CN103946738A - Method for manufacturing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element - Google Patents

Method for manufacturing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element Download PDF

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Publication number
CN103946738A
CN103946738A CN201280056047.9A CN201280056047A CN103946738A CN 103946738 A CN103946738 A CN 103946738A CN 201280056047 A CN201280056047 A CN 201280056047A CN 103946738 A CN103946738 A CN 103946738A
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liquid crystal
formula
crystal orientation
film
orientation film
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CN103946738B (en
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堀隆夫
作本直树
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • 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
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Liquid Crystal (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Provided is a method for manufacturing a liquid crystal alignment film whereby anisotropy is increased and unevenness caused by processing can be suppressed. A film obtained by applying a liquid crystal alignment agent containing at least one type of polymer selected from the group consisting of a polyimide and a precursor of the polyimide on a substrate and firing the product is irradiated with polarized radiation, then treated by contact with a solution containing at least one type of organic solvent selected from the group consisting of formula (A-1), formula (A-2), formula (A-3), formula (A-4), and formula (A-5). (In the formulas, A1 represents a hydrogen atom or an acetyl group, A2 represents a C1-6 alkyl group, R2 represents a hydrogen atom or a methyl group, n represents 1 or 2, A3 represents a C1-4 alkyl group, R3 and R4 represent a hydrogen atom or a methyl group, A5 and A6 represent a C1-4 alkyl group, and A6 represents a C3-6 alkyl group or cycloalkyl group.)

Description

Manufacture method, liquid crystal orientation film and the liquid crystal display cells of liquid crystal orientation film
Technical field
The liquid crystal orientation film that the present invention relates to the manufacture method of the liquid crystal orientation film that optical alignment method uses, obtain by this manufacture method and the liquid crystal display cells of the rewarding liquid crystal orientation film of tool.
Background technology
Conventionally in element, be provided with the liquid crystal orientation film of the state of orientation for controlling liquid crystal for the liquid crystal display cells of LCD TV, liquid crystal display etc.
At present, the most general industrial liquid crystal orientation film be by with the cloth such as cotton, nylon, polyester towards a direction wiping be formed on electrode base board by polyamic acid and/or by its imidizate the film surface that forms of polyimide, so-called friction treatment is made.
The industrial useful method that the friction treatment of the face in the orientation process of liquid crystal orientation film is easy and productivity is excellent.But, the requirement of high performance to liquid crystal display cells, high-definition, maximization improves day by day, and the variety of issues such as the unevenness in impact and then the orientation process face of scar, airborne dust, mechanical force or the static of the alignment layer surface being caused by friction treatment are day by day obvious.
The instead method of friction treatment, the known radioactive ray by irradiation polarization are given the optical alignment method of liquid crystal aligning ability.To the liquid crystal aligning processing based on optical alignment method, processing, the processing that utilizes photo-crosslinking, the processing that utilizes photolysis reactions etc. (with reference to non-patent literature 1) that utilize photoisomerization to react are proposed.
On the other hand, when polyimide is applied to light orientation and uses liquid crystal orientation film, there is high-fire resistance compared with other situations, therefore can expect its serviceability.
In patent documentation 1, propose on main chain, to there is the polyimide film of the alicyclic structures such as cyclo-butane ring for the method for optical alignment method.
But compared with adopting the liquid crystal orientation film of friction, there is the problem little with respect to the anisotropy in the direction of orientation of high molecule liquid crystal alignment films in the liquid crystal orientation film obtaining by optical alignment method.If anisotropy is little, cannot obtain enough liquid crystal alignings, while making liquid crystal display cells, also there will be problems such as producing ghost.As the anisotropic method that improves the liquid crystal orientation film obtaining by optical alignment method, propose after irradiation, the main chain that causes described polyimide because of irradiation to be cut off the method (referring to Patent Document 2) that the low molecular weight compositions that generates is removed.
Prior art document
Patent documentation
Patent documentation 1: Japanese patent laid-open 9-297313 communique
Patent documentation 2: Japanese Patent Laid-Open 2011-107266 communique
Non-patent literature
Non-patent literature 1: " liquid crystal photo-alignment film " wooden family rib, village of city functional material in November, 1997 Vol.17, No.1113～22 page (" liquid crystal light alignment film " wooden Kobe side, village of city Machine energy material)
Summary of the invention
Invent technical matters to be solved
The inventor confirms after deliberation afterwards, by to polyimide film or by polyimide precursor coating, burn till the polyimide film obtain and irradiate the radioactive ray of polarization, be then immersed in the medium processing of water or organic solvent, the anisotropy raising of the liquid crystal orientation film of gained.But the inventor finds, carry out in the situation of these processing, the liquid crystal orientation film of gained occurs producing unequal problem, and the characteristic of liquid crystal orientation film is significantly impaired.
The object of the present invention is to provide and can improve the anisotropy of the liquid crystal orientation film obtaining by optical alignment method and be suppressed at the liquid crystal display cells that produces the manufacture method of uneven liquid crystal orientation film, the liquid crystal orientation film obtaining by the manufacture method of this liquid crystal orientation film and there is the liquid crystal orientation film obtaining by the manufacture method of this liquid crystal orientation film in the process of processing.
The technical scheme that technical solution problem adopts
The inventor has carried out conscientiously research in order to achieve the above object repeatedly, found that, by being coated with, burning till the radioactive ray of the film irradiation polarization obtaining, then carry out impregnating contact processing with the solution that comprises specific organic solvent to polyimide film or by polyimide precursor, can significantly improve the anisotropy of the liquid crystal orientation film of gained, and can solve and on above-mentioned liquid crystal orientation film, produce uneven problem.
In sum, the present invention is using following content as technology contents.
1. the manufacture method of liquid crystal orientation film, it is characterized in that, for being selected from least one polymkeric substance of precursor of polyimide and this polyimide and the film of the imidizate that the aligning agent for liquid crystal of organic solvent is coated with, burns till and obtains on substrate by containing, irradiate the radioactive ray of polarization, then contact processing with comprising the following formula (A-1) that is selected from, formula (A-2), formula (A-3), formula (A-4) and the solution of at least one organic solvent of formula (A-5);
[changing 1]
In formula (A-1), A 1for hydrogen atom or acetyl group, A 2for the alkyl of carbon number 1～6, R 2for hydrogen atom or methyl, n is 1 or 2 integer; In formula (A-2), A 3for the alkyl of carbon number 1～4; In formula (A-3), R 3and R 4be hydrogen atom or methyl independently respectively; In formula (A-4), A 5and A 6be the alkyl of carbon number 1～4 independently respectively; In formula (A-5), A 6for the alkyl or cycloalkyl of carbon number 3～6.
2. the manufacture method of the liquid crystal orientation film described in above-mentioned 1, wherein, described organic solvent has the boiling point of 100～180 DEG C.
3. the manufacture method of the liquid crystal orientation film described in above-mentioned 1 or 2, wherein, described organic solvent is 1-methoxy-2-propanol, ethyl lactate, diacetone alcohol, 3-methoxy methyl propionate or 3-ethoxyl ethyl propionate.
4. the manufacture method of the liquid crystal orientation film described in any one in above-mentioned 1～3, wherein, described polymkeric substance contain be selected from have following formula (3) represent the polyimide precursor of structural unit and at least one polymkeric substance of the imide amination polymer of this polyimide precursor;
[changing 2]
In formula (3), X 1for being selected from least one of structure that following formula (X1-1)～(X1-9) represents, Y 1for divalent organic group, R 1for the alkyl of hydrogen atom or carbon number 1～4;
[changing 3]
In formula (X1-1), R 3, R 4, R 5and R 6be the alkyl of hydrogen atom, halogen atom, carbon number 1～6, alkenyl, alkenyl or the phenyl of carbon number 2～6 independently respectively.
5. the manufacture method of the liquid crystal orientation film described in above-mentioned 4, wherein, described polymkeric substance is to be selected from the polyimide precursor of structural unit of above-mentioned formulas (3) expression more than containing 60 % by mole with respect to whole polymkeric substance of 1 mole and at least one of the imide amination polymer of this polyimide precursor.
6. the manufacture method of the liquid crystal orientation film described in above-mentioned 4, wherein, in above-mentioned formula (3), X 1represent with above-mentioned formula (X1-1).
7. the manufacture method of the liquid crystal orientation film described in above-mentioned 4, wherein, in above-mentioned formula (3), X 1for being selected from least one of structure that following formula (X1-10)～(X1-11) represents.
[changing 4]
8. the manufacture method of the liquid crystal orientation film described in above-mentioned 4, wherein, in above-mentioned formula (3), Y 1for being selected from least one of structure that following formula (4) and (5) represent;
[changing 5]
In formula (5), Z 1for the divalent organic group of singly-bound, ester bond, amido link, thioester bond or carbon number 2～10.
9. the manufacture method of the liquid crystal orientation film described in above-mentioned 8, wherein, in above-mentioned formula (3), Y 1for the structure of above-mentioned formula (4) expression.
10. the contact treating fluid of liquid crystal orientation film, its be for the aligning agent for liquid crystal of at least one polymkeric substance that contains the precursor that is selected from polyimide and this polyimide is coated with, is burnt till on substrate film irradiate the radioactive ray of polarization and the liquid crystal orientation film that forms contact treating fluid, it is characterized in that, formed by the solution of at least one organic solvent that comprises the above-mentioned formula (A-1) that is selected from, formula (A-2), formula (A-3), formula (A-4) and formula (A-5).
11. liquid crystal orientation films, its manufacture method by the liquid crystal orientation film described in any one in above-mentioned 1～9 obtains.
12. liquid crystal display cells, it has the liquid crystal orientation film described in above-mentioned 11.
The effect of invention
By the manufacture method of liquid crystal orientation film of the present invention, can obtain the liquid crystal orientation film with high anisotropy that has carried out orientation process by optical alignment method, meanwhile, the liquid crystal orientation film of gained can obtain the film of the homogeneous that there is no film inequality.
In sum, the anisotropy of the liquid crystal orientation film being obtained by manufacture method of the present invention is high, and therefore liquid crystal aligning restraint is high, and ghost excellent, in the situation for liquid crystal display cells, can obtain high-grade liquid crystal display cells.
From " table 1 " that following embodiment and comparative example are contrasted, the effect of the generation of the anisotropic effect of above-mentioned raising realizing by the manufacture method of liquid crystal orientation film of the present invention, film inequality while suppressing to process has very big-difference according to the solvent using.
That is, from following " table 1 ", make, in the situation as solvent such as water, isopropyl alcohol, almost to have no the anisotropic raising of the liquid crystal orientation film of gained, meanwhile, use in the situation of these solvents, the liquid crystal orientation film of gained has also produced inequality.
But, carry out in situation that contact processes with the solution of at least one organic solvent that comprises the compound that the above-mentioned formula (A-1) that is selected from～(A-5) represents of the present invention, the anisotropic raising of liquid crystal orientation film is greatly improved, meanwhile, can significantly suppress the uneven generation on the liquid crystal orientation film of gained.
Embodiment
The precursor > of < polyimide and this polyimide
In the present invention, use and be selected from least one polymkeric substance (below also referred to as polymkeric substance) of giving the precursor of anisotropic polyimide and this polyimide by the radioactive ray of irradiation polarization.As long as meeting polyimide or the polyimide precursor of this condition, its structure is just not particularly limited.
If enumerate concrete example, because the anisotropy of the liquid crystal orientation film of gained is high, so as polymkeric substance used in the present invention, preferably there is the polyimide precursor of structural unit and the imide amination polymer of this polyimide precursor that following formula (3) represents.Consider particularly preferably there is the polyimide precursor of the structural unit of following formula (3) expression from the deliquescent viewpoint organic solvent.
[changing 6]
In formula (3), R 1for the alkyl of hydrogen atom or carbon number 1～4.From undertaken by heating imidizate complexity viewpoint consider, particularly preferably hydrogen atom or methyl.
X 1to be selected from least one of structure that following formula (X1-1)～(X1-9) represents.
[changing 7]
In formula (X1-1), R 3, R 4, R 5and R 6be the alkyl of hydrogen atom, halogen atom, carbon number 1～6, alkenyl, alkenyl or the phenyl of carbon number 2～6 independently respectively, can be the same or different.Consider R from the viewpoint of liquid crystal aligning 3, R 4, R 5and R 6difference is preferred hydrogen atom, halogen atom, methyl or ethyl, more preferably hydrogen atom or methyl independently.X 1be more preferably at least one of structure that the following formula (X1-10) that is selected from～(X1-11) represents.
[changing 8]
Y 1for divalent organic group, its structure is not particularly limited.Because the anisotropy of the liquid crystal orientation film of gained is high, so be to be better selected from following formula (Y1-1) and (Y1-2) at least one of structure of representing.
[changing 9]
In formula (5), Z 1for the divalent organic group of singly-bound, ester bond, amido link, thioester bond or carbon number 2～10.
Z 1in, ester bond with-C (O) O-or-OC (O)-represent.Amido link can illustrate with-C (O) NH-,-C (O) NR-,-NHC (O)-or-structure of NRC (O)-represent.R is alkyl, alkenyl, alkynyl, aryl or their combination of carbon number 1～10.
As the concrete example of abovementioned alkyl, can exemplified by methyl, ethyl, propyl group, butyl, the tert-butyl group, hexyl, octyl group, cyclopentyl, cyclohexyl, dicyclohexyl etc.As alkenyl, can exemplify 1 the above CH existing in abovementioned alkyl 2-CH 2structure is substituted by the group of CH=CH structure, more specifically, and can exemplified by vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl group, 1,3-butadiene base, 2-pentenyl, 2-hexenyl, cyclopropanyl, cyclopentenyl, cyclohexenyl group etc.As alkynyl, can exemplify 1 the above CH existing in abovementioned alkyl 2-CH 2structure is substituted by the group of C ≡ C-structure, more specifically, can exemplify ethinyl, 1-propinyl, 2-propynyl etc.As aryl, can exemplify as phenyl.
Thioester bond can illustrate with-C (O) S-or-structure of SC (O)-represent.
Z 1during for the organic group of carbon number 2～10, can be with the representation of following formula (6).
[changing 10]
In formula (6), Z 4, Z 5and Z 6be singly-bound ,-O-,-S-,-NR independently respectively 11-, ester bond, amido link, thioester bond, urea key, carbonic acid ester bond or amino-formate bond.R 11for hydrogen atom, methyl or tert-butoxycarbonyl.
Z 4, Z 5and Z 6in ester bond, amido link and thioester bond the structure same with above-mentioned ester bond, amido link and thioester bond can be shown.
Urea key can illustrate with-NH-C (O) NH-or-structure that NR-C (O) NR-represents.R is alkyl, alkenyl, alkynyl, aryl or their combination of carbon number 1～10, and these groups can exemplify the example same with abovementioned alkyl, alkenyl, alkynyl and aryl.
Carbonic acid ester bond can illustrate with-structure that O-C (O)-O-represents.
Amino-formate bond can illustrate with-NH-C (O)-O-,-O-C (O)-NH-,-NR-C (O)-O-or-structure that O-C (O)-NR-represents.R is alkyl, alkenyl, alkynyl, aryl or their combination of carbon number 1～10, and these groups can exemplify the example same with abovementioned alkyl, alkenyl, alkynyl and aryl.
R in formula (6) 9and R 10respectively independently for being selected from alkylidene, alkylene group, alkynylene, the arlydene of singly-bound, carbon number 1～10 or the structure of the group that combined by them.R 9and R 10in any situation that is singly-bound under, R 9or R 10in any be the structure of alkylidene, alkylene group, alkynylene, the arlydene that is selected from carbon number 2～10 or the group being combined by them.
Above-mentioned alkylidene can exemplify the structure of removing 1 hydrogen atom from abovementioned alkyl.More specifically, can exemplify methylene, 1,1-ethylidene, 1,2-ethylidene, 1,2-propylidene, 1,3-propylidene, 1,4-butylidene, 1,2-butylidene, 1,2-pentylidene, 1,2-hexylidene, 2,3-butylidene, 2,4-pentylidene, 1,2-cyclopropylidene, 1, the sub-cyclobutyl, 1 of 2-, the sub-cyclobutyl, 1 of 3-, 2-cyclopentylene, 1,2-cyclohexylidene etc.
Alkylene group can exemplify the structure of removing 1 hydrogen atom from above-mentioned alkenyl.More specifically, can exemplify 1,1-ethenylidene, 1,2-ethenylidene, 1, the sub-ethene methylene of 2-, 1-methyl isophthalic acid, 2-ethenylidene, 1, sub-ethene-1 of 2-, 1-ethylidene, 1, sub-ethene-1 of 2-, 2-ethylidene, 1, sub-ethene-1 of 2-, 2-propylidene, 1, sub-ethene-1 of 2-, 3-propylidene, 1, sub-ethene-1 of 2-, 4-butylidene, 1, sub-ethene-1 of 2-, 2-butylidene etc.
Alkynylene can exemplify the structure of removing 1 hydrogen atom from above-mentioned alkynyl.More specifically, can exemplify ethynylene, ethynylene methylene, ethynylene-1,1-ethylidene, ethynylene-1,2-ethylidene, ethynylene-1,2-propylidene, ethynylene-1,3-propylidene, ethynylene-1,4-butylidene, ethynylene-1,2-butylidene etc.
Arlydene can exemplify the structure of removing 1 hydrogen atom from above-mentioned aryl.More specifically, can exemplify 1,2-phenylene, 1,3-phenylene, Isosorbide-5-Nitrae-phenylene etc.
Y 1in the situation that contains linear high structure and rigid structure, in order to obtain having the liquid crystal orientation film of good liquid crystal aligning, as Z 1the structure of more preferably singly-bound or following formula (A1-1) of structure～(A15-25).
