.79 g of white polyamic acid ester resin powder C-2). The yield was 87.6%. Moreover, the molecular weight of this polyamic acid ester was Mn = 20,886 and Mw = 45,830.
撹拌装置付きの300mL四つ口フラスコ内を窒素雰囲気とし、p-PDAを1.50 g (13.87mmol)、DA-Eを1.597g(3.468mmol)、NMPを 65.26g、及び塩基としてピリジン3.13g (39.53mmol) を入れ、撹拌して溶解させた。次に、このジアミン溶液を撹拌しながら、1,3DM-CBDE-Clを5.3556g (16.47mmol)添加し、水冷下4時間反応させた。4時間後、反応溶液にNMP72.51gを加え、室温(20℃)で15分撹拌した。得られたポリアミック酸エステルの溶液を、725g の水に撹拌しながら投入し、析出した白色沈殿をろ取した。続いて、725g の水で1回、725g のエタノールで1回、181g のエタノールで3回洗浄し、乾燥して白色のポリアミック酸エステル樹脂粉末(C-3)3.76gを得た。収率は、51.8%であった。また、このポリアミック酸エステルの分子量はMn=20,525、Mw=43,395であった。 <Example 23> Preparation of polyamic acid ester resin (C-3) A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 1.50 g (13.87 mmol) of p-PDA and 1 DA-E were added. .597 g (3.468 mmol), 65.26 g of NMP, and 3.13 g (39.53 mmol) of pyridine as a base were added and dissolved by stirring. Next, while stirring this diamine solution, 5.3556 g (16.47 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 72.51 g of NMP was added to the reaction solution, and the mixture was stirred at room temperature (20 ° C.) for 15 minutes. The obtained polyamic acid ester solution was poured into 725 g of water while stirring, and the precipitated white precipitate was collected by filtration. Subsequently, it was washed once with 725 g of water, once with 725 g of ethanol, three times with 181 g of ethanol, and dried to obtain 3.76 g of white polyamic acid ester resin powder (C-3). The yield was 51.8%. Moreover, the molecular weight of this polyamic acid ester was Mn = 20,525 and Mw = 43,395.
撹拌装置付きの300mL四つ口フラスコ内を窒素雰囲気とし、p-PDAを2.50 g (23.11mmol)、DA-Aを1.3715g(5.80mmol)、NMPを 97.16g、及び塩基としてピリジン5.21g(65.89mmol) を入れ、撹拌して溶解させた。次に、このジアミン溶液を撹拌しながら、1,3DM-CBDE-Clを8.926g(27.45mmol))添加し、水冷下4時間反応させた。4時間後、反応溶液にNMP107.95gを加え、室温(20℃)にて15分撹拌した。得られたポリアミック酸エステルの溶液を、1080g の水に撹拌しながら投入し、析出した白色沈殿をろ取した。続いて、1080g の水で1回、1080g のエタノールで1回、270g のエタノールで3回洗浄し、乾燥して白色のポリアミック酸エステル樹脂粉末(C-4)9.17gを得た。収率は、85.2%であった。また、このポリアミック酸エステルの分子量はMn=17,573、Mw=37,258であった。 <Example 24> Preparation of polyamic acid ester resin (C-4) The inside of a 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, p-PDA was 2.50 g (23.11 mmol), and DA-A was 1 3715 g (5.80 mmol), 97.16 g of NMP, and 5.21 g (65.89 mmol) of pyridine as a base were added and dissolved by stirring. Next, while stirring the diamine solution, 8.926 g (27.45 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 107.95 g of NMP was added to the reaction solution, and the mixture was stirred at room temperature (20 ° C.) for 15 minutes. The obtained polyamic acid ester solution was added to 1080 g of water with stirring, and the precipitated white precipitate was collected by filtration. Subsequently, it was washed once with 1080 g of water, once with 1080 g of ethanol, three times with 270 g of ethanol, and dried to obtain 9.17 g of white polyamic acid ester resin powder (C-4). The yield was 85.2%. Moreover, the molecular weight of this polyamic acid ester was Mn = 17,573 and Mw = 37,258.
撹拌装置付きの300mL四つ口フラスコ内を窒素雰囲気とし、p-PDAを1.420 g (13.13mmol)、DA-Hを1.3872g(3.283mmol)、NMPを59.54g、及び塩基としてピリジン2.87g (36.24mmol) を入れ、撹拌して溶解させた。次に、このジアミン溶液を撹拌しながら、1,3DM-CBDE-Clを4.9099g (15.10mmol)添加し、水冷下4時間反応させた。4時間後、反応溶液にNMP66.15gを加え、室温(20℃)で15分撹拌した。得られたポリアミック酸エステルの溶液を、662g の水に撹拌しながら投入し、析出した白色沈殿をろ取した。続いて、662g の水で1回、662g のエタノールで1回、165g のエタノールで3回洗浄し、乾燥して白色のポリアミック酸エステル樹脂粉末(C-5)5.11gを得た。収率は、77.3%であった。また、このポリアミック酸エステルの分子量はMn=14,724、Mw=27,150であった。 <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. After 4 hours, 66.15 g of NMP was added to the reaction solution, and the mixture was stirred at room temperature (20 ° C.) for 15 minutes. The obtained polyamic acid ester solution was poured into 662 g of water while stirring, and the precipitated white precipitate was collected by filtration. Subsequently, it was washed once with 662 g of water, once with 662 g of ethanol, three times with 165 g of ethanol, and dried to obtain 5.11 g of white polyamic acid ester resin powder (C-5). The yield was 77.3%. Moreover, the molecular weight of this polyamic acid ester was Mn = 14,724 and Mw = 27,150.
