CN102051186A - 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 PDFInfo
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- CN102051186A CN102051186A CN2010105270634A CN201010527063A CN102051186A CN 102051186 A CN102051186 A CN 102051186A CN 2010105270634 A CN2010105270634 A CN 2010105270634A CN 201010527063 A CN201010527063 A CN 201010527063A CN 102051186 A CN102051186 A CN 102051186A
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- 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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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
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- 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 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
Technical field
The present invention relates to liquid crystal aligning agent, liquid crystal display device, polyamic acid, polyimide and compound.In more detail, even the present invention relates to the long-time continuous operation, also can not produce the not good such display quality of electrical property deterioration and liquid crystal aligning reduces, and in the saving liquid coated technique of the manufacturing process of liquid crystal display device, can give the liquid crystal aligning agent of good printing, even and relate to display quality excellence long-time continuous operation, the liquid crystal display device that display quality can variation yet.
Background technology
At present, as liquid crystal display device, known TN type liquid crystal display device with so-called TN type (twisted-nematic) liquid crystal cell, it forms liquid crystal orientation film being provided with on the substrate surface of nesa coating, as the substrate of used for liquid crystal display element, its two are oppositely arranged, form nematic liquid crystal layer betwixt in the crack with positive dielectric anisotropy, constitute the box of sandwich structure, the major axis of this liquid crystal molecule reverses 90 ° (patent documentations 1) from a substrate continuously to another piece substrate.In addition, also developed IPS (switching face in) type liquid crystal display device (patent documentation 3) that the contrast gradient STN higher than TN type liquid crystal display device (supertwist is to row) type liquid crystal display device (patent documentation 2) and view angle dependency lack, view angle dependency is few and optical compensation curved (OCB) type liquid crystal display device (patent documentation 4) of the high-speed response excellence of image frame, use have VA (vertical orientated) the type liquid crystal display device (patent documentation 5) etc. of the nematic liquid crystal of negative dielectric anisotropy.
As the material of the liquid crystal orientation film in these liquid crystal display device, known have present polyamic acid, polyimide, polymeric amide and a polyester etc.; Excellences such as the affinity of the thermotolerance of polyamic acid and polyimide and liquid crystal, physical strength particularly are so use (patent documentation 6～11) in most liquid crystal display device.
In recent years, along with the progress of research to the display quality raising that turns to representative with liquid crystal display device high-accuracy, low power consumption etc., the scope of utilizing of liquid crystal display device increases gradually.Particularly, the LCD TV purposes of picture tube TV and being extensive use of instead.Thus, need electrical property more excellent than present, display quality is higher, and liquid crystal display device that can the long-time continuous operation.
Yet, also pointed out to have the liquid crystal display device of the liquid crystal orientation film that forms by present known polyamic acid or polyimide, when long-time continuous is thrown light on, can be easy to generate the problem that the not good such display quality of electrical property variation or liquid crystal molecular orientation obviously reduces owing to light and heat make the liquid crystal orientation film variation.
Therefore, even when wishing to develop the long-time continuous illumination, there is not the liquid crystal orientation film of the not good such display quality variation of orientation of electrical property variation and liquid crystal molecule 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 that uses when attempting reducing printing.Yet, present alignment agent at the amount of liquid in when coating after a little while, when having coating, the solvent evaporation in the liquid crystal aligning agent, the concentration of alignment agent raises, and produces the not good and resinous principle of coating and separates out so unusual problem.Therefore, in order when keeping the amount of liquid of saving liquid crystal aligning agent, to keep the coating quality,, also can demonstrate the liquid crystal aligning agent of excellent printing even wish have amount of liquid few.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese kokai publication hei 6-138457 communique
[patent documentation 2] Japanese kokai publication hei 5-19231 communique
[patent documentation 3] Japanese kokai publication hei 11-24109 communique
[patent documentation 4] Japanese kokai publication hei 8-327822 communique
[patent documentation 5] Japanese kokai publication hei 5-113561 communique
[patent documentation 6] Japanese kokai publication hei 4-153622 communique
[patent documentation 7] TOHKEMY 60-107020 communique
[patent documentation 8] TOHKEMY 56-91277 communique
[patent documentation 9] United States Patent (USP) 5,928,733A
[patent documentation 10] Japanese kokai publication hei 11-258605 communique
[patent documentation 11] TOHKEMY 62-165628 communique
[patent documentation 12] Japanese kokai publication hei 6-222366 communique
[patent documentation 13] Japanese kokai publication hei 6-281937 communique
[patent documentation 14] Japanese kokai publication hei 5-107544 communique
[patent documentation 15] TOHKEMY 2010-97188 communique
Summary of the invention
The present invention proposes according to the problems referred to above, its purpose is to relate to a kind of liquid crystal aligning agent, even during this liquid crystal aligning agent long-time continuous illumination, also can form and can not produce the liquid crystal orientation film that electrical property worsens or the not good such display quality of the orientation of liquid crystal molecule reduces, even when printing under few amount of liquid, printing is also excellent; And relate to the display quality excellence, though long-time continuous operation, the liquid crystal display device that display quality can variation yet.
Other purposes of the present invention and advantage are clear and definite by following explanation.
According to the present invention, above-mentioned purpose of the present invention and advantage, the firstth, realize by a kind of liquid crystal aligning agent, this liquid crystal aligning agent contains at least a polymkeric substance of selecting from the group that is made of polyamic acid and polyimide (wherein, this polymkeric substance has following formula (A in intramolecular at least a portion
0) shown in structure).
Formula (A
0) in, X is the divalent group of any expression of following formula (X-1)～(X-4),
—O— (X-3)
—S— (X-4)
Formula (X-1) and (X-2) in, R
IIBe that hydrogen atom, carbonatoms are that 1～4 alkyl, carboxyl or carbonatoms are 2～5 carboxyalkyl.
R
IBe that hydrogen atom or carbonatoms are 1～4 alkyl, m is 1 or 2, and n is 0 or 1.
Above-mentioned purpose of the present invention and advantage, the secondth, realize that by a kind of liquid crystal display device this liquid crystal display device has the liquid crystal orientation film that is formed by above-mentioned liquid crystal aligning agent.
When even liquid crystal aligning agent of the present invention can form the long-time continuous operation, there is not electrical property to worsen and liquid crystal orientation film that the not good such display quality of orientation of liquid crystal molecule reduces yet, even when under few amount of liquid, printing, also demonstrate excellent printing.
Have the liquid crystal display device of the present invention of the liquid crystal orientation film that is formed by this liquid crystal aligning agent, can show high-qualityly, even during long-play, display performance can variation yet.Therefore, liquid crystal display device of the present invention can be applicable to various devices effectively, for example can use in 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 a polymkeric substance of selecting from the group that is made of polyamic acid and polyimide, wherein aforementioned polymer has above-mentioned formula (A in its intramolecular at least a portion
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, perhaps can be present in simultaneously in the main chain and side chain of polymkeric substance.
As above-mentioned formula (A
0) in X, be preferably the divalent group of above-mentioned formula (X-1)～(X-3) shown in any.As above-mentioned formula (X-1) with the R (X-2)
IICarbonatoms be 1～4 alkyl, can list for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl etc.As carbonatoms is 2～5 carboxyalkyl, can list for example carboxymethyl, 2-carboxy ethyl, 3-carboxyl-n-propyl, 4-carboxyl-normal-butyl etc.As formula (X-1) with the R (X-2)
II, be preferably hydrogen atom, methyl, ethyl, sec.-propyl or carboxyl, more preferably hydrogen atom, methyl or carboxyl are preferably carboxyl especially.
As R
ICarbonatoms be 1～4 alkyl, be preferably carbonatoms and be 1 or 2 alkyl, just 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, perhaps m be 2 and n be 0.
As the above-mentioned formula (A in the polymkeric substance
0) shown in structure contain proportionally, be preferably 0.00005～0.0035mol/g, more preferably 0.00025～0.0025mol/g.
