CN104838311B - 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

Info

Publication number
CN104838311B
CN104838311B CN201380062441.8A CN201380062441A CN104838311B CN 104838311 B CN104838311 B CN 104838311B CN 201380062441 A CN201380062441 A CN 201380062441A CN 104838311 B CN104838311 B CN 104838311B
Authority
CN
China
Prior art keywords
liquid crystal
formula
orientation film
crystal orientation
organic solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201380062441.8A
Other languages
Chinese (zh)
Other versions
CN104838311A (en
Inventor
作本直树
饭沼洋介
野口勇步
堀隆夫
山极大辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
Original Assignee
Nissan Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Publication of CN104838311A publication Critical patent/CN104838311A/en
Application granted granted Critical
Publication of CN104838311B publication Critical patent/CN104838311B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—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
    • G02F1/13378—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

Landscapes

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

Abstract

The present invention provides a kind of manufacture method that can suppress the light orientation liquid crystal orientation film of ghost because caused by driving exchange.The aligning agent for liquid crystal at least one polymer for containing the imide amination polymer for being selected from polyimide precursor and the polyimide precursor with the construction unit represented by formula (1) is coated on substrate, film is obtained through burning till, radioactive ray through polarization are irradiated to the film, then the organic solvent with the boiling point with 110~180 DEG C carries out contact processing, again with water or the water-miscible organic solvent with 50~105 DEG C of boiling point carries out contact processing, then heated in more than 150 DEG C.(X1For formula (XA-1), Y1For divalent organic base, R1For H etc., R3~R6For H etc.).

