CN102051186B - Liquid crystal aligning agent, liquid crystal display element, polyamide acids, polyimide and compound - Google Patents

Liquid crystal aligning agent, liquid crystal display element, polyamide acids, polyimide and compound Download PDF

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CN102051186B
CN102051186B CN201010527063.4A CN201010527063A CN102051186B CN 102051186 B CN102051186 B CN 102051186B CN 201010527063 A CN201010527063 A CN 201010527063A CN 102051186 B CN102051186 B CN 102051186B
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liquid crystal
aligning agent
polyamic acid
crystal aligning
compound
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CN102051186A (en
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石川晓
秋池利之
菅野尚基
阿部翼
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JSR Corp
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    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • 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
    • 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
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/53—Physical properties liquid-crystalline

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Polymers & Plastics (AREA)
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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Liquid Crystal (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention relates to a liquid crystal aligning agent, a liquid crystal display element, a polyamide acids, a polyimide and a compound. Even when the liquid crystal aligning agent is under continuous lighting for a long time, a liquid crystal alignment film which has no low display quality like electrical property deterioration or bad alignment of liquid crystal molecules can be generated. With the liquid crystal aligning agent, the printing ability is excellent even when the fluid amount is small. The liquid crystal aligning agent comprises polyamic acid or polyimide with specific structure, represented by the following polyamic acid which is obtained by the reaction of tetracarboxylic acid diimide and diamine containing the compound shown in the following formula (A-1).

Description

Liquid crystal aligning agent, liquid crystal display device, polyamic acid, polyimide and compound
Technical field
The present invention relates to liquid crystal aligning agent, liquid crystal display device, polyamic acid, polyimide and compound.In more detail, even if the present invention relates to long-time continuous to run, also can not produce electrical property to worsen and the not good such display quality reduction of liquid crystal aligning, and in the saving liquid coated technique of the manufacturing process of liquid crystal display device, the liquid crystal aligning agent of good printing can be given, even and if relate to the operation of display quality excellence long-time continuous, the liquid crystal display device that display quality also can not be deteriorated.
Background technology
At present, as liquid crystal display device, the known TN type liquid crystal display device with so-called TN type (twisted-nematic) liquid crystal cell, it forms liquid crystal orientation film on the substrate surface being provided with nesa coating, as substrate used for liquid crystal display element, its two pieces are oppositely arranged, the nematic liquid crystal layer with positive dielectric anisotropy is formed betwixt in gap, form the box of sandwich structure, the major axis of this liquid crystal molecule reverses 90 ° (patent documentations 1) continuously from one piece of substrate to another block substrate.In addition, also developed optical compensation curved (OCB) type liquid crystal display device (patent documentation 4) of the high-speed response excellence of the few and image frame of the contrast gradient STN higher than TN type liquid crystal display device (supertwist to row) type liquid crystal display device (patent documentation 2) and few IPS (switching) the type liquid crystal display device (patent documentation 3) of view angle dependency, view angle dependency in the face in, VA (vertical orientated) type liquid crystal display device (patent documentation 5) etc. that use has the nematic liquid crystal of negative dielectric anisotropy.
As the material of the liquid crystal orientation film in these liquid crystal display device, known has current polyamic acid, polyimide, polymeric amide and polyester etc.; The particularly thermotolerance of polyamic acid and polyimide and the excellence such as affinity, physical strength of liquid crystal, so use (patent documentation 6 ~ 11) in most liquid crystal display device.
In recent years, along with to the high-accuracy progress of research turning to the display quality raising, low power consumption etc. of representative of liquid crystal display device, the scope that utilizes of liquid crystal display device increases gradually.Particularly, instead picture tube television LCD TV purposes and widely use.Thus, need electrical property more excellent than current, display quality is higher, and can the liquid crystal display device that runs of long-time continuous.
But, also indicate the liquid crystal display device with the liquid crystal orientation film formed by polyamic acid known at present or polyimide, when long-time continuous is thrown light on, liquid crystal orientation film can be deteriorated due to light and heat, easily produce the problem that electrical property is deteriorated or the not good such display quality of liquid crystal molecular orientation obviously reduces.
Therefore, even if when wishing to develop long-time continuous illumination, the liquid crystal orientation film that the not good such display quality of the orientation of electrical property variation and liquid crystal molecule is deteriorated is not had yet.
On the other hand, in recent years, in the coated technique of liquid crystal aligning agent, in order to effectively utilize liquid crystal aligning agent, the amount of liquid of the liquid crystal aligning agent used when attempting reducing printing.But when the amount of liquid of current alignment agent when applying is few, when having coating, the solvent evaporation in liquid crystal aligning agent, the concentration of alignment agent raises, and produces the problem that the not good and resinous principle of coating separates out such exception.Therefore, in order to maintain coating quality while maintaining the amount of liquid saving liquid crystal aligning agent, even if wish that amount of liquid is few, the liquid crystal aligning agent of excellent printing can also be demonstrated.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Unexamined Patent Publication 6-138457 publication
[patent documentation 2] Japanese Unexamined Patent Publication 5-19231 publication
[patent documentation 3] Japanese Unexamined Patent Publication 11-24109 publication
[patent documentation 4] Japanese Unexamined Patent Publication 8-327822 publication
[patent documentation 5] Japanese Unexamined Patent Publication 5-113561 publication
[patent documentation 6] Japanese Unexamined Patent Publication 4-153622 publication
[patent documentation 7] Japanese Unexamined Patent Publication 60-107020 publication
[patent documentation 8] Japanese Unexamined Patent Publication 56-91277 publication
[patent documentation 9] United States Patent (USP) 5,928,733A
[patent documentation 10] Japanese Unexamined Patent Publication 11-258605 publication
[patent documentation 11] Japanese Unexamined Patent Publication 62-165628 publication
[patent documentation 12] Japanese Unexamined Patent Publication 6-222366 publication
[patent documentation 13] Japanese Unexamined Patent Publication 6-281937 publication
[patent documentation 14] Japanese Unexamined Patent Publication 5-107544 publication
[patent documentation 15] Japanese Unexamined Patent Publication 2010-97188 publication
Summary of the invention
The present invention proposes according to the problems referred to above, its object is to relate to a kind of liquid crystal aligning agent, even if during the illumination of this liquid crystal aligning agent long-time continuous, also the liquid crystal orientation film of the not good such display quality reduction of the orientation that can not produce electrical property deterioration or liquid crystal molecule can be formed, even if when printing under few amount of liquid, printing is also excellent; And relate to display quality excellence, and even if long-time continuous is run, the liquid crystal display device that display quality also can not be deteriorated.
Other objects of the present invention and advantage are clear and definite by following explanation.
According to the present invention, above object and advantages of the present invention, first is realized by a kind of liquid crystal aligning agent, this liquid crystal aligning agent contain select from the group be made up of polyamic acid and polyimide at least one polymkeric substance (wherein, this polymkeric substance intramolecular at least partially in there is following formula (A 0) shown in structure).
Formula (A 0) in, X is any one divalent group represented of following formula (X-1) ~ (X-4),
—O— (X-3)
—S— (X-4)
In formula (X-1) and (X-2), R iIhydrogen atom, carbonatoms be 1 ~ 4 alkyl, carboxyl or carbonatoms be the carboxyalkyl of 2 ~ 5.
R ito be hydrogen atom or carbonatoms be 1 ~ 4 alkyl, m be 1 or 2, n be 0 or 1.
Above object and advantages of the present invention, second is realized by a kind of liquid crystal display device, and this liquid crystal display device has the liquid crystal orientation film formed by above-mentioned liquid crystal aligning agent.
Even if when liquid crystal aligning agent of the present invention can form long-time continuous operation, the liquid crystal orientation film that the not good such display quality of orientation of electrical property deterioration and liquid crystal molecule reduces is not had yet, even if when printing under few amount of liquid, also demonstrate excellent printing.
Have the liquid crystal display device of the present invention of the liquid crystal orientation film formed by this liquid crystal aligning agent, can show on high-quality ground, even if during long-play, display performance also can not be deteriorated.Therefore, liquid crystal display device of the present invention can be applicable to various device effectively, such as, can use in the display unit such as clock and watch, pocket game machine, word processor, notebook computer, navigationsystem, pick up camera, portable information terminal, digital camera, mobile telephone, various watch-dog, LCD TV.
Embodiment
Below, the present invention is described in detail.
Liquid crystal aligning agent of the present invention contains at least one polymkeric substance selected from the group be made up of polyamic acid and polyimide, wherein aforementioned polymer its intramolecular at least partially in there is above-mentioned formula (A 0) shown in group.In this manual, this polymkeric substance is called " particular polymers " hereinafter.In this particular polymers, above-mentioned formula (A 0) shown in structure, may reside in the main chain of polymkeric substance, also may reside in the side chain of polymkeric substance, or in the main chain that can simultaneously be present in polymkeric substance and side chain.
As above-mentioned formula (A 0) in X, be preferably the divalent group of above-mentioned formula (X-1) ~ (X-3) shown in any one.As the R in above-mentioned formula (X-1) and (X-2) iIcarbonatoms be the alkyl of 1 ~ 4, such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl etc. can be listed.Be the carboxyalkyl of 2 ~ 5 as carbonatoms, such as carboxymethyl, 2-carboxy ethyl, 3-carboxyl-n-propyl, 4-carboxyl-normal-butyl etc. can be listed.As the R in formula (X-1) and (X-2) iI, be preferably hydrogen atom, methyl, ethyl, sec.-propyl or carboxyl, be more preferably hydrogen atom, methyl or carboxyl, be particularly preferably carboxyl.
As R icarbonatoms be the alkyl of 1 ~ 4, being preferably carbonatoms is the alkyl of 1 or 2, namely methyl or ethyl.As R i, be preferably hydrogen atom.
Above-mentioned formula (A 0) in m and n, preferred m is 1, n is 0 or 1, or m is 2 and n is 0.
As the above-mentioned formula (A in polymkeric substance 0) shown in structure containing proportional, be preferably 0.00005 ~ 0.0035mol/g, be more preferably 0.00025 ~ 0.0025mol/g.
Intramolecular have above-mentioned formula (A at least partially 0) shown in the polyamic acid of structure, can list such as to make to comprise there is above-mentioned formula (A 0) shown in structure and the tetracarboxylic dianhydride of compound of two acid anhydrides and diamine reactant, or make tetracarboxylic dianhydride have above-mentioned formula (A with comprising 0) shown in structure and the diamine reactant of two amino compounds obtain; Intramolecular have above-mentioned formula (A at least partially 0) shown in the polyamic acid of structure, such as can by the polyamic acid dehydration closed-loop as above obtained be obtained.
Be preferably from by least one polymkeric substance selected polyamic acid and the group that formed by the polyimide that this polyamic acid dehydration closed-loop is formed as the particular polymers contained in liquid crystal aligning agent of the present invention, wherein this polyamic acid makes tetracarboxylic dianhydride and comprise to have above-mentioned formula (A 0) shown in structure and the diamine reactant of two amino compounds obtain.
Below, illustrate successively as the polyamic acid of particular polymers preferred in the present invention and polyimide.
< polyamic acid >
As implied above, in the present invention, preferred polyamic acid makes tetracarboxylic dianhydride and comprise to have above-mentioned formula (A 0) shown in structure and the diamine reactant of two amino compounds obtain.
[tetracarboxylic dianhydride]
As the tetracarboxylic dianhydride for the synthesis of the polyamic acid in the present invention, such as aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc. can be listed.As their concrete example, wherein as aliphatics tetracarboxylic dianhydride, such as butane tetracarboxylic acid dianhydride etc. can be listed;
As ester ring type tetracarboxylic dianhydride, such as 1 can be listed, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 3-oxabicyclo [3.2.1] pungent-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxotetrahydro-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic acid anhydride, 3, 5, 6-tri-carboxyl-2-carboxymethyl norbornane-2:3, 5:6-dianhydride, 2, 4, 6, 8-tetracarboxylic two ring [3.3.0] octane-2:4, 6:8-dianhydride, 4, 9-dioxa three ring [5.3.1.02, 6] undecane-3, 5, 8, 10-tetraketone etc.,
As aromatic tetracarboxylic acid's dianhydride, such as equal benzene tertacarbonic acid's dianhydride etc. can be listed;
And use the tetracarboxylic dianhydride recorded in patent documentation 15 (Japanese Unexamined Patent Publication 2010-97188 publication).
As the tetracarboxylic dianhydride for the synthesis of foregoing polyamides acid, preferably use those containing ester ring type tetracarboxylic dianhydride among them, particularly preferably use those containing 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride.
As the tetracarboxylic dianhydride for the synthesis of foregoing polyamides acid, relative to whole tetracarboxylic dianhydride, preferably containing more than 10mol%, 2,3, the 5-tricarboxylic cyclopentyl acetic acid dianhydrides more preferably containing more than 20mol%.
As the tetracarboxylic dianhydride for the synthesis of foregoing polyamides acid, most preferably only by 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride is formed, or is only made up of following: from by 1, and 2,3,4-tetramethylene tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1, the at least one selected in the group that 3-diketone is formed and 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride.
For the synthesis of the diamines of polyamic acid preferred in liquid crystal aligning agent of the present invention, be comprise there is above-mentioned formula (A 0) shown in structure and the diamines of two amino compounds (following, also referred to as " compound (A) ").
As compound (A) the preferably compound shown in following formula (A),
In formula (A), X, R i, m and n respectively with above-mentioned formula (A 0) in definition identical,
Particularly preferably use from least one the group be made up of the compound that following formula (A-1) ~ (A-17) represents respectively.
This compound (A) can by appropriately combined vitochemical ordinary method synthesis.Such as, by by following formula (A 0-1) compound shown in and the reaction of halo dinitrobenzene, after obtaining the dinitrobenzene compound as intermediate, by using suitable reduction system, being converted to amino by the nitro that this intermediate has, can easily synthesizing.
Formula (A 0-1) in, X, R i, m and n respectively with above-mentioned formula (A 0) in definition identical.
As the compound used in the present invention (A), be preferably the compound that above-mentioned formula (A-1) ~ (A-4) and (A-7) ~ (A-16) represents respectively.Among them, if use at least one selected from the group be made up of (A-1) ~ (A-4) and compound that (A-9) ~ (A-16) represents respectively, if particularly use at least one selected from the group is made up of (A-1) ~ (A-4) and compound that (A-14) ~ (A-16) represents respectively, be then preferred in the photostabilization of the liquid crystal orientation film of raising formation further;
If use at least one selected from the group be made up of above-mentioned formula (A-3), compound that (A-4) and (A-7) ~ (A-10) represents respectively, be then preferred in the printing of the liquid crystal aligning agent making to obtain is better.
As the diamines for the synthesis of polyamic acid preferred in the present invention, only can use compound (A), also compound (A) and other diamines can be combinationally used.
As other diamines that can use, such as aliphatie diamine, ester ring type diamines, aromatic diamine, diamino organo-siloxane etc. can be listed here.
As their object lesson, be as aliphatie diamine respectively, such as 1,1-m-xylene diamine, 1,3-propylene diamine, Putriscine, 1,5-pentamethylene diamine, 1,6-hexanediamine etc. can be listed;
As ester ring type diamines, such as Isosorbide-5-Nitrae-diamino-cyclohexane, 4 can be listed, 4 '-methylene radical two (cyclo-hexylamine), 1,3-bis-(amino methyl) hexanaphthene etc.;
As aromatic diamine, such as Ursol D can be listed, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 9,9-bis-(4-aminophenyl) fluorenes, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-bis-(4-aminophenyl) HFC-236fa, 4,4 '-(to phenylenediisopropylidene) two (aniline), 4,4 '-(metaphenylene two isopropylidene) two (aniline), Isosorbide-5-Nitrae-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N '-two (4-aminophenyl)-p-diaminodiphenyl, N, N '-two (4-aminophenyl)-N, N '-dimethyl p-diaminodiphenyl, dodecyloxy-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, n-Hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecane oxygen base-2,5-diaminobenzene, n-Hexadecane oxygen base-2,5-diaminobenzene, octadecane oxygen base-2,5-diaminobenzene, cholestane oxygen base-3,5-diaminobenzene, cholestene oxygen base-3,5-diaminobenzene, cholestane oxygen base-2,4-diaminobenzene, cholestene oxygen base-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestane base ester, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid lanostane base ester, 2,5-diaminobenzoic acid, N, N '-two (4-aminophenyl)-croak piperazine, compound etc. shown in following formula (D-1),
As diamino organo-siloxane, such as 1,3-bis-(3-aminopropyl)-tetramethyl disiloxane etc. can be listed; Except at least one diamines be selected among them can be used (following, be called " other specific diamines ") beyond, the diamines recorded in patent documentation 15 (Japanese Unexamined Patent Publication 2010-97188 publication) can also be made to use together with them or replace them to use.
As other diamines used in the present invention, preferably use other specific diamines, particularly preferably use from least one in the group be made up of 3,5-diaminobenzoic acid, cholestane oxygen base-2,4-diaminobenzene and 3,5-diaminobenzoic acid cholestane base ester.
As the diamines that the polyamic acid preferably contained in synthesis liquid crystal aligning agent of the present invention uses, relative to whole diamines, preferably containing more than 1mol%, more preferably containing more than 5mol%, particularly preferably containing 10 ~ 90mol% compound (A).In addition, for the synthesis of the diamines of preferred polyamic acid except compound (A), preferably also comprise other specific diamines as above.As the usage ratio of other specific diamines in this case, relative to whole diamines, be preferably more than 30mol%, be more preferably more than 50mol%, be particularly preferably more than 80mol%.
Diamines for the synthesis of the polyamic acid preferably contained in liquid crystal aligning agent of the present invention is preferably only made up of compound (A), or is only made up of compound (A) and other specific diamines.
[synthesis of polyamic acid]
The polyamic acid contained in liquid crystal aligning agent of the present invention can obtain by making the diamine reactant of tetracarboxylic dianhydride and inclusion compound (A).
As the usage ratio of the tetracarboxylic dianhydride used in the building-up reactions of polyamic acid and diamines, relative to the amino of 1 equivalent diamines, the ratio of preferred 0.2 ~ 2 equivalent of the anhydride group of tetracarboxylic dianhydride, the more preferably ratio of 0.3 ~ 1.2 equivalent.
The building-up reactions of polyamic acid is preferably carried out in organic solvent, preferably at-20 DEG C ~ 150 DEG C, more preferably under the temperature condition of 0 DEG C ~ 100 DEG C, preferably carries out 0.1 ~ 24 hour, more preferably carries out 0.5 ~ 12 hour.
Operable organic solvent during synthesis as polyamic acid, can list such as aprotic polar solvent, phenol and its derivatives, alcohol, ketone, ester, ether, halohydrocarbon, hydrocarbon etc.As above-mentioned aprotic polar solvent, such as METHYLPYRROLIDONE, N,N-dimethylacetamide, DMF, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA etc. can be listed;
As above-mentioned phenol derivatives, such as meta-cresol, xylenol, halogenated phenol etc. can be listed;
As above-mentioned alcohol, such as methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, BDO, triglycol, ethylene glycol monomethyl ether etc. can be listed;
As above-mentioned ketone, such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone etc. can be listed;
As above-mentioned ester, such as ethyl lactate, n-Butyl lactate, methyl acetate, ethyl acetate, butylacetate, methoxy methyl propionate, ethoxyl ethyl propionate, oxalic acid diethyl ester, diethyl malonate etc. can be listed;
As above-mentioned ether, such as Anaesthetie Ether, Ethylene Glycol Methyl ether, glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol monomethyl ether acetic ester, TC acetic ester, tetrahydrofuran (THF) etc. can be listed;
As above-mentioned halohydrocarbon, such as methylene dichloride, 1,2-ethylene dichloride, Isosorbide-5-Nitrae-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene etc. can be listed;
As above-mentioned hydrocarbon, such as hexane, heptane, octane, benzene,toluene,xylene, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether etc. can be listed.
In these organic solvents, preferred use select from the group be made up of aprotic polar solvent and phenol and its derivatives (organic solvent of the first group) more than one, or be selected from more than one and more than one the mixture in being selected from group's (organic solvent of the second group) of being made up of alcohol, ketone, ester, ether, halohydrocarbon and hydrocarbon of organic solvent of aforementioned first group.In the case of the latter, the usage ratio of the organic solvent of the second group, relative to the total amount of the organic solvent of the first group and the organic solvent of the second group, is preferably less than 50 % by weight, be more preferably less than 40 % by weight, more preferably less than 30 % by weight.
As above, the reaction soln dissolving polyamic acid formation can be obtained.
This reaction soln can be directly used in prepares liquid crystal aligning agent, after the polyamic acid that also can contain in separating reaction solution, for the preparation of liquid crystal aligning agent, or after being refined by the polyamic acid be separated, for the preparation of liquid crystal aligning agent.
When polyamic acid dehydration closed-loop is formed polyimide, above-mentioned reaction soln can be directly used in dehydration closed-loop reaction; After the polyamic acid that also can contain in separating reaction solution, react for dehydration closed-loop; Or after the polyamic acid be separated is refined, react for dehydration closed-loop.
The separation of polyamic acid by above-mentioned reaction soln is injected a large amount of lean solvents, can obtain precipitate, by the method for this precipitate drying under reduced pressure; Or undertaken by the method for the solvent in vaporizer underpressure distillation reaction soln.In addition, also can by this polyamic acid be dissolved in organic solvent again, the method then separated out in lean solvent; Or by repeating 1 time or being repeatedly again dissolved in organic solvent by polyamic acid, after washing this solution, the method for the organic solvent distillated in this solution with vaporizer decompression refines polyamic acid.
< polyimide >
The polyimide that can contain in liquid crystal aligning agent of the present invention can by obtaining the polyamic acid dehydration closed-loop imidization as above obtained.
As the tetracarboxylic dianhydride that polyimide preferred in synthesis the present invention uses, the compound identical with the tetracarboxylic dianhydride used in the synthesis of above-mentioned polyamic acid can be listed.Kind and the preferred usage ratio thereof of preferred tetracarboxylic dianhydride are also identical with the situation of polyamic acid.
As the diamines for the synthesis of polyimide preferred in the present invention, can list and synthesize the diamines of the diamines identical type that above-mentioned polyamic acid uses.Namely, diamines for the synthesis of the polyimide contained in liquid crystal aligning agent of the present invention is the diamines of inclusion compound (A), only can use compound (A), also compound (A) and other diamines can be used together.
As the diamines that the polyamic acid preferably contained in synthesis liquid crystal aligning agent of the present invention uses, relative to whole diamines, preferably containing more than 1mol%, more preferably containing 1 ~ 50mol%, the compound (A) particularly preferably containing 5 ~ 40mol%.In addition, for the synthesis of the diamines of preferred polyamic acid except compound (A), preferably also comprise other specific diamines as above.As the usage ratio of other specific diamines in this case, relative to whole diamines, be preferably more than 30mol%, be more preferably more than 50mol%, be particularly preferably more than 80mol%.
Diamines for the synthesis of the polyamic acid preferably contained in liquid crystal aligning agent of the present invention is preferably only made up of compound (A) and other specific diamines.
The polyimide preferably contained in liquid crystal aligning agent of the present invention can be the complete imide compound of the amido acid structure fully dehydrating closed loop had as the polyamic acid of raw material; Also can be a part of dehydration closed-loop of amido acid structure, amido acid structure and imide ring structure the part imide compound of depositing.The imide rate of the polyimide preferably contained in liquid crystal aligning agent of the present invention is preferably more than 30%, is more preferably more than 40%, is particularly preferably 50 ~ 80%.Above-mentioned imide rate represents that the quantity of imide ring structure occupies the ratio of the total amount of the quantity of the amido acid structure of polyimide and the quantity of imide ring structure with percentage.Now, a part for imide ring can be different imide ring.
The dehydration closed-loop preferred (i) of polyamic acid is with the method by heating polyamic acid, or (ii) polyamic acid is dissolved in organic solvent, in this solution, add dewatering agent and dehydration closed-loop catalyzer, the method heated as required is carried out.
50 ~ 200 DEG C are preferably, more preferably 60 ~ 170 DEG C as the temperature of reaction in the method for the heating polyamic acid of above-mentioned (i).When temperature of reaction is less than 50 DEG C, fully cannot carry out dehydration closed-loop reaction; If temperature of reaction is more than 200 DEG C, then the molecular weight of the polyimide of gained may reduce.Be preferably 1.0 ~ 24 hours as the reaction times, be more preferably 1.0 ~ 12 hours.
On the other hand, above-mentioned (ii) adds in the method for dewatering agent and dehydration closed-loop catalyzer in polyamic acid solution, as dewatering agent, can use the acid anhydrides such as such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride.The usage ratio of dewatering agent, determines according to desired imide rate, relative to the amido acid structure of 1mol polyamic acid, is preferably 0.01 ~ 20mol.In addition, as dehydration closed-loop catalyzer, the tertiary amines such as such as pyridine, trimethylpyridine, lutidine, triethylamine can be listed.But, be not limited to this.The usage ratio of dehydration closed-loop catalyzer, relative to the dewatering agent that 1mol uses, is preferably 0.01 ~ 10mol.Imide rate can be above-mentioned dewatering agent, dehydration closed-loop catalyzer consumption more much higher.As the organic solvent used in dehydration closed-loop reaction, the illustrative organic solvent of solvent used as synthesizing polyamides acid can be listed.The temperature of reaction of dehydration closed-loop reaction is preferably 0 ~ 180 DEG C, is more preferably 10 ~ 150 DEG C.Reaction times is preferably 1.0 ~ 120 hours, is more preferably 2.0 ~ 30 hours.
The polyimide obtained in aforesaid method (i) can be directly used in prepares liquid crystal aligning agent, or after the polyimide of gained is refined, for the preparation of liquid crystal aligning agent.On the other hand, in aforesaid method (ii), the reaction soln containing polyimide can be obtained.This reaction soln can be directly used in prepares liquid crystal aligning agent, after also can removing dewatering agent and dehydration closed-loop catalyzer from reaction soln, for the preparation of liquid crystal aligning agent; After can also being separated polyimide, for the preparation of liquid crystal aligning agent; Or after the polyimide be separated is refined, for the preparation of liquid crystal aligning agent.In order to from reaction soln removing dewatering agent and dehydration closed-loop catalyzer, such as, be applicable to using the methods such as solvent exchange.The separation of polyimide, refining can by as the separation of polyamic acid, process for purification and the above-mentioned operation equally carried out is carried out.
-polymkeric substance of end modified type-
The polyamic acid contained in liquid crystal aligning agent of the present invention and polyimide can be the end modified property polymkeric substance that have adjusted molecular weight respectively.By using end modified type polymkeric substance, the coating property etc. that effect of the present invention ground improves liquid crystal aligning agent further can not be damaged.This end modified type polymkeric substance, when synthesizing polyamides acid, can be undertaken by adding suitable molecular weight regulator in polymerization reaction system.As molecular weight regulator, such as sour single acid anhydride, monoamine compound, monoisocyanate compound etc. can be listed.
As the single acid anhydride of above-mentioned acid, such as maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl bigcatkin willow acid anhydrides, dodecyl bigcatkin willow acid anhydrides, n-tetradecane base bigcatkin willow acid anhydrides, n-hexadecyl bigcatkin willow acid anhydrides etc. can be listed.As above-mentioned monoamine compound, such as aniline, cyclo-hexylamine, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octylamine, n-nonyl amine, positive decyl amine, n-undecane base amine, dodecyl amine, n-tridecane base amine, n-tetradecane base amine, Pentadecane base amine, n-hexadecyl amine, n-heptadecane base amine, Octadecane base amine, NSC 62789 base amine etc. can be listed.As above-mentioned monoisocyanate compound, such as phenyl isocyanate, isocyanic acid naphthyl ester etc. can be listed.
The usage ratio of molecular weight regulator, amounts to 100 weight parts relative to the tetracarboxylic dianhydride used during synthesizing polyamides acid and diamines, is preferably below 20 weight parts, is more preferably below 10 weight parts.
-soltion viscosity-
As above the polyamic acid obtained and polyimide, when forming the solution of concentration 10 % by weight respectively, preferably have the soltion viscosity of 20 ~ 800mPas, more preferably have the soltion viscosity of 30 ~ 500mPas.
The soltion viscosity (mpas) of above-mentioned polymkeric substance be use this polymkeric substance good solvent (such as, gamma-butyrolactone, METHYLPYRROLIDONE etc.) prepare the polymers soln of concentration 10 % by weight, use E type rotational viscosimeter, to the value that it measures at 25 DEG C.
Other additive of < >
Liquid crystal orientation film of the present invention as required composition, also can contain other composition containing, for example upper particular polymers as required.As this other composition, such as other polymkeric substance can be listed, there is the compound (hereinafter referred to as " epoxy compounds "), functional silanes compound etc. of at least 1 epoxy group(ing) in molecule.
[other polymkeric substance]
Other polymkeric substance above-mentioned may be used for improving SOLUTION PROPERTIES and electrical property.As this other polymkeric substance, it is the polymkeric substance beyond particular polymers, the polyamic acid that such as tetracarboxylic dianhydride obtains with the diamine reactant containing compound (A) can be listed (following, be called " other polyamic acid "), polyimide (hereinafter referred to as " other polyimide "), poly amic acid ester, polyester, polymeric amide, polysiloxane, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative, poly-(methyl) acrylate etc. that this polyamic acid dehydration closed-loop is formed.Among them, preferably other polyamic acid or other polyimide.
As the usage ratio of other polymkeric substance, (refer to the total amount of above-mentioned particular polymers and other polymkeric substance relative to the total amount of polymkeric substance.Identical below), be preferably less than 85 % by weight, be more preferably less than 50 % by weight, more preferably less than 40 % by weight, be particularly preferably less than 30 % by weight, more preferably do not use other polymkeric substance further.
[epoxy compounds]
As above-mentioned epoxy compounds, preferably there is the compound of at least two epoxy group(ing) in molecule, such as ethylene glycol diglycidylether can be listed, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 2, 2-bis-bromo neopentylglycol diglycidyl ether, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, 3-bis-(N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzyl amine, N, N-diglycidyl-aminomethyl cyclohexane, N, N-diglycidyl-cyclo-hexylamine etc. are as preferred material.
Amount to 100 weight parts relative to polymkeric substance, the blending ratio of these epoxy compoundss is preferably below 40 weight parts, is more preferably 0.1 ~ 30 weight part.
[functional silanes compound]
As above-mentioned functional silanes compound, such as 3-TSL 8330 can be listed, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-uride propyl trimethoxy silicane, 3-uride propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, 9-trimethoxysilyl-3,6-diaza methyl pelargonate, 9-triethoxysilyl-3,6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, glycidoxypropyl methyltrimethoxy silane, glycidoxypropyl Union carbide A-162, 2-glycidoxypropyl ethyl trimethoxy silane, 2-glycidoxypropyl ethyl triethoxysilane, 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane etc.
Amount to 100 weight parts relative to polymkeric substance, the blending ratio of these functional silanes compounds is preferably below 2 weight parts, is more preferably below 0.2 weight part.
< liquid crystal aligning agent >
As above other additive of particular polymers and mixing arbitrarily as required dissolves containing and forms by liquid crystal aligning agent of the present invention in preferred organic solvent.
As the organic solvent that can use in liquid crystal aligning agent of the present invention, METHYLPYRROLIDONE can be listed, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, n-Butyl lactate, butylacetate, methoxy methyl propionate, ethoxyl ethyl propionate, Ethylene Glycol Methyl ether, glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (ethylene glycol butyl ether), ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol monomethyl ether acetic ester, TC acetic ester, diisobutyl ketone, propionic acid isopentyl ester, isopropylformic acid isopentyl ester, diisoamyl ether, ethylene carbonate, propylene carbonate etc.They can be used alone, or also can mix two or more use.
Solid component concentration (gross weight of the composition beyond the solvent of liquid crystal aligning agent occupies the ratio of the gross weight of liquid crystal aligning agent) in liquid crystal aligning agent of the present invention, consider that viscosity, volatility etc. are suitably selected, be preferably the scope of 1 ~ 10 % by weight.Namely, liquid crystal aligning agent of the present invention as described later, is coated to substrate surface, preferably by heating, form the film of liquid crystal orientation film, but when solid component concentration is less than 1 % by weight, the thickness of this film is too small, may be difficult to obtain good liquid crystal orientation film; On the other hand, when solid component concentration is more than 10 % by weight, the thickness of film is excessive, is difficult to obtain good liquid crystal orientation film, and the viscosity of liquid crystal aligning agent increases, and screening characteristics qualitative change is poor.
The scope of particularly preferred solid component concentration is different according to the method adopted during coated with liquid crystal alignment agent on substrate.Such as, when using spin-coating method to carry out, solid component concentration is particularly preferably the scope of 1.5 ~ 4.5 % by weight.When using print process to carry out, solid component concentration is the scope of 3 ~ 9 % by weight, and thus, soltion viscosity is particularly preferably the scope of 12 ~ 50mPas.When using ink jet method to carry out, solid component concentration is the scope of 1 ~ 5 % by weight, and thus, soltion viscosity is particularly preferably the scope of 3 ~ 15mpas.
Temperature when preparing liquid crystal aligning agent of the present invention is preferably 10 DEG C ~ 50 DEG C, is more preferably 20 DEG C ~ 30 DEG C.
< liquid crystal display device >
Liquid crystal display device of the present invention has the liquid crystal orientation film formed by as above liquid crystal aligning agent of the present invention.
Liquid crystal display device of the present invention such as can by the operation manufacture of following (1) and (3).Operation (1) is according to desired operational mode, and the substrate of use is different.Operation (2) and (3) are identical under various operational mode.
(1) first, substrate applies liquid crystal aligning agent of the present invention, then, by heating applicator surface, substrate forms film.
(1-1) when manufacturing TN type, STN type or VA type liquid crystal display device, the two pieces of substrates being provided with the nesa coating forming pattern are formed a pair, in their each transparent conductive film forming surface, preferably by adherography, spin-coating method or ink jet printing method, apply liquid crystal aligning agent of the present invention respectively, then, by heating each applicator surface, film is formed.Now, as substrate, can use such as by the glass such as float glass, soda glass; The transparency carrier that the plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-(ester ring type alkene) are formed.As the nesa coating arranged in the one side of substrate, can use by stannic oxide (SnO 2) the NESA film (registered trademark of PPG company of the U.S.), the indium oxide-tin oxide (In that are formed 2o 3-SnO 2) ito film etc. that formed, in order to obtain the nesa coating forming pattern, can by such as being formed without after figure nesa coating, by the method for photoetch formation pattern; When forming nesa coating, the method etc. with the mask of desired pattern is used to obtain.During coated with liquid crystal alignment agent, in order to make the cohesiveness of substrate surface and nesa coating and film better, in substrate surface, can should be formed on the face of film, applying functional silanes compound, functionality titanium compound etc. in advance and carrying out pre-treatment.
After coated with liquid crystal alignment agent, based on objects such as the alignment agent liquid drips preventing from applying, preferably carry out preheating (prebake).The temperature of prebake is preferably 30 ~ 200 DEG C, is more preferably 40 ~ 150 DEG C, is particularly preferably 40 ~ 100 DEG C.The time of prebake is preferably 0.25 ~ 10 minute, is more preferably 0.5 ~ 5 minute.Afterwards, based on completely except desolventizing, as required by the object of polyamic acid hot-imide, carry out firing (curing afterwards) operation.This is fired (curing afterwards), and temperature is preferably 80 ~ 300 DEG C, is more preferably 120 ~ 250 DEG C.After the time of curing be preferably 5 ~ 200 minutes, be more preferably 10 ~ 100 minutes.So, the thickness of the film of formation is preferably 0.001 ~ 1 μm, is more preferably 0.005 ~ 0.5 μm.
(1-2) on the other hand, when manufacturing IPS type liquid crystal display device, to the face of the formation conducting film of the substrate of the nesa coating forming interdigitated electrode structure pattern be provided with and not arrange in the one side of subtend substrate of conducting film, preferably by adherography, spin-coating method or ink jet printing method, apply liquid crystal aligning agent of the present invention respectively, then, by heating each applicator surface, film is formed.
Heating means after the material of the substrate now used and nesa coating, the formation patterning method of nesa coating, the pre-treatment of substrate and coated with liquid crystal alignment agent are identical with above-mentioned (1-1).
The preferred thickness of the film formed is identical with above-mentioned (1-1).
(2), when the liquid crystal display device manufactured by method of the present invention is VA type liquid crystal display device, the film as above formed can directly use as liquid crystal orientation film, but re-uses after desirably can carrying out grinding process described later.
On the other hand, then when manufacturing the liquid crystal display device beyond VA type, by carrying out grinding process to the film as above formed, liquid crystal orientation film is formed.
Grinding process is the coated surface to as above being formed, and by winding such as by the roller of the fibroplastic cloth such as nylon, artificial silk, cotton, carries out in certain orientation polishing.Thus, the orientation of liquid crystal molecule can give film, forms liquid crystal orientation film.
Then, as above the liquid crystal orientation film formed is processed, by making each region of liquid crystal orientation film, there is different liquid crystal orientation films, the perspective nature of the liquid crystal display device of gained can be improved, wherein the process that liquid crystal film carries out is comprised: such as recorded in patent documentation 12 (Japanese Unexamined Patent Publication 6-222366 publication) or patent documentation 13 (Japanese Unexamined Patent Publication 6-281937 publication), to a part of irradiation ultraviolet radiation of liquid crystal orientation film, change the process of the tilt angle in a part of region of liquid crystal orientation film; And as recorded in patent documentation 14 (Japanese Unexamined Patent Publication 5-107544 publication), after etchant resist is formed to the part on liquid crystal orientation film surface, on the direction different with grinding process before, after carrying out grinding process, the process of removing etchant resist.
(3) prepare two pieces of substrates as above forming liquid crystal orientation film, configure liquid crystal, manufacture liquid crystal cell by between two pieces of substrates configure in subtend.Here, when carrying out grinding process to film, two pieces of substrate subtend configurations to make the polishing direction phase predetermined angular each other of each film, such as, are orthogonal or antiparallels.
When manufacturing liquid crystal cell, such as following two kinds of methods can be listed.
First method is method known at present.First, arrange to make each liquid crystal orientation film subtend, by gap (box gap), by two pieces of substrate subtend configurations, use sealing agent, the peripheral part of two pieces of substrates is fitted, inject filling liquid crystal in the box gap split by substrate surface and sealing agent after, sealing filling orifice, can manufacture liquid crystal cell.
Second method is the method being called ODF (One Drop Fill, instillation) mode.Prescribed position on a substrate in the two pieces of substrates forming liquid crystal orientation film, apply the sealing material of such as ultraviolet light curable, then after dripping liquid crystal on liquid crystal aligning face, to fit another substrate make liquid crystal orientation film subtend, then, in whole irradiating ultraviolet light of substrate, make sealant cures, can liquid crystal cell be manufactured.
When any one method, wishing the liquid crystal cell to as above manufacturing, after reheating the isotropic temperature of liquid crystal used, progressively cooling to room temperature, flow orientation when removing liquid crystal is filled.
Then, by the outer surface laminating polaroid at liquid crystal cell, liquid crystal display device of the present invention can be obtained.
Now, as sealing agent, the epoxy resin etc. such as containing solidifying agent and the alumina balls as partition can be used.
As foregoing liquid crystal, such as nematic liquid crystal, dish-like liquid crystal etc. can be used, preferred nematic liquid crystal among them.When for VA type liquid crystal cell, preferably there is the nematic liquid crystal of negative dielectric anisotropy, such as dicyanobenzenes class liquid crystal, pyridazine class liquid crystal, schiff alkali class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal etc. can be used.When for TN type liquid crystal cell or STN type liquid crystal cell, preferably there is the nematic liquid crystal of positive dielectric anisotropy, such as biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cubane-like liquid crystal etc. can be used.In these liquid crystal, cholesterol liquid crystals such as using such as chlorination beta-cholestanol (cholestyl chloride), Cholesteryl pelargonate, cholesterol carbonic ether can be added further; With the chiral reagent that trade(brand)name C-15, CB-15 (manufacture of メ ルク company) sell; To oxygen base benzylidene-to Ferroelectric liquid Crystals etc. such as amino-2-methyl butyl laurates in the last of the ten Heavenly stems.
As the polaroid fitting to liquid crystal cell outside surface, limit can be listed and polyvinyl alcohol to be extended orientation, while clamp the polaroid absorbing light polarizing film that iodine is called " H film " and formed with cellulose acetate protective membrane, or the polaroid formed by H film itself.
[embodiment]
Below, by embodiment, the present invention is further illustrated, but the present invention is not subject to the restriction of these embodiments.The soltion viscosity of the polymers soln in following synthesis example and the imide rate of polyimide are by following method evaluation.
[soltion viscosity of polymkeric substance]
The soltion viscosity (mPas) of polymkeric substance be polymer concentration is adjusted to respectively 10 % by weight N-Methyl pyrrolidone solution, use E type rotational viscosimeter, measure at 25 DEG C.
[the imide rate of polyimide]
The imide rate of polymkeric substance is that the solution of the polyimide each synthesis example obtained marginally is put in pure water, reclaim the precipitation generated, at room temperature after abundant drying under reduced pressure, be dissolved in heavy-hydrogenated dimethyl sulfoxide (DMSO), using tetramethylsilane as primary standard, measure from room temperature 1h-NMR wave spectrum, is tried to achieve by following mathematical expression (1).
Imide rate (%)=(1-A 1/ A 2× α) × 100 (1)
In mathematical expression (1), A 1the peak area of the proton from the NH base shown near chemical shift 10ppm, A 2be the peak area from other proton, α is the ratio of number relative to the proton of the NH base in the precursor (polyamic acid) of 1 polymkeric substance of other proton.
The synthesis example > of < compound (A)
Synthesis example S-1
According to following synthetic route 1, synthesize the compound (compound (A-1)) shown in above-mentioned formula (A-1).
synthetic route 1
3, in the single port flask of 000mL, mixing 186.1g (1.00mol) 2,4-dinitrofluorobenzene, 152.0g (1.10mol) salt of wormwood and 1,000mL dimethyl sulfoxide (DMSO), add 148.5mL (1.50mol) piperidines wherein, stir at 80 DEG C and react for 1 hour.After reaction terminates, add 4,000mL ethyl acetate in the reactive mixture, the organic layer obtained 1,000mL ion-exchange water washing 4 times, after magnesium sulfate dehydration, cross and filter magnesium sulfate.By decompression, from filtrate except desolventizing, the solid 500mL ethyl alcohol recrystallization obtained, obtains 231.1g (0.92mol) compound (A-1-a).
Then, under nitrogen atmosphere, in the there-necked flask of 5,000mL, mixing 226.1g (0.90mol) compound obtained above (A-1-a), 21.8g palladium carbon (Pd/C), 2,000mL ethanol and 1,000mL tetrahydrofuran (THF).While note temperature, add 220mL hydrazine monohydrate wherein lentamente and after making the temperature of reaction system can not reach 40 DEG C, at nitrogen, at 25 DEG C, stirring reaction 1 hour, then stirring reaction 4 hours at 70 DEG C.After reaction terminates, from reaction mixture, filtered by diatomite (cerite), after removing catalyzer, decompression, from filtrate except desolventizing, obtains solid.By the dissolution of solid that obtains in 4,000mL ethyl acetate, the solution obtained 1,000mL ion-exchange water washing 4 times, after magnesium sulfate dehydration, crosses and filters magnesium sulfate.By decompression, from filtrate except desolventizing, the mixed solvent recrystallization that the solid 50mL ethyl acetate obtained and 400mL hexane are formed, obtains 99.5g (0.52mol) compound (A-1).
Synthesis example S-2
According to following synthetic route 2, synthesize the compound (compound (A-3)) shown in above-mentioned formula (A-3).
synthetic route 2
3, in the single port flask of 000mL, mixing 193.7g (1.50mol) isonipecotic acid, 186.1g (1.00mol) DNF, 167.1g (1.10mol) cesium fluoride and 1,000mL dimethyl sulfoxide (DMSO), stirs and reacts for 12 hours at 25 DEG C.After reaction terminates, add 3,000mL ethyl acetate in the reactive mixture, the organic layer obtained 1,000mL ion-exchange water washing 4 times, after magnesium sulfate dehydration, cross and filter magnesium sulfate.By decompression, from filtrate except desolventizing, the solid obtained 1,000mL re-crystallizing in ethyl acetate, obtains 224.4g (0.76mol) compound (A-3-a).
Then, under nitrogen atmosphere, in the there-necked flask of 5,000mL, mixing 221.4g (0.75mol) compound obtained above (A-3-a), 18.7g palladium carbon (Pd/C), 1,200mL ethanol and 1,200mL tetrahydrofuran (THF), notes temperature, on one side adds 185mL hydrazine monohydrate wherein lentamente and after making the temperature of reaction system can not reach 40 DEG C, stirring reaction 1 hour at 25 DEG C, then stirring reaction 1.5 hours at 70 DEG C.After reaction terminates, from reaction mixture, by diatomite filtration, after removing catalyzer, decompression, from filtrate except desolventizing, obtains solid.The solid obtained is by column chromatography (packing material: (メ ルク company manufactures silica gel, trade(brand)name " シ リ カ ゲ Le 60 "), developing solvent: the mixed solvent (chloroform: ethanol=20: 1 (volume ratio)) formed by chloroform and ethanol refine, from this cut except desolventizing, obtain 35.3g (0.15mol) compound (A-3).
Synthesis example S-3
According to following synthetic route 3, synthesize the compound (compound (A-12)) shown in above-mentioned formula (A-12).
synthetic route 3
3, in the single port flask of 000mL, mixing 186.1g (1.00mol) 2,4-dinitrofluorobenzene, 152.0g (1.10mol) salt of wormwood, 204.6mL (1.50mol) 3,5-lupetidine and 1,000mL dimethyl sulfoxide (DMSO), stirs and reacts for 5 hours at 80 DEG C.After reaction terminates, add 4,000mL ethyl acetate in the reactive mixture, the organic layer obtained 1,000mL ion-exchange water washing 4 times, after magnesium sulfate dehydration, cross and filter magnesium sulfate.By decompression, from filtrate except desolventizing, the solid 500mL ethyl alcohol recrystallization obtained, obtains 262.5g (0.94mol) compound (A-12-a).
Then, under nitrogen atmosphere, in the there-necked flask of 5,000mL, mixing 251.4g (0.90mol) compound obtained above (A-12-a), 21.8g palladium carbon (Pd/C), 2,000mL ethanol and 1,000mL tetrahydrofuran (THF), note temperature, on one side add 220mL hydrazine monohydrate wherein lentamente and after making the temperature of reaction system can not reach 40 DEG C, at 25 DEG C, stirring reaction 1 hour, then stirring reaction 4 hours at 70 DEG C.After reaction terminates, from reaction mixture, by diatomite filtration, after removing catalyzer, decompression, from filtrate except desolventizing, obtains solid.By the dissolution of solid that obtains in 4,000mL ethyl acetate, the solution obtained 1,000mL ion-exchange water washing 4 times, after magnesium sulfate dehydration, crosses and filters magnesium sulfate.By decompression, from filtrate except desolventizing, the mixed solvent recrystallization that the solid 80mL ethyl acetate obtained and 400mL hexane are formed, obtains 142.6g (0.65mol) compound (A-12).
Synthesis example S-4
According to following synthetic route 4, synthesize the compound (compound (A-14)) shown in above-mentioned formula (A-14).
synthetic route 4
3, in the single port flask of 000mL, mixing 202.6g (1.0mol) DNFB, 120.2g (1.2mol) 1-methylpiperazine, 92.4g (1.1mol) sodium bicarbonate and 1,000mL ethanol, stirs and reacts for 12 hours at 25 DEG C.After reaction terminates, add 3,000mL ethyl acetate in the reactive mixture, the organic layer obtained 1,000mL ion-exchange water washing 4 times, after magnesium sulfate dehydration, cross and filter magnesium sulfate.By decompression, from filtrate except desolventizing, obtain 242.3g (0.91mol) compound (A-14-a).
Then, under nitrogen atmosphere, in the there-necked flask of 5,000mL, mixing 239.6g (0.90mol) compound obtained above (A-14-a), 21.8g palladium carbon (Pd/C), 1,350mL ethanol and 1,350mL tetrahydrofuran (THF), note temperature, on one side add 220mL hydrazine monohydrate wherein lentamente and after making the temperature of reaction system can not reach 40 DEG C, at 25 DEG C, stirring reaction 1 hour, then stirring reaction 4 hours at 70 DEG C.After reaction terminates, from reaction mixture, by diatomite filtration, after removing catalyzer, decompression, from filtrate except desolventizing, obtains solid.By the dissolution of solid that obtains in 4,000mL ethyl acetate, the solution obtained 1,000mL ion-exchange water washing 4 times, after magnesium sulfate dehydration, crosses after filtering magnesium sulfate, by decompression from filtrate except desolventizing, obtain solid.The solid obtained is by column chromatography (packing material: (メ ルク company manufactures silica gel, trade(brand)name " シ リ カ ゲ Le 60 "), developing solvent: the mixed solvent (chloroform: ethanol=20: 1 (volume ratio)) formed by chloroform and ethanol refine, from this cut except desolventizing, obtain 169.2g (0.82mol) compound (A-14).