Intramolecular at least a portion has above-mentioned formula (A
0) shown in the polyamic acid of structure, can list for example to make to comprise and have above-mentioned formula (A
0) shown in structure and the tetracarboxylic dianhydride and the diamine reactant of two acid anhydrides' compound, perhaps make the tetracarboxylic dianhydride have above-mentioned formula (A with comprising
0) shown in structure and the diamine reactant of the compound of two amino obtain; Intramolecular at least a portion has above-mentioned formula (A
0) shown in the polyamic acid of structure, for example can obtain by the polyamic acid dehydration closed-loop that will as above obtain.
Be preferably at least a polymkeric substance of selecting as the particular polymers that contains in the liquid crystal aligning agent of the present invention from the group that is made of polyamic acid and polyimide that this polyamic acid dehydration closed-loop is formed, wherein this polyamic acid is to make the tetracarboxylic dianhydride have above-mentioned formula (A with comprising
0) shown in the structure and the diamine reactant of the compound of two amino obtain.
Below, polyamic acid and polyimide as preferred particular polymers among the present invention are illustrated successively.
＜polyamic acid 〉
As implied above, preferred polyamic acid is to make the tetracarboxylic dianhydride and comprise to have above-mentioned formula (A among the present invention
0) shown in the structure and the diamine reactant of the compound of two amino obtain.
[tetracarboxylic dianhydride]
Tetracarboxylic dianhydride as the polyamic acid that is used for synthetic the present invention can list for example aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.As their concrete example,, can list for example butane tetracarboxylic acid dianhydride etc. wherein as the aliphatics tetracarboxylic dianhydride;
As the ester ring type tetracarboxylic dianhydride, for example can list 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c] furans-1, the 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, the 3-diketone, 3-oxabicyclo [3.2.1] suffering-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic acid anhydride, 3,5,6-three carboxyls-2-carboxymethyl norbornane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxylic two ring [3.3.0] octane-2:4, the 6:8-dianhydride, 4,9-two oxatricyclos [5.3.1.02,6] undecane-3,5,8,10-tetraketone etc.;
As aromatic tetracarboxylic acid's dianhydride, for example can list all benzene tertacarbonic acid's dianhydride etc.;
And the tetracarboxylic dianhydride who uses record in the patent documentation 15 (TOHKEMY 2010-97188 communique).
As the tetracarboxylic dianhydride who is used for synthetic aforementioned polyamic acid, preferred those that contain the ester ring type tetracarboxylic dianhydride that use among them, preferred especially the use contains 2,3, those of 5-tricarboxylic basic ring amyl group acetate dianhydride.
As the tetracarboxylic dianhydride who is used for synthetic aforementioned polyamic acid, with respect to whole tetracarboxylic dianhydrides, preferably contain 10mol% above, more preferably contain 20mol% above 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride.
As the tetracarboxylic dianhydride who is used for synthetic aforementioned polyamic acid, most preferably only by 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride constitutes, and perhaps only is made of following: from by 1,2,3,4-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, select in the group that the 3-diketone constitutes at least a and 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride.
Being used for the diamines of the preferred polyamic acid of synthetic liquid crystal aligning agent of the present invention, is to comprise to have above-mentioned formula (A
0) shown in structure and the diamines of the compound of two amino (below, be also referred to as " compound (A) ").
As the compound shown in the preferred following formula of compound (A) (A),
In the formula (A), X, R
I, m and n respectively with above-mentioned formula (A
0) in definition identical,
Preferably especially use at least a from the group of the compound formation represent respectively by following formula (A-1)～(A-17).
This compound (A) can be synthetic by the vitochemical ordinary method of appropriate combination.For example, by with following formula (A
0-1) reaction of the compound shown in and halo dinitrobenzene, obtain dinitrobenzene thing as intermediate after, by using suitable reduction system, the nitro that this intermediate had is converted to amino, can easily synthesize.
Formula (A
0-1) in, X, R
I, m and n respectively with above-mentioned formula (A
0) in definition identical.
As the compound that uses among the present invention (A), the compound that is preferably above-mentioned formula (A-1)～(A-4) and (A-7)～(A-16) represents respectively.Among them, if use from group, select at least a by (A-1)～(A-4) and the compound formation of (A-9)～(A-16) representing respectively, if particularly use from group, select at least a, be preferred aspect the photostabilization of the liquid crystal orientation film that further improves formation then by (A-1)～(A-4) and the compound formation of (A-14)～(A-16) representing respectively;
If use from by above-mentioned formula (A-3), (A-4) and (A-7)～(A-10) select the group of the compound of expression formation respectively at least a, be preferred aspect better then in the printing that makes the liquid crystal aligning agent that obtains.
Diamines as being used for the preferred polyamic acid of synthetic the present invention can only use compound (A), also compound (A) and other diamines can be used in combination.
As other diamines that can use, can list for example aliphatie diamine, ester ring type diamines, aromatic diamine, diamino organo-siloxane etc. here.
As their object lesson, be respectively as aliphatie diamine, for example can list 1,1-m-xylene diamine, 1,3-propylene diamine, 1,4-butanediamine, 1,5-pentamethylene diamine, 1,6-hexanediamine etc.;
As the ester ring type diamines, for example can list 1,4-diamino-cyclohexane, 4,4 '-methylene radical two (cyclo-hexylamine), 1,3-two (amino methyl) hexanaphthene etc.;
As aromatic diamine, can list for example Ursol D, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl thioether, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 2, the 7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(to phenylene two isopropylidenes) two (aniline), 4,4 '-(metaphenylene two isopropylidenes) two (aniline), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-two (4-aminophenyl)-p-diaminodiphenyl, N, N '-two (4-aminophenyl)-N, N '-tolidine, dodecyloxy-2, the 4-diaminobenzene, pentadecane oxygen base-2, the 4-diaminobenzene, n-Hexadecane oxygen base-2, the 4-diaminobenzene, octadecane oxygen base-2, the 4-diaminobenzene, dodecyloxy-2, the 5-diaminobenzene, pentadecane oxygen base-2, the 5-diaminobenzene, n-Hexadecane oxygen base-2, the 5-diaminobenzene, octadecane oxygen base-2, the 5-diaminobenzene, cholestane oxygen base-3, the 5-diaminobenzene, cholestene oxygen base-3, the 5-diaminobenzene, cholestane oxygen base-2, the 4-diaminobenzene, cholestene oxygen base-2, the 4-diaminobenzene, 3,5-diaminobenzoic acid cholestane base ester, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid lanostane base ester, 2, the 5-diaminobenzoic acid, N, N '-two (4-aminophenyl)-croak piperazine, compound shown in the following formula (D-1) etc.;
As the diamino organo-siloxane, for example can list 1,3-two (3-aminopropyl)-tetramethyl disiloxane etc.; Except can use at least a diamines that is selected among them (below, be called " other specific diamines ") in addition, the diamines of record in the patent documentation 15 (TOHKEMY 2010-97188 communique) and they are used together or replace their to use.
As other diamines that uses among the present invention, preferably use other specific diamines, preferred especially the use from by 3,5-diaminobenzoic acid, cholestane oxygen base-2,4-diaminobenzene and 3, at least a in the group that 5-diaminobenzoic acid cholestane base ester constitutes.
Diamines as the polyamic acid that preferably contains in the synthetic liquid crystal aligning agent of the present invention uses with respect to whole diamines, preferably contains more than the 1mol%, more preferably contains more than the 5mol%, especially preferably contains 10～90mol% compound (A).In addition, the diamines that is used for synthetic preferred polyamic acid preferably also comprises aforesaid other specific diamines except compound (A).Usage ratio as in this case other specific diamines with respect to whole diamines, is preferably more than the 30mol%, more preferably more than the 50mol%, is preferably more than the 80mol% especially.
Be used for that the diamines of the polyamic acid that synthetic liquid crystal aligning agent of the present invention preferably contains is preferred only to be made of compound (A), perhaps only by compound (A) and other specific diamines formation.
[synthesizing of polyamic acid]
The polyamic acid that contains in the liquid crystal aligning agent of the present invention can obtain by the diamine reactant that makes tetracarboxylic dianhydride and inclusion compound (A).