撹拌装置付きの50mL四つ口フラスコ内を窒素雰囲気とし、p-PDAを0.699 g (64.64mmol)、NMPを427.1 g、及び塩基としてピリジン 11.65 g (147.38mmol) を入れ、撹拌して溶解させた。次に、このジアミン溶液を撹拌しながら、1,3DM-CBDE-Clを19.9657g(61.41mmol)添加し、水冷下4時間反応させた。得られたポリアミック酸エステルの溶液を、2248gの水に撹拌しながら投入し、析出した白色沈殿をろ取した。続いて、2248g の水で1回、2248gのエタノールで1回、562gのエタノールで3回洗浄し、乾燥して白色のポリアミック酸エステル樹脂(D-1)粉末22.10gを得た。収率は、98.4%であった。また、このポリアミック酸エステルの分子量はMn=16,813、Mw=38,585であった。 Comparative Synthesis Example 2 Preparation of Polyamic Acid Ester Resin (D-1) The inside of a 50 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 0.699 g (64.64 mmol) of p-PDA, and 427. of NMP. 1 g and 11.65 g (147.38 mmol) of pyridine as a base were added and dissolved by stirring. Next, with stirring this diamine solution, 19.3657 g (61.41 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. The obtained polyamic acid ester solution was added to 2248 g of water while stirring, and the precipitated white precipitate was collected by filtration. Subsequently, it was washed once with 2248 g of water, once with 2248 g of ethanol, three times with 562 g of ethanol, and dried to obtain 22.10 g of a white polyamic acid ester resin (D-1) powder. The yield was 98.4%. Moreover, the molecular weight of this polyamic acid ester was Mn = 16,813 and Mw = 38,585.
実施例19で得られたポリアミック酸(A-4)の溶液6.18gを撹拌子の入った50mL三角フラスコに分取し、NMP1.60g 、及びBCS1.99gを加え、マグネチックスターラーで30分間撹拌して液晶配向剤(A-4)を得た。 <Example 26> Preparation of liquid crystal aligning agent (A-4) 6.18 g of the solution of polyamic acid (A-4) obtained in Example 19 was dispensed into a 50 mL Erlenmeyer flask containing a stir bar, and NMP1. 60 g and 1.99 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-4).
実施例20で得られたポリアミック酸(A-5)の溶液5.87gを撹拌子の入った50mL三角フラスコに分取し、NMP1.15g 、及びBCS1.76gを加え、マグネチックスターラーで30分間撹拌して液晶配向剤(A-5)を得た。 <Example 27> Preparation of liquid crystal aligning agent (A-5) 5.87 g of the solution of polyamic acid (A-5) obtained in Example 20 was dispensed into a 50 mL Erlenmeyer flask containing a stir bar, and NMP1. 15 g and 1.76 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-5).
実施例21で得られたポリアミック酸エステル樹脂粉末1.65gを三角フラスコにとり、γ‐BL 14.95g を加え、室温で24時間撹拌し溶解させた。この溶液にγ-BL5.43g、及びBCS5.55gを加えてマグネチックスターラーで30分間撹拌し液晶配向剤(C-1)を得た。 <Example 28> Preparation of liquid crystal aligning agent (C-1) 1.65 g of the polyamic acid ester resin powder obtained in Example 21 was placed in an Erlenmeyer flask, 14.95 g of γ-BL was added, and the mixture was stirred at room temperature for 24 hours. Dissolved. Γ-BL (5.43 g) and BCS (5.55 g) were added to this solution, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (C-1).
実施例22で得られたポリアミック酸エステル樹脂粉末0.733gを三角フラスコにとり、γ‐BL6.60g を加え、室温で24時間撹拌し溶解させた。この溶液にγ-BL2.48g、及びBCS2.45gを加えてマグネチックスターラーで30分間撹拌し液晶配向剤(C-2)を得た。 <Example 29> Preparation of liquid crystal aligning agent (C-2) 0.733 g of the polyamic acid ester resin powder obtained in Example 22 was placed in an Erlenmeyer flask, 6.60 g of γ-BL was added, and the mixture was stirred for 24 hours at room temperature to dissolve. I let you. To this solution, 2.48 g of γ-BL and 2.45 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (C-2).
