CN101824327A - Alignment agent and liquid crystalline polyimide used therein - Google Patents

Alignment agent and liquid crystalline polyimide used therein Download PDF

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CN101824327A
CN101824327A CN201010111595A CN201010111595A CN101824327A CN 101824327 A CN101824327 A CN 101824327A CN 201010111595 A CN201010111595 A CN 201010111595A CN 201010111595 A CN201010111595 A CN 201010111595A CN 101824327 A CN101824327 A CN 101824327A
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CN101824327B (en
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田村典央
小口雄二郎
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Changsha Dao'anjie New Materials Co ltd
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Chisso Petrochemical Corp
Chisso Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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    • C09K19/00—Liquid crystal materials
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    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

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Abstract

The invention relates to an alignment agent and liquid crystalline polyimide used therein. The invention provides an alignment film which has excellent alignment performance, high light sensitivity and stability. The alignment agent contains at least one polymer in the polyimide obtained from polyamic acid and by the dehydration reaction of the polyamic acid and the composition of the solvent. The concentration of the polymer in the composition is 0.1wt%-40wt%, the total amount of the film forming components contained in the composition is 50wt%-100wt% of the reference polymer proportionality, and the composition can be formed into a film having the liquid crystal temperature range between 100 DEG C and 300 DEG C by film forming of the composition.

Description

Employed liquid crystalline polyimide in orientation agent and this orientation agent
Technical field
The present invention relates to a kind of orientation agent of mainly in the manufacturing of liquid crystal display device, using.
Background technology
Liquid crystal display device is used to also be used to recently in the TV (television) with in the view finder (view finder) of the pick up camera (video camera) headed by the watch-dog (monitor) of notebook computer (notebook personal computer) or desktop computer (desktop personal computer), the projection formula indicating meter various liquid crystal indicators such as (projectiondisplay).In addition, liquid crystal display device also is used as optical print head (optical printer head), optical Fourier transform element (optical Fourier transform device), light valve photoelectron (optoelectronics) related elements such as (light valve).The main flow of previous liquid crystal display device has been to use the display element of nematic liquid crystal (nematic liquid crystal), and near the alignment direction of the liquid crystal the alignment direction that is positioned near the liquid crystal a side the substrate and the substrate that is positioned at the opposing party is with twisted-nematic (the Twisted Nematic of the angles distortion of 90 degree, TN) pattern and described alignment direction are usually so that (Super TwistedNematic, STN) liquid crystal display device of pattern etc. just is being able to practicability to row more than or equal to the supertwist of the angles distortion of 180 degree.And (Thin-film-transistor, TFT) liquid crystal display device of pattern also just is being able to practicability to have used the so-called thin film transistor of thin film transistor (transistor).
Yet these liquid crystal display device visual angle of recognition image rightly are narrow and small, the situation that exists brightness or contrast gradient (contrast) to descend during from oblique watching, and produce the brightness counter-rotating with middle tone sometimes.In recent years, the problem at this visual angle the TN type liquid crystal display device by using optical compensation films, and with multizone arranged vertical (the Multi-domainVertical Alignment of the technology of vertical orientation and protruding structure, MVA) (In-Plane Switching, IPS) pattern (for example with reference to patent documentation 2) etc. obtains improvement to the plane conversion of pattern (for example with reference to patent documentation 1) or transverse electric field mode.
The development of liquid crystal display device technology is not only reached by type of drive or the component structure of improveing these liquid crystal display device, and reaches by employed component parts in the improvement display element.Among the employed component parts, especially liquid crystal orienting film is one of important factor relevant with the display quality of liquid crystal display device in the display element, and along with high-qualityization of display element, it is important that the effect of liquid crystal orienting film becomes day by day.
For this kind liquid crystal orienting film, uniform display characteristic for liquid crystal display device, must control the molecular arrangement of liquid crystal equably, therefore require to make on the substrate liquid crystal molecule equably orientation show fixed inclination angle (tilt angle (pretiltangle)) from real estate in addition in one direction.As mentioned above, the direction of the liquid crystal molecule on the substrate is arranged in consistent liquid crystal orienting film and becomes technology important and indispensable in the manufacturing step of liquid crystal display device.
Liquid crystal orienting film is prepared by the LCD alignment agent.At present, the main LCD alignment agent of using is to make the polyimide (polyimide) of polyamic acid (polyamic acid) or solubility be dissolved in the solution that forms in the organic solvent.After on the substrate, making its film forming form polyimide by methods such as heating is liquid crystal orienting film with this kind solution coat.Industry is also studied the various LCD alignment agent except that polyamic acid, but with regard to aspects such as thermotolerance, chemical-resistant (anti-liquid crystal liquid crystal property), coating, LCD alignment, electrical property, optical characteristics, display characteristic, almost practicability not.
Both easy and friction (rubbing) method that can carry out large-area high speed processing of industrial extensive utilization is as the orientation facture.Rubbing manipulation is to use the cloth of implanting the fiber that nylon (nylon), artificial silk (rayon), polyester (polyester) etc. are arranged, along the rub processing on surface of liquid crystal orienting film of a direction, can obtain the orientation of the unanimity of liquid crystal molecule thus.Yet rubbing manipulation is pointed out to exist problem points such as producing dust, static.
Up to now, as the orientation mechanism of the liquid crystal on the alignment film of implementing the orientation processing by friction treatment, proposing has following two kinds:
(1) by the surface shape effect of the caused liquid crystal orienting film of the microflute that utilizes friction treatment to produce (microgroove);
(2) carry out the molecular interaction of the liquid crystal unimolecular layer that the liquid crystal orienting film of single shaft orientation contacts with liquid crystal orienting film therewith by friction treatment.
In recent years, can confirm that the contribution of surface shape effect of (1) is less, the contribution of the molecular interaction of (2) is dominant.
Known when adopting this kind rubbing manipulation, can give the bigger orientation restraint for liquid crystal (anchoring energy (anchoring energy)) to polyimide film usually.Yet when adopting this rubbing manipulation, there are the following problems, promptly, if observe with molecular level (molecular level) by the direction that is implanted in the hair friction film in the friction cloth, so also inhomogeneous, the result causes the LCD alignment at alignment film interface to get muddled.In addition, exactly because also on film, produce scar etc. by the contact of cloth, making liquid crystal display device when not applying voltage is that black display is when (normally showing black formula (normallyblack mode)), black level (black level) is less than ideal situation, and this kind phenomenon is by known to the industry.
On the other hand, implement the light orientation method that orientation is handled about irradiates light, propose to have multiple orientation mechanism (for example with reference to non-patent literature 1, patent documentation 3 and patent documentation 4) such as photolysis method, photoisomerization method, photodimerization method, optical cross-linking method.Especially, it is generally acknowledged and therefore, have only the molecular interaction of (2) to play a role as the orientation mechanism of liquid crystal because light orientation method is the non-contacting alignment method different with rubbing manipulation.
The known following phenomenon of dealer: the homogeneity of the orientation of light orientation facture is higher than rubbing manipulation, and is the orientation method of noncontact, so can not produce scar on the film, and for rubbing manipulation, easier raising black level.And light orientation facture can reduce sends out dirt or static etc. produce unfavorable condition when making liquid crystal display device reason, and its advantage is more.Yet the anchoring energy of light orientation facture is less than rubbing manipulation, and this situation can cause the decline or the trace of response speed, therefore need be improved.
In order to overcome the shortcoming of this kind light orientation, people such as present inventor have found following method: by the method that is disclosed in the patent documentation 3 for example, irradiates light after the LCD alignment agent that will comprise polyamic acid is coated on the substrate is calcined then.Can obtain to have the light alignment film of bigger anchoring energy by this method, but, have to increase the rayed energy, and must further improve in order to obtain to have the liquid crystal orienting film of sufficient anchoring energy.
No. 2947350 communique of [patent documentation 1] Japanese Patent
No. 2940354 communique of [patent documentation 2] Japanese Patent
[patent documentation 3] Japanese Patent spy opens the 2005-275364 communique
[patent documentation 4] Japanese patent laid-open 11-15001 communique
[non-patent literature 1] liquid crystal, the 3rd volume, No. 4, the 262nd page, 1999 years
Summary of the invention
The object of the present invention is to provide a kind of homogeneity higher friction alignment film of orientation.And, the object of the present invention is to provide the light alignment film that a kind of light sensitivity is good and stability is higher.
People such as present inventor research and develop hardy, found that by friction or light and give after the anisotropy having the higher polyimide material of liquid crystal liquid crystal property and thermotolerance, heat till the liquid crystal temperature of this polyimide, regiospecific increases by this, thereby finishes the present invention.Essence of the present invention is liquid crystalline polyimide as alignment film material.The present invention be by following [1] represented.
[1] a kind of orientation agent, it contains and is selected from polyamic acid and by at least a polymkeric substance in the polyimide that dehydration reaction obtained of this polyamic acid and solvent composition thing, it is characterized in that: the concentration of the polymkeric substance in this constituent is 0.1wt%～40wt% (weight percent), the total amount that forms composition with the film that contained in this constituent is that the ratio of the described polymkeric substance of benchmark is 50wt%～100wt%, and can be formed on the film that has liquid crystal temperature range between 100 ℃～300 ℃ by making this constituent film forming.
[effect of invention]
If for example as the LCD alignment agent, can provide the homogeneity higher friction alignment film of orientation so with orientation agent of the present invention.And, the light alignment film that light sensitivity is good and stability is higher can be provided.
Description of drawings: do not have
Embodiment
The term that uses among the present invention is described.
Sometimes will be labeled as compound (I-1) by the represented compound of formula (I-1).Sometimes to also noting by abridging in an identical manner by the represented compound of other formulas.
Employed term " arbitrarily " expression " not only the position can freely be selected, and quantity also can freely be selected " during chemical formula defined.For example the statement of " A can be replaced by B, C, D or E arbitrarily " can be by the implication of B, C, D or E replacement except that an A, and any one of a plurality of A all can be by beyond the implication of any one replacement among B, C, D and the E, the A that also has the A that replaced by B, replaced by C, the A that is replaced by D and the A that replaced by E both can mix the implication of existence at least.Yet, when arbitrarily-CH 2-in the time of can being replaced by other groups, precondition be successive a plurality of-CH 2-can't be replaced by other identical groups.
In chemical structural formula, surround the group (ring A) of the group representative ring structure of literal (for example A) by sexangle, Me represents methyl.
With the carbon that constitutes ring any not clearly the substituting group of bond represent that its bond position is freely in the scope of no chemical problem.
In a plurality of formulas, use the situation of identical mark to represent that this group has the identical range of definition, must not be identical group simultaneously but be not illustrated in all formulas.When this kind situation, can in a plurality of formulas, select identical group, also can in each formula, select different groups.
The present invention be by described [1] with [2]～[22] following formation.
[2] according to [1] described orientation agent, polyamic acid is the polyamic acid that has photosensitive group on the main chain.
[3] according to [2] described orientation agent, photosensitive group is at least a by the represented group of formula (I)～formula (VI):
-R 1-C≡C-R 2-??????????????(I)
-R 1-C≡C-C≡C-R 2-?????????(II)
-R 1-C≡C-CH＝CH-R 2-???????(III)
-R 1-C≡C-R 2-C≡C-R 3-??????(IV)
-R 1-C≡C-R 2-CH＝CH-R 3-????(V)
-N＝N-????????????????????(VI)
Herein, R 1, R 2And R 3Independent is aromatic divalent group.
[4] according to [2] described orientation agent, the polyamic acid that the polyamic acid that has photosensitive group on the main chain is in the following way to be obtained, that is, make by formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), the diamines that formula (V-1) and formula (VI-1)～formula (VI-7) is represented with photosensitive group at least a with by formula (A-1), formula (A-2), formula (A-12), formula (A-14), formula (A-18), formula (A-20), formula (A-21), formula (A-37), formula (VII-4), formula (VII-5), formula (VIII-7) and represented at least a of tetracarboxylic dianhydride of formula (VIII-8) react:
Figure GSA00000016952200051
Figure GSA00000016952200061
Figure GSA00000016952200071
Herein, R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group (alkylene).