Description

Manufacture method, liquid crystal orientation film and the liquid crystal display cells of liquid crystal orientation film
Technical field
The present invention relates to the manufacture method of the liquid crystal orientation film of optical alignment method, the liquid crystal aligning as made from the manufacture method Film and the liquid crystal display cells for possessing obtained liquid crystal orientation film.
Background technology
Liquid crystal display cells for LCD TV, liquid crystal display etc. are generally provided for controlling liquid crystal in element The liquid crystal orientation film of ordered state.
At present, industrial most popular liquid crystal orientation film is the cloth by using cotton, nylon, polyester etc. to being formed at electrode base The surface for the film that the polyimides formed by polyamic acid and/or its acid imide on plate is formed is wiped towards a direction, i.e., So-called friction treatment is carried out to make.
Film surface rubbing treatment method in the orientation process of liquid crystal orientation film is easy and excellent productivity industrial reality Method.But the high performance to liquid crystal display cells, high resolution, maximization requirement increasingly increase, by rubbing Inhomogeneity in the scar of alignment layer surface caused by processing, airborne dust, mechanical force or the influence of electrostatic and then orientation process face It is increasingly obvious etc. various problems.
As the method for replacing friction treatment, it is known that assign liquid crystal aligning ability by irradiating the radioactive ray through polarization Optical alignment method.Handled for the liquid crystal aligning carried out by optical alignment method, it is proposed that using the processing of photoisomerization reaction, utilize The processing of photo-crosslinking, utilize processing of photolysis reactionses etc. (with reference to non-patent literature 1).
On the other hand, using the light orientation of polyimides with liquid crystal orientation film compared with other liquid crystal orientation films, have height Heat resistance, therefore its practicality enjoys expectation.In patent document 1, it is proposed that will there is the alicyclic structures such as cyclobutane ring on main chain Polyamide-imide film be used for optical alignment method scheme.
For above-mentioned optical alignment method as friction orientation processing method, not only having can be with industrially also easy manufacturing process The advantages of to produce, and IPS (In-Place-Switching, plane conversion) type of drive or fringe field conversion (with It is referred to as FFS down) in the liquid crystal display cells of type of drive, by using the liquid crystal orientation film obtained by above-mentioned optical alignment method, with The liquid crystal orientation film obtained by friction treatment method is compared, and can expect the contrast of liquid crystal display cells or the raising of viewing angle characteristic etc. The raising of liquid crystal display cells performance, therefore got most of the attention as having promising liquid crystal aligning processing method.
As the liquid crystal orientation film for IPS type of drive or the liquid crystal display cells of FFS type of drive, except excellent Beyond the fundamental characteristics such as liquid crystal aligning or electrical characteristics, it is also necessary to suppress the liquid crystal display of IPS type of drive or FFS type of drive The caused ghost because caused by exchanging driving for a long time in element.
But liquid crystal orientation film is deposited compared with the liquid crystal orientation film as obtained by friction treatment method as obtained by optical alignment method The anisotropy relative to polymeric membrane differently- oriented directivity is small the problem of.Sufficient liquid crystal can not be obtained if anisotropy is small Orientation, under the occasion that liquid crystal display cells are made, produce ghost generation etc. the problem of.
In addition, as the anisotropic method for improving the liquid crystal orientation film as obtained by optical alignment method, it is proposed that in illumination Carry out cleaning treatment or heating by using water-miscible organic solvent after penetrating makes foregoing polyamides sub- to remove because of light irradiation The main chain of amine is cut off the scheme of caused low molecular weight compositions, but can not yet suppress ghost (with reference to 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
The wooden family side of body of non-patent literature 1 " liquid crystal photo-alignment film ", village of city functional material (" liquid crystal light alignment film " Mu Kobe side, city Village Machine can material) in November, 1997 Vol.17 No.11 13-22 page
The content of the invention
The technical problems to be solved by the invention
It is an object of the invention to provide a kind of liquid crystal display member that can suppress IPS type of drive or FFS type of drive The manufacture of the light orientation position logos liquid crystal orientation film, the liquid crystal orientation film of the caused ghost because caused by driving exchange in part Method and the liquid crystal display cells with the liquid crystal orientation film.
Technical scheme used by solution technical problem
The present inventor has made intensive studies in order to achieve the above object, as a result finds, will include has specific structure Polyimide precursor or the aligning agent for liquid crystal of imide amination polymer of the polyimide precursor be coated on substrate, through burning till And film is obtained, the radioactive ray through polarization are irradiated to the film, then at least two kinds of solvents of the selection with the boiling point in particular range, And the contact processing of impregnating is carried out using at least two kinds of solvents in a particular order, then heated in more than 150 DEG C Processing, by liquid crystal orientation film obtained by thus, above-mentioned purpose can be reached.
In this way, the technology contents of the present invention are as follows.
1. the manufacture method of liquid crystal orientation film, the polyamides Asia being selected from the construction unit represented by following formula (1) will be contained The aligning agent for liquid crystal of at least one polymer of the imide amination polymer of amine precursor and the polyimide precursor is coated on substrate On, film is obtained through burning till, the radioactive ray through polarization are irradiated to the film, it is then organic molten with the boiling point with 110~180 DEG C Agent carries out contact processing, then with water or the water-miscible organic solvent with 50~105 DEG C of boiling point carries out contact processing, Ran Houyu More than 150 DEG C are heated,
【Change 1】
(X1For the structure represented by following formula (XA-1),
Y1For divalent organic base, R1For hydrogen atom or the alkyl of carbon number 1~4.)
【Change 2】
(R3、R4、R5And R6It is separately hydrogen atom, halogen atom, the alkyl of carbon number 1~6, the alkenyl of carbon number 2~6 Or alkynyl or phenyl.
2. the manufacture method of the liquid crystal orientation film as described in above-mentioned 1, wherein, irradiated the radioactive ray through polarization it Afterwards, the water-miscible organic solvent of the boiling point with the organic solvent and water of the boiling point with 110~180 DEG C or with 50~105 DEG C Mixed solvent carry out contact processing, then with water or the water-miscible organic solvent with 50~105 DEG C of boiling point carries out contact position Reason, is then heated in more than 150 DEG C.
3. the manufacture method of the liquid crystal orientation film as described in above-mentioned 1 or 2, wherein, the boiling point with 110~180 DEG C Organic solvent be at least one selected from following formula (A-1), formula (A-2), formula (A-3), formula (A-4) and formula (A-5),
【Change 3】
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.
4. the manufacture method of liquid crystal orientation film as any one of above-mentioned 1~3, wherein, it is described that there are 110~180 DEG C Boiling point organic solvent be selected from 1- methoxyl group 2- propyl alcohol, ethyl lactate, diacetone alcohol, 3- methoxy methyl propionates and At least one of 3- ethoxyl ethyl propionates.
5. the manufacture method of the liquid crystal orientation film as any one of above-mentioned 1~4, wherein, it is described that there are 50~105 DEG C The water-miscible organic solvent of boiling point be at least one selected from methanol, ethanol, 2- propyl alcohol and acetone.
6. the manufacture method of the liquid crystal orientation film as any one of above-mentioned 1~5, wherein, the mixed solvent contains Organic solvent with 110~180 DEG C of boiling point and water that quality ratio is 95/5~5/95 or with 50~105 DEG C of boiling point Water-miscible organic solvent.
7. the manufacture method of the liquid crystal orientation film as any one of above-mentioned 1~6, wherein, selected from containing relative to complete 1 mole of portion's polymer is the polyimide precursor and the polyamides of the construction unit represented by 60 moles of more than % formula (1) The polymer of the imide amination polymer of imines precursor is to be selected from that to contain relative to whole 1 mole of polymer be 60 moles of % The polyimide precursor of construction unit represented by the formula (1) above and the imide amination polymer of the polyimide precursor At least one.
8. the manufacture method of the liquid crystal orientation film as any one of above-mentioned 1~7, wherein, X in above formula (1)1For selected from At least one of following formula (X1-1) and the structure represented by (X1-2),
【Change 4】
9. the manufacture method of the liquid crystal orientation film as any one of above-mentioned 1~8, wherein, Y in above formula (1)1For selected from At least one of structure represented by following formula (4) and (5),
【Change 5】
In formula (5), Z1For the divalent organic base of singly-bound, ester bond, amido link, thioester bond or carbon number 2~10.
10. the manufacture method of the liquid crystal orientation film as any one of above-mentioned 1~9, wherein, Y in above formula (1)1For choosing At least one structure of structure represented by self-ascending type (4) and following formula (Y1-1),
【Change 6】
11. liquid crystal orientation film, it is made as the manufacture method of the liquid crystal orientation film any one of above-mentioned 1~10.
12. liquid crystal display cells, possesses the liquid crystal orientation film described in above-mentioned 11.
Invention effect
Liquid crystal orientation film is in the liquid crystal display cells as IPS type of drive or FFS type of drive as obtained by the present invention Liquid crystal orientation film occasion under, the ghost because of caused by long-term exchange driving can be mitigated.
It is still not clear why the liquid crystal orientation film as obtained by the present invention can solve technical problem of the invention, but according to this hair The research of a person of good sense, judge that its reason is as follows.That is, it was found from the comparison of aftermentioned embodiment and comparative example, in the present invention, will use The aligning agent for liquid crystal of the polyimide precursor of specific structure is coated on substrate, film obtained through burning till, to film irradiation through inclined The contact implemented by solvent carried out after the radioactive ray to shake is handled, it is necessary to is carried out successively by the boiling point with 110~180 DEG C The contact processing implemented of organic solvent and by water or what the water-miscible organic solvent with 50~105 DEG C of boiling point was implemented connects Synapsis is managed, and its either party processing can not all obtain the effect above.
Known anisotropy and/or the phase interaction of raising liquid crystal orientation film and liquid crystal typically by improving liquid crystal orientation film With, can suppress in the liquid crystal display cells of IPS type of drive or FFS type of drive caused by it is residual because caused by driving exchange Shadow, but think in the present case, the contact carried out in a particular order by using above-mentioned specific at least two kinds of solvents Handling, caused foreign matter is completely removed in the process of radioactive ray of the irradiation carried out through polarization before, and by afterwards Heating under the specified conditions of progress, the reorientation of the strand of the composition liquid crystal orientation film of residual are promoted, as a result The anisotropy of liquid crystal orientation film improves, and the interaction of liquid crystal orientation film and liquid crystal improves, thus reaches the effect above.