実施例23で得られたポリアミック酸エステル樹脂粉末0.907gを三角フラスコにとり、γ‐BL8.18g を加え、室温で24時間撹拌し溶解させた。この溶液にγ-BL3.06g、及びBCS3.04gを加えてマグネチックスターラーで30分間撹拌し液晶配向剤(C-3)を得た。 <Example 30> Preparation of liquid crystal aligning agent (C-3) 0.907 g of the polyamic acid ester resin powder obtained in Example 23 was placed in an Erlenmeyer flask, and 8.18 g of γ-BL was added and dissolved by stirring at room temperature for 24 hours. I let you. To this solution, 3.06 g of γ-BL and 3.04 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (C-3).
実施例24で得られたポリアミック酸エステル樹脂粉末0.802gを三角フラスコにとり、γ‐BL7.23g を加え、室温で24時間撹拌し溶解させた。この溶液にγ-BL2.78g、及びBCS2.68gを加えてマグネチックスターラーで30分間撹拌し液
晶配向剤(C-4)を得た。 <Example 31> Preparation of liquid crystal aligning agent (C-4) 0.802 g of the polyamic acid ester resin powder obtained in Example 24 was placed in an Erlenmeyer flask, 7.23 g of γ-BL was added, and the mixture was stirred at room temperature for 24 hours to dissolve. I let you. To this solution, 2.78 g of γ-BL and 2.68 g of BCS were added and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (C-4).
実施例25で得られたポリアミック酸エステル樹脂粉末0.755gを三角フラスコにとり、γ‐BL7.57g を加え、室温で24時間撹拌し溶解させた。この溶液にγ-BL2.65g、及びBCS2.55gを加えてマグネチックスターラーで30分間撹拌し液晶配向剤(C-5)を得た。 <Example 32> Preparation of liquid crystal aligning agent (C-5) 0.755 g of the polyamic acid ester resin powder obtained in Example 25 was placed in an Erlenmeyer flask, γ-BL7.57 g was added, and the mixture was stirred for 24 hours at room temperature to dissolve. I let you. To this solution, 2.65 g of γ-BL and 2.55 g of BCS were added and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (C-5).
比較合成例2で得られたポリアミック酸エステル樹脂粉末1.02gを三角フラスコにとり、DMF9.21g を加え、室温で24時間撹拌し溶解させた。この溶液にγ-BL3.29g、及びBCS3.39gを加えてマグネチックスターラーで30分間撹拌し液晶配向剤(D-1)を得た。 Comparative Example 4 Preparation of Liquid Crystal Alignment Agent (D-1) 1.02 g of the polyamic acid ester resin powder obtained in Comparative Synthesis Example 2 is placed in an Erlenmeyer flask, added with 9.21 g of DMF, and stirred at room temperature for 24 hours to dissolve. It was. To this solution, 3.29 g of γ-BL and 3.39 g of BCS were added and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (D-1).
実施例26で得られた液晶配向剤(A-4)を用いた以外は、実施例11と同様の方法でポリイミド膜を作製し、ラビング処理を行った。ポリイミド膜の表面状態を観察したところ、ラビングによる傷は観察されたが、比較例2の結果よりも軽微であった。ポリイミド膜の削れカス、及びポリイミド膜の剥離は観察されなかった。 <Example 33>
A polyimide film was produced in the same manner as in Example 11 except that the liquid crystal aligning agent (A-4) obtained in Example 26 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing were observed, but the results were smaller than those of Comparative Example 2. No chipping of the polyimide film and peeling of the polyimide film were observed.
実施例27で得られた液晶配向剤(A-5)を用いた以外は、実施例11と同様の方法でポリイミド膜を作製し、ラビング処理を行った。ポリイミド膜の表面状態を観察したところ、ラビングによる傷、ポリイミド膜の削れカス、及びポリイミド膜の剥離は観察されなかった。 <Example 34>
A polyimide film was produced in the same manner as in Example 11 except that the liquid crystal aligning agent (A-5) obtained in Example 27 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were not observed.
実施例28で得られた液晶配向剤(C-1)を1.0μmのフィルターで濾過した後、透明電極付きガラス基板上にスピンコートし、温度80℃のホットプレート上で5分間の乾燥、温度230℃で1時間の焼成を経て、膜厚100nmのポリイミド膜を得た。このポリイミド膜をレーヨン布でラビング(ロール径120mm、回転数1000rpm、移動速度20mm/sec、押し込み量0.4mm)した後、ポリイミド膜の表面状態を観察したところ、ラビングによる傷、ポリイミド膜の削れカス、及びポリイミド膜の剥離は観察されなかった。 <Example 35>
The liquid crystal aligning agent (C-1) obtained in Example 28 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, and dried for 5 minutes on a hot plate at a temperature of 80 ° C. After baking for 1 hour at a temperature of 230 ° C., a polyimide film having a thickness of 100 nm was obtained. This polyimide film was rubbed with a rayon cloth (roll diameter: 120 mm, rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation amount: 0.4 mm), and then the surface condition of the polyimide film was observed. No debris or peeling of the polyimide film was observed.