[5] according to [2] described orientation agent, the polyamic acid that the polyamic acid that has photosensitive group on the main chain is in the following way to be obtained, that is, make by at least a of the represented tetracarboxylic dianhydride of formula (IV-4) and formula (VI-8) with photosensitive group with react by represented at least a of diamines of formula (VII-1)～formula (VII-3) and formula (VIII-1)～formula (VIII-6):
Figure GSA00000016952200072
Figure GSA00000016952200081
Herein, R 4Be that carbon number is 6～20 alkylidene group; R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group.
Figure GSA00000016952200082
[6] according to [2] described orientation agent, the polyamic acid that the polyamic acid that has photosensitive group on the main chain is in the following way to be obtained, that is, make disclosed in [4] by formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), the diamines that formula (V-1) and formula (VI-1)～formula (VI-7) is represented with photosensitive group at least a with by disclosed among at least a mixture of the represented diamines of formula (VII-1)～formula (VII-3) and formula (VIII-1)～formula (VIII-6) and [4] by formula (A-1), formula (A-2), formula (A-12), formula (A-14), formula (A-18), formula (A-20), formula (A-21), formula (A-37), formula (VII-4), formula (VII-5), formula (VIII-7) and represented at least a of tetracarboxylic dianhydride of formula (VIII-8) react:
H 2N-R 4-NH 2????????(VII-1)
Figure GSA00000016952200091
Herein, R 4Be that carbon number is 6～20 alkylidene group; R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group.
Figure GSA00000016952200092
[7] according to [2] described orientation agent, the polyamic acid that the polyamic acid that has photosensitive group on the main chain is in the following way to be obtained, that is, make disclosed in [5] by at least a of the represented tetracarboxylic dianhydride of formula (IV-4) and formula (VI-8) with photosensitive group with by formula (VII-4), formula (VII-5), that is disclosed among the tetracarboxylic dianhydride's that formula (VIII-7) and formula (VIII-8) are represented at least a mixture and [5] is reacted by formula (VII-1)～formula (VII-3) and formula (VIII-1)～represented at least a of diamines of formula (VIII-6):
Figure GSA00000016952200101
Herein, R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group.
[8] according to [2] described orientation agent, the polyamic acid that the polyamic acid that has photosensitive group on the main chain is in the following way to be obtained, that is, make disclosed in [4] by formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), the diamines that formula (V-1) and formula (VI-1)～formula (VI-7) is represented with photosensitive group at least a with select disclosed among at least a mixture in the represented diamines of free style (2)～formula (4) and [4] by formula (A-1), formula (A-2), formula (A-12), formula (A-14), formula (A-18), formula (A-20), formula (A-21), formula (A-37), formula (VII-4), formula (VII-5), formula (VIII-7) and represented at least a of tetracarboxylic dianhydride of formula (VIII-8) react:
Figure GSA00000016952200102
Herein, A 1, A 2, A 3And A 4Independent of stretching cyclohexyl (cyclohexylene) or inferior benzene (phenyl); X 3And X 4Independent for singly-bound, carbon number be 1～5 alkylidene group or-O-; X 5And X 6Independent be singly-bound ,-CH 2-,-CH 2CH 2-,-O-or-S-; Y 1Be-CH 2-,-C (R 11) (R 12)-,-CO-or-SO 2-, R 11And R 12Independent for hydrogen, carbon number be that 1～12 alkyl or carbon number are 1～12 fluorinated alkyl; M1, m2, m3, m4 and n independently represent 0 or 1.And, stretch in cyclohexyl and the inferior benzene described, hydrogen can be 1～4 alkyl or benzyl replacement by carbon number arbitrarily, these substituent bond positions are arbitrarily; But, work as A 1, A 2, A 3And A 4All be 1, during the benzene of 4-Asia, X 3, X 4, X 5And X 6All be not singly-bound:
Figure GSA00000016952200111
Herein, X 1And X 2Be singly-bound ,-O-,-COO-,-OCO-,-NH-,-CONH-or carbon number are 1～12 alkylidene group; G 1And G 2Be that to be selected from carbon number be that 6～12 aromatic ring and carbon number are the divalent group of 1～3 rings in 3～12 the ester ring type ring for singly-bound or contain; R 6Be hydrogen, fluorine ,-CN ,-OH, carbon number are that 1～30 alkyl, carbon number are that 1～30 fluorinated alkyl or carbon number are 1～30 alkoxyl group; And, work as X 1, G 1, X 2And G 2When all being singly-bound, R 6Be that carbon number is that 3～30 alkyl, carbon number are that 3～30 fluorinated alkyl or carbon number are 3～30 alkoxyl group, work as G 2Be singly-bound and X 2Neither when singly-bound neither alkylidene group, R 6Be that hydrogen or carbon number are 3～30 alkyl, work as G 1And G 2When being singly-bound, X 1, X 2And R 6The total carbon number more than or equal to 3:
Figure GSA00000016952200112
Herein, R 7Be that hydrogen or carbon number are 1～12 alkyl; Ring B be arbitrarily hydrogen can by carbon number be 1～4 alkyl replace 1, the inferior benzene of 4-or arbitrarily hydrogen can by carbon number be 1～4 alkyl replace 1,4-stretches cyclohexyl; X 0Be that singly-bound or carbon number are 1～5 alkylidene group, and s is 0～3 integer; When s was 2 or 3, a plurality of ring B can all be identical ring, also can be made of a plurality of X at least 2 different rings 0Can all be identical group, also can constitute by at least 2 different groups; Z 1And Z 2Independent be singly-bound ,-CH 2-,-CH 2CH 2-or-O-, t1 and t2 independently are 0～3 integer; When t1 is 2 or 3, a plurality of Z 1Can all be identical group, also can constitute by at least 2 different groups; When t2 is 2 or 3, a plurality of Z 2Can all be identical group, also can constitute by at least 2 different groups.
[9] according to [2] described orientation agent, the polyamic acid that the polyamic acid that has photosensitive group on the main chain is in the following way to be obtained, promptly, make that [4] discipline disclosed by formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), the diamines that formula (V-1) and formula (VI-1)～formula (VI-7) is represented at least a with photosensitive group, at least a by the represented diamines of formula (VII-1)～formula (VII-3) and formula (VIII-1)～formula (VIII-6) of being disclosed in [6], and selecting of being disclosed in [8] disclosed among at least a mixture in the represented diamines of free style (2)～formula (4) and [4] by formula (A-1), formula (A-2), formula (A-12), formula (A-14), formula (A-18), formula (A-20), formula (A-21), formula (A-37), formula (VII-4), formula (VII-5), formula (VIII-7) and represented at least a of tetracarboxylic dianhydride of formula (VIII-8) react.
[10] according to [1] described orientation agent, polyamic acid is by making by at least a of the represented diamines of formula (VII-1)～formula (VII-3) and at least a polyamic acid that is obtained that reacts by the represented tetracarboxylic dianhydride of formula (VIII-7) and formula (VIII-8), or by making by at least a of the represented diamines of formula (VIII-1)～formula (VIII-6) and at least a polyamic acid that is obtained that reacts by the represented tetracarboxylic dianhydride of formula (VII-4) and formula (VII-5):
H 2N-R 4-NH 2????????(VII-1)
Figure GSA00000016952200121
Herein, R 4Be that carbon number is 6～20 alkylidene group; And, R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group.
Figure GSA00000016952200122
Figure GSA00000016952200131
[11] a kind of liquid crystal orienting film, it is to obtain in the following way, that is, to giving anisotropy, be heated to then till the liquid crystal temperature range of film and make the anisotropy increase of film according to the film that [1] described orientation agent is coated on the substrate to be obtained by friction or rayed.
[12] a kind of liquid crystal orienting film, it is to obtain in the following way, promptly,, be heated to then till the liquid crystal temperature range of film and the anisotropy of film is increased giving anisotropy by rayed according to the film that each described orientation agent in [2] to [9] is coated on the substrate to be obtained.
[13] a kind of liquid crystal orienting film, it is to obtain in the following way, that is,, be heated to then till the liquid crystal temperature range of film and the anisotropy of film is increased giving the friction anisotropy according to the film that [10] described orientation agent is coated on the substrate to be obtained.
[14] a kind of liquid crystal display device has according to [11] described liquid crystal orienting film.
[15] a kind of liquid crystal display device has according to [12] described liquid crystal orienting film.
[16] a kind of liquid crystal display device has according to [13] described liquid crystal orienting film.
[17] a kind of polyimide or as the polyamic acid of its precursor comprises by the represented formation unit of formula (IX), and have liquid crystal temperature range in 100 ℃～300 ℃:
Figure GSA00000016952200132
Herein, R 5Be that carbon number is 6～12 alkylidene group; R 9Be by any one the residue in the represented diamines of formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), formula (V-1) and formula (VI-1)～formula (VI-7).
Figure GSA00000016952200141
Figure GSA00000016952200151
[18] a kind of polyimide or as the polyamic acid of its precursor comprises by the represented formation unit of formula (X), and have liquid crystal temperature range in 100 ℃～300 ℃:
Figure GSA00000016952200152
Herein, R 5Be that carbon number is 6～12 alkylidene group; R 9Be by any one the residue in the represented diamines of formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), formula (V-1) and formula (VI-1)～formula (VI-7).
Figure GSA00000016952200161
[19] according to [17] described polyimide or as the polyamic acid of its precursor, R 9Be by any one the residue in the represented diamines of formula (VIII-1)～formula (VIII-6).
Figure GSA00000016952200172
[20] according to [18] described polyimide or as the polyamic acid of its precursor, R 9Be by any one the residue in the represented diamines of formula (VIII-1)～formula (VIII-6).
Figure GSA00000016952200181
[21] a kind of polyimide or as the polyamic acid of its precursor comprises by the represented formation unit of formula (IX) and by the represented formation unit of formula (XI), and have liquid crystal temperature range in 100 ℃～300 ℃:
Figure GSA00000016952200182
Herein, R 5Be that carbon number is 6～12 alkylidene group; R 9Be by any one the residue in the represented diamines of formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), formula (V-1) and formula (VI-1)～formula (VI-7); R 10Be by any one the residue in the represented diamines of formula (VIII-1)～formula (VIII-6).
Figure GSA00000016952200183
Figure GSA00000016952200191
[22] a kind of polyimide or as the polyamic acid of its precursor comprises by the represented formation unit of formula (X) and by the represented formation unit of formula (XII), and have liquid crystal temperature range in 100 ℃～300 ℃:
Figure GSA00000016952200202
Herein, R 5Be that carbon number is 6～12 alkylidene group; R 9Be by any one the residue in the represented diamines of formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), formula (V-1) and formula (VI-1)～formula (VI-7); R 10Be by any one the residue in the represented diamines of formula (VIII-1)～formula (VIII-6).
Figure GSA00000016952200203
Figure GSA00000016952200211
Orientation agent of the present invention is to contain to be selected from polyamic acid and the constituent by at least a polymkeric substance in the polyimide that dehydration reaction obtained of this polyamic acid, and is that the ratio of the described polymkeric substance of benchmark is 50wt%～100wt% with the total amount that the film that is contained in this constituent forms composition.And, by making this constituent film forming, can be formed on the film that has liquid crystal temperature range between 100 ℃ to 300 ℃.That is, this orientation agent is coated on the substrate and makes its film forming, and film is given after the anisotropy, heat till the liquid crystal temperature range of this film by friction or irradiates light, can form regiospecific by this and increase, and have the alignment film of higher regiospecific.Contain of the orientation agent of described polymkeric substance by use, can make the higher film of thermostability and chemical stability as principal constituent.
Glass transition point (glasstransition point) when employed polyamic acid is made polyimide among the present invention moves less than common polyimide easily because of main polymer chain, and smaller or equal to liquid crystal temperature.Therefore, utilizing with this kind polyamic acid is the orientation agent of the present invention of principal constituent, even if be the calcining of lower temperature, also can obtain the higher film of imidization rate.In the following description, do not specify, just " employed polyamic acid among the present invention " only is expressed as " polyamic acid " as long as have in advance.