Embodiment
<The precursor of polyimides and the polyimides>
Aligning agent for liquid crystal used in the present invention contains before the polyimides with the construction unit represented by following formula (1) At least one polymer of the imide amination polymer of body and the polyimide precursor.
【Change 7】
In formula (1), X1For the structure represented by following formula (XA-1), Y1For divalent organic base, R1For hydrogen atom or carbon number 1~ 4 alkyl.
【Change 8】
In formula (XA-1), R3、R4、R5And R6It is separately hydrogen atom, halogen atom, the alkyl of carbon number 1~6, carbon number 2 ~6 alkenyl or alkynyl or phenyl.
Wherein, from the viewpoint of liquid crystal aligning, preferably R3、R4、R5And R6Separately for hydrogen atom, halogen atom, Methyl or ethyl, more preferably hydrogen atom or methyl.X1More preferably selected from represented by following formula (X1-1) and (X1-2) At least one of structure.
【Change 9】
Y1For divalent organic base, its structure is not particularly limited.In order to improve the anisotropy of the liquid crystal orientation film of gained, At least one of following formula (Y1-1) and the structure represented by (Y1-2) is preferably selected from,
【Change 10】
In formula (5), Z1For the divalent organic base of singly-bound, ester bond, amido link, thioester bond or carbon number 2~10.
Z1In, as ester bond, with-C (O) O- or-OC (O)-represent.As amido link, can show with-C (O) NH- ,-C (O) NR- ,-NHC (O)-or the structure of-NRC (O)-expression.Herein, R is alkyl, the alkene of carbon number 1~10 Base, alkynyl, aryl or group that they are combined.
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- CH2Instead CH=CH is tied structure The group of structure, more specifically, vinyl, pi-allyl, 1- acrylic, isopropenyl, 2- cyclobutenyls, 1,3- fourths can be enumerated Dialkylene, 2- pentenyls, 2- hexenyls, cyclopropanyl, cyclopentenyl, cyclohexenyl group etc..
As alkynyl, can enumerate the CH of more than 1 present in abovementioned alkyl2- CH2Structure instead C ≡ C-structure Group, more specifically, acetenyl, 1- propinyls, 2-propynyl etc. can be enumerated.
As aryl, such as phenyl can be enumerated.
As thioester bond, the structure with-C (O) S- or-SC (O)-represent can be shown.
In Z1Under occasion for the organic group of carbon number 2~10, it can be represented with the structure of following formula (6).
【Change 11】
——Z4-R9-Z5-R10-Z6—— (6)
In formula (6), Z4、Z5And Z6It is separately singly-bound ,-O- ,-S- ,-NR11-, ester bond, amido link, thioesters Key, urea bond, carbonic acid ester bond or amino-formate bond.Herein, R11For hydrogen atom, methyl or tert-butoxycarbonyl.
For Z4、Z5And Z6In ester bond, amido link and thioester bond, can show and above-mentioned ester bond, amido link and thioester bond phase Same structure.
As urea bond, the structure represented with-NH-C (O) NH- or-NR-C (O) NR- can be shown.R be carbon number 1~ 10 alkyl, alkenyl, alkynyl, aryl or group that they are combined, these groups can enumerate and abovementioned alkyl, alkene Base, alkynyl, aryl identical example.
As carbonic acid ester bond, the structure represented with-O-C (O)-O- can be shown.
As amino-formate bond, can show with-NH-C (O)-O- ,-O-C (O)-NH- ,-NR-C (O)- The structure that O- or-O-C (O)-NR- is represented.Herein, R be the alkyl of carbon number 1~10, alkenyl, alkynyl, aryl or they The group combined, these groups can enumerate and abovementioned alkyl, alkenyl, alkynyl, aryl identical example.
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 group that they are combined.R9And R10Either party when being singly-bound, R9And R10The opposing party be The structure of alkylidene, alkylene group, alkynylene, arlydene selected from carbon number 2~10 or group that they are combined.
As above-mentioned alkylidene, it can enumerate and the structure that 1 hydrogen atom forms is removed from abovementioned alkyl.More specifically, Methylene, 1,1- ethylidene, 1,2- ethylidene, 1,2- propylidene, 1,3- propylidene, 1,4- butylidenes, 1 can be enumerated, 2- butylidenes, 1,2- pentylidene, 1,2- hexylidenes, 2,3- butylidenes, 2,4- pentylidene, 1,2- cyclopropylidenes, 1,2- Sub- cyclobutyl, 1,3- Asias cyclobutyl, 1,2- cyclopentylenes, 1,2- cyclohexylidenes etc..
As alkylene group, it can enumerate and the structure that 1 hydrogen atom forms is removed from above-mentioned alkenyl.More specifically, It can enumerate 1,1- ethenylidenes, 1,2- ethenylidenes, 1,2- ethenylidenes methylene, 1- methyl isophthalic acids, 2- ethenylidenes, 1,2- ethenylidene -1,1- ethylidene, 1,2- ethenylidene -1,2- ethylidene, 1,2- ethenylidenes -1,2- are sub- Propyl group, 1,2- ethenylidene -1,3- propylidene, 1,2- ethenylidene -1,4- butylidenes, 1,2- ethenylidene -1, 2- butylidenes etc..
As alkynylene, it can enumerate and the structure that 1 hydrogen atom forms is removed from above-mentioned alkynyl.More specifically, can example Lift ethynylene, ethynylene methylene, ethynylene -1,1- ethylidene, ethynylene -1,2- ethylidene, sub- acetylene Base -1,2- propylidene, ethynylene -1,3- propylidene, ethynylene -1,4- butylidenes, ethynylene -1,2- are sub- Butyl etc..
As arlydene, it can enumerate and the structure that 1 hydrogen atom forms is removed from above-mentioned aryl.More specifically, can example Lift 1,2- phenylenes, 1,3- phenylenes, 1,4- phenylenes etc..
Y1In the case of containing linear high structure or rigid structure, in order to obtain that there is the liquid crystal of good liquid crystal aligning Alignment films, as Z1Structure, more preferably singly-bound or following formula (A1-1)~(A1-25) structure.
【Change 12】
【Change 13】
【Change 14】
【Change 15】
It is good from the removability of analyte caused by the contact processing implemented as above-mentioned solvent and liquid crystal aligning is excellent From the viewpoint of, as Y1Structure, particularly preferred above formula (4) or following formula (Y1-1).
【Change 16】
Gather with the polyimide precursor of construction unit represented by above formula (1) and the imidizate of the polyimide precursor In compound, the ratio of the construction unit represented by above formula (1) is preferred relative to 1 mole of entire infrastructure unit in whole polymer For 60~100 moles of %.The ratio of construction unit represented by above formula (1) is higher, and can more obtain has good liquid crystal aligning Liquid crystal orientation film, 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 represented by above formula (1) (7) polyimide precursor of the construction unit represented by and the imide amination polymer of the polyimide precursor.
【Change 17】
In formula (7), R1With the R of above formula (1)1Define identical.
X3For quadrivalent organic radical, its structure is not particularly limited.If lifting concrete example, following formula (X-1)~(X- can be enumerated 42) structure.Consider from the difficulty that obtains of compound, X3Structure be preferably X-17, X-25, X-26, X-27, X- 28th, X-32 or X-39.In addition, from the fast liquid crystal orientation film of the mitigation that can obtain the residual charge put aside by DC voltage Viewpoint considers, it is preferred to use has the tetracarboxylic dianhydride of aromatic ring structure, as X3Structure, more preferably X-26, X-27, X-28, X-32, X-35 or X-37.
【Change 18】
【Change 19】
【Change 20】
【Change 21】
【Change 22】
In above formula (7), Y4For divalent organic base, its structure is not particularly limited.If lift Y4Concrete example, following formula can be enumerated (Y-1)~(Y-74) structure.
【Change 23】
【Change 24】
【Change 25】
【Change 26】
【Change 27】
To make component of polymer excellent to the dissolubility of organic solvent, as the Y in formula (7)4, preferably comprise with Y- 8th, the construction unit of Y-20, Y-21, Y-22, Y-28, Y-29, Y-30, Y-72, Y-73 or Y-74 structure.
Under the high occasion of the ratio of construction unit in component of polymer represented by above formula (7), the liquid crystal of liquid crystal orientation film Orientation can decline, therefore the ratio of the construction unit represented by above formula (7) is preferably 0 relative to 1 mole of entire infrastructure unit ~40 moles of %, more preferably 0~20 mole of %.
<The manufacture method of poly amic acid ester>
In the case that polyimide precursor used in the present invention is poly amic acid ester, poly amic acid ester can be by described below The methods of (1)~(3) synthesized.
(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 preferred that 0 DEG C~50 DEG C are reacted 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 Formamide di neo-pentyl butyl acetal, N,N-dimethylformamide di-t-butyl acetal, the nitrogen of 1- methyl -3- p-methylphenyls three Alkene, 1- ethyl -3- p-methylphenyls triazenes, 1- propyl group -3- p-methylphenyls triazenes, chlorination 4- (4,6- dimethoxies Base -1,3,5- triazine -2- bases) -4- methyl morpholinesSalt etc..The addition of esterifying agent relative to polyamic acid repetition 1 mole of unit preferably 2~6 molar equivalents, more preferably 2~4 molar equivalents.
Solvent used considers from the dissolubility of polymer in above-mentioned reaction, preferably DMF, N- first Base -2-Pyrrolidone, gamma-butyrolacton etc., these 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 susceptible to polymer and being readily available HMW body Polymer concentration 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 synthesizing by tetracarboxylic acid acid diesters diacid chloride and diamines.
Specifically, can be 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 using the amount that easily removes and from the viewpoint of being readily available HMW body, the addition of alkali is relative to tetrabasic carboxylic acid Diester diacid chloride is preferably 2~4 times moles, more preferably 2~3 times moles.
Consider from the dissolubility of monomer and polymer, in above-mentioned reaction organic solvent used be preferably N- methyl- 2-Pyrrolidone, gamma-butyrolacton etc., these organic solvents can be used in mixed way with one kind or two or more.
From the viewpoint of the precipitation for being not susceptible to polymer and being readily available HMW body, organic solvent during synthesis In polymer concentration be preferably 1~30 mass %, more preferably 5~20 mass %.In addition, in order to prevent the acyl of tetracarboxylic acid acid diesters two The hydrolysis of chlorine, organic solvent used is preferably dehydrated as much as possible in the synthesis of poly amic acid ester, is reacted preferably in nitrogen atmosphere Middle progress, to prevent being mixed into for foreign gas.
(3) by tetracarboxylic acid acid diesters and diamines come the situation of synthesizing polyamides acid esters
Poly amic acid ester can be by synthesizing tetracarboxylic acid acid diesters and diamines polycondensation.
Specifically, can by making tetracarboxylic acid acid diesters and diamines in the presence of condensing agent, alkali, 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- bis- can be used Dimethylaminopropyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy -1,3,5- triazines methyl morpholine, O- (BTA -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 Deng.The addition of condensing agent is preferably 2~3 times moles relative to tetracarboxylic acid acid diesters, more preferably 2~2.5 times moles.
The tertiary amines such as pyridine, triethylamine can be used in above-mentioned alkali.From using the amount that easily removes and being readily available HMW body From the viewpoint of, 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, N, N- dimethyl methyls can be enumerated Acid amides etc..
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 0~1.0 times relative to diamine component and rubbed You, more preferably 2.0~3.0 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 Above-mentioned (1) or the synthetic method of above-mentioned (2).
The solution of poly amic acid ester prepared above can be by being sufficiently stirred while being injected into poor solvent to make Polymer separates out.Carry out after separating out and being cleaned with poor solvent for several times, through normal temperature or heat drying, sublimed polyamides can be obtained The powder of amino acid ester.
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 polyamic acid>
In the case that polyimide precursor used in the present invention is polyamic acid, polyamic acid can pass through side as shown below Method synthesizes.