The tetracarboxylic dianhydride who uses in the building-up reactions as polyamic acid and the usage ratio of diamines, with respect to the amino of 1 equivalent diamines, tetracarboxylic dianhydride's anhydride group preferred 0.2～2 normal ratio, more preferably 0.3～1.2 normal ratio.
The building-up reactions of polyamic acid is preferably carried out in organic solvent, preferably at-20 ℃～150 ℃, more preferably under 0 ℃～100 ℃ temperature condition, preferably carries out 0.1～24 hour, more preferably carries out 0.5～12 hour.
Operable organic solvent during as polyamic acid synthetic can list for example non-proton property polar solvent, phenol derivmives blend biology, alcohol, ketone, ester, ether, halohydrocarbon, hydrocarbon etc.As above-mentioned non-proton property polar solvent, can list for example N-N-methyl-2-2-pyrrolidone N-, N,N-dimethylacetamide, N, dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA etc.;
As above-mentioned phenol derivatives, can list for example meta-cresol, xylenol, halogenated phenol etc.;
As above-mentioned alcohol, can list for example methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, 1,4-butyleneglycol, triglycol, glycol monomethyl methyl ether etc.;
As above-mentioned ketone, can list for example acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.;
As above-mentioned ester, can list for example ethyl lactate, n-Butyl lactate, methyl acetate, ethyl acetate, butylacetate, methoxypropionic acid methyl esters, ethoxyl ethyl propionate, oxalic acid diethyl ester, diethyl malonate etc.;
As above-mentioned ether, can list for example 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.;
As above-mentioned halohydrocarbon, can list for example methylene dichloride, 1,2-ethylene dichloride, 1,4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene etc.;
As above-mentioned hydrocarbon, can list for example hexane, heptane, octane, benzene,toluene,xylene, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether etc.
In these organic solvents, preferred more than one that from the group's (organic solvent of first group) that constitutes by non-proton property polar solvent and phenol derivmives blend biology, select that use, perhaps be selected from aforementioned first group organic solvent more than one and be selected from more than one mixture in the group's (organic solvent of second group) that constitutes by alcohol, ketone, ester, ether, halohydrocarbon and hydrocarbon.Under latter event, the usage ratio of the organic solvent of second group, the total amount with respect to the organic solvent of the organic solvent of first group and second group is preferably below the 50 weight %, more preferably below the 40 weight %, more preferably below the 30 weight %.
As above, can obtain dissolving the reaction soln that polyamic acid forms.
This reaction soln can be directly used in the preparation liquid crystal aligning agent, also behind the polyamic acid that can contain, is used to prepare liquid crystal aligning agent in separating reaction solution, after perhaps isolating polyamic acid being made with extra care, is used to prepare liquid crystal aligning agent.
When the polyamic acid dehydration closed-loop is formed polyimide, above-mentioned reaction soln can be directly used in the dehydration closed-loop reaction; Behind the polyamic acid that contains in also can separating reaction solution, be used for the dehydration closed-loop reaction; After perhaps isolating polyamic acid being made with extra care, be used for the dehydration closed-loop reaction.
The separation of polyamic acid can obtain precipitate, with the method for this precipitate drying under reduced pressure by above-mentioned reaction soln is injected a large amount of lean solvents; Perhaps undertaken by the method for the solvent in the vaporizer underpressure distillation reaction soln.In addition, also can be by this polyamic acid being dissolved in the organic solvent once more the method for in lean solvent, separating out then; Perhaps by repeating 1 time or repeatedly polyamic acid be dissolved in the organic solvent once more, wash this solution after, distillate the refining polyamic acid of method of the organic solvent in this solution with the vaporizer decompression.
＜polyimide 〉
The polyimide that can contain in the liquid crystal aligning agent of the present invention can obtain by the polyamic acid dehydration closed-loop imidization that will as above obtain.
As the tetracarboxylic dianhydride that preferred polyimide among synthetic the present invention uses, can list the synthetic middle identical compound of tetracarboxylic dianhydride that uses with above-mentioned polyamic acid.Also the situation with polyamic acid is identical for preferred tetracarboxylic dianhydride's kind and preferred usage ratio thereof.
As the diamines that is used for the preferred polyimide of synthetic the present invention, can list and synthesize the diamines of the diamines identical type of above-mentioned polyamic acid use.Just, the diamines that is used for the polyimide that synthetic liquid crystal aligning agent of the present invention contains is the diamines of inclusion compound (A), can only use compound (A), also compound (A) and other diamines can be used together.
Diamines as the polyamic acid that preferably contains in the synthetic liquid crystal aligning agent of the present invention uses with respect to whole diamines, preferably contains more than the 1mol%, more preferably contains 1～50mol%, especially preferably contains the compound (A) of 5～40mol%.In addition, the diamines that is used for synthetic preferred polyamic acid preferably also comprises aforesaid other specific diamines except compound (A).Usage ratio as in this case other specific diamines with respect to whole diamines, is preferably more than the 30mol%, more preferably more than the 50mol%, is preferably more than the 80mol% especially.
The diamines that is used for the polyamic acid that synthetic liquid crystal aligning agent of the present invention preferably contains is preferred only by compound (A) and other specific diamines formation.
The polyimide that preferably contains in the liquid crystal aligning agent of the present invention can be the complete imidization thing as the amido acid structure fully dehydrating closed loop that polyamic acid had of raw material; Also can be a part of dehydration closed-loop of amido acid structure, amido acid structure and imide ring structure and the part imidization thing of depositing.The imidization rate of the polyimide that preferably contains in the liquid crystal aligning agent of the present invention is preferably more than 30%, more preferably more than 40%, is preferably 50～80% especially.Above-mentioned imidization rate is to represent that with percentage the quantity of imide ring structure occupies the ratio of total amount of the quantity of the quantity of amido acid structure of polyimide and imide ring structure.At this moment, the part of imide ring can be different imide ring.
The dehydration closed-loop of polyamic acid preferred (i) perhaps (ii) is dissolved in polyamic acid in the organic solvent with the method by the heating polyamic acid, adds dewatering agent and dehydration closed-loop catalyzer in this solution, and Jia Re method is carried out as required.
Be preferably 50～200 ℃, more preferably 60～170 ℃ as the temperature of reaction in the method for the heating polyamic acid of above-mentioned (i).During 50 ℃ of temperature of reaction less thaies, can't fully carry out the dehydration closed-loop reaction; If temperature of reaction surpasses 200 ℃, then the molecular weight of the polyimide of gained may reduce.Be preferably 1.0～24 hours, more preferably 1.0～12 hours as the reaction times.
On the other hand, in the above-mentioned method of in polyamic acid solution, adding dewatering agent and dehydration closed-loop catalyzer (ii),, can use for example acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride as dewatering agent.The usage ratio of dewatering agent determines that according to desirable imidization rate the amido acid structure with respect to the 1mol polyamic acid is preferably 0.01～20mol.In addition, as the dehydration closed-loop catalyzer, can list for example tertiary amines such as pyridine, trimethylpyridine, lutidine, triethylamine.But, be not limited to this.The usage ratio of dehydration closed-loop catalyzer, the dewatering agent with respect to 1mol uses is preferably 0.01～10mol.The imidization rate can be that above-mentioned dewatering agent, dehydration closed-loop catalyst consumption are many more high more.As the organic solvent that uses in the dehydration closed-loop reaction, can list the illustrative organic solvent of solvent that acid is used as synthesizing polyamides.The temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, more preferably 10～150 ℃.Reaction times is preferably 1.0～120 hours, more preferably 2.0～30 hours.
The polyimide that obtains in the aforesaid method (i) can be directly used in it preparation liquid crystal aligning agent, after perhaps the polyimide of gained being made with extra care, is used to prepare liquid crystal aligning agent.On the other hand, aforesaid method (ii) in, can obtain containing the reaction soln of polyimide.This reaction soln can be directly used in it preparation liquid crystal aligning agent, also can remove dewatering agent and dehydration closed-loop catalyzer from reaction soln after, be used to prepare liquid crystal aligning agent; After polyimide can also be separated, be used to prepare liquid crystal aligning agent; After perhaps isolating polyimide being made with extra care, be used to prepare liquid crystal aligning agent.In order to remove dewatering agent and dehydration closed-loop catalyzer from reaction soln, for example be fit to use methods such as solvent exchange.The separation of polyimide, the refining above-mentioned same operation that can be undertaken by separation, the process for purification as polyamic acid are carried out.
