CN103946738B - Manufacture method, liquid crystal orientation film and the liquid crystal display cells of liquid crystal orientation film - Google Patents

Manufacture method, liquid crystal orientation film and the liquid crystal display cells of liquid crystal orientation film Download PDF

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CN103946738B
CN103946738B CN201280056047.9A CN201280056047A CN103946738B CN 103946738 B CN103946738 B CN 103946738B CN 201280056047 A CN201280056047 A CN 201280056047A CN 103946738 B CN103946738 B CN 103946738B
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liquid crystal
crystal orientation
orientation film
formula
film
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CN103946738A (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)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Liquid Crystal (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The present invention, which provides, can improve anisotropy, suppress by handling and the manufacture method of caused uneven liquid crystal orientation film.For the radioactive ray of film irradiation polarization obtained by being coated with, burn till on substrate containing the aligning agent for liquid crystal selected from polyimides and at least one polymer of the precursor of the polyimides, then contact processing is carried out with the solution comprising at least one organic solvent selected from following formula (A 1), formula (A 2), formula (A 3), formula (A 4) and formula (A 5).(changing 1)(A1For hydrogen atom or acetyl group, A2For the alkyl of carbon number 1~6, R2For hydrogen atom or methyl, n is 1 or 2.A3For the alkyl of carbon number 1~4.R3、R4For hydrogen atom or methyl.A5、A6For the alkyl of carbon number 1~4.A6For the alkyl or cycloalkyl of carbon number 3~6.).

Description

Manufacture method, liquid crystal orientation film and the liquid crystal display cells of liquid crystal orientation film
Technical field
Taken the present invention relates to the manufacture method of the liquid crystal orientation film of optical alignment method, by liquid crystal obtained by the manufacture method To film and the liquid crystal display cells of the rewarding liquid crystal orientation film of tool.
Background technology
Liquid crystal display cells for LCD TV, liquid crystal display etc. are provided with generally in element to be used to control liquid crystal The liquid crystal orientation film of state of orientation.
At present, industrial most common liquid crystal orientation film is to wipe to be formed towards a direction by using cloth such as cotton, nylon, polyester In the film surface that the polyimides on electrode base board by polyamic acid and/or by its imidizate is formed, i.e. so-called rub Erasure is managed to make.
It is industrial useful that the friction treatment of film surface in the orientation process of liquid crystal orientation film is easy and productivity is excellent Method.But the high performance to liquid crystal display cells, high-definition, maximization requirement increasingly improve, by friction treatment Inhomogeneities in the scar of caused alignment layer surface, airborne dust, mechanical force or the influence of electrostatic and then orientation process face etc. is each Kind problem is increasingly obvious.
As the method for replacing friction treatment, it is known that assign the light of liquid crystal aligning ability by irradiating the radioactive ray of polarization Alignment method.Liquid crystal aligning based on optical alignment method is handled, it is proposed that utilize the processing, anti-using photo-crosslinking of photoisomerization reaction The processing answered, utilize processing of photolysis reactionses etc. (referring to non-patent literature 1).
On the other hand, when polyimides being applied into light orientation liquid crystal orientation film, have compared with other situations high resistance to It is hot, therefore its serviceability can be expected.
In patent document 1, it is proposed that the polyimide film for having the alicyclic structures such as cyclobutane ring on main chain is used for into light The method of alignment method.
But by liquid crystal orientation film obtained by optical alignment method compared with using the liquid crystal orientation film of friction, exist relative In the anisotropy in the differently- oriented directivity of high molecule liquid crystal alignment films is small the problem of.If anisotropy is small, foot can not be obtained Enough liquid crystal alignings, the problems such as producing ghost also occurs when liquid crystal display cells are made.Pass through optical alignment method as raising Obtained by liquid crystal orientation film anisotropic method, it is proposed that the polyimides will be caused because of light irradiation after light irradiation Main chain be cut off and generate low molecular weight compositions remove method (referenced patent document 2).
Prior art literature
Patent document
Patent document 1：Japanese Patent Laid-Open 9-297313 publications
Patent document 2：Japanese Patent Laid-Open 2011-107266 publications
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 " Mu Kobe side, Shi Cun Machine energy material)
The content of the invention
The technical problems to be solved by the invention
The present inventor confirms after research, obtained by being coated with, burning till to polyimide film or by polyimide precursor The radioactive ray and then carry out of polyimide film irradiation polarization are immersed in water or the medium processing of organic solvent, the liquid crystal of gained take Improved to the anisotropy of film.But the inventors discovered that, in the case of having carried out these processing, the liquid crystal orientation film of gained Occur producing the problems such as uneven, the characteristic of liquid crystal orientation film is significantly damaged.
It is an object of the invention to provide can improve by the anisotropy of liquid crystal orientation film obtained by optical alignment method and Suppress to produce the manufacture method of the liquid crystal orientation film of inequality, the manufacturer by the liquid crystal orientation film during being handled Liquid crystal orientation film obtained by method and the liquid crystal with liquid crystal orientation film obtained by the manufacture method by the liquid crystal orientation film Show element.
Technical scheme used by solution technical problem
The present inventor has been repeated conscientiously has studied in order to achieve the above object, as a result finds, by polyimide film Or polyimide precursor is coated with, burn till obtained by film irradiation polarization radioactive ray, then with comprising specific organic solvent Solution carries out impregnating contact processing, can significantly improve the anisotropy of the liquid crystal orientation film of gained, and can solve above-mentioned liquid The problem of uneven is produced in brilliant alignment films.
In summary, the present invention is used as technology contents using the description below.
1. the manufacture method of liquid crystal orientation film, it is characterised in that for that will contain selected from polyimides and the polyimides Precursor at least one polymer and organic solvent aligning agent for liquid crystal be coated with substrate, burn till obtained by imidizate Film, the radioactive ray of polarization are irradiated, then with comprising selected from following formula (A-1), formula (A-2), formula (A-3), formula (A-4) and formula (A- 5) solution of at least one organic solvent carries out contact processing；
[changing 1]
In formula (A-1), A1For hydrogen atom or acetyl group, A2For the alkyl of carbon number 1~6, R2For hydrogen atom or methyl, n 1 Or 2 integer；In formula (A-2), A3For the alkyl of carbon number 1~4；In formula (A-3), R3And R4It is separately hydrogen atom or first Base；In formula (A-4), A5And A6It is separately the alkyl of carbon number 1~4；In formula (A-5), A6For the alkyl or ring of carbon number 3~6 Alkyl.
2. the manufacture method of the liquid crystal orientation film described in above-mentioned 1, wherein, the organic solvent has 100~180 DEG C of boiling Point.
3. the manufacture method of the liquid crystal orientation film described in above-mentioned 1 or 2, wherein, the organic solvent is 1- methoxyl groups -2- third Alcohol, ethyl lactate, diacetone alcohol, 3- methoxy methyl propionates or 3- ethoxyl ethyl propionates.
4. the manufacture method of the liquid crystal orientation film any one of above-mentioned 1~3, wherein, the polymer, which contains, to be selected from The polyimide precursor of the construction unit represented with following formula (3) and the imide amination polymer of the polyimide precursor are extremely A kind of few polymer；
[changing 2]
In formula (3), X1For at least one of the structure represented selected from following formula (X1-1)~(X1-9), Y1For divalent organic group Group, R1For hydrogen atom or the alkyl of carbon number 1~4；
[changing 3]
In formula (X1-1), R3、R4、R5And R6It is separately hydrogen atom, halogen atom, the alkyl of carbon number 1~6, carbon number 2~6 alkenyl, alkenyl or phenyl.
5. the manufacture method of the liquid crystal orientation film described in above-mentioned 4, wherein, the polymer is selected from relative to 1 mole The polyimide precursor and the polyimides for the construction unit that the above-mentioned formula (3) that whole polymer contain 60 moles of more than % represents At least one of the imide amination polymer of precursor.
6. the manufacture method of the liquid crystal orientation film described in above-mentioned 4, wherein, in above-mentioned formula (3), X1With above-mentioned formula (X1-1) table Show.
7. the manufacture method of the liquid crystal orientation film described in above-mentioned 4, wherein, in above-mentioned formula (3), X1For selected from following formula (X1- 10) at least one of the structure~(X1-11) represented.
[changing 4]
8. the manufacture method of the liquid crystal orientation film described in above-mentioned 4, wherein, in above-mentioned formula (3), Y1For selected from following formula (4) (5) at least one of the structure represented；
[changing 5]
In formula (5), Z1For 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), Y1Represented for above-mentioned formula (4) Structure.
10. the contact treatment fluid of liquid crystal orientation film, it is for by containing before polyimides and the polyimides The aligning agent for liquid crystal of at least one polymer of body is coated with substrate, burn till obtained by film irradiation polarization radioactive ray and formed Liquid crystal orientation film contact treatment fluid, it is characterised in that by comprising selected from above-mentioned formula (A-1), formula (A-2), formula (A-3), formula (A-4) and at least one organic solvent of formula (A-5) solution form.
11. liquid crystal orientation film, it is obtained by the manufacture method of the liquid crystal orientation film any one of above-mentioned 1~9.
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 the liquid crystal orientation film of the present invention, it can obtain and the tool of orientation process has been carried out by optical alignment method There is the liquid crystal orientation film of high anisotropy, at the same time, the liquid crystal orientation film of gained can obtain the film of the uneven homogeneous of no film.
In summary, the anisotropy of liquid crystal orientation film as obtained by the manufacture method of the present invention is high, therefore liquid crystal aligning Restraint is high, ghost excellent, for liquid crystal display cells in the case of, high-grade liquid crystal display cells can be obtained.