Synthesis example S-5
According to following synthetic route 5, synthesize the compound (compound (A-16)) shown in above-mentioned formula (A-16).
synthetic route 5
3, in the single port flask of 000mL, mixing 202.6g (1.0mol) DNFB, 104.5g (1.2mol) morpholine, 92.4g (1.1mol) sodium bicarbonate and 1,000mL ethanol, stirs and reacts for 12 hours at 25 DEG C.After reaction terminates, add 3,000mL ethyl acetate in the reactive mixture, the organic layer obtained 1,000mL ion-exchange water washing 4 times, after magnesium sulfate dehydration, cross and filter magnesium sulfate.By decompression, from filtrate except desolventizing, obtain 220.3g (0.87mol) compound (A-16-a).
Then, under nitrogen atmosphere, in the there-necked flask of 5,000mL, mixing 202.6g (0.80mol) compound obtained above (A-16-a), 20.0g palladium carbon (Pd/C), 1,200mL ethanol and 1,200mL tetrahydrofuran (THF), note temperature, on one side add 187mL hydrazine monohydrate wherein lentamente and after making the temperature of reaction system can not reach 40 DEG C, at 25 DEG C, stirring reaction 1 hour, then stirring reaction 3.5 hours at 70 DEG C.After reaction terminates, from reaction mixture, by diatomite filtration, after removing catalyzer, decompression, from filtrate except desolventizing, obtains solid.The solid obtained is by column chromatography (packing material: (メ ルク company manufactures silica gel, trade(brand)name " シ リ カ ゲ Le 60 "), developing solvent: the mixed solvent (chloroform: ethanol=20: 1 (volume ratio)) formed by chloroform and ethanol refine, from this cut except desolventizing, obtain 146.87g (0.76mol) compound (A-16).
The synthesis > of < polymkeric substance
Synthesis example 1 ~ 11
The diamines of the amount shown in table 1 and tetracarboxylic dianhydride are joined in METHYLPYRROLIDONE with this order, form the solution of monomer concentration 20 % by weight, react 4 hours at 60 DEG C, obtain the solution containing polyamic acid (PA-1) ~ (PA-11) respectively.Get each solution, add METHYLPYRROLIDONE for a small amount of point, form the solution of polyamic acid concentration 10 % by weight, the soltion viscosity of mensuration represents in Table 1.
Guarantee each half amount in these polyamic acid solutions, use in embodiment 17 ~ 28 afterwards and comparative example 5 ~ 8 respectively.
In the remaining half amount of above-mentioned each polyamic acid solution, with the amido acid unit had relative to each polyamic acid of 1mol, after the pyridine adding mol ratio described in table 1 and diacetyl oxide, be heated to 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, the new METHYLPYRROLIDONE of intrasystem solvent carries out solvent exchange (by this operation, the pyridine used in being reacted by dehydration closed-loop and diacetyl oxide are except going to system, identical below), thus obtain the solution containing 16 % by weight polyimide (PI-1) ~ (PI-11) respectively.Imide rate and a small amount of the dividing of each polyimide contained in these polyimide solutions get each solution, and form the METHYLPYRROLIDONE solution of polyimide concentration 10 % by weight, the soltion viscosity of mensuration represents respectively in Table 1.
These polyimide solutions use respectively in embodiment 1 ~ 16 and 28 afterwards and comparative example 1 ~ 4.
Synthesis example 12 ~ 17
The diamines of the amount shown in table 1 and tetracarboxylic dianhydride are joined in METHYLPYRROLIDONE with this order, form the solution of monomer concentration 20 % by weight, react 4 hours at 60 DEG C, obtain the solution containing polyamic acid (PA-12) ~ (PA-17) respectively.Get each solution, add METHYLPYRROLIDONE for a small amount of point, form the solution of polyamic acid concentration 10 % by weight, the soltion viscosity of mensuration represents in Table 1.
These polyamic acid solutions use respectively in embodiment 29 ~ 35 afterwards.
Synthesis example 18 and 19
The diamines of the amount shown in table 1 and tetracarboxylic dianhydride are joined in METHYLPYRROLIDONE with this order, form the solution of monomer concentration 20 % by weight, react 4 hours at 60 DEG C, obtain the solution containing polyamic acid (PA-18) and (PA-19) respectively.Get each solution, add METHYLPYRROLIDONE for a small amount of point, form the solution of polyamic acid concentration 10 % by weight, the soltion viscosity of mensuration represents in Table 1.
In above-mentioned each polyamic acid solution, with the amido acid unit had relative to each polyamic acid of 1mol, after the pyridine adding mol ratio described in table 1 and diacetyl oxide, be heated to 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, the new METHYLPYRROLIDONE solvent exchange of intrasystem solvent, obtains respectively containing the polyimide (PI-18) of 16 % by weight and the solution of (PI-19).The imide rate of each polyimide contained in these polyimide solutions and representing in Table 1 respectively with the soltion viscosity of the METHYLPYRROLIDONE measured in solution of polyimide concentration 10 % by weight.These polyamic acid solutions use respectively in embodiment 36 afterwards and comparative example 9.
In addition, in table 1, the abbreviation of diamines and tetracarboxylic dianhydride is following implication respectively.
< diamines >
A-1, A-3, A-12, A-14 and A-16 are the above-mentioned synthesis example S-1 ~ compound (A-1) of S-5 synthesis, (A-3), (A-12), (A-14) and (A-16) respectively
D-1:3,5-diaminobenzoic acid
D-2: cholestane oxygen base-2,4-diaminobenzene
D-3:3,5-diaminobenzoic acid cholestane base ester
D-4: P-pHENYLENE dI AMINE
D-5:4,4 '-diaminodiphenyl-methane
D-6:N, N '-two (4-aminophenyl) piperazine
D-7: the compound shown in above-mentioned formula (D-1)
< tetracarboxylic dianhydride >
T-1:2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride
T-2:1,2,3,4-tetramethylene tetracarboxylic dianhydride
T-3:1,3,3a, 4,5,9a-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1,3-diketone
The preparation of < liquid crystal aligning agent and evaluation >
Embodiment 1
(I) preparation of liquid crystal aligning agent
(1) preparation of printing evaluation liquid crystal aligning agent
In the solution of the polyimide (PI-1) obtained containing the above-mentioned synthesis example 1 of 100 weight part, add METHYLPYRROLIDONE (NMP) and ethylene glycol butyl ether (BC), form the solution of solvent composition NMP: BC=70: 30 (weight ratio), solid component concentration 6.5 % by weight.This solution uses the metre filter in 1 μm, aperture, preparation printing evaluation liquid crystal aligning agent.
(2) preparation of liquid crystal display device manufacture liquid crystal aligning agent
Except when preparing above-mentioned printing evaluation liquid crystal aligning agent, make the solid component concentration of the solution before filtration be beyond 4.0 % by weight, and above-mentionedly similarly prepare liquid crystal display device manufacture liquid crystal aligning agent.
(II) evaluation of liquid crystal aligning agent
Two kinds of alignment agents of above-mentioned preparation are evaluated respectively by following method.Evaluation result is as shown in table 2.
(1) evaluation of printing
Use liquid crystal orientation film printing press (Japan's description printing (Co., Ltd.) manufactures), under the dripping quantity of liquid crystal aligning agent to anilox roll (anilox roll) is the condition of repetition 15 (about 0.15g), the printing evaluation liquid crystal aligning agent of above-mentioned preparation is coated on the transparent electrical pole-face with the glass substrate of the transparency electrode formed by ito film.Herein, the dripping quantity (repeating 30, about 0.3g) that the dripping quantity of above-mentioned liquid crystal aligning agent and the printing press of same model adopt usually is compared, and amount of liquid is few, is stricter printing condition.Substrate after coated with liquid crystal alignment agent heats 1 minute (prebake) at 80 DEG C, after desolventizing, at 180 DEG C, heats 10 minutes (curing afterwards), forms average film thickness film.This film multiplying power is the microscopic examination of 20 times, and research has is stained with and crawling invariably, when all not observing these two kinds, being evaluated as screening characteristics " well ", when observing any one, being evaluated as screening characteristics " bad ".In addition, in the alignment agent being evaluated as screening characteristics " well ", good especially to the rectilinearity of the outboard end of film, as screening characteristics " very good ".
To the film of above-mentioned formation, use contact pin type film thickness gauge (manufacture of KLA-Tencor company), measure the thickness of substrate center and the thickness in the position of the central authorities of 15mm from the outboard end of film respectively, the film thickness difference of both research.As long as this film thickness difference below, then think that film uniformity is good.In addition, as long as above-mentioned film thickness difference below, then think that film uniformity is very good.
(2) manufacture of vertical alignment-type liquid crystal display device
Use spinner, the one side liquid crystal display device manufacture liquid crystal aligning agent of above-mentioned preparation being coated in the glass substrate of thickness 1mm is arranged by the nesa coating that ito film is formed, on hot plate, at 80 DEG C, prebake 1 minute, then after at 220 DEG C, cure 15 minutes, form thickness film (liquid crystal orientation film).Repeat this operation, manufacture the substrate that two pieces (a pair) has liquid crystal orientation film.
The external margin with the face of liquid crystal orientation film of one piece in these a pair substrate, after coating adds the epoxy resin binder of the alumina balls of diameter 3.5 μm, tackiness agent, to make liquid crystal aligning face relative, solidifies by the crimping that overlaps.Then, from liquid crystal injecting port, in the gap of a pair substrate, (メ ルク company manufactures to fill negative type liquid crystal, MLC-6608) after, with acrylic acid or the like Photocurable adhesive encapsulated liquid crystals inlet, by the two sides laminating polaroid outside substrate, manufacture vertical alignment-type liquid crystal display device.
(3) sunproof evaluation
To the liquid crystal display device of above-mentioned manufacture, at 70 DEG C, after applying the voltage of 5V with the application time of 60 microseconds, the interval of 167 milliseconds, by (" VHR-1 " that strain) East Yang テ Network ニ カ manufactures measures from removing the voltage retention that is applied to after 167 milliseconds.Using numerical value now as initial voltage conservation rate (VHR bF).
Then, to the liquid crystal cell measured after initial voltage conservation rate, using with carbon arc is the Ageing machine of light source, rayed 5,000 hour.
To the liquid crystal cell after rayed, by with above-mentioned same method, again measure voltage retention.Using numerical value now as the voltage retention (VHR after rayed aF).
From the VHR of said determination bFand VHR aF, try to achieve the velocity of variation of the voltage retention before and after rayed.Their value represents respectively in table 2.When above-mentioned velocity of variation is less than 5.0%, Investigation on Photodegradation is " well ", and when above-mentioned velocity of variation is more than 5.0%, Investigation on Photodegradation is " bad ".
Embodiment 2 ~ 35 and comparative example 1 ~ 8
Except using the solution containing polymkeric substance shown in table 2 as containing polymers soln respectively, when table 2 is recorded, when preparing liquid crystal aligning agent, after adding NMP and BC in a polymer solution, add beyond the kind of table 2 record and the epoxy compounds of amount further, with embodiment 1 similarly, prepare liquid crystal aligning agent respectively, evaluate.Evaluation result is merged in table 2 and represents.In addition, in embodiment 28 ~ 35, the polymers soln of two kinds of the kind recorded by table 2 and amount is used in combination.
In addition, in table 2, the abbreviation of epoxy compounds is following implication respectively.
G-1:N, N, N, ' N '-four glycidyl group-4,4 '-diaminodiphenyl-methane
G-2:N, N, N, ' N '-four glycidyl group-m-xylene base diamines
Table 2 evaluation result
Table 2 evaluation result (continued)
Table 2 evaluation result (continued)
Embodiment 36 and comparative example 9
(I) preparation of liquid crystal aligning agent
Except using the solution containing polymkeric substance shown in table 3 as containing polymers soln respectively, after adding NMP and BC in a polymer solution, add beyond the kind of table 3 record and the epoxy compounds of amount further, with embodiment 1 similarly, prepare printing evaluation liquid crystal aligning agent and liquid crystal display device manufacture liquid crystal aligning agent respectively.
(II) evaluation of liquid crystal aligning agent
(1) evaluation of printing
Use the printing evaluation liquid crystal aligning agent of above-mentioned preparation, and embodiment 1 similarly evaluates printing.Evaluation result is as shown in table 3.
(2) manufacture of TN type liquid crystal display device
Use spinner, the one side liquid crystal display device manufacture liquid crystal aligning agent of above-mentioned preparation being coated in the glass substrate of thickness 1mm is arranged by the nesa coating that ito film is formed, on hot plate, at 80 DEG C, prebake 1 minute, then after at 220 DEG C, cure 15 minutes, form average film thickness film.To this film, use the sander with the roller of the artificial silk cloth that reeled, at roller revolution 400rpm, bedplate moving speed 3cm/s, under the condition of fine hair press-in length 0.4mm, carry out grinding process.Then, by the substrate of film that has after this grinding process ultrasonic washing 1 minute in ultrapure water, in the cleaning oven of 100 DEG C dry 10 minutes, thus liquid crystal orientation film is formed on the transparent electrical pole-face of glass substrate.Repeat this operation, manufacture the substrate that two pieces (a pair) has liquid crystal orientation film.
The external margin with the face of liquid crystal orientation film of one piece in these a pair substrate, after coating adds the epoxy resin binder of the alumina balls of diameter 3.5 μm, tackiness agent, to make liquid crystal orientation film relative, solidifies by the crimping that overlaps.Then, from liquid crystal injecting port, in the gap of a pair substrate, after filling positive type liquid crystal (メ ルク company manufactures, MLC-6621), with acrylic acid or the like Photocurable adhesive encapsulated liquid crystals inlet, by the two sides laminating polaroid outside substrate, manufacture TN type liquid crystal display device.
(3) sunproof evaluation
To the liquid crystal display device of above-mentioned manufacture, and embodiment 1 similarly evaluates photostabilization.Evaluation result is as shown in table 3.
Table 3 evaluation result

Claims (8)

1. a liquid crystal aligning agent, is characterized in that: containing at least one polymkeric substance selected from the group be made up of polyamic acid and polyimide, wherein, this polymkeric substance intramolecular at least partially in there is following formula (A 0) shown in structure,
Formula (A 0) in, X is any one divalent group represented of following formula (X-1) ~ (X-4),
In formula (X-1) and (X-2), R iIto be carbonatoms be 1 ~ 4 alkyl, carboxyl or carbonatoms be the carboxyalkyl of 2 ~ 5,
R ito be hydrogen atom or carbonatoms be 1 ~ 4 alkyl, m be 1 or 2, n be 0 or 1.
2. the liquid crystal aligning agent described in claim 1, wherein aforementioned polymer is at least one polymkeric substance selected from the polyamic acid obtained by tetracarboxylic dianhydride and diamine reactant and the group formed by the polyimide that this polyamic acid dehydration closed-loop is formed, and this diamines comprises the compound shown in following formula (A)
In formula (A), X, R i, m and n respectively with above-mentioned formula (A 0) in definition identical.
3. the liquid crystal aligning agent described in claim 2, the X wherein in above-mentioned formula (A) is the divalent group of above-mentioned formula (X-1) ~ (X-3) shown in any one.
4. the liquid crystal aligning agent described in Claims 2 or 3, the R wherein in above-mentioned formula (X-1) and (X-2) iIit is carboxyl.
5. a liquid crystal display device, is characterized in that: have the liquid crystal orientation film that the liquid crystal aligning agent described in any one of Claims 1 to 4 is formed.
6. a polyamic acid, this polyamic acid is obtained by tetracarboxylic dianhydride and the diamine reactant comprising the compound shown in following formula (A),
In formula (A), X is any one divalent group represented of following formula (X-1) ~ (X-4),
In formula (X-1) and (X-2), R iIto be carbonatoms be 1 ~ 4 alkyl, carboxyl or carbonatoms be the carboxyalkyl of 2 ~ 5,
R ito be hydrogen atom or carbonatoms be 1 ~ 4 alkyl, m be 1 or 2, n be 0 or 1.
7. a polyimide, polyamic acid dehydration closed-loop is formed by this polyimide, and this polyamic acid is obtained by tetracarboxylic dianhydride and the diamine reactant comprising the compound shown in following formula (A),
In formula (A), X is any one divalent group represented of following formula (X-1) ~ (X-4),
In formula (X-1) and (X-2), R iIto be carbonatoms be 1 ~ 4 alkyl, carboxyl or carbonatoms be the carboxyalkyl of 2 ~ 5,
R ito be hydrogen atom or carbonatoms be 1 ~ 4 alkyl, m be 1 or 2, n be 0 or 1.
8. the compound shown in following formula (A),
In formula (A), X is divalent group that in following formula (X-1) and (X-4), any one represents,
In formula (X-1), R iIto be carboxyl or carbonatoms be 2 ~ 5 carboxyalkyl,
R ito be hydrogen atom or carbonatoms be 1 ~ 4 alkyl, m be 1 or 2, n be 0 or 1.
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