The polymkeric substance of-end modified type-
Polyamic acid that contains in the liquid crystal aligning agent of the present invention and polyimide can be respectively the end modified property polymkeric substance of having regulated molecular weight.By using end modified type polymkeric substance, further improve the coating character of liquid crystal aligning agent etc. with can not damaging effect of the present invention.This end modified type polymkeric substance can be undertaken by add suitable molecular weight regulator in polymerization reaction system when synthesizing polyamides acid.As molecular weight regulator, can list for example sour single acid anhydride, monoamine compound, monoisocyanates compound etc.
As the single acid anhydride of above-mentioned acid, can list for example 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.As above-mentioned monoamine compound, can list for example 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.As above-mentioned monoisocyanates compound, can list for example isocyanic acid phenylester, isocyanic acid naphthyl ester etc.
The usage ratio of molecular weight regulator, the tetracarboxylic dianhydride and the diamines that use during with respect to synthesizing polyamides acid amount to 100 weight parts, are preferably below 20 weight parts, more preferably below 10 weight parts.
-soltion viscosity-
Polyamic acid that as above obtains and polyimide preferably have the soltion viscosity of 20～800mPas when forming the solution of concentration 10 weight % respectively, more preferably have the soltion viscosity of 30～500mPas.
The soltion viscosity of above-mentioned polymkeric substance (mpas) is to use the polymers soln of good solvent (for example, gamma-butyrolactone, N-N-methyl-2-2-pyrrolidone N-etc.) the preparation concentration 10 weight % of this polymkeric substance, uses E type rotational viscosimeter, under 25 ℃ to the value of its mensuration.
＜other additive 〉
Liquid crystal orientation film of the present invention contains the essential composition of particular polymers conduct as above, also can contain other composition as required.As this other composition, can list other polymkeric substance for example, have compound (below, be called " epoxy compounds "), functional silanes compound of at least 1 epoxy group(ing) etc. at intramolecularly.
[other polymkeric substance]
Above-mentioned other polymkeric substance can be used to improve SOLUTION PROPERTIES and electrical property.As this other polymkeric substance, it is the polymkeric substance beyond the particular polymers, can list the polyamic acid that tetracarboxylic dianhydride for example and the diamine reactant that does not contain compound (A) obtain (below, be called " other polyamic acid "), polyimide that this polyamic acid dehydration closed-loop is formed (below, be called " other polyimide "), poly amic acid ester, polyester, polymeric amide, polysiloxane, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative, poly-(methyl) acrylate etc.Among them, preferably other polyamic acid or other polyimide.
As the usage ratio of other polymkeric substance, (be meant the total amount of above-mentioned particular polymers and other polymkeric substance with respect to the total amount of polymkeric substance.Below identical), be preferably below the 85 weight %, more preferably below the 50 weight %, more preferably below the 40 weight %, be preferably especially below the 30 weight %, further preferably do not use other polymkeric substance again.
[epoxy compounds]
As above-mentioned epoxy compounds, be preferably the compound that has at least two epoxy group(ing) at intramolecularly, can list for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 2,2-two bromo neopentylglycol diglycidyl ethers, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3-two (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-amino methyl hexanaphthene, N, N-diglycidyl-cyclo-hexylamine etc. are as preferred material.
Amount to 100 weight parts with respect to polymkeric substance, the blending ratio of these epoxy compoundss is preferably below 40 weight parts, more preferably 0.1～30 weight part.
[functional silanes compound]
As above-mentioned functional silanes compound, can list for example 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-uride propyl trimethoxy silicane, 3-uride propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-3-aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4,7-three 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-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, the glycidoxypropyl methyltrimethoxy silane, the glycidoxypropyl Union carbide A-162,2-glycidoxypropyl ethyl trimethoxy silane, 2-glycidoxypropyl ethyl triethoxysilane, the 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane etc.
Amount to 100 weight parts with respect to polymkeric substance, the blending ratio of these functional silanes compounds is preferably below 2 weight parts, more preferably below 0.2 weight part.
＜liquid crystal aligning agent 〉
Liquid crystal aligning agent of the present invention as above particular polymers and any as required other additive of blended dissolves in preferred organic and contains and constitute.
As the organic solvent that can in liquid crystal aligning agent of the present invention, use, can list the N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2 pentanone, the glycol monomethyl methyl ether, n-Butyl lactate, butylacetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, Ethylene Glycol Methyl ether, glycol ethyl ether, the ethylene glycol n-propyl ether, the 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, the diethylene glycol monomethyl ether acetic ester, the TC acetic ester, diisobutyl ketone, propionic acid isopentyl ester, isopropylformic acid isopentyl ester, diisoamyl ether, ethylene carbonate, propylene carbonate etc.They can use separately, perhaps also can mix two or more uses.
Solid component concentration in the liquid crystal aligning agent of the present invention (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) is considered suitably selection such as viscosity, volatility, is preferably the scope of 1～10 weight %.Just, liquid crystal aligning agent of the present invention is coated to substrate surface as described later, preferably, form filming of liquid crystal orientation film by heating, but when solid component concentration less than 1 weight %, this thickness of filming is too small, may be difficult to obtain good liquid crystal orientation film; On the other hand, when solid component concentration surpassed 10 weight %, the thickness of filming was excessive, be difficult to obtain good liquid crystal orientation film, and the increase of the viscosity of liquid crystal aligning agent, the screening characteristics qualitative change is poor.
The method that the scope of particularly preferred solid component concentration adopts during according to coated with liquid crystal alignment agent on substrate and different.For example, when using spin-coating method to carry out, solid component concentration is preferably the scope of 1.5～4.5 weight % especially.When using print process to carry out, solid component concentration is the scope of 3～9 weight %, and thus, soltion viscosity is preferably the scope of 12～50mPas especially.When using ink jet method to carry out, solid component concentration is the scope of 1～5 weight %, and thus, soltion viscosity is preferably the scope of 3～15mpas especially.
Temperature when preparing liquid crystal aligning agent of the present invention is preferably 10 ℃～50 ℃, more preferably 20 ℃～30 ℃.
＜liquid crystal display device 〉
Liquid crystal display device of the present invention has the liquid crystal orientation film that is formed by as above liquid crystal aligning agent of the present invention.
Liquid crystal display device of the present invention for example can be by the operation manufacturing of following (1) and (3).Operation (1) is according to desirable operational mode, the substrate difference of use.Operation (2) is identical with (3) under various operational modes.
(1) at first, coating liquid crystal aligning agent of the present invention on substrate then, by the heating applicator surface, forms on substrate and films.
(1-1) when making TN type, STN type or VA type liquid crystal display device, form two substrates that are provided with the nesa coating that forms pattern a pair of, on their each transparent conducting film formation face, 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, formation is filmed.At this moment, as substrate, can use for example by glass such as float glass, soda glass; The transparency carrier that polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-plastics such as (ester ring type alkene) form.As the nesa coating that on the one side of substrate, is provided with, can use by stannic oxide (SnO
2) the NESA film (registered trademark of U.S. PPG company), the Indium sesquioxide-stannic oxide (In that form
2O
3-SnO
2) the ITO film that forms etc., in order to obtain forming the nesa coating of pattern, can be by after for example forming no figure nesa coating, by photoetch formation method of patterning; When forming nesa coating, use the method etc. of mask to obtain with desirable pattern.During the coated with liquid crystal alignment agent, better for the cohesiveness that makes substrate surface and nesa coating and film, can in substrate surface, should form on the face of filming, apply functional silanes compound, functionality titanium compound etc. in advance and carry out pre-treatment.
Behind the coated with liquid crystal alignment agent, the purposes such as alignment agent liquid drip based on preventing to apply preferably preheat (prebake).The temperature of prebake is preferably 30～200 ℃, more preferably 40～150 ℃, is preferably 40～100 ℃ especially.The time of prebake is preferably 0.25～10 minute, more preferably 0.5～5 minute.Afterwards, desolvate,, fire (afterwards curing) operation as required with the purpose of polyamic acid hot-imide based on removing fully.This is fired (afterwards curing) temperature and is preferably 80～300 ℃, more preferably 120～250 ℃.After the time of curing be preferably 5～200 minutes, more preferably 10～100 minutes.So, the thickness of the film of formation is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(1-2) on the other hand, when making IPS type liquid crystal display device, with be provided with the nesa coating that forms the interdigitated electrode structure pattern substrate the formation conducting film face and be not provided with on 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, formation is filmed.
The pre-treatment and the heating means behind the coated with liquid crystal alignment agent of the formation pattern method of the material of substrate that uses and nesa coating, nesa coating, substrate are identical with above-mentioned (1-1) at this moment.
The preferred thickness of filming that forms is identical with above-mentioned (1-1).
When (2) liquid crystal display device by method manufacturing of the present invention was VA type liquid crystal display device, filming of as above forming can directly be used as liquid crystal orientation film, but can carry out re-using after the grinding process described later according to hope.
On the other hand, when making the liquid crystal display device beyond the VA type again,, form liquid crystal orientation film by filming of as above forming carried out grinding process.
Grinding process is the coated surface that forms as above,, carries out in the certain orientation polishing for example by the roller of fibroplastic cloth such as nylon, artificial silk, cotton by coiling.Thus, the orientation of liquid crystal molecule can be filmed, and forms liquid crystal orientation film.
Then, the liquid crystal orientation film that as above forms is handled, has different liquid crystal orientation films by each zone that makes liquid crystal orientation film, can improve the perspective nature of the liquid crystal display device of gained, wherein the processing that liquid crystal film is carried out comprises: for example as patent documentation 12 (Japanese kokai publication hei 6-222366 communique) or patent documentation 13 (Japanese kokai publication hei 6-281937 communique) record, to a part of irradiation ultraviolet radiation of liquid crystal orientation film, change the processing of a part of regional tilt angle of liquid crystal orientation film; And as patent documentation 14 (Japanese kokai publication hei 5-107544 communique) record like that, behind the part formation etchant resist to the liquid crystal orientation film surface, on the direction different with before grinding process, carry out grinding process after, the processing of removing etchant resist.
(3) prepare two substrates that as above form liquid crystal orientation film,, make liquid crystal cell by between two substrates of subtend configuration, disposing liquid crystal.Here, when carrying out grinding process to filming, the configuration of two substrate subtends is so that the polishing direction of respectively filming predetermined angular each other mutually for example is quadrature or antiparallel.
When making liquid crystal cell, can list for example following two kinds of methods.
First method is present known method.At first, in order to make each liquid crystal orientation film subtend setting, by gap (box gap), with two substrate subtend configurations, use sealing agent, fitted in the peripheral position of two substrates, in the box gap of cutting apart by substrate surface and sealing agent, inject filling liquid crystal after, the sealing filling orifice can be made liquid crystal cell.
Second method is the method that is called ODF (One Drop Fill, instillation) mode.Prescribed position on the substrate in two substrates that form liquid crystal orientation film, apply for example sealing material of ultraviolet light curable, then after dripping liquid crystal on the liquid crystal aligning face, fit another substrate and make the liquid crystal orientation film subtend, then, whole irradiating ultraviolet light at substrate makes sealant cures, can make liquid crystal cell.
Under the situation of any method, the liquid crystal cell of hope to as above making, after reheat arrives the isotropic temperature of using of liquid crystal, slow cool to room temperature, the flow orientation when removing the liquid crystal filling.
Then, the outer surface applying polaroid by at liquid crystal cell can obtain liquid crystal display device of the present invention.
At this moment, as sealing agent, can use and for example contain solidifying agent and as Resins, epoxy of the alumina balls of partition etc.
As foregoing liquid crystal, can use for example nematic liquid crystal, dish-like liquid crystal etc., preferred nematic liquid crystal among them.When being VA type liquid crystal cell, the nematic liquid crystal that preferably has negative dielectric anisotropy can use for example 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.When being TN type liquid crystal cell or STN type liquid crystal cell, the nematic liquid crystal that preferably has positive dielectric anisotropy can use for example 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, cube alkanes liquid crystal etc.In these liquid crystal, can further add and use for example cholesterol liquid crystals such as chlorination beta-cholestanol (cholestyl chloride), Cholesteryl pelargonate, cholesterol carbonic ether; Chiral reagent with trade(brand)name C-15, CB-15 (manufacturing of メ Le Network company) sale; To oxygen base benzylidene-to strong dielectricity liquid crystal such as amino-2-methyl butyl laurate etc. in the last of the ten Heavenly stems.
As the polaroid that fits to the liquid crystal cell outside surface, can list the limit with the polyvinyl alcohol orientation that extends, the film formed polaroid of polarisation that absorption iodine is called " H film " is clamped with the cellulose acetate protective membrane in the limit, or the polaroid that is formed by H film itself.
[embodiment]
Below, by embodiment, the present invention is described more specifically, but the present invention is not subjected to the qualification of these embodiment.The soltion viscosity of the polymers soln in the following synthesis example and the imidization rate of polyimide are by following method evaluation.
[soltion viscosity of polymkeric substance]
The soltion viscosity of polymkeric substance (mPas) is the N-Methyl pyrrolidone solution that polymer concentration is adjusted to 10 weight % respectively, uses E type rotational viscosimeter, measures down at 25 ℃.
[the imidization rate of polyimide]
The imidization rate of polymkeric substance is that the solution of polyimide that each synthesis example is obtained is put in the pure water slightly, reclaim the precipitation that generates, behind the at room temperature abundant drying under reduced pressure, it is dissolved in the heavy-hydrogenated dimethyl sulfoxide (DMSO),, measure under the room temperature as primary standard with tetramethylsilane
1The H-NMR wave spectrum is tried to achieve by following mathematical expression (1).
Imidization rate (%)=(1-A
1/ A
2* α) * 100 (1)
In the mathematical expression (1), A
1Be peak area near the proton of the NH base that shows the chemical shift 10ppm, A
2Be the peak area from other proton, α is the ratio of the number of other proton with respect to the proton of the NH base in the precursor (polyamic acid) of 1 polymkeric substance.
The synthesis example of＜compound (A) 〉
Synthesis example S-1
According to following synthetic route 1, the compound (compound (A-1)) shown in the synthetic above-mentioned formula (A-1).
Synthetic route 1
3, in the single port flask of 000mL, mix 186.1g (1.00mol) 2,4-dinitrofluorobenzene, 152.0g (1.10mol) salt of wormwood and 1, the 000mL dimethyl sulfoxide (DMSO) adds 148.5mL (1.50mol) piperidines therein, stirs down at 80 ℃ and reacts in 1 hour.Reaction adds 4 after finishing in reaction mixture, the 000mL ethyl acetate, and the organic layer that obtains is with 1, and 000mL ion-exchange water washing 4 times after the sal epsom dehydration, removes by filter sal epsom.By decompression, desolvate from filtrate removing, the solid that obtains 500mL ethyl alcohol recrystallization obtains 231.1g (0.92mol) compound (A-1-a).
Then, under nitrogen atmosphere,, in the there-necked flask of 000mL, mix 226.1g (0.90mol) the above-mentioned compound that obtains (A-1-a), 21.8g palladium carbon (Pd/C), 2,000mL ethanol and 1,000mL tetrahydrofuran (THF) 5.On one side note temperature, after adding 220mL hydrazine monohydrate lentamente therein on one side and making the temperature of reaction system can not reach 40 ℃, under nitrogen, 25 ℃, stirring reaction 1 hour is followed 70 ℃ of following stirring reactions 4 hours.After reaction finishes,, filter by diatomite (cerite) from reaction mixture, remove catalyzer after, decompression is desolvated from filtrate removing, and obtains solid.The solid that obtains is dissolved into 4, and in the 000mL ethyl acetate, the solution that obtains is with 1, and 000mL ion-exchange water washing 4 times after the sal epsom dehydration, removes by filter sal epsom.By decompression, desolvate from filtrate removing, the solid that obtains obtains 99.5g (0.52mol) compound (A-1) with the mixed solvent recrystallization that 50mL ethyl acetate and 400mL hexane form.
Synthesis example S-2
According to following synthetic route 2, the compound (compound (A-3)) shown in the synthetic above-mentioned formula (A-3).
Synthetic route 2
3, in the single port flask of 000mL, mix 193.7g (1.50mol) isonipecotic acid, 186.1g (1.00mol) 2,4-dinitrofluorobenzene, 167.1g (1.10mol) cesium fluoride and 1, the 000mL dimethyl sulfoxide (DMSO) stirs under 25 ℃ and reacted in 12 hours.Reaction adds 3 after finishing in reaction mixture, the 000mL ethyl acetate, and the organic layer that obtains is with 1, and 000mL ion-exchange water washing 4 times after the sal epsom dehydration, removes by filter sal epsom.By decompression, desolvate from filtrate removing, the solid that obtains is with 1, and the 000mL re-crystallizing in ethyl acetate obtains 224.4g (0.76mol) compound (A-3-a).
Then, under nitrogen atmosphere, 5, in the there-necked flask of 000mL, mix 221.4g (0.75mol) the above-mentioned compound that obtains (A-3-a), 18.7g palladium carbon (Pd/C), 1,200mL ethanol and 1, the 200mL tetrahydrofuran (THF), Yi Bian note temperature, Yi Bian after adding 185mL hydrazine monohydrate lentamente therein and making the temperature of reaction system can not reach 40 ℃, 25 ℃ of following stirring reactions 1 hour, then 70 ℃ of following stirring reactions 1.5 hours.After reaction finishes, from reaction mixture, by diatomite filtration, remove catalyzer after, decompression is desolvated from filtrate removing, and obtains solid.(packing material: (メ Le Network company makes silica gel the solid that obtains by column chromatography, trade(brand)name " シ リ カ ゲ Le 60 "), launch solvent: the mixed solvent (chloroform: ethanol=20: 1 (volume ratio)) make with extra care that forms by chloroform and ethanol, except that desolvating, obtain 35.3g (0.15mol) compound (A-3) from this cut.
Synthesis example S-3
According to following synthetic route 3, the compound (compound (A-12)) shown in the synthetic above-mentioned formula (A-12).
Synthetic route 3
3, in the single port flask of 000mL, mix 186.1g (1.00mol) 2,4-dinitrofluorobenzene, 152.0g (1.10mol) salt of wormwood, 204.6mL (1.50mol) 3,5-lupetidine and 1, the 000mL dimethyl sulfoxide (DMSO) stirs under 80 ℃ and reacted in 5 hours.Reaction adds 4 after finishing in reaction mixture, the 000mL ethyl acetate, and the organic layer that obtains is with 1, and 000mL ion-exchange water washing 4 times after the sal epsom dehydration, removes by filter sal epsom.By decompression, desolvate from filtrate removing, the solid that obtains 500mL ethyl alcohol recrystallization obtains 262.5g (0.94mol) compound (A-12-a).
Then, under nitrogen atmosphere, 5, in the there-necked flask of 000mL, mix 251.4g (0.90mol) the above-mentioned compound that obtains (A-12-a), 21.8g palladium carbon (Pd/C), 2,000mL ethanol and 1, the 000mL tetrahydrofuran (THF) is Yi Bian note temperature, after on one side adding 220mL hydrazine monohydrate lentamente therein and making the temperature of reaction system can not reach 40 ℃, under 25 ℃, stirring reaction 1 hour is then 70 ℃ of following stirring reactions 4 hours.After reaction finishes, from reaction mixture, by diatomite filtration, remove catalyzer after, decompression is desolvated from filtrate removing, and obtains solid.The solid that obtains is dissolved into 4, and in the 000mL ethyl acetate, the solution that obtains is with 1, and 000mL ion-exchange water washing 4 times after the sal epsom dehydration, removes by filter sal epsom.By decompression, desolvate from filtrate removing, the solid that obtains obtains 142.6g (0.65mol) compound (A-12) with the mixed solvent recrystallization that 80mL ethyl acetate and 400mL hexane form.
Synthesis example S-4
According to following synthetic route 4, the compound (compound (A-14)) shown in the synthetic above-mentioned formula (A-14).
Synthetic route 4
3, in the single port flask of 000mL, mix 202.6g (1.0mol) 2,4-dinitrochlorobenzene, 120.2g (1.2mol) 1-methylpiperazine, 92.4g (1.1mol) sodium bicarbonate and 1,000mL ethanol stirs under 25 ℃ and reacted in 12 hours.Reaction adds 3 after finishing in reaction mixture, the 000mL ethyl acetate, and the organic layer that obtains is with 1, and 000mL ion-exchange water washing 4 times after the sal epsom dehydration, removes by filter sal epsom.By decompression, desolvate from filtrate removing, obtain 242.3g (0.91mol) compound (A-14-a).
Then, under nitrogen atmosphere, 5, in the there-necked flask of 000mL, mix 239.6g (0.90mol) the above-mentioned compound that obtains (A-14-a), 21.8g palladium carbon (Pd/C), 1,350mL ethanol and 1, the 350mL tetrahydrofuran (THF) is Yi Bian note temperature, after on one side adding 220mL hydrazine monohydrate lentamente therein and making the temperature of reaction system can not reach 40 ℃, under 25 ℃, stirring reaction 1 hour is then 70 ℃ of following stirring reactions 4 hours.After reaction finishes, from reaction mixture, by diatomite filtration, remove catalyzer after, decompression is desolvated from filtrate removing, and obtains solid.The solid that obtains is dissolved into 4, and in the 000mL ethyl acetate, the solution that obtains is with 1,000mL ion-exchange water washing 4 times, after the sal epsom dehydration, remove by filter sal epsom after, desolvate from filtrate removing by decompression, obtain solid.(packing material: (メ Le Network company makes silica gel the solid that obtains by column chromatography, trade(brand)name " シ リ カ ゲ Le 60 "), launch solvent: the mixed solvent (chloroform: ethanol=20: 1 (volume ratio)) make with extra care that forms by chloroform and ethanol, except that desolvating, obtain 169.2g (0.82mol) compound (A-14) from this cut.
Synthesis example S-5
According to following synthetic route 5, the compound (compound (A-16)) shown in the synthetic above-mentioned formula (A-16).
Synthetic route 5
3, in the single port flask of 000mL, mix 202.6g (1.0mol) 2,4-dinitrochlorobenzene, 104.5g (1.2mol) morpholine, 92.4g (1.1mol) sodium bicarbonate and 1,000mL ethanol stirs under 25 ℃ and reacted in 12 hours.Reaction adds 3 after finishing in reaction mixture, the 000mL ethyl acetate, and the organic layer that obtains is with 1, and 000mL ion-exchange water washing 4 times after the sal epsom dehydration, removes by filter sal epsom.By decompression, desolvate from filtrate removing, obtain 220.3g (0.87mol) compound (A-16-a).
Then, under nitrogen atmosphere, 5, in the there-necked flask of 000mL, mix 202.6g (0.80mol) the above-mentioned compound that obtains (A-16-a), 20.0g palladium carbon (Pd/C), 1,200mL ethanol and 1, the 200mL tetrahydrofuran (THF) is Yi Bian note temperature, after on one side adding 187mL hydrazine monohydrate lentamente therein and making the temperature of reaction system can not reach 40 ℃, under 25 ℃, stirring reaction 1 hour is then 70 ℃ of following stirring reactions 3.5 hours.After reaction finishes, from reaction mixture, by diatomite filtration, remove catalyzer after, decompression is desolvated from filtrate removing, and obtains solid.(packing material: (メ Le Network company makes silica gel the solid that obtains by column chromatography, trade(brand)name " シ リ カ ゲ Le 60 "), launch solvent: the mixed solvent (chloroform: ethanol=20: 1 (volume ratio)) make with extra care that forms by chloroform and ethanol, except that desolvating, obtain 146.87g (0.76mol) compound (A-16) from this cut.
Synthesizing of＜polymkeric substance 〉
Synthesis example 1～11
The diamines and the tetracarboxylic dianhydride of the amount shown in the table 1 are joined in the N-N-methyl-2-2-pyrrolidone N-in proper order with this, form the solution of monomer concentration 20 weight %, reacted 4 hours down, obtain containing the solution of polyamic acid (PA-1)～(PA-11) respectively at 60 ℃.Get each solution a small amount of the branch, adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyamic acid concentration 10 weight %, and the soltion viscosity of mensuration is represented in table 1.
Guarantee each half amount in these polyamic acid solutions, respectively after embodiment 17～28 and comparative example 5～8 in use.
In remaining half amount of above-mentioned each polyamic acid solution, with the amido acid unit that is had with respect to each polyamic acid of 1mol, behind the pyridine and diacetyl oxide of the mol ratio that interpolation table 1 is put down in writing, be heated to 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, intrasystem solvent carries out solvent exchange (by this operation with new N-N-methyl-2-2-pyrrolidone N-, with the pyridine that uses in the dehydration closed-loop reaction and diacetyl oxide except that going to system, below identical), thereby obtain containing the solution of 16 weight % polyimide (PI-1)～(PI-11) respectively.The imidization rate of each polyimide that contains in these polyimide solutions and a small amount of the branch are got each solution, form the N-N-methyl-2-2-pyrrolidone N-solution of polyimide concentration 10 weight %, the expression in table 1 respectively of the soltion viscosity of mensuration.
These polyimide solutions respectively after embodiment 1～16 and 28 and comparative example 1～4 in use.
Synthesis example 12～17
The diamines and the tetracarboxylic dianhydride of the amount shown in the table 1 are joined in the N-N-methyl-2-2-pyrrolidone N-in proper order with this, form the solution of monomer concentration 20 weight %, reacted 4 hours down, obtain containing the solution of polyamic acid (PA-12)～(PA-17) respectively at 60 ℃.Get each solution a small amount of the branch, adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyamic acid concentration 10 weight %, and the soltion viscosity of mensuration is represented in table 1.
These polyamic acid solutions respectively after embodiment 29～35 in use.
Synthesis example 18 and 19
The diamines and the tetracarboxylic dianhydride of the amount shown in the table 1 are joined in the N-N-methyl-2-2-pyrrolidone N-in proper order with this, form the solution of monomer concentration 20 weight %, reacted 4 hours down, obtain containing polyamic acid (PA-18) and solution (PA-19) respectively at 60 ℃.Get each solution a small amount of the branch, adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyamic acid concentration 10 weight %, and the soltion viscosity of mensuration is represented in table 1.
In above-mentioned each polyamic acid solution, with the amido acid unit that is had with respect to each polyamic acid of 1mol, behind the pyridine and diacetyl oxide of the mol ratio that interpolation table 1 is put down in writing, be heated to 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, intrasystem solvent obtains containing polyimide (PI-18) and the solution (PI-19) of 16 weight % respectively with new N-N-methyl-2-2-pyrrolidone N-solvent exchange.The imidization rate of each polyimide that contains in these polyimide solutions and with the soltion viscosity expression in table 1 respectively of the N-N-methyl-2-2-pyrrolidone N-measured in solution of polyimide concentration 10 weight %.These polyamic acid solutions respectively after embodiment 36 and comparative example 9 in use.
In addition, in the table 1, diamines and tetracarboxylic dianhydride's abbreviation is respectively following implication.
＜diamines 〉
A-1, A-3, A-12, A-14 and A-16 are respectively above-mentioned synthesis example S-1～S-5 synthetic compound (A-1), (A-3), (A-12), (A-14) and (A-16)
D-1:3, the 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 the above-mentioned formula (D-1)
＜tetracarboxylic dianhydride 〉
T-1:2,3,5-tricarboxylic basic ring amyl group acetate 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) the printing evaluation preparation of liquid crystal aligning agent
In the solution that contains the polyimide (PI-1) that the above-mentioned synthesis example 1 of 100 weight parts obtains, add N-N-methyl-2-2-pyrrolidone N-(NMP) and ethylene glycol butyl ether (BC), form solvent composition NMP: BC=70: the solution of 30 (weight ratios), solid component concentration 6.5 weight %.This solution uses the strainer of aperture 1 μ m to filter, preparation printing evaluation liquid crystal aligning agent.
(2) the liquid crystal display device manufacturing preparation of liquid crystal aligning agent
Except when liquid crystal aligning agent is used in the above-mentioned printing evaluation of preparation, making the solid component concentration of the solution before filtering is beyond the 4.0 weight % and the above-mentioned liquid crystal display device manufacturing liquid crystal aligning agent that similarly prepares.
(II) evaluation of liquid crystal aligning agent
Two kinds of alignment agents to above-mentioned preparation are estimated by following method respectively.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.) is made), liquid crystal aligning agent to the dripping quantity of anilox roll (anilox roll) for the condition that repeats 15 (about 0.15g) under, the printing evaluation of above-mentioned preparation is coated on the transparency electrode face that has by the glass substrate of the film formed transparency electrode of ITO with liquid crystal aligning agent.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 is usually compared, and amount of liquid is few, is stricter printing condition.Substrate behind the coated with liquid crystal alignment agent heats 1 minute (prebake) down at 80 ℃, except that after desolvating, heats 10 minutes (afterwards curing) down at 180 ℃, forms average film thickness
Film.This is filmed with multiplying power is 20 times microscopic examination, and research has is stained with and crawling invariably, when all not observing these two kinds, is evaluated as screening characteristics " well ", when observing any one, is evaluated as screening characteristics " bad ".In addition, good especially to the rectilinearity of the outboard end of filming in the alignment agent that is evaluated as screening characteristics " well ", as screening characteristics " very good ".
To filming of above-mentioned formation, use contact pin type film thickness gauge (manufacturings of KLA-Tencor company), measure the thickness the position of the thickness of substrate center and close central authorities from the outboard end 15mm that films respectively, study both film thickness differences.This film thickness difference so long as
Below, think that then film uniformity is good.In addition, above-mentioned film thickness difference so long as
Below, think that then film uniformity is very good.
(2) manufacturing of vertical alignment-type liquid crystal display device
Use spinner, the liquid crystal display device manufacturing of above-mentioned preparation is coated in liquid crystal aligning agent on the nesa coating that constitutes by the ITO film that is provided with on the one side of glass substrate of thickness 1mm, on hot plate, under 80 ℃, prebake 1 minute, then, form thickness by after under 220 ℃, curing 15 minutes
Film (liquid crystal orientation film).Repeat this operation, make the substrate that two (a pair of) has liquid crystal orientation film.
The external margin of one the face with liquid crystal orientation film in these a pair of substrates after coating has added the epoxy resin binder of alumina balls of diameter 3.5 μ m, overlaps crimping so that the liquid crystal aligning face is relative, and tackiness agent is solidified.Then, from liquid crystal injecting port, in the gap of a pair of substrate, fill negative type liquid crystal (メ Le Network company makes, MLC-6608) after, with acrylic acid or the like Photocurable adhesive encapsulated liquid crystals inlet, by two sides applying polaroid, make vertical alignment-type liquid crystal display device in the substrate outside.
(3) sunproof evaluation
To the liquid crystal display device of above-mentioned manufacturing, under 70 ℃, apply the voltage of 5V with the application time of 60 microseconds, 167 milliseconds interval after, by (" VHR-1 " that strain) East Yang テ Network ニ カ makes measures from releasing and be applied to voltage retention after 167 milliseconds.With this moment numerical value as initial stage voltage retention (VHR
BF).
Then, the liquid crystal cell to after the mensuration initial stage voltage retention uses with the weather resistance test machine of carbon arc as light source, rayed 5,000 hours.
To the liquid crystal cell after the rayed, by with above-mentioned same method, measure voltage retention once more.The voltage retention (VHR of numerical value after with this moment as rayed
AF).
VHR from said determination
BFAnd VHR
AF, try to achieve the velocity of variation of the voltage retention before and after the rayed.The expression in table 2 respectively of their value.During above-mentioned velocity of variation less than 5.0%, photostabilization is evaluated as " well ", and above-mentioned velocity of variation is 5.0% when above, and photostabilization is evaluated as " bad ".
Embodiment 2～35 and comparative example 1～8
Except the solution that contains polymkeric substance shown in the use table 2 respectively as containing polymers soln, under the situation of table 2 record, when the preparation liquid crystal aligning agent, after in polymers soln, adding NMP and BC, further beyond the epoxy compounds of the kind of adding table 2 record and amount, with embodiment 1 similarly, prepare liquid crystal aligning agent respectively, estimate.Evaluation result merges to expression in the table 2.In addition, among the embodiment 28～35, the kind of table 2 record and two kinds polymers soln of amount are mixed use.
In addition, in the table 2, the abbreviation of epoxy compounds is respectively following implication.
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 (continuous table)
Table 2 evaluation result (continuous table)
Embodiment 36 and comparative example 9
(I) preparation of liquid crystal aligning agent
Except the solution that contains polymkeric substance shown in the use table 3 respectively as containing polymers soln, after in polymers soln, adding NMP and BC, further beyond the epoxy compounds of the kind of adding table 3 record and amount, with embodiment 1 similarly, prepare the printing evaluation respectively with liquid crystal aligning agent and liquid crystal display device manufacturing liquid crystal aligning agent.
(II) evaluation of liquid crystal aligning agent
(1) evaluation of printing
Use the printing evaluation of above-mentioned preparation to use liquid crystal aligning agent and embodiment 1 similarly to estimate printing.Evaluation result is as shown in table 3.
(2) manufacturing of TN type liquid crystal display device
Use spinner, the liquid crystal display device manufacturing of above-mentioned preparation is coated in liquid crystal aligning agent on the nesa coating that constitutes by the ITO film that is provided with on the one side of glass substrate of thickness 1mm, on hot plate, under 80 ℃, prebake 1 minute, then, form average film thickness by after under 220 ℃, curing 15 minutes
Film.This is filmed, use the sander of the roller with the artificial silk cloth of having reeled, at roller revolution 400rpm, platen translational speed 3cm/s, fine hair is pressed under the condition of length 0.4mm and carries out grinding process.Then, will have the substrate of filming after this grinding process ultrasonic washing 1 minute in ultrapure water, in 100 ℃ cleaning oven dry 10 minutes, thus on the transparency electrode face of glass substrate, form liquid crystal orientation film.Repeat this operation, make the substrate that two (a pair of) has liquid crystal orientation film.
The external margin of one the face with liquid crystal orientation film in these a pair of substrates after coating has added the epoxy resin binder of alumina balls of diameter 3.5 μ m, overlaps crimping so that liquid crystal orientation film is relative, and tackiness agent is solidified.Then, from liquid crystal injecting port, in the gap of a pair of substrate, fill the eurymeric liquid crystal (メ Le Network company makes, MLC-6621) after, with acrylic acid or the like Photocurable adhesive encapsulated liquid crystals inlet, by two sides applying polaroid, make TN type liquid crystal display device in the substrate outside.
(3) sunproof evaluation
Liquid crystal display device and embodiment 1 to above-mentioned manufacturing similarly estimate photostabilization.Evaluation result is as shown in table 3.
Table 3 evaluation result
Claims (8)
1. liquid crystal aligning agent, it is characterized in that: contain at least a polymkeric substance of selecting from the group that is made of polyamic acid and polyimide, wherein, this polymkeric substance has following formula (A in intramolecular at least a portion
0) shown in structure,
Formula (A
0) in, X is the divalent group of any expression of following formula (X-1)～(X-4),
One O-(X-3)
—S— (X-4)
Formula (X-1) and (X-2) in, R
IIBe that hydrogen atom, carbonatoms are that 1～4 alkyl, carboxyl or carbonatoms are 2～5 carboxyalkyl,
R
IBe that hydrogen atom or carbonatoms are 1～4 alkyl, m is 1 or 2, and n is 0 or 1.
2. the liquid crystal aligning agent of putting down in writing according to claim 1, wherein aforementioned polymer is at least a polymkeric substance of selecting from the group that the polyamic acid that is obtained by tetracarboxylic dianhydride and diamine reactant and the polyimide that this polyamic acid dehydration closed-loop is formed constitute, and this diamines comprises the compound shown in the following formula (A)
In the formula (A), X, R
I, m and n respectively with above-mentioned formula (A
0) in definition identical.
3. the liquid crystal aligning agent of putting down in writing according to claim 2, the X in the wherein above-mentioned formula (A) is the divalent group of above-mentioned formula (X-1)～(X-3) shown in any.
4. according to claim 2 or 3 liquid crystal aligning agent of being put down in writing, wherein above-mentioned formula (X-1) and (X-2) in R
IIBe hydrogen atom or carboxyl.
5. a liquid crystal display device is characterized in that: have the liquid crystal orientation film that is formed by each liquid crystal aligning agent of being put down in writing of claim 1～4.
6. polyamic acid, this polyamic acid is obtained with the diamine reactant that comprises the compound shown in the above-mentioned formula (A) by the tetracarboxylic dianhydride.
7. polyimide, this polyimide forms the polyamic acid dehydration closed-loop, and this polyamic acid is obtained with the diamine reactant that comprises the compound shown in the above-mentioned formula (A) by the tetracarboxylic dianhydride.
8. the compound shown in the above-mentioned formula (A).
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| CN102558096A (en) * | 2010-12-30 | 2012-07-11 | 达兴材料股份有限公司 | Aromatic diamine compound, polyamic acid and polyimide prepared from aromatic diamine compound, and liquid crystal aligning agent |
| CN103045268A (en) * | 2011-10-13 | 2013-04-17 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device |
| CN107880901A (en) * | 2016-09-27 | 2018-04-06 | Jsr株式会社 | Liquid crystal cell and its manufacture method |
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| TWI417317B (en) * | 2010-07-21 | 2013-12-01 | Daxin Materials Corp | Aromatic diamine compound, polyamic acid and polyimide prepared using the same and liquid crystal alignment agent |
| TWI452088B (en) * | 2011-04-14 | 2014-09-11 | Daxin Materials Corp | Liquid crystal aligning agent |
| KR20140045556A (en) * | 2011-07-12 | 2014-04-16 | 닛산 가가쿠 고교 가부시키 가이샤 | Composition liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element |
| JP6398480B2 (en) * | 2014-07-15 | 2018-10-03 | Jnc株式会社 | Diamine, polyamic acid or derivative thereof, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| JP6786861B2 (en) * | 2016-04-26 | 2020-11-18 | 宇部興産株式会社 | Polyimide precursor, polyimide, polyimide film, polyimide laminate, polyimide / hard coat laminate |
| CN114479882A (en) * | 2022-01-17 | 2022-05-13 | 广州华星光电半导体显示技术有限公司 | Liquid crystal alignment film, preparation method thereof, liquid crystal panel and display device |
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| CN103045268A (en) * | 2011-10-13 | 2013-04-17 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device |
| CN103045268B (en) * | 2011-10-13 | 2016-09-14 | Jsr株式会社 | Crystal aligning agent, liquid crystal orienting film and liquid crystal display cells |
| CN107880901A (en) * | 2016-09-27 | 2018-04-06 | Jsr株式会社 | Liquid crystal cell and its manufacture method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011118354A (en) | 2011-06-16 |
| JP5712524B2 (en) | 2015-05-07 |
| KR101647292B1 (en) | 2016-08-10 |
| CN102051186B (en) | 2014-12-17 |
| KR20110046257A (en) | 2011-05-04 |
| TW201120100A (en) | 2011-06-16 |
| TWI513734B (en) | 2015-12-21 |
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