" table 1 ", pass through the system of the liquid crystal orientation film of the present invention from contrasted following embodiments and comparative example The anisotropic effect of above-mentioned raising making method and realize, film when suppressing processing uneven caused effect is according to using Solvent and have very big difference.
That is, from it is following " table 1 ", using water, isopropanol etc. as solvent in the case of, the liquid crystal of nearly no gained The anisotropic raising of alignment films, at the same time, in the case of using these solvents, the liquid crystal orientation film of gained also generates It is uneven.
But including selected from least one organic molten of above-mentioned formula (A-1)~(A-5) compounds represented with the present invention In the case that the solution of agent has carried out contact processing, the anisotropic raising of liquid crystal orientation film is greatly improved, same with this When, the uneven generation on the liquid crystal orientation film of gained can be significantly inhibited.
Embodiment
<The precursor of polyimides and the polyimides>
In the present invention, anisotropic polyimides and the polyamides are assigned using selected from the radioactive ray by irradiating polarization At least one polymer (hereinafter also referred to as polymer) of the precursor of imines.As long as meet the polyimides or poly- of the condition Imide precursor, its structure are just not particularly limited.
If enumerating concrete example, because the anisotropy of the liquid crystal orientation film of gained is high, as in the present invention Polymer used, polyimide precursor and the polyimide precursor of the construction unit preferably represented with following formula (3) Imide amination polymer.From the viewpoint of dissolubility in organic solvent, particularly preferably with following formula (3) represent knot The polyimide precursor of structure unit.
[changing 6]
In formula (3), R1For hydrogen atom or the alkyl of carbon number 1~4.From the complexity that imidizate is carried out by heating Viewpoint consideration, particularly preferred hydrogen atom or methyl.
X1It is at least one selected from following formula (X1-1)~(X1-9) structures represented.
[changing 7]
In formula (X1-1), R3、R4、R5And R6It is separately hydrogen atom, halogen atom, the alkyl of carbon number 1~6, carbon number 2~6 alkenyl, alkenyl or phenyl, can be the same or different.From the viewpoint of liquid crystal aligning, R3、R4、R5With R6Separately preferred hydrogen atom, halogen atom, methyl or ethyl, more preferably hydrogen atom or methyl.X1It is more preferably selected from following At least one for the structure that formula (X1-10)~(X1-11) is represented.
[changing 8]
Y1For divalent organic group, its structure is not particularly limited.Because the anisotropy of the liquid crystal orientation film of gained is high, institute With at least one of the structure preferably represented selected from following formula (Y1-1) and (Y1-2).
[changing 9]
In formula (5), Z1For the divalent organic group of singly-bound, ester bond, amido link, thioester bond or carbon number 2~10.
Z1In, ester bond is with-C (O) O- or-OC (O)-represent.Amido link can show with-C (O) NH- ,-C (O) NR- ,- The structure of NHC (O)-or-NRC (O)-expression.R is alkyl, alkenyl, alkynyl, aryl or the combinations thereof of carbon number 1~10.
As the concrete example of abovementioned alkyl, methyl, ethyl, propyl group, butyl, the tert-butyl group, hexyl, octyl group, ring penta can be enumerated Base, cyclohexyl, dicyclohexyl etc..As alkenyl, can enumerate the CH of more than 1 present in abovementioned alkyl2-CH2Structure takes On behalf of the group of CH=CH structures, more specifically, vinyl, pi-allyl, 1- acrylic, isopropenyl, 2- butylene can be enumerated Base, 1,3- butadienyls, 2- pentenyls, 2- hexenyls, cyclopropanyl, cyclopentenyl, cyclohexenyl group etc.., can example as alkynyl Lift the CH of more than 1 present in abovementioned alkyl2-CH2Structure is substituted by the group of C ≡ C-structure, more specifically, can enumerate Acetenyl, 1- propinyls, 2-propynyl etc..As aryl, can enumerate such as phenyl.
Thioester bond can show the structure with-C (O) S- or-SC (O)-represent.
Z1For carbon number 2~10 organic group when, can use following formula (6) representation.
[changing 10]
In formula (6), Z4、Z5And Z6It is separately singly-bound ,-O- ,-S- ,-NR11-, ester bond, amido link, thioester bond, urea Key, carbonic acid ester bond or amino-formate bond.R11For hydrogen atom, methyl or tert-butoxycarbonyl.
Z4、Z5And Z6In ester bond, amido link and thioester bond can show it is same with above-mentioned ester bond, amido link and thioester bond The structure of sample.
Urea bond can show the structure represented with-NH-C (O) NH- or-NR-C (O) NR-.R be carbon number 1~10 alkyl, Alkenyl, alkynyl, aryl or combinations thereof, these groups can enumerate same with abovementioned alkyl, alkenyl, alkynyl and aryl Example.
Carbonic acid ester bond can show the structure represented with-O-C (O)-O-.
Amino-formate bond can show with-NH-C (O)-O- ,-O-C (O)-NH- ,-NR-C (O)-O- or-O-C (O)- The structure that NR- is represented.R is alkyl, alkenyl, alkynyl, aryl or the combinations thereof of carbon number 1~10, and these groups can example For the example same with abovementioned alkyl, alkenyl, alkynyl and aryl.
R in formula (6)9And R10It is separately selected from singly-bound, the alkylidene of carbon number 1~10, alkylene group, sub- alkynes The structure of base, arlydene or the group combined by them.R9And R10In any one be singly-bound in the case of, R9Or R10In Any one be the alkylidene selected from carbon number 2~10, alkylene group, alkynylene, arlydene or the group combined by them Structure.
Above-mentioned alkylidene can enumerate the structure that 1 hydrogen atom is removed from abovementioned alkyl.More specifically, methylene can be enumerated Base, 1,1- ethylidene, 1,2- ethylidene, 1,2- propylidene, 1,3- propylidene, 1,4- butylidenes, 1,2- butylidenes, 1,2- Asias penta Base, 1,2- hexylidenes, 2,3- butylidenes, 2,4- pentylidene, 1,2- cyclopropylidenes, 1,2- Asias cyclobutyl, 1,3- Asias cyclobutyl, 1, 2- cyclopentylenes, 1,2- cyclohexylidenes etc..
Alkylene group can enumerate the structure that 1 hydrogen atom is removed from above-mentioned alkenyl.More specifically, 1,1- can be enumerated Ethenylidene, 1,2- ethenylidenes, 1,2- Asias ethene methylene, 1- methyl isophthalic acids, 2- ethenylidenes, 1,2- Asias ethene -1,1- are sub- Ethyl, 1,2- Asias ethene -1,2- ethylidene, 1,2- Asias ethene -1,2- propylidene, 1,2- Asias ethene -1,3- propylidene, 1,2- are sub- Ethene -1,4- butylidenes, 1,2- Asias ethene -1,2- butylidenes etc..
Alkynylene can enumerate the structure that 1 hydrogen atom is removed from above-mentioned alkynyl.More specifically, sub- acetylene can be enumerated Base, ethynylene methylene, ethynylene -1,1- ethylidene, ethynylene -1,2- ethylidene, ethynylene -1,2- Asias third Base, ethynylene -1,3- propylidene, ethynylene -1,4- butylidenes, ethynylene -1,2- butylidenes etc..
Arlydene can enumerate the structure that 1 hydrogen atom is removed from above-mentioned aryl.More specifically, 1,2- Asias benzene can be enumerated Base, 1,3- phenylenes, 1,4- phenylenes etc..
Y1In the case of containing linear high structure and rigid structure, in order to obtain that there is the liquid of good liquid crystal aligning Brilliant alignment films, as Z1Structure more preferably singly-bound or following formula (A1-1)~(A15-25) structure.
[changing 11]
[changing 12]
Y1Structure be more rigid structure, the more excellent liquid crystal orientation film of liquid crystal aligning can be obtained, therefore be used as Y1's Structure, the structure that particularly preferably above-mentioned formula (4) represents.
The polyimide precursor of construction unit and the imidizate of the polyimide precursor represented containing above-mentioned formula (3) gathers In compound, the ratio for the construction unit that above-mentioned formula (3) represents is excellent relative to the entire infrastructure unit in 1 mole of whole polymer Elect 60~100 moles of % as.The ratio for the construction unit that above-mentioned formula (3) represents is higher, can obtain having better liquid crystal aligning The liquid crystal orientation film of property, therefore more preferably 80~100 moles of %, more preferably 90~100 moles of %.
The component of polymer of the present invention can also also contain following formula in addition to the construction unit that above-mentioned formula (3) represents (7) polyimide precursor and the polyimide precursor of the construction unit represented.
[changing 13]
In formula (7), R1It is the R with above-mentioned formula (3)1Identical defines.
X3For 4 valency organic groups, its structure is not particularly limited.If enumerating concrete example, following formula (X-9) can be enumerated ~(X-42) structure.From compound obtain difficulty from the viewpoint of, X3Structure preferred X-17, X-25, X-26, X- 27th, X-28, X-32 or X-39.In addition, from the fast liquid crystal of the mitigation for obtaining the residual charge accumulated in the presence of DC voltage From the viewpoint of alignment films, preferably using the tetracarboxylic dianhydride with aromatic ring structure, as X3Structure, more preferably X- 26th, X-27, X-28, X-32, X-35 or X-37.
[changing 14]
[changing 15]
In above-mentioned formula (7), Y4For divalent organic group, its structure is not particularly limited.If enumerate Y4Concrete example, then may be used Enumerate following formula (Y-1)~(Y-74) structure.
[changing 16]
[changing 17]
[changing 18]
[changing 19]
[changing 20]
Because the dissolubility of component of polymer in organic solvent is excellent, as the Y in formula (7)4, preferably comprise tool There is the construction unit of Y-8, Y-20, Y-21, Y-22, Y-28, Y-29, Y-30, Y-72, Y-73 or Y-74 structure.