実施例29で得られた液晶配向剤(C-2)を用いた以外は、実施例35と同様の方法でポリイミド膜を作製し、ラビング処理を行った。ポリイミド膜の表面状態を観察したところ、ラビングによる傷、ポリイミド膜の削れカス、及びポリイミド膜の剥離は観察されなかった。 <Example 36>
A polyimide film was produced in the same manner as in Example 35 except that the liquid crystal aligning agent (C-2) obtained in Example 29 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were not observed.
実施例30で得られた液晶配向剤(C-3)を用いた以外は、実施例35と同様の方法でポリイミド膜を作製し、ラビング処理を行った。ポリイミド膜の表面状態を観察したところ、ラビングによる傷、及びポリイミド膜の削れカスが観察されたが、後述の比較例5の結果よりも軽微であった。ポリイミドの剥離は観察されなかった。 <Example 37>
A polyimide film was produced in the same manner as in Example 35 except that the liquid crystal aligning agent (C-3) obtained in Example 30 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, which were less than the results of Comparative Example 5 described later. No peeling of the polyimide was observed.
実施例31で得られた液晶配向剤(C-4)を用いた以外は、実施例35と同様の方法でポリイミド膜を作製し、ラビング処理を行った。ポリイミド膜の表面状態を観察したところ、ラビングによる傷が観察されたが、後述の比較例5の結果よりも軽微であった。ポリイミド膜の削れカス、及びポリイミド膜の剥離は観察されなかった。 <Example 38>
A polyimide film was produced in the same manner as in Example 35 except that the liquid crystal aligning agent (C-4) obtained in Example 31 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing were observed, but they were less than the results of Comparative Example 5 described later. No chipping of the polyimide film and peeling of the polyimide film were observed.
実施例32で得られた液晶配向剤(C-5)を用いた以外は、実施例35と同様の方法でポリイミド膜を作製し、ラビング処理を行った。ポリイミド膜の表面状態を観察したところ、ラビングによる傷、ポリイミド膜の削れカス、及びポリイミド膜の剥離は観察されなかった。 <Example 39>
A polyimide film was produced in the same manner as in Example 35 except that the liquid crystal aligning agent (C-5) obtained in Example 32 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were not observed.
比較例4で得られた液晶配向剤(D-1)を用いた以外は、実施例35と同様の方法でポリイミド膜を作製し、ラビング処理を行った。ポリイミド膜の表面状態を観察したところ、ラビングによる傷、ポリイミド膜の削れカス、及びポリイミド膜の剥離が観察された。 <Comparative Example 5>
A polyimide film was produced in the same manner as in Example 35 except that the liquid crystal aligning agent (D-1) obtained in Comparative Example 4 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were observed.
実施例26で得られた液晶配向剤(A-4)を用いた以外は、実施例14と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表1に示す。 <Example 40>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 14 except that the liquid crystal aligning agent (A-4) obtained in Example 26 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.
実施例27で得られた液晶配向剤(A-5)を用いた以外は、実施例14と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表1に示す。 <Example 41>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 14 except that the liquid crystal aligning agent (A-5) obtained in Example 27 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.
実施例28で得られた液晶配向剤(C-1)を1.0μmのフィルターで濾過した後、透明電極付きガラス基板上にスピンコートし、温度80℃のホットプレート上で5分間の乾燥、温度230℃で1時間の焼成を経て、膜厚100nmのポリイミド膜を得た。このポリイミド膜をレーヨン布でラビング(ロール径120mm、回転数1000rpm、移動速度20mm/sec、押し込み量0.4mm)し、純水中にて1分間超音波照射をして洗浄を行い、エアーブローにて水滴を除去した後、80℃で10分間乾燥して液晶配向膜付き基板を得た。このような液晶配向膜付き基板を2枚用意し、一方の基板の液晶配向膜面に6μmのスペーサーを散布した後、2枚の基板のラビング方向が逆平行から85度捩れるように組み合わせ、液晶注入口を残して周囲をシールし、セルギャップが6μmの空セルを作製した。この空セルに液晶(MLC-2003、メルク社製)を常温で真空注入し、注入口を封止してツイストネマチック液晶セルとした。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表1に示す。 <Example 42>
The liquid crystal aligning agent (C-1) obtained in Example 28 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, and dried for 5 minutes on a hot plate at a temperature of 80 ° C. After baking for 1 hour at a temperature of 230 ° C., a polyimide film having a thickness of 100 nm was obtained. This polyimide film is rubbed with a rayon cloth (roll diameter: 120 mm, rotation speed: 1000 rpm, moving speed: 20 mm / sec, pushing amount: 0.4 mm), washed by irradiating with ultrasonic waves in pure water for 1 minute, and air blown After removing the water droplets at, the substrate was dried at 80 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Two such substrates with a liquid crystal alignment film are prepared, and after a 6 μm spacer is dispersed on the liquid crystal alignment film surface of one substrate, the rubbing directions of the two substrates are combined so that the rubbing direction can be twisted by 85 degrees from antiparallel, The periphery was sealed leaving the liquid crystal injection port, and an empty cell with a cell gap of 6 μm was produced. Liquid crystal (MLC-2003, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. 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.
実施例29で得られた液晶配向剤(C-2)を用いた以外は、実施例42と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表1に示す。 <Example 43>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 42 except that the liquid crystal aligning agent (C-2) obtained in Example 29 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.