Specifically, can by making tetracarboxylic dianhydride and diamines in presence of organic solvent, in -20 DEG C~150 DEG C, It is preferred that 0 DEG C~50 DEG C are reacted 30 minutes~24 hours, preferably 1~12 hour to synthesize.
Consider from the dissolubility of monomer and polymer, the preferred N of organic solvent used, N- dimethyl methyls in above-mentioned reaction Acid amides, METHYLPYRROLIDONE, gamma-butyrolacton etc., these organic solvents can use one kind or two or more mixing to make With.
From the viewpoint of the precipitation for being not susceptible to polymer and being readily available HMW body, the concentration of polymer is excellent Select 1~30 mass %, more preferably 5~20 mass %.
Polyamic acid prepared above can be by being sufficiently stirred reaction solution while being injected into poor solvent to make Polymer is separated out and reclaimed.In addition, carrying out after separating out and being cleaned with poor solvent for several times, through normal temperature or heat drying, can obtain The powder of sublimed polyamic acid.
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 in the present invention can pass through the poly amic acid ester or polyamide to being used as above-mentioned polyimide precursor Acid carries out imidizate to manufacture.
In the case where manufacturing polyimides by poly amic acid ester, easy is in above-mentioned polyamic acid ester solution or polyamides Amino acid ester toner is dissolved in the chemical imidization that base catalyst is added in polyamic acid solution obtained by organic solvent. Chemical imidization carries out imidization reaction at a lower temperature, and is not susceptible to polymerize during imidizate The reduction of thing molecular weight, thus preferably.
Chemical imidization can be by the way that stirring desire imidizate be poly- in organic solvent, in the presence of base catalyst Amic acid esters are carried out.As organic solvent, solvent used when can be used above-mentioned polymerisation., can as base catalyst Enumerate pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc..Wherein triethylamine is due to the enough alkalescence for carrying out reaction And it is preferred that.
Temperature when carrying out imidization reaction is -20 DEG C~140 DEG C, preferably 0 DEG C~100 DEG C, and the reaction time can be 1~100 hour.
The amount of base catalyst is 0.5~30 times mole, 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 in the reaction by diamine component and tetracarboxylic dianhydride The chemical imidization of catalyst is added in the solution of obtained above-mentioned polyamic acid.Chemical imidization is in relatively low temperature Lower carry out imidization reaction, and the reduction of polymer molecular weight is not susceptible to during imidizate, thus 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 pyridine is because with the appropriate alkaline for carrying out reaction And it is preferred that.In addition, as acid anhydrides, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc. can be enumerated, wherein, during using acetic anhydride It is easy to carry out the purifying after reaction terminates, thus preferably.
Temperature when carrying out imidization reaction can be -20 DEG C~140 DEG C, preferably 0 DEG C~100 DEG C, and the reaction time can Think 1~100 hour.
The amount of base catalyst is 0.5~30 times mole of polyamide acidic group, preferably 2~20 times moles, and the amount of acid anhydrides is 1~50 times mole of polyamide acidic group, preferably 3~30 times moles.
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 It is preferred that by following methods, after obtained imide amination polymer is reclaimed and is redissolved with organic solvent, the present invention is used as Aligning agent for liquid crystal.
The solution of polyimides prepared above can be by being sufficiently stirred while being injected into poor solvent to make to gather Compound separates out.Carry out after separating out and being cleaned with poor solvent for several times, through normal temperature or heat drying, sublimed polymer can be obtained Powder.
Foregoing poor solvent is not particularly limited, and can enumerate methanol, 2- propyl alcohol, acetone, hexane, butyl cellosolve, heptan Alkane, MEK, methylisobutylketone, ethanol, toluene, benzene etc., preferably methanol, ethanol, 2- propyl alcohol, acetone etc..
<Aligning agent for liquid crystal>
Aligning agent for liquid crystal used in the present invention has the form that component of polymer is dissolved in the solution formed in organic solvent.
The molecular weight of polymer enters one with Weight-average molecular gauge preferably 2000~500000, more preferably 5000~300000 Step preferably 10000~100000.In addition, number-average molecular weight preferably 1000~250000, more preferably 2500~150000, further It is preferred that 5000~50000.
The polymer concentration of aligning agent for liquid crystal used in the present invention can according to the setting of the thickness of the film of desired formation come Appropriate change, but from being formed from the viewpoint of uniform and flawless film preferably more than 1 mass %, the preservation from solution is steady From the viewpoint of qualitative preferably below 10 mass %.Particularly preferred polymer concentration is 2~8 mass %.
As long as the organic solvent energy uniform dissolution component of polymer contained in the aligning agent for liquid crystal used in the present invention has Solvent, it is not particularly limited.If lifting its concrete example, DMF, N, N- diethyl formyls can be enumerated Amine, 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- diformazans Base-imidazolone, 3- methoxyl groups-N, N- dimethylpropionamide etc..These solvents can use one kind or two or more mixing Use.Even in addition, can not individually uniform dissolution component of polymer solvent, as long as the scope not separated out in polymer It is interior, it can also be mixed with above-mentioned organic solvent.
Aligning agent for liquid crystal used in the present invention can also wrap in addition to comprising the organic solvent for dissolving component of polymer Solvent containing painting film uniformity when aligning agent for liquid crystal being coated on to substrate for improving.The solvent it is usually used with it is above-mentioned organic Solvent compares the solvent of low surface tension.If lifting its concrete example, can enumerate ethyl cellosolve, butyl cellosolve, ethyl card must Alcohol, butyl carbitol, ethylcarbitol acetate, ethylene glycol, 1- methoxy-2-propanols, 1- ethyoxyl -2- propyl alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy group -2- propyl alcohol, single propylene glycol acetate, propylene glycol diacetate, propane diols - 1- monomethyl ether -2- acetic acid esters, propane diols -1- list ether -2- acetic acid esters, butyl cellosolve acetate, DPG, 2- (2- ethoxy-cs epoxide) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate Deng.These solvents and can use two or more.
In the aligning agent for liquid crystal of the present invention, in addition to mentioned component, as long as in the range of effect of the present invention is not damaged, also Electricity 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 be added Medium or conductive materials, the silane coupler for the purpose of the adaptation for improving liquid crystal orientation film and substrate, to improve liquid is made Cross-linked compound for the purpose of the hardness or consistency of film during brilliant alignment films and to make polyamic acid when burning till film Imidizate efficiently carry out for the purpose of imidizate accelerator etc..
<The manufacture of liquid crystal orientation film>
The manufacture method of the liquid crystal orientation film of the present invention includes following process：Aligning agent for liquid crystal is coated on substrate, passed through Burn till and obtain film, the process of the radioactive ray through polarization is irradiated to the film；The film of radioactive ray will have been irradiated with having 110~180 DEG C the organic solvent of boiling point carry out contact processing, then with water or the water-miscible organic solvent with 50~105 DEG C of boiling point enters The process of row contact processing；Film after contact is handled is in more than the 150 DEG C processes heated.Each operation is said below It is bright.
(1) process aligning agent for liquid crystal is coated on substrate, burnt till
By the way that aligning agent for liquid crystal prepared above is coated on substrate, through drying, burn till, can be made polyimide film, Or polyimide precursor is through film obtained by imidizate.
As the substrate of the coating of liquid crystalline alignment agent used in the present invention, as long as transparent high substrate is not limited especially then It is fixed, plastic bases such as glass substrate, silicon nitride board, acrylic acid substrate or polycarbonate substrate etc. can be used, from making technique From the viewpoint of simplification, the substrate formed with liquid crystal drive ITO (indium tin oxide) electrode etc. is preferably used.In addition, reflection In type liquid crystal display cells, the opaque materials such as silicon wafer can be used, but are only limitted to the substrate of side, electrode now The material of the reflected lights such as aluminium can be used.
As the coating method of the aligning agent for liquid crystal used in the present invention, spin-coating method, print process, ink-jet method etc. can be enumerated.
Arbitrary temp and time may be selected in drying, firing process after coating of liquid crystalline alignment agent.Generally, in order to fully remove Contained organic solvent, 50 DEG C~120 DEG C, preferably make at 60~100 DEG C its dry 1~10 minute, then 150 DEG C~ Burnt till at 300 DEG C, preferably 200~250 DEG C 5~120 minutes.The thickness of film after burning till is not particularly limited, but if mistake Thin, then the reliability of liquid crystal display cells can reduce sometimes, therefore preferably 5~300nm, more preferably 10~200nm.
(2) process of the radioactive ray through polarization is irradiated
As irradiating the radioactive ray (hereinafter referred to as light orientation processing) through polarization to the film obtained by the process as above-mentioned (1), The anisotropy in vertical direction relative to polarization direction can be assigned.
As the concrete example of light orientation processing, it can enumerate and the radiation through polarization is irradiated in a certain direction to foregoing film coated surface Line, the method for assigning liquid crystal aligning ability.As the wavelength of radioactive ray, can use ultraviolet with 100~800nm wavelength or Visible ray.Wherein, the ultraviolet preferably with 100~400nm wavelength, particularly preferably with the ultraviolet of 200~400nm wavelength Line.
The exposure of foregoing radioactive ray is preferably in 1~10000mJ/cm2In the range of, particularly preferably in 100~5000mJ/ cm2In the range of.Temperature to radioactive ray of the film irradiation through polarization is preferably 10~100 DEG C, more preferably 20~50 DEG C.
(3) process for contacting processing is carried out using solvent
The film that the radioactive ray through polarization have been irradiated in the process of above-mentioned (2) carries out contact processing using specific 2 kinds of solvents. In contact processing, using the organic solvent with 110~180 DEG C, preferably 115~160 DEG C of boiling point, and water or with 50~ 105 DEG C, at least two kinds of solvents of the water-miscible organic solvent of preferably 50~80 DEG C of boiling point.
It is so-called to use 2 kinds of solvents, refer at least use this 2 kinds of solvents, it is other using also containing in addition to this 2 kinds of solvents In the situation of the solvent of solvent is also included within.Further, in addition to the processing of the contact except with 2 kinds of solvents, can also be adopted Handled with the contact of other solvents beyond described 2 kinds.
As it is above-mentioned have 110~180 DEG C boiling point organic solvent, be preferably selected from following formula (A-1), formula (A-2), At least one organic solvent of formula (A-3), formula (A-4) and formula (A-5).
【Change 28】
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.
In the organic solvent of above-mentioned formula (A-1)~formula (A-5), 1- methoxy-2-propanols, 1- methoxies are preferably selected from Base -2- propanol acetates, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3- methoxy methyl propionates, 3- Ethoxyl ethyl propionate, propyl acetate, at least one of butyl acetate and cyclohexyl acetate.Particularly preferably it is selected from 1- methoxies At least one of base -2- propyl alcohol and ethyl lactate.