In the case of the ratio height for the construction unit that above-mentioned formula (7) in component of polymer represents, taken to reduce liquid crystal To the liquid crystal aligning of film, the ratio for the construction unit that above-mentioned formula (7) represents is preferably relative to 1 mole of entire infrastructure unit 0~40 mole of %, more preferably 0~20 mole of %.
<The manufacture method of poly amic acid ester>
The poly amic acid ester as polyimide precursor used can pass through (1) as shown below~(3) in the present invention Method synthesizes.
(1) situation about being synthesized by polyamic acid
Poly amic acid ester can be by the way that the polyamic acid obtained by tetracarboxylic dianhydride and diamines be esterified to synthesize.
Specifically, can by making polyamic acid and esterifying agent in presence of organic solvent, in -20 DEG C~150 DEG C, it is excellent 0 DEG C~50 DEG C are selected to react 30 minutes~24 hours, preferably 1~4 hour to synthesize.
As esterifying agent, preferably DMF two can be enumerated by purifying the esterifying agent easily removed Methyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N, N- dimethyl formyls Amine di neo-pentyl butyl acetal, N,N-dimethylformamide di-t-butyl acetal, 1- methyl -3- p-methylphenyls triazenes, 1- second Base -3- p-methylphenyls triazenes, 1- propyl group -3- p-methylphenyls triazenes, 4- (4,6- dimethoxy -1,3,5- triazine -2- bases) - 4- methyl morpholinesChloride etc..The addition of esterifying agent is preferably 2~6 relative to the repeat unit of 1 mole of polyamic acid Molar equivalent, more preferably 2~4 molar equivalents.
Consider from the dissolubility of polymer, the organic solvent used in above-mentioned reaction be preferably DMF, METHYLPYRROLIDONE, gamma-butyrolacton etc., these organic solvents can use one kind or two or more be used in mixed way.
It is organic molten during synthesis from the viewpoint of the precipitation for being not easy to cause polymer and being readily available HMW body The concentration of polymer in agent is preferably 1~30 mass %, more preferably 5~20 mass %.
(2) situation about being synthesized by the reaction of tetracarboxylic acid acid diesters diacid chloride and diamines
Poly amic acid ester can be synthesized by tetracarboxylic acid acid diesters diacid chloride and diamines.
Specifically, can by making tetracarboxylic acid acid diesters diacid chloride and diamines in the presence of alkali and organic solvent, in -20~ 150 DEG C, preferably 0~50 DEG C are reacted 30 minutes~24 hours, preferably 1~4 hour to synthesize.
Pyridine, triethylamine, 4-dimethylaminopyridine etc. can be used in above-mentioned alkali, in order that reaction is leniently carried out, preferably Pyridine.From the amount easily removed and from the viewpoint of being readily available HMW body, the addition of alkali is relative to tetracarboxylic acid acid diesters two Acyl chlorides is preferably 2~4 times moles, more preferably 2~3 times moles.
Consider that the organic solvent used in above-mentioned reaction is preferably N- methyl -2- pyrroles from the dissolubility of monomer and polymer Pyrrolidone, gamma-butyrolacton etc., these organic solvents can use one kind or two or more be used in mixed way.
It is organic molten during synthesis from the viewpoint of the precipitation for being not easy to cause polymer and being readily available HMW body Polymer concentration in agent is preferably 1~30 mass %, more preferably 5~20 mass %.In addition, in order to prevent tetracarboxylic acid acid diesters The hydrolysis of diacid chloride, the organic solvent used in the synthesis of poly amic acid ester preferably at most degree it is dehydrated, reacts preferably in nitrogen Carried out in atmosphere to prevent being mixed into for ambient atmos.
(3) by tetracarboxylic acid acid diesters and diamines come the situation of synthesizing polyamides acid
Poly amic acid ester can be by synthesizing tetracarboxylic acid acid diesters and diamines polycondensation.
Specifically, can be by making tetracarboxylic acid acid diesters and diamines in the presence of condensing agent, alkali and organic solvent, in 0 DEG C ~150 DEG C, preferably 0 DEG C~100 DEG C are reacted 30 minutes~24 hours, preferably 3~15 hours to synthesize.
As above-mentioned condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1- ethyls -3- (3- dimethyl can be used Aminopropyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy -1,3,5- triazines methyl morpholine, O- (benzos three Azoles -1- bases)-N, N, N ', N '-tetramethylureaTetrafluoroborate, O- (BTA -1- bases)-N, N, N ', N '-tetramethylureaHexafluorophosphate, the (thio -3- benzos of 2,3- dihydros -2-Oxazolyl) phosphonic acid diphenyl ester etc..The addition of condensing agent relative to Tetracarboxylic acid acid diesters are preferably 2~3 times moles, more preferably 2~2.5 times moles.
The tertiary amines such as pyridine, triethylamine can be used in above-mentioned alkali.From for the amount easily removed and being readily available the sight of HMW body Point considers that the addition of alkali is preferably 2~4 times moles relative to diamine component, more preferably 2~3 times moles.
As above-mentioned organic solvent, METHYLPYRROLIDONE, gamma-butyrolacton, DMF can be enumerated Deng.
In addition, in above-mentioned reaction, adding lewis acid can be such that reaction efficiently carries out as additive.As Louis The lithium halide such as acid, preferably lithium chloride, lithium bromide.Lewis acidic addition is preferably 0.1~5 times relative to diamine component and rubbed You, 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 HMW, particularly preferably The synthetic method of above-mentioned (1) or (2).
Be injected into while the solution of obtained poly amic acid ester can be by being sufficiently stirred as described above in poor solvent come Separate out polymer.Separate out for several times and after being cleaned with poor solvent, at normal temperatures or heat drying, can obtain purified Poly amic acid ester powder.Poor solvent is not particularly limited, it is molten that water, methanol, ethanol, 2- propyl alcohol, hexane, butyl can be enumerated Fine agent, acetone, toluene etc., preferably water, methanol, ethanol, 2- propyl alcohol etc..
<The manufacture method of polyamic acid>
The poly amic acid ester as polyimide precursor used can be synthesized by method as shown below in the present invention.
Specifically, can by making tetracarboxylic dianhydride and diamines in presence of organic solvent, in -20 DEG C~150 DEG C, it is excellent 0 DEG C~50 DEG C are selected to react 30 minutes~24 hours, preferably 1~12 hour to synthesize.
Consider from the dissolubility of monomer and polymer, the organic solvent used in above-mentioned reaction is preferably N, N- dimethyl methyls Acid amides, METHYLPYRROLIDONE, gamma-butyrolacton etc., these organic solvents can use one kind or two or more be used in mixed way.
From the viewpoint of the precipitation for being not susceptible to polymer and being readily available HMW body, the concentration of polymer is excellent Elect 1~30 mass %, more preferably 5~20 mass % as.
Obtained polyamic acid can be by being injected into poor solvent while reaction solution is sufficiently stirred as described above In the polymer is separated out and is reclaimed.In addition, carrying out after separating out and being cleaned with poor solvent for several times, pass through normal temperature or heat drying The powder of purified polyamic acid can be obtained.Poor solvent is not particularly limited, can enumerate water, methanol, ethanol, 2- propyl alcohol, Hexane, butyl cellosolve, acetone, toluene etc., preferably water, methanol, ethanol, 2- propyl alcohol etc..
<The manufacture method of polyimides>
Polyimides used can be by the way that above-mentioned poly amic acid ester or polyamic acid imidizate be manufactured in the present invention.
In the case of manufacturing polyimides by poly amic acid ester, easy is chemical imidization, the chemical imidization It is above-mentioned polyamic acid ester solution or poly amic acid ester toner is dissolved in organic solvent, in the polyamic acid solution of gained Middle addition base catalyst.Chemical imidization is to carry out imidization reaction at a lower temperature, and in imidizate During be not susceptible to the reduction of polymer molecular weight, therefore preferably.
Chemical imidization can by be intended to the poly amic acid ester of imidizate in organic solvent, in base catalyst In the presence of stirring come carry out.As organic solvent, solvent used when can be used above-mentioned polymerisation.As base catalyst, Pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be enumerated.Wherein preferred triethylamine, carry out reaction because it has Enough alkalescence.
Carry out imidization reaction when temperature can be -20 DEG C~140 DEG C, preferably 0 DEG C~100 DEG C, the reaction time It can be 1~100 hour.The amount of base catalyst is 0.5~30 times mole, preferably 2~20 times moles of amic acid ester group. The acid imide rate of the polymer of acquisition can by adjusting catalytic amount, temperature, reaction time control.
In the case of manufacturing polyimides by polyamic acid, easy is chemical imidization, and the chemical imidization is Catalyst is added in the solution of above-mentioned polyamic acid made from the reaction as diamine component and tetracarboxylic dianhydride.Chemical acid imide Change is to carry out imidization reaction at a lower temperature, and polymer molecular weight is not susceptible to during imidizate Reduction, therefore preferably.
Chemical imidization can be by stirring desire acid imide in organic solvent, in the presence of base catalyst and acid anhydrides The polymer of change is carried out.As organic solvent, solvent used when can be used above-mentioned polymerisation.As base catalyst, Pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be enumerated.Wherein preferred pyridine, because it, which has, makes what reaction was carried out Suitable alkalescence.In addition, as acid anhydrides, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc. can be enumerated, wherein, use acetic acid It is easy to carry out the purifying after reaction terminates during acid anhydride, therefore preferably.