実施例30で得られた液晶配向剤(C-3)を用いた以外は、実施例42と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表1に示す。 <Example 44>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 42 except that the liquid crystal aligning agent (C-3) obtained in Example 30 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.
実施例31で得られた液晶配向剤(C-4)を用いた以外は、実施例42と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表1に示す。 <Example 45>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 42 except that the liquid crystal aligning agent (C-4) obtained in Example 31 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.
実施例32で得られた液晶配向剤(C-5)を用いた以外は、実施例42と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表1に示す。 <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.
比較例4で得られた液晶配向剤(D-1)を用いた以外は、実施例42と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表1に示す。 <Comparative Example 6>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 42 except that the liquid crystal aligning agent (D-1) obtained in Comparative Example 4 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. 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.
実施例8で得られた液晶配向剤(A-1)を1.0μmのフィルターで濾過した後、透明電極付きガラス基板上にスピンコートし、温度80℃のホットプレート上で5分間の乾燥、温度230℃で20分間の焼成を経て、膜厚100nmのポリイミド膜を得た。この塗膜面に偏光板を介して254nmの紫外線を1.0J/cm2照射し、液晶配向膜付き基板を得た。このような液晶配向膜付き基板を2枚用意し、一方の基板の液晶配向膜面に6μmのスペーサーを散布した後、2枚の基板の配向方向が平行から85度捩れるように組み合わせ、液晶注入口を残して周囲をシールし、セルギャップが6μmの空セルを作製した。この空セルに液晶(MLC-2003、メルク社製)を常温で真空注入し、注入口を封止してツイストネマチック液晶セルとした。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表2に示す。 <Example 47>
The liquid crystal aligning agent (A-1) obtained in Example 8 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, and dried for 5 minutes on a hot plate at a temperature of 80 ° C. After baking for 20 minutes at a temperature of 230 ° C., a polyimide film having a thickness of 100 nm was obtained. The coating film surface was irradiated with 1.0 J / cm 2 of 254 nm ultraviolet light through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Two substrates with such a liquid crystal alignment film are prepared, and a 6 μm spacer is dispersed on the liquid crystal alignment film surface of one of the substrates, and then the two substrates are combined so that the alignment directions of the two substrates are twisted from parallel to 85 degrees. The periphery was sealed leaving the inlet, and an empty cell with a cell gap of 6 μm was produced. Liquid crystal (MLC-2003, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. 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.
実施例9で得られた液晶配向剤(A-2)を用いた以外は、実施例47と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表2に示す。 <Example 48>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 47 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. 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.
実施例10で得られた液晶配向剤(A-3)を用いた以外は、実施例47と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表2に示す。 <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.
実施例26で得られた液晶配向剤(A-4)を用いた以外は、実施例47と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表2に示す。 <Example 50>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 47 except that the liquid crystal aligning agent (A-4) obtained in Example 26 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.
実施例27で得られた液晶配向剤(A-5)を用いた以外は、実施例47と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表2に示す。 <Example 51>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 47 except that the liquid crystal aligning agent (A-5) obtained in Example 27 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.
比較例1で得られた液晶配向剤(B-1)を用いた以外は、実施例47と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表2に示す。 <Comparative Example 7>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 47 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. 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.
実施例28で得られた液晶配向剤(C-1)を1.0μmのフィルターで濾過した後、透明電極付きガラス基板上にスピンコートし、温度80℃のホットプレート上で5分間の乾燥、温度230℃で1時間の焼成を経て、膜厚100nmのポリイミド膜を得た。この塗膜面に偏光板を介して254nmの紫外線を1.0J/cm2照射し、液晶配向膜付き基板を得た。このような液晶配向膜付き基板を2枚用意し、一方の基板の液晶配向膜面に6μmのスペーサーを散布した後、2枚の基板の配向方向が平行から85度捩れるように組み合わせ、液晶注入口を残して周囲をシールし、セルギャップが4μmの空セルを作製した。この空セルに液晶(MLC-2003、メルク社製)を常温で真空注入し、注入口を封止してツイストネマチック液晶セルとした。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表2に示す。 <Example 52>
The liquid crystal aligning agent (C-1) obtained in Example 28 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, and dried for 5 minutes on a hot plate at a temperature of 80 ° C. After baking for 1 hour at a temperature of 230 ° C., a polyimide film having a thickness of 100 nm was obtained. The coating film surface was irradiated with 1.0 J / cm 2 of 254 nm ultraviolet light through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Two substrates with such a liquid crystal alignment film are prepared, and a 6 μm spacer is dispersed on the liquid crystal alignment film surface of one of the substrates, and then the two substrates are combined so that the alignment directions of the two substrates are twisted from parallel to 85 degrees. The periphery was sealed leaving the inlet, and an empty cell with a cell gap of 4 μm was produced. Liquid crystal (MLC-2003, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. 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.
実施例29で得られた液晶配向剤(C-2)を用いた以外は、実施例52と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表2に示す。 <Example 53>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 52 except that the liquid crystal aligning agent (C-2) obtained in Example 29 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.