As mentioned above, alignment film of the present invention is by bringing into play its performance till the liquid crystal temperature range that is heated to material.When giving anisotropy to film by rubbing manipulation, in order to prevent the fracture of film, generally carry out following processing, that is, the orientation agent is coated on the substrate, remove after the solvent by precalcining, under about 200 ℃, calcine, rub then.Yet,,, about 200 ℃, calcine simultaneously with also harmless down then in order to increase anisotropic heat treated even if after precalcining, rub so if can prevent the fracture of film by the selection of material.
Because light orientation method can be given anisotropy to alignment film in the noncontact mode, therefore needn't worry the film fracture.That is, because it is light orientation method can be carried out hot-imide and heat treated simultaneously after the use polyamic acid carries out the light orientation, therefore better as alignment film of the present invention being given anisotropic method.According to this reason, be preferably the temperature of selecting hot-imide and be in the interior material of liquid crystal temperature range.
Sometimes according to the kind of base material, the ultimate temperature of heat treated is restricted, but the orientation agent of the application of the invention, can be formed on the film that has liquid crystal temperature range in 100 ℃～300 ℃ the scope.At this moment, when forming the alignment film with respect to employed nematic liquid crystal, in order to keep the stability of orientation, comparatively ideal being selected at is preferably 150～300 ℃, is more preferably the material that has liquid crystal temperature range in 180 ℃～300 ℃ the scope.
In order to utilize described smooth orientation method, orientation agent of the present invention is preferably and contains the polymkeric substance with photosensitive group.As this photosensitive group, can select to have well-known all photosensitive groups of light orientation ability.Yet,, follow the rayed condition so and the possibility that causes the liquid crystal temperature range of material to change is higher if use the photosensitive group that shows the orientation ability by photodimerizationization or photolysis.Therefore, in the present invention, be preferably the photosensitive group that uses the photoisomerization type.
That is, in the present invention, be preferably and use at least a polymkeric substance that has following photosensitive group on the main chain.
-R 1-C≡C-R 2-??????????????(I)
-R 1-C≡C-C≡C-R 2-?????????(II)
-R 1-C≡C-CH＝CH-R 2-???????(III)
-R 1-C≡C-R 2-C≡C-R 3-??????(IV)
-R 1-C≡C-R 2-CH＝CH-R 3-????(V)
-N＝N-????????????????????(VI)
R 1, R 2And R 3Independent is aromatic divalent group, and the preferable example of aromatic series divalent group is 1, the inferior benzene, 1 of 4-, and the inferior benzene, 4,4 of 3-'-Lian Ya benzene and ditan-4,4 '-two bases.The hydrogen arbitrarily of these rings can be replaced by methyl, methoxyl group, trifluoromethyl, methoxycarbonyl, fluorine or chlorine.And, among these groups, be more preferably 1, the inferior benzene and 1 of 4-, the inferior benzene of 3-, best is 1, the inferior benzene of 4-.
By selecting, the light regiospecific is manifested to greatest extent than characteristic big and the of the present invention smooth orientation agent that light sensitivity is higher by formula (I)～represented photosensitive group of formula (VI).Two kinds of isomer that in two keys of the photosensitive group of formula (III) and formula V, have cis (cis) or trans (trans), but smooth orientation agent of the present invention can be used in these isomer any.
In order to obtain to have on the main chain at least a polyamic acid, be used as raw material as long as will have the diamines or the carboxylic acid dianhydride of this kind photosensitive group by the represented photosensitive group of formula (I)～formula (VI).Especially, in order to obtain higher light regiospecific, be preferably and use the raw material that has photosensitive group in the diamines.
Having the diamines of this kind photosensitive group and tetracarboxylic dianhydride's preferable example is compound (I-1)～compound (I-3), compound (II-1)～compound (II-3), compound (III-1), compound (IV-1)～compound (IV-4), compound (V-1) and compound (VI-1)～compound (VI-8).In addition, in the following description, abbreviate the tetracarboxylic dianhydride as acid anhydrides sometimes.
Figure GSA00000016952200241
Figure GSA00000016952200251
Figure GSA00000016952200261
When making polyamic acid, can will not have diamines or the acid anhydrides and the described compound of photosensitive group and use.At this moment, can be that 6～20 alkylidene group imports to diamines or the acid anhydrides on the main chain of polymkeric substance with carbon number in order to reduce easily Tg, to be preferably selection by the polyimide that dehydration reaction obtained of this polyamic acid.In order further to reduce Tg, this alkylidene group arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-the COO-replacement.As this kind diamines and acid anhydrides, good especially is by following formula (VII-1)～represented compound of formula (VII-5).
H 2N-R 4-NH 2????(VII-1)
Figure GSA00000016952200262
Herein, R 4Be that carbon number is 6～20 alkylidene group, carbon number is preferably 6～12.R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group.R preferably 5Be one-CH 2-the carbon number that can be replaced by-O-is 6～12 alkylidene group.And, R 5Better example be do not exist with group in-CH 2The carbon number of-relevant replacement is 6～12 alkylidene group, that is-C 6H 12The C of-～- 12H 24-.
And, in order easily to show liquid crystal liquid crystal property, and use that the diamines or the acid anhydrides that form of straight line bond is also preferable as much as possible with aromatic nucleus aggregate and 2 amidos or 2 carboxyls.As this kind diamines and acid anhydrides, good especially is by following formula (VIII-1)～represented compound of formula (VIII-8).
Figure GSA00000016952200263
Figure GSA00000016952200271
In the present invention, also can be also with the diamines the diamines that in explanation so far, has listed.For example, when the alignment film in the liquid-crystal display purposes, alignment film used as the nematic liquid crystal constituent, can use the expression voltage retention (Voltage Holding Ratio, VHR) higher and be difficult to produce the well-known diamines of the so-called electrical property excellence of characteristic such as trace.
As the preferable example of the well-known diamines of this kind, can enumerate by the represented diamines of formula (2).
Figure GSA00000016952200272
In formula (2), A 1, A 2, A 3And A 4Independent of stretching cyclohexyl or inferior benzene; X 3And X 4Independent for singly-bound, carbon number be 1～5 alkylidene group or-O-; X 5And X 6Independent be singly-bound ,-CH 2-,-CH 2CH 2-,-O-or-S-; Y 1Be-CH 2-,-C (R 11) (R 12)-,-CO-or-SO 2-, R 11And R 12Independent of hydrogen, carbon number are that 1～12 alkyl or carbon number are 1～12 fluorinated alkyl, be preferably hydrogen, methyl or-CF 3M1, m2, m3, m4 and n independently represent 0 or 1.And, stretch in cyclohexyl and the inferior benzene described, hydrogen can be 1～4 alkyl or benzyl replacement by carbon number arbitrarily, these substituent bond positions are freely in the scope of no chemical problem.But, work as A 1, A 2, A 3And A 4Be 1, during the benzene of 4-Asia, X 3, X 4, X 5And X 6It or not singly-bound.
Below expression is by the preferable example of the represented diamines of formula (2).
Figure GSA00000016952200281
Figure GSA00000016952200291
Figure GSA00000016952200301
Among these diamines, with regard to the viewpoint of liquid crystal orienting film being given higher VHR and inhibition trace phenomenon, be more preferably by formula (2-6)～formula (2-24), formula (2-36), formula (2-42), formula (2-43) or formula (2-48)～represented diamines of formula (2-52), and then be more preferably by formula (2-6), formula (2-11), formula (2-12), formula (2-13), formula (2-17), formula (2-22), formula (2-23), formula (2-24) or the represented diamines of formula (2-49).
The usage ratio of the diamines of the described formula (2) among the present invention can be according to as the regiospecific of target, electrical property and selected arbitrarily.Yet, if the usage ratio of these diamines is bigger, liquid crystal liquid crystal property can descend so, so the usage ratio of these diamines is preferably the scope of the 0mol%～30mol% (molar percentage) in synthesizing polyamides employed total diamines amount of when acid, is more preferably 0mol%～10mol%.
Other examples that can be used for making the diamines that does not have photosensitive group of polyamic acid preferably are by formula (3) or the represented diamines with side-chain radical of formula (4).
Figure GSA00000016952200302
In formula (3), X 1And X 2Independent for singly-bound ,-O-,-COO-,-OCO-,-NH-,-CONH-or carbon number are 1～12 alkylidene group; G 1And G 2Independent for singly-bound or comprise that to be selected from carbon number be that 6～12 aromatic ring and carbon number are the divalent group of 1～3 rings in 3～12 the ester ring type ring; R 6Expression hydrogen, fluorine ,-CN ,-OH, carbon number are that 1～30 alkyl, carbon number are that 1～30 fluorinated alkyl or carbon number are 1～30 alkoxyl group.But, work as X 1, G 1, X 2And G 2When all being singly-bound, R 6Be that carbon number is that 3～30 alkyl, carbon number are that 3～30 fluorinated alkyl or carbon number are 3～30 alkoxyl group; Work as G 2Be singly-bound and X 2Neither when singly-bound neither alkylidene group, R 6It is hydrogen or alkyl; And, work as G 1And G 2When being singly-bound, X 1, X 2And R 6The total carbon number more than or equal to 3.
In described formula (3), 2 amidos are binding on the carbon of phenyl ring, position (meta position) or contraposition (para position) between the bond position relation of 2 amidos is preferably.And, when with X 1Bond position when being made as 1, be preferably 2 amidos be binding on respectively 3 with 5 or 2 with 5, good especially is be binding on 3 with 5.
Figure GSA00000016952200311
In formula (4), R 7Be that hydrogen or carbon number are 1～12 alkyl; Ring B be arbitrarily hydrogen can by carbon number be 1～4 alkyl replace 1, the inferior benzene of 4-or arbitrarily hydrogen can by carbon number be 1～4 alkyl replace 1,4-stretches cyclohexyl; X 0Be that singly-bound or carbon number are 1～5 alkylidene group, and s is 0～3 integer; When s was 2 or 3, a plurality of ring B can all be identical ring, also can be made of a plurality of X at least 2 different rings 0Can all be identical group, also can constitute by at least 2 different groups; Z 1And Z 2Independent be singly-bound ,-CH 2-,-CH 2CH 2-or-O-, t1 and t2 independently are 0～3 integer; When t1 is 2 or 3, a plurality of Z 1Can all be identical group, also can constitute by at least 2 different groups; When t2 is 2 or 3, a plurality of Z 2Can all be identical group, also can constitute by at least 2 different groups.
Below expression is by the preferable example of the represented diamines of formula (3).
Figure GSA00000016952200321
Figure GSA00000016952200331
In formula (3-1)～formula (3-25), R 20Be that carbon number is 1～20 alkyl or alkoxyl group, be preferably carbon number and be 5～16 alkyl.R 21Be that carbon number is 1～20 alkyl or alkoxyl group, be preferably carbon number and be 3～10 alkyl.R 22Be that carbon number is 4～20 alkyl, be preferably carbon number and be 6～16 alkyl.R 23Be that carbon number is 6～20 alkyl, be preferably carbon number and be 8～20 alkyl.R 24Be that carbon number is 3～20 alkyl or alkoxyl group, be preferably carbon number and be 5～12 alkyl.R 25Be that carbon number is 1～20 alkyl or alkoxyl group, be preferably carbon number and be 3～10 alkyl.
Among these diamines, better example is by formula (3-1), formula (3-2), formula (3-4), formula (3-5) and the represented separately diamines of formula (3-6), and then better example is by formula (3-1) and the represented separately diamines of formula (3-2).
Below expression is by the preferable example of the represented diamines of formula (4).
Figure GSA00000016952200332
Figure GSA00000016952200341
In formula (4-1)～formula (4-16), R 26Be that hydrogen or carbon number are 1～12 alkyl or alkoxyl group, be preferably carbon number and be 4～7 alkyl.
The usage ratio of the described formula (3) among the present invention or the diamines with side-chain radical of formula (4) can be according to as regiospecific, electrical property or the tilt angle of target and selected arbitrarily.Especially in order to show the tilt angle more than or equal to 2 degree, the usage ratio that is preferably these diamines is made as the 1mol%～50mol% in the employed diamines total amount when making polyamic acid, is more preferably and is made as 5mol%～30mol%.Yet if the usage ratio of the diamines with side-chain radical of described formula (3) or (4) is bigger, liquid crystal liquid crystal property can descend so, therefore is preferably and is made as necessary inferior limit.
Among the diamines with side-chain radical of described formula (3) or formula (4),, be preferably the diamines of selecting type (3-5), formula (3-6) or formula (3-10) for the liquid crystal liquid crystal property that keeps alignment film of the present invention to have.
In the present invention, except described diamines, also can use at least a of siloxane-based diamines.As the preferable example of this siloxane-based diamines, can enumerate by the represented diamines of formula (15).
Figure GSA00000016952200351
In formula (15), R 30And R 31Independent of respectively carbon number is 1～3 alkyl or phenyl, R 32Be that carbon number is 1～6 alkylidene group, inferior benzene or the inferior benzene that replaces through alkyl, y is 1～10 integer.
As concrete example, can enumerate following compound or polymkeric substance by the represented diamines of formula (15).
In these formulas, Me is a methyl, and the molecular weight of the polymkeric substance of formula (15-2) is 850～3000.
In order to show described effect and to prevent the deterioration of other characteristics, the addition of these siloxane-based diamines as the total amount of the diamines of raw material, is preferably 0.5mol%～30mol% when making polyamic acid, is more preferably 1mol%～10mol%.
According to the characteristic that requires of alignment film, when making polyamic acid, can use expression voltage retention (VHR) higher and be difficult to produce the well-known acid anhydrides of the so-called electrical property excellence of characteristic such as trace.
As the acid anhydrides of the manufacturing raw material of polyamic acid, can from well-known compound, unrestrictedly select.Acid anhydrides can be the acid anhydrides that belongs to any one cohort in the acid anhydrides of the acid anhydrides of fragrant family (comprising assorted aromatic ring) and fatty family (comprising heterocycle system).Polyimide or polyamic acid are preferably the oxygen of ester bond with the decrease reason that does not comprise the electrical property that becomes liquid crystal display device easily or ehter bond etc. or the structure of sulphur.Therefore, acid anhydrides also is to have the structure that does not comprise oxygen or sulphur preferably.Yet,, do not have any problem so even if can not cause amount in the dysgenic scope to electrical property if having this kind structure yet.
Acid anhydrides is to be represented by formula (20).
Figure GSA00000016952200361
R in the formula (20) 40Preferable example be by formula (21)～represented quaternary groups of formula (29).
G 3Be that singly-bound, carbon number are 1～12 alkylidene group, 1, the inferior benzene or 1 of 4-, 4-stretches cyclohexyl, X 7Independent be singly-bound or-CH 2-.
Figure GSA00000016952200363
R 41, R 42, R 43And R 44Independent is hydrogen, methyl, ethyl or phenyl.
Figure GSA00000016952200364
Ring D 1Be cyclohexane ring or phenyl ring.
Figure GSA00000016952200365
G 4Be singly-bound ,-CH 2-,-CH 2CH 2-,-O-,-CO-,-S-,-C (CH 3) 2-or-C (CF 3) 2-, ring D 2Independent is cyclohexane ring or phenyl ring.
Figure GSA00000016952200366
R 45Be hydrogen or methyl.
Figure GSA00000016952200367
X 8Independent be singly-bound or-CH 2-, v is 1 or 2.
Figure GSA00000016952200368
X 6Be singly-bound or-CH 2-.
Figure GSA00000016952200369
R 46Be hydrogen, methyl, ethyl or phenyl, ring D 3Be cyclohexane ring or phenyl ring.
Figure GSA00000016952200371
W1 and w2 independently are 0 or 1.
The concrete example of below representing described acid anhydrides.
Figure GSA00000016952200381
Figure GSA00000016952200391
In these acid anhydrides,, be preferably the compound of use formula (A-1), formula (A-2), formula (A-12), formula (A-14), formula (A-18), formula (A-20), formula (A-21) or formula (A-37) in order to keep the liquid crystal liquid crystal property of polyamic acid.And, with regard to the viewpoint of the light orientation ability that improves alignment film, be preferably the compound of use formula (A-1), formula (A-2), formula (A-12), formula (A-14), formula (A-18), formula (A-20), formula (A-21), formula (A-28), formula (A-30), formula (A-37) or formula (A-40), the good especially compound that is to use formula (A-1), formula (A-12), formula (A-14) or formula (A-18).In addition, with regard to the VHR that improves liquid crystal orienting film or alleviate with regard to the painted viewpoint, be preferably the compound of use formula (A-14), formula (A-18), formula (A-19), formula (A-20), formula (A-21), formula (A-28), formula (A-29), formula (A-30), formula (A-32), formula (A-39), formula (A-40), formula (A-41), formula (A-43) or formula (A-44), the good especially compound that is to use formula (A-14), formula (A-18), formula (A-21) or formula (A-44).Acid anhydrides is not limited to these compounds, also can use other well-known compounds in reaching the scope of the object of the invention.And these acid anhydrides can use separately, perhaps two or more compound can be used in combination.
In the present invention, by being reacted, described diamines and acid anhydrides appropriate combination make polyamic acid.The polyamic acid that the 1st good example of this polyamic acid is in the following way to be obtained, that is, at least a and acid anhydrides that makes conduct have compound (I-1)～compound (I-3), compound (II-1)～compound (II-3), compound (III-1), compound (IV-1)～compound (IV-3), compound (V-1) and compound (the VI-1)～compound (VI-7) of the diamines of photosensitive group reacts.
Figure GSA00000016952200402
This moment, the preferable example of employed acid anhydrides was the acid anhydrides that is selected from compound (A-1), compound (A-2), compound (A-12), compound (A-14), compound (A-18), compound (A-20), compound (A-21), compound (A-37), compound (VII-4), compound (VII-5), compound (VIII-7) and the compound (VIII-8).And good especially is compound (VII-4) and compound (VII-5).
Figure GSA00000016952200422
Figure GSA00000016952200431
Herein, R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group.And, R 5Be preferably carbon number and be 6～12 alkylidene group, that is-C 6H 12The C of-～- 12H 24-in any one.
The polyamic acid that the 2nd good example of polyamic acid is in the following way to be obtained promptly, reacts at least a and diamines by the represented acid anhydrides of formula (IV-4) and formula (VI-8) as described acid anhydrides with photosensitive group.
This moment, the preferable example of employed diamines was the diamines that selects in the represented compound of free style (VII-1)～formula (VII-3) and formula (VIII-1)～formula (VIII-6).
H 2N-R 4-NH 2????????????(VII-1)
Herein, R 4Be that carbon number is 6～20 alkylidene group, carbon number is preferably 6～12.R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group.And, R 5Be preferably-C 6H 12The C of-～- 12H 24-in any one.
Figure GSA00000016952200442
The polyamic acid that the 3rd good example of polyamic acid is in the following way to be obtained, that is, make and be selected from described compound (I-1)～compound (I-3), compound (II-1)～compound (II-3), compound (III-1), compound (IV-1)～compound (IV-3), at least a and at least a mixture and the acid anhydrides that are selected from the diamines in described compound (VII-1)～compound (VII-3) and compound (the VIII-1)～compound (VIII-6) of the diamines in compound (V-1) and compound (VI-1)～compound (VI-7) react.The preferable example of this acid anhydrides is the acid anhydrides that is selected from described compound (A-1), compound (A-2), compound (A-12), compound (A-14), compound (A-18), compound (A-20), compound (A-21), compound (A-37), compound (VII-4), compound (VII-5), compound (VIII-7) and the compound (VIII-8).And, when diamines that selection from compound (VII-1)～compound (VII-3) can be made up with the diamines with photosensitive group, good especially acid anhydrides is compound (VIII-7) or compound (VIII-8), when diamines that selection from compound (VIII-1)～compound (VIII-6) can be made up with the diamines with photosensitive group, good especially acid anhydrides is compound (VII-4) or compound (VII-5).
The polyamic acid that the 4th good example of polyamic acid is in the following way to be obtained, that is, described at least a mixture and diamines at least a and by the represented acid anhydrides of formula (VII-4), formula (VII-5), formula (VIII-7) and formula (VIII-8) by the represented acid anhydrides with photosensitive group of formula (IV-4) and formula (VI-8) reacted.The preferable example of this diamines be selected from described by the diamines in the represented compound of formula (VII-1)～formula (VII-3) and formula (VIII-1)～formula (VIII-6).
Figure GSA00000016952200451
(the R in these formulas 5Implication as mentioned above)
The polyamic acid that the 5th good example of polyamic acid is in the following way to be obtained, that is, make and describedly describedly react with being selected from by at least a mixture and acid anhydrides in the represented diamines of formula (2)～formula (4) by at least a of the represented diamines of formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), formula (V-1) and formula (VI-1)～formula (VI-7) with photosensitive group.The preferable example of this acid anhydrides be selected from described by the acid anhydrides in the represented compound of formula (A-1), formula (A-2), formula (A-12), formula (A-14), formula (A-18), formula (A-20), formula (A-21), formula (A-37), formula (VII-4), formula (VII-5), formula (VIII-7) and formula (VIII-8).And what this acid anhydrides was good especially is compound (VII-4) and compound (VII-5).
The polyamic acid that the 6th good example of polyamic acid is in the following way to be obtained, that is, make described by formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), the diamines that formula (V-1) and formula (VI-1)～formula (VI-7) is represented at least a with photosensitive group, described by at least a of the represented diamines of formula (VII-1)～formula (VII-3) and formula (VIII-1)～formula (VIII-6) and be selected from and describedly react by at least a mixture and acid anhydrides in the represented diamines of formula (2)～formula (4).The preferable example of this acid anhydrides be selected from described by the acid anhydrides in the represented compound of formula (A-1), formula (A-2), formula (A-12), formula (A-14), formula (A-18), formula (A-20), formula (A-21), formula (A-37), formula (VII-4), formula (VII-5), formula (VIII-7) and formula (VIII-8).
The 7th good example of polyamic acid be by make by at least a of the represented diamines of formula (VII-1)～formula (VII-3) with reacted the polyamic acid that obtains by the represented tetracarboxylic dianhydride of formula (VIII-7) and formula (VIII-8) at least a or by making by at least a of the represented diamines of formula (VIII-1)～formula (VIII-6) and at least a polyamic acid that obtains that reacts by the represented tetracarboxylic dianhydride of formula (VII-4) and formula (VII-5).
H 2N-R 4-NH 2????????????????(VII-1)
Figure GSA00000016952200461
(the R in these formulas 4And R 5Implication for as mentioned above).
Figure GSA00000016952200471
And, the preferable example of orientation agent of the present invention is the orientation agent that contains a kind of polyamic acid that is selected from described 7 kinds of preferable polyamic acids or the polyimide that dehydration reaction obtained by this polyamic acid, but selected polyamic acid also can be two or more.In addition, if do not hinder in the scope of effect of the present invention, orientation agent so of the present invention also can contain the general polyamic acid except described example except comprising described 7 kinds of polyamic acids at least a.That is, in the present invention, as long as satisfy the condition that has the film of liquid crystal temperature range between 100 ℃ to 300 ℃ that is formed on, just can be except described polyamic acid, and maybe can't be formed on polyamic acid of the film that has liquid crystal temperature range between 100 ℃ to 300 ℃ etc. with the polyamic acid that does not have photosensitive group on the main chain.When the polyamic acid that uses this kind except described example, the ratio of this polyamic acid is preferably less than 20wt% less than the 50wt% in the formation of the film in the orientation agent composition total amount.
Just regulate alignment film for regard to the viewpoint of the connecting airtight property of glass substrate, orientation agent of the present invention also can further include organic silicon compound.The example of silicoorganic compound is aminopropyl trimethoxysilane (aminopropyltrimethoxysilane), aminopropyl triethoxysilane, vinyltrimethoxy silane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, vinyltriethoxysilane, the 3-methacryloxypropyl trimethoxy silane, the 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 2-(3,4-epoxy group(ing) cyclohexyl) silane coupling agent such as ethyl trimethoxy silane, and dimethyl polysiloxane (dimethylpolysiloxane), polydimethylsiloxane, silicone oil (silicone oil) such as poly-diphenyl siloxane.
The adding proportion of these silicoorganic compound in the orientation agent is so long as can obtain the scope of effect of the present invention, and there is no particular restriction so.Yet,, have the orientation condition of poor that produces liquid crystal when making alignment film so if add a large amount of described silicoorganic compound.Therefore, when being added with organic silicon compound, the concentration of these silicoorganic compound is preferably the scope of 0.01wt%～5wt% with respect to the total amount of the component of polymer that is contained in the orientation agent, and good especially is the scope of 0.1wt%～3wt%.
The deterioration or for the viewpoint of the caused deterioration of environment with regard to preventing characteristic from changing in time, orientation agent of the present invention also can further contain the compound with the functional group who reacts with the carboxylic acid residues of polyamic acid more than 2 or 2, promptly so-called linking agent.As the example of this kind linking agent, can enumerate: open the multi-functional epoxyization thing that disclosed in 2005-275360 communique, the Japanese patent laid-open 10-212484 communique etc., isocyanic ester (isocyanate) material etc. as Japanese Patent No. 3049699 communique, Japanese Patent spy.
And, react and become cancellated polymkeric substance as linking agent itself, thereby the linking agent that improves the film toughness of polyamic acid or polyimide also can be used for the purpose identical with described purpose.As this kind linking agent, can enumerate: open multifunctional Vinyl Ether (vinyl ether), maleimide (maleimide) or diallyl Na Dike imide (bis-allyl-nadi-imide) derivative etc. that disclosed in 2004-341030 communique etc. as Japanese patent laid-open 10-310608 communique, Japanese Patent spy.The ratio of these linking agents is preferably 0wt%～50wt% with respect to the total amount of component of polymer, is more preferably 0wt%～30wt%.
Orientation agent of the present invention contains the solvent of the ability with dissolving polyamic acid.Described solvent widely be included in the manufacturing of polyamic acid or derivatives thereof or use in the solvent that generally uses, can suitably select according to application target.If it is enumerate these solvents, so as follows.
As for polyamic acid, being the example of the non-proton property polar organic solvent of good solvent (good solvent), can enumerate: N-N-methyl-2-2-pyrrolidone N-(N-Methyl-2-pyrrolidinone, NMP), dimethyl-imidazolinone (dimethylimidazolidinone), N-methyl caprolactam (N-Methyl caprolactam), N-methyl propanamide (N-methyl propionamide), N, N-N,N-DIMETHYLACETAMIDE (N, N-dimethylacetamide), dimethyl sulfoxide (DMSO) (dimethyl sulfoxide), N, dinethylformamide (N, N-dimethyl formamide, DMF), N, N-diethylformamide (N, N-diethyl formamide), N, N-diethyl acetamide (N, N-diethylacetamide, DEAc), and gamma-butyrolactone (γ-butyrolactone, GBL) lactone (lactone) such as grade.
As except that described solvent, being the example of other solvents of purpose to improve coating etc., can enumerate: lactic acid alkyl ester (alkyl lactate), 3-methyl-3-methoxybutanol (3-methyl-3-methoxybutanol), tetraline (tetralin), isophorone (isophorone), ethylene glycol monobutyl ether (ethylene glycol monobutyl ether, ethylene glycol monoalkyl ether such as BCS), Diethylene Glycol monoalky lethers such as diethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetate and ethyleneglycol monophenylether acetic ester, the triethylene glycol monoalky lether, propylene-glycol monoalky lethers such as propylene glycol monobutyl ether, dialkyl malonates such as diethyl malonate, dipropylene glycol monoalky lethers such as dipropylene glycol monomethyl ether, and the ester cpds of these glycol monoethers etc.Among these compounds, can in described solvent, use NMP, dimethyl-imidazolinone, GBL, BCS, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether etc. particularly well.
Orientation agent of the present invention also can be according to required and further contain various additives.For example, when expectation further improves coating, tensio-active agent can be contained in right amount, when needs further improve antistatic effect, static inhibitor can be contained in right amount according to described purpose.
The concentration of the polyamic acid in the orientation agent of the present invention is preferably 0.1wt%～40wt%.When being coated on this orientation agent on the substrate,, must carry out diluting by solvent in advance the operation of the polyamic acid that is contained sometimes in order to adjust thickness.
Be not particularly limited for the solid component concentration in the orientation agent of the present invention, as long as select optimum value according to following various coating methods.Usually, the inequality in order to suppress to be coated with or hole (pinhole) etc., solid component concentration is preferably 0.1wt%～30wt% with respect to varnish (varnish) weight, is more preferably 1wt%～10wt%.
Alignment film of the present invention is to obtain in the following way,, gives anisotropy by friction or rayed to the film that is coated on described orientation agent on the substrate to be obtained that is, the anisotropy of film is increased till being heated to the liquid crystal temperature range of film then.
With regard to the viewpoint that shows sufficient regiospecific this moment, be preferably according to following order manufacturing:
(1) by hairbrush coating method, pickling process, method of spin coating, spray method, print process etc., described varnish is coated on the substrate;
(2) 50 ℃～120 ℃, be preferably formed film on 80 ℃～100 ℃ following heated substrates, and make solvent evaporation;
(3) described film irradiates light is made polyamic acid orientation in the described film;
(4) 150 ℃～300 ℃, be preferably 180 ℃～250 ℃ down heating make the described film of polyamic acid orientation, and make described film imidization.
In addition, when wanting in the liquid crystal display device of use alignment film, to show the tilt angle of regulation, can carry out by the following method, promptly when irradiates light, from angle arbitrarily substrate is shone rectilinearly polarized light, perhaps will to substrate carry out from the rectilinearly polarized light irradiation of vertical direction with made up from the non-polarized light irradiation of angle arbitrarily.
In the manufacturing of alignment film of the present invention, when the orientation of described polyamic acid, use rectilinearly polarized light.The polyamic acid main chain because of the irradiation of rectilinearly polarized light with the vertical direction of the direction of polarized light of rectilinearly polarized light on orientation.Described rectilinearly polarized light is not particularly limited so so long as can make the light of the polyamic acid orientation in the described film.Alignment film of the present invention can make the film orientation by low-energy rayed.The irradiation dose of the rectilinearly polarized light during therefore, the light orientation of described polyamic acid is handled is preferably 0.5J/cm 2～10J/cm 2And the wavelength of rectilinearly polarized light is preferably 300nm～400nm.The irradiating angle for the film surface of rectilinearly polarized light is not particularly limited, but when the stronger orientation restraint wanting to show for liquid crystal, and with regard to the viewpoint that shortens the orientation treatment time, irradiating angle is preferably as far as possible and the film Surface Vertical.
And in the manufacturing of alignment film of the present invention, the light that shines described film when wanting to show tilt angle both can be that polarized light can be a non-polarized light.The irradiation dose that shines the light of described film when wanting to show tilt angle is preferably 0.5J/cm 2～10J/cm 2, this light wavelength is preferably 300nm～400nm.The irradiating angle for described film surface that shines the light of described film when wanting to show tilt angle is not particularly limited, but with regard to the viewpoint that shortens the orientation treatment time, is preferably 30 degree～60 degree.
Alignment film of the present invention is characterised in that the anisotropy with king-sized orientation.The anisotropic size of this kind can be opened the use polarized light infrared rays that is disclosed among 2005-275364 etc. by the Japanese Patent spy, and (Infra-red, method IR) is estimated.And, shown in following examples, also can estimate by the method for utilizing ellipsometry (ellipsometry).When alignment film of the present invention is used alignment film as liquid-crystal composition, it is generally acknowledged that the anisotropic material with bigger film has bigger orientation restraint for liquid-crystal composition.
The orientation purposes of the liquid-crystal composition that alignment film of the present invention is used except liquid-crystal display, can be used to control the orientation of optical compensation material or other all liquid crystal materials.And, because alignment film of the present invention has bigger anisotropy, therefore can be used for the optical compensation material applications separately.
The invention provides a kind of liquid crystal display device, this liquid crystal display device comprise subtend configuration a pair of substrate, a side of the face of described a pair of substrate subtend separately or the formed electrode of both sides, the formed liquid crystal orienting film of face of described a pair of substrate subtend separately and between described a pair of substrate formed liquid crystal layer, described liquid crystal orienting film is an alignment film of the present invention.
Described electrode is so long as at the formed electrode of the one side of substrate, be not particularly limited so.This kind electrode for example can enumerate tin indium oxide (Indium Tin Oxide, ITO) or the vapor-deposited film of metal etc.And electrode also can be formed on whole of one side of substrate, for example can form patterned required shape.The described required shape of electrode for example can be enumerated interdigitated electrode structure or broached-tooth design etc.Electrode can be formed on the substrate in a pair of substrate, also can be formed on two substrates.The formation form of electrode is according to the kind of liquid crystal display device and different, for example when IPS type liquid crystal display device, described a pair of substrate one on configured electrodes, when other liquid crystal display device, electrode is configured in described a pair of substrate on both.On described substrate or electrode, form described liquid crystal orienting film.
Described liquid crystal layer is with by the form of the described a pair of substrate holding liquid crystal constituent of the face institute subtend that is formed with liquid crystal orienting film and form.When forming liquid crystal layer, can use micropartical or resin sheet etc. between described a pair of substrate and form the spacing piece (spacer) of appropriate intervals as required.Be not particularly limited for described liquid-crystal composition, can use well-known liquid-crystal composition.
When alignment film of the present invention forms liquid crystal display device as liquid crystal orienting film, with respect to well-known all liquid-crystal compositions, can improve the characteristic of liquid crystal display device, but adopt the alignment film of the present invention of described method manufacturing, especially to the orientation defective of the big view display that is difficult to carry out friction treatment to improve effect bigger.The big view display of this kind is to drive control by TFT.And employed liquid-crystal composition discloses in No. 3086228 communique of Japanese Patent, No. 2635435 communiques of Japanese Patent, the special flat 5-501735 communique of table of Japanese Patent and Japanese patent laid-open 9-255956 communique to some extent in this kind TFT type liquid crystal display device.Therefore, alignment film of the present invention be preferably with these communiques in the liquid-crystal composition that disclosed be used in combination.
The liquid crystal characteristic evaluating apparatus OMS-CA3 type that tilt angle in the liquid crystal display device of the present invention can use for example central smart machine to make, and employing Journal of Applied Physics, Vol.48, No.5, the crystal rotation method (Crystal rotationmethod) that is p.1783-1792 disclosed in (1977) is measured.
Liquid crystal display device of the present invention is more excellent aspect the electrical property relevant with the reliability of liquid crystal display device.As this kind electrical property, can enumerate voltage retention and ion density (iondensity).
Voltage retention (VHR) is that the voltage that is applied to liquid crystal display device during the frame period (frame period) remains in the ratio in the liquid crystal display device, and this voltage retention is represented the display characteristic of liquid crystal display device.With regard to preventing to show bad viewpoint, liquid crystal display device of the present invention is preferably and uses 5V and the frequency square wave as 30Hz, and the voltage retention of measuring under 60 ℃ temperature condition is more than or equal to 90.0%, perhaps use 5V and frequency square wave, and the voltage retention of measuring is more than or equal to 85.0% under 60 ℃ temperature condition as 0.3Hz.
Ion density be produce when liquid crystal display device is applied voltage except by the transient current the caused electric current of liquid crystal drive (transient current), this ion density is represented the size of the concentration of the ionic impurity that contained in the liquid crystal in the liquid crystal display device.With regard to the viewpoint of the trace that prevents liquid crystal display device, the ion density of liquid crystal display device of the present invention is preferably smaller or equal to 500pC.
[embodiment]
Below, the present invention will be described by embodiment and comparative example, but the present invention is not limited to these embodiment.Pyromellitic acid anhydride (pyromellitic anhydride, PMDA, compound (A-1)), 1,2,3,4-tetramethylene tetracarboxylic acid (1,2,3,4-cyclobutanetet racarboxylic acid, CBTA, compound (A-14)) and compound (2-13) be to be used for experiment after with commercially available compound purifying by recrystallize.1,8-octamethylenediamine (1,8-Diaminooctane, DAO, compound (VII-1-1)) is that commercially available product distillation back is used.Compound (II-1), compound (A-21) are to open clear 58-109479 communique according to special fair 5-65530 communique of Japanese Patent and Japanese Patent spy respectively and synthesize.Following compound (VII-2-1), compound (VII-2-2) and compound (VII-5-1) are according to Japanese patent laid-open 11-160712 communique and Bulletin de la Societe Chimique de France, 9-10, Pr.2, the method that is disclosed in 2195 (1975) and synthesizing.Compound (VIII-5) and compound (VIII-6) are commercially available product not to be carried out purifying and it is directly used in the experiment.Compound (VIII-8) is to be used for experiment after with the commercially available product recrystallize by ethanol.Compound (2-22) and compound (3-5-1) are to adopt and Journal of Polymer Science Part A:PolymerChemistry, 30 (6), 1099 (1992), it is synthetic that the Japanese Patent spy opens the identical method of the method that disclosed in the 2002-162630 communique.Compound (A-21) is to open clear 58-109479 communique and synthesize according to the Japanese Patent spy.The preparation of polymkeric substance is to carry out in nitrogen gas stream.
Figure GSA00000016952200531
Rayed is to use contains the 250W high pressure mercury vapour lamp that flourish hall is sold in the well, illumination wavelength is the ultraviolet ray about 300nm～380nm.Irradiation is to carry out in room temperature, air.
The evaluation assessment of below representing employed liquid crystal display device among the embodiment.
Delay of＜alignment film (retardation) and determining film thickness 〉
Use elliptic polarization spectrometer (spectroscopic ellipsometer) M-2000U (J.A.Woollam Co.Inc. manufacturing) to obtain.In the present embodiment, the orientation degree of the length of delay of film and main polymer chain increases pro rata.That is the film with bigger length of delay has bigger orientation degree.
＜ultraviolet-visible (ultraviolet-visible spectrum, UV-Vis) spectrographic is measured 〉
Using UV-Vis spectrometry device (Japanese beam split V-660), is that reference (reference) is measured with the glass substrate that is not formed with alignment film.
＜voltage retention 〉
Adopt the method that is disclosed in " water island etc., the 14th liquid crystal discussion preliminary draft collection p78 (1988) " to measure.Mensuration is unit (cell) to be applied wave height carry out for the square wave of ± 4.5V.Mensuration is to carry out under 60 ℃.This value is the index that the voltage that applied of expression with which kind of degree was maintained after the frame period, if this value reaches 100%, represents that so whole electric charges all are maintained.
Ionic weight in the＜liquid crystal is measured (ion density) 〉
According to Applied Physics, the 65th volume, the method that disclosed in No. 10,1065 (1996), liquid crystal physical property measurement system 6254 types that use Toyo Corporation company to make are measured.Frequency of utilization is the choppy sea of 0.01Hz, measures under 60 ℃ temperature with the voltage range of ± 10V.If ion density is bigger, be easy to generate so by unfavorable conditions such as the caused traces of ionic impurity.That is ion density is the physics value that becomes the index of prediction trace generation.
＜viscosity 〉
Use rotational viscosimeter (TV-22L, eastern machine industry (TOKI SANGYO) company makes) to measure.
＜weight average molecular weight (weight-average molecular weight, Mw) 〉
The weight average molecular weight of the polyamic acid in the LCD alignment agent (Mw) is utilized gel permeation chromatograph (Gel Permeation chromatography, GPC), and use that 0.6wt%'s contain phosphoric acid DMF as dissolution fluid, under 50 ℃ tubing string temperature, polystyrene is measured as standardized solution.Tubing string uses Shodex GF-7M HQ (clear and electrician company makes).
The affirmation of＜high molecule liquid crystal 〉
Under 230 ℃ to film forming film on substrate (the about 70nm of thickness) calcining 10 minutes after, utilize polarization microscope to observe.In addition, heat-up rate is made as 3 ℃/min.
＜glass tansition temperature 〉
(Differential Scanning Calorimet ry DSC) measures to use differential scanning calorimetric measurement device.Heat-up rate is made as 8 ℃/min.
＜unitary black level (black level) is confirmed 〉
Unit to made carries out polarized light microscope observing, and judges according to following table.
Figure GSA00000016952200541
[synthesis example 1]
Synthesizing of＜compound (VII-2-3) 〉
Figure GSA00000016952200542
Synthesize in the mode identical with the compound of (VII-2-2).Fusing point: 98.0 ℃～99.2 ℃.
[synthesis example 2]
Synthesizing of＜compound (VII-4-1) 〉
Figure GSA00000016952200543
With 4-phthalate bromine diethyl ester (50g, 166mmol), 1, hot diine (the 8.7g of 7-, 82mmol), triphenylphosphine palladium chloride (II) (290mg, 0.41mmol) and cupric iodide (158mmol, 0.83mmol) mixture under nitrogen gas stream, in triethylamine (200ml), refluxed 4 hours.After question response finishes, add toluene (500ml) and pure water (500ml) and extract.After cleaning once with pure water (300ml) organic layer, utilize anhydrous magnesium sulfate to carry out drying.Filter and underpressure distillation removal solvent, thereby obtain, two (3,4-dicarboxyl phenyl) the ethynyl butane tetra-ethyl esters of 4-as 1 of target compound.Output is 42g, and productive rate is 95%.This compound is purified and be directly used in the next reaction.
1, two (3,4-dicarboxyl phenyl) the ethynyl butane tetra-ethyl esters of 4-(42g, 77mmol) palladium-carbon catalyst (Pd/C) of middle interpolation 5wt% is (2.1g), then in toluene/ethanol mixed solvent (300ml/300ml), carry out hydrogenation with the hydrogen pressure of 720MPa.After question response finishes, filter and remove catalyzer, and solvent is removed in underpressure distillation.With residue utilization tubing string chromatography (columnchromatography) (silica gel/toluene: vinyl acetic monomer=10: 1v/v) carry out purifying, thereby obtain, two (3,4-dicarboxyl phenyl) the octane tetra-ethyl esters of 8-as 1 of target compound.Output is 43g, and productive rate is 100%.
With 1, (43g 77mmol) is dissolved in the ethanol (250ml) two (3,4-dicarboxyl phenyl) the octane tetra-ethyl esters of 8-, and adds 5.7% aqueous sodium hydroxide solution (250ml), refluxes then 2 hours.Behind the question response, solvent is removed in underpressure distillation, adds concentrated hydrochloric acid then and reaches till 1 until the pH value.Filter after the throw out that is produced, throw out is cleaned 3 times with pure water (200ml).Drying under reduced pressure is carried out in the crystallization that is obtained, obtain 1 thus, two (3, the 4-dicarboxyl phenyl) octanes of 8-.Output is 31g, and productive rate is 90%.
1, (10g, 23mmol) the middle acetic anhydride (50ml) that adds refluxed 2 hours two (3, the 4-dicarboxyl phenyl) octanes of 8-then.Underpressure distillation is removed after the acetic anhydride, adds hexanaphthene (50ml) in residuum, filters the throw out that is produced.Drying under reduced pressure is carried out in the crystallization that is obtained, obtain compound (VII-4-1) thus.Output is 9.2g, and productive rate is 97%.Fusing point: 109.7～111.2 ℃.
1H?NMR(500Hz，CDCl 3)；δ(ppm)7.92(d，4H，J＝7.80Hz)，7.70(d，4H，J＝8.1Hz)，2.82(t，4H，J＝7.65Hz)，1.3-1.7(m，12H).
[synthesis example 3]
The preparation of＜polyamide acid varnish A 〉
With compound (II-1) (0.1818g, 0.7827mmol) be dissolved in the N-N-methyl-2-2-pyrrolidone N-(NMP, 3.0g) in, (0.3182g 0.7829mmol) remains in room temperature or below the room temperature to one side, and one side is added with compound (VII-4-1).After stirring an evening, (BSC 3.0g) prepares varnish A to add NMP (3.5g) and ethylene glycol monobutyl ether.The viscosity of varnish A is 49.8mPas.The weight average molecular weight of the polyamic acid of this varnish is 74,000, has mesomorphic phase in 200 ℃～300 ℃ scope.
[synthesis example 4～14]
The preparation of＜polyamide acid varnish B～L 〉
Press the raw material shown in the table 1 and form, adopt the method identical to prepare the varnish B～varnish L of polyamic acid, and measure rerum natura in the mode identical with synthesis example 1 with synthesis example 1.Expression mol% in the bracket.In addition, according to described assay method these all varnish are carried out the affirmation of mesomorphic phase, there is mesomorphic phase in the result in 170 ℃～250 ℃ scope.
＜table 1 〉
Synthesis example No. The varnish title Diamines Acid anhydrides Viscosity (mPa.s) Weight average molecular weight
??3 ??A ??II-1 ??VII-4-1 ??49.8 ??74,000
??4 ??B ??VI-1 ??VII-4-1 ??25.8 ??48,000
??5 ??C ??VII-1-1(80)??I-1(20) ??VIII-8 ??33.3 ??55,000
??6 ??D ??VII-1-1(80)??VI-1(20) ??VIII-8 ??28.3 ??50,000
??7 ??E ??VII-1-1(80)??VI-1(20) ??VIII-8(90)??A-14(10) ??37.9 ??68,000
Synthesis example No. The varnish title Diamines Acid anhydrides Viscosity (mPa.s) Weight average molecular weight
??8 ??F ??II-1(40)??VI-1(40)??(2-22)(20) ??VII-4-1 ??30.8 ??51,000
??9 ??G ??VII-2 ??VIII-8 ??30.4 ??60,000
??10 ??H ??VIII-1 ??VII-4-1 ??27.6 ??48,000
??11 ??I ??VIII-5 ??VII-4-1 ??34.2 ??54,000
??12 ??J ??VIII-6 ??VII-4-1 ??37.1 ??62,000
??13 ??K ??VIII-6 ??VII-5-1 ??19.2 ??28,000
??14 ??L ??VI-1 ??VII-4-1(90)??A-21(10) ??28.7 ??49,000
[embodiment 1]
In sample bottle, take by weighing the varnish A of 1.0g, and add NMP/BC=1/1 (weight ratio) and reach 1.67g.On transparent glass substrate, drip the polyamic acid solution of this about 3wt%, and adopt method of spin coating to be coated with (2,000rpm, 15 seconds).After to be coated, 80 ℃ of following heated substrates 3 minutes, make after the solvent evaporation, being situated between, (365nm and energy are about 1.3J/cm every polarization plate irradiation rectilinearly polarized light 2).In baking oven (oven), the substrate after the rayed is carried out 15 minutes heat treated, thereby obtain the alignment film A that thickness is about 100nm with 210 ℃.Measure the delay of this alignment film A, the result is 12.9nm.
[embodiment 2～embodiment 6]
Use the varnish shown in the table 2, obtain alignment film B～alignment film F in the mode identical with embodiment 1.Represent in the lump measuring the result of delay gained and the result of embodiment 1.
＜table 2 〉
Embodiment No. The varnish title The alignment film title Postpone (nm)
??1??2??3??4??5??6 ??A??B??C??D??E??F ??A??B??C??D??E??F ??12.9??27.8??13.7??7.9??5.6??24.0
[embodiment 7]
Use respectively mixes the varnish M that 0.5g forms respectively with varnish A and varnish B and replaces varnish A, in addition, makes alignment film M according to the method identical with embodiment 1.The length of delay of this alignment film M is 30.5nm.
[comparative example 1]
With compound (II-1) (2.6432g 11.38mmol) is dissolved among the NMP (35.0g), one side with PMDA (1.2410g, 5.690mmol) and CBTA (1.1158g 5.690mmol) remains in room temperature or below the room temperature, and one side is added.After at room temperature stirring an evening, add NMP (35g) and BSC (25g).The viscosity of this solution is 120mPas.60 ℃ of following stir abouts 4 hours, is the varnish N of 28.0mPas thereby obtain viscosity with this solution.The weight average molecular weight of the polyamic acid of this varnish is 37,000, and glass tansition temperature (Tg) is above 300 ℃.
Use varnish N, obtain alignment film N in the mode identical, and measure the delay of this alignment film N with embodiment 1.The result is 0.4nm.
[comparative example 2]
Use compound (VI-1) to replace compound (II-1), in addition, obtain the varnish P that viscosity is 34.0mPas in the mode identical with comparative example 1.The weight average molecular weight of the polyamic acid of this varnish is 54,000, and glass tansition temperature (Tg) is above 300 ℃.
Use varnish P, obtain alignment film P in the mode identical, and measure the delay of this alignment film P with embodiment 1.The result is 0.8nm.
If embodiment and comparative example 1 and comparative example 2 are compared, the alignment film of the present invention that uses polymkeric substance of the present invention so as can be known and obtained is than the alignment film by the polymkeric substance made that does not have liquid crystal liquid crystal property, even if with less irradiation energy, also has very large length of delay.
[embodiment 8]
Glass substrate replaced in one side be provided with the transparent glass substrate of ITO electrode, in addition, obtain the alignment film A that thickness is about 100nm in the mode identical with embodiment 1.2 substrates that are formed with these alignment films on I TO electrode are fitted as follows: make the direction of polarized light of the rectilinearly polarized light that shines each alignment film parallel, and make be formed with alignment film face relatively to, and then relatively to alignment film between be formed for injecting the space of liquid-crystal composition, thereby be assembled into the liquid crystal cells A (liquid crystal display device) that element thickness is 7 μ m.And, liquid-crystal composition A shown below is injected in these unit.
＜liquid-crystal composition A 〉
Figure GSA00000016952200581
By this liquid crystal cells of visual observation A, the result does not observe the mobile orientation of what is called that liquid crystal is arranged along liquid crystal mobile direction fully.If polarization microscope is made as crossed polarized light (crossnicol) state, and make liquid crystal cells A rotation, observe bright clearly attitude (light state) and dark attitude (dark state) so.The tilt angle of this liquid crystal cells A is 0.0 °.And VHR (voltage retention) is 99.0% (30Hz), 85.0% (0.3Hz), and ion density is 120pC.
And, observe the result of the black level of this liquid crystal cells A, in observed all zones, see smaller particles shape spot, but still be good black level.
[embodiment 9]
Employed varnish is replaced to varnish B, in addition, make liquid crystal cells B in the mode identical with embodiment 8.The tilt angle of this liquid crystal cells B is 0.0 °.And VHR (voltage retention) is 92.2% (30Hz), 76.3% (0.3Hz), and ion density is 340pC.
And, observe the result of the black level of this liquid crystal cells B, in observed all zones, can't see the particulate state spot fully, this black level is very good black level.
[embodiment 10]
Employed varnish is replaced to varnish F, in addition, make liquid crystal cells F in the mode identical with embodiment 8.The tilt angle of this liquid crystal cells F is 0.0 °.And VHR (voltage retention) is 99.2% (30Hz), 85.3% (0.3Hz), and ion density is 80pC.
Observe the result of the black level of this liquid crystal cells F, can't see the particulate state spot fully in observed all zones, this black level is very good black level.
[embodiment 11]
Employed varnish is replaced to varnish L, in addition, make liquid crystal cells L in the mode identical with embodiment 8.The tilt angle of this liquid crystal cells L is 0.0 °.And VHR (voltage retention) is 99.4% (30Hz), 88.2% (0.3Hz), and ion density is 35pC.
And, observe the result of the black level of this liquid crystal cells L, in observed all zones, can't see the particulate state spot fully, this black level is very good black level.
[embodiment 12]
Employed varnish is replaced to varnish M, in addition, make liquid crystal cells M in the mode identical with embodiment 8.The tilt angle of this liquid crystal cells M is 0.1 °.And VHR (voltage retention) is 99.0% (30Hz), 82.1% (0.3Hz), and ion density is 120pC.
And, observe the result of the black level of this liquid crystal cells M, in observed all zones, can't see the particulate state spot fully, this black level is very good black level.
[comparative example 3]
Employed varnish is replaced to varnish N, in addition, make liquid crystal cells N in the mode identical with embodiment 8.The tilt angle of this liquid crystal cells N is 0.1 °.And VHR (voltage retention) is 99.1% (30Hz), 76.0% (0.3Hz), and ion density is 300pC.
And, observe the result of the black level of this liquid crystal cells N, in observed all zones, see bigger particulate state spot, comparing with the liquid crystal display device that uses alignment film of the present invention is the black level of non-constant.
[comparative example 4]
Employed varnish is replaced to varnish P, in addition, make liquid crystal cells P in the mode identical with embodiment 8.The tilt angle of this liquid crystal cells P is 0.0 °.And VHR (voltage retention) is 92.4% (30Hz), 85.3% (0.3Hz), and ion density is 110pC.
And, observe the result of the black level of this liquid crystal cells P, in observed all zones, see bigger particulate state spot, comparing with the liquid crystal display device that uses alignment film of the present invention is relatively poor black level.
[embodiment 13]
In the mode identical with embodiment 1, be provided with rotary coating varnish A on the transparent glass substrate of ITO electrode in one side, then with substrate 80 ℃ of heating 3 minutes and after making solvent evaporation down, in baking oven with 210 ℃ of heating and calcinings that carry out 15 minutes.The polyimide film that the thickness that is obtained is about 100nm carries out friction treatment (amount of being pressed into: 0.3mm, platform transfer rate: 60m/s, rotating speed: 1000rpm, friction cloth: YA-18-R (artificial silk)).Then, in ultrapure water, alignment film is carried out after 5 minutes the ultrasonic cleaning, in baking oven with 200 ℃ of dryings 15 minutes.
2 substrates that are formed with these alignment films on the ITO electrode are fitted as follows: make for the frictional direction of each alignment film antiparallel, and make be formed with alignment film face relatively to, and then relatively to alignment film between be formed for injecting the space of liquid-crystal composition, thereby be assembled into the liquid crystal cells Ar that element thickness is 7 μ m.And, described liquid-crystal composition A is injected in these unit.
The tilt angle of this liquid crystal cells Ar is 0.3 °, and VHR (voltage retention) is 98.7% (30Hz), 80.2% (0.3Hz), and ion density is 230pC.And, observe the result of the black level of this liquid crystal cells Ar, in observed all zones, can't see the scar that is produced by friction fully, this black level is and then very good black level.
[embodiment 14]
Used varnish J to replace varnish A, in addition, be assembled into the liquid crystal cells Jr that element thickness is 7 μ m in the mode identical with embodiment 13.The tilt angle of this liquid crystal cells Jr is 0.5 degree, and VHR (voltage retention) is 99.1% (30Hz), 87.5% (0.3Hz), and ion density is 78pC.
And, observe the result of the black level of this liquid crystal cells Jr, in observed all zones, can't see the scar that is produced by friction fully, this black level is and then very good black level.
As mentioned above, when alignment film of the present invention is applied to the alignment film of used for liquid crystal display element, can increase substantially black level.And, alignment film of the present invention as can be known have can be durable sufficient electrical property.

Claims (22)

1. orientation agent, it is to contain to be selected from polyamic acid and by at least a polymkeric substance in the polyimide that dehydration reaction obtained of this polyamic acid and the constituent of solvent, to it is characterized in that:
The concentration of the polymkeric substance in this constituent is 0.1wt%～40wt%, the total amount that forms composition with the film that contained in this constituent is that the ratio of the described polymkeric substance of benchmark is 50wt%～100wt%, and can be formed on the film that has liquid crystal temperature range between 100 ℃～300 ℃ by making this constituent film forming.
2. orientation agent according to claim 1 is characterized in that:
Polyamic acid is the polyamic acid that has photosensitive group on the main chain.
3. orientation agent according to claim 2 is characterized in that:
Photosensitive group is at least a by the represented group of formula (I)～formula (VI):
-R 1-C≡C-R 2-????????????(I)
-R 1-C≡C-C≡C-R 2-???????(II)
-R 1-C≡C-CH＝CH-R 2-?????(III)
-R 1-C≡C-R 2-C≡C-R 3-????(IV)
-R 1-C≡C-R 2-CH＝CH-R 3-??(V)
-N＝N-??????????????????(VI)
Herein, R 1, R 2And R 3Independent is aromatic divalent group.
4. orientation agent according to claim 2 is characterized in that:
The polyamic acid that the polyamic acid that has photosensitive group on the main chain is in the following way to be obtained makes by formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), the diamines that formula (V-1) and formula (VI-1)～formula (VI-7) is represented with photosensitive group at least a with by formula (A-1), formula (A-2), formula (A-12), formula (A-14), formula (A-18), formula (A-20), formula (A-21), formula (A-37), formula (VII-4), formula (VII-5), formula (VIII-7) and represented at least a of tetracarboxylic dianhydride of formula (VIII-8) react:
Figure FSA00000016952100011
Figure FSA00000016952100021
Herein, R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group.
5. orientation agent according to claim 2 is characterized in that:
The polyamic acid that the polyamic acid that has photosensitive group on the main chain is in the following way to be obtained, make by at least a of the represented tetracarboxylic dianhydride of formula (IV-4) and formula (VI-8) with photosensitive group with react by represented at least a of diamines of formula (VII-1)～formula (VII-3) and formula (VIII-1)～formula (VIII-6):
Herein, R 4Be that carbon number is 6～20 alkylidene group; R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group;
Figure FSA00000016952100042
6. orientation agent according to claim 2 is characterized in that:
The polyamic acid that the polyamic acid that has photosensitive group on the main chain is in the following way to be obtained makes by formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), the diamines that formula (V-1) and formula (VI-1)～formula (VI-7) is represented with photosensitive group at least a with by at least a mixture of the represented diamines of formula (VII-1)～formula (VII-3) and formula (VIII-1)～formula (VIII-6) with by formula (A-1), formula (A-2), formula (A-12), formula (A-14), formula (A-18), formula (A-20), formula (A-21), formula (A-37), formula (VII-4), formula (VII-5), formula (VIII-7) and represented at least a of tetracarboxylic dianhydride of formula (VIII-8) react:
Herein, R 4Be that carbon number is 6～20 alkylidene group; R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group;
Figure FSA00000016952100062
Figure FSA00000016952100081
Herein, R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group.
7. orientation agent according to claim 2 is characterized in that:
The polyamic acid that the polyamic acid that has photosensitive group on the main chain is in the following way to be obtained, make by at least a of the represented tetracarboxylic dianhydride of formula (IV-4) and formula (VI-8) with photosensitive group with react by the represented tetracarboxylic dianhydride's of formula (VII-4), formula (VII-5), formula (VIII-7) and formula (VIII-8) at least a mixture with by represented at least a of diamines of formula (VII-1)～formula (VII-3) and formula (VIII-1)～formula (VIII-6):
Figure FSA00000016952100082
Herein, R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group;
H 2N-R 4-NH 2????????????????????????(VII-1)
Figure FSA00000016952100091
Herein, R 4Be that carbon number is 6～20 alkylidene group; R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group;
Figure FSA00000016952100092
8. orientation agent according to claim 2 is characterized in that:
The polyamic acid that the polyamic acid that has photosensitive group on the main chain is in the following way to be obtained makes by formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), the diamines that formula (V-1) and formula (VI-1)～formula (VI-7) is represented with photosensitive group at least a with select in the represented diamines of free style (2)～formula (4) at least a mixture and by formula (A-1), formula (A-2), formula (A-12), formula (A-14), formula (A-18), formula (A-20), formula (A-21), formula (A-37), formula (VII-4), formula (VII-5), formula (VIII-7) and represented at least a of tetracarboxylic dianhydride of formula (VIII-8) react:
Figure FSA00000016952100111
Herein, A 1, A 2, A 3And A 4Independent of stretching cyclohexyl or inferior benzene; X 3And X 4Independent for singly-bound, carbon number be 1～5 alkylidene group or-O-; X 5And X 6Independent be singly-bound ,-CH 2-,-CH 2CH 2-,-O-or-S-; Y 1Be-CH 2-,-C (R 11) (R 12)-,-CO-or-SO 2-, R 11And R 12Independent for hydrogen, carbon number be that 1～12 alkyl or carbon number are 1～12 fluorinated alkyl; M1, m2, m3, m4 and n independently represent 0 or 1; And, stretch in cyclohexyl and the inferior benzene described, hydrogen can be 1～4 alkyl or benzyl replacement by carbon number arbitrarily, those substituent bond positions are arbitrarily; But, work as A 1, A 2, A 3And A 4All be 1, during the benzene of 4-Asia, X 3, X 4, X 5And X 6It all not singly-bound;
Figure FSA00000016952100112
Herein, X 1And X 2Be singly-bound ,-O-,-COO-,-OCO-,-NH-,-CONH-or carbon number are 1～12 alkylidene group; G 1And G 2Be that to be selected from carbon number be that 6～12 aromatic ring and carbon number are the divalent group of 1～3 rings in 3～12 the ester ring type ring for singly-bound or comprise; R 6Be hydrogen, fluorine ,-CN ,-OH, carbon number are that 1～30 alkyl, carbon number are that 1～30 fluorinated alkyl or carbon number are 1～30 alkoxyl group; And, work as X 1, G 1, X 2And G 2When all being singly-bound, R 6Be that carbon number is that 3～30 alkyl, carbon number are that 3～30 fluorinated alkyl or carbon number are 3～30 alkoxyl group, work as G 2Be singly-bound and X 2Neither when singly-bound neither alkylidene group, R 6Be that hydrogen or carbon number are 3～30 alkyl, work as G 1And G 2When being singly-bound, X 1, X 2And R 6The total carbon number more than or equal to 3;
Figure FSA00000016952100121
Herein, R 7Be that hydrogen or carbon number are 1～12 alkyl; Ring B be arbitrarily hydrogen can by carbon number be 1～4 alkyl replace 1, the inferior benzene of 4-or arbitrarily hydrogen can by carbon number be 1～4 alkyl replace 1,4-stretches cyclohexyl; X 0Be that singly-bound or carbon number are 1～5 alkylidene group, and s is 0～3 integer; When s was 2 or 3, a plurality of ring B can all be identical ring, also can be made of a plurality of X at least 2 different rings 0Can all be identical group, also can constitute by at least 2 different groups; Z 1And Z 2Independent be singly-bound ,-CH 2-,-CH 2CH 2-or-O-, t1 and t2 independently are 0～3 integer; When t1 is 2 or 3, a plurality of Z 1Can all be identical group, also can constitute by at least 2 different groups; When t2 is 2 or 3, a plurality of Z 2Can all be identical group, also can constitute by at least 2 different groups;
Figure FSA00000016952100122
Figure FSA00000016952100131
Herein, R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group.
9. orientation agent according to claim 2 is characterized in that:
The polyamic acid that the polyamic acid that has photosensitive group on the main chain is in the following way to be obtained, make by formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), the diamines that formula (V-1) and formula (VI-1)～formula (VI-7) is represented at least a with photosensitive group, at least a by the represented diamines of formula (VII-1)～formula (VII-3) and formula (VIII-1)～formula (VIII-6), and select in the represented diamines of free style (2)～formula (4) at least a mixture and by formula (A-1), formula (A-2), formula (A-12), formula (A-14), formula (A-18), formula (A-20), formula (A-21), formula (A-37), formula (VII-4), formula (VII-5), formula (VIII-7) and represented at least a of tetracarboxylic dianhydride of formula (VIII-8) react:
Figure FSA00000016952100132
H 2N-R 4-NH 2????????????????????(VII-1)
Figure FSA00000016952100151
Herein, R 4Be that carbon number is 6～20 alkylidene group; R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group;
Figure FSA00000016952100152
Herein, A 1, A 2, A 3And A 4Independent of stretching cyclohexyl or inferior benzene; X 3And X 4Independent for singly-bound, carbon number be 1～5 alkylidene group or-O-; X 5And X 6Independent be singly-bound ,-CH 2-,-CH 2CH 2-,-O-or-S-; Y 1Be-CH 2-,-C (R 11) (R 12)-,-CO-or-SO 2-, R 11And R 12Independent for hydrogen, carbon number be that 1～12 alkyl or carbon number are 1～12 fluorinated alkyl; M1, m2, m3, m4 and n independently represent 0 or 1; And, stretch in cyclohexyl and the inferior benzene described, hydrogen can be 1～4 alkyl or benzyl replacement by carbon number arbitrarily, those substituent bond positions are arbitrarily; But, work as A 1, A 2, A 3And A 4All be 1, during the benzene of 4-Asia, X 3, X 4, X 5And X 6It all not singly-bound;
Figure FSA00000016952100161
Herein, X 1And X 2Be singly-bound ,-O-,-COO-,-OCO-,-NH-,-CONH-or carbon number are 1～12 alkylidene group; G 1And G 2Be that to be selected from carbon number be that 6～12 aromatic ring and carbon number are the divalent group of 1～3 rings in 3～12 the ester ring type ring for singly-bound or comprise; R 6Be hydrogen, fluorine ,-CN ,-OH, carbon number are that 1～30 alkyl, carbon number are that 1～30 fluorinated alkyl or carbon number are 1～30 alkoxyl group; And, work as X 1, G 1, X 2And G 2When all being singly-bound, R 6Be that carbon number is that 3～30 alkyl, carbon number are that 3～30 fluorinated alkyl or carbon number are 3～30 alkoxyl group, work as G 2Be singly-bound and X 2Neither when singly-bound neither alkylidene group, R 6Be that hydrogen or carbon number are 3～30 alkyl, work as G 1And G 2When being singly-bound, X 1, X 2And R 6The total carbon number more than or equal to 3;
Figure FSA00000016952100162
Herein, R 7Be that hydrogen or carbon number are 1～12 alkyl; Ring B be arbitrarily hydrogen can by carbon number be 1～4 alkyl replace 1, the inferior benzene of 4-or arbitrarily hydrogen can by carbon number be 1～4 alkyl replace 1,4-stretches cyclohexyl; X 0Be that singly-bound or carbon number are 1～5 alkylidene group, and s is 0～3 integer; When s was 2 or 3, a plurality of ring B can all be identical ring, also can be made of a plurality of X at least 2 different rings 0Can all be identical group, also can constitute by at least 2 different groups; Z 1And Z 2Independent be singly-bound ,-CH 2-,-CH 2CH 2-or-O-, t1 and t2 independently are 0～3 integer; When t1 is 2 or 3, a plurality of Z 1Can all be identical group, also can constitute by at least 2 different groups; When t2 is 2 or 3, a plurality of Z 2Can all be identical group, also can constitute by at least 2 different groups;
Figure FSA00000016952100163
Herein, R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group.
10. orientation agent according to claim 1 is characterized in that:
Polyamic acid is by making by at least a of the represented diamines of formula (VII-1)～formula (VII-3) and at least a polyamic acid that is obtained that reacts by the represented tetracarboxylic dianhydride of formula (VIII-7) and formula (VIII-8), or by making by at least a of the represented diamines of formula (VIII-1)～formula (VIII-6) and at least a polyamic acid that is obtained that reacts by the represented tetracarboxylic dianhydride of formula (VII-4) and formula (VII-5):
H 2N-R 4-NH 2????????????????(VII-1)
Figure FSA00000016952100172
Figure FSA00000016952100181
Herein, R 4Be that carbon number is 6～20 alkylidene group; And, R 5Be arbitrarily-CH 2-can by-O-,-NH-,-N (CH 3)-,-Si (CH 3) 2OSi (CH 3) 2-or-carbon number that COO-replaces is 6～20 alkylidene group;
Figure FSA00000016952100182
11. liquid crystal orienting film, it is characterized in that: it is to obtain in the following way, give anisotropy by friction or rayed to the film that is coated on orientation agent according to claim 1 on the substrate to be obtained, be heated to then till the liquid crystal temperature range of film and the anisotropy of film is increased.
12. liquid crystal orienting film, it is characterized in that: it is to obtain in the following way,, be heated to then till the liquid crystal temperature range of film and the anisotropy of film is increased giving anisotropy by rayed according to the film that each described orientation agent in the claim 2 to 9 is coated on the substrate to be obtained.
13. liquid crystal orienting film, it is characterized in that: it is to obtain in the following way, that is, give the friction anisotropy, be heated to then till the liquid crystal temperature range of film and the anisotropy of film is increased the film that is coated on orientation agent according to claim 10 on the substrate to be obtained.
14. a liquid crystal display device is characterized in that: comprise liquid crystal orienting film according to claim 11.
15. a liquid crystal display device is characterized in that: comprise liquid crystal orienting film according to claim 12.
16. a liquid crystal display device is characterized in that: comprise liquid crystal orienting film according to claim 13.
17. a polyimide or as the polyamic acid of its precursor is characterized in that:
Comprise by the represented formation unit of formula (IX), and have liquid crystal temperature range at 100 ℃～300 ℃:
Figure FSA00000016952100191
Herein, R 5Be that carbon number is 6～12 alkylidene group; R 9Be by any one the residue in the represented diamines of formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), formula (V-1) and formula (VI-1)～formula (VI-7):
Figure FSA00000016952100192
Figure FSA00000016952100201
18. a polyimide or as the polyamic acid of its precursor is characterized in that:
Comprise by the represented formation unit of formula (X), and have liquid crystal temperature range at 100 ℃～300 ℃:
Figure FSA00000016952100211
Herein, R 5Be that carbon number is 6～12 alkylidene group; R 9Be by any one the residue in the represented diamines of formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), formula (V-1) and formula (VI-1)～formula (VI-7):
Figure FSA00000016952100212
Figure FSA00000016952100221
19. polyimide according to claim 17 or as the polyamic acid of its precursor is characterized in that:
R 9Be by any one the residue in the represented diamines of formula (VIII-1)～formula (VIII-6):
Figure FSA00000016952100222
Figure FSA00000016952100231
20. polyimide according to claim 18 or as the polyamic acid of its precursor is characterized in that:
R 9Be by any one the residue in the represented diamines of formula (VIII-1)～formula (VIII-6):
21. a polyimide or as the polyamic acid of its precursor is characterized in that:
Comprise by the represented formation unit of formula (IX) and by the represented formation unit of formula (XI), and have liquid crystal temperature range at 100 ℃～300 ℃:
Herein, R 5Be that carbon number is 6～12 alkylidene group; R 9Be by any one the residue in the represented diamines of formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), formula (V-1) and formula (VI-1)～formula (VI-7); R 10Be by any one the residue in the represented diamines of formula (VIII-1)～formula (VIII-6):
Figure FSA00000016952100241
Figure FSA00000016952100251
Figure FSA00000016952100261
22. a polyimide or as the polyamic acid of its precursor is characterized in that:
Comprise by the represented formation unit of formula (X) and by the represented formation unit of formula (XII), and have liquid crystal temperature range at 100 ℃～300 ℃:
Figure FSA00000016952100262
Herein, R 5Be that carbon number is 6～12 alkylidene group; R 9Be by any one the residue in the represented diamines of formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), formula (V-1) and formula (VI-1)～formula (VI-7); R10 is by any one the residue in the represented diamines of formula (VIII-1)～formula (VIII-6):
Figure FSA00000016952100263
Figure FSA00000016952100271
Figure FSA00000016952100281
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CN104058993A (en) * 2013-03-19 2014-09-24 捷恩智株式会社 Photosensitive Diamines, Polyamide Acid And Derivatives Thereof, Liquid Crystal Aligning Agents, Liquid Crystal Alignment Films And Liquid Crystal Display Devices
US9228130B2 (en) 2013-06-25 2016-01-05 Shenzhen China Star Optoelectronics Technology Co., Ltd Alignment film, a method of fabricating the same, and a liquid crystal display using the same
US9274378B2 (en) 2013-06-25 2016-03-01 Shenzhen China Star Optoelectronics Technology Co., Ltd. Alignment film, a method of fabricating the same, and a liquid crystal display using the same
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CN103305236A (en) * 2013-06-25 2013-09-18 深圳市华星光电技术有限公司 Liquid crystal display (LCD) panel, alignment films thereof and preparation method of alignment films
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CN107557023A (en) * 2016-06-30 2018-01-09 捷恩智株式会社 To form the aligning agent for liquid crystal of light orientation liquid crystal orientation film, liquid crystal orientation film and use its liquid crystal display cells
CN107557023B (en) * 2016-06-30 2022-08-16 捷恩智株式会社 Liquid crystal aligning agent for forming liquid crystal alignment film for photo-alignment, liquid crystal alignment film, and liquid crystal display element using same
CN112805270A (en) * 2018-08-15 2021-05-14 现代生物科学有限公司 1-methyl-4- [ (4-phenylphenyl) sulfonylmethyl ] cyclohexanol and 1-methyl-4- [ [4- (2-pyridinyl) phenyl ] sulfonylmethyl ] cyclohexanol compounds and therapeutic uses thereof

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