Carry out imidization reaction when temperature can be -20 DEG C~140 DEG C, preferably 0 DEG C~100 DEG C, the reaction time It can be 1~100 hour.The amount of base catalyst is 0.5~30 times mole of polyamide acidic group, preferably 2~20 times moles, The amount of acid anhydrides is 1~50 times mole, preferably 3~30 times moles of polyamide acidic group.The acid imide rate of the polymer of acquisition Can by adjusting catalytic amount, temperature, reaction time control.
Catalyst of addition etc. is remained in solution after the imidization reaction of poly amic acid ester or polyamic acid, therefore Preferably by following methods, imide amination polymer made from recovery and after being redissolved with organic solvent, as the present invention's Aligning agent for liquid crystal.
As described above the solution of obtained polyimides can by be injected into while being sufficiently stirred in poor solvent come Separate out polymer.Separate out for several times and after being cleaned with poor solvent, at normal temperatures or heat drying, can obtain purified Polymer powder.
Above-mentioned poor solvent is not particularly limited, can enumerate methanol, 2- propyl alcohol, acetone, hexane, butyl cellosolve, heptane, Methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene etc., preferably methanol, ethanol, 2- propyl alcohol, acetone etc..
<Aligning agent for liquid crystal>
Aligning agent for liquid crystal used has the form of the solution of component of polymer dissolving in organic solvent in the present invention.It is poly- The molecular weight of compound is preferably 2000~500000 with Weight-average molecular gauge, and more preferably 5000~300000, further preferably For 10000~100000.In addition, number-average molecular weight is preferably 1000~250000, more preferably 2500~150000, further Preferably 5000~50000.
The concentration of the polymer of aligning agent for liquid crystal used can be according to the thickness of the film of desired formation in the present invention Set and suitably change, from the viewpoint of uniform flawless film is formed, preferably more than 1 mass %, from solution It is preferably below 10 mass % from the viewpoint of storage stability.The concentration of particularly preferred polymer is 2~8 mass %.
As long as organic solvent component of polymer contained in aligning agent for liquid crystal used equably dissolves in the present invention Organic solvent, be not particularly limited.If enumerating its concrete example, DMF, N, N- bis- can be enumerated Ethyl-formamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones, N- methyl acyl in oneself Amine, 2-Pyrrolidone, NVP, dimethyl sulfoxide, dimethyl sulfone, gamma-butyrolacton, 1,3- dimethyl-imidazolidins Ketone, 3- methoxyl groups-N, N- dimethylpropionamide etc..These solvents can use a kind or be used in mixed way two or more.In addition, i.e. The solvent of component of polymer can not be equably dissolved when making to be single use, as long as in the range of polymer does not separate out, also may be used Mixed with above-mentioned organic solvent.
Aligning agent for liquid crystal used is in addition to comprising the organic solvent for the purpose of dissolving component of polymer in the present invention, Solvent for the purpose of painting film uniformity when aligning agent for liquid crystal being coated on to substrate to improve can also be included.The solvent is usually used The solvent of low surface tension compared with above-mentioned organic solvent.As its concrete example, can enumerate ethyl cellosolve, butyl cellosolve, Ethyl carbitol, butyl carbitol, ethylcarbitol acetate, ethylene glycol, 1- methoxy-2-propanols, 1- ethyoxyls -2- third Alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy group -2- propyl alcohol, single propylene glycol acetate, propylene glycol diacetate, propane diols -1- are single Methyl ether -2- acetic acid esters, propane diols -1- list ethylether -2- acetic acid esters, butyl cellosolve acetate, DPG, 2- (2- second Epoxide propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc..These solvents And two or more can be used.
In the aligning agent for liquid crystal of the present invention, in addition to mentioned component, as long as in the range of the effect of the present invention is not damaged, For the purpose of the electrical characteristics such as the polymer beyond polymer, the dielectric constant to change liquid crystal orientation film or electric conductivity can also be added Dielectric or conductive materials, the silane coupler for the purpose of the adaptation for improving liquid crystal orientation film and substrate, with improve system Into the cross-linked compound for the purpose of the hardness or consistency of film during liquid crystal orientation film and to make polyamides when burning till film The imidizate of amino acid efficiently carry out for the purpose of imidizate accelerator etc..
<The manufacture method of liquid crystal orientation film>
The manufacture method of the liquid crystal orientation film of the present invention includes：The work for aligning agent for liquid crystal is coated on substrate, being burnt till Sequence；To the process of the radioactive ray of the film irradiation polarization of gained；The film for being irradiated radioactive ray is connect with specific organic solvent The process of synapsis reason.
(1) process for aligning agent for liquid crystal is coated on substrate, being burnt till
Obtained aligning agent for liquid crystal as described above is coated on substrate, dries, burns till, so as to obtain polyimide film or poly- The film of imide precursor imidizate.
As the substrate of aligning agent for liquid crystal used in the coating present invention, as long as transparent high substrate is then without special limit It is fixed, plastic bases such as glass substrate, silicon nitride board, acrylic acid substrate or polycarbonate substrate etc. can be used, from making production The angle that technique simplifies is set out, and preferably uses the substrate formed with the ITO electrode for liquid crystal drive etc..In addition, reflection-type liquid In crystal display element, the opaque materials such as silicon wafer can be used, but are only limitted to the substrate of side, electrode now can also Use the reflectorized materials such as aluminium.As the coating method of aligning agent for liquid crystal used in the present invention, can enumerate spin-coating method, print process, Ink-jet method etc..
Arbitrary temp and time may be selected in drying, firing process after coating of liquid crystalline alignment agent.Generally, in order to fully remove The organic solvent contained, 50~120 DEG C, preferably 60~100 DEG C make its dry 1~10 minute, then 150~300 DEG C, it is excellent 200~250 DEG C are selected to burn till 5~120 minutes.The thickness of film after burning till is not particularly limited, but if excessively thin, then liquid crystal sometimes The reliability of display element can reduce, therefore be 5~300nm, preferably 10~200nm.
(2) process of the radioactive ray polarized is irradiated to the film of gained
The radioactive ray (hereinafter also referred to light orientation processing) of the film irradiation polarization obtained to the method by above-mentioned (1), from And assign anisotropy on the direction vertical with polarization direction.
As the concrete example of light orientation processing, the radiation irradiated in above-mentioned film coated surface and polarized to certain orientation can be enumerated Line, according to circumstances further heated at a temperature of 150~250 DEG C, the method for assigning liquid crystal aligning ability.Radiation The wavelength of line can use the ultraviolet and visible ray of the wavelength with 100~800nm.Wherein, preferably with 100~400nm Wavelength ultraviolet, the particularly preferably wavelength with 200~400nm ultraviolet.
The exposure of above-mentioned radioactive ray is preferably in 1~10000mJ/cm2In the range of, particularly preferably in 100~5000mJ/ cm2In the range of.
(3) film that radioactive ray were penetrated with the solution control comprising organic solvent carries out the process for contacting processing
The film for being irradiated the radioactive ray of polarization as described above is then contacted with the solution comprising specific organic solvent Processing.It is to be selected from following formula (A-1), formula (A-2), formula (A-3), formula (A-4) and formula (A-5) extremely used herein of organic solvent Few a kind of organic solvent or organic solvent.
[changing 21]
In formula (A-1), A1For hydrogen atom or acetyl group, A2For the alkyl of carbon number 1~6, R2For hydrogen atom or methyl, n 1 Or 2 integer.
In formula (A-2), A3For the alkyl of carbon number 1~4.
In formula (A-3), R3And R4It is separately hydrogen atom or methyl.
In formula (A-4), A5And A6It is separately the alkyl of carbon number 1~4.
In formula (A-5), A6For the alkyl or cycloalkyl of carbon number 3~6.
As above-mentioned formula (A-1)~(A-5) organic solvent, suitably boiling point is preferably 100~180 DEG C, more preferably For 110~160 DEG C of water miscible organic solvent.In the case of boiling point height, it can remain in film, to the characteristic of liquid crystal orientation film Have undesirable effect, on the other hand, in the case of low boiling point, because readily volatilized, film easily produces inequality, undesirable.
In above-mentioned formula (A-1)~(A-5) organic solvent, because being readily available, anisotropy is high, is taken without uneven liquid crystal To film, thus preferably selected from 1- methoxy-2-propanols, 1- methoxy-2-propanols acetic acid esters, butyl cellosolve, ethyl lactate, Methyl lactate, diacetone alcohol, 3- methoxy methyl propionates, 3- ethoxyl ethyl propionates, propyl acetate, butyl acetate and acetic acid ring At least one of own ester.The particularly preferably at least one selected from 1- methoxy-2-propanols and ethyl lactate.
The solution of the organic solvent used in being handled comprising contact can also be in the range of the effect of the present invention not be damaged Other solvents or solvent beyond organic solvent comprising above-mentioned formula (A-1)~(A-5).It is not particularly limited as other solvents, Water, methanol, ethanol, 2- propyl alcohol, acetone, methyl ethyl ketone etc. can be enumerated.Particularly from the viewpoint of versatility and security, More preferably water.
In the case of containing above-mentioned other solvents, at least one organic solvent selected from above-mentioned formula (A-1)~(A-5) contains The total amount for the solution that amount uses in being handled relative to contact is preferably 10~100 mass %, more preferably 30~100 mass %, Particularly preferably 50~100 mass %.
In the present invention, film contact with the solution comprising the organic solvent processing for being irradiated the radioactive ray of polarization passes through dipping Processing, spraying (spray) processing etc., preferably make the processing that film and liquid fully contact to carry out.Wherein, preferably film is being wrapped Impregnation preferably 10 seconds~1 hour, the method for more preferably 1~30 minute in solution containing organic solvent.Contact processing can be with Carry out to carry out under heating at normal temperatures, be preferable over 10~80 DEG C, more preferably in 20~50 DEG C of implementations.Furthermore it is possible to Implement the method for the contact-enhancings such as ultrasonic wave as needed.
After above-mentioned contact processing, in order to remove the organic solvent in used solution, water, methanol, ethanol, 2- can be used The low boiling point solvents such as propyl alcohol, acetone, methyl ethyl ketone are washed any one of (flushing) and drying or both.As drying When temperature, preferably 80~250 DEG C, more preferably 80~150 DEG C.
<Liquid crystal display cells>
The liquid crystal display cells of the present invention are to carry to be obtained by aligning agent for liquid crystal by the manufacture method of the present invention in acquisition Liquid crystal orientation film substrate after, manufacture liquid crystal cell with known method, liquid crystal display cells be made with the liquid crystal cell.
As one of the manufacture method of liquid crystal cell, said by taking the liquid crystal display cells of passive-matrix structure as an example It is bright.Alternatively, it is also possible to being that each pixel portion in pie graph as shown in is provided with TFT (thin film transistor (TFT) (Thin Film The liquid crystal display cells of the active matrix structure of switch element such as Transistor)).
First, prepare the substrate of transparent glass system, common electrode is set on the substrate of a side, in the substrate of the opposing party Upper setting segment electrode.These electrodes can be for example ITO electrode, be formed to the pattern that image needed for carrying out is shown.Then, exist Dielectric film is set in the form of coated common electrode and segment electrode on each substrate.Insulating film such as can be to pass through sol-gel Method formed by SiO2-TiO2The film of composition.
Then, the liquid crystal orientation film of the present invention is formed on each substrate.
Then, on the substrate of a side by it is mutual orientation film surface it is opposite in a manner of overlapping the opposing party substrate, by periphery It is bonded with encapsulant.For control base board gap, sept is generally mixed into advance in encapsulant.In addition, preferably exist The face inside points for being not provided with encapsulant also spread sept for control base board gap in advance.In a part for encapsulant Pre-setting can be from the opening portion of outside filling liquid crystal.
Then, by being arranged at the opening portion of encapsulant, noted into the space surrounded by two pieces of substrates and encapsulant Enter liquid crystal material.Then, the opening portion is sealed with bonding agent.Injection can use vacuum impregnation, can also use big The method that capillarity is utilized in gas.Then, the setting of polarizer is carried out.Specifically, in two pieces of substrates and liquid crystal layer phase A pair of polarizers are pasted on the face of anti-side.By above process, liquid crystal display cells of the invention can be obtained.The liquid crystal Show that element is used as liquid crystal orientation film due to using by liquid crystal orientation film made from the manufacture method of the liquid crystal orientation film of the present invention, So ghost excellent, can be suitable for big picture and the LCD TV of high-resolution etc..
Embodiment
Hereinafter, enumerate embodiment and more specific description is carried out to the present invention, but the present invention is not limited to this.
The assay method of the abbreviation of the compound used in embodiment and comparative example and each characteristic is as described below.
NMP：METHYLPYRROLIDONE
GBL：Gamma-butyrolacton
BCS：Butyl cellosolve
IPA：2- propyl alcohol
PGMEA：1- methoxy-2-propanol acetic acid esters
PG：Propane diols
MMP：3- methoxy methyl propionates
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- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine
[changing 22]
Molecular weight, the anisotropy of alignment films and the evaluation method of film inequality described below.
[molecular weight]
The molecular weight of poly amic acid ester is measured using GPC (normal temperature gel permeation chromatography) device, with polyethylene glycol Number-average molecular weight (Mn) and weight average molecular weight (Mw) are calculated with PEO scaled value.
GPC devices：Shodex companies (Showa Denko K. K) make (GPC-101)
Post：Showa Denko K. K's system (KD803, KD805 series connection)
Column temperature：50℃
Eluent：DMF is (as additive, lithium bromide-hydrate (LiBrH2O) it is 30mmol/L (liter), phosphoric anhydride crystallization (o- phosphoric acid) are 30mmol/L, tetrahydrofuran (THF) is 10ml/L)
Flow velocity：1.0ml/ minute
Calibration curve making standard specimen：Dong Cao companies (East ソ ー societies) TSK standards PEO (Weight-average molecular processed Measure (Mw) about 900000,150000,100000,30000) and Polymer Laboratory company (Port リ マ ー ラ ボ ラ ト リ ー societies) system Polyethylene glycol (spike molecular weight (Mp) about 12000,4000,1000).In order to avoid overlap of peaks, two samples are surveyed respectively It is fixed, that is, it is mixed with 900000,100000,12000,1000 this 4 kinds sample and is mixed with 150000,30000,4000 this 3 kinds Sample.
[anisotropy of alignment films]
Proceed as described below the anisotropic measure of alignment films.
Ultraviolet-visible-near infrared spectrometer (the UV- made with Shimadzu Corporation (Island Tianjin System Zuo Suo societies) 3100PC) it is measured.According to the absorbance (235nm value) and and differently- oriented directivity in the differently- oriented directivity of the alignment films of gained Absorbance on vertical direction determines anisotropic size.
[film is uneven]
The uneven evaluation of film is the band ilm substrate after impregnation that detects by an unaided eye, and proceeds as described below classification.
○：Without inequality
△：It can be seen that less inequality
×：It can be seen that larger uneven or albefaction
<Synthesis example 1>
Make to turn into blanket of nitrogen in the 500mL four-hole boiling flasks with agitating device, put into 4.58g (42.4mmol) to benzene two Amine, and then after input 1.79g (4.71mmol) DA-1, add 84.7g NMP, 254g GBL and the 8.40g as alkali (106mmol) pyridine, stirring make its dissolving.Then, while stirring the diamine solution, while addition 14.4g (44.2mmol) DE-1, a Dinner is reacted at 15 DEG C.After stirring an evening, 1.23g (13.6mmol) acryloyl chloride is added, reacts 4 at 15 DEG C Hour.Stir while obtained polyamic acid ester solution is added in 1477g IPA, the white precipitate that leaching separates out, Then cleaned 5 times with 738g IPA, the poly amic acid ester toner of 17.3g whites is obtained through drying.Yield is 96.9%. In addition, the molecular weight of the poly amic acid ester is Mn=14288, Mw=29956.
The poly amic acid ester toner that 3.69g is obtained is taken into 100ml conical flasks, adds 33.2g GBL, Stirring 24 hours at room temperature makes its dissolving, obtains polyamic acid ester solution.
<Synthesis example 2>
The polyamic acid ester solution obtained in 5.26g synthesis examples 1 is taken in the 20mL probe tubes for having stirrer are added, is added 3.16g GBL, 2.11g BCS and 0.19g additive A, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal A.
<Synthesis example 3>
Make to turn into blanket of nitrogen in the 500mL four-hole boiling flasks with agitating device, put into 2.50g (23.1mmol) to benzene two Amine, and then after input 0.59g (1.22mmol) DA-2, add 42.8g NMP, 129g GBL and the 4.34g as alkali (54.9mmol) pyridine, stirring make its dissolving.Then, while stirring the diamine solution, while addition 7.44g (22.9mmol) DE-1, a Dinner is reacted at 15 DEG C.After stirring an evening, 0.63g (7.01mmol) acryloyl chloride is added, reacts 4 at 15 DEG C Hour.Stir while obtained polyamic acid ester solution is added in 574g IPA, the white precipitate that leaching separates out, Then cleaned 5 times with 382g IPA, the poly amic acid ester toner of 8.82g whites is obtained through drying.Yield is 97.8%. In addition, the molecular weight of the poly amic acid ester is Mn=16617, Mw=37387.
The poly amic acid ester toner that 0.80g is obtained is taken into 100ml conical flasks, adds 7.20g GBL, Stirring 24 hours at room temperature makes its dissolving, obtains polyamic acid ester solution.
<Synthesis example 4>
The polyamic acid ester solution obtained in 8.00g synthesis examples 3 is taken in the 20mL probe tubes for having stirrer are added, is added 8.01g GBL, 4.00g BCS and 0.28g additive A, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal B.
<Synthesis example 5>
Make to turn into blanket of nitrogen in the 500mL four-hole boiling flasks with agitating device, put into 1.23g (11.3mmol) to benzene two Amine, and then the 4 of 0.80g (3.77mmol) are put into, 4 '-diaminostilbene, after 2- diphenylethanes, add 27.0g NMP, 91.2g GBL and 2.69g (34.0mmol) pyridine as alkali, stirring make its dissolving.Then, while stirring the diamine solution, on one side 4.61g (14.2mmol) DE-1 is added, a Dinner is reacted at 15 DEG C.After stirring an evening, the third of 0.39g (4.34mmol) is added Alkene acyl chlorides, reacted 4 hours at 15 DEG C.Stir while obtained polyamic acid ester solution is added in 384g IPA, The white precipitate that leaching separates out, is then cleaned 5 times with 256g IPA, and the poly amic acid ester resin of 5.11g whites is obtained through drying Powder.Yield is 89.6%.In addition, the molecular weight of the poly amic acid ester is Mn=14806, Mw=32719.
The poly amic acid ester toner that 0.80g is obtained is taken into 100ml conical flasks, adds 7.20g GBL, Stirring 24 hours at room temperature makes its dissolving, obtains polyamic acid ester solution.
<Synthesis example 6>
The polyamic acid ester solution obtained in 8.01g synthesis examples 5 is taken in the 20mL probe tubes for having stirrer are added, is added 8.01g GBL, 4.00g BCS and 0.28g additive A, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal C.
<Synthesis example 7>
Make to turn into blanket of nitrogen in the 500mL four-hole boiling flasks with agitating device, put into 2.80g (25.9mmol) to benzene two Amine, and then after input 1.45g (6.47mmol) DA-3, add 111g NMP and 6.18g (78.1mmol) pyrrole as alkali Pyridine, stirring make its dissolving.Then, while stirring the diamine solution, while addition 9.89g (30.4mmol) DE-1, at 15 DEG C One Dinner of lower reaction.After stirring an evening, 0.38g (4.21mmol) acryloyl chloride is added, is reacted 4 hours at 15 DEG C.While stir Mix while obtained polyamic acid ester solution is added in 1230g water, the white precipitate that leaching separates out, then use 1230g IPA clean 5 times, through dry obtain 10.2g white poly amic acid ester toner.Yield is 83.0%.In addition, the polyamides The molecular weight of amino acid ester is Mn=20786, Mw=40973.
The poly amic acid ester toner that 0.798g is obtained is taken into 100ml conical flasks, adds 7.18g GBL, Stirring 24 hours at room temperature makes its dissolving, obtains polyamic acid ester solution.
<Synthesis example 8>
The polyamic acid ester solution obtained in 7.98g synthesis examples 7 is taken in the 20mL probe tubes for having stirrer are added, is added 8.03g GBL, 4.00g BCS and 0.28g additive A, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal D.
<Synthesis example 9>
In the 300mL four-hole boiling flasks with agitating device and nitrogen ingress pipe put into 46.0g (0.43mol) to benzene two Amine, 17.8g (0.075mol) DA-3 and 1389g NMP, stirring make its dissolving.The solution is stirred while adding 107g 1, the 3- dimethyl -1,2 of (0.48mol), 3,4- cyclobutane tetracarboxylic dianhydrides, adding NMP makes solid component concentration reach 10 Quality %, it is stirred at room temperature 24 hours, obtains polyamic acid (PAA-1) solution.The polyamic acid solution is in 25 DEG C of temperature Under viscosity be 215mPas.In addition, the molecular weight of the polyamic acid is Mn=12629, Mw=29521.
<Synthesis example 10>
Polyamic acid solution (the PAA- obtained in 11.0g synthesis examples 9 is taken in the 50mL probe tubes for having stirrer are added 1), 5.00g NMP, 4.01g BCS and 0.15g additive A, with magnetic stirrer 30 minutes, liquid crystal aligning is obtained Agent E.
<Synthesis example 11>
4.25g (20.0mmol) 4,4 '-diamino is taken in the 100ml four-hole boiling flasks with agitating device and nitrogen ingress pipe Base -1,2- diphenylethane, 70.9g NMP is added, being stirred when being passed through nitrogen makes its dissolving.While stir the diamine solution one Side addition 3.82g (19.5mmol) 1,2,3,4- cyclobutane tetracarboxylic dianhydrides, adding NMP makes solid component concentration reach 10 Quality %, it is stirred at room temperature 24 hours, obtains polyamic acid (PAA-2) solution.The polyamic acid solution is in 25 DEG C of temperature Under viscosity be 156mPas.In addition, the molecular weight of the polyamic acid is Mn=13966, Mw=33163.
<Synthesis example 12>
Polyamic acid solution (the PAA- obtained in 12.2g synthesis examples 11 is taken in the 20ml probe tubes for having stirrer are added 2) 5.12g NMP and 2.90g BCS, are added, with magnetic stirrer 30 minutes, obtains aligning agent for liquid crystal F.
<Synthesis example 13>
5.17g (20.0mmol) double (4- of 1,3- are taken in the 100ml four-hole boiling flasks with agitating device and nitrogen ingress pipe Amino-benzene oxygen) propane, 72.0g NMP is added, being stirred when being passed through nitrogen makes its dissolving.Stir the diamine solution while 3.79g (19.3mmol) 1,2,3,4- cyclobutane tetracarboxylic dianhydrides are added, adding NMP makes solid component concentration reach 10 matter % is measured, is stirred at room temperature 24 hours, obtains polyamic acid (PAA-3) solution.The polyamic acid solution is at 25 DEG C of temperature Viscosity be 162mPas.In addition, the molecular weight of the polyamic acid is Mn=25902, Mw=40413.
<Synthesis example 14>
Polyamic acid solution (the PAA- obtained in 11.9g synthesis examples 13 is taken in the 20ml probe tubes for having stirrer are added 3) 3.98g NMP and 3.97g BCS, are added, with magnetic stirrer 30 minutes, obtains aligning agent for liquid crystal G.
<Embodiment 1>
By the aligning agent for liquid crystal A obtained in synthesis example 2 with after the filtering of 1.0 μm of filter, spin coating on the glass substrate, in temperature After being dried 3 minutes in the heating plate of 80 DEG C of degree, burnt till in 230 DEG C 10 minutes, obtain the polyimide film that thickness is 100nm.Every Polarizer and 1.2J/cm is irradiated to the coated surface2254nm ultraviolets.
Then, by obtained band ilm substrate as described above in PGME (boiling points:120 DEG C) in 25 DEG C dipping 3 minutes after, use IPA rinses (washing) 1 minute, is dried 10 minutes in 80 DEG C of baking oven, obtains liquid crystal orientation film.Measure gained liquid crystal orientation film Differently- oriented directivity on anisotropy, as a result anisotropic size be 1.84.In addition, the liquid crystal orientation film that detects by an unaided eye, knot Fruit has no uneven.
<Embodiment 2>
Similarly to Example 1, using the aligning agent for liquid crystal A obtained in synthesis example 2, it is coated with, dries, burns on substrate Into irradiating ultraviolet to the polyimide film of gained and obtain band ilm substrate, by the band ilm substrate in PGMEA (boiling points:146℃) In in 25 DEG C dipping 3 minutes after, with IPA rinse 1 minute, in 80 DEG C of baking oven dry 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.51.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 3>
Similarly to Example 1, using the aligning agent for liquid crystal A obtained in synthesis example 2, it is coated with, dries, burns on substrate Into irradiating ultraviolet to the polyimide film of gained and obtain band ilm substrate, by the band ilm substrate in PGME/ water=1/1 (volume Than) in the mixed solvent impregnate 3 minutes after, with IPA rinse 1 minute, in 80 DEG C of baking oven dry 10 minutes, obtain liquid crystal aligning Film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.69.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 4>
Similarly to Example 1, using the aligning agent for liquid crystal A obtained in synthesis example 2, it is coated with, dries, burns on substrate Into irradiating ultraviolet to the polyimide film of gained and obtain band ilm substrate, by the band ilm substrate in ethyl lactate (boiling point:154 DEG C) in 25 DEG C dipping 3 minutes after, with IPA rinse 1 minute, in 80 DEG C of baking oven dry 10 minutes, obtain liquid crystal aligning Film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.9.In addition, the liquid crystal that detects by an unaided eye takes To film, as a result have no uneven.
<Embodiment 5>
Similarly to Example 1, using the aligning agent for liquid crystal A obtained in synthesis example 2, it is coated with, dries, burns on substrate Into irradiating ultraviolet to the polyimide film of gained and obtain band ilm substrate, by the band ilm substrate in butyl cellosolve (boiling point: 169 DEG C) in 25 DEG C dipping 10 minutes after, with IPA rinse 1 minute, in 80 DEG C of baking oven dry 10 minutes, obtain liquid crystal and take To film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.69.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 6>
Similarly to Example 1, using the aligning agent for liquid crystal A obtained in synthesis example 2, it is coated with, dries, burns on substrate Into irradiating ultraviolet to the polyimide film of gained and obtain band ilm substrate, by the band ilm substrate in PGME (boiling points:124℃) In in 25 DEG C dipping 3 minutes after, with water rinse 1 minute, in 80 DEG C of baking oven dry 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.82.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 7>
Similarly to Example 1, using the aligning agent for liquid crystal A obtained in synthesis example 2, it is coated with, dries, burns on substrate Into irradiating ultraviolet to the polyimide film of gained and obtain band ilm substrate, by the band ilm substrate in ethyl lactate (boiling point:154 DEG C) in 25 DEG C dipping 3 minutes after, with water rinse 1 minute, in 80 DEG C of baking oven dry 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.84.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 8>
Similarly to Example 1, using the aligning agent for liquid crystal A obtained in synthesis example 2, it is coated with, dries, burns on substrate Into irradiating ultraviolet to the polyimide film of gained and obtain band ilm substrate, by the band ilm substrate in diacetone alcohol (boiling point:169 DEG C) in 25 DEG C dipping 3 minutes after, with water rinse 1 minute, in 80 DEG C of baking oven dry 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.77.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 9>
Similarly to Example 1, using the aligning agent for liquid crystal A obtained in synthesis example 2, it is coated with, dries, burns on substrate Into irradiating ultraviolet to the polyimide film of gained and obtain band ilm substrate, by the band ilm substrate in MMP (boiling points:145 DEG C) in After 25 DEG C impregnate 3 minutes, rinsed 1 minute with water, dried 10 minutes in 80 DEG C of baking oven, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.77.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 10>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 4 The aligning agent for liquid crystal B arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, by the band ilm substrate in PGME (boiling points:120 DEG C) in 25 DEG C dipping 3 minutes after, with IPA rinse 1 minute, at 80 DEG C Baking oven in dry 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.72.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 11>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 4 The aligning agent for liquid crystal B arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, by the band ilm substrate in ethyl lactate (boiling point:154 DEG C) in 25 DEG C dipping 3 minutes after, with IPA rinse 1 minute, Dried 10 minutes in 80 DEG C of baking oven, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 2.11.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 12>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 6 The aligning agent for liquid crystal C arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, by the band ilm substrate in PGME (boiling points:120 DEG C) in 25 DEG C dipping 3 minutes after, with IPA rinse 1 minute, at 80 DEG C Baking oven in dry 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.53.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 13>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 6 The aligning agent for liquid crystal C arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, by the band ilm substrate in ethyl lactate (boiling point:154 DEG C) in 25 DEG C dipping 3 minutes after, with IPA rinse 1 minute, Dried 10 minutes in 80 DEG C of baking oven, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.94.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 14>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 8 The aligning agent for liquid crystal D arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, by the band ilm substrate in PGME (boiling points:120 DEG C) in 25 DEG C dipping 3 minutes after, with IPA rinse 1 minute, at 80 DEG C Baking oven in dry 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.40.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 15>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 8 The aligning agent for liquid crystal D arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, by the band ilm substrate in ethyl lactate (boiling point:154 DEG C) in 25 DEG C dipping 3 minutes after, with IPA rinse 1 minute, Dried 10 minutes in 80 DEG C of baking oven, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.70.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 16>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 2 The aligning agent for liquid crystal A arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, by the band ilm substrate in PGME (boiling points:120 DEG C) in 25 DEG C dipping 3 minutes after, with IPA rinse 1 minute, at 80 DEG C Baking oven in dry 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.37.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 17>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 2 The aligning agent for liquid crystal A arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, by the band ilm substrate in ethyl lactate (boiling point:154 DEG C) in 25 DEG C dipping 3 minutes after, with IPA rinse 1 minute, Dried 10 minutes in 80 DEG C of baking oven, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.77.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 18>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Using in synthesis example 10 Obtained aligning agent for liquid crystal E, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band Ilm substrate, by the band ilm substrate in PGME (boiling points:120 DEG C) in 25 DEG C dipping 3 minutes after, with IPA rinse 1 minute, 80 DEG C baking oven in dry 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.33.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 19>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Using in synthesis example 10 Obtained aligning agent for liquid crystal E, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band Ilm substrate, by the band ilm substrate in ethyl lactate (boiling point:154 DEG C) in 25 DEG C dipping 3 minutes after, with IPA rinse 1 minute, Dried 10 minutes in 80 DEG C of baking oven, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.2.In addition, the liquid crystal that detects by an unaided eye takes To film, as a result have no uneven.
<Embodiment 20>
Except irradiating 1.0J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Using in synthesis example 12 Obtained aligning agent for liquid crystal F, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band Ilm substrate, by the band ilm substrate in PGME (boiling points:120 DEG C) in 25 DEG C dipping 3 minutes after, with IPA rinse 1 minute, 80 DEG C baking oven in dry 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.15.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 21>
Except irradiating 1.0J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Using in synthesis example 12 Obtained aligning agent for liquid crystal F, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band Ilm substrate, by the band ilm substrate in ethyl lactate (boiling point:154 DEG C) in 25 DEG C dipping 3 minutes after, with IPA rinse 1 minute, Dried 10 minutes in 80 DEG C of baking oven, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.12.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 22>
Except irradiating 1.0J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Using in synthesis example 14 Obtained aligning agent for liquid crystal G, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band Ilm substrate, by the band ilm substrate in PGME (boiling points:120 DEG C) in 25 DEG C dipping 3 minutes after, with IPA rinse 1 minute, 80 DEG C baking oven in dry 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.11.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Embodiment 23>
Except irradiating 1.0J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Using in synthesis example 14 Obtained aligning agent for liquid crystal G, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band Ilm substrate, by the band ilm substrate in ethyl lactate (boiling point:154 DEG C) in 25 DEG C dipping 3 minutes after, with IPA rinse 1 minute, Dried 10 minutes in 80 DEG C of baking oven, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.10.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result have no uneven.
<Comparative example 1>
Similarly to Example 1, using the aligning agent for liquid crystal A obtained in synthesis example 2, it is coated with, dries, burns on substrate Into irradiating ultraviolet to the polyimide film of gained and obtain band ilm substrate, by the band ilm substrate in IPA (boiling points:82.4℃) In in 25 DEG C dipping 3 minutes after, in 80 DEG C of baking oven dry 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.2.In addition, the orientation that detects by an unaided eye Film, as a result visible less inequality.
<Comparative example 2>
Similarly to Example 1, using the aligning agent for liquid crystal A obtained in synthesis example 2, it is coated with, dries, burns on substrate Into irradiating ultraviolet to the polyimide film of gained and obtain band ilm substrate, by the band ilm substrate in water (boiling point:100 DEG C) in Dipping is rinsed 1 minute after 3 minutes with IPA, is dried 10 minutes in 80 DEG C of baking oven, is obtained liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.25.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result visible less inequality.
<Comparative example 3>
Similarly to Example 1, using the aligning agent for liquid crystal A obtained in synthesis example 2, it is coated with, dries, burns on substrate Into irradiating ultraviolet to the polyimide film of gained and obtain band ilm substrate, by the band ilm substrate in PG (boiling points:187 DEG C) in After 25 DEG C impregnate 3 minutes, rinsed 1 minute with IPA, dried 10 minutes in 80 DEG C of baking oven, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.45.In addition, the orientation that detects by an unaided eye Film, as a result visible larger uneven or albefaction.
<Comparative example 4>
Similarly to Example 1, using the aligning agent for liquid crystal A obtained in synthesis example 2, it is coated with, dries, burns on substrate Into irradiating ultraviolet to the polyimide film of gained and obtain band ilm substrate, by the band ilm substrate in GBL (boiling points:204 DEG C) in After 25 DEG C impregnate 3 minutes, rinsed 1 minute with IPA, dried 10 minutes in 80 DEG C of baking oven, obtain liquid crystal orientation film.
The film of the liquid crystal orientation film of gained is completely dissolved, and can not carry out anisotropic measure and the measure of thickness.
<Comparative example 5>
Similarly to Example 1, using the aligning agent for liquid crystal A obtained in synthesis example 2, it is coated with, dries, burns on substrate Into irradiating ultraviolet to the polyimide film of gained and obtain band ilm substrate, by the band ilm substrate in NMP (boiling points:202 DEG C) in After 25 DEG C impregnate 3 minutes, rinsed 1 minute with IPA, dried 10 minutes in 80 DEG C of baking oven, obtain liquid crystal orientation film.
The film of the liquid crystal orientation film of gained is completely dissolved, and can not carry out anisotropic measure and the measure of thickness.
<Comparative example 6>
Similarly to Example 1, using the aligning agent for liquid crystal A obtained in synthesis example 2, it is coated with, dries, burns on substrate Into, ultraviolet is irradiated to the polyimide film of gained and obtains band ilm substrate, the orientation with the liquid crystal orientation film in ilm substrate Anisotropic size on direction is 1.18.Not it was observed that the film of liquid crystal orientation film is uneven.
<Comparative example 7>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 4 The aligning agent for liquid crystal B arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, by the band ilm substrate in IPA (boiling points:82.4 DEG C) in 25 DEG C dipping 3 minutes after, in 80 DEG C of baking oven dry 10 points Clock, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.19.In addition, the orientation that detects by an unaided eye Film, as a result visible less inequality.
<Comparative example 8>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 4 The aligning agent for liquid crystal B arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, by the band ilm substrate in water (boiling point:100 DEG C) in dipping 3 minutes after, with IPA rinse 1 minute, in 80 DEG C of baking oven Dry 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.17.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result visible less inequality.
<Comparative example 9>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 4 The aligning agent for liquid crystal B arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, the anisotropic size in the differently- oriented directivity with the liquid crystal orientation film in ilm substrate are 1.12.Not it was observed that liquid crystal The film of alignment films is uneven.
<Comparative example 10>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 6 The aligning agent for liquid crystal C arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, by the band ilm substrate in IPA (boiling points:82.4 DEG C) in 25 DEG C dipping 3 minutes after, in 80 DEG C of baking oven dry 10 points Clock, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.12.In addition, the orientation that detects by an unaided eye Film, as a result visible less inequality.
<Comparative example 11>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 6 The aligning agent for liquid crystal C arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, by the band ilm substrate in water (boiling point:100 DEG C) in dipping 3 minutes after, with IPA rinse 1 minute, in 80 DEG C of baking oven Dry 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.16.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result visible less inequality.
<Comparative example 12>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 6 The aligning agent for liquid crystal C arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, the anisotropic size in the differently- oriented directivity with the liquid crystal orientation film in ilm substrate are 1.11.Not it was observed that liquid crystal The film of alignment films is uneven.
<Comparative example 13>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 8 The aligning agent for liquid crystal D arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, by the band ilm substrate in IPA (boiling points:82.4 DEG C) in 25 DEG C dipping 3 minutes after, in 80 DEG C of baking oven dry 10 points Clock, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.19.In addition, the orientation that detects by an unaided eye Film, as a result visible less inequality.
<Comparative example 14>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 8 The aligning agent for liquid crystal D arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, by the band ilm substrate in water (boiling point:100 DEG C) in dipping 3 minutes after, with IPA rinse 1 minute, in 80 DEG C of baking oven Dry 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.19.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result visible less inequality.
<Comparative example 15>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 8 The aligning agent for liquid crystal D arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, the anisotropic size in the differently- oriented directivity with the liquid crystal orientation film in ilm substrate are 1.12.Not it was observed that liquid crystal The film of alignment films is uneven.
<Comparative example 16>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 2 The aligning agent for liquid crystal A arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, by the band ilm substrate in IPA (boiling points:82.4 DEG C) in 25 DEG C dipping 3 minutes after, in 80 DEG C of baking oven dry 10 points Clock, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.17.In addition, the orientation that detects by an unaided eye Film, as a result visible less inequality.