[changing 11]
[changing 12]
Y 1structure be the structure of rigidity more, can obtain the more excellent liquid crystal orientation film of liquid crystal aligning, therefore as Y 1structure, particularly preferably above-mentioned formula (4) represent structure.
In the polyimide precursor of structural unit and the imide amination polymer of this polyimide precursor that contains above-mentioned formula (3) expression, the entire infrastructure unit in whole polymkeric substance of the ratio of the structural unit that above-mentioned formula (3) represents with respect to 1 mole is preferably 60～100 % by mole.The ratio of structural unit that above-mentioned formula (3) represents is higher, the liquid crystal orientation film of the liquid crystal aligning that can obtain having had, therefore more preferably 80～100 % by mole, more preferably 90～100 % by mole.
Component of polymer of the present invention can be also polyimide precursor and this polyimide precursor that also contains the structural unit of following formula (7) expression except the structural unit that above-mentioned formula (3) represents.
[changing 13]
In formula (7), R 1the R with above-mentioned formula (3) 1identical definition.
X 3be 4 valency organic groups, its structure is not particularly limited.If enumerate concrete example, can exemplify the structure of following formula (X-9)～(X-42).Consider X from the viewpoint that obtains difficulty of compound 3the preferred X-17 of structure, X-25, X-26, X-27, X-28, X-32 or X-39.In addition, consider from the viewpoint that obtains the liquid crystal orientation film that the mitigation of the residual charge of accumulating is fast under the effect of DC voltage, preferably use the tetracarboxylic dianhydride with aromatic ring structure, as X 3structure, more preferably X-26, X-27, X-28, X-32, X-35 or X-37.
[changing 14]
[changing 15]
In above-mentioned formula (7), Y 4for divalent organic group, its structure is not particularly limited.If enumerate Y 4concrete example, can exemplify the structure of following formula (Y-1)～(Y-74).
[changing 16]
[changing 17]
[changing 18]
[changing 19]
[changing 20]
Because the dissolubility excellence of component of polymer in organic solvent, so as the Y in formula (7) 4, preferably contain the structural unit of the structure with Y-8, Y-20, Y-21, Y-22, Y-28, Y-29, Y-30, Y-72, Y-73 or Y-74.
In the high situation of the ratio of the structural unit that above-mentioned formula (7) in component of polymer represents, in order to reduce the liquid crystal aligning of liquid crystal orientation film, the entire infrastructure unit of the ratio of the structural unit that above-mentioned formula (7) represents with respect to 1 mole is preferably 0～40 % by mole, more preferably 0～20 % by mole.
The manufacture method > of < poly amic acid ester
Poly amic acid ester as polyimide precursor used in the present invention can synthesize by the method for (1) shown below～(3).
(1) carry out synthetic situation by polyamic acid
Poly amic acid ester can synthesize by the polyamic acid being obtained by tetracarboxylic dianhydride and diamines is carried out to esterification.
Particularly, can be by making polyamic acid and esterifying agent under the existence of organic solvent, in-20 DEG C～150 DEG C, preferably 0 DEG C～50 DEG C reactions 30 minutes～24 hours, preferably within 1～4 hour, synthesize.
As esterifying agent, the esterifying agent that preferably can easily remove by purifying, can exemplify N, dinethylformamide dimethylacetal, N, dinethylformamide diethyl acetal, N, dinethylformamide dipropyl acetal, N, dinethylformamide di neo-pentyl butyl acetal, N, dinethylformamide di-t-butyl acetal, 1-methyl-3-p-methylphenyl triazenes, 1-ethyl-3-p-methylphenyl triazenes, 1-propyl group-3-p-methylphenyl triazenes, 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methyl morpholine chloride etc.The repetitive of the polyamic acid of the addition of esterifying agent with respect to 1 mole is preferably 2～6 molar equivalents, more preferably 2～4 molar equivalents.
Consider from the dissolubility of polymkeric substance, the organic solvent using in above-mentioned reaction is better DMF, METHYLPYRROLIDONE, gamma-butyrolacton etc., and these organic solvents can use one kind or two or more mixing to use.
From being difficult for causing the viewpoint consideration of separating out and easily obtain high molecular body of polymkeric substance, the concentration of the polymkeric substance in the organic solvent when synthetic is preferably 1～30 quality %, more preferably 5～20 quality %.
(2) carry out synthetic situation by the reaction of tetrabasic carboxylic acid diester diacid chloride and diamines
Poly amic acid ester can be synthetic by tetrabasic carboxylic acid diester diacid chloride and diamines.
Particularly, can be by making tetrabasic carboxylic acid diester diacid chloride and diamines under the existence of alkali and organic solvent, in-20～150 DEG C, preferably 0～50 DEG C of reaction 30 minutes～24 hours, preferably within 1～4 hour, synthesize.
Above-mentioned alkali can use pyridine, triethylamine, 4-dimethylaminopyridine etc., for reaction is leniently carried out, and preferably pyridine.Consider from the amount of easily removing and the viewpoint that easily obtains high molecular body, the addition of alkali is preferably 2～4 times moles with respect to tetrabasic carboxylic acid diester diacid chloride, more preferably 2～3 times moles.
Consider from the dissolubility of monomer and polymkeric substance, the organic solvent using in above-mentioned reaction is better METHYLPYRROLIDONE, gamma-butyrolacton etc., and these organic solvents can use one kind or two or more mixing to use.
From being difficult for causing the viewpoint consideration of separating out and easily obtain high molecular body of polymkeric substance, the polymer concentration in the organic solvent when synthetic is preferably 1～30 quality %, more preferably 5～20 quality %.In addition, in order to prevent the hydrolysis of tetrabasic carboxylic acid diester diacid chloride, the preferably farthest dehydration of the synthetic middle organic solvent using of poly amic acid ester, reaction preferably carries out preventing sneaking into of ambient atmos in blanket of nitrogen.
(3) carried out the situation of synthesizing polyamides acid by tetrabasic carboxylic acid diester and diamines
Poly amic acid ester can be by synthesizing tetrabasic carboxylic acid diester and diamines polycondensation.
Particularly, can be by making tetrabasic carboxylic acid diester and diamines under the existence of condensation agent, alkali and organic solvent, in 0 DEG C～150 DEG C, preferably 0 DEG C～100 DEG C reactions 30 minutes～24 hours, preferably within 3～15 hours, synthesize.
As above-mentioned condensation agent, can use triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazine methyl morpholine, O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea tetrafluoroborate, O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea hexafluorophosphate, (2,3-dihydro-2-sulfo--3-benzo azoles base) phosphonic acid diphenyl ester etc.The addition of condensation agent is preferably 2～3 times moles with respect to tetrabasic carboxylic acid diester, more preferably 2～2.5 times moles.
Above-mentioned alkali can use the tertiary amine such as pyridine, triethylamine.From being that the amount of easily removing and the viewpoint that easily obtains high molecular body are considered, the addition of alkali is preferably 2～4 times moles with respect to two amine components, more preferably 2～3 times moles.
As above-mentioned organic solvent, can exemplify METHYLPYRROLIDONE, gamma-butyrolacton, DMF etc.
In addition, in above-mentioned reaction, add lewis acid can make reaction carry out efficiently as adjuvant.As lewis acid, the lithium halides such as preferred lithium chloride, lithium bromide.Lewis acidic addition is preferably 0.1～5 times mole with respect to two amine components, more preferably 2～3 times moles.
In the synthetic method of above-mentioned 3 kinds of poly amic acid esters, in order to obtain the poly amic acid ester of high molecular, the particularly preferably synthetic method of above-mentioned (1) or (2).
The solution of the poly amic acid ester making as mentioned above can separate out polymkeric substance by well-beaten being injected in poor solvent simultaneously.After carrying out that several is separated out and cleaning with poor solvent, at normal temperatures or heat drying, can obtain the powder of purified poly amic acid ester.Poor solvent is not particularly limited, can exemplifies water, methyl alcohol, ethanol, 2-propyl alcohol, hexane, butyl cellosolve, acetone, toluene etc., preferred water, methyl alcohol, ethanol, 2-propyl alcohol etc.
The manufacture method > of < polyamic acid
Poly amic acid ester as polyimide precursor used in the present invention can synthesize by method shown below.
Particularly, can be by making tetracarboxylic dianhydride and diamines under the existence of organic solvent, in-20 DEG C～150 DEG C, preferably 0 DEG C～50 DEG C reactions 30 minutes～24 hours, preferably within 1～12 hour, synthesize.
Consider from the dissolubility of monomer and polymkeric substance, the organic solvent using in above-mentioned reaction is better DMF, METHYLPYRROLIDONE, gamma-butyrolacton etc., and these organic solvents can use one kind or two or more mixing to use.
From being difficult for occurring the viewpoint consideration of separating out and easily obtain high molecular body of polymkeric substance, the concentration of polymkeric substance is preferably 1～30 quality %, more preferably 5～20 quality %.
The polyamic acid making as mentioned above can be by make polymkeric substance separate out and reclaim reaction solution is well-beaten in being injected into poor solvent simultaneously.In addition, after carrying out that several is separated out and cleaning with poor solvent, can obtain the powder of purified polyamic acid by normal temperature or heat drying.Poor solvent is not particularly limited, can exemplifies water, methyl alcohol, ethanol, 2-propyl alcohol, hexane, butyl cellosolve, acetone, toluene etc., preferred water, methyl alcohol, ethanol, 2-propyl alcohol etc.
The manufacture method > of < polyimide
Polyimide used in the present invention can be by manufacturing above-mentioned poly amic acid ester or polyamic acid imidizate.
Manufactured by poly amic acid ester in the situation of polyimide, easy is chemical imidization, this chemical imidization is to make above-mentioned polyamic acid ester solution or poly amic acid ester toner be dissolved in organic solvent, in the polyamic acid solution of gained, adds base catalyst.Chemical imidization is at lower temperature, to carry out imidization reaction, and in the process of imidizate, is difficult for occurring the reduction of polymer molecular weight, therefore preferred.
Chemical imidization can be by stirring the poly amic acid ester of wanting imidizate to carry out in organic solvent, under the existence of base catalyst.As organic solvent, solvent used can use above-mentioned polyreaction time.As base catalyst, can exemplify pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc.Wherein preferred triethylamine, because it has the enough alkalescence that the reaction of making is carried out.
Temperature while carrying out imidization reaction can be-20 DEG C～140 DEG C, is preferably 0 DEG C～100 DEG C, and the reaction time can be 1～100 hour.The amount of base catalyst is 0.5～30 times mole of amic acid ester group, is preferably 2～20 times moles.The acid imide rate of the polymkeric substance obtaining can be by regulating catalytic amount, temperature, reaction time to control.
Manufactured by polyamic acid in the situation of polyimide, easy is chemical imidization, and this chemical imidization is to add catalyzer in the solution of the above-mentioned polyamic acid being made by two amine components and tetracarboxylic dianhydride's reaction.Chemical imidization is at lower temperature, to carry out imidization reaction, and in the process of imidizate, is difficult for occurring the reduction of polymer molecular weight, therefore preferred.
The polymkeric substance that chemical imidization can be wanted by stirring in organic solvent, under the existence of base catalyst and acid anhydrides imidizate carries out.As organic solvent, solvent used can use above-mentioned polyreaction time.As base catalyst, can exemplify pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc.Wherein preferred pyridine, because it has the suitable alkalescence that the reaction of making is carried out.In addition, as acid anhydrides, can exemplify acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc., wherein, while using acetic anhydride, be easy to react the purifying after finishing, therefore preferred.
Temperature while carrying out imidization reaction can be-20 DEG C～140 DEG C, is preferably 0 DEG C～100 DEG C, and the reaction time can be 1～100 hour.The amount of base catalyst is 0.5～30 times mole of polyamide acidic group, is preferably 2～20 times moles, and the amount of acid anhydrides is 1～50 times mole of polyamide acidic group, is preferably 3～30 times moles.The acid imide rate of the polymkeric substance obtaining can be by regulating catalytic amount, temperature, reaction time to control.
In solution after the imidization reaction of poly amic acid ester or polyamic acid, remaining the catalyzer of interpolation etc., is better therefore by following method, after reclaiming the imide amination polymer that makes and dissolving with organic solvent again, as aligning agent for liquid crystal of the present invention.
The solution of the polyimide making as mentioned above can be by separate out polymkeric substance well-beaten in being injected into poor solvent simultaneously.After carrying out that several is separated out and cleaning with poor solvent, at normal temperatures or heat drying, can obtain the powder of purified polymkeric substance.
Above-mentioned poor solvent is not particularly limited, can exemplifies methyl alcohol, 2-propyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene etc., particular methanol, ethanol, 2-propyl alcohol, acetone etc.
< aligning agent for liquid crystal >
In the present invention, aligning agent for liquid crystal used has component of polymer and is dissolved in the form of the solution in organic solvent.The molecular weight of polymkeric substance is preferably 2000～500000 in weight-average molecular weight, and more preferably 5000～300000, more preferably 10000～100000.In addition, number-average molecular weight is preferably 1000～250000, and more preferably 2500～150000, more preferably 5000～50000.
In the present invention the concentration of the polymkeric substance of aligning agent for liquid crystal used can be according to wanting the setting of thickness of the film forming appropriate change, consider from the viewpoint that forms uniform flawless film, be better more than 1 quality %, consider it is better below 10 quality % from the viewpoint of the storage stability of solution.The concentration of particularly preferred polymkeric substance is 2～8 quality %.
In the present invention, in aligning agent for liquid crystal used, contained organic solvent, as long as the organic solvent that component of polymer dissolves equably, is not particularly limited.If enumerate its concrete example, can exemplify N, dinethylformamide, N, N-diethylformamide, N, N-dimethyl acetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, 2-Pyrrolidone, NVP, dimethyl sulfoxide, dimethyl sulfone, gamma-butyrolacton, 1,3-dimethyl-2-imidazolidinone, 3-methoxyl-N, N-dimethyl propylene acid amides etc.These solvents can use a kind or by two or more mix use.In addition, even the solvent of dissolve polymer composition equably while use separately, as long as in the scope of not separating out at polymkeric substance, also can mix with above-mentioned organic solvent.
Aligning agent for liquid crystal used in the present invention, except comprising the organic solvent taking dissolve polymer composition as object, also can comprise to improve the solvent that painting film uniformity when aligning agent for liquid crystal is coated to substrate is object.This solvent uses the solvent of low surface tension compared with above-mentioned organic solvent conventionally.As its concrete example, can exemplify ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetic acid esters, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, single acetic acid propylene glycol ester, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, mono-ethylether-the 2-of propylene glycol-1-acetic acid esters, butyl cellosolve acetate, dipropylene glycol, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc.These solvents can and be used two or more.
In aligning agent for liquid crystal of the present invention, except mentioned component, as long as not damaging in the scope of effect of the present invention, also can add polymkeric substance polymkeric substance in addition, to change the electrical characteristics such as specific inductive capacity or electric conductivity of liquid crystal orientation film as dielectric or the conductive materials of object, to improve the adaptation of liquid crystal orientation film and substrate as the silane coupling agent of object, the hardness of the film while making liquid crystal orientation film to improve or density are the cross-linked compound of object, and taking the imidizate that makes polyamic acid in the time burning till film efficiently as imidizate promoter of object etc.
The manufacture method > of < liquid crystal orientation film
The manufacture method of liquid crystal orientation film of the present invention comprises: the operation that aligning agent for liquid crystal is coated to substrate, burnt till; The film of gained is irradiated to the operation of the radioactive ray of polarization; Contacted the operation of processing to irradiating the film of radioactive ray with specific organic solvent.
(1) operation of aligning agent for liquid crystal is coated to substrate, burning till
The aligning agent for liquid crystal making is as mentioned above coated to substrate, dry, burn till, thereby obtain the film of polyimide film or polyimide precursor imidizate.
As the substrate of aligning agent for liquid crystal used in coating the present invention, the substrate high as long as the transparency is not particularly limited, can use the plastic bases such as glass substrate, silicon nitride board, acrylic acid substrate or polycarbonate substrate etc., from the angle that production technology is simplified, preferably use the substrate being formed with for the ITO electrode of liquid crystal drive etc.In addition, in reflection type liquid crystal display element, can use the opaque materials such as silicon wafer, but only limit to the substrate of a side, electrode now also can use the reflectorized materials such as aluminium.As the coating process of aligning agent for liquid crystal used in the present invention, can exemplify spin-coating method, print process, ink-jet method etc.
Dry, firing process after coating of liquid crystalline alignment agent can be selected arbitrary temp and time.Conventionally, in order fully to remove the organic solvent containing, 50～120 DEG C, preferably 60～100 DEG C make its dry 1～10 minute, then 150～300 DEG C, preferably 200～250 DEG C burn till 5～120 minutes.The thickness of the film after burning till is not particularly limited, if but excessively thin, the reliability of liquid crystal display cells can reduce sometimes, is therefore 5～300nm, preferably 10～200nm.
(2) operation of the radioactive ray of the film irradiation polarization to gained
The film obtaining by the method for above-mentioned (1) is irradiated to the radioactive ray (below also referred to as light orientation process) of polarization, thereby give anisotropy in the direction vertical with polarization direction.
As the concrete example of light orientation process, can exemplify and in above-mentioned film coated surface, irradiate the radioactive ray to certain orientation polarization, according to circumstances further at the temperature of 150～250 DEG C, carry out heat treated, give the method for liquid crystal aligning ability.The wavelength of radioactive ray can use ultraviolet ray and the visible ray of the wavelength with 100～800nm.Wherein, preferably there is the ultraviolet ray of the wavelength of 100～400nm, particularly preferably there is the ultraviolet ray of the wavelength of 200～400nm.
The exposure of above-mentioned radioactive ray is preferably at 1～10000mJ/cm 2scope in, particularly preferably in 100～5000mJ/cm 2scope in.
(3) contacted to irradiating the film of radioactive ray the operation of processing with the solution that comprises organic solvent
The film that irradiated as mentioned above the radioactive ray of polarization contacts processing with the solution that comprises specific organic solvent subsequently.Here organic solvent used is at least one organic solvent or the organic solvent that is selected from following formula (A-1), formula (A-2), formula (A-3), formula (A-4) and formula (A-5).
[changing 21]
In formula (A-1), A 1for hydrogen atom or acetyl group, A 2for the alkyl of carbon number 1～6, R 2for hydrogen atom or methyl, n is 1 or 2 integer.
In formula (A-2), A 3for the alkyl of carbon number 1～4.
In formula (A-3), R 3and R 4be hydrogen atom or methyl independently respectively.
In formula (A-4), A 5and A 6be the alkyl of carbon number 1～4 independently respectively.
In formula (A-5), A 6for the alkyl or cycloalkyl of carbon number 3～6.
As the organic solvent of above-mentioned formula (A-1)～(A-5), suitable is boiling point is preferably 100～180 DEG C, the water miscible organic solvent of 110～160 DEG C more preferably.In the high situation of boiling point, can remain in film, the characteristic of liquid crystal orientation film is caused to harmful effect, on the other hand, in low-boiling situation, because easily volatilization is so film easily produces inequality, undesirable.
In the organic solvent of above-mentioned formula (A-1)～(A-5), because easily obtain anisotropy high, without uneven liquid crystal orientation film, so be to be better selected from least one of 1-methoxy-2-propanol, 1-methoxy-2-propanol acetic acid esters, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3-methoxy methyl propionate, 3-ethoxyl ethyl propionate, propyl acetate, butyl acetate and cyclohexyl acetate.Particularly preferably be selected from least one of 1-methoxy-2-propanol and ethyl lactate.
Comprise other solvent or solvent beyond the organic solvent that the solution of organic solvent that contact uses in processing also can comprise above-mentioned formula (A-1)～(A-5) in the scope of not damaging effect of the present invention.Be not particularly limited as other solvent, can exemplify water, methyl alcohol, ethanol, 2-propyl alcohol, acetone, methyl ethyl ketone etc.Particularly consider more preferably water from the viewpoint of versatility and security.
In the situation that contains above-mentioned other solvent, the total amount of the solution that the content that is selected from least one organic solvent of above-mentioned formula (A-1)～(A-5) uses in processing with respect to contact is preferably 10～100 quality %, more preferably 30～100 quality %, are particularly preferably 50～100 quality %.
In the present invention, the film that irradiated the radioactive ray of polarization is processed by dip treating, spraying (spray) processing etc., preferably the processing that film fully contacts with liquid is carried out with contacting of the solution that comprises organic solvent.Wherein, be better by film dip treating preferably 10 seconds～1 hour, more preferably method of 1～30 minute in the solution that comprises organic solvent.Contact is processed and can be carried out at normal temperatures also can under heating, carrying out, and is preferable over 10～80 DEG C, more preferably in 20～50 DEG C of enforcements.In addition, can implement as required the method for the contact-enhancings such as ultrasound wave.
After above-mentioned contact is processed, in order to remove the organic solvent in used solution, can water, the low boiling point solvent such as methyl alcohol, ethanol, 2-propyl alcohol, acetone, methyl ethyl ketone wash (flushings) and be dried in any one or both.Temperature when dry, is better 80～250 DEG C, is more preferably 80～150 DEG C.
< liquid crystal display cells >
Liquid crystal display cells of the present invention is to obtain after substrate with the liquid crystal orientation film being obtained by aligning agent for liquid crystal by manufacture method of the present invention, with known method manufacture liquid crystal structure cell, makes liquid crystal display cells with this liquid crystal structure cell.
As an example of the manufacture method of liquid crystal structure cell, describe as an example of the liquid crystal display cells of passive-matrix structure example.In addition, can be also the liquid crystal display cells that is provided with the active matrix structure of the on-off elements such as TFT (thin film transistor (TFT) (Thin Film Transistor)) in each pixel portion of composing images demonstration.
First, prepare the substrate of transparent glass system, on a side substrate, common electrode is set, on the opposing party's substrate, segment electrode is set.These electrodes can be for example ITO electrodes, are formed as carrying out the pattern of required image demonstration.Then, on each substrate, with the form of coating common electrode and segment electrode, dielectric film is set.Dielectric film can be for example form by sol-gel process by SiO 2-TiO 2the film forming.
Then, on each substrate, form liquid crystal orientation film of the present invention.
Then, with orientation face each other overlapping the opposing party's of mode in opposite directions substrate, periphery is bonding with encapsulant on a side substrate.In order to control substrate gap, in encapsulant, conventionally sneak in advance sept.In addition, be better that part is also scattered the sept for controlling substrate gap in advance in the face that encapsulant is not set.Setting in advance in a part for encapsulant can be from the peristome of outside filling liquid crystal.
Then,, by being arranged at the peristome of encapsulant, in the space being surrounded by two substrates and encapsulant, inject liquid crystal material.Then, this peristome is sealed with bonding agent.Injection can be used vacuum impregnation, also can use the method for utilizing capillarity in atmosphere.Then, carry out the setting of polaroid.Particularly, on the face of the side contrary with liquid crystal layer of two substrates, paste a pair of polaroid.Through above operation, can obtain liquid crystal display cells of the present invention.This liquid crystal display cells is owing to using the liquid crystal orientation film making by the manufacture method of liquid crystal orientation film of the present invention as liquid crystal orientation film, so ghost excellent can be suitable for the LCD TV of large picture and high-resolution etc.
Embodiment
Below, exemplify embodiment the present invention is carried out to more specific description, but the present invention is not limited thereto.
The abbreviation of the compound using in embodiment and comparative example and the assay method of each characteristic are as described below.
NMP:N-N-methyl-2-2-pyrrolidone N-
GBL: gamma-butyrolacton
BCS: butyl cellosolve
IPA:2-propyl alcohol
PGMEA:1-methoxy-2-propanol acetic acid esters
PG: propylene glycol
MMP:3-methoxy methyl propionate
DE-1: following formula (DE-1)
DA-1: following formula (DA-1)
DA-2: following formula (DA-2)
DA-3: following formula (DA-3)
Additive A: N-α-(9-fluorenyl methoxy carbonyl)-N-τ-tert-butoxycarbonyl-L-Histidine
[changing 22]
The anisotropy of molecular weight, alignment films and the evaluation method of film inequality are below shown.
[molecular weight]
The molecular weight of poly amic acid ester is to adopt GPC (normal temperature gel permeation chromatography) device to measure, and calculates number-average molecular weight (Mn) and weight-average molecular weight (Mw) with polyglycol and polyethylene oxide scaled value.
GPC device: Shodex company (Showa Denko K. K) system (GPC-101)
Post: Showa Denko K. K's system (series connection of KD803, KD805)
Column temperature: 50 DEG C
Eluent: DMF (as adjuvant, lithium bromide-hydrate (LiBrH 2o) be that 30mmol/L (liter), phosphoric anhydride crystallization (o-phosphoric acid) are that 30mmol/L, tetrahydrofuran (THF) are 10ml/L)
Flow velocity: 1.0ml/ minute
Calibration curve making standard sample: Dong Cao company (East ソ ー society) TSK standard polyethylene oxide processed (weight-average molecular weight (Mw) approximately 900000,150000,100000,30000) and polymkeric substance laboratory company (Port リ マ ー ラ ボ ラ ト リ ー society) polyglycol processed (spike molecular weight (Mp) approximately 12000,4000,1000).For fear of overlap of peaks, two samples are measured respectively, mix 900000,100000,12000,1000 these samples of 4 kinds and mixed 150000,30000,4000 these samples of 3 kinds.
[anisotropy of alignment films]
Anisotropic mensuration of carrying out alignment films as described below.
Measure with the ultraviolet-visible-near infrared spectrometer (UV-3100PC) of Shimadzu Corporation (Island Tianjin System Zuo Suo society) system.Measure anisotropic size according to the absorbance in the absorbance in the direction of orientation of the alignment films of gained (value of 235nm) and the direction vertical with direction of orientation.
[film inequality]
The evaluation of film inequality is the band film substrate detecting by an unaided eye after dip treating, the as described below classification.
Zero: without uneven
△: visible less inequality
×: larger inequality or albefaction as seen
< synthesis example 1>
Making becomes blanket of nitrogen in the 500mL four-hole boiling flask with stirring apparatus, drop into the p-phenylenediamine (PPD) of 4.58g (42.4mmol), and then drop into after the DA-1 of 1.79g (4.71mmol), add 84.7g NMP, 254g GBL and as 8.40g (106mmol) pyridine of alkali, stir and make its dissolving.Then, stir this two amine aqueous solution on one side, add the DE-1 of 14.4g (44.2mmol) on one side, at 15 DEG C, react a Dinner.Stir after the evening, add the acryloyl chloride of 1.23g (13.6mmol), at 15 DEG C, react 4 hours.Stir while the polyamic acid ester solution obtaining is joined in the IPA of 1477g, the white precipitate that leaching is separated out, then cleans 5 times with the IPA of 738g, and drying obtains the poly amic acid ester toner of 17.3g white.Yield is 96.9%.In addition, the molecular weight of this poly amic acid ester is Mn=14288, Mw=29956.
The poly amic acid ester toner that 3.69g is obtained is taken in 100ml Erlenmeyer flask, adds the GBL of 33.2g, at room temperature stirs and within 24 hours, makes it dissolve, and obtains polyamic acid ester solution.
< synthesis example 2>
Adding the polyamic acid ester solution obtaining in getting 5.26g synthesis example 1 in having the 20mL of stirrer stopple coupon, add the BCS of GBL, 2.11g and the additive A of 0.19g of 3.16g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal A.
< synthesis example 3>
Making becomes blanket of nitrogen in the 500mL four-hole boiling flask with stirring apparatus, drop into the p-phenylenediamine (PPD) of 2.50g (23.1mmol), and then drop into after the DA-2 of 0.59g (1.22mmol), add 42.8g NMP, 129g GBL and as 4.34g (54.9mmol) pyridine of alkali, stir and make its dissolving.Then, stir this two amine aqueous solution on one side, add the DE-1 of 7.44g (22.9mmol) on one side, at 15 DEG C, react a Dinner.Stir after the evening, add the acryloyl chloride of 0.63g (7.01mmol), at 15 DEG C, react 4 hours.Stir while the polyamic acid ester solution obtaining is joined in the IPA of 574g, the white precipitate that leaching is separated out, then cleans 5 times with the IPA of 382g, and drying obtains the poly amic acid ester toner of 8.82g white.Yield is 97.8%.In addition, the molecular weight of this poly amic acid ester is Mn=16617, Mw=37387.
The poly amic acid ester toner that 0.80g is obtained is taken in 100ml Erlenmeyer flask, adds the GBL of 7.20g, at room temperature stirs and within 24 hours, makes it dissolve, and obtains polyamic acid ester solution.
< synthesis example 4>
Adding the polyamic acid ester solution obtaining in getting 8.00g synthesis example 3 in having the 20mL of stirrer stopple coupon, add the BCS of GBL, 4.00g and the additive A of 0.28g of 8.01g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal B.
< synthesis example 5>
Making becomes blanket of nitrogen in the 500mL four-hole boiling flask with stirring apparatus, drop into the p-phenylenediamine (PPD) of 1.23g (11.3mmol), and then drop into 0.80g (3.77mmol) 4,4 '-diaminostilbene, after 2-diphenylethane, add 27.0g NMP, 91.2g GBL and as 2.69g (34.0mmol) pyridine of alkali, stir and make its dissolving.Then, stir this two amine aqueous solution on one side, add the DE-1 of 4.61g (14.2mmol) on one side, at 15 DEG C, react a Dinner.Stir after the evening, add the acryloyl chloride of 0.39g (4.34mmol), at 15 DEG C, react 4 hours.Stir while the polyamic acid ester solution obtaining is joined in the IPA of 384g, the white precipitate that leaching is separated out, then cleans 5 times with the IPA of 256g, and drying obtains the poly amic acid ester toner of 5.11g white.Yield is 89.6%.In addition, the molecular weight of this poly amic acid ester is Mn=14806, Mw=32719.
The poly amic acid ester toner that 0.80g is obtained is taken in 100ml Erlenmeyer flask, adds the GBL of 7.20g, at room temperature stirs and within 24 hours, makes it dissolve, and obtains polyamic acid ester solution.
< synthesis example 6>
Adding the polyamic acid ester solution obtaining in getting 8.01g synthesis example 5 in having the 20mL of stirrer stopple coupon, add the BCS of GBL, 4.00g and the additive A of 0.28g of 8.01g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal C.
< synthesis example 7>
Making becomes blanket of nitrogen in the 500mL four-hole boiling flask with stirring apparatus, drop into the p-phenylenediamine (PPD) of 2.80g (25.9mmol), and then drop into after the DA-3 of 1.45g (6.47mmol), add the NMP of 111g and 6.18g (78.1mmol) pyridine as alkali, stir and make its dissolving.Then, stir this two amine aqueous solution on one side, add the DE-1 of 9.89g (30.4mmol) on one side, at 15 DEG C, react a Dinner.Stir after the evening, add the acryloyl chloride of 0.38g (4.21mmol), at 15 DEG C, react 4 hours.Stir while the polyamic acid ester solution obtaining is joined in the water of 1230g, the white precipitate that leaching is separated out, then cleans 5 times with the IPA of 1230g, and drying obtains the poly amic acid ester toner of 10.2g white.Yield is 83.0%.In addition, the molecular weight of this poly amic acid ester is Mn=20786, Mw=40973.
The poly amic acid ester toner that 0.798g is obtained is taken in 100ml Erlenmeyer flask, adds the GBL of 7.18g, at room temperature stirs and within 24 hours, makes it dissolve, and obtains polyamic acid ester solution.
< synthesis example 8>
Adding the polyamic acid ester solution obtaining in getting 7.98g synthesis example 7 in having the 20mL of stirrer stopple coupon, add the BCS of GBL, 4.00g and the additive A of 0.28g of 8.03g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal D.
< synthesis example 9>
In the 300mL four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, drop into the p-phenylenediamine (PPD) of 46.0g (0.43mol), the DA-3 of 17.8g (0.075mol) and the NMP of 1389g, stir and make its dissolving.Stir this solution while add 1 of 107g (0.48mol), 3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, then add NMP to make solid component concentration reach 10 quality %, at room temperature stir 24 hours, obtain the solution of polyamic acid (PAA-1).The viscosity of this polyamic acid solution at 25 DEG C of temperature is 215mPas.In addition, the molecular weight of this polyamic acid is Mn=12629, Mw=29521.
< synthesis example 10>
Adding the polyamic acid solution (PAA-1) obtaining in getting 11.0g synthesis example 9 in having the 50mL of stirrer stopple coupon, the BCS of NMP, 4.01g and the additive A of 0.15g of 5.00g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal E.
< synthesis example 11>
In the 100ml four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, get 4 of 4.25g (20.0mmol), 4 '-diaminostilbene, 2-diphenylethane, adds the NMP of 70.9g, limit to pass into nitrogen limit and stirs and make its dissolving.Stir this two amine aqueous solution while add 1,2,3 of 3.82g (19.5mmol), 4-cyclo-butane tetracarboxylic dianhydride, add again NMP to make solid component concentration reach 10 quality %, at room temperature stir 24 hours, obtain the solution of polyamic acid (PAA-2).The viscosity of this polyamic acid solution at 25 DEG C of temperature is 156mPas.In addition, the molecular weight of this polyamic acid is Mn=13966, Mw=33163.
< synthesis example 12>
Adding the polyamic acid solution (PAA-2) obtaining in getting 12.2g synthesis example 11 in having the 20ml of stirrer stopple coupon, add the NMP of 5.12g and the BCS of 2.90g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal F.
< synthesis example 13>
In the 100ml four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, get 1 of 5.17g (20.0mmol), two (4-amino-benzene oxygen) propane of 3-, adds the NMP of 72.0g, limit to pass into nitrogen limit and stirs and make its dissolving.Stir this two amine aqueous solution while add 1,2,3 of 3.79g (19.3mmol), 4-cyclo-butane tetracarboxylic dianhydride, add again NMP to make solid component concentration reach 10 quality %, at room temperature stir 24 hours, obtain the solution of polyamic acid (PAA-3).The viscosity of this polyamic acid solution at 25 DEG C of temperature is 162mPas.In addition, the molecular weight of this polyamic acid is Mn=25902, Mw=40413.
< synthesis example 14>
Adding the polyamic acid solution (PAA-3) obtaining in getting 11.9g synthesis example 13 in having the 20ml of stirrer stopple coupon, add the NMP of 3.98g and the BCS of 3.97g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal G.
< embodiment 1>
After the aligning agent for liquid crystal A obtaining in synthesis example 2 is filtered with the filter of 1.0 μ m, be spin-coated on glass substrate, dry after 3 minutes on the heating plate of 80 DEG C of temperature, burn till 10 minutes in 230 DEG C, obtain the polyimide film that thickness is 100nm.Across polaroid, this coated surface is irradiated to 1.2J/cm 2254nm ultraviolet ray.
Then, by the band film substrate making as mentioned above in PGME (boiling point: 120 DEG C) in 25 DEG C of dippings after 3 minutes, rinse (washing) 1 minute with IPA, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.Anisotropy in the direction of orientation of mensuration gained liquid crystal orientation film, the anisotropic size of result is 1.84.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 2>
Similarly to Example 1, use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in PGMEA (boiling point: 146 DEG C), rinse 1 minute with IPA, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.51.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 3>
Similarly to Example 1, use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in the mixed solvent of PGME/ water=1/1 (volume ratio), rinse 1 minute with IPA, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.69.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 4>
Similarly to Example 1, use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in ethyl lactate (boiling point: 154 DEG C), rinse 1 minute with IPA, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.9.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 5>
Similarly to Example 1, use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 10 minutes in 25 DEG C in butyl cellosolve (boiling point: 169 DEG C), rinse 1 minute with IPA, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.69.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 6>
Similarly to Example 1, use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in PGME (boiling point: 124 DEG C), water rinses 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtains liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.82.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 7>
Similarly to Example 1, use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in ethyl lactate (boiling point: 154 DEG C), water rinses 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtains liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.84.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 8>
Similarly to Example 1, use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in diacetone alcohol (boiling point: 169 DEG C), water rinses 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtains liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.77.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 9>
Similarly to Example 1, use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in MMP (boiling point: 145 DEG C), water rinses 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtains liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.77.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 10>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal B obtaining in synthesis example 4, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in PGME (boiling point: 120 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.72.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 11>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal B obtaining in synthesis example 4, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in ethyl lactate (boiling point: 154 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 2.11.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 12>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal C obtaining in synthesis example 6, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in PGME (boiling point: 120 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.53.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 13>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal C obtaining in synthesis example 6, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in ethyl lactate (boiling point: 154 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.94.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 14>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal D obtaining in synthesis example 8, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in PGME (boiling point: 120 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.40.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 15>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal D obtaining in synthesis example 8, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in ethyl lactate (boiling point: 154 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.70.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 16>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in PGME (boiling point: 120 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.37.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 17>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in ethyl lactate (boiling point: 154 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.77.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 18>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal E obtaining in synthesis example 10, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in PGME (boiling point: 120 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.33.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 19>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal E obtaining in synthesis example 10, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in ethyl lactate (boiling point: 154 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.2.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 20>
Except irradiating 1.0J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal F obtaining in synthesis example 12, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in PGME (boiling point: 120 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.15.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 21>
Except irradiating 1.0J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal F obtaining in synthesis example 12, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in ethyl lactate (boiling point: 154 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.12.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 22>
Except irradiating 1.0J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal G obtaining in synthesis example 14, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in PGME (boiling point: 120 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.11.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< embodiment 23>
Except irradiating 1.0J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal G obtaining in synthesis example 14, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in ethyl lactate (boiling point: 154 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.10.In addition, the liquid crystal orientation film that detects by an unaided eye, it is uneven that result has no.
< comparative example 1>
Similarly to Example 1, use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in IPA (boiling point: 82.4 DEG C), the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.2.In addition, the alignment films that detects by an unaided eye, the visible less inequality of result.
< comparative example 2>
Similarly to Example 1, use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate was flooded after 3 minutes in water (boiling point: 100 DEG C), rinse 1 minute with IPA, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.25.In addition, the liquid crystal orientation film that detects by an unaided eye, the visible less inequality of result.
< comparative example 3>
Similarly to Example 1, use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in PG (boiling point: 187 DEG C), rinse 1 minute with IPA, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.45.In addition, the alignment films that detects by an unaided eye, result is larger inequality or albefaction as seen.
< comparative example 4>
Similarly to Example 1, use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in GBL (boiling point: 204 DEG C), rinse 1 minute with IPA, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
The film of the liquid crystal orientation film of gained dissolves completely, cannot carry out the mensuration of anisotropic mensuration and thickness.
< comparative example 5>
Similarly to Example 1, use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in NMP (boiling point: 202 DEG C), rinse 1 minute with IPA, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
The film of the liquid crystal orientation film of gained dissolves completely, cannot carry out the mensuration of anisotropic mensuration and thickness.
< comparative example 6>
Similarly to Example 1, use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, the polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, the anisotropic size in this direction of orientation with the liquid crystal orientation film on film substrate is 1.18.Do not observe the film inequality of liquid crystal orientation film.
< comparative example 7>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal B obtaining in synthesis example 4, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in IPA (boiling point: 82.4 DEG C), the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.19.In addition, the alignment films that detects by an unaided eye, the visible less inequality of result.
< comparative example 8>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal B obtaining in synthesis example 4, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate was flooded after 3 minutes in water (boiling point: 100 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.17.In addition, the liquid crystal orientation film that detects by an unaided eye, the visible less inequality of result.
< comparative example 9>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal B obtaining in synthesis example 4, on substrate, be coated with, be dried, burn till, the polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, the anisotropic size in this direction of orientation with the liquid crystal orientation film on film substrate is 1.12.Do not observe the film inequality of liquid crystal orientation film.
< comparative example 10>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal C obtaining in synthesis example 6, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in IPA (boiling point: 82.4 DEG C), the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.12.In addition, the alignment films that detects by an unaided eye, the visible less inequality of result.
< comparative example 11>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal C obtaining in synthesis example 6, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate was flooded after 3 minutes in water (boiling point: 100 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.16.In addition, the liquid crystal orientation film that detects by an unaided eye, the visible less inequality of result.
< comparative example 12>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal C obtaining in synthesis example 6, on substrate, be coated with, be dried, burn till, the polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, the anisotropic size in this direction of orientation with the liquid crystal orientation film on film substrate is 1.11.Do not observe the film inequality of liquid crystal orientation film.
< comparative example 13>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal D obtaining in synthesis example 8, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in IPA (boiling point: 82.4 DEG C), the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.19.In addition, the alignment films that detects by an unaided eye, the visible less inequality of result.
< comparative example 14>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal D obtaining in synthesis example 8, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate was flooded after 3 minutes in water (boiling point: 100 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.19.In addition, the liquid crystal orientation film that detects by an unaided eye, the visible less inequality of result.
< comparative example 15>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal D obtaining in synthesis example 8, on substrate, be coated with, be dried, burn till, the polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, the anisotropic size in this direction of orientation with the liquid crystal orientation film on film substrate is 1.12.Do not observe the film inequality of liquid crystal orientation film.
< comparative example 16>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in IPA (boiling point: 82.4 DEG C), the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.17.In addition, the alignment films that detects by an unaided eye, the visible less inequality of result.
< comparative example 17>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate was flooded after 3 minutes in water (boiling point: 100 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.17.In addition, the liquid crystal orientation film that detects by an unaided eye, the visible less inequality of result.
< comparative example 18>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal A obtaining in synthesis example 2, on substrate, be coated with, be dried, burn till, the polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, the anisotropic size in this direction of orientation with the liquid crystal orientation film on film substrate is 1.12.Do not observe the film inequality of liquid crystal orientation film.
< comparative example 19>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal E obtaining in synthesis example 10, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in IPA (boiling point: 82.4 DEG C), the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.11.In addition, the alignment films that detects by an unaided eye, the visible less inequality of result.
< comparative example 20>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal E obtaining in synthesis example 10, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate was flooded after 3 minutes in water (boiling point: 100 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.11.In addition, the liquid crystal orientation film that detects by an unaided eye, the visible less inequality of result.
< comparative example 21>
Except irradiating 0.5J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal E obtaining in synthesis example 10, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, the anisotropic size in this direction of orientation with the liquid crystal orientation film on film substrate is 1.08.Do not observe the film inequality of liquid crystal orientation film.
< comparative example 22>
Except irradiating 1.0J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal F obtaining in synthesis example 12, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in IPA (boiling point: 82.4 DEG C), the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.04.In addition, the alignment films that detects by an unaided eye, result is uneven as seen.
< comparative example 23>
Except irradiating 1.0J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal F obtaining in synthesis example 12, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate was flooded after 3 minutes in water (boiling point: 100 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.10.In addition, the liquid crystal orientation film that detects by an unaided eye, the visible less inequality of result.
< comparative example 24>
Except irradiating 1.0J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal F obtaining in synthesis example 12, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, the anisotropic size in this direction of orientation with the liquid crystal orientation film on film substrate is 1.06.Do not observe the film inequality of liquid crystal orientation film.
< comparative example 25>
Except irradiating 1.0J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal G obtaining in synthesis example 14, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate is flooded after 3 minutes in 25 DEG C in IPA (boiling point: 82.4 DEG C), the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.09.In addition, the alignment films that detects by an unaided eye, result is uneven as seen.
< comparative example 26>
Except irradiating 1.0J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal G obtaining in synthesis example 14, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, this band film substrate was flooded after 3 minutes in water (boiling point: 100 DEG C), with IPA flushing 1 minute, the baking oven inner dryings of 80 DEG C 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the direction of orientation of gained liquid crystal orientation film is 1.09.In addition, the liquid crystal orientation film that detects by an unaided eye, the visible less inequality of result.
< comparative example 27>
Except irradiating 1.0J/cm 2254nm ultraviolet ray beyond, carry out similarly to Example 1.Use the aligning agent for liquid crystal G obtaining in synthesis example 14, on substrate, be coated with, be dried, burn till, polyimide film irradiation ultraviolet radiation to gained and obtain being with film substrate, the anisotropic size in this direction of orientation with the liquid crystal orientation film on film substrate is 1.07.Do not observe the film inequality of liquid crystal orientation film.
About above-described embodiment 1～22 and comparative example 1～27, the situation of the anisotropic size of the liquid crystal orientation film of the kind of the solvent of use, gained and film inequality is gathered and is shown in table 1.
[table 1]
? Solvent Washing fluid Anisotropic size Film inequality
Embodiment 1 PGME IPA 1.84 ○
Embodiment 2 PGMEA IPA 1.51 ○
Embodiment 3 PGME/ water=1/1 IPA 1.69 ○
Embodiment 4 Ethyl lactate IPA 1.9 ○
Embodiment 5 Butyl cellosolve IPA 1.69 ○
Embodiment 6 PGME Water 1.82 ○
Embodiment 7 Ethyl lactate Water 1.84 ○
Embodiment 8 Diacetone alcohol Water 1.77 ○
Embodiment 9 MMP Water 1.77 ○
Embodiment 10 PGME IPA 1.72 ○
Embodiment 11 Ethyl lactate IPA 2.11 ○
Embodiment 12 PGME IPA 1.53 ○
Embodiment 13 Ethyl lactate IPA 1.94 ○
Embodiment 14 PGME IPA 1.40 ○
Embodiment 15 Ethyl lactate IPA 1.70 ○
Embodiment 16 PGME IPA 1.37 ○
Embodiment 17 Ethyl lactate IPA 1.77 ○
Embodiment 18 PGME IPA 1.33 ○
Embodiment 19 Ethyl lactate IPA 1.20 ○
Embodiment 20 PGME IPA 1.15 ○
Embodiment 21 Ethyl lactate IPA 1.12 ○
Embodiment 22 PGME IPA 1.11 ○
Embodiment 23 Ethyl lactate IPA 1.10 ○
Comparative example 1 IPA - 1.2 Δ
Comparative example 2 Water IPA 1.25 Δ
Comparative example 3 PG IPA 1.45 ×
Comparative example 4 GBL - Cannot measure All dissolve
Comparative example 5 NMP - Cannot measure All dissolve
Comparative example 6 Non-processor - 1.18 -
Comparative example 7 IPA - 1.19 Δ
Comparative example 8 Water IPA 1.17 Δ
Comparative example 9 Non-processor - 1.12 -
Comparative example 10 IPA - 1.12 Δ
Comparative example 11 Water IPA 1.16 Δ
Comparative example 12 Non-processor - 1.11 -
Comparative example 13 IPA - 1.19 Δ
Comparative example 14 Water IPA 1.19 Δ
Comparative example 15 Non-processor - 1.12 -
Comparative example 16 IPA - 1.7 Δ
Comparative example 17 Water IPA 1.17 Δ
Comparative example 18 Non-processor - 1.12 -
Comparative example 19 IPA - 1.11 Δ
Comparative example 20 Water IPA 1.11 Δ
Comparative example 21 Non-processor - 1.11 -
Comparative example 22 IPA - 1.04 Δ
Comparative example 23 Water IPA 1.10 Δ
Comparative example 24 Non-processor - 1.06 -
Comparative example 25 IPA - 1.09 Δ
Comparative example 26 Water IPA 1.09 Δ
Comparative example 27 Non-processor - 1.07 -
The possibility of utilizing in industry
The liquid crystal orientation film making by manufacture method of the present invention has high anisotropy, can be widely used in the liquid crystal display cells of TN element, STN element, TFT liquid crystal cell and vertical orientating type etc.Also have, by giving high anisotropy, can reduce come from the ghost of liquid crystal aligning, for example in the liquid crystal display cells of IPS type of drive or FFS type of drive, produce drive by exchanging the ghost that causes, particularly useful as IPS type of drive or the liquid crystal display cells of FFS type of drive or the liquid crystal orientation film of LCD TV.
Quote the full content of instructions, claims and specification digest of No. 2011-202229, the Japanese patent application of filing an application on September 15th, 2011 here as the announcement of instructions of the present invention.

Claims (12)

1. the manufacture method of liquid crystal orientation film, it is characterized in that, for being selected from least one polymkeric substance of precursor of polyimide and this polyimide and the film of the imidizate that the aligning agent for liquid crystal of organic solvent is coated with, burns till and obtains on substrate by containing, irradiate the radioactive ray of polarization, then contact processing with comprising the following formula (A-1) that is selected from, formula (A-2), formula (A-3), formula (A-4) and the solution of at least one organic solvent of formula (A-5);
[changing 1]
In formula (A-1), A 1for hydrogen atom or acetyl group, A 2for the alkyl of carbon number 1～6, R 2for hydrogen atom or methyl, n is 1 or 2 integer; In formula (A-2), A 3for the alkyl of carbon number 1～4; In formula (A-3), R 3and R 4be hydrogen atom or methyl independently respectively; In formula (A-4), A 5and A 6be the alkyl of carbon number 1～4 independently respectively; In formula (A-5), A 6for the alkyl or cycloalkyl of carbon number 3～6.
2. the manufacture method of liquid crystal orientation film as claimed in claim 1, wherein, described organic solvent has the boiling point of 100～180 DEG C.
3. the manufacture method of liquid crystal orientation film as claimed in claim 1 or 2, wherein, described organic solvent is 1-methoxy-2-propanol, ethyl lactate, diacetone alcohol, 3-methoxy methyl propionate or 3-ethoxyl ethyl propionate.
4. the manufacture method of the liquid crystal orientation film as described in any one in claim 1～3, wherein, described polymkeric substance contain be selected from have following formula (3) represent the polyimide precursor of structural unit and at least one polymkeric substance of the imide amination polymer of this polyimide precursor;
[changing 2]
In formula (3), X 1for being selected from least one of structure that following formula (X1-1)～(X1-9) represents, Y 1for divalent organic group, R 1for the alkyl of hydrogen atom or carbon number 1～4;
[changing 3]
In formula (X1-1), R 3, R 4, R 5and R 6be the alkyl of hydrogen atom, halogen atom, carbon number 1～6, alkenyl, alkenyl or the phenyl of carbon number 2～6 independently respectively.
5. the manufacture method of liquid crystal orientation film as claimed in claim 4, wherein, described polymkeric substance is to be selected from the polyimide precursor of structural unit of above-mentioned formulas (3) expression more than containing 60 % by mole with respect to whole polymkeric substance of 1 mole and at least one of the imide amination polymer of this polyimide precursor.
6. the manufacture method of liquid crystal orientation film as claimed in claim 4, wherein, in above-mentioned formula (3), X 1represent with above-mentioned formula (X1-1).
7. the manufacture method of liquid crystal orientation film as claimed in claim 4, wherein, in above-mentioned formula (3), X 1for being selected from least one of structure that following formula (X1-10)～(X1-11) represents;
[changing 4]
8. the manufacture method of liquid crystal orientation film as claimed in claim 4, wherein, in above-mentioned formula (3), Y 1for being selected from least one of structure that following formula (4) and (5) represent;
[changing 5]
In formula (5), Z 1for the divalent organic group of singly-bound, ester bond, amido link, thioester bond or carbon number 2～10.
9. the manufacture method of liquid crystal orientation film as claimed in claim 8, wherein, in above-mentioned formula (3), Y 1for the structure of above-mentioned formula (4) expression.
10. the contact treating fluid of liquid crystal orientation film, its be for the aligning agent for liquid crystal of at least one polymkeric substance that contains the precursor that is selected from polyimide and this polyimide is coated with, is burnt till on substrate film irradiate the radioactive ray of polarization and the liquid crystal orientation film that forms contact treating fluid
It is characterized in that, formed by the solution of at least one organic solvent that comprises the following formula (A-1) that is selected from, formula (A-2), formula (A-3), formula (A-4) and formula (A-5);
[changing 6]
In formula (A-1), A 1for hydrogen atom or acetyl group, A 2for the alkyl of carbon number 1～6, R 2for hydrogen atom or methyl, n is 1 or 2 integer; In formula (A-2), A 3for the alkyl of carbon number 1～4; In formula (A-3), R 3and R 4be hydrogen atom or methyl independently respectively; In formula (A-4), A 5and A 6be the alkyl of carbon number 1～4 independently respectively; In formula (A-5), A 6for the alkyl or cycloalkyl of carbon number 3～6.
11. liquid crystal orientation films, its manufacture method by the liquid crystal orientation film described in any one in claim 1～9 obtains.
12. liquid crystal display cells, is characterized in that, have the liquid crystal orientation film described in claim 11.
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