In addition, as above-mentioned water or the water-miscible organic solvent with 50~105 DEG C of boiling point preference, can enumerate Water, methanol, ethanol, 2- propyl alcohol, acetone.Wherein, more preferably water, 2- propyl alcohol.
In the present invention, the film for having irradiated the radioactive ray through polarization is impregnated with preferably being used using the contact processing of 2 kinds of solvents Processing, spraying (spray) processing etc. make the processing that film fully contacts with liquid to carry out.Wherein preferably by film in a solvent with excellent Select 10 seconds~1 hour, more preferably 1~30 minute method for carrying out impregnation.Contact handles the temperature by controlling film or solvent Degree, can carry out also at a temperature of normal temperature above and below implementing at normal temperatures, but preferably 10~80 DEG C, more preferably 20~ Implement at 50 DEG C.In addition, as needed, the means of the contact-enhancing of stirring or ultrasonic wave etc. can be implemented.
It is above-mentioned with the organic solvent with 110~180 DEG C of boiling point, again with water or the boiling point with 50~105 DEG C water Solubleness organic solvent successively contact processing in the case of, both contact processing can be carried out continuously, also can every when carry out.The latter's Occasion can expend the excessive time and unsuitable, therefore preferably be carried out continuously.
On the other hand, by the organic solvent comprising the boiling point with 110~180 DEG C and water or with 50~105 DEG C of boiling In the case that the mixed solvent of the water-miscible organic solvent of point carries out contact processing, the mixed solvent preferably comprises quality ratio For 95/5~5/95, more preferably 95/5~50/50 organic solvent with 110~180 DEG C of boiling point and water or with 50 The water-miscible organic solvent of~105 DEG C of boiling point.
(4) process heated more than 150 DEG C
The film that contact processing has been carried out using 2 kinds of solvents is heated at it after more than 150 DEG C.At the heating Reason can also be carried out in the film that contact processing has been carried out using solvent after drying.Preferably 80~150 DEG C of the drying of film.When drying Between preferably 10 seconds~30 minutes.
As the temperature of heating, preferably 150~300 DEG C.Temperature is higher, can more promote the reorientation of strand, but Temperature is too high, there is the anxiety for the decomposition for producing strand therewith.Therefore, as heating-up temperature, more preferably 180~250 DEG C, especially It is preferred that 200~230 DEG C.
Heat time such as too short, it is likely that can not obtain the effect of the present invention, it is long then may strand decompose, therefore It is preferred that 10 seconds~30 minutes, more preferably 1~10 minute.
<Liquid crystal display cells>
The liquid crystal display cells of the present invention are that the aligning agent for liquid crystal as made from the manufacture method of the present invention obtains band liquid After the substrate of brilliant alignment films, structure cell, the manufactured liquid crystal display cells using the structure cell are manufactured by known method.
As one of the preparation 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 transparent glass substrate of electrode, (Common) electrode altogether is set on one piece of substrate, in another piece of substrate Upper setting section (Segment) electrode.These electrodes can be such as ITO electrode, be formed to the figure that image needed for carrying out is shown Case.Then, dielectric film is set in a manner of coated common electrode and segment electrode on each substrate.Dielectric film can be for example by molten Glue-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 one piece of substrate in a manner of mutual alignment films are opposite overlapping another piece of substrate, by periphery seal Material is bonded.For control base board gap, sept is generally mixed into encapsulant.In addition, do not setting the face of encapsulant Inside points are it is also preferred that spread the sept of substrate gap control.A part for encapsulant can be provided with can be from outside filling liquid Brilliant opening portion.
Then, by setting opening portion on the sealing material, into the space surrounded by 2 pieces of substrates and encapsulant Inject liquid crystal material.Afterwards, with the first binding agent seal opening portion.Injection can use vacuum impregnation, can also use in atmospheric pressure The middle method using capillarity.Hereafter, the setting of polarizer is carried out.Specifically, it is in 2 pieces of substrates and liquid crystal layer phase A pair of polarizers are pasted on the face of anti-side.By above process, the liquid crystal display cells of the present invention are can obtain.
The liquid crystal display cells are due to using by liquid crystal orientation film produced by the present invention as liquid crystal orientation film, therefore ghost Excellent, big picture and the liquid crystal display of high-resolution etc. can be applied to.
Embodiment
Hereinafter, enumerate embodiment the present invention will be described in more detail, 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
DA-2：Following formula (DA-2) (Boc basis representations tert-butoxycarbonyl)
Additive A：N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine
【Change 29】
Viscosity given below, molecular weight, acid imide rate, liquid crystal cell make with because it is long-term exchange drive caused by The evaluation method of ghost.
[viscosity]
In synthesis example, the viscosity of poly amic acid ester and polyamic acid solution utilizes E type viscosimeters TVE-22H (eastern machine productions (East Machine industries society of industry Co., Ltd.) system), in sample size 1.1mL, coniform rotor (コ ー ン ロ ー タ) TE-1 (1 ° 34 ', R24), determined under conditions of 25 DEG C of temperature.
[molecular weight]
The molecular weight of poly amic acid ester is measured using GPC (normal temperature gel permeation chromatography) device, with polyethylene glycol and PEO scaled value calculates number-average molecular weight (Mn) and weight average molecular weight (Mw).
GPC devices：Showa Denko K. K (Shodex societies) makes (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 acid anhydrous crystal (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 (peak molecular weight (Mp) about 12000,4000,1000).In order to avoid peak value repeats, 2 samples are determined respectively, It is mixed with 900000,100000,12000,1000 this 4 kinds sample and is mixed with 150000,30000,4000 this 3 kinds Sample.
[measure of acid imide rate]
The acid imide rate of polyimides in synthesis example determines as follows.Polyimide powder 20mg is put into NMR samples In pipe (specification of NMR coupons, wasteland's science Co., Ltd. of φ 5 (wasteland's science society) system), deuterated dimethyl sulfoxide is added (DMSO-d6,0.05%TMS (tetramethylsilane) melange) (0.53ml), is completely dissolved it with ultrasonic wave.Determined with NMR Instrument (JNW-ECA500) (De Temu companies of JEOL (Japanese Electricity デ ー タ system society) system) determines the 500MHz's of the solution Proton NMR.Acid imide rate is tried to achieve as follows：The proton for coming from unconverted structure before and after imidizate is set to benchmark matter Son, the proton peak integration of the NH bases from amic acid occurred using the peak integrated value of the proton and near 9.5~10.0ppm Value is tried to achieve by following formula.
Acid imide rate (%)=(1- α x/y) × 100
In above formula, x is the proton peak integrated value of the NH bases from amic acid, and the peak integrated value of proton on the basis of y, α is poly- Reference proton is relative to the sub number ratio of the NH matrix of an amic acid during amic acid (acid imide rate is 0%).
[making of liquid crystal cell]
Making possesses fringe field conversion (Fringe Field Switching：Hereinafter referred to as FFS) mode liquid crystal shows The liquid crystal cell of the composition of element.
First prepare electroded substrate.The glass substrate that substrate uses 30mm × 50mm size, thickness is 0.7mm. On substrate, formation forms the counter electrode as first layer, possesses the ITO electrode of whole face (ベ タ) pattern.In pair of first layer To on electrode, SiN (silicon nitride) film formed by CVD (chemical vapour deposition technique) method film forming as the second layer is formed.The The thickness of two layers of SiN film is 500nm, plays the function as interlayer dielectric.On the SiN film of the second layer, conduct is formed Being configured with that ito film is patterned of third layer and the first pixel and the second pixel this 2 pictures of the comb teeth-shaped pixel electrode that are formed Element.The size of each pixel is long 10mm, width about 5mm.Now, the counter electrode of first layer and the pixel electrode of third layer are because of second Layer SiN film effect and be electrically insulated.
What the pixel electrode of third layer had the electrode member arrangement of " く " word shape of multiple middle body bendings and formed The shape of comb teeth-shaped.The short side direction width of each electrode member be 3 μm, between electrode member at intervals of 6 μm.Form each pixel The electrode member of " く " word shape that pixel electrode is bent by multiple middle bodies is arranged and formed, therefore the shape of each pixel is not Oblong-shaped, but with the same manner as electrode member middle body bend, the shape of similar thick " く " word.Then, each picture Element is split up and down using its central bent portion as boundary, has the secondth area of the first area and downside on the upside of bent portion Domain.
If the first area of each pixel and second area are compared, the electrode member of their pixel electrode is formed Formation direction be different.That is, in the case of using the frictional direction of liquid crystal orientation film described later as benchmark, the of pixel The electrode member of pixel electrode is formed in a manner of in+10 ° of angle (clockwise direction) in one region, the second area of pixel The electrode member of middle pixel electrode is formed in a manner of in -10 ° of angle (clockwise direction).That is, the of each pixel In one region and second area, to be applied by the voltage between pixel electrode and counter electrode, the liquid crystal that evokes is in real estate The direction of spinning movement (in-plane changes) formed for the modes of opposite directions.
Then, the aligning agent for liquid crystal of gained is filtered with 1.0 μm of filter, standard is then applied in a manner of spin coating On the glass substrate with high 4 μm of column spacer of the above-mentioned electroded substrate and inner face got ready formed with ito film. After drying 5 minutes on 80 DEG C of hot plate, in 230 DEG C of heated air circulation type stove burn till within 20 minutes, form thickness 100nm Film.It is 10 to irradiate extinction ratio to the coated surface across polarizer：The wavelength 254nm of more than 1 linear polarization ultraviolet. The substrate in the organic solvent of the boiling point with 110~180 DEG C or is included into the organic solvent of the boiling point with 110~180 DEG C With water or the in the mixed solvent of the organic solvent with 50~105 DEG C of boiling point is impregnated 3 minutes, and 1 point is then impregnated in pure water Clock, dried 5 minutes on 150~300 DEG C of hot plate, obtain the substrate with liquid crystal orientation film.Using above-mentioned 2 pieces of substrates as one Group, the printing and sealing agent on substrate, another piece of substrate is bonded in a manner of the relative orientation direction for making liquid crystal orientation film is 0 °, so After make sealant cures and negative crystal born of the same parents be made.In the negative crystal born of the same parents liquid crystal MLC-2041 (Merck public affairs are injected by depressurizing injection method Take charge of (メ ルク societies) system), inlet is sealed, obtains FFS driving liquid crystal cells.Then, the liquid crystal cell of gained is added in 110 DEG C Heat 1 hour, each evaluation is used it for after placing an evening.
[evaluation of ghost because of caused by long-term exchange driving]
Prepare the liquid crystal cell with the above-mentioned liquid crystal cell identical construction for ghost evaluation.
Using the liquid crystal cell, under 60 DEG C of isoperibol, apply ± the 5V of 120 hours alternating current with frequency 60Hz Pressure.Afterwards, make the state in short circuit between the pixel electrode of liquid crystal cell and counter electrode, retain that state for room temperature placement One day.
After placement, liquid crystal cell is arranged between the 2 pieces of polarizers configured in a manner of polarizing axis is orthogonal, do not applied Backlight is lighted in the state of voltage, adjust the arrangement angles of liquid crystal cell so that the brightness of transmitted light reaches minimum.Then, From the second area of the first pixel it is that most dark angle rotates to rotation when first area is most dark angle by liquid crystal cell Angle calculates as angle △.It is also identical to the second pixel, compare second area and first area, calculate same angle △. Then, the average value of the first pixel and the angle △ values of the second pixel is calculated as the angle △ of liquid crystal cell.
(synthesis example 1)
In the 3000mL four-hole boiling flasks with agitating device and nitrogen ingress pipe, double (the 4- aminobenzene oxygen of 1,2- are taken into Base) ethane 124.60g (510mmol) and DA-2 0.95g (90.0mmol), it is additionally added NMP 2236g, one side supplying nitrogen one Side stirring makes its dissolving.1,3- dimethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acid two is added while the diamine solution is stirred Acid anhydride 130.06g (580.2mmol), add NMP so that solid component concentration reaches 10 mass %, be stirred at room temperature 24 hours and Obtain polyamic acid (PAA-2) solution.Viscosity at 25 DEG C of the temperature of the polyamic acid solution is 511mPas.In addition, The molecular weight of the polyamic acid is Mn=19100, Mw=46880.
(synthesis example 2)
In the 500mL four-hole boiling flasks with agitating device and nitrogen ingress pipe, obtained polyamic acid solution is taken into (PAA-2) 200g, NMP 85.68g are added, stirred 30 minutes.In the polyamic acid solution of gained, acetic anhydride is added 22.22g and pyridine 6.86g, heated 3 hours in 50 DEG C, carry out chemical imidization.The reaction solution of gained is stirred while Put into 1100g methanol, the sediment separated out is taken out in filtering, is then cleaned 3 times with 1100g methanol, with 200g methanol Cleaning 2 times.The toner of gained is dried 12 hours in 60 DEG C, and polyimide resin powder end is thereby made.
The acid imide rate at polyimide resin powder end is 68%, molecular weight Mn=9155, Mw=21430.
Then, in the 200mL coupons of stirrer are enclosed, the polyimide resin powder end 12.53g of gained is taken into, NMP 91.89g are added, being stirred at room temperature 24 hours makes its dissolving, and polyimide solution (PI-1) is made.
(synthesis example 3)
In the 200mL coupons of stirrer are enclosed, obtained polyimide solution (PI-1) in synthesis example 2 is taken into 59.59g, add nmp solution 7.17g, NMP of 0.3 mass % 3- glycidoxypropyl diethoxy silanes 11.26g, BCS 26.0g and additive A 2.08g, with magnetic stirrer 30 minutes, aligning agent for liquid crystal (AL-1) is made.
<Embodiment 1>
Obtained aligning agent for liquid crystal (AL-1) in synthesis example 3 is filtered with 1.0 μm of filters, then in a manner of spin coating It is applied to the column spacer with high 4 μm of ready above-mentioned electroded substrate and inner face formed with ito film On glass substrate.After drying 5 minutes on 80 DEG C of hot plate, in 230 DEG C of heated air circulation type stove burn till within 20 minutes, shape Into thickness 100nm film.Under room temperature (25 DEG C), across polarizer to the coated surface with 0.2J/cm2It is 26 to irradiate extinction ratio：1 Linear polarization wavelength 254nm ultraviolet.By the substrate in ethyl lactate in room temperature immersion 3 minutes, then in pure water Middle dipping 1 minute, heats 5 minutes on 200 DEG C of hot plate, obtains the substrate with liquid crystal orientation film.Using above-mentioned 2 pieces of substrates as One group, the printing and sealing agent on substrate, another piece of substrate is bonded in a manner of the relative orientation direction for making liquid crystal orientation film is 0 °, Then make sealant cures and negative crystal born of the same parents are made.In the negative crystal born of the same parents liquid crystal MLC-2041 (Merck is injected by depressurizing injection method Company system), inlet is sealed, obtains FFS driving liquid crystal cells.Then, the liquid crystal cell of gained is heated 1 hour in 110 DEG C, After placing an evening, implement the evaluation of the ghost because of caused by long-term exchange driving.The angle of the liquid crystal cell after long-term exchange driving It is 0.06 degree to spend △.
<Embodiment 2>
Except after polarized UV rays have been irradiated to the coated surface of substrate, the substrate is soaked in ethyl lactate in room temperature Stain 3 minutes, then impregnated 1 minute in pure water, beyond being heated 1 minute on 230 DEG C of hot plate, using identical with embodiment 1 Method make FFS driving liquid crystal cell.Implement the ghost because of caused by long-term exchange driving to FFS driving liquid crystal cells Evaluation.The angle △ of the liquid crystal cell is 0.04 degree after long-term exchange driving.
<Embodiment 3>
Except after polarized UV rays have been irradiated to the coated surface of substrate, the substrate is soaked in ethyl lactate in room temperature Stain 3 minutes, then impregnated 1 minute in pure water, beyond being heated 3 minutes on 230 DEG C of hot plate, using identical with embodiment 1 Method make FFS driving liquid crystal cell.Implement the ghost because of caused by long-term exchange driving to FFS driving liquid crystal cells Evaluation.The angle △ of the liquid crystal cell is 0.03 degree after long-term exchange driving.
<Embodiment 4>
Except after polarized UV rays have been irradiated to the coated surface of substrate, the substrate is soaked in ethyl lactate in room temperature Stain 3 minutes, then impregnated 1 minute in pure water, beyond being heated 5 minutes on 230 DEG C of hot plate, using identical with embodiment 1 Method make FFS driving liquid crystal cell.Implement the ghost because of caused by long-term exchange driving to FFS driving liquid crystal cells Evaluation.The angle △ of the liquid crystal cell is 0.03 degree after long-term exchange driving.
<Embodiment 5>
Except after polarized UV rays have been irradiated to the coated surface of substrate, the substrate is soaked in ethyl lactate in room temperature Stain 3 minutes, then impregnated 1 minute in pure water, beyond being heated 10 minutes on 230 DEG C of hot plate, using identical with embodiment 1 Method make FFS driving liquid crystal cell.Implement the ghost because of caused by long-term exchange driving to FFS driving liquid crystal cells Evaluation.The angle △ of the liquid crystal cell is 0.04 degree after long-term exchange driving.
<Embodiment 6>
Except after polarized UV rays have been irradiated to the coated surface of substrate, by the substrate in the mixed of ethyl lactate and IPA Bonding solvent (mass ratio：Ethyl lactate/IPA=50/50) in room temperature immersion 3 minutes, then impregnated 1 minute in pure water, Beyond being heated 5 minutes on 230 DEG C of hot plate, FFS driving liquid crystal cells are made using with the identical method of embodiment 1.To the FFS Liquid crystal cell is driven to implement the evaluation of the ghost because of caused by long-term exchange driving.The angle of the liquid crystal cell after long-term exchange driving It is 0.03 degree to spend △.
<Embodiment 7>
Except after polarized UV rays have been irradiated to the coated surface of substrate, by the substrate in the mixed of ethyl lactate and pure water Bonding solvent (mass ratio：Ethyl lactate/pure water=85/15) in 20 DEG C impregnate 3 minutes, then impregnated 1 minute in pure water, Beyond being heated 5 minutes on 230 DEG C of hot plate, FFS driving liquid crystal cells are made using with the identical method of embodiment 1.To the FFS Liquid crystal cell is driven to implement the evaluation of the ghost because of caused by long-term exchange driving.The angle of the liquid crystal cell after long-term exchange driving It is 0.09 degree to spend △.
<Comparative example 1>
Obtained aligning agent for liquid crystal (AL-1) in synthesis example 3 is filtered with 1.0 μm of filters, then in a manner of spin coating It is applied to the column spacer with high 4 μm of ready above-mentioned electroded substrate and inner face formed with ito film On glass substrate.After drying 5 minutes on 80 DEG C of hot plate, in 230 DEG C of heated air circulation type stove burn till within 20 minutes, shape Into thickness 100nm film.At room temperature, across polarizer to the coated surface with 0.2J/cm2It is 26 to irradiate extinction ratio：1 straight line The wavelength 254nm of polarization ultraviolet.The substrate is heated 20 minutes on 230 DEG C of hot plate, obtained with liquid crystal orientation film Substrate.Using above-mentioned 2 pieces of substrates as one group, the printing and sealing agent on substrate, so that the relative orientation direction of liquid crystal orientation film is 0 ° of mode is bonded another piece of substrate, then makes sealant cures and negative crystal born of the same parents are made.Injected in negative crystal born of the same parents by depressurizing Method injection liquid crystal MLC-2041 (Merck ＆ Co., Inc.'s system), inlet is sealed, obtain FFS driving liquid crystal cells.Then, by gained Liquid crystal cell heats 1 hour in 110 DEG C, after placing an evening, implements the evaluation of the ghost because of caused by long-term exchange driving.For a long time The angle △ of the liquid crystal cell is 3.0 degree after exchange driving.
<Comparative example 2>
Except after polarized UV rays have been irradiated to the coated surface of substrate, the substrate is soaked in ethyl lactate in room temperature Stain 3 minutes, then impregnated 1 minute in pure water, beyond being heated 5 minutes on 80 DEG C of hot plate, using with the identical of embodiment 1 Method makes FFS driving liquid crystal cells.Implement the ghost because of caused by long-term exchange driving to FFS driving liquid crystal cells to comment Valency.The angle △ of the liquid crystal cell is 0.10 degree after long-term exchange driving.
<Comparative example 3>
Except after polarized UV rays have been irradiated to the coated surface of substrate, by the substrate in the mixed of ethyl lactate and IPA Bonding solvent (mass ratio：Ethyl lactate/IPA=50/50) in room temperature immersion 3 minutes, then impregnated 1 minute in pure water, Beyond being heated 5 minutes on 80 DEG C of hot plate, FFS driving liquid crystal cells are made using with the identical method of embodiment 1.To the FFS Liquid crystal cell is driven to implement the evaluation of the ghost because of caused by long-term exchange driving.The angle of the liquid crystal cell after long-term exchange driving It is 0.12 degree to spend △.
<Comparative example 4>
Except after polarized UV rays have been irradiated to the coated surface of substrate, by the substrate in the mixed of ethyl lactate and pure water Bonding solvent (mass ratio：Ethyl lactate/pure water=85/15) in room temperature immersion 3 minutes, then impregnated 1 minute in pure water, Beyond being heated 5 minutes on 80 DEG C of hot plate, FFS driving liquid crystal cells are made using with the identical method of embodiment 1.To the FFS Liquid crystal cell is driven to implement the evaluation of the ghost because of caused by long-term exchange driving.The angle of the liquid crystal cell after long-term exchange driving It is 0.48 degree to spend △.
[utilization feasibility in industry]
IPS type of drive or FFS driving sides can be mitigated as the liquid crystal orientation film obtained by the aligning agent for liquid crystal of the present invention The caused ghost because caused by driving exchange in the liquid crystal display cells of formula, obtain the IPS type of drive of ghost excellent Or the liquid crystal display cells of FFS type of drive.Therefore, as IPS type of drive or FFS type of drive liquid crystal display cells or The liquid crystal orientation film of LCD TV is particularly useful.
In addition, it is hereby incorporated the explanation for the Japanese patent application 2012-263386 filed an application on November 30th, 2012 Announcement of the full content of book, claims and summary as description of the invention.