実施例30で得られた液晶配向剤(C-3)を用いた以外は、実施例52と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表2に示す。 <Example 54>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 52 except that the liquid crystal aligning agent (C-3) obtained in Example 30 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.
実施例31で得られた液晶配向剤(C-4)を用いた以外は、実施例52と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表2に示す。 <Example 55>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 52 except that the liquid crystal aligning agent (C-4) obtained in Example 31 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.
実施例32で得られた液晶配向剤(C-5)を用いた以外は、実施例52と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表2に示す。 <Example 56>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 52 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 2 described later.
比較例4で得られた液晶配向剤(D-1)を用いた以外は、実施例52と同様にしてツイストネマチック液晶セルを作製し、液晶の配向状態の確認及び、電圧保持率、イオン密度の測定を行った。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った。電圧保持率及びイオン密度の測定結果は後述する表2に示す。
表2には、実施例47~実施例56及び比較例7~比較例8における電圧保持率とイオン密度の測定結果を示す。 <Comparative Example 8>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 52 except that the liquid crystal aligning agent (D-1) obtained in Comparative Example 4 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. 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.
Table 2 shows the measurement results of the voltage holding ratio and the ion density in Examples 47 to 56 and Comparative Examples 7 to 8.
撹拌装置付きの300mL四つ口フラスコ内を窒素雰囲気とし、p-PDAを1.50 g (13.87mmol)、DA-Bを0.4090g(1.541mmol)、NMP を107.47g、及び塩基としてピリジン 2.82g (35.67mmol) を入れ、撹拌して溶解させた。次に、このジアミン溶液を撹拌しながら、1,3DMCBDE-Clを4.83 g (14.86mmol)添加し、水冷下で4時間反応させた。得られたポリアミック酸エステルの溶液を、566g の水に撹拌しながら投入し、析出した白色沈殿をろ取した。続いて、566 g の水で1回、566 g のエタノールで1回、141 g のエタノールで3回洗浄し、乾燥して白色のポリアミック酸エステル樹脂(E-1)粉末4.92gを得た。収率は、87.0%であった。また、このポリアミック酸エステルの分子量はMn=17,828、Mw=31,832であった。 Example 57 Preparation of Polyamic Acid Ester Resin (E-1) A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, p-PDA was 1.50 g (13.87 mmol), and DA-B was 0. 4090 g (1.541 mmol), 107.47 g of NMP and 2.82 g (35.67 mmol) of pyridine as a base were added and dissolved by stirring. Next, while stirring this diamine solution, 4.83 g (14.86 mmol) of 1,3DMCBDE-Cl was added, and the mixture was reacted for 4 hours under water cooling. The obtained polyamic acid ester solution was poured into 565 g of water while stirring, and the precipitated white precipitate was collected by filtration. Subsequently, it was washed once with 566 g of water, once with 566 g of ethanol, three times with 141 g of ethanol, and dried to obtain 4.92 g of a white polyamic acid ester resin (E-1) powder. . The yield was 87.0%. Moreover, the molecular weight of this polyamic acid ester was Mn = 17,828 and Mw = 31,832.
合成例57で得られたポリアミック酸エステル樹脂粉末1.02gを三角フラスコに入れ、さらにγ‐BL 9.18g を加え、室温で24時間撹拌し溶解させた。この溶液にシランカップリング剤として、3-グリシドキシプロピルメチルジエトキシシラン(以下、GPSと略す)の1.0質量%γ‐ブチルラクトン溶液を1.03g加え、50℃で24時間加熱撹拌した。得られた溶液にγ-Bz2.41 g、及びBCS3.41gを加えて、マグネチックスターラーで30分間撹拌し、ポリアミック酸エステル溶液を調製した。
上記のポリアミック酸エステル溶液5.75gに、イミド化促進剤としてN-α, N-ω1, N-ω2-トリ-t-ブトキシカルボニル-L-アルギニン(以下、Boc-Argと略す)を0.0906g(アミック酸エステル基1モルに対して0.1モル当量)加え、室温で30分攪拌し、Boc-Argを完全に溶解させて、本発明の液晶配向剤 (E-1a)を得た。 <Example 58>
1.02 g of the polyamic acid ester resin powder obtained in Synthesis Example 57 was put in an Erlenmeyer flask, and 9.18 g of γ-BL was further added, and the mixture was stirred and dissolved at room temperature for 24 hours. To this solution was added 1.03 g of a 1.0 mass% γ-butyllactone solution of 3-glycidoxypropylmethyldiethoxysilane (hereinafter abbreviated as GPS) as a silane coupling agent, and the mixture was heated and stirred at 50 ° C. for 24 hours. did. To the obtained solution, 2.41 g of γ-Bz and 3.41 g of BCS were added, and stirred for 30 minutes with a magnetic stirrer to prepare a polyamic acid ester solution.
To 5.75 g of the above polyamic acid ester solution, N-α, N-ω1, N-ω2-tri-t-butoxycarbonyl-L-arginine (hereinafter abbreviated as Boc-Arg) was added as an imidization accelerator. 0906 g (0.1 molar equivalent with respect to 1 mole of amic acid ester group) was added, and the mixture was stirred at room temperature for 30 minutes to completely dissolve Boc-Arg to obtain the liquid crystal aligning agent (E-1a) of the present invention. .
比較合成例2で得られたポリアミック酸エステル樹脂粉末1.04gを三角フラスコに入れ、さらにDMF9.35g を加え、室温で24時間撹拌し溶解させた。この溶液にシランカップリング剤として、GPSの1.0質量%γ‐ブチルラクトン溶液を1.07g加え、50℃で24時間加熱撹拌した。得られた溶液にγ-BL2.71 g、及びBCS 3.06gを加えて、マグネチックスターラーで30分間撹拌し、ポリアミック酸エステル溶液を調製した。
上記のポリアミック酸エステル溶液5.42gに、イミド化促進剤としてBoc-Argを0.0775g(アミック酸エステル基1モルに対して0.1モル当量)加え、室温で30分撹拌し、Boc-Argを完全に溶解させて、液晶配向剤 (D-1a)を得た。 <Comparative Example 9>
1.04 g of the polyamic acid ester resin powder obtained in Comparative Synthesis Example 2 was put in an Erlenmeyer flask, and further 9.35 g of DMF was added, and the mixture was stirred and dissolved at room temperature for 24 hours. To this solution, 1.07 g of a 1.0 mass% γ-butyllactone solution of GPS was added as a silane coupling agent, and the mixture was heated and stirred at 50 ° C. for 24 hours. To the resulting solution, 2.71 g of γ-BL and 3.06 g of BCS were added, and stirred for 30 minutes with a magnetic stirrer to prepare a polyamic acid ester solution.
To 5.42 g of the above polyamic acid ester solution, 0.0775 g of Boc-Arg as an imidization accelerator (0.1 molar equivalent with respect to 1 mol of the amic acid ester group) was added, and the mixture was stirred at room temperature for 30 minutes. Arg was completely dissolved to obtain a liquid crystal aligning agent (D-1a).
実施例58で得られた液晶配向剤(E-1a)を1.0μmのフィルターで濾過した後、透明電極付きガラス基板上にスピンコートし、温度80℃のホットプレート上で5分間の乾燥、温度230℃で20分間の焼成を経て、膜厚100nmのポリイミド膜を得た。この塗膜面に偏光板を介して254nmの紫外線を1.0J/cm2照射し、液晶配向膜付き基板を得た。このような液晶配向膜付き基板を2枚用意し、一方の基板の液晶配向膜面に4μmのスペーサーを散布した後、2枚の基板の配向方向が平行から85度捩れるように組み合わせ、液晶注入口を残して周囲をシールし、セルギャップが4μmの空セルを作製した。この空セルに液晶(MLC-2041、メルク社製)を常温で真空注入し、注入口を封止してツイストネマチック液晶セルとした。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った結果、電圧保持率は温度23℃で99.4%、温度60℃で98.6%、温度90℃で95.3%であり、イオン密度は23℃で85pC/cm2、60℃で507pC/cm2であった。 <Example 59>
The liquid crystal aligning agent (E-1a) obtained in Example 58 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C. for 5 minutes. After baking for 20 minutes at a temperature of 230 ° C., a polyimide film having a thickness of 100 nm was obtained. The coating film surface was irradiated with 1.0 J / cm 2 of 254 nm ultraviolet light through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Two substrates with such a liquid crystal alignment film are prepared, and a 4 μm spacer is dispersed on the surface of the liquid crystal alignment film of one of the substrates, and then combined so that the alignment directions of the two substrates are twisted by 85 degrees from parallel. The periphery was sealed leaving the inlet, and an empty cell with a cell gap of 4 μm was produced. Liquid crystal (MLC-2041, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. 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 99.4% at a temperature of 23 ° C., 98.6% at a temperature of 60 ° C., and 95 at a temperature of 90 ° C. a .3%, the ion density was 507pC / cm 2 at 85pC / cm 2, 60 ℃ at 23 ° C..
比較例9で得られた液晶配向剤(D-1a)を用いた以外は、実施例59と同様にしてツイストネマチック液晶セルを作製した。この液晶セルの配向状態を偏光顕微鏡にて観察したところ、欠陥のない均一な配向をしていることが確認された。この液晶セルについて、電圧保持率を測定し、その後、イオン密度の測定を行った結果、電圧保持率は温度23℃で99.2%、温度60℃で98.1%、温度90℃で94.9%であり、イオン密度は23℃で159pC/cm2、60℃で644pC/cm2であった。
以上の結果から、本発明の液晶配向剤から得られる液晶配向膜は、架橋剤等を添加しなくても、ラビング処理によるラビング傷が付きにくい機械的強度に優れた液晶配向膜となることが確認された。
また、本発明の液晶配向剤から得られる液晶配向膜を有する液晶表示素子は、高温時でも電圧保持率が高く、イオン密度が低い信頼性に優れた液晶表示素子となることが確認された。
さらに、本発明の液晶配向膜に偏光された紫外光を照射し、配光処理を施して液晶配向能を付与した場合においても、本発明の液晶配向剤から得られる液晶配向膜を有する液晶表示素子は、高温時でも電圧保持率が高く、イオン密度が低い信頼性に優れた液晶表示素子となることが確認された。 <Comparative Example 10>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 59 except that the liquid crystal aligning agent (D-1a) obtained in Comparative Example 9 was used. 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 this liquid crystal cell and then measuring the ion density, the voltage holding ratio was 99.2% at a temperature of 23 ° C., 98.1% at a temperature of 60 ° C., and 94 at a temperature of 90 ° C. a .9%, ion density was 644pC / cm 2 at 159pC / cm 2, 60 ℃ at 23 ° C..
From the above results, 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.
Furthermore, the liquid crystal display having the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention even when the liquid crystal alignment film of the present invention is irradiated with polarized ultraviolet light and subjected to a light distribution treatment to give the liquid crystal alignment ability It was confirmed that the device was a liquid crystal display device having a high voltage holding ratio even at high temperatures and a low ion density and excellent reliability.
また、本発明のジアミン化合物は、Boc基で保護された1級又は2級の脂肪族アミンを含有する構造であり、本発明のポリイミド前駆体及びポリイミド及びこれらを用いた液晶配向膜を得るための原料として最適である。
なお、2008年10月29日に出願された日本特許出願2008-278317号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The polyimide precursor and polyimide of the present invention contain a primary or secondary aliphatic amine protected with a Boc group, and the Boc group is eliminated at the time of firing to advance an intermolecular crosslinking reaction. An excellent polyimide film can be provided, and the polyimide film can be suitably used as a protective film or an electronic device, particularly as a liquid crystal alignment film.
In addition, the diamine compound of the present invention has a structure containing a primary or secondary aliphatic amine protected with a Boc group, and the polyimide precursor and polyimide of the present invention and a liquid crystal alignment film using them are obtained. It is optimal as a raw material.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2008-278317 filed on Oct. 29, 2008 are incorporated herein as the disclosure of the specification of the present invention. Is.
Claims (15)
- 下記式(1)で表される構造の置換基を有するポリイミド前駆体又は該ポリイミド前駆体のイミド化重合体を含有することを特徴とする液晶配向剤。
- ポリイミド前駆体又は該ポリイミド前駆体のイミド化重合体が、式(1)で表される置換基を有するジアミン化合物及び式(1)で表される置換基を有するテトラカルボン酸誘導体からなる群から選ばれる少なくとも1つを用いて得られる請求項1に記載の液晶配向剤。 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). The liquid crystal aligning agent of Claim 1 obtained using at least 1 chosen.
- 式(1)で表される置換基を有するジアミン化合物及び/又は式(1)で表される置換基を有するテトラカルボン酸誘導体を、全ジアミン化合物及びテトラカルボン酸誘導体の2~100モル%を用いて得られるポリイミド前駆体又は該ポリイミド前駆体のイミド化重合体である請求項2に記載の液晶配向剤。 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 of Claim 2 which is the polyimide precursor obtained by using or the imidation polymer of this polyimide precursor.
- ポリイミド前駆体が、下記式(2)の構造単位を有する請求項1~3のいずれかに記載の液晶配向剤。
- ポリイミド前駆体が、下記式(3)の構造単位を含有する構造である請求項1~3のいずれかに記載の液晶配向剤。
- ポリイミド前駆体が、下記式(4)で表される構造単位を含有する構造である請求項1~3のいずれかに記載の液晶配向剤。
- ポリイミド前駆体が、下記式(5)で表される構造単位を含有する構造である請求項1~3のいずれかに記載の液晶配向剤。
- 請求項1~7のいずれかに記載の液晶配向剤を150~300℃にて焼成して得られる液晶配向膜。 A liquid crystal alignment film obtained by baking the liquid crystal aligning agent according to any one of claims 1 to 7 at 150 to 300 ° C.
- 下記式(6)で表される構造単位を含有するポリイミド前駆体。
- 下記式(7)で表される構造単位を含有するポリイミド。
- 下記式(8)で表される構造単位を含有するポリイミド前駆体。
- 下記式(9)で表される構造単位を含有するポリイミド。
- 下記式(10)で表される構造単位を含有するポリイミド前駆体。
- 下記式(11)で表される構造単位を含有するポリイミド。
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JP2014144955A (en) | 2014-08-14 |
CN102224452B (en) | 2014-07-09 |
CN102224452A (en) | 2011-10-19 |
KR20110079733A (en) | 2011-07-07 |
KR20150140847A (en) | 2015-12-16 |
KR101613756B1 (en) | 2016-04-19 |
KR101649839B1 (en) | 2016-08-19 |
JP5614284B2 (en) | 2014-10-29 |
TW201033249A (en) | 2010-09-16 |
JP5846230B2 (en) | 2016-01-20 |
TWI480312B (en) | 2015-04-11 |
JPWO2010050523A1 (en) | 2012-03-29 |
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