<Comparative example 17>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 2 The aligning agent for liquid crystal A arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, by the band ilm substrate in water (boiling point:100 DEG C) in dipping 3 minutes after, with IPA rinse 1 minute, in 80 DEG C of baking oven Dry 10 minutes, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.17.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result visible less inequality.
<Comparative example 18>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Obtained using in synthesis example 2 The aligning agent for liquid crystal A arrived, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band film Substrate, the anisotropic size in the differently- oriented directivity with the liquid crystal orientation film in ilm substrate are 1.12.Not it was observed that liquid crystal The film of alignment films is uneven.
<Comparative example 19>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Using in synthesis example 10 Obtained aligning agent for liquid crystal E, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band Ilm substrate, by the band ilm substrate in IPA (boiling points:82.4 DEG C) in 25 DEG C dipping 3 minutes after, in 80 DEG C of baking oven dry 10 Minute, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.11.In addition, the orientation that detects by an unaided eye Film, as a result visible less inequality.
<Comparative example 20>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Using in synthesis example 10 Obtained aligning agent for liquid crystal E, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band Ilm substrate, by the band ilm substrate in water (boiling point:100 DEG C) in dipping 3 minutes after, with IPA rinse 1 minute, in 80 DEG C of baking oven Interior drying 10 minutes, obtains liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.11.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result visible less inequality.
<Comparative example 21>
Except irradiating 0.5J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Using in synthesis example 10 Obtained aligning agent for liquid crystal E, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band Ilm substrate, the anisotropic size in the differently- oriented directivity with the liquid crystal orientation film in ilm substrate are 1.08.Not it was observed that liquid The film of brilliant alignment films is uneven.
<Comparative example 22>
Except irradiating 1.0J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Using in synthesis example 12 Obtained aligning agent for liquid crystal F, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band Ilm substrate, by the band ilm substrate in IPA (boiling points:82.4 DEG C) in 25 DEG C dipping 3 minutes after, in 80 DEG C of baking oven dry 10 Minute, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.04.In addition, the orientation that detects by an unaided eye Film, as a result visible inequality.
<Comparative example 23>
Except irradiating 1.0J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Using in synthesis example 12 Obtained aligning agent for liquid crystal F, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band Ilm substrate, by the band ilm substrate in water (boiling point:100 DEG C) in dipping 3 minutes after, with IPA rinse 1 minute, in 80 DEG C of baking oven Interior drying 10 minutes, obtains liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.10.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result visible less inequality.
<Comparative example 24>
Except irradiating 1.0J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Using in synthesis example 12 Obtained aligning agent for liquid crystal F, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band Ilm substrate, the anisotropic size in the differently- oriented directivity with the liquid crystal orientation film in ilm substrate are 1.06.Not it was observed that liquid The film of brilliant alignment films is uneven.
<Comparative example 25>
Except irradiating 1.0J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Using in synthesis example 14 Obtained aligning agent for liquid crystal G, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band Ilm substrate, by the band ilm substrate in IPA (boiling points:82.4 DEG C) in 25 DEG C dipping 3 minutes after, in 80 DEG C of baking oven dry 10 Minute, obtain liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.09.In addition, the orientation that detects by an unaided eye Film, as a result visible inequality.
<Comparative example 26>
Except irradiating 1.0J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Using in synthesis example 14 Obtained aligning agent for liquid crystal G, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band Ilm substrate, by the band ilm substrate in water (boiling point:100 DEG C) in dipping 3 minutes after, with IPA rinse 1 minute, in 80 DEG C of baking oven Interior drying 10 minutes, obtains liquid crystal orientation film.
Anisotropic size in the differently- oriented directivity of gained liquid crystal orientation film is 1.09.In addition, the liquid crystal that detects by an unaided eye Alignment films, as a result visible less inequality.
<Comparative example 27>
Except irradiating 1.0J/cm2254nm ultraviolets beyond, carry out similarly to Example 1.Using in synthesis example 14 Obtained aligning agent for liquid crystal G, it is coated with substrate, dries, burn till, ultraviolet is irradiated to the polyimide film of gained and obtains band Ilm substrate, the anisotropic size in the differently- oriented directivity with the liquid crystal orientation film in ilm substrate are 1.07.Not it was observed that liquid The film of brilliant alignment films is uneven.
On above-described embodiment 1~22 and comparative example 1~27, by the species of the solvent used, the liquid crystal orientation film of gained Anisotropic size and the uneven situation of film collect and be shown in table 1.
[table 1]
Solvent Flushing liquor Anisotropic size Film is uneven
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 - It can not determine All dissolvings
Comparative example 5 NMP - It can not determine All dissolvings
Comparative example 6 Without processing - 1.18 -
Comparative example 7 IPA - 1.19 Δ
Comparative example 8 Water IPA 1.17 Δ
Comparative example 9 Without processing - 1.12 -
Comparative example 10 IPA - 1.12 Δ
Comparative example 11 Water IPA 1.16 Δ
Comparative example 12 Without processing - 1.11 -
Comparative example 13 IPA - 1.19 Δ
Comparative example 14 Water IPA 1.19 Δ
Comparative example 15 Without processing - 1.12 -
Comparative example 16 IPA - 1.7 Δ
Comparative example 17 Water IPA 1.17 Δ
Comparative example 18 Without processing - 1.12 -
Comparative example 19 IPA - 1.11 Δ
Comparative example 20 Water IPA 1.11 Δ
Comparative example 21 Without processing - 1.11 -
Comparative example 22 IPA - 1.04 Δ
Comparative example 23 Water IPA 1.10 Δ
Comparative example 24 Without processing - 1.06 -
Comparative example 25 IPA - 1.09 Δ
Comparative example 26 Water IPA 1.09 Δ
Comparative example 27 Without processing - 1.07 -
The possibility utilized in industry
By the present invention manufacture method made from liquid crystal orientation film there is high anisotropy, can be widely used for TN elements, Liquid crystal display cells of STN elements, TFT liquid crystal cells and vertical orientating type etc..Further, can by assigning high anisotropy Reduce and come from the ghost of liquid crystal aligning, for example produced in the liquid crystal display cells of IPS type of drive or FFS type of drive Ghost, liquid crystal display cells or LCD TV as IPS type of drive or FFS type of drive as caused by exchange driving Liquid crystal orientation film is particularly useful.
Specification, the power for the Japanese patent application 2011-202229 that September in 2011 is filed an application on the 15th are quoted herein The announcement of sharp claim and the full content of specification digest as description of the invention.

Claims (10)

1. the manufacture method of liquid crystal orientation film, it is characterised in that be selected from the structure list represented with following formula (3) for that will contain At least one polymer and organic solvent of the polyimide precursor of member and the imide amination polymer of the polyimide precursor Aligning agent for liquid crystal is coated with substrate, burn till obtained by imidizate film, irradiate the radioactive ray of polarization, then with comprising selected from 1- methoxy-2-propanols, 1- methoxy-2-propanols acetic acid esters, formula (A-2), formula (A-3), formula (A-4) and formula (A-5) are at least A kind of solution of organic solvent carries out contact processing；
[changing 1]
In formula (A-2), A3For the alkyl of carbon number 1~4；In formula (A-3), R3And R4It is separately hydrogen atom or methyl；Formula (A-4) in, A5And A6It is separately the alkyl of carbon number 1~4；In formula (A-5), A6For the alkyl or cycloalkyl of carbon number 3~6；
[changing 2]
In formula (3), X1For at least one of the structure represented selected from following formula (X1-1)~(X1-9), Y1For divalent organic group, R1For hydrogen atom or the alkyl of carbon number 1~4；
[changing 3]
In formula (X1-1), R3、R4、R5And R6It is separately hydrogen atom, halogen atom, the alkyl of carbon number 1~6, carbon number 2~6 Alkenyl, alkenyl or phenyl.
2. the manufacture method of liquid crystal orientation film as claimed in claim 1, wherein, the organic solvent is with 100~180 DEG C Boiling point.
3. the manufacture method of liquid crystal orientation film as claimed in claim 1 or 2, wherein, the organic solvent is 1- methoxyl groups -2- Propyl alcohol, ethyl lactate, diacetone alcohol, 3- methoxy methyl propionates or 3- ethoxyl ethyl propionates.
4. the manufacture method of liquid crystal orientation film as claimed in claim 1, wherein, the polymer is selected from relative to 1 mole The polyimide precursor of construction unit that represents of whole polymer above-mentioned formula (3) for containing 60 moles of more than % and the polyamides it is sub- At least one of the imide amination polymer of amine precursor.
5. the manufacture method of liquid crystal orientation film as claimed in claim 1, wherein, in above-mentioned formula (3), X1With above-mentioned formula (X1-1) Represent.
6. the manufacture method of liquid crystal orientation film as claimed in claim 1, wherein, in above-mentioned formula (3), X1For selected from following formula (X1-10) at least one of the structure~(X1-11) represented；
[changing 4]
7. the manufacture method of liquid crystal orientation film as claimed in claim 1, wherein, in above-mentioned formula (3), Y1For selected from following formula (4) (5) at least one of the structure represented；
[changing 5]
In formula (5), Z1For the divalent organic group of singly-bound, ester bond, amido link, thioester bond or carbon number 2~10.
8. the manufacture method of liquid crystal orientation film as claimed in claim 7, wherein, in above-mentioned formula (3), Y1Represented for above-mentioned formula (4) Structure.
9. liquid crystal orientation film, it is obtained by the manufacture method of liquid crystal orientation film according to any one of claims 1 to 8.
10. liquid crystal display cells, it is characterised in that there is the liquid crystal orientation film described in claim 9.
CN201280056047.9A 2011-09-15 2012-09-13 Manufacture method, liquid crystal orientation film and the liquid crystal display cells of liquid crystal orientation film Active CN103946738B (en)

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