Claims (12)

1. the manufacture method of liquid crystal orientation film, it is characterised in that will contain and be selected from the construction unit represented by following formula (1) The aligning agent for liquid crystal coating of at least one polymer of the imide amination polymer of polyimide precursor and the polyimide precursor In on substrate, film is obtained through burning till, to the film irradiate the radioactive ray through polarization, then with the boiling point with 110~180 DEG C Organic solvent carries out contact processing, then with water or the water-miscible organic solvent with 50~105 DEG C of boiling point carries out contact processing, Then heated in more than 150 DEG C,
【Change 1】
X1For the structure represented by following formula (XA-1),
Y1For divalent organic base, R1For hydrogen atom or the alkyl of carbon number 1~4,
【Change 2】
R3、R4、R5And R6It is separately hydrogen atom, halogen atom, the alkyl of carbon number 1~6, the alkenyl or alkynes of carbon number 2~6 Base or phenyl.
2. the manufacture method of liquid crystal orientation film, it is characterised in that will contain and be selected from the construction unit represented by following formula (1) The aligning agent for liquid crystal coating of at least one polymer of the imide amination polymer of polyimide precursor and the polyimide precursor In on substrate, film is obtained through burning till, to the film irradiate the radioactive ray through polarization, then with the boiling point with 110~180 DEG C Organic solvent and the mixed solvent of water or the organic solvent with 110~180 DEG C of boiling point and with 50~105 DEG C of boiling point The mixed solvent of water-miscible organic solvent carry out contact processing, then with water or the water solubility with 50~105 DEG C of boiling point has Solvent carries out contact processing, is then heated in more than 150 DEG C,
【Change 1】
X1For the structure represented by following formula (XA-1),
Y1For divalent organic base, R1For hydrogen atom or the alkyl of carbon number 1~4,
【Change 2】
R3、R4、R5And R6It is separately hydrogen atom, halogen atom, the alkyl of carbon number 1~6, the alkenyl or alkynes of carbon number 2~6 Base or phenyl.
3. the manufacture method of liquid crystal orientation film as claimed in claim 1 or 2, it is characterised in that described that there are 110~180 DEG C Boiling point organic solvent for selected from following formula (A-1), formula (A-2), formula (A-3), formula (A-4) and formula (A-5) at least one Kind,
【Change 3】
In formula (A-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 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.
4. the manufacture method of liquid crystal orientation film as claimed in claim 1 or 2, it is characterised in that described that there are 110~180 DEG C Boiling point organic solvent be selected from 1- methoxyl group 2- propyl alcohol, ethyl lactate, diacetone alcohol, 3- methoxy methyl propionates and At least one of 3- ethoxyl ethyl propionates.
5. the manufacture method of liquid crystal orientation film as claimed in claim 1 or 2, it is characterised in that described that there are 50~105 DEG C The water-miscible organic solvent of boiling point is at least one selected from methanol, ethanol, 2- propyl alcohol and acetone.
6. the manufacture method of liquid crystal orientation film as claimed in claim 2, it is characterised in that the mixed solvent contains mass ratio The organic solvent and water with 110~180 DEG C of boiling point that rate is 95/5~5/95, or containing quality ratio be 95/5~5/95 The organic solvent with 110~180 DEG C of boiling point and the boiling point with 50~105 DEG C water-miscible organic solvent.
7. the manufacture method of liquid crystal orientation film as claimed in claim 1 or 2, it is characterised in that selected from the formula (1) institute At least one polymer of the polyimide precursor of the construction unit of expression and the imide amination polymer of the polyimide precursor In, relative to the entire infrastructure unit at least one polymer, represented by the formula (1) containing 60 moles of more than % Construction unit.
8. the manufacture method of liquid crystal orientation film as claimed in claim 1 or 2, it is characterised in that X in above formula (1)1For under At least one of formula (X1-1) and the structure represented by (X1-2),
【Change 4】
9. the manufacture method of liquid crystal orientation film as claimed in claim 1 or 2, it is characterised in that Y in above formula (1)1For under At least one of structure represented by formula (4) and (5),
【Change 5】
In formula (5), Z1For the divalent organic base of singly-bound, ester bond, amido link, thioester bond or carbon number 2~10.
10. the manufacture method of liquid crystal orientation film as claimed in claim 1 or 2, it is characterised in that Y in above formula (1)1For selected from upper At least one structure of structure represented by formula (4) and following formula (Y1-1),
【Change 6】
11. liquid crystal orientation film, it is made by the manufacture method of liquid crystal orientation film according to any one of claims 1 to 10.
12. liquid crystal display cells, possesses the liquid crystal orientation film described in claim 11.
CN201380062441.8A 2012-11-30 2013-11-29 Manufacture method, liquid crystal orientation film and the liquid crystal display cells of liquid crystal orientation film Active CN104838311B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2012-263386 2012-11-30
JP2012263386 2012-11-30
PCT/JP2013/082212 WO2014084362A1 (en) 2012-11-30 2013-11-29 Method for producing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element

Publications (2)

Publication Number Publication Date
CN104838311A CN104838311A (en) 2015-08-12
CN104838311B true CN104838311B (en) 2017-12-19

Family

ID=50827990

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201380062441.8A Active CN104838311B (en) 2012-11-30 2013-11-29 Manufacture method, liquid crystal orientation film and the liquid crystal display cells of liquid crystal orientation film

Country Status (5)

Country Link
JP (1) JP6217648B2 (en)
KR (1) KR102101530B1 (en)
CN (1) CN104838311B (en)
TW (1) TWI597305B (en)
WO (1) WO2014084362A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017119461A1 (en) * 2016-01-07 2017-07-13 日産化学工業株式会社 Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element using same
JP6841069B2 (en) 2016-04-28 2021-03-10 Jsr株式会社 Liquid crystal alignment agent, liquid crystal alignment film and its manufacturing method, and liquid crystal element
TWI820010B (en) * 2016-12-21 2023-11-01 日商日產化學工業股份有限公司 Manufacturing method of liquid crystal alignment film, liquid crystal alignment film and liquid crystal display element
KR102176161B1 (en) 2019-07-23 2020-11-09 주식회사 옵티팜 PERV EnvC- GGTA1/CMAH/iGb3s/β4GalNT2 quadra gene knock-out and human CD46 and TBM expression transgenic pigs for xenotransplantation, and producing method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11125812A (en) * 1997-10-22 1999-05-11 Sumitomo Bakelite Co Ltd Insulating agent for active matrix liquid crystal display element
JP2000080164A (en) * 1998-09-03 2000-03-21 Nissan Chem Ind Ltd Polyimide precursor, polyimide, and aligning agent for liquid crystal cell
CN101495915A (en) * 2006-07-28 2009-07-29 日产化学工业株式会社 Liquid crystal aligning agent and liquid crystal displays made by using the same
CN101910931A (en) * 2008-01-11 2010-12-08 日产化学工业株式会社 Liquid crystal aligning agent and liquid crystal display device using the same

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2858195B2 (en) * 1993-03-26 1999-02-17 小糸工業株式会社 Camera with shutter synchronized LED emitter
JPH06282081A (en) * 1993-03-26 1994-10-07 Asahi Chem Ind Co Ltd Method for forming pattern
JP3893659B2 (en) 1996-03-05 2007-03-14 日産化学工業株式会社 Liquid crystal alignment treatment method
JPH11183907A (en) * 1997-12-19 1999-07-09 Matsushita Electric Ind Co Ltd Liquid crystal display element and manufacture thereof
JP4222125B2 (en) 2002-06-25 2009-02-12 チッソ株式会社 Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element
JP4839194B2 (en) * 2005-12-26 2011-12-21 株式会社 日立ディスプレイズ Liquid crystal display device and manufacturing method thereof
JP5614284B2 (en) 2008-10-29 2014-10-29 日産化学工業株式会社 Diamine, polyimide, liquid crystal aligning agent and liquid crystal aligning film
JP5654228B2 (en) 2009-11-13 2015-01-14 株式会社ジャパンディスプレイ Liquid crystal display device and method of manufacturing liquid crystal display device
KR20130038243A (en) 2010-03-15 2013-04-17 닛산 가가쿠 고교 가부시키 가이샤 Liquid crystal alignment agent for use in photo-alignment process, and liquid crystal alignment film using same
KR101418465B1 (en) * 2010-10-28 2014-07-10 제이에스알 가부시끼가이샤 Process for producing liquid crystal alignment film, and liquid crystal display element

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11125812A (en) * 1997-10-22 1999-05-11 Sumitomo Bakelite Co Ltd Insulating agent for active matrix liquid crystal display element
JP2000080164A (en) * 1998-09-03 2000-03-21 Nissan Chem Ind Ltd Polyimide precursor, polyimide, and aligning agent for liquid crystal cell
CN101495915A (en) * 2006-07-28 2009-07-29 日产化学工业株式会社 Liquid crystal aligning agent and liquid crystal displays made by using the same
CN101910931A (en) * 2008-01-11 2010-12-08 日产化学工业株式会社 Liquid crystal aligning agent and liquid crystal display device using the same

Also Published As

Publication number Publication date
TW201439150A (en) 2014-10-16
KR20150092205A (en) 2015-08-12
CN104838311A (en) 2015-08-12
KR102101530B1 (en) 2020-04-16
WO2014084362A1 (en) 2014-06-05
TWI597305B (en) 2017-09-01
JPWO2014084362A1 (en) 2017-01-05
JP6217648B2 (en) 2017-10-25

Similar Documents

Publication Publication Date Title
CN104823104B (en) Manufacture method, liquid crystal orientation film and the liquid crystal display cells of liquid crystal orientation film
CN104395820B (en) The aligning agent for liquid crystal of optical alignment method, liquid crystal orientation film and liquid crystal display cells
KR102391044B1 (en) Liquid crystal aligning agent, and liquid crystal display element using same
CN103946738B (en) Manufacture method, liquid crystal orientation film and the liquid crystal display cells of liquid crystal orientation film
CN104106001B (en) Liquid crystal orientation film, the manufacture method of liquid crystal orientation film and liquid crystal display cells
KR102169221B1 (en) Diamine, polymer, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
WO2015050133A1 (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using same
CN104838311B (en) Manufacture method, liquid crystal orientation film and the liquid crystal display cells of liquid crystal orientation film
CN110325902B (en) Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
JP7078033B2 (en) Polymer and liquid crystal alignment agent using it
TWI820010B (en) Manufacturing method of liquid crystal alignment film, liquid crystal alignment film and liquid crystal display element
KR102278973B1 (en) Liquid crystal aligning agent and liquid crystal display element using same
CN104969123B (en) Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element
TWI839328B (en) Polymer and liquid crystal alignment agent using the same
TW202130704A (en) Liquid crystal aligning agent, radical generation film and method for producing in-plane switching liquid crystal cell
WO2019142927A1 (en) Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same
JP2018040979A (en) Production method of liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element

Legal Events

Date Code Title Description
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant