CN102250626B - Liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device - Google Patents

Liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device Download PDF

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CN102250626B
CN102250626B CN201110119321.XA CN201110119321A CN102250626B CN 102250626 B CN102250626 B CN 102250626B CN 201110119321 A CN201110119321 A CN 201110119321A CN 102250626 B CN102250626 B CN 102250626B
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liquid crystal
aligning agent
crystal aligning
formula
orientation film
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CN102250626A (en
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马场淳
内山克博
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JSR Corp
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    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • 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
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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
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    • 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
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    • 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
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    • 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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Abstract

The present invention relates to a kind of liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device.Even if when providing long-time continuous to run, the display quality that the deterioration etc. of electrical property also can be suppressed to cause reduces, and again operation time the liquid crystal orientation film easily peeled off, and be suitable as the liquid crystal aligning agent of the material forming this alignment films, and there is the liquid crystal display device of this liquid crystal orientation film.The present invention is a kind of liquid crystal aligning agent, and it comprises: at least one polymkeric substance selected in the group that [A] is made up of polyamic acid and polyimide, and the epoxy compounds containing imide ring shown in [B] following formula (I).

Description

Liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device
Technical field
The present invention relates to the liquid crystal aligning agent of the formation material being suitable as liquid crystal orientation film, the liquid crystal orientation film formed by this liquid crystal aligning agent and there is the liquid crystal display device of this liquid crystal orientation film.
Background technology
Liquid crystal display device owing to having the advantages such as little, the easy miniaturization of current consumption and panelized, so use in the purposes widely of picture liquid crystal indicator large from small-scale liquid crystal devices such as mobile telephones to LCD TV etc.
As the operational mode of liquid crystal indicator according to the change of the state of orientation of liquid crystal molecule, the known liquid crystal display device with the liquid crystal cell such as switch type (IPS type), vertical orientating type (VA type) in twisted nematic (TN type), super-twist nematic (STN type), face.In any one display format, the state of orientation of liquid crystal molecule is controlled by liquid crystal orientation film, so the character of liquid crystal aligning agent of liquid crystal orientation film and the material that becomes this liquid crystal orientation film can bring impact to the performance of liquid crystal display device character.
As the material of this liquid crystal aligning agent, such as in patent documentation 1 ~ 6, disclose the resin materials such as polyamic acid, polyimide, polymeric amide, polyester, the excellence such as affinity, thermotolerance, physical strength of the liquid crystal orientation film particularly formed by the liquid crystal aligning agent being material with polyamic acid or polyimide and liquid crystal, is used in liquid crystal display device in a large number.
But, in recent years, liquid crystal display device utilize range extension, even if require that long-time continuous is run, the liquid crystal display device that display quality also can not reduce, the liquid crystal display device being material with current polyamic acid or polyimide, when long-time continuous is run, due to heat or light, liquid crystal orientation film may be caused to be deteriorated, generation electrical property is deteriorated, the orientation of liquid crystal molecule is not good.In order to solve this problem, have developed the technology (with reference to Japan's No. 3799700 patent gazette, Japanese Unexamined Patent Publication 2008-299318 publication) that use comprises the liquid crystal aligning agent of multi-functional epoxy compound in a large number.
On the other hand, contain the pore of the film produced in the manufacturing process of liquid crystal orientation film, be coated with the substrate of the defect such as irregular, in order to reuse, peel off possibly film (following, also referred to as " again operation ".), in this again operation, require that liquid crystal orientation film has separability to substrate.But if use the liquid crystal aligning agent comprising above-mentioned polyfunctional epoxy group(ing) in a large number, then the crosslinking reaction of epoxy group(ing) time owing to curing, likely reduces the separability of liquid crystal orientation film during operation again.
In view of the situation, even if wish to develop long-time continuous when running, the display quality that the deterioration etc. of electrical property also can be suppressed to cause is low, and the liquid crystal orientation film easily peeled off when operation again.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Unexamined Patent Publication 4-153622 publication
[patent documentation 2] Japanese Laid-Open Patent Publication 60-107020 publication
[patent documentation 3] Japanese Laid-Open Patent Publication 56-91277 publication
[patent documentation 4] U.S. the 5th, 928, No. 733 patent gazettes
[patent documentation 5] Japanese Laid-Open Patent Publication 62-165628 publication
[patent documentation 6] Japanese Unexamined Patent Publication 11-258605 publication
[patent documentation 7] Japan No. 3799700 patent
[patent documentation 8] Japanese Unexamined Patent Publication 2008-299318 publication
Summary of the invention
The present invention proposes based on the problems referred to above, its object is to: even if when providing long-time continuous to run, the display quality that the deterioration etc. of electrical property also can be suppressed to cause reduces, and again operation time the liquid crystal orientation film easily peeled off, and be suitable as the liquid crystal aligning agent of the material forming this alignment films, and there is the liquid crystal display device of this liquid crystal orientation film.
The present invention proposed to solve the problem is a kind of liquid crystal aligning agent, and it comprises:
At least one polymkeric substance (following, also referred to as polymkeric substance [A]) selected in the group that [A] is made up of polyamic acid and polyimide, and
The epoxy compounds containing imide ring (following, also referred to as epoxy compounds [B]) shown in [B] following formula (I).
In formula (I), R ato be singly-bound or carbonatoms be 1 ~ 4 alkane two base.R bthe chain alkyl of divalent, the alicyclic hydrocarbon radical of divalent, the aromatic group of divalent, the heterocyclic radical of divalent or combine their formed group.N is the integer of 0 or 1.
This liquid crystal aligning agent by containing specific polymkeric substance [A] and epoxy compounds [B], can be formed: suppress the display quality that caused by electrical property deterioration etc. lowly, and again operation time the liquid crystal orientation film easily peeled off.
At least one selected in the group that above-mentioned formula (I) is preferably made up of the compound shown in following formula (I-1) and formula (I-2).
In formula (I-1) and formula (I-2), R aidentical with the definition of above-mentioned formula (I).R 1, R 2and R 3respective independence, for comprising-O-,-COO-, the carbonatoms of-OCO-is the straight-chain of 1 ~ 20 or the alkyl of branched.In addition, R 1and R 2, or R 1and R 2and R 3be interconnected, form part or all ring structure that can be substituted of hydrogen atom.N is the integer of 0 or 1.
By choosing above-mentioned formula (I) for specific compound, can be formed: suppress to cause display quality low by the deterioration etc. of electrical property, and again operation time the liquid crystal orientation film easily peeled off.
Above-mentioned polymkeric substance [A] is preferably by least one selected in polyamic acid and the group that formed by the polyimide that this polyamic acid dehydration closed-loop is formed, wherein polyamic acid uses tetracarboxylic dianhydride to synthesize, and this tetracarboxylic dianhydride comprises by 2, and 3,5-tricarboxylic cyclopentyl acetic acid dianhydride, 3,5,6-tri-carboxyl-2-carboxymethyl norbornane-2: 3,5: 6-dianhydride and 2,4, the at least one selected in the group that 6,8-tetracarboxylic two ring [3.3.0]-octane-2: 4,6: 8-dianhydride is formed.As tetracarboxylic dianhydride by using the polymkeric substance [A] of this specific compound synthesis, desired character can be shown further.
The R of above-mentioned formula (I) abe preferably first two base.In addition, in above-mentioned formula (I-1) and formula (I-2), R 1and R 2preferably be interconnected, form part or all phenyl ring that can be substituted of hydrogen atom.Epoxy compounds [B] by having above-mentioned ad hoc structure, can improve further electrical property and again operation time separability.
Liquid crystal display device of the present invention has the liquid crystal orientation film formed by this liquid crystal aligning agent.This liquid crystal display device is suitable for various device, such as, can use in the display unit such as clock and watch, pocket game machine, word processor, notebook computer, navigationsystem, field camera, portable information terminal, digital camera, mobile telephone, various watch-dog, LCD TV.
A kind of polymer composition, it comprises: at least one polymkeric substance selected in the group that [A] is made up of polyamic acid and polyimide, and the epoxy compounds containing imide ring shown in [B] following formula (I).
In formula (I), R ato be singly-bound or carbonatoms be 1 ~ 4 alkane two base.R bthe chain alkyl of divalent, the alicyclic hydrocarbon radical of divalent, the aromatic group of divalent, the heterocyclic radical of divalent or combine their formed group.N is the integer of 0 or 1.
The composition that this polymer composition is suitable as the formation of the liquid crystal aligning agent etc. of liquid crystal orientation film uses.In addition, the film formed by this polymer composition can also use as electronic material insulating film.
According to the present invention, can be formed: suppress to cause display quality low by the deterioration etc. of electrical property, and the liquid crystal orientation film easily peeled off when again peeling off.This liquid crystal display device is suitable for various device, such as, can use in the display unit such as clock and watch, pocket game machine, word processor, notebook computer, navigationsystem, field camera, portable information terminal, digital camera, mobile telephone, various watch-dog, LCD TV.
Embodiment
Below, embodiment of the present invention are described in detail.
< liquid crystal aligning agent >
Liquid crystal aligning agent of the present invention contains polymkeric substance [A] and epoxy compounds [B].This liquid crystal aligning agent, by containing specific polymkeric substance [A] and epoxy compounds [B], can be formed: suppress to cause display quality low by the deterioration etc. of electrical property, and the liquid crystal orientation film easily peeled off when again peeling off.In addition, only otherwise infringement effect of the present invention, this liquid crystal aligning agent can contain optional member.Below, polymkeric substance [A], epoxy compounds [B] and optional member are described in detail.
< polymkeric substance [A] >
The polymkeric substance [A] contained in liquid crystal aligning agent of the present invention is at least one polymkeric substance selected in the group be made up of polyamic acid and polyimide.Below, polyamic acid and polyimide are described in detail.
[polyamic acid]
Polyamic acid can be obtained by reacting by making tetracarboxylic dianhydride and diamine compound.
As tetracarboxylic dianhydride, such as aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic series tetracarboxylic dianhydride etc. can be listed.In addition, the tetracarboxylic dianhydride recorded in No. 2009-157556, Japanese Patent Application can also be used.These tetracarboxylic dianhydrides can two or more use alone or in combination.
As aliphatics tetracarboxylic dianhydride, such as fourth tetracarboxylic dianhydride etc. can be listed.
As ester ring type tetracarboxylic dianhydride, such as 1 can be listed, 2, 3, 4-ring fourth 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 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 [5.3.1.0 2,6] 11 carbon-3,5,8,10-tetraketones etc.
As aromatic series tetracarboxylic dianhydride, such as pyromellitic acid dianhydride etc. can be listed.
In these tetracarboxylic dianhydrides, preferred ester ring type tetracarboxylic dianhydride, aromatic series tetracarboxylic dianhydride, more preferably 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 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, 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, 1, 2, 3, 4-ring fourth tetracarboxylic dianhydride, pyromellitic acid dianhydride, particularly preferably 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride.As tetracarboxylic dianhydride, by using the polymkeric substance [A] synthesized by this specific compound, desired character can be shown further.
As the consumption of preferred tetracarboxylic dianhydride, relative to whole tetracarboxylic dianhydride, preferably containing more than 10mol%, be more preferably more than 20mol%, particularly preferably only use by 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride, 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, 1,2,3,4-ring fourth tetracarboxylic dianhydride form group in select more than one.
As diamine compound, such as aliphatie diamine, ester ring type diamines, diamino organo-siloxane, aromatic diamine etc. can be listed.In addition, the diamine compound recorded in No. 2009-157556, Japanese Patent Application can also be used.These diamine compounds can two or more use alone or in combination.
As aliphatie diamine, such as 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 diamino organo-siloxane, such as 1,3-bis-(3-aminopropyl)-tetramethyl disiloxane etc. can be listed.
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 benzene two isopropylidene) two (aniline), 4,4 '-(isophthalic two isopropylidene) two (aniline), Isosorbide-5-Nitrae-two (4-amino-benzene oxygen) benzene, 3,4-diamino-pyridine, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 3,6-diaminocarbazole, DAP, 2,4-di-amino-pyrimidine, 3,6-proflavin, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, Isosorbide-5-Nitrae-two (4-aminophenyl) piperazine, 3,5-diaminobenzoic acid, 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, tetradecyloxyaniline-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, tetradecyloxyaniline-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, 3,6-bis-(4-aminobenzoic acyl-oxygen base) cholestane, 3,6-bis-(4-amino-benzene oxygen) cholestane, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethylbenzoyl oxygen base) cyclohexyl-3,5-diaminobenzoic acid ester, 1,1-bis-(4-((aminophenyl) methyl) phenyl)-4-butyl cyclohexane, 1,1-bis-(4-((aminophenyl) methyl) phenyl)-4-heptylcyclohexane, 1,1-bis-(4-((amino-benzene oxygen) methyl) phenyl)-4-heptylcyclohexane, 1,1-bis-(4-((aminophenyl) methyl) phenyl)-4-(4-heptyl cyclohexyl) hexanaphthene, 2,4-diamino-N, N-diallyl aniline, 4-aminobenzyl amine, compound etc. shown in 3-aminobenzyl amine and following formula (1).
In formula (1), X to be carbonatoms be 1 ~ 3 alkylidene group ,-O-,-COO-or-OCO-.A is 0 or 1.B is the integer of 0 ~ 2.C is the integer of 1 ~ 20.
In above-mentioned formula (1), as C ch 2c+1the object lesson of base, can list the methyl of such as straight-chain or branched, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl etc.
As the diamine compound shown in above-mentioned formula (1), the such as compound etc. shown in following formula (1-1) ~ (1-5) can be listed.
In above-mentioned formula (1), be 0 when a and b is preferably different.
In these diamine compounds, optimization aromatic diamines, diamino organo-siloxane, more preferably Ursol D, 4,4 '-diaminodiphenyl-methane, 2,2 '-dimethyl-4,4 '-benzidine, 3,6-bis-(4-aminobenzoic acyl-oxygen base) cholestane, 3,5-diaminobenzoic acid cholestane base ester, cholestane oxygen base-2,4-diaminobenzene, 1,3-bis-(3-aminopropyl)-tetramethyl disiloxane.
[synthesis of polyamic acid]
As the usage ratio of the tetracarboxylic dianhydride used in the building-up reactions of polyamic acid and diamine compound, relative to the amino contained in 1 equivalent diamine compound, anhydride group preferably 0.2 equivalent ~ 2 equivalent of tetracarboxylic dianhydride, more preferably 0.3 equivalent ~ 1.2 equivalent.
The building-up reactions of polyamic acid is preferably carried out in organic solvent.Be preferably-20 DEG C ~ 150 DEG C as temperature of reaction, be more preferably 0 DEG C ~ 100 DEG C.Be preferably 0.1 hour ~ 24 hours as the reaction times, be more preferably 0.5 hour ~ 12 hours.
As organic solvent, as long as the polyamic acid that can dissolve synthesis just has no particular limits, such as aprotic polar solvent, phenol and derivative thereof, alcohols, ethers, halogenated hydrocarbon, hydro carbons etc. can be listed.These organic solvents can be used alone one or use and use two or more together.
As aprotic polar solvent, such as amides, ketone, ester class, other aprotic polar solvent can be listed.
As amides, such as METHYLPYRROLIDONE (NMP), DMF, N,N-dimethylacetamide etc. can be listed.
As ketone, such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone etc. can be listed.
As ester class, such as ethyl lactate, n-Butyl lactate, methyl acetate, ethyl acetate, butylacetate, methoxy methyl propionate, ethoxyl ethyl propionate, oxalic acid diethyl ester, diethyl malonate, gamma-butyrolactone, propionic acid isopentyl ester, isopropylformic acid isopentyl ester etc. can be listed.
As other aprotic polar solvent, such as dimethyl sulfoxide (DMSO), tetramethyl-urea, HMPA etc. can be listed.
As phenol derivatives, such as meta-cresol, xylenol, halogenated phenol etc. can be listed.
As alcohols, such as methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, BDO, triglycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, TC etc. can be listed.
As ethers, such as Anaesthetie Ether, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethyl ether, ethylene glycol bisthioglycolate n-propyl ether, ethylene glycol bisthioglycolate isopropyl ether, ethylene glycol bisthioglycolate n-butyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether acetic ester, TC acetic ester, tetrahydrofuran (THF), diisoamyl ether etc. can be listed.
As halogenated hydrocarbon, such as methylene dichloride, 1,2-ethylene dichloride, Isosorbide-5-Nitrae-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene etc. can be listed.
As hydro carbons, such as hexane, heptane, octane, benzene,toluene,xylene etc. can be listed.
In these organic solvents, preferred aprotic polar solvent, more preferably NMP, gamma-butyrolactone.
Relative to tetracarboxylic dianhydride and the total amount (b) of the diamine compound total amount (a+b) with the consumption (a) of organic solvent, the consumption (a) as organic solvent is preferably 0.1 % by weight ~ 50 % by weight.
The polyamic acid solution obtained after reaction can be directly used in prepares liquid crystal aligning agent, after the polyamic acid that also can comprise 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.As the separation method of polyamic acid, can list and such as reaction soln be injected a large amount of poor solvents, the method for the precipitate that the lower drying of decompression obtains; The method etc. of reaction soln is distillated by vaporizer decompression.As the process for purification of polyamic acid, can list and isolated polyamic acid is dissolved in organic solvent again, the method separated out in poor solvent; Repeat one or many distillates the step of organic solvent etc. method by vaporizer decompression.
When synthesizing polyamides acid, suitable molecular weight regulator can be used, with tetracarboxylic dianhydride together with diamine compound, synthesize end modified type polymkeric substance.By forming this end modified type polymkeric substance, the coating (printing) that effect of the present invention ground improves liquid crystal aligning agent further can not be damaged.
As molecular weight regulator, such as sour single acid anhydride, monoamine compound, monoisocyanate compound etc. can be listed.
As acid list acid anhydride, such as maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide etc. can be listed.
As monoamine compound, such as aniline, cyclo-hexylamine, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octylamine etc. can be listed.
As monoisocyanate compound, such as phenyl isocyanate, isocyanic acid naphthyl ester etc. can be listed.
As the usage ratio of molecular weight regulator, relative to making tetracarboxylic dianhydride and diamines amount to 100 mass parts, being preferably below 20 mass parts, being more preferably below 10 mass parts.
[polyimide]
The amido acid structure dehydration closed-loop imidization manufacture of polyimide by above-mentioned polyamic acid is had.
Polyimide can be the complete imide compound of the amido acid structure fully dehydrating closed loop had as the polyamic acid of its precursor; 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.Here, a part for imide ring can be different imide ring.
The imide rate of polyimide is preferably more than 30%, is more preferably 40% ~ 99%.Described 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.In addition, imide rate puts in pure water by the solution of polyimide, reclaims the precipitation obtained, at room temperature after drying under reduced pressure, be dissolved in heavy-hydrogenated dimethyl sulfoxide (DMSO), using tetramethylsilane as primary standard, measure from room temperature 1h-NMR obtains 1h-NMR spectrogram, is tried to achieve by the formula shown in following formula (2).
Imide rate (%)={ 1-(A 1/ A 2) × α } × 100 (2)
In formula (2), A 1it is the peak area (10ppm) of the proton from NH base.A 2it is the peak area from other proton.α is the ratio of number relative to the proton of the NH base in a polyamic acid of other proton.
As the synthetic method of polyimide, the method that such as (i) heats polyamic acid can be listed, (ii) polyamic acid is dissolved in organic solvent, dewatering agent and dehydration closed-loop catalyzer is added in this solution, the method that heats as required (following, also referred to as " method (ii)) etc. reacts the method for carrying out by the dehydration closed-loop of polyamic acid.In these methods, preferred method (ii).
As the dewatering agent in method (ii), the acid anhydrides such as such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride can be listed.
As the consumption of dewatering agent, suitably select according to desired imide rate, relative to the amido acid structure of 1mol polyamic acid, be preferably 0.01mol ~ 20mol.
As the dehydration closed-loop catalyzer in method (ii), the tertiary amines such as such as pyridine, trimethylpyridine, lutidine, triethylamine can be listed.
As the consumption of dehydration closed-loop catalyzer, relative to the dewatering agent that 1mol contains, be preferably 0.01mol ~ 10mol.
As the organic solvent used in method (ii), can list the organic solvent etc. identical with following organic solvent, this organic solvent illustrates at the solvent such as used as synthesizing polyamides acid.
Be preferably 0 DEG C ~ 180 DEG C as the temperature of reaction in method (ii), be more preferably 10 DEG C ~ 150 DEG C.Be preferably 1.0 hours ~ 120 hours as the reaction times, be more preferably 2.0 hours ~ 30 hours.By making reaction conditions be above-mentioned scope, dehydration closed-loop sufficient reacting carries out, and the molecular weight of the polyimide obtained can be made suitable.
In 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.As from reaction soln removing dewatering agent and the method for dehydration closed-loop catalyzer, can carry out according to known method, can list: such as the separation method of polyamic acid and process for purification and illustrative same method etc.
Concentration as the polymkeric substance obtained above [A] is the soltion viscosity in the solution of 10 quality %, is preferably 20mPas ~ 800mPas, is more preferably 30mPas ~ 500mPas.The soltion viscosity (mPas) of polymkeric substance is the polymers soln to the concentration 10 quality % using gamma-butyrolactone or NMP to prepare, and uses E type rotational viscosimeter, the value measured at 25 DEG C.
< epoxy compounds [B] >
The epoxy compounds [B] contained in liquid crystal aligning agent of the present invention is the epoxy compounds containing imide ring shown in above-mentioned formula (I).
In above-mentioned formula (I), R ato be singly-bound or carbonatoms be 1 ~ 4 alkane two base.R bthe chain alkyl of divalent, the alicyclic hydrocarbon radical of divalent, the aromatic group of divalent, the heterocyclic radical of divalent or combine their formed group.N is the integer of 0 or 1.
Be the alkylidene group of 1 ~ 4 as carbonatoms, such as methylene radical, ethylidene, propylidene, butylidene etc. can be listed.Among them, preferred singly-bound or methylene radical.
Above-mentioned formula (I) is preferably selected from least one of the group be made up of the compound shown in above-mentioned formula (I-1) and formula (I-2).By choosing above-mentioned formula (I) for specific compound, can be formed: suppress to cause display quality low by the deterioration etc. of electrical property, and again operation time the liquid crystal orientation film easily peeled off.
In above-mentioned formula (I-1) and formula (I-2), R aidentical with the definition of above-mentioned formula (I).R 1, R 2and R 3respective independence, be can comprise-O-,-COO-, the carbonatoms of-OCO-is the straight-chain of 1 ~ 20 or the alkyl of branched.In addition, R 1and R 2, or R 1and R 2and R 3can be interconnected, form part or all ring structure be substituted of hydrogen atom.N is the integer of 0 or 1.
Be the straight-chain of 1 ~ 20 or the alkyl of branched as carbonatoms, can list: such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl etc.Among them, preferable methyl, ethyl, propyl group.
In addition, the R in above-mentioned formula (I-1) and (I-2) 1, R 2and R 3r can be formed 1and R 2or R 1and R 2and R 3be interconnected, form part or all ring structure be substituted of hydrogen atom.As ring structure, aromatic ring, aliphatics ring, heterocycle, condensed ring can be listed and combine the ring of their formation.Among them, preferred aromatic ring, more preferably phenyl ring, naphthalene nucleus.
As the substituting group that the ring structure that can be substituted has, such as halogen atom, hydroxyl, nitro, cyano group, alkyl, carboxyl, cycloalkyl, aryl, alkoxyl group, acyl group, acyloxy, alkoxy carbonyl, cyanoalkyl, haloalkyl etc. can be listed.Among them, preferred halogen atom, alkyl, cyanoalkyl, alkoxyl group, be more preferably fluorine atom, chlorine atom, bromine atoms, methyl, cyano methyl, methoxyl group.
N in above-mentioned formula (I-1) and (I-2) is the integer of 0 or 1.N preferably 0.
The R of above-mentioned formula (I) abe preferably first two base.In addition, in above-mentioned formula (I-1) and formula (I-2), R 1and R 2preferably be interconnected, form part or all phenyl ring that can be substituted of hydrogen atom.Epoxy compounds [B] by having above-mentioned ad hoc structure, can improve further electrical property and again operation time separability.
As the compound shown in above-mentioned formula (I-1) and (I-2), can list: the such as compound shown in following formula (I-1-1) ~ (I-1-16) and (I-2-1) ~ (I-2-14).
In above-mentioned formula (I-1-1) ~ (I-1-16) and (I-2-1) ~ (I-2-14), particularly preferably (I-1-1), (I-1-4), (I-1-15), (I-1-16), (I-2-6), most preferably (I-1-4), (I-2-6).
In addition, the epoxy group(ing) in formula (I) can be substituted.Alternatively base, can list such as halogen atom, hydroxyl, nitro, cyano group, alkyl, carboxyl, cycloalkyl, aryl, alkoxyl group, acyl group, acyloxy, alkoxy carbonyl, cyanoalkyl, haloalkyl etc.
As the synthetic method of this epoxy compounds [B], there is no particular limitation, can combine existing known method and carry out.In addition, the product of market sale can also be used.
Proportional as containing of epoxy compounds [B], relative to 100 mass parts polymkeric substance [A], be preferably 0.1 mass parts ~ 50 mass parts, be more preferably 1 mass parts ~ 40 mass parts, be particularly preferably 3 mass parts ~ 30 mass parts.By make epoxy compounds [B] containing proportional for above-mentioned scope, even if when one can be provided to form long-play, the liquid crystal orientation film of the liquid crystal display device that the deterioration of electrical property also less, display quality is high, can provide the liquid crystal aligning agent that the separability during operation again of the film of formation is good simultaneously.
< optional member >
Optionally composition, can list such as functional silanes compound etc.
[functional silanes compound]
Functional silanes compound, can use the fusible object of substrate surface based on improving the liquid crystal orientation film formed.
As functional silanes compound, can list: such as 3-TSL 8330, 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, N-benzyl-3-TSL 8330, 9-trimethoxysilyl-3,6-diaza methyl pelargonate, 9-triethoxysilyl-3,6-diaza methyl pelargonate, 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.
As the usage ratio of functional silanes compound, relative to 100 mass parts polymkeric substance [A], be preferably below 2 mass parts, be more preferably 0.02 mass parts ~ 0.2 mass parts.
The preparation method > of < liquid crystal aligning agent
This liquid crystal aligning agent is described above, containing polymkeric substance [A] and epoxy compounds [B], can contain optional member as required, preferably by each component dissolves in organic solvent, be allocated as composition.
As organic solvent, NMP 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.These organic solvents can be used alone one or use two or more together.
The solid component concentration of liquid crystal aligning agent of the present invention, the quality of the whole compositions beyond the solvent namely in liquid crystal aligning agent, occupies the ratio of the all-mass of liquid crystal aligning agent, considers the selection such as viscosity, volatility, is preferably 1 quality % ~ 10 quality %.When solid component concentration is less than 1 quality %, the thickness of the liquid crystal orientation film formed by this liquid crystal aligning agent is too small, possibly cannot obtain good liquid crystal orientation film.On the other hand, if solid component concentration is more than 10 quality %, then the thickness of film is excessive, possibly cannot obtain good liquid crystal orientation film, or the viscosity of liquid crystal aligning agent increases, and coating property may be not enough.Scope as preferred solid component concentration is different according to the method adopted during coating of liquid crystalline alignment agent on substrate.Such as, when using spin-coating method to carry out, solid component concentration is preferably 1.5 quality % ~ 4.5 quality %.When being undertaken by print process, preferred solid component concentration is 3 quality % ~ 9 quality %, and soltion viscosity is 12mPas ~ 50mPas thus.When using ink jet method to carry out, preferred solid component concentration is the scope of 1 quality % ~ 5 quality %, and thus, soltion viscosity is the scope of 3mPas ~ 15mPas.
Be preferably 10 DEG C ~ 50 DEG C as temperature during this liquid crystal aligning agent of preparation, be more preferably 20 DEG C ~ 30 DEG C.
< liquid crystal orientation film >
Liquid crystal orientation film of the present invention is formed by this liquid crystal aligning agent.Therefore, this liquid crystal orientation film can suppress to cause display quality low by the deterioration etc. of electrical property, and again operation time easily peel off.
The formation method > of < liquid crystal orientation film
Liquid crystal orientation film of the present invention, by being coated with this liquid crystal aligning agent on substrate, then heating coated face, substrate forms film, display format desirably, carry out friction treatment formation further.
When manufacture display format is the liquid crystal display device of TN type, STN type or VA type, 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, be coated with this liquid crystal aligning agent respectively, then, by heating each coated face, film is formed.
As substrate, can list: such as comprise the glass baseplate such as float glass, soda-lime glass, the transparency carrier etc. of the plastic basis materials such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate (ester ring type alkene).
As the nesa coating arranged in the one side of substrate, can list by stannic oxide (SnO 2) formed NESA film (registered trademark of PPG company of the U.S.), by indium oxide-tin oxide (In 2o 3-SnO 2) ito film etc. that formed.
As the method obtaining the nesa coating forming pattern, can list: such as formed without after figure nesa coating, be formed the method for pattern by photoetch; When forming nesa coating, use the method etc. with the mask of desired pattern.During coating of liquid crystalline alignment agent, in order to make the cohesiveness of substrate surface and nesa coating and film better, on the face of the formation film of substrate surface, functional silanes compound, functionality titanium compound etc. can be coated with in advance and carry out pre-treatment.
After this liquid crystal aligning agent of coating, based on preventing the objects such as liquid drip, preferably carry out preheating (prebake).Temperature as prebake is preferably 30 DEG C ~ 200 DEG C, is more preferably 40 DEG C ~ 150 DEG C, is particularly preferably 40 DEG C ~ 100 DEG C.As the time of prebake, be preferably 0.25 minute ~ 10 minutes, more preferably 0.5 minute ~ 5 minutes.
Then, completely except desolventizing, based on as required by the object of polyamic acid hot-imide, carry out firing (curing afterwards).As after the temperature of curing be preferably 80 DEG C ~ 300 DEG C, be more preferably 120 DEG C ~ 250 DEG C.As after time of curing, be preferably 5 minutes ~ 200 minutes, more preferably 10 minutes ~ 100 minutes.
The thickness of the film of such formation is preferably 10nm ~ 500nm, is more preferably 10nm ~ 200nm.
When manufacture display format is IPS type liquid crystal display device, in the conducting film forming surface of substrate being provided with the nesa coating forming interdigitated electrode structure pattern, do not arrange in the one side of subtend substrate of conducting film, this liquid crystal aligning agent is coated with preferably by adherography, spin-coating method or ink jet printing method, then, film is formed by heating each coated face.The preferred thickness of the heating means after the formation patterning method of the material of substrate, the material of nesa coating, nesa coating, the pre-treatment of substrate and coating of liquid crystalline alignment agent, the film of formation and to manufacture display format be cited identical in the situation of the liquid crystal display device of TN type, STN type or VA type.
When display format is the liquid crystal display device of VA type, the film as above formed directly can be used as liquid crystal orientation film, use after also can carrying out friction treatment as described below as required.
Display format, when manufacturing the liquid crystal display device beyond VA type, by carrying out friction treatment to the film as above formed, forms liquid crystal orientation film.Friction treatment 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 friction.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: it is such that such as Japanese Unexamined Patent Publication 6-222366 publication or Japanese Unexamined Patent Publication 6-281937 publication are recorded, 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 thus; And as recorded in Japanese Unexamined Patent Publication 5-107544 publication, after etchant resist is formed to the part on liquid crystal orientation film surface, after friction treatment is carried out in the direction different with friction treatment before, the process of removing etchant resist.
< liquid crystal display device >
Liquid crystal display device of the present invention has this liquid crystal orientation film.This liquid crystal display device is suitable for various device, such as, can use in the display unit such as clock and watch, pocket game machine, WP, notebook computer, navigationsystem, camcorders, portable information terminal, digital camera, mobile telephone, various watch-dog, LCD TV.
The formation method > of < liquid crystal display device
Liquid crystal display device of the present invention such as can manufacture as follows.Prepare two pieces and form the substrate of these liquid crystal orientation films, configure liquid crystal, manufacture liquid crystal cell by between two pieces of substrates configure in subtend.Here, when carrying out friction treatment to film, two pieces of substrate subtend configurations to make the frictional 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.
As the method that first method is known at present, first in order to make each liquid crystal orientation film subtend arrange, (following by gap, also referred to as " box gap "), by two pieces of substrate subtend configurations, sealing agent is used the peripheral part of two pieces of substrates to be 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 called ODF (to instil, One Drop Fill) method of mode, prescribed position on a substrate in the two pieces of substrates forming liquid crystal orientation film, be coated with such as ultraviolet light curable sealing material, after then dripping liquid crystal on liquid crystal aligning face, another substrate make liquid crystal orientation film subtend of fitting, then, in whole irradiating ultraviolet light of substrate, make sealant cures, manufacture liquid crystal cell.
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 during removing Liquid crystal pour.Then, by the outer surface laminating polaroid at liquid crystal cell, this liquid crystal display device can be obtained.
As sealing agent, can list and such as contain as the alumina balls of partition and the epoxy resin etc. of solidifying agent.
As liquid crystal, such as nematic liquid crystal, dish-like liquid crystal etc. can be listed.Among them, preferred nematic liquid crystal.When for VA type liquid crystal cell, preferably there is the nematic liquid crystal of negative dielectric anisotropy.As this liquid crystal, 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 listed.During for TN type liquid crystal cell or STN type liquid crystal cell, preferably there is the nematic liquid crystal of positive dielectric anisotropy.As this liquid crystal, 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 listed.In addition, in above-mentioned liquid crystal, cholesterol liquid crystals such as using such as chlorination beta-cholestanol, Cholesteryl pelargonate, cholesterol carbonic ether can be added further; With the chiral reagent that " C-15 ", " CB-15 " (メ Le ケ 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, the polaroid while clamp absorption iodine with cellulose acetate protective membrane, being called the polaroid that the light polarizing film of " H film " is formed or being formed by H film itself.
< polymer composition >
Polymer composition of the present invention comprises at least one polymkeric substance selected in the group that [A] be made up of polyamic acid and polyimide, and the epoxy compounds containing imide ring shown in [B] above-mentioned formula (I).The composition such as liquid crystal aligning agent that this polymer composition is suitable as the formation of liquid crystal orientation film uses.In addition, the film formed by this polymer composition can also use as electronic material insulating film.
In above-mentioned formula (I), R ato be singly-bound or carbonatoms be 1 ~ 4 alkane two base.R bthe chain alkyl of divalent, the alicyclic hydrocarbon radical of divalent, the aromatic group of divalent, the heterocyclic radical of divalent or combine their formed group.N is the integer of 0 or 1.
[embodiment]
Below, based on embodiment, describe the present invention, but the record of this embodiment is not the explanation of limitation of the invention.
The synthesis > of < polyamic acid
[synthesis example 1]
Using the 98g (0.50mol) 1 as tetracarboxylic dianhydride, 2,3,4-ring fourth tetracarboxylic dianhydride and 109g (0.50mol) pyromellitic acid dianhydride and the 198g (1.0mol) 4 as diamine compound, 4 '-tetramethyl triaminotriphenyl methane NH2 is dissolved in the mixed solvent formed by the gamma-butyrolactone of the NMP of 230g and 2,060g, react at 40 DEG C after 3 hours, add the gamma-butyrolactone of 1,350g, obtain the solution containing 10 quality % polyamic acids (PA-1).The soltion viscosity of this solution is 118mPas.
[synthesis example 2]
Using the 196g (1.0mol) 1 as tetracarboxylic dianhydride, 2,3,2 of 4-ring fourth tetracarboxylic dianhydride and the 212g (1.0mol) as diamine compound, 2 '-dimethyl-4,4 '-benzidine, be dissolved into by the NMP of 370g and 3, in the mixed solvent of the gamma-butyrolactone formation of 300g, react 3 hours at 40 DEG C, obtain the solution containing polyamic acid (PA-2).The soltion viscosity of this solution is 154mPas.
The synthesis > of < polyimide
[synthesis example 3]
Using the 224g (1.0mol) 2 as tetracarboxylic dianhydride, 3,5-tricarboxylic cyclopentyl acetic acid dianhydride and as 106g (0.985mol) Ursol D of diamine compound and 7.8g (0.015mol) 3,5-diaminobenzoic acid cholestane base ester is dissolved into 3, in the NMP of 042g, react 6 hours at 60 DEG C.The soltion viscosity of the polyamic acid solution obtained is 181mPas.Then, in the polyamic acid solution of gained, add the NMP of 3,380g, add 395g pyridine and 306g diacetyl oxide, at 110 DEG C, carry out 4 hours dehydration closed-loops.After imidization reaction, the new gamma-butyrolactone solvent exchange of intrasystem solvent, by pyridine, diacetyl oxide except going to system.Like this, the solution of the polyimide (PI-1) containing 15 quality % imide rates about 95% is obtained.Divide the polyimide solution getting gained on a small quantity, add gamma-butyrolactone, form the solution of polyimide concentration 10 quality %, the soltion viscosity of mensuration is 102mPas.
[synthesis example 4]
Using the 110g (0.50mol) 2 as tetracarboxylic dianhydride, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride and 160g (0.50mol) 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, and as 94g (0.87mol) Ursol D of diamine compound, 25g (0.10mol) 1, 3-bis-(3-aminopropyl) tetramethyl disiloxane and 9.6g (0.015mol) 3, 6-bis-(4-aminobenzoic acyl-oxygen base) cholestane, as 8.1g (0.030mol) octadecylamine of monoamine, be dissolved in the NMP of 960g, react 6 hours at 60 DEG C.Divide the polyamic acid solution getting gained on a small quantity, adding NMP, to the measured in solution viscosity of solid component concentration 10%, is 58mPas.Then, in the polyamic acid solution of gained, add the NMP of 2,700g, add 400g pyridine and 410g diacetyl oxide, at 110 DEG C, carry out 4 hours dehydration closed-loops.After imidization reaction, the new gamma-butyrolactone solvent exchange of intrasystem solvent, by pyridine, diacetyl oxide except going to system.Like this, the solution of the polyimide (PI-2) containing 15 quality % imide rates 95% of having an appointment is obtained.Divide the polyimide solution getting gained on a small quantity, add gamma-butyrolactone, form the solution of polyimide concentration 10 quality %, the soltion viscosity of mensuration is 72mPas.
[synthesis example 5]
Using the 226g (1.0mol) 2 as tetracarboxylic dianhydride, 3,5-tricarboxylic cyclopentyl acetic acid dianhydride and 76g (0.80mol) Ursol D, 53g (0.10mol) 3 as diamine compound, 5-diaminobenzoic acid cholestane base ester and 100g (0.2mol) cholestane oxygen base-2,4-diaminobenzene is dissolved into 1, in the NMP of 820g, react 6 hours at 60 DEG C.Divide the polyamic acid solution getting gained on a small quantity, adding NMP, to the measured in solution viscosity of solid component concentration 10%, is 80mPas.Then, in the polyamic acid solution of gained, add the NMP of 4,225g, add 104g pyridine and 134g diacetyl oxide, at 110 DEG C, carry out 4 hours dehydration closed-loops.After imidization reaction, the new nmp solvent displacement of intrasystem solvent, by pyridine, diacetyl oxide except going to system.Like this, the solution of the polyimide (PI-3) containing 15 quality % imide rates 66% of having an appointment is obtained.Divide the polyimide solution getting gained on a small quantity, add NMP, form the solution of polyimide concentration 10 quality %, the soltion viscosity of mensuration is 98mPas.
[synthesis example 6]
Using the 224g (1.0mol) 2 as tetracarboxylic dianhydride, 3,5-tricarboxylic cyclopentyl acetic acid dianhydride and as 87g (0.80mol) Ursol D of diamine compound and 99g (0.20mol) cholestane oxygen base-2,4-diaminobenzene is dissolved into 1, in the NMP of 848g, react 6 hours at 60 DEG C.Divide the polyamic acid solution getting gained on a small quantity, adding NMP, to the measured in solution viscosity of solid component concentration 10%, is 120mPas.Then, in the polyamic acid solution of gained, add the NMP of 3,809g, add 79g pyridine and 102g diacetyl oxide, at 110 DEG C, carry out 4 hours dehydration closed-loops.After imidization reaction, the new nmp solvent displacement of intrasystem solvent, by pyridine, diacetyl oxide except going to system.Like this, the solution of the polyimide (PI-4) containing 15 quality % imide rates 49% of having an appointment is obtained.Divide the polyimide solution getting gained on a small quantity, add NMP, form the solution of polyimide concentration 10 quality %, the soltion viscosity of mensuration is 155mPas.
[synthesis example 7]
Using the 224g (1.0mol) 2 as tetracarboxylic dianhydride, 3,5-tricarboxylic cyclopentyl acetic acid dianhydride and 76g (0.70mol) Ursol D, 40g (0.20mol) 4 as diamine compound, 4 '-diaminodiphenyl-methane and 50g (0.10mol) cholestane oxygen base-2,4-diaminobenzene, be dissolved in the NMP of 1,556g, react 6 hours at 60 DEG C.Divide the polyamic acid solution getting gained on a small quantity, adding NMP, to the measured in solution viscosity of solid component concentration 10%, is 133mPas.Then, in the polyamic acid solution of gained, add the NMP of 3,614g, add 79g pyridine and 102g diacetyl oxide, at 110 DEG C, carry out 4 hours dehydration closed-loops.After dehydration closed-loop reaction, the new NMP of intrasystem solvent carries out solvent exchange (by this operation, by use in imidization reaction pyridine, diacetyl oxide is except going to system), obtaining is the solution of the polyimide (PI-5) of 46% containing 15 quality % imide rates of having an appointment.Divide the polyimide solution getting gained on a small quantity, add NMP, form the solution of polyimide concentration 10 quality %, the soltion viscosity of mensuration is 133mPas.
The preparation > of < liquid crystal aligning agent (use of TN type liquid crystal display device)
[embodiment 1]
As the solution containing polymeric amide (PA-1) of polymkeric substance [A] and will mix containing the solution of polyimide (PI-1), and make polyamic acid (PA-1): polyimide (PI-1)=80: 20 (mass ratio), add gamma-butyrolactone wherein, NMP and ethylene glycol monobutyl ether, then to amount to 100 mass parts relative to polymkeric substance [A], add the formula (I-1-1) being equivalent to 10 mass parts, this formula (I-1-1) is the formula exemplified for example with above-mentioned formula (I-1) as epoxy compounds [B], abundant stirring, formation solvent composition is gamma-butyrolactone: NMP: ethylene glycol list n-butyl ether=71: 17: 12 (mass ratioes), the solution of solid component concentration 3.5 quality %.This solution uses the metre filter in 1 μm, aperture, prepares liquid crystal aligning agent (S-1).
[embodiment 2 ~ 13, comparative example 1 ~ 12]
The kind of polymkeric substance [A] and epoxy compounds [B] and usage quantity thereof is made to distinguish as shown in table 1, similarly operate with embodiment 1, prepare liquid crystal aligning agent (S-2) ~ (S-13) and (CS-1) ~ (CS-12), using them as embodiment 2 ~ 13, comparative example 1 ~ 12.
In addition, in comparative example, and epoxy compounds [B] is corresponding and (G-1) ~ (G-3) that be that use is respectively as follows.In addition, (I-1-4), (I-1-15), (I-1-16) in table 1, (I-2-6) refer to the compound that the example as above-mentioned formula (I-1) and formula (I-2) is enumerated respectively.
G-1:N, N, N, ' N '-four glycidyl group-m-xylene base diamines
G-2:N, N, N, ' N '-four glycidyl group-4,4 '-diaminodiphenyl-methane
G-3: polyoxyethylene (5) phenyl glycidyl ether (Na ガ セ ケ system テ Star ケ ス company, EX145)
The preparation > of < liquid crystal aligning agent (use of VA type liquid crystal display device)
[embodiment 14]
As polymkeric substance [A] containing polyimide (PI-3) solution in, add NMP and ethylene glycol list n-butyl ether, then, 100 mass parts are amounted to relative [A] polymkeric substance, add be equivalent to 10 mass parts above-mentioned (I-1-1) as epoxy compounds [B], abundant stirring, forming solvent composition is NMP: ethylene glycol list n-butyl ether=60: 40 (mass ratioes), solid component concentration is the solution of 3.5 quality %.This solution uses the metre filter in 1 μm, aperture, prepares liquid crystal aligning agent (S-14).
[embodiment 15 ~ 27, comparative example 13 ~ 25]
The kind of polymkeric substance [A] and epoxy compounds [B] and usage quantity thereof is made to distinguish as shown in table 1, similarly operate with embodiment 14, prepare liquid crystal aligning agent (S-15) ~ (S-27) and (CS-13) ~ (CS-25), using them as embodiment 15 ~ 27, comparative example 13 ~ 25.
The manufacture > of <TN type liquid crystal display device
[embodiment 28]
Pass through spinner, liquid crystal aligning agent (S-1) is coated on by the nesa coating that ito film is formed, this ito film is arranged in the one side of the glass substrate of thickness 1mm, on hot plate, prebake 1 minute at 80 DEG C, then by heating 30 minutes at 200 DEG C, the film of thickness 80nm is formed.To this film, use the strigil with the roller of the artificial silk cloth that reeled, at roller revolution 500rpm, bedplate moving speed 3cm/s, carry out friction treatment under fine hair press-in length 0.4mm, give liquid crystal aligning energy.Afterwards, in ultrapure water, carry out 1 minute ultrasonic washing, then, drying 10 minutes in the cleaning oven of 100 DEG C, thus obtain the substrate with liquid crystal orientation film.Repeat this operation, obtain the substrate that a pair (two pieces) have liquid crystal orientation film.Then, at the respective external margin with liquid crystal orientation film of above-mentioned a pair substrate, after coating adds the epoxy resin binder of the alumina balls of diameter 5.5 μm, tackiness agent, to make liquid crystal aligning face relative, solidifies by the crimping that overlaps.Then, from liquid crystal injecting port, between a pair substrate, after filling nematic liquid crystal (メ Le ケ company, MLC-6221), with acrylic acid or the like Photocurable adhesive encapsulated liquid crystals inlet, manufacture liquid crystal cell, it can be used as embodiment 28.
[embodiment 29 ~ 40 and comparative example 26 ~ 37]
Use liquid crystal aligning agent (S-1) ~ (S-13) of embodiment 1 ~ 13 and liquid crystal aligning agent (CS-1) ~ (CS-12) of comparative example 1 ~ 12, similarly operate with embodiment 28, manufacture liquid crystal display device, using them as embodiment 29 ~ 40 and comparative example 26 ~ 37.
The manufacture > of <VA type liquid crystal display device
[embodiment 41]
Pass through spinner, liquid crystal aligning agent (S-14) is coated on the nesa coating of ito film formation, this ito film is arranged in the one side of the glass substrate of thickness 1mm, on hot plate, at 80 DEG C, prebake 1 minute, then by heating 30 minutes at 210 DEG C, forms the film (liquid crystal orientation film) of thickness 80nm.Repeat this operation, obtain the substrate that a pair (two pieces) have liquid crystal orientation film.Then, at the respective external margin with liquid crystal orientation film of above-mentioned a pair substrate, after coating adds the epoxy resin binder of the alumina balls of diameter 5.5 μm, tackiness agent, to make liquid crystal aligning face relative, solidifies by the crimping that overlaps.Then, from liquid crystal injecting port, between a pair substrate, after filling nematic liquid crystal (メ Le ケ company, MLC-6608), with acrylic acid or the like Photocurable adhesive encapsulated liquid crystals inlet, manufacture liquid crystal cell, it can be used as embodiment 41.
[embodiment 42 ~ 54 and comparative example 38 ~ 50]
Use liquid crystal aligning agent (CS-13) ~ (CS-25) of liquid crystal aligning agent (S-14) ~ (S-27) and comparative example 13 ~ 25, similarly operate with embodiment 41, manufacture liquid crystal display device, using them as embodiment 42 ~ 54 and comparative example 38 ~ 50.
< evaluates >
Following evaluation is carried out to embodiment 1 ~ 27 and the liquid crystal aligning agent of comparative example 1 ~ 25 and the liquid crystal display device of embodiment 28 ~ 54 and comparative example 26 ~ 50.
[mensuration of separability]
By spinner, be coated on by the nesa coating that ito film is formed by each liquid crystal aligning agent of embodiment 1 ~ 27 and comparative example 1 ~ 25, this ito film is arranged in the one side of the glass substrate of thickness 1mm, on hot plate, at 100 DEG C, prebake 90 second, form the film that thickness is about 80nm.Repeat this operation, manufacture the substrate of two pieces of band films.Then, by the substrate that obtains in a nitrogen environment, keeping in the darkroom of 25 DEG C, respectively after 12h, after 72 hours, takes out from darkroom, add 40 DEG C NMP beaker in dipping 2 minutes.After 2 minutes, from beaker take out substrate, with milli-Q water several times after, by blowing, remove surface water droplet, observe substrate, observe have noresidue film.After 72 hours, take out from darkroom, not residual film after dipping NMP, separability is good, is denoted as "○"; After 72 hours, the substrate taken out from darkroom cannot be peeled off, but after 12 hours, the substrate taken out from darkroom, that can peel off is denoted as " △ ", and that cannot peel off is denoted as "×".Result represents in Table 1.
[mensuration of voltage retention]
To the electrical property deterioration problem of being lowly correlated with display quality, by the voltage retention evaluation of liquid crystal display device.To each liquid crystal display device of embodiment 28 ~ 54 and comparative example 26 ~ 50, apply the voltage of 5V with the application time of 60 microseconds, the interval of 167 milliseconds at 70 DEG C after; led to the VHR-1 that East Yang テ ケ ニ カ company manufactures and measure from removing the voltage retention that is applied to after 167 milliseconds, using this value as initial voltage conservation rate (VH 1N).Then, to the liquid crystal cell measured after initial voltage conservation rate, using with carbon arc is the weather instrument of light source, rayed 1,000 hour.To the liquid crystal display device after rayed, by with above-mentioned same method, again measure voltage retention, using this value as postradiation voltage retention (VH aF).Will by VH iN-VH aFthe reduction of the voltage retention of trying to achieve is defined as Δ VHR and calculates.
The liquid crystal display device (embodiment 28 ~ 40 and comparative example 26 ~ 37) of TN type is when the reduction Δ VHR of voltage retention is less than 7%, and reliability is denoted as " ◎ "; More than 7%, when being less than 10%, reliability is denoted as "○"; When more than 10%, reliability is denoted as "×".
The liquid crystal display device (embodiment 41 ~ 54 and comparative example 38 ~ 50) of VA type is when the reduction Δ VHR of voltage retention is less than 2.5%, and reliability is denoted as " ◎ "; Time more than 2.5%, less than 5%, reliability is denoted as "○"; When more than 5%, reliability is denoted as "×".Result represents in table 2.
[table 1]
[table 2]
As shown in the result of table 1 and table 2, the liquid crystal orientation film formed by liquid crystal aligning agent of the present invention, the liquid crystal orientation film easily peeled off when can form operation again.In addition, can also know the liquid crystal display device of the present invention with this liquid crystal orientation film, no matter under any display format of TN type and VA type, voltage retention is all good, and electrical property can not worsen, and display quality can be suppressed low.
Industrial applicibility
According to the present invention, can be formed: suppress low by display qualities such as the deteriorations of electrical property, and again operation time the liquid crystal orientation film easily peeled off.This liquid crystal display device is suitable for various device, such as, can use in the display unit such as clock and watch, pocket game machine, WP, notebook computer, navigationsystem, camcorders, portable information terminal, digital camera, mobile telephone, various watch-dog, LCD TV.In addition, the film formed by this polymer composition can also use as electronic material insulating film.

Claims (7)

1. a liquid crystal aligning agent, it comprises:
At least one polymkeric substance selected in the group that [A] is made up of polyamic acid and polyimide, and
The epoxy compounds containing imide ring shown in [B] following formula (I),
In formula (I), R ato be singly-bound or carbonatoms be 1 ~ 4 alkane two base; R bthe chain alkyl of divalent, the alicyclic hydrocarbon radical of divalent, the aromatic group of divalent, the heterocyclic radical of divalent or combine their formed group; N is the integer of 0 or 1.
2. the liquid crystal aligning agent described in claim 1, at least one of its Chinese style (I) for selecting in the group that is made up of the compound shown in following formula (I-1) and formula (I-2),
In formula (I-1) and formula (I-2), R aidentical with the definition of formula (I); R 1, R 2and R 3respective independence, for comprising-O-,-COO-, the carbonatoms of-OCO-is the straight-chain of 1 ~ 20 or the alkyl of branched; In addition, R 1and R 2, or R 1and R 2and R 3can be interconnected, form part or all ring structure that can be substituted of hydrogen atom; N is the integer of 0 or 1.
3. the liquid crystal aligning agent described in claim 1 or 2, wherein [A] polymkeric substance is: by least one selected in polyamic acid and the group that formed by the polyimide that this polyamic acid dehydration closed-loop is formed, wherein polyamic acid uses tetracarboxylic dianhydride synthesis, this tetracarboxylic dianhydride comprises by 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride, 3,5,6-tri-carboxyl-2-carboxymethyl norbornane-2:3,5:6-dianhydride and 2,4,6, the at least one selected in the group that 8-tetracarboxylic two ring [3.3.0]-octane-2:4,6:8-dianhydride is formed.
4. the liquid crystal aligning agent described in claim 1 or 2, the R of its Chinese style (I) ait is first two base.
5. the liquid crystal aligning agent described in claim 2, wherein in formula (I-1) and formula (I-2), R 1and R 2be interconnected, form part or all phenyl ring that can be substituted of hydrogen atom.
6. the liquid crystal orientation film that formed of the liquid crystal aligning agent described in any one of Claims 1 to 5.
7. there is the liquid crystal display device of the liquid crystal orientation film described in claim 6.
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