CN101735824A - Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device - Google Patents
Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device Download PDFInfo
- Publication number
- CN101735824A CN101735824A CN200910212152A CN200910212152A CN101735824A CN 101735824 A CN101735824 A CN 101735824A CN 200910212152 A CN200910212152 A CN 200910212152A CN 200910212152 A CN200910212152 A CN 200910212152A CN 101735824 A CN101735824 A CN 101735824A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- group
- crystal aligning
- aligning agent
- expression
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device. The liquid crystal aligning agent can be used for forming the liquid crystal aligning film having good liquid crystal oriented control force (pretilt angle expressive) and improved burn-in performance and high reliability and preventing the residual DC voltage accumulation after the thermal stress is exerted in a long term. The liquid crystal aligning agent comprises a polymer with specific repeating units represented by the formula (1-1) and at least one polymer selected from a group comprising polyamide acids from tetracarboxylicdianhydride and diamines by reacting andimidizated polymers.
Description
Technical field
The present invention relates to liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device.More particularly, relate to form and show good liquid crystal aligning control (tilt angle expression power) and have high voltage retention and reliability and can suppressing applies the liquid crystal aligning agent of the liquid crystal orientation film of the burning screen after the thermal stresses for a long time, with the liquid crystal orientation film that forms by this liquid crystal aligning agent, and the liquid crystal display device with this liquid crystal orientation film.
Background technology
Since the liquid crystal counter begins to produce in batches, from save space, low power consumption equal angles, liquid crystal display device has been applied to many-sided purposes such as clock and watch, portable game machine, word processor, subnotebook PC, automobile navigation instrument, pick up camera, portable data assistance, digital camera, mobile telephone, various watch-dogs, and active exploitation is also continuing.
As liquid crystal display device, TN (twisted-nematic) the type liquid crystal display device that adopts the major axis of nematic liquid crystal, liquid crystal molecule to turn round continuously to another piece substrate to turn 90 degrees from a substrate with compare the higher STN of contrast gradient (supertwist is to row) type liquid crystal display device with TN type liquid crystal display device and be widely used.And, in order further to improve the display quality of liquid-crystal display, also good optical compensation curved (the type liquid crystal display device of optical compensation birefringence=OCB) etc. of view angle dependency little VA (vertical orientated) type liquid crystal display device, IPS (switching in the face) type liquid crystal display device, video pictures high-speed response of little while of view angle dependency have also been developed.
In liquid crystal display device, used the liquid crystal orientation film that is used to control liquid crystal molecular orientation.Liquid crystal orientation film is coated on substrate by the liquid crystal aligning agent that will contain organic resin usually, and removing then desolvates forms and film, and this is filmed rub with certain orientation, promptly carries out " grinding process " and forms.Because liquid crystal orientation film is the parts that directly contact with liquid crystal molecule, the electric property of known liquid crystal orientation film shields (accumulating of electric charge) and voltage retention etc. to the burning of liquid crystal panel can produce very large influence.Therefore, by improving liquid crystal orientation film, be expected to improve the anti-burning screen property of liquid crystal panel.For example, in patent documentation 1 and the patent documentation 2, proposed to make the electric charge of accumulating spread the technology of (shorten image retention and eliminate the time) easily by the composition that changes liquid crystal orientation film.
In recent years, liquid crystal display device has been applied to high-quality watch-dog, and particularly the exploitation of liquid crystal TV set purposes is very active.The liquid crystal display device that is used for the liquid crystal TV set purposes except the response speed of the bright-coloured of display frame and height, also requires to have the long durability that can match in excellence or beauty with cathode ray tube television receiver.From before the use-pattern of liquid crystal display device, do not consider this long durability, even the technology of describing in above-mentioned patent documentation 1 and 2 not have imagination to shield performance and improve applying burning after the thermal stresses for a long time, to reach the required level of televisor purposes yet.
[patent documentation 1] TOHKEMY 2003-295194 communique
[patent documentation 2] TOHKEMY 2004-94179 communique
[patent documentation 3] TOHKEMY 2002-327058 communique
[patent documentation 4] Japanese kokai publication hei 6-222366 communique
[patent documentation 5] Japanese kokai publication hei 6-281937 communique
[patent documentation 6] Japanese kokai publication hei 5-107544 communique
Summary of the invention
The present invention In view of the foregoing makes, its objective is the liquid crystal aligning agent of the liquid crystal orientation film that the residual DC voltage after burning screen performance, the reliability highly that can form the good liquid crystal aligning control (tilt angle expression power) of demonstration and have improvement being provided and can suppressing to apply for a long time thermal stresses is accumulated, the liquid crystal display device of the anti-burning screen excellent property after having the liquid crystal orientation film of above-mentioned performance and applying thermal stresses for a long time.
Other purposes of the present invention and advantage can be learned by the following description.
According to the present invention, above-mentioned purpose of the present invention and advantage, first, reach by a kind of liquid crystal aligning agent, it comprises the polymkeric substance of the repeating unit with following formula (1) expression and is selected from least a polymkeric substance in the group that makes polyamic acid that the tetracarboxylic dianhydride obtains with diamine reactant and imide amination polymer formation thereof
In the formula (1), R
IBe hydrogen atom or methyl, A
1For singly-bound, methylene radical, carbonatoms are the divalent group of 2～10 alkylidene group or following formula (2) expression,
(in the formula (2), n is 5～150 integer) works as A
1When being 2～10 alkylidene group for singly-bound, methylene radical or carbonatoms, B
1For carbonatoms is 1～10 fluoro-alkyl, work as A
1During for the divalent group of above-mentioned formula (2) expression, B
1For carbonatoms is that 1～10 alkyl or carbonatoms are 1～10 fluoro-alkyl.
Above-mentioned purpose of the present invention and advantage, the second, reach by the liquid crystal orientation film that above-mentioned liquid crystal aligning agent forms, the 3rd, reach by liquid crystal display device with above-mentioned liquid crystal orientation film.
According to the present invention, the reliability that can form the burning screen performance that shows good liquid crystal aligning control (tilt angle expression power) and have improvement, height can be provided, particularly can suppress to apply for a long time the liquid crystal aligning agent of the liquid crystal orientation film that the residual DC voltage after the thermal stresses accumulates, the liquid crystal display device of the anti-burning screen excellent property after having the liquid crystal orientation film of above-mentioned performance and applying thermal stresses for a long time.
Embodiment
Below, the present invention will be described in detail.
Liquid crystal aligning agent of the present invention comprise the polymkeric substance (hereinafter referred to as " polymkeric substance (1) ") of repeating unit with above-mentioned formula (1) expression and be selected from the polyamic acid that makes tetracarboxylic dianhydride and diamine reactant and obtain and the group of imide amination polymer formation at least a polymkeric substance.
A in the above-mentioned formula (1)
1The divalent group of above-mentioned formula (2) expression in, n is 5～150 integer, and this value is preferably 7～15.
As B in the above-mentioned formula (1)
1Carbonatoms be 1～10 fluoro-alkyl, can enumerate for example trifluoromethyl, 1,1,2,2-tetrafluoro ethyl, 1,1,2,2,2-pentafluoroethyl group, perfluor-5-methyl hexyl, perfluoro capryl, perfluor decyl, 2-(perfluoro capryl) ethyl etc.
As the object lesson of the repeating unit of above-mentioned formula (1) expression, can enumerate repeating unit that for example following formula (1-1)～(1-10) represents separately etc.
N among formula (1-5) and (1-10) is identical with implication in the above-mentioned formula (2) separately.In the middle of them, the repeating unit of above-mentioned formula (1-6) expression is considered from the aspect that can form the particularly preferred liquid crystal orientation film of electric property, is preferred.
Polymkeric substance (1), except the repeating unit of above-mentioned formula (1) expression, can also further contain at least a repeating unit in the group that the repeating unit of the repeating unit of repeating unit, following formula (7) expression of repeating unit, following formula (6) expression of repeating unit, following formula (5) expression of the repeating unit that is selected from following formula (3) expression, following formula (4) expression and following formula (8) expression constitutes.
In the formula (3), R
IIBe hydrogen atom or methyl, A
2For singly-bound, methylene radical or carbonatoms are 2～10 alkylidene group, B
2It for carbonatoms 2～10 group with cyclic ether structure.
In the formula (4), R
IIIBe hydrogen atom or methyl, A
3Be singly-bound, phenylene or following formula (A
3-1)～(A
3-6) divalent group of any one expression,
-(CH
2)
k-O-
＊(A
3-5)
-(CH
2)
m-COO-
＊(A
3-6)
(i respectively does for oneself 0 or 2 in the above-mentioned formula, and j respectively does for oneself 0 or 1, respectively do for oneself 1～6 integer of k and m, and " * " represents to have its connecting key and B separately
3Connect).B
3For the carbonatoms with steroid backbone is 17～30 any monovalent organic radical group, to have carbonatoms be that alkyl-cyclohexyl, the carbonatoms of 4～8 alkyl is 3～30 alkyl, difluorophenyl, trifluoromethyl or Trifluoromethoxyphen-l.
In the formula (5), R
IVBe hydrogen atom, methyl or carboxymethyl, B
4Be hydrogen atom, methyl or carboxyl, but work as R
IVDuring for carboxymethyl, B
4It is not carboxyl.
In the formula (6), A
5Be singly-bound, Sauerstoffatom or sulphur atom, perhaps contain the divalent group of Sauerstoffatom, sulphur atom, nitrogen-atoms or Siliciumatom, B
5For carbonatoms is that 6～30 aryl or carbonatoms are 4～10 ester ring type group.
In the formula (7), R
VBe hydrogen atom or methyl, A
6Be singly-bound, Sauerstoffatom or sulphur atom, perhaps contain the divalent group of Sauerstoffatom, sulphur atom, nitrogen-atoms or Siliciumatom, B
6For hydrogen atom, carbonatoms are that 1～20 alkyl or carbonatoms are 6～30 aryl.
In the formula (8), R
VIBe hydrogen atom or methyl, A
7For singly-bound or-COO-
*(wherein " * " expression has its key arm and B
7Connect), B
7For carbonatoms is that 2～10 alkylidene group, carbonatoms are that 6～30 arylidene or carbonatoms are 4～10 divalence ester ring type group.
Contained cyclic ether structure in the repeating unit of above-mentioned formula (3) expression, after coating liquid crystal aligning agent formation of the present invention is filmed, the heat cross-linking reaction takes place through carrying out heat treated (afterwards curing), can further improve the thermotolerance of gained liquid crystal orientation film like this, anti-liquid crystal liquid crystal property (solvent resistance), film density, can further reduce the diffusion of foreign ion contained in the liquid crystal in liquid crystal orientation film, because these effects, can obtain to give the liquid crystal aligning agent of following liquid crystal orientation film, even this liquid crystal orientation film applies thermal stresses or drives liquid crystal panel for a long time the gained liquid crystal display device, also can solve voltage retention decline really and burn the screen problem.And the repeating unit by above-mentioned formula (4) expression can further improve liquid crystal aligning.Therefore, polymkeric substance (1) preferably has repeating unit and the repeating unit of above-mentioned formula (3) expression and the repeating unit of above-mentioned formula (4) expression of above-mentioned formula (1) expression simultaneously.
Therefore, as B in the above-mentioned formula (3)
2Carbonatoms be 2～10 cyclic ether structure, it is reactive 1 preferably to have a heat cross-linking, 2-epoxy group(ing) structure or 1,3-epoxy group(ing) structure is considered from the good aspect of reactivity, more preferably 1,2-epoxy group(ing) structure.As the repeating unit of above-mentioned formula (3) expression, A in the preferred above-mentioned formula (3)
2For methylene radical or carbonatoms 2～10 alkylidene group, B
2For having 1, the repeating unit of the group of 2-epoxy group(ing) structure, more preferably A
2For methylene radical or carbonatoms 2 or 5 alkylidene group, B
2For having 1, the repeating unit of the group of 2-epoxy group(ing) structure.
The repeating unit of above-mentioned formula (4) expression can be for liquid crystal aligning that improves the gained liquid crystal orientation film and further electric property and being contained in the polymkeric substance (1).As the B in the above-mentioned formula (4)
3Can enumerate the carbonatoms with steroid backbone and be 17～30 any monovalent organic radical group, have carbonatoms is that alkyl-cyclohexyl, the carbonatoms of 4～8 alkyl is 3～30 alkyl, difluorophenyl, trifluoromethyl, Trifluoromethoxyphen-l etc., and the carbonatoms that especially preferably has steroid backbone is 17～30 any monovalent organic radical group or has the alkyl-cyclohexyl that carbonatoms is 4～8 alkyl.Here, be 17～30 any monovalent organic radical group as carbonatoms with steroid backbone, can enumerate for example cholestane-3-base, courage steroid-5-alkene-3-base, courage steroid-24-alkene-3-base, courage steroid-5,24-diene-3-base, lanostane-3-base etc.
The repeating unit of above-mentioned formula (5) expression, can be in order to improve polymkeric substance (1) and the consistency that is selected from least a polymkeric substance in the group that polyamic acid and imide amination polymer thereof constitute, and when polymkeric substance (1) has the repeating unit of above-mentioned formula (3) expression for the purpose of the crosslinking reaction that promotes its cyclic ether structure, and be contained in the polymkeric substance (1).
The repeating unit of the repeating unit of above-mentioned formula (6) expression and above-mentioned formula (7) expression can be to be contained in the polymkeric substance (1) in order further to improve the thermotolerance of gained liquid crystal orientation film separately.
As the A in the above-mentioned formula (6)
5, preferred singly-bound.As B in the above-mentioned formula (6)
5Carbonatoms be the example of 6～30 aryl, can enumerate for example phenyl, naphthyl, anthryl, phenanthryl etc.; As carbonatoms is 4～10 ester ring type group, can enumerate for example cyclopentyl, cyclohexyl etc., preferred especially phenyl or cyclohexyl.
As the A in the above-mentioned formula (7)
6, preferred singly-bound.As B in the above-mentioned formula (7)
6Carbonatoms be 1～20 alkyl, can enumerate for example methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl etc.; As carbonatoms is 6～30 aryl, can enumerate for example phenyl, 4-xenyl, 2-xenyl, 1-naphthyl, 2-naphthyl etc., wherein preferred phenyl.
The repeating unit of above-mentioned formula (8) expression can be to be contained in the polymkeric substance (1) with the purpose of the consistency that is selected from least a polymkeric substance in the group that polyamic acid and imide amination polymer thereof constitute in order to improve polymkeric substance (1).
As B in the above-mentioned formula (8)
7Carbonatoms be 2～10 alkylidene group, can enumerate for example ethylidene, tetramethylene etc.; As carbonatoms is 6～30 arylidene, can enumerate for example phenylene etc.; As carbonatoms is 4～10 divalence ester ring type group, can enumerate for example hexanaphthene-1,4-two bases etc.
In the polymkeric substance (1) repeating unit of above-mentioned formula (1) expression contain ratio, based on the gross weight of polymkeric substance (1), be preferably more than the 1 weight %, 1～50 weight % more preferably, more preferably 1～30 weight % is preferably 1～20 weight % especially.The ratio that contains of the repeating unit by making above-mentioned formula (1) expression drops in this scope, can make the gained liquid crystal orientation film have good electric property.
The repeating unit of above-mentioned formula (3) expression contain ratio, based on the gross weight of polymkeric substance (1), be preferably below the 50 weight %, 5～50 weight % more preferably, more preferably 15～45 weight % are preferably 20～40 weight % especially.The ratio that contains of the repeating unit by making above-mentioned formula (3) expression drops in this scope, can further improve the film density of gained liquid crystal orientation film, the diffusion of foreign ion contained in the liquid crystal can be further reduced like this, thereby the burning screen of liquid crystal display device can be further suppressed to liquid crystal orientation film.
The repeating unit of above-mentioned formula (4) expression contain ratio, based on the gross weight of polymkeric substance (1), be preferably below the 60 weight %, 1～60 weight % more preferably, more preferably 2～40 weight % are preferably 3～30 weight % especially.The ratio that contains of the repeating unit by making above-mentioned formula (4) expression drops in this scope, can make the gained liquid crystal orientation film have better tilt angle expression power.
The repeating unit of above-mentioned formula (5) expression contain ratio, based on the gross weight of polymkeric substance (1), be preferably below the 50 weight %, 1～50 weight % more preferably, more preferably 1～45 weight % is preferably 1～40 weight % especially.
The repeating unit of above-mentioned formula (6) expression contain ratio, based on the gross weight of polymkeric substance (1), be preferably below the 20 weight %, more preferably 1～20 weight %, more preferably 1～10 weight %.
The repeating unit of above-mentioned formula (7) expression contain ratio, based on the gross weight of polymkeric substance (1), be preferably below the 20 weight %, more preferably 1～20 weight %, more preferably 1～10 weight %.
The repeating unit of above-mentioned formula (8) expression contain ratio, based on the gross weight of polymkeric substance (1), be preferably below the 50 weight %, 1～50 weight % more preferably, more preferably 1～45 weight % is preferably 1～40 weight % especially.
For polymkeric substance (1), adopt the weight-average molecular weight (hereinafter referred to as " Mw ") of the polystyrene conversion of gel permeation chromatography (GPC) mensuration, be preferably 2 * 10
3～1 * 10
6, more preferably 5 * 10
3～5 * 10
5, be preferably 1 * 10 especially
4～4 * 10
5If Mw less than 2 * 10
3, the problem that the low molecular composition stripping causes panel performance degradation (becoming the major cause that voltage retention descends or panel burns screen) then can appear.On the other hand, if surpass 1 * 10
6, the soltion viscosity situation too high, that have problems aspect screening characteristics of gained liquid crystal aligning agent then can appear.In addition, molecular weight distribution (hereinafter referred to as " Mw/Mn ", Mn represents the number-average molecular weight with the polystyrene conversion of GPC mensuration) is preferably below 20.0, more preferably below 15.0, is preferably below 10.0 especially.By reducing Mw/Mn, can easily obtain the screening characteristics excellence and the liquid crystal aligning agent of the problem of the panel performance degradation that the stripping etc. by above-mentioned low molecular composition causes can not occur.
Aforesaid polymkeric substance (1) can be by compound (hereinafter referred to as " monomer (1 ') ") or the monomer of for example following formula (1 ') being represented (1 ') and the compound (hereinafter referred to as " monomer (3 ') ") that is selected from following formula (3 ') expression, the compound (hereinafter referred to as " monomer (4 ') ") of following formula (4 ') expression, the compound (hereinafter referred to as " monomer (5 ') ") of following formula (5 ') expression, the compound (hereinafter referred to as " monomer (6 ') ") of following formula (6 ') expression, at least a in the group of compound (hereinafter referred to as " monomer (8 ') ") formation of the compound (hereinafter referred to as " monomer (7 ') ") of following formula (7 ') expression and following formula (8 ') expression, preferably in appropriate solvent, in the presence of suitable polymerization starter, carry out radical polymerization and synthesize.
In the formula (1 '), R
I, A
1And B
1Identical with the definition in the above-mentioned formula (1) respectively;
In the formula (3 '), R
II, A
2And B
2Identical with the definition in the above-mentioned formula (3) respectively;
In the formula (4 '), R
III, A
3And B
3Identical with the definition in the above-mentioned formula (4) respectively;
In the formula (5 '), R
IVAnd B
4Identical with the definition in the above-mentioned formula (5) respectively;
In the formula (6 '), A
5And B
5Identical with the definition in the above-mentioned formula (6) respectively;
In the formula (7 '), R
V, A
6And B
6Identical with the definition in the above-mentioned formula (7) respectively;
In the formula (8 '), R
VI, A
7And B
7Identical with the definition in the above-mentioned formula (8) respectively;
Monomer (1 ') is a monomer of introducing the repeating unit of above-mentioned formula (1) expression.Preferred object lesson as monomer (1 '), can enumerate for example vinylformic acid 2,2, the 2-trifluoro ethyl ester, vinylformic acid 3,3,4,4-tetrafluoro butyl ester, vinylformic acid 3,3,4,4,4-five fluorine butyl esters, vinylformic acid 2-(perfluoro capryl) ethyl ester, vinylformic acid (trifluoromethyl) polydimethylsiloxane, vinylformic acid (perfluor ethyl) polydimethylsiloxane, vinylformic acid (perfluoro capryl) polydimethylsiloxane, methacrylic acid 2,2, the 2-trifluoro ethyl ester, methacrylic acid 3,3,4,4-tetrafluoro butyl ester, methacrylic acid 3,3,4,4,4-five fluorine butyl esters, methacrylic acid 2-(perfluoro capryl) ethyl ester, methacrylic acid (trifluoromethyl) polydimethylsiloxane, methacrylic acid (perfluor ethyl) polydimethylsiloxane, methacrylic acid (perfluoro capryl) polydimethylsiloxane etc.Wherein, consider, can enumerate vinylformic acid 2 from showing good electric property aspect, 2,2-trifluoro ethyl ester, vinylformic acid (trifluoromethyl) polydimethylsiloxane, methacrylic acid 2,2,2-trifluoro ethyl ester, methacrylic acid (trifluoromethyl) polydimethylsiloxane etc.The divalent group that " organopolysiloxane " in the above-claimed cpd represented for following formula,
In the above-mentioned formula, p is a number of repeat unit, is preferably 7～15 integer.
Monomer (3 ') is a monomer of introducing the repeating unit of above-mentioned formula (3) expression, as its object lesson, can enumerate for example glycidyl acrylate, glycidyl methacrylate, vinylformic acid 3,4-epoxy group(ing) butyl ester, methacrylic acid 3,4-epoxy group(ing) butyl ester, vinylformic acid 6,7-epoxy group(ing) heptyl ester, methacrylic acid 6,7-epoxy group(ing) heptyl ester, α-Yi Jibingxisuan 6,7-epoxy group(ing) heptyl ester etc.Wherein, consider preferred glycidyl acrylate or glycidyl methacrylate from the film density that improves the gained liquid crystal orientation film, the aspect that makes its reliability that can show good electric property and electric property.
Monomer (4 ') is a monomer of introducing the repeating unit of above-mentioned formula (4) expression, as monomer (4 ') object lesson, can enumerate for example methacrylic acid cholestane base ester, methacrylic acid 4-(4 '-amyl group dicyclohexyl-4-yl) phenylester, methacrylic acid Renascin etc.This monomer (4 ') can be by for example making (methyl) acryloyl halide and compd B according to known esterification
1-A
1-OH reacts and makes.
Monomer (5 ') is a monomer of introducing the repeating unit of above-mentioned formula (5) expression, as its object lesson, can enumerate for example toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, methylene-succinic acid, vinylformic acid, methacrylic acid, Ba Dousuan etc.Wherein, preferred acrylic or methacrylic acid is considered in the film density height of and gained liquid crystal orientation film good from the consistency of polymkeric substance (1) and polyamic acid and imide amination polymer thereof, the aspect that can show the height reliability of electric property and electric property.
Monomer (6 ') is a monomer of introducing the repeating unit of above-mentioned formula (6) expression, as its object lesson, can enumerate for example N-phenylmaleimide, N-naphthyl maleimide, N-anthryl maleimide, N-fluorenyl maleimide, N-cyclopentyl maleimide, N-cyclohexyl maleimide etc., wherein preferred N-phenylmaleimide or N-cyclohexyl maleimide.
Monomer (7 ') is a monomer of introducing the repeating unit of above-mentioned formula (7) expression, as its object lesson, for example can enumerate alpha-olefin such as ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and vinylbenzene, 4-vinyl biphenyl, 2-vinyl biphenyl, 1-vinyl naphthalene, 2-vinyl naphthalene, alpha-methyl styrene etc., wherein optimization styrene.
Monomer (8 ') is a monomer of introducing the repeating unit of above-mentioned formula (8) expression, as its object lesson, can enumerate for example isopropenyl phenol, 2-hydroxyethyl methacrylate, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 4-hydroxyl butyl ester, 1,4 cyclohexane dimethanol mono acrylic ester etc.
When synthetic polymer (1), the usage rate of monomer (1 ')～(8 ') (copolymerization ratio) can suitably be set according to the composition of required polymkeric substance (1).
Thereby the copolymerization ratio of monomer (1 ') based on monomeric total weight, is preferably more than the 1 weight %, 1～50 weight % more preferably, and more preferably 1～30 weight % is preferably 1～20 weight % especially.
The copolymerization ratio of monomer (3 ') based on monomeric total weight, is preferably below the 50 weight %, 5～50 weight % more preferably, and more preferably 15～45 weight % are preferably 20～40 weight % especially.
The copolymerization ratio of monomer (4 ') based on monomeric total weight, is preferably below the 60 weight %, 1～60 weight % more preferably, and more preferably 2～40 weight % are preferably 3～30 weight % especially.
The copolymerization ratio of monomer (5 ') based on monomeric total weight, is preferably below the 50 weight %, 1～50 weight % more preferably, and more preferably 1～45 weight % is preferably 1～40 weight % especially.
The copolymerization ratio of monomer (6 ') based on monomeric total weight, is preferably below the 20 weight %, more preferably 1～20 weight %, more preferably 1～10 weight %.
The copolymerization ratio of monomer (7 ') based on monomeric total weight, is preferably below the 20 weight %, more preferably 1～20 weight %, more preferably 1～10 weight %.
The copolymerization ratio of monomer (8 ') based on monomeric total weight, is preferably below the 50 weight %, 1～50 weight % more preferably, and more preferably 1～45 weight % is preferably 1～40 weight % especially.
As the synthetic middle solvent that uses of polymkeric substance (1), can enumerate for example alcohol, ether, glycol ether, ethylene glycol alkyl oxide acetic ester, glycol ether alkyl oxide, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, propylene glycol alkyl ether propionic ester, aromatic hydrocarbons, ketone, ester etc.
As its object lesson,, can enumerate for example methyl alcohol, ethanol, benzylalcohol, 2-phenylethyl alcohol, 3-phenyl-1-propyl alcohol etc. as alcohol; As ether, can enumerate tetrahydrofuran (THF), two n-pentyl ethers etc.; As glycol ether, can enumerate for example ethylene glycol monomethyl ether, ethylene glycol monoethyl ether etc.; As ethylene glycol alkyl oxide acetic ester, can enumerate for example methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate etc.;
As the glycol ether alkyl oxide, can enumerate for example diglycol monotertiary methyl ether, carbiphene, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, glycol ether ethyl-methyl ether etc.; As propylene-glycol monoalky lether, can enumerate for example propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether etc.;
As propylene glycol alkyl ether propionic ester, can enumerate for example methyl proxitol propionic ester, propylene glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester, propylene glycol butyl ether propionic ester etc.;
As propylene glycol alkyl ether acetic acid ester, can enumerate for example methyl proxitol acetate, propylene glycol ethyl ether acetic ester, propylene glycol propyl ether acetic ester, propylene glycol butyl ether acetic ester etc.;
As aromatic hydrocarbons, can enumerate for example toluene, dimethylbenzene etc.;
As ketone, can enumerate for example methyl ethyl ketone, pimelinketone, 4-hydroxy-4-methyl-2 pentanone, diisobutyl ketone etc.;
As ester, can enumerate for example methyl acetate, ethyl acetate, propyl acetate, butylacetate, the 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, the oxyacetic acid butyl ester, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, the 3-hydroxy methyl propionate, 3-hydroxy-propionic acid ethyl ester, 3-hydroxy-propionic acid propyl ester, 3-hydroxy-propionic acid butyl ester, 2-hydroxy-3-methyl methyl-butyrate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid propyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, the ethoxyacetic acid propyl ester, the ethoxyacetic acid butyl ester, the propoxy-methyl acetate, the propoxy-ethyl acetate, the propoxy-propyl acetate, the propoxy-butylacetate, the butoxy acetic acid methyl esters, the butoxy acetic acid ethyl ester, the butoxy acetic acid propyl ester, the butoxy acetic acid butyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxy-methyl propionate, 3-propoxy-ethyl propionate, 3-propoxy-propyl propionate, 3-propoxy-butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, 3-butoxy butyl propionate etc.
Wherein, preferred ethylene glycol alkyl oxide acetic ester, glycol ether alkyl oxide, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, preferred especially diethylene glycol dimethyl ether, glycol ether ethyl-methyl ether, methyl proxitol, propylene glycol ethyl ether, methyl proxitol acetate or 3-methoxypropionic acid methyl esters.
As used polymerization starter in polymkeric substance (1) synthetic, can use known initiator usually as radical polymerization initiator, for example can enumerate 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two-(2, the 4-methyl pentane nitrile), 2,2 '-azo two-azo-compounds such as (4-methoxyl group-2,4-methyl pentane nitriles); Benzoyl peroxide, lauroyl peroxide, tert-butyl hydroperoxide pivalate, 1, organo-peroxides such as 1 '-two (tert-butyl hydroperoxide) hexanaphthene; And hydrogen peroxide.When using superoxide, superoxide and reductive agent can also be used simultaneously as the oxidation-reduction type initiator as radical polymerization initiator.
In polymkeric substance (1) synthetic, can also use the molecular weight regulator of the molecular weight that is used for telomerized polymer (1).As its object lesson, can enumerate halogenated hydrocarbons such as chloroform, carbon tetrabromide; Thio-alcohols such as positive hexylmercaptan, octyl mercaptan, n-dodecane mercaptan, uncle's dodecyl mercaptans, Thiovanic acid; Dimethyl yellow essence sulfide (ジ メ チ Le キ サ Application ト ゲ Application ス Le Off イ De), plain disulphide xanthan element (the キ サ Application ト ゲ Application) classes such as (ジ イ ソ プ ロ ピ Le キ サ Application ト ゲ Application ジ ス Le Off イ De) of di-isopropyl xanthan; Terpinolene, α-Jia Jibenyixierjuwu etc.
In polymkeric substance (1) synthetic, preferably, it is controlled in the above-mentioned molecular weight ranges by suitably adjusting polymerizing condition (solvent species, solvent and monomeric feed ratio, polymerization temperature, initiator type and addition thereof, molecular weight regulator kind and addition thereof etc.).For reaching the suitable polymeric condition of above-mentioned molecular weight ranges, be that the technician can easily be known by carrying out a spot of preliminary experiment.
Can obtain containing the polymers soln of polymkeric substance (1) as mentioned above.This polymers soln can directly be supplied with the modulation of liquid crystal aligning agent, also polymkeric substance contained in the polymers soln (1) can be separated the back and supply with the modulation of liquid crystal aligning agent, perhaps the refining back of the polymkeric substance of separating (1) be supplied with the modulation of liquid crystal aligning agent.The separation of polymkeric substance (1) can obtain precipitate by above-mentioned polymers soln is put in a large amount of poor solvents, and the method for this precipitate of drying under reduced pressure is perhaps carried out polymers soln with vaporizer decompression distilled method again.In addition,, make its method of separating out with poor solvent then, perhaps carry out once or, can make with extra care polymkeric substance (1) several times with the method for vaporizer decompression distilled operation by isolating polymkeric substance (1) is dissolved in the organic solvent once more.
＜polyamic acid 〉
Polyamic acid among the present invention can make by making tetracarboxylic dianhydride and diamine reactant.
[tetracarboxylic dianhydride]
As used tetracarboxylic dianhydride in above-mentioned polyamic acid synthetic, can enumerate for example butane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-two chloro-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 3,5,6-three carboxyls norbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 5-(2, the 5-dioxotetrahydrofuryl)-and 3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxymethyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8,10-tetraketone, following formula (T-I) and aliphatics or the ester ring type tetracarboxylic dianhydrides such as compound that (T-II) represent separately;
(formula (T-I) and (T-II) in, R
1And R
3Expression has the divalent organic group of aromatic nucleus, R separately
2And R
4Represent hydrogen atom or alkyl separately, a plurality of R of existence
2And R
4Separately can be identical, also can be different);
Pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) sulfobenzide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two O-phthalic acid dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, two (phthalic acid) phosphniline oxide compound dianhydride, to phenylene-two (triphenyl phthalic acid) dianhydride, metaphenylene-two (triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-phenyl ether dianhydride, two (triphenyl phthalic acids)-4,4 '-ditan dianhydride, ethylene glycol-two (dehydration trimellitate), propylene glycol-two (dehydration trimellitate), 1,4-butyleneglycol-two (dehydration trimellitate), 1,6-hexylene glycol-two (dehydration trimellitate), 1,8-ethohexadiol-two (dehydration trimellitate), 2,2-two (4-hydroxyphenyl) propane-two (dehydration trimellitate), aromatic tetracarboxylic acid's dianhydrides such as the compound that following formula (T-1)～(T-3) is represented separately etc.They can a kind ofly be used alone or in combination of two or more.
As the tetracarboxylic dianhydride who uses in polyamic acid synthetic, above-mentioned in the middle of, from making the angle of the good liquid crystal aligning of its performance, preferably include and be selected from the butane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxymethyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8,10-tetraketone, pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 1,4,5, the tetracarboxylic dianhydride of at least a (hereinafter referred to as " specific tetracarboxylic dianhydride (1) ") in the group that the compound of following formula (T-7) expression in the compound that the following formula (T-4)～(T-6) in the compound of 8-naphthalene tetracarboxylic acid dianhydride, above-mentioned formula (T-I) expression is represented separately and the compound of above-mentioned formula (T-II) expression constitutes.
Particularly preferred specific tetracarboxylic dianhydride (1) is for being selected from 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxymethyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8, at least a in the group that 10-tetraketone and pyromellitic acid dianhydride constitute.
As the synthetic middle tetracarboxylic dianhydride who uses of polyamic acid, preferably contain 30 moles of aforesaid specific tetracarboxylic dianhydrides (1) more than the % with respect to whole tetracarboxylic dianhydrides, more preferably contain 50 moles more than the %.
The synthetic middle diamines that uses as above-mentioned polyamic acid, can enumerate for example Ursol D, mphenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formylaniline, 4,4 '-diaminodiphenyl oxide, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 3,3 '-two (trifluoromethyl)-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diamino benzophenone, 3,4 '-diamino benzophenone, 4,4 '-diamino benzophenone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 2,2-two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,4-two (4-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 9,9-two (4-aminophenyl)-10-hydrogen anthracene, 2, the 7-diamino-fluorene, 9,9-dimethyl-2,7 diamin of luorene, 9,9-two (4-aminophenyl) fluorenes, 4,4 '-methylene radical-two (2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 4,4 '-(to the phenylene diisopropylidene) pentanoic, 4,4 '-(metaphenylene diisopropylidene) pentanoic, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-aromatic diamines such as octafluoro biphenyl;
2,3 diamino pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 5,6-diamino-2,3-dicyano pyrazine, 5,6-diamino-2,4-dihydroxy-pyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazines, 1,4-two (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazines, 2,4-diamino-6-methoxyl group-1,3, the 5-triazine, 2,4-diamino-6-phenyl-1,3, the 5-triazine, 2,4-diamino-6-methyl-s-triazine, 2, the 4-diaminostilbene, 3, the 5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenyl thiazole, 2, the 6-diaminopurine, 5, the 6-diaminostilbene, the 3-dimethyl uracil, 3, the 5-diaminostilbene, 2, the 4-triazole, 6,9-diamino-2-oxyethyl group acridine lactate, 3,8-diamino-6-phenylphenanthridineand, 1,4-diamino piperazine, 3, the 6-proflavin, two (4-aminophenyl) phenyl amine, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-two (4-aminophenyl) p-diaminodiphenyl, the compound of following formula (D-I) expression
(in the formula (D-I), R
5Expression has any monovalent organic radical group of the nitrogen atom ring texture in the group that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine formation, X
1The organic group of expression divalence, R
6For carbonatoms is 1～4 alkyl, a1 is 0～3 integer), have the diamines of the nitrogen-atoms beyond 2 primary aminos and this primary amino in the compound equimolecular of following formula (D-II) expression,
(in the formula (D-II), R
7Expression has the divalent organic group of the nitrogen atom ring texture in the group that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine formation, X
2The organic group of representing divalence separately, a plurality of X of existence
2Separately can be identical, also can be different, R
8The carbonatoms of respectively doing for oneself is 1～4 alkyl, respectively do for oneself 0～4 integer of a2);
1,3-two (amino methyl) hexanaphthene, 1,3-propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene Dicyclopentadiene (DCPD) diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.0
2,7] 11 alkylidene group dimethyl diamines, 4,4 '-methylene radical two aliphatics or ester ring type diamines such as (hexahydroaniline);
The diamino organo-siloxanes such as compound of following formula (D-III) expression etc.,
(in the formula (D-III), R
9Represent that separately carbonatoms is 1～12 alkyl, a plurality of R of existence
9Separately can be identical, also can be different, respectively do for oneself 1～3 integer of s, t is 1～20 integer).These diamines can be used alone or in combination of two or more.
The phenyl ring of above-mentioned aromatic diamine, optional can be that 1～4 alkyl (preferable methyl) replaces by one or more carbonatoms.Above-mentioned formula (D-I) and (D-II) in R
6And R
8Be preferably methyl separately, a1 and a2 are preferably 0 or 1 separately, and more preferably 0.
The synthetic middle diamines that uses as the polyamic acid among the present invention, in the middle of above-mentioned, be preferably selected from Ursol D, 4,4 '-diaminodiphenylmethane, 4,4 '-diamino-diphenyl thioether, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-diamino-2,2 '-dimethyl diphenyl, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, the compound of following formula (D-1) expression in the compound of above-mentioned formula (D-I) expression, the compound of following formula (D-2) expression in the compound of above-mentioned formula (D-II) expression;
1,3-two (amino methyl) hexanaphthene, 1,4-cyclohexane diamine, 4,4 '-methylene radical two (hexahydroaniline),
3,3 '-(tetramethyl disiloxane-1,3-two bases) two (propylamine) of following formula (D-3) expression in the compound of above-mentioned formula (D-III) expression,
3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole and N, at least a (hereinafter referred to as " the specific diamines ") in the group that N '-two (4-aminophenyl) p-diaminodiphenyl constitutes.
Particularly preferred specific diamines is a Ursol D, 4,4 '-diaminodiphenylmethane, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 4,4 '-diamino-2, at least a in the group that 2 '-dimethyl diphenyl and 1,3-two (amino methyl) hexanaphthene constitute.
The synthetic middle diamines that uses as polyamic acid preferably contains 1 mole of aforesaid specific diamines more than the % with respect to whole diamines, more preferably contains 10 moles more than the %.
Liquid crystal aligning agent of the present invention, by polymkeric substance (1) in the composition of above-mentioned polymkeric substance (1) and the liquid crystal aligning agent contained rate regulation in suitable scope, can make it show required tilt angle, and when liquid crystal aligning agent of the present invention is used for TN type, STN type, OCB type or VA type liquid crystal display device, have the synthetic middle diamines that use of the diamines at tilt angle performance position by use, also can control the tilt angle of gained liquid crystal orientation film as contained polyamic acid or its imide amination polymer in the liquid crystal aligning agent.
As this diamines, can enumerate the compound of for example following formula (D-IV) expression or the compound of following formula (D-V) expression etc. with tilt angle performance position.
(in the formula (D-IV), R
10And R
11Be hydrogen atom or methyl independently of one another, R
12For the carbonatoms of straight or branched is 1～20 alkyl, R
13And R
14Be the organic group of divalence independently of one another);
(in the formula (D-V), R
15For Sauerstoffatom, sulphur atom ,-CO-,-COO-,-OCO-,-NHCO-,-CONH-or methylene radical, R
16For the univalent perssad with cholestane skeleton or cholestene skeleton, the univalent perssad with trifluoromethyl or Trifluoromethoxyphen-l or carbonatoms are 1～22 alkyl, R
17For carbonatoms is 1～4 alkyl, a3 is 0～3 integer).These diamine compounds with tilt angle performance position can a kind ofly be used alone or in combination of two or more.
As R in the above-mentioned formula (D-V)
16The univalent perssad with cholestane skeleton or cholestene skeleton, preferred carbonatoms is 17～30 group, can enumerate for example 3-cholestane base, 3-cholesteryl etc.R
17Be preferably methyl, a3 is preferably 0 or 1, and more preferably 0.
As the object lesson of the compound of above-mentioned formula (D-IV) expression, can enumerate for example following formula (D-4) and the compound (D-5) represented separately etc.;
As the object lesson of the compound of above-mentioned formula (D-V) expression, can enumerate compound that for example following formula (D-6)～(D-10) represents separately etc.
When liquid crystal aligning agent of the present invention is used for VA type liquid crystal display device, from showing good liquid crystal vertical-tropism, the preferred compound that uses formula (D-V) expression in the above-mentioned diamine compound with tilt angle performance position, more preferably use to be selected from least a in the compound that above-mentioned formula (D-6)～(D-10) represent separately, preferably especially use at least a in the compound that the compound that is selected from above-mentioned formula (D-6) expression and above-mentioned formula (D-7) represent.
Have the usage rate of the diamines at tilt angle performance position, with respect to whole diamines, be preferably 8～60 moles of %, more preferably 9～50 moles of % are preferably 10～40 moles of % especially.In this case, also can have the diamines and the above-mentioned specific diamines coupling at tilt angle performance position, the usage rate of above-mentioned specific diamines with respect to whole diamines, is preferably 1～90 mole of %, more preferably 10～90 moles of % at this moment.
[synthesizing of polyamic acid]
Supply with the tetracarboxylic dianhydride of polyamic acid building-up reactions and the usage rate of diamines, preferably with respect to 1 contained in diamines equivalent amino, the anhydride group that makes the tetracarboxylic dianhydride is 0.2～2 normal ratio, more preferably is 0.3～1.2 normal ratio.
The building-up reactions of polyamic acid preferably in organic solvent, is preferable over-20～150 ℃, more preferably carries out under 0～100 ℃ temperature condition.Reaction times is preferably 0.1～100 hour, more preferably 1～50 hour.
As operable organic solvent here, as long as can dissolve the polyamic acid of generation, then it is had no particular limits, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, N, N-N,N-DIMETHYLACETAMIDE, N, aprotic polar solvents such as dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA; Between phenol solvent such as sylvan, xylenol, phenol, halogenated phenol.In addition, the consumption of organic solvent (a), being preferably the total amount (b) that makes tetracarboxylic dianhydride and diamine compound is the amount of 0.1～30 weight % with respect to the total amount (a+b) of reaction soln.Here, when the poor solvent coupling of organic solvent and the following stated, the consumption of above-mentioned organic solvent (a) should be understood to the implication of the total amount of organic solvent and poor solvent.
In the above-mentioned organic solvent, can also be in the scope that the polyamic acid that does not make generation is separated out, coupling is commonly referred to be alcohols, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons of the poor solvent of polyamic acid etc.Object lesson as this poor solvent, can enumerate for example methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, 1, the 4-butyleneglycol, triglycol, ethylene glycol monomethyl ether, ethyl lactate, n-Butyl lactate, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, ritalin, vinyl acetic monomer, N-BUTYL ACETATE, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, oxalic acid diethyl ester, diethyl malonate, ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the ethylene glycol positive propyl ether, glycol isopropyl ether, the ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethyl cellosolve acetate, diglyme, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic ester, the diethylene glycol monoethyl ether acetic ester, tetrahydrofuran (THF), methylene dichloride, 1, the 2-ethylene dichloride, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene, isoamyl propionate, isoamyl isobutyrate, isoamyl ether etc.
When with organic solvent during with aforesaid poor solvent coupling, the usage rate of poor solvent can suitably be set in the scope that the polyamic acid that generated is separated out, with respect to whole solvents, be preferably below the 70 weight %, more preferably below the 50 weight %.
As mentioned above, obtained dissolving the reaction soln of polyamic acid.This reaction soln directly can be supplied with the modulation of liquid crystal aligning agent, also polyamic acid contained in the reaction soln can be separated the back and supply with the modulation of liquid crystal aligning agent, resupply the modulation of liquid crystal aligning agent after perhaps also isolated polyamic acid can being made with extra care.The separation of polyamic acid can obtain precipitate by above-mentioned reaction soln is put in a large amount of poor solvents, and the method for this precipitate of drying under reduced pressure is perhaps carried out reaction soln with vaporizer decompression distilled method again.In addition,, make its method of separating out with poor solvent then, perhaps carry out once or, can make with extra care polyamic acid several times with the method for vaporizer decompression distilled operation by this polyamic acid is dissolved in the organic solvent once more.
＜imide amination polymer 〉
The imide amination polymer of the polyamic acid among the present invention can carry out dehydration closed-loop and make by the polyamic acid that will as above make.Here so-called imide amination polymer is meant the implication of the complete imidization thing of the part imidization thing that comprises above-mentioned polyamic acid part imidization and 100% imidization, below it is referred to as " imide amination polymer ".
[tetracarboxylic dianhydride]
As the tetracarboxylic dianhydride who uses in above-mentioned imide amination polymer synthetic, can enumerate and above-mentioned polyamic acid synthetic in the identical compound of tetracarboxylic dianhydride that uses.
As used tetracarboxylic dianhydride in imide amination polymer contained in the liquid crystal aligning agent of the present invention synthetic, preferably contain the tetracarboxylic dianhydride who is selected from least a (hereinafter referred to as " specific tetracarboxylic dianhydride (2) ") in the group that ester ring type tetracarboxylic dianhydride and pyromellitic acid dianhydride constitute.
Particularly preferred specific tetracarboxylic dianhydride (2) is for being selected from 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxymethyl norbornane-2:3,5:6-dianhydride and 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8, at least a in the group that the 10-tetraketone constitutes.
As used tetracarboxylic dianhydride in imide amination polymer synthetic, preferably with respect to whole tetracarboxylic dianhydrides, contain the above above-mentioned specific tetracarboxylic dianhydride (2) of 30 moles of %, more preferably contain 50 moles more than the %.
[diamines]
As used diamines in above-mentioned imide amination polymer synthetic, can enumerate and above-mentioned polyamic acid synthetic in the identical diamines of diamines that uses.
[synthetic method of imide amination polymer]
The reaction of the dehydration closed-loop of polyamic acid can (i) by the method for heating polyamic acid, perhaps (ii) by polyamic acid is dissolved in the organic solvent, in this solution, adds the method for dewatering agent and dehydration closed-loop catalyzer and heating as required and carry out.
Temperature of reaction in the method for the heating polyamic acid of above-mentioned (i) is preferably 50～300 ℃, more preferably 60～170 ℃.When 50 ℃ of temperature of reaction less thaies, then the dehydration closed-loop reaction can not be carried out fully, if temperature of reaction surpasses 300 ℃, the situation of the molecular weight and molecular weight of gained imide amination polymer then can occur.Reaction times is preferably 2～24 hours, more preferably 3～10 hours.
On the other hand, in the above-mentioned method of in polyamic acid solution, adding dewatering agent and dehydration closed-loop catalyzer (ii),, can use for example acid anhydrides such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride as dewatering agent.The consumption of dewatering agent, 1 mole of amido acid structure with respect to polyamic acid is preferably 0.01～20 mole.In addition, as the dehydration closed-loop catalyzer, can use for example tertiary amines such as pyridine, collidine, lutidine, triethylamine.But, be not limited to these.The dehydration closed-loop catalyst consumption with respect to 1 mole of used dewatering agent, is preferably 0.01～10 mole.In addition, as used organic solvent in the dehydration closed-loop reaction, can enumerate as polyamic acid and synthesize middle solvent for use and illustrative organic solvent.And the temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, and more preferably 10～150 ℃, the reaction times is preferably 2～8 hours, more preferably 3～6 hours.
The imide amination polymer that makes in the aforesaid method (i) can directly be supplied with it modulation of liquid crystal aligning agent, resupplies the modulation of liquid crystal aligning agent after perhaps also the imide amination polymer that makes can being made with extra care.In addition, aforesaid method (ii) in, obtain containing the reaction soln of imide amination polymer.This reaction soln, it directly can be supplied with the modulation of liquid crystal aligning agent, also can from reaction soln, remove dewatering agent and dehydration closed-loop catalyzer and supply with the modulation of liquid crystal aligning agent afterwards, imide amination polymer can also be separated the back and supply with the modulation of liquid crystal aligning agent, resupply the modulation of liquid crystal aligning agent after perhaps also isolating imide amination polymer can being made with extra care.From reaction soln, remove dewatering agent and dehydration closed-loop catalyzer, can adopt for example method such as solvent exchange.The separation of imide amination polymer, refining can be taked to carry out with the above same operation of describing as the separating of polyamic acid, process for purification.
The imidization rate of-imide amination polymer-
The imidization rate of used imide amination polymer among the present invention is preferably 10～99 moles of %, and more preferably 20～99 moles of % are preferably 45～99 moles of % especially.Here, so-called " imidization rate " is meant the total quantity with respect to amido acid structure number in the imide amination polymer and imide ring structure number, the value that the quantity ratios of imide ring structure is represented with percentage.At this moment, the part of imide ring is different imide ring, is also included within the quantity of imide structure.This imidization rate can be dissolved in the suitable deuterated solvent (for example deuterated dimethyl sulfoxide) by with after the preferred thorough drying of imide amination polymer, is primary standard with the tetramethylsilane, at room temperature measures
1H-NMR is obtained by following formula (A) by measurement result.
Imidization rate (%)=(1-A
1/ A
2* α) * 100 (A)
A
1: near the peak area that comes from NH matrix that occurs the 10ppm
A
2: the peak area that comes from other protons
α: with respect to 1 NH matrix in the precursor (polyamic acid) of imide amination polymer, the individual percentage of other protons
The polymkeric substance of-end modified type-
Contained polyamic acid and imide amination polymer in the liquid crystal aligning agent of the present invention can also be the end modified type polymkeric substance that has carried out molecular-weight adjusting separately.By using the polymkeric substance of end modified type, can under the prerequisite of not damaging effect of the present invention, further improve the coating performance of liquid crystal aligning agent etc.This end modified type polymkeric substance can be by when polyamic acid synthetic, adds molecular weight regulator and prepare in polymerization reaction system.As molecular weight regulator, can enumerate for example single acid anhydride, monoamine compound, monoisocyanates compound etc.
As above-mentioned single acid anhydride, can enumerate for example maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide etc.As above-mentioned monoamine compound, can enumerate for example aniline, hexahydroaniline, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, Pentadecane amine, n-hexadecane amine, n-heptadecane amine, Octadecane amine, NSC 62789 amine etc.As above-mentioned monoisocyanates compound, can enumerate for example phenylcarbimide, isocyanic acid naphthyl ester etc.
The usage rate of molecular weight regulator, under the situation of single acid anhydride, the whole tetracarboxylic dianhydrides that use during with respect to synthesizing polyamides acid, under the situation of monoamine compound, the whole diamines that use during with respect to synthesizing polyamides acid, under the situation of monoisocyanates compound, the whole tetracarboxylic dianhydrides that use during with respect to synthesizing polyamides acid, be preferably 5 moles respectively below the %, more preferably 2 moles below the %.
-soltion viscosity-
The polyamic acid that as above makes or its imide amination polymer when being made into concentration when being the solution of 20 weight %, preferably have the soltion viscosity of 500～10000mPas, more preferably have the soltion viscosity of 1000～7000mPas.
The soltion viscosity of above-mentioned polymkeric substance (mPas) is to be the polymers soln of 20 weight % to the synthetic concentration of good solvent (for example N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolactone etc.) that adopts this polymkeric substance, with E type rotational viscosimeter 25 ℃ of values of measuring down.
[usage rate of polyamic acid and imide amination polymer]
Be selected from the usage rate of at least a polymkeric substance in the group that polyamic acid and imide amination polymer constitute in the liquid crystal aligning agent of the present invention, be preferably the weight (W of the polymkeric substance (1) that makes in the liquid crystal aligning agent
1) with the total weight (W of polyamic acid and imide amination polymer
2) ratio W
1: W
2=1: 99～90: 10 amount, more preferably W
1: W
2=2: 98～80: 20 amount is preferably W especially
1: W
2=3: 97～60: 40 amount.
＜other additives 〉
Liquid crystal orientation film of the present invention contain aforesaid polymkeric substance (1) and be selected from polyamic acid and group that imide amination polymer constitutes in the essential composition of at least a conduct, and can also contain other compositions as required.As this other compositions, for example can enumerating, functional silanes compound, intramolecularly have low molecular compound (hereinafter referred to as " epoxy compounds ") of 2 above epoxy group(ing) etc.These functional silanes compounds or epoxy compounds can be in order further to improve the gained liquid crystal orientation film binding property of substrate surface and electric property to be added in the liquid crystal aligning agent of the present invention.
As above-mentioned functional silanes compound, can enumerate for example 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxycarbonyl-3-TSL 8330, N-ethoxycarbonyl-3-aminopropyltriethoxywerene werene, N-tri-ethoxy silylpropyl diethylenetriamine, N-Trimethoxy silane base propyl group diethylenetriamine, 10-Trimethoxy silane base-1,4,7-three azepine decane, 10-triethoxysilicane alkyl-1,4,7-three azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, N-two (oxyethylene group)-3-TSL 8330, N-two (oxyethylene group)-3-aminopropyltriethoxywerene werene etc.When using these functional silanes compounds, its usage rate, total amount with respect to 100 parts by weight polymer (is meant the total amount of polymkeric substance (1), polyamic acid and imide amination polymer, down together), be preferably 1～50 weight part, more preferably 2～40 weight parts are preferably 3～20 weight parts especially.
Above-mentioned epoxy compounds is the different compound of situation that has the cyclic ether structure with above-mentioned polymkeric substance (1), specifically, is meant the compound of molecular weight less than 2000.As this epoxy compounds, preferably can enumerate for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidylether, 1,3,5,6-four glycidyl group-2, the 4-hexylene glycol, N, N, N ', N '-four glycidyl group-m-benzene dimethylamine, 1,3-two (N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N, N, N ', N '-four glycidyl group Ursol D, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethyl hexanaphthene etc.When using these epoxy compounds, its usage rate, the total amount with respect to 100 parts by weight polymer is preferably 1～50 weight part, and more preferably 1～30 weight part is preferably 1～20 weight part especially.
＜liquid crystal aligning agent 〉
Liquid crystal aligning agent of the present invention is with aforesaid polymkeric substance (1), is selected from least a and optional as required other additives of blended in the group that polyamic acid and imide amination polymer thereof constitute, and preferred dissolution is contained in the organic solvent and constitutes.
As operable organic solvent in the liquid crystal aligning agent of the present invention, can enumerate with building-up reactions as polymkeric substance (1) in used solvent and illustrative same solvent.
As the particularly preferred organic solvent that uses in the liquid crystal aligning agent of the present invention, consider from the printing angle, can enumerate the N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2 pentanone, ethylene glycol monomethyl ether, n-Butyl lactate, butylacetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol n-butyl ether (ethylene glycol butyl ether), ethylene glycol dimethyl ether, ethyl cellosolve acetate, diglyme, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic ester, the diethylene glycol monoethyl ether acetic ester, isoamyl propionate, isoamyl isobutyrate, isoamyl ether etc.They can use separately, perhaps also can two or more mixing use.
Particularly preferred solvent composition in the liquid crystal aligning agent of the present invention is the composition that above-mentioned solvent is made up gained, is to make in the liquid crystal aligning agent can not separate out solids component, and makes the surface tension of liquid crystal aligning agent drop on the composition of 25～40mN/m scope.
The solids content concn of liquid crystal aligning agent of the present invention (gross weight of the composition in the liquid crystal aligning agent beyond the solvent accounts for the ratio of liquid crystal aligning agent gross weight) is considered viscosity, volatility etc. and is selected, be preferably 1～50 weight %, more preferably 2～40 weight %, the more preferably scope of 3～30 weight %.That is to say, liquid crystal aligning agent of the present invention, form as the filming of liquid crystal orientation film by it being coated on substrate surface and removing to desolvate, when solids content concn less than 1 weight %, it is too small and be difficult to obtain the situation of good liquid crystal orientation film this thickness of filming to occur.On the other hand, when solids content concn surpassed 50 weight %, the thickness that will occur filming was blocked up and be difficult to obtain good liquid crystal orientation film, and, the viscosity of liquid crystal aligning agent increases, and causes applying degradation and the situation that can not obtain the good liquid crystal orientation film of internal homogeneity.
In addition, particularly preferred solids content concn scope, the coating method that is adopted when liquid crystal aligning agent is coated on substrate and difference.More particularly, have suitable soltion viscosity for each coating method, preferably liquid crystal aligning agent is adjusted to suitable solids content concn in order to make it.For example, when adopting spin-coating method, preferably the soltion viscosity of liquid crystal aligning agent is adjusted to the scope of 3.0～10.0mPas.When adopting print process, preferably the soltion viscosity of liquid crystal aligning agent is adjusted to the scope of 12～50mPas.When adopting ink jet method, preferably the soltion viscosity of liquid crystal aligning agent is adjusted to the scope of 3～15mPas.
Temperature when modulating liquid crystal aligning agent of the present invention is preferably 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
＜liquid crystal display device 〉
Liquid crystal display device of the present invention has the liquid crystal orientation film that is formed by aforesaid liquid crystal aligning agent of the present invention.
Liquid crystal display device of the present invention can be by for example following method manufacturing.
(1) at first, coating liquid crystal aligning agent of the present invention removes and desolvates on a pair of substrate, and formation is filmed.Here, when the display format of the liquid crystal display device that will make is vertical electric field mode such as TN type, STN type, VA type, use as a pair of substrate with two substrates that on single face, are provided with the nesa coating that forms pattern.In addition, when the display format of the liquid crystal display device that will make is lateral electric field type, will be provided with the substrate of nesa coating and have the substrate of nesa coating to use as a pair of substrate with broach shape pattern.
Under above-mentioned arbitrary situation, all liquid crystal aligning agent is coated on the substrate and (when substrate has nesa coating, is coated on the face with nesa coating of substrate).As substrate, can use for example glass such as float glass, soda-lime glass; Polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-plastics system transparency carriers such as (ester ring type alkene).Simultaneously go up the nesa coating that is provided with as substrate, can use for example stannic oxide (SnO
2) system NESA film (U.S. PPG register of company trade mark), Indium sesquioxide-stannic oxide (In
2O
3-SnO
2) the ITO film etc. of system.In addition, these form the acquisition of the nesa coating of patterns, can adopt after forming patternless nesa coating by photoetch method to form method of patterning, adopt the directly method etc. of the nesa coating of formation patterning such as mask with required pattern when nesa coating forms.
Coated with liquid crystal alignment agent on substrate can adopt suitable coating methods such as rolling method, spin-coating method, print process, ink jet method to carry out.When the coating of liquid crystal aligning agent,, can also on coated of substrate, apply functional silanes compound, functionality titanium compound etc. in advance for the binding property of further improving substrate surface and nesa coating and filming.
After the coating, the purpose for the sagging grade of alignment agent liquid that prevents to apply preferably preheats (prebake).The prebake temperature is preferably 30～200 ℃, and more preferably 40～150 ℃, preferred especially 40～100 ℃.The prebake time is preferably 0.5～10 minute, more preferably 0.5～5 minute.Then, in order to remove purpose such as desolvate fully, carry out roasting (afterwards curing) operation.Cure after this, except so that solvent from film, remove fully to the purpose, when polymkeric substance contained in the liquid crystal aligning agent of the present invention (1) is when containing the polymkeric substance of repeating unit of the cyclic ether structure with above-mentioned formula (2) expression, can also be that purpose is carried out with the heat cross-linking reaction that promotes this cyclic ether structure.After the temperature of curing, be preferably 80～300 ℃, more preferably 120～250 ℃.After the time of curing be preferably 5～180 minutes, more preferably 10～120 minutes.
Like this, can form filming as liquid crystal orientation film.Formed thickness of filming is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
In addition, when the liquid crystal display device of using liquid crystal aligning agent of the present invention is VA type liquid crystal display device, can also be described in for example patent documentation 3 (TOHKEMY 2002-327058 communique), coated with liquid crystal alignment agent again after forming the overshooting shape structure on the substrate is to reach the purpose of improving viewing angle properties.
(2) when the display format of the liquid crystal display device that will make is the VA type, filming of as above forming can directly be used as liquid crystal orientation film, also can carry out following grinding process as required.On the other hand, when vertical electric field mode beyond the display format of the liquid crystal display device that will make is the VA type and lateral electric field type, the coated surface that forms is carried out grinding process.
Grinding process adopts by be tied with the method that the roller of fibrous cloth such as nylon, regenerated fiber, cotton for example rubs on certain orientation is undertaken.Like this, give and filming, make liquid crystal orientation film with the liquid crystal molecular orientation energy.In addition, by to filming after the grinding process, carry out shown in patent documentation 4 (Japanese kokai publication hei 6-222366 communique) for example or the patent documentation 5 (Japanese kokai publication hei 6-281937 communique), to a part of irradiation ultraviolet radiation of liquid crystal orientation film and the processing that the tilt angle of the subregion of liquid crystal orientation film is changed, perhaps carry out shown in the patent documentation 6 (Japanese kokai publication hei 5-107544 communique), after forming etchant resist on the part on liquid crystal orientation film surface, carry out the processing of removing etchant resist after the grinding process with the direction different with previous grinding process, make each zone of liquid crystal orientation film have different liquid crystal aligning energy, can improve the visual field performance of gained liquid crystal display device like this.
(3) as above prepare two substrates that form liquid crystal orientation film,, make liquid crystal cell by will between two substrates that are provided with, arranging liquid crystal relatively.Here, when having carried out grinding process, make the polishing direction of respectively filming be in the angle of regulation to filming, for example vertical or antiparallel, with two substrates relatively to the ground setting.
The making of liquid crystal cell can be enumerated for example following two kinds of methods.
First method is previously known method.At first, make separately liquid crystal orientation film relatively to, with two substrates by gap (box gap) relatively to the ground setting, fitted with sealing agent in the peripheral position of two substrates, annotate the topping up crystalline substance in the box gap that is surrounded by substrate surface and sealing agent after, the sealing filling orifice can make liquid crystal cell.
Second method is the method that is called ODF (One Drop Fill) mode.Regulation position on the substrate in two substrates that form liquid crystal orientation film, apply for example ultra-violet solidified sealant material, again behind the liquid crystal that drips on the liquid crystal aligning face, make liquid crystal orientation film relatively to ground another piece substrate of fitting, then to whole irradiation ultraviolet radiation of substrate, make sealant cures, can make liquid crystal cell.
Adopting under the situation of arbitrary method, all needing further the liquid crystal cell of as above making is heated to after used liquid crystal is the temperature of isotropic phase, slowly cooling to room temperature, the flow orientation when eliminating liquid crystal and filling.
Then, the polaroid of fitting on the outer surface of liquid crystal cell can make liquid crystal display device of the present invention.
Here, as sealing agent, can use Resins, epoxy that for example contains as the alumina balls of solidifying agent and separator etc.
As above-mentioned liquid crystal, can use for example nematic liquid crystal, dish shape type liquid crystal etc., wherein preferred nematic liquid crystal.When being VA type liquid crystal cell, preferably have the nematic liquid crystal of negative dielectric anisotropic, can use for example diaminobenzene class liquid crystal, pyridazine class liquid crystal, schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal etc.When being TN type liquid crystal cell or STN type liquid crystal cell, the nematic liquid crystal that preferably has positive dielectric anisotropy can use for example biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cube alkanes liquid crystal etc.Can also further add for example cholesteryl liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal; Chirality agent with trade(brand)name " C-15 ", " CB-15 " (production of メ Le Network society) sale; To oxygen base Ben Yajiaji-to ferroelectric liquid crystals such as amino-2-methyl butyl laurate etc. and using in the last of the ten Heavenly stems.
As the polaroid of fitting on the liquid crystal cell outside surface, can enumerate polyvinyl alcohol is extended that the light polarizing film that is referred to as " H film " that orientation absorbs iodine simultaneously is clipped in the cellulose acetate protective membrane and the polaroid of making, perhaps the polaroid made of H film self.
[embodiment]
Below, by embodiment the present invention is carried out more specific description, but the present invention is not limited to these embodiment.
The evaluation of the vertical orientated property of the mensuration of the soltion viscosity of the polymkeric substance in embodiment and the comparative example, weight-average molecular weight and molecular weight distribution, the manufacturing of liquid crystal display device and liquid crystal display device, voltage retention and anti-burning screen property is carried out according to following method.
[mensuration of soltion viscosity]
The soltion viscosity of polymkeric substance (mPas) adopts E type rotational viscosimeter under 25 ℃ the polymers soln shown in each synthesis example to be measured.
[mensuration of weight-average molecular weight and molecular weight distribution]
Adopt gel permeation chromatography (GPC) to measure the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) of polystyrene conversion under the following conditions, try to achieve the value of molecular weight distribution (Mw/Mn).
" HLC-8020 " that GPC determinator: East ソ one (strain) made
Post " TSK guardcolum α ", " the TSK gel α-M " that pillar: East ソ one (strain) made is connected with " TSK gel α-2500 " and uses.
Solvent: 9.4g lithiumbromide monohydrate and 1.7g phosphoric acid are dissolved in the solution in the 3L dimethyl formamide
Measure temperature: 35 ℃.
[manufacturing of liquid crystal display device]
Adopting spin coater that synthetic liquid crystal aligning agent in each embodiment or the comparative example is coated in glass substrate simultaneously goes up on the ITO film system nesa coating that is provided with, on the hot-plate in 80 ℃ of prebake after 1 minute, cured 1 hour after under 200 ℃ in cleaning oven (under the nitrogen environment), making and form thickness on nesa coating is the substrate of filming of 60nm.The sander of the roller that twines Artificial Fibers cloth is equipped with in employing, is that 400rpm, operator's console translational speed are 30mm/ second at the roller rotating speed, and fine hair is clamp-oned under the condition that length is 0.4mm, and this substrate is carried out grinding process 1 time, and making films produces the liquid crystal aligning energy.Use ultrasonic washing after 1 minute in pure water this substrate then, drying is 10 minutes in 100 ℃ cleaning oven, makes the substrate with liquid crystal orientation film.Repeat these operations, make the substrate that a pair of (2) have liquid crystal orientation film.
Then, on each outer rim of the face with liquid crystal orientation film of above-mentioned a pair of substrate with liquid crystal orientation film, coating relatively overlaps the liquid crystal aligning face and pressing after having added the epoxy resin binder of alumina balls that diameter is 5.5 μ m, and tackiness agent is solidified.
Then, in substrate gap, fill negative type liquid crystal (メ Le Network society system by liquid crystal injecting port, MLC-2038) after, with the acrylic acid or the like Photocurable adhesive liquid crystal injecting port is sealed, the polaroid of fitting on two outer sides of substrate produces liquid crystal display device (vertical alignment-type liquid crystal display device).
[evaluation of vertical orientated property]
To the vertical alignment-type liquid crystal display device of as above making, the anchoring strength determinator " OMS-J3 " that adopts Zhong Yang Jing Machine (strain) to make is measured tilt angle, this tilt angle is more than 87 °, vertical orientated property can be chosen as " well ", less than 87 °, vertical orientated property can be chosen as " defective ".
[evaluation of voltage retention]
Under 60 ℃, under 1670 milliseconds time span, the liquid crystal display device of as above making is applied the voltage of 5V, the voltage application time is 60 microseconds, then in the voltage retention of measuring under 60 ℃ the environment after removing to 1670 milliseconds from voltage.The voltage retention determinator adopts the (VHR-1 of strain) East Yang テ Network ニ カ system.If the value of voltage retention is more than 97.5%, then voltage retention can be chosen as " well ", if less than 97.5% then can be chosen as " defective ".
[reliability test of liquid crystal display device (free of surface defects is arranged)]
Under hot and humid degree environment (70 ℃ of temperature, relative humidity 80%),, after 1500 hours, have or not the display defect of leukasmus point-like with microscopic examination with 5V, 60Hz rectangular wave drive liquid crystal display device.Its result does not have the situation of the display defect of leukasmus point-like, and reliability evaluation is " well ", has the situation of leukasmus point-like display defect, and reliability evaluation is " defective ".
[evaluation (mensuration of residual DC voltage, accelerated test) of anti-burning screen property]
After under 100 ℃ the environment liquid crystal display device of as above making being applied the volts DS of 20 hours 17V, remove this voltage application, under room temperature environment, leave standstill 15 minutes after, adopt the flicker null method to obtain residual voltage (residual DC voltage) in the liquid crystal cell.The residual DC magnitude of voltage is little, can be evaluated as long-term anti-burning screen property liquid crystal display device with excellent.The residual DC magnitude of voltage is the following liquid crystal display device of 200mV, and anti-burning screen property can be chosen as " well ", and when the residual DC magnitude of voltage was higher than 200mV, anti-burning screen property can be chosen as " defective ".
Synthesis example 1 (synthesizing of compound (4 '))
800g β-cholesterol is dissolved in the 8000ml dehydration tetrahydrofuran (THF) (THF), behind the adding 270g triethylamine, slowly drips the 360g methacrylic chloride, at room temperature stir and reacted in 3 hours.After reaction finishes, by removing by filter triethylamine hydrochloride, by decompression distillate remove THF after, add the 4000ml chloroform.Wash this gained solution, organic layer with dried over mgso after, distillate by decompression and to remove chloroform.Then, carry out recrystallization, obtain 540g white solid methacrylic acid cholestane base ester (yield rate: 57.4%) with ethanol.
Synthesis example 2 (synthetic (1) of polymkeric substance (1))
To stirring rod is housed, in the four neck flasks of T-valve and thermometer, adding is as monomeric methacrylic acid 2,2,2-trifluoro ethyl ester 10.0g (0.0595 mole), the methacrylic acid cholestane base ester 30.0g (0.0657 mole) that makes in the above-mentioned synthesis example 1, glycidyl methacrylate 25.0g (0.176 mole), methacrylic acid 10.0g (0.116 mole), vinylbenzene 2.50g (0.0240 mole), N-cyclohexyl maleimide 2.50g (0.0139 mole) and methacrylic acid 2-hydroxyethyl ester 20.0g (0.154 mole), add glycol ether ethyl-methyl ether 200g again as solvent, as 2 of polymerization starter, 2 '-azo two (2, the 4-methyl pentane nitrile) 4.50g and as the α-Jia Jibenyixierjuwu 2.00g of molecular weight regulator.With it with about 10 minutes of nitrogen gas stream bubbling, carry out the nitrogen ventilation in the system after, under nitrogen environment, under 70 ℃, carry out reaction in 5 hours, obtain containing the solution of 33.2 weight % polymkeric substance (1-1).By GPC polymkeric substance (1-1) is carried out molecular weight determination, Mw=21000, Mw/Mn=2.3 does not identify the peak that residual monomer produces.
Synthesis example 3 (synthetic (2) of polymkeric substance (1))
To stirring rod is housed, in the four neck flasks of T-valve and thermometer, adding is as monomeric methacrylic acid 2-(perfluoro capryl) ethyl ester 5.00g (0.00940 mole), the methacrylic acid cholestane base ester 30.0g (0.0657 mole) that makes in the above-mentioned synthesis example 1, glycidyl methacrylate 25.0g (0.176 mole), methacrylic acid 10.0g (0.116 mole), vinylbenzene 2.50g (0.0240 mole), N-cyclohexyl maleimide 2.50g (0.0139 mole) and methacrylic acid 2-hydroxyethyl ester 25.0g (0.192 mole), add glycol ether ethyl-methyl ether 200g again as solvent, as 2 of polymerization starter, 2 '-azo two (2, the 4-methyl pentane nitrile) 4.50g and as the α-Jia Jibenyixierjuwu 2.00g of molecular weight regulator.With it with about 10 minutes of nitrogen gas stream bubbling, carry out the nitrogen ventilation in the system after, under nitrogen environment, under 70 ℃, carry out reaction in 5 hours, obtain containing the solution of 33.5 weight % polymkeric substance (1-2).By GPC polymkeric substance (1-2) is carried out molecular weight determination, Mw=16000, Mw/Mn=2.0 does not identify the peak that residual monomer produces.
Synthesis example 4 (synthetic (1) of imide amination polymer)
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 112g (0.50 mole), be dissolved in the 830g N-N-methyl-2-2-pyrrolidone N-(NMP) as the Ursol D 43g (0.40 mole) of diamines and the compound 52g (0.10 mole) of above-mentioned formula (D-6) expression, under 60 ℃, carry out reaction in 6 hours, obtain polyamic acid solution.The gained polyamic acid solution that takes a morsel adds NMP, is made into the solution that polyamic acid concentration is 10 weight %, measures viscosity, is 60mPas.
Then, in the gained polyamic acid solution, append 1900g NMP, add 40g pyridine and 51g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction,, (in this operation, the pyridine and the acetic anhydride that use in the dehydration closed-loop reaction are removed to system by the solvent in the system by being carried out solvent exchange with new NMP.Down with), obtain about 1200g and contain the solution that 15 weight % imidization rates are about 50% imide amination polymer (PI-1).This solution that takes a morsel adds NMP and is made into the solution that imide amination polymer concentration is 10 weight %, and the soltion viscosity of mensuration is 47mPas.
Synthesis example 5 (synthetic (2) of imide amination polymer)
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 112g (0.50 mole), Ursol D 38g (0.35 mole), 4 as diamines, the compound 26g (0.050 mole) of 4 '-diaminodiphenyl-methane 20g (0.10 mole) and above-mentioned formula (D-6) expression is dissolved among the 800g NMP, under 60 ℃, carry out reaction in 6 hours, obtain polyamic acid solution.The gained polyamic acid solution that takes a morsel adds NMP, is made into the solution that polyamic acid concentration is 10 weight %, measures viscosity, is 60mPas.
Then, in the gained polyamic acid solution, append 1800g NMP, add 80g pyridine and 100g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction,, obtain about 1100g and contain the solution that 15 weight % imidization rates are about 80% imide amination polymer (PI-2) by the solvent in the system is carried out solvent exchange with new gamma-butyrolactone.This solution that takes a morsel adds gamma-butyrolactone and is made into the solution that imide amination polymer concentration is 10 weight %, and the soltion viscosity of mensuration is 87mPas.
Synthesis example 6 (synthetic (3) of imide amination polymer)
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 112g (0.50 mole), be dissolved among the 820g NMP as the Ursol D 43g (0.40 mole) of diamines and the compound 49g (0.10 mole) of above-mentioned formula (D-7) expression, under 60 ℃, carry out reaction in 6 hours, obtain polyamic acid solution.The gained polyamic acid solution that takes a morsel adds NMP, is made into the solution that polyamic acid concentration is 10 weight %, measures viscosity, is 60mPas.
Then, in the gained polyamic acid solution, append 1910g NMP, add 40g pyridine and 51g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction,, obtain about 1200g and contain the solution that 15 weight % imidization rates are about 50% imide amination polymer (PI-3) by the solvent in the system is carried out solvent exchange with new NMP.This solution that takes a morsel adds NMP and is made into the solution that imide amination polymer concentration is 10 weight %, and the soltion viscosity of mensuration is 47mPas.
Synthesis example 7 (synthetic (4) of imide amination polymer)
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 112g (0.50 mole), be dissolved among the 740g NMP as the Ursol D 49g (0.45 mole) of diamines and the compound 25g (0.050 mole) of above-mentioned formula (D-7) expression, under 60 ℃, carry out reaction in 6 hours, obtain polyamic acid solution.The gained polyamic acid solution that takes a morsel adds NMP, is made into the solution that polyamic acid concentration is 10 weight %, measures viscosity, is 60mPas.
Then, in the gained polyamic acid solution, append 1720g NMP, add 40g pyridine and 51g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction,, obtain about 1200g and contain the solution that 15 weight % imidization rates are about 50% imide amination polymer (PI-4) by the solvent in the system is carried out solvent exchange with new NMP.This solution that takes a morsel adds NMP and is made into the solution that imide amination polymer concentration is 10 weight %, and the soltion viscosity of mensuration is 47mPas.
Synthesis example 8 (synthetic (5) of imide amination polymer)
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 112g (0.50 mole), be dissolved among the 740g NMP as the Ursol D 49g (0.45 mole) of diamines and the compound 25g (0.050 mole) of above-mentioned formula (D-7) expression, under 60 ℃, carry out reaction in 6 hours, obtain polyamic acid solution.The gained polyamic acid solution that takes a morsel adds NMP, is made into the solution that polyamic acid concentration is 10 weight %, measures viscosity, is 60mPas.
Then, in the gained polyamic acid solution, append 1720g NMP, add 59g pyridine and 77g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction,, obtain about 1200g and contain the solution that 15 weight % imidization rates are about 65% imide amination polymer (PI-5) by the solvent in the system is carried out solvent exchange with new NMP.This solution that takes a morsel adds NMP and is made into the solution that imide amination polymer concentration is 10 weight %, and the soltion viscosity of mensuration is 67mPas.
Compare synthesis example 1 (relatively synthesizing) with polymkeric substance
In the four neck flasks that stirring rod, T-valve and thermometer are housed, adding is as monomeric glycidyl methacrylate 40g (0.28 mole), methacrylic acid 20g (0.23 mole), vinylbenzene 20g (0.19 mole) and N-cyclohexyl maleimide 20g (0.11 mole), add glycol ether ethyl-methyl ether 200g again as solvent, as 2 of initiator, 2 '-azo two (2, the 4-methyl pentane nitrile) 4.5g and as the α-Jia Jibenyixierjuwu 2.0g of molecular weight regulator.With it with about 10 minutes of nitrogen gas stream bubbling, carry out the nitrogen ventilation in the system after, under nitrogen environment, carry out reaction in 5 hours in 70 ℃, obtain containing the polymers soln that 33 weight % relatively use polymkeric substance (R-1).
Adopt GPC that polymkeric substance (R-1) is carried out molecular weight determination, Mw=22000, Mw/Mn=2.4 does not identify the peak that residual monomer produces.
Embodiment 1
With the solution that contains imide amination polymer (PI-1) that makes in the solution that contains polymkeric substance (1-1) that makes in the above-mentioned synthesis example 2 and the above-mentioned synthesis example 4, make polymkeric substance (1-1): the weight ratio of imide amination polymer (PI-1) is to mix at 5: 95, to wherein adding N-N-methyl-2-2-pyrrolidone N-(NMP) and ethylene glycol butyl ether, making solvent composition is NMP: ethylene glycol butyl ether: glycol ether ethyl-methyl ether=49.6: 50: 0.4 (weight ratio), solids content concn are the solution of 3.5 weight %.After this solution fully stirred, be that the filter of 0.2 μ m filters, modulate liquid crystal aligning agent with the aperture.
Adopt this liquid crystal aligning agent, estimate according to the method described above.Evaluation result is listed in the table 1.
Embodiment 2
With the solution that contains imide amination polymer (PI-1) that makes in the solution that contains polymkeric substance (1-1) that makes in the above-mentioned synthesis example 2 and the above-mentioned synthesis example 4, make polymkeric substance (1-1): the weight ratio of imide amination polymer (PI-1) is to mix at 5: 95, total amount with respect to 100 parts by weight polymer, to wherein adding the N of 10 weight parts as epoxy compounds, N, N ', N '-four glycidyl group-m-xylene diamine.To wherein adding NMP and ethylene glycol butyl ether, making solvent composition is NMP: ethylene glycol butyl ether again: glycol ether ethyl-methyl ether=49.6: 50: 0.4 (weight ratio), solids content concn are the solution of 3.5 weight %.After this solution fully stirred, be that the filter of 0.2 μ m filters, modulate liquid crystal aligning agent with the aperture.
Adopt this liquid crystal aligning agent, estimate according to the method described above.Evaluation result is listed in the table 1.
Embodiment 3
With the solution that contains imide amination polymer (PI-2) that makes in the solution that contains polymkeric substance (1-1) that makes in the above-mentioned synthesis example 2 and the above-mentioned synthesis example 5, make polymkeric substance (1-1): the weight ratio of imide amination polymer (PI-2) is to mix at 5: 95, total amount with respect to 100 parts by weight polymer, to wherein adding the N of 10 weight parts as epoxy compounds, N, N ', N '-four glycidyl group-m-xylene diamine.To wherein adding gamma-butyrolactone, NMP and ethylene glycol butyl ether, making solvent composition is gamma-butyrolactone: NMP: ethylene glycol butyl ether: glycol ether ethyl-methyl ether=40: 29.6: 30: 0.4 (weight ratio), solids content concn are the solution of 3.5 weight % again.After this solution fully stirred, be that the filter of 0.2 μ m filters, modulate liquid crystal aligning agent with the aperture.
Adopt this liquid crystal aligning agent, estimate according to the method described above.Evaluation result is listed in the table 1.
Embodiment 4～7,9～12 and 14～16 and comparative example 1 and 2
In the foregoing description 2,, use the solution that contains the polymkeric substance shown in the table 1 respectively as polymers soln, the mixture ratio of polymkeric substance and solvent changes into as shown in table 1 respectively, in addition, modulate liquid crystal aligning agent similarly to Example 2, and estimate.
Evaluation result is listed in table 1.
Embodiment 8 and 13
In the foregoing description 3, except the mixture ratio of polymkeric substance and solvent change into respectively as shown in table 1, modulate liquid crystal aligning agent similarly to Example 3, and estimate.
Evaluation result is listed in table 1.
Embodiment 17
In the foregoing description 1, the solution that contains polymkeric substance (1-2) that makes in using above-mentioned synthesis example 3 replaces containing the solution of polymkeric substance (1-1), modulates liquid crystal aligning agent similarly to Example 1, and estimates.
Evaluation result is listed in table 1.
Embodiment 18 and 20～22
In the foregoing description 2,, modulate liquid crystal aligning agent similarly to Example 2, and estimate except using the solution that contains the polymkeric substance shown in the table 1 respectively as the polymers soln.
Evaluation result is listed in table 1.
Embodiment 19
In the foregoing description 3, the solution that contains polymkeric substance (1-2) that makes in using above-mentioned synthesis example 3 replaces containing the solution of polymkeric substance (1-1), modulates liquid crystal aligning agent similarly to Example 3, and estimates.
Evaluation result is listed in table 1.
Comparative example 3
Adding NMP and ethylene glycol butyl ether dilute in the solution that contains imide amination polymer (PI-1) that makes in above-mentioned synthesis example 4, and being made into solvent composition is NMP: ethylene glycol butyl ether=50: 50 (weight ratio), solids content concn are the solution of 3.5 weight %.After this solution fully stirred, be that the filter of 0.2 μ m filters, modulate liquid crystal aligning agent with the aperture.
Adopt this liquid crystal aligning agent, estimate according to the method described above.Evaluation result is listed in the table 1.
Comparative example 4
With respect to 100 parts by weight polymer, add the N of 5 weight parts in the solution that contains imide amination polymer (PI-1) that in above-mentioned synthesis example 4, makes as epoxy compounds, N, N ', N '-four glycidyl group-m-xylene diamine, to wherein adding NMP and ethylene glycol butyl ether dilutes, being made into solvent composition is NMP: ethylene glycol butyl ether=50: 50 (weight ratio), solids content concn are the solution of 3.5 weight % again.After this solution fully stirred, be that the filter of 0.2 μ m filters, modulate liquid crystal aligning agent with the aperture.
Adopt this liquid crystal aligning agent, estimate according to the method described above.Evaluation result is listed in the table 1.
Comparative example 5
With respect to 100 parts by weight polymer, add the N of 10 weight parts in the solution that contains imide amination polymer (PI-5) that in above-mentioned synthesis example 8, makes as epoxy compounds, N, N ', N '-four glycidyl group-m-xylene diamine, dilute to wherein adding gamma-butyrolactone, NMP and ethylene glycol butyl ether, being made into solvent composition is gamma-butyrolactone: NMP: ethylene glycol butyl ether=40: 30: 30 (weight ratio), solids content concn are the solution of 3.5 weight % again.After this solution fully stirred, be that the filter of 0.2 μ m filters, modulate liquid crystal aligning agent with the aperture.
Adopt this liquid crystal aligning agent, estimate according to the method described above.Evaluation result is listed in the table 1.
Comparative example 6～8
In above-mentioned comparative example 4,, similarly modulate liquid crystal aligning agent with comparative example 4, and estimate except using the solution that contains the polymkeric substance shown in the table 1 respectively as the polymers soln.
Evaluation result is listed in table 1.
Wherein, the abbreviation in the solvent composition hurdle of table 1 is respectively following implication.
The NMP:N-N-methyl-2-2-pyrrolidone N-
BC: ethylene glycol butyl ether (ethylene glycol monobutyl ether)
EDM: glycol ether ethyl-methyl ether
γ-BL: gamma-butyrolactone
In above-mentioned table 1, the visible liquid crystal orientation film that is formed by liquid crystal aligning agent of the present invention can all realize that good reliability, the high anti-burning of the good good long term of voltage retention shield property (embodiment 1～embodiment 12) simultaneously.On the other hand, by the liquid crystal orientation film that previously known liquid crystal aligning agent forms, can not satisfy all above-mentioned performances (comparative example 1～8) simultaneously.
Liquid crystal display cells of the present invention with aforesaid liquid crystal orientation film has the advantage that the burning screen that shows good reliability and can suppress the accumulating of residual DC, liquid crystal display cells when applying thermal stress reduces.
Claims (10)
1. liquid crystal aligning agent is characterized in that comprising the polymkeric substance of the repeating unit with following formula (1) expression and is selected from least a polymkeric substance in the group that makes polyamic acid that the tetracarboxylic dianhydride obtains with diamine reactant and imide amination polymer formation thereof,
In the formula (1), R
IBe hydrogen atom or methyl, A
1For singly-bound, methylene radical, carbonatoms are the divalent group of 2～10 alkylidene group or following formula (2) expression,
In the formula (2), n is 5～150 integer,
Work as A
1When being 2～10 alkylidene group for singly-bound, methylene radical or carbonatoms, B
1For carbonatoms is 1～10 fluoro-alkyl, work as A
1During for the divalent group of above-mentioned formula (2) expression, B
1For carbonatoms is that 1～10 alkyl or carbonatoms are 1～10 fluoro-alkyl.
2. the described liquid crystal aligning agent of claim 1, the polymkeric substance that wherein has the repeating unit of above-mentioned formula (1) expression is the polymkeric substance of the repeating unit that further comprises following formula (3) expression,
In the formula (3), R
IIBe hydrogen atom or methyl, A
2For singly-bound, methylene radical or carbonatoms are 2～10 alkylidene group, B
2It for carbonatoms 2～10 group with cyclic ether structure.
3. the described liquid crystal aligning agent of claim 2, the B in the wherein above-mentioned formula (3)
2For having 1,2-epoxy group(ing) structure or 1, the group of 3-epoxy group(ing) structure.
4. the described liquid crystal aligning agent of claim 3, the A in the wherein above-mentioned formula (3)
2For methylene radical or carbonatoms are 2～10 alkylidene group, B
2For having 1, the group of 2-epoxy group(ing) structure.
5. claim 1 or 2 described liquid crystal aligning agent, the polymkeric substance that wherein has the repeating unit of above-mentioned formula (1) expression is the polymkeric substance of the repeating unit that further comprises following formula (4) expression,
In the formula (4), R
IIIBe hydrogen atom or methyl, A
3Be singly-bound, phenylene or following formula (A
3-1)～(A
3-6) divalent group of any one expression,
-(CH
2)
k-O-
＊(A
3-5)
-(CH
2)
m-COO-
＊(A
3-6)
I respectively does for oneself 0 or 2 in the above-mentioned formula, and j respectively does for oneself 0 or 1, respectively do for oneself 1～6 integer of k and m, "
*" separately expression have its connecting key and B
3Connect;
B
3For the carbonatoms with steroid backbone is 17～30 any monovalent organic radical group, to have carbonatoms be that alkyl-cyclohexyl, the carbonatoms of 4～8 alkyl is 3～30 alkyl, difluorophenyl, trifluoromethyl or Trifluoromethoxyphen-l.
6. the described liquid crystal aligning agent of claim 5, in the wherein above-mentioned formula (4), B
3It for carbonatoms 17～30 any monovalent organic radical group with steroid backbone.
7. each described liquid crystal aligning agent of claim 1～4, at least a polymkeric substance that wherein is selected from the group that polyamic acid and imide amination polymer thereof constitute is: be selected to make to contain and be selected from 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxymethyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8, at least a tetracarboxylic dianhydride in the group that 10-tetraketone and pyromellitic acid dianhydride constitute is selected from Ursol D, 4,4 '-diaminodiphenylmethane, 2,7 diamin of luorene, 4 with containing, 4 '-diamino-diphenyl ether, 4,4 '-diamino-2, at least a diamine reactant in the group that 2 '-dimethyl diphenyl and 1,3-two (amino methyl) hexanaphthene constitute and at least a polymkeric substance in the group that the polyamic acid that obtains and imide amination polymer thereof constitute.
8. each described liquid crystal aligning agent of claim 1～4, wherein diamines comprises the compound of following formula (D-V) expression,
In the formula (D-V), R
15For Sauerstoffatom, sulphur atom ,-CO-,-COO-,-OCO-,-NHCO-,-CONH-or methylene radical, R
16For the univalent perssad with cholestane skeleton or cholestene skeleton, the univalent perssad with trifluoromethyl or Trifluoromethoxyphen-l or carbonatoms are 1～22 alkyl, R
17For carbonatoms is 1～4 alkyl, a3 is 0～3 integer.
9. the liquid crystal orientation film that forms by each described liquid crystal aligning agent of claim 1～4.
10. the liquid crystal display device that has the described liquid crystal orientation film of claim 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008292647A JP5365774B2 (en) | 2008-11-14 | 2008-11-14 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| JP2008-292647 | 2008-11-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101735824A true CN101735824A (en) | 2010-06-16 |
| CN101735824B CN101735824B (en) | 2013-10-02 |
Family
ID=42279410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910212152 Active CN101735824B (en) | 2008-11-14 | 2009-11-11 | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5365774B2 (en) |
| KR (1) | KR101530720B1 (en) |
| CN (1) | CN101735824B (en) |
| TW (1) | TW201026770A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649908A (en) * | 2011-02-28 | 2012-08-29 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| CN104090431A (en) * | 2014-07-02 | 2014-10-08 | 京东方科技集团股份有限公司 | Cholesteric liquid crystal polymer alignment layer, preparing method thereof and liquid crystal display panel |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5994564B2 (en) * | 2012-10-22 | 2016-09-21 | Jnc株式会社 | Thermosetting composition having photo-alignment |
| JP6819051B2 (en) * | 2015-03-04 | 2021-01-27 | 住友化学株式会社 | Curable resin composition |
| TWI671358B (en) * | 2016-10-26 | 2019-09-11 | 奇美實業股份有限公司 | Liquid crystal alignment agent and production method thereof, liquid crystal alignment film and production method thereof, and liquid crystal display element and production method thereof |
| CN111386493B (en) * | 2017-11-21 | 2023-05-23 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, method for producing liquid crystal alignment film, and liquid crystal display element |
| WO2020095789A1 (en) * | 2018-11-08 | 2020-05-14 | 昭和電工株式会社 | Copolymer, and resin composition containing said copolymer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1408817A (en) * | 2001-10-03 | 2003-04-09 | 捷时雅株式会社 | Liquid crystal oriented agent and liquid crystal display element |
| JP2007262124A (en) * | 2006-03-27 | 2007-10-11 | Jsr Corp | Curable resin composition and antireflection film |
| CN101144942A (en) * | 2006-09-11 | 2008-03-19 | Jsr株式会社 | Liquid crystal orientating agent, liquid crystal orientating film and liquid crystal displaying element |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06160863A (en) * | 1992-11-27 | 1994-06-07 | Hitachi Chem Co Ltd | Composition for liquid crystal oriented film and liquid crystal oriented film formed by using the composition, liquid crystal holding substrate and liquid crystal display element |
| JP4032405B2 (en) * | 1999-03-03 | 2008-01-16 | Ｊｓｒ株式会社 | Liquid crystal alignment agent |
| JP4054506B2 (en) * | 2000-03-17 | 2008-02-27 | 日本放送協会 | Liquid crystal light modulator and display device |
| JP2003049069A (en) * | 2001-08-07 | 2003-02-21 | Jsr Corp | Liquid crystal-orienting agent and liquid crystal display element |
| JP2003295194A (en) * | 2002-03-29 | 2003-10-15 | Jsr Corp | Vertical alignment type liquid crystal aligning agent |
| JP3894085B2 (en) * | 2002-07-11 | 2007-03-14 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and method for producing liquid crystal display element |
| TWI359189B (en) * | 2004-01-27 | 2012-03-01 | Jsr Corp | Liquid crystal alignment agent, liquid crystal ali |
| JP4793536B2 (en) * | 2004-11-10 | 2011-10-12 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
-
2008
- 2008-11-14 JP JP2008292647A patent/JP5365774B2/en active Active
-
2009
- 2009-11-11 CN CN 200910212152 patent/CN101735824B/en active Active
- 2009-11-13 TW TW98138600A patent/TW201026770A/en unknown
- 2009-11-13 KR KR1020090109617A patent/KR101530720B1/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1408817A (en) * | 2001-10-03 | 2003-04-09 | 捷时雅株式会社 | Liquid crystal oriented agent and liquid crystal display element |
| JP2007262124A (en) * | 2006-03-27 | 2007-10-11 | Jsr Corp | Curable resin composition and antireflection film |
| CN101144942A (en) * | 2006-09-11 | 2008-03-19 | Jsr株式会社 | Liquid crystal orientating agent, liquid crystal orientating film and liquid crystal displaying element |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649908A (en) * | 2011-02-28 | 2012-08-29 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| CN102649908B (en) * | 2011-02-28 | 2016-02-24 | Jsr株式会社 | Crystal aligning agent, liquid crystal orienting film and liquid crystal display device |
| CN104090431A (en) * | 2014-07-02 | 2014-10-08 | 京东方科技集团股份有限公司 | Cholesteric liquid crystal polymer alignment layer, preparing method thereof and liquid crystal display panel |
| CN104090431B (en) * | 2014-07-02 | 2016-09-28 | 京东方科技集团股份有限公司 | A kind of cholesteric liquid crystal polymer orientation layer and preparation method thereof, display panels |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20100054746A (en) | 2010-05-25 |
| JP5365774B2 (en) | 2013-12-11 |
| TW201026770A (en) | 2010-07-16 |
| CN101735824B (en) | 2013-10-02 |
| KR101530720B1 (en) | 2015-06-22 |
| JP2010117684A (en) | 2010-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101024773B (en) | Liquid crystal aligning agent and liquid crystal display device | |
| CN101676363B (en) | Liquid crystal aligning agent, liquid crystal display element and compound | |
| CN101602949B (en) | Liquid crystal alignment agent and liquid crystal display element | |
| CN101382703B (en) | Liquid crystal aligning agent and liquid crystal display element | |
| CN101452153B (en) | Liquid crystal oriented agent and liquid crystal display element | |
| CN101608124B (en) | Liquid crystal aligning agent and liquid crystal display element | |
| CN101591544B (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element | |
| CN101735824B (en) | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device | |
| CN101544828B (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element | |
| CN101671566B (en) | Liquid crystal alignment agent and liquid crystal display element | |
| CN101539687B (en) | Liquid crystal alignment agent and liquid crystal display element | |
| CN102585842B (en) | Liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device | |
| CN101597498B (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element | |
| CN101526700A (en) | Liquid crystal aligning agent and liquid crystal display device | |
| CN107022358A (en) | Aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal cell, polymer and diamines | |
| CN101114085A (en) | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device | |
| CN101539688A (en) | Liquid crystal alignment agent and liquid crystal display element | |
| CN101608122B (en) | Liquid crystal aligning agent and liquid crystal display element | |
| CN101921597A (en) | Liquid crystal aligning agent and liquid crystal display device | |
| CN101570635A (en) | Liquid crystal orientation agent, liquid crystal display element, poly-amic acid, polyimide and compound | |
| CN101458427B (en) | Liquid crystal oriented agent and liquid crystal display element | |
| CN101220279B (en) | Vertical orientation type aligning agent for liquid crystal and vertical orientation type liquid crystal display device | |
| CN101747907B (en) | Liquid crystal alignment agent, liquid crystal display element, polyamic acid and imidization polymer thereof | |
| CN101487954B (en) | Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element | |
| CN101921598B (en) | Liquid crystal alignment agent and liquid crystal display element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |