CN110036337A - Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal expression element using it - Google Patents

Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal expression element using it Download PDF

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CN110036337A
CN110036337A CN201780073289.1A CN201780073289A CN110036337A CN 110036337 A CN110036337 A CN 110036337A CN 201780073289 A CN201780073289 A CN 201780073289A CN 110036337 A CN110036337 A CN 110036337A
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liquid crystal
formula
aligning agent
indicate
diamines
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CN110036337B (en
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相马早纪
森本佳道
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Nissan Chemical Corp
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/335—Radicals substituted by nitrogen atoms not forming part of a nitro radical
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/02—Polyamines
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G02F1/134309—Electrodes characterised by their geometrical arrangement
    • G02F1/134363—Electrodes characterised by their geometrical arrangement for applying an electric field parallel to the substrate, i.e. in-plane switching [IPS]

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Abstract

The aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal expression element that voltage retention is excellent, stored charge mitigation is fast, the liquid crystal orientation film flashed is not susceptible in driving can be obtained by providing one kind.A kind of aligning agent for liquid crystal, which is characterized in that contain the polymer and organic solvent obtained as the diamines with structure shown in following formula (1).(R1、R2For hydrogen atom or 1 valence organic group.Any hydrogen atom of phenyl ring is optionally replaced by 1 valence organic group.* bonding position is indicated)

Description

Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal expression element using it
Technical field
The present invention relates to the aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal expression member for using it that use new polymers Part.
Background technique
Liquid crystal indicates that element is widely used as the display unit of computer, mobile phone, smart phone, TV etc..Liquid crystal indicates element packet It includes, for example, being clipped in the liquid crystal layer between device substrate and filter substrate, applying the pixel electrode of electric field to liquid crystal layer and share The film for the electric signal that electrode, the alignment films of orientation of liquid crystal molecule for controlling liquid crystal layer, switching are supplied to pixel electrode is brilliant Body pipe (TFT) etc..Driving method as liquid crystal molecule, it is known to the longitudinal electric fields mode such as TN mode, VA mode, IPS mode, The Transverse electric-field types such as FFS mode.In Transverse electric-field type, electrode only is formed in the side of substrate, is being parallel to substrate Apply electric field on direction, with the previous longitudinal electric field for driving liquid crystal to the electrode being formed on upper and lower base plate application voltage Mode is compared, have wider field angle characteristic, and as can high-quality show liquid crystal expression element it is well-known.
Although the field angle characteristic of the liquid crystal cells of Transverse electric-field type is excellent, due to the electrode portion being formed in substrate Divide less, so will not apply enough voltage if voltage retention is low to liquid crystal, display contrast reduction.In addition, if The stability of liquid crystal aligning is small, then for a long time driving liquid crystal when, liquid crystal does not return to original state, become contrast reduce, The reason of ghost, therefore the stability of liquid crystal aligning is important.Moreover, electrostatic is easy to accumulate in liquid crystal cells, by driving The application of the positive and negative asymmetrical voltage generated also results in charge and accumulates in liquid crystal cells, and the charge of these accumulations can be with liquid crystal The form influence display of orientation disorder, ghost, significantly reduces the display quality of liquid crystal cell.In addition, upon activation immediately to liquid Brilliant unit irradiation backlight also results in charge accumulation, it may occur that even the driving of short time can also generate ghost；It is dodged in driving The problems such as size variation of bright (flicker).
Indicate that voltage retention is excellent and reduces charge when using in element as in the liquid crystal of this Transverse electric-field type The aligning agent for liquid crystal of accumulation, patent document 1 disclose a kind of liquid crystal containing specific diamines and aliphatic tetracarboxylic acid derivatives Alignment agent.But as liquid crystal indicates the high performance of element, performance required by liquid crystal orientation film also becomes strictly, these The prior art is difficult to sufficiently meet all properties requirement.
Existing technical literature
Patent document
Patent document 1: International Publication bulletin WO2004/021076 pamphlet
Summary of the invention
Problems to be solved by the invention
Technical problem of the invention be to provide it is a kind of can obtain voltage retention is excellent, stored charge mitigation is fast, The aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal that the liquid crystal orientation film of flashing (flicker) is not susceptible in driving indicate element.
The solution to the problem
In order to solve the above-mentioned technical problem the inventors of the present invention further investigate, as a result, it has been found that, by liquid crystal aligning Specific structure is introduced in polymer contained in agent, can improve various characteristics simultaneously, so as to complete the present invention.
The present invention is completed based on the opinion, and purport is as follows.
1. a kind of aligning agent for liquid crystal, which is characterized in that poly- containing being obtained as the diamines with structure shown in following formula (1) Close object and organic solvent.
(in formula (1), R1、R2For hydrogen atom or 1 valence organic group.Any hydrogen atom of phenyl ring is optionally by 1 valence organic group Replace.* bonding position is indicated.)
2. the aligning agent for liquid crystal according to aforementioned 1, wherein the polymer is selected from by polyimide precursor and its acyl At least one kind of polymer in imines compound, that is, polyimides composition group, the polyimide precursor is with the formula (1) institute Show the diamines of structure and the condensation polymer of tetracarboxylic dianhydride.
3. the aligning agent for liquid crystal according to aforementioned 1 or 2, wherein the diamines is indicated by following formula (2).
(in formula (2), R1And R2Definition it is identical as above-mentioned formula (1), R3Each independently represent the knot of singly-bound or following formula (3) Structure, n indicate 1~3 integer.Any hydrogen atom of phenyl ring is optionally replaced by 1 valence organic group.)
(in formula (3), R4It indicates singly-bound, be selected from-O- ,-COO- ,-OCO- ,-(CH2)l-、-O(CH2)mO- ,-CONH- and- The divalent organic group (l, m indicate 1~5 integer) of NHCO-, *1Indicate the position being bonded with the phenyl ring in formula (2), *2Indicate with The position of amino bonded in formula (2).)
4. the aligning agent for liquid crystal according to aforementioned 1~3, wherein the polyimide precursor has shown in following formula (4) Structure.
(in formula (4), X1For the 4 valence organic groups from tetracarboxylic acid derivatives, Y1For from diamines shown in the formula (1) Divalent organic group, R5For hydrogen atom or the alkyl of carbon number 1~5.)
5. the aligning agent for liquid crystal according to aforementioned 4, wherein in the formula (6), X1For selected from by following (A-1)~(A- 21) at least one kind of in the group of structure composition shown in.
6. the aligning agent for liquid crystal according to aforementioned 4 or 5, wherein relative to the whole polymerization contained in aligning agent for liquid crystal Object, the polymer with structural unit shown in the formula (4) containing 10 moles of % or more.
7. the aligning agent for liquid crystal according to aforementioned any one of 1~6, wherein the organic solvent contains selected from by 4- It is at least one kind of in the group of hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether composition.
8. a kind of liquid crystal orientation film is obtained using aligning agent for liquid crystal described in aforementioned any one of 1~7.
9. a kind of liquid crystal indicates element, have aforementioned 8 described in liquid crystal orientation film.
10. the liquid crystal according to aforementioned 9 indicates element, wherein liquid crystal indicates that element is transverse electric field driving method.
11. a kind of polymer, for selected from the group being made of polyimide precursor and its acid imide compound, that is, polyimides In it is at least one kind of, the polyimide precursor be with the diamines of structure shown in following formula (1) and the polycondensation of tetracarboxylic dianhydride Object.
(in formula (1), R1、R2For hydrogen atom or 1 valence organic group.Any hydrogen atom of phenyl ring is optionally by 1 valence organic group Replace.* bonding position is indicated.)
12. the polymer according to aforementioned 11, wherein above-mentioned diamines is indicated by following formula (2).
(in formula (2), R1And R2Definition it is identical as above-mentioned formula (1), R3Have shown in singly-bound or following formula (3) each independently Structure, n indicate 1~3 integer.Any hydrogen atom of phenyl ring is optionally replaced by 1 valence organic group.)
(in formula (3), R4It indicates singly-bound, be selected from-O- ,-COO- ,-OCO- ,-(CH2)l-、-O(CH2)mO- ,-CONH- and- The divalent organic group (l, m indicate 1~5 integer) of NHCO-, *1Indicate the position being bonded with the phenyl ring in formula (2), *2Indicate with The position of amino bonded in formula (2).)
(in formula (4), X1For the 4 valence organic groups from tetracarboxylic acid derivatives, Y1For from diamines shown in the formula (1) Divalent organic group, R5For hydrogen atom or the alkyl of carbon number 1~5.)
14. the polymer according to aforementioned 13, wherein in the formula (6), X1For selected from by following (A-1)~(A- 21) at least one kind of in the group of structure composition shown in.
15. a kind of diamines is indicated by following formula (2).
(in formula (2), R1And R2Definition it is identical as above-mentioned formula (1), R3Have shown in singly-bound or following formula (3) each independently Structure, n indicate 1~3 integer.Any hydrogen atom of phenyl ring is optionally replaced by 1 valence organic group.)
The effect of invention
By using aligning agent for liquid crystal of the invention, the mitigation that can provide a kind of stored charge is not easy to send out fastly, in driving The liquid crystal that the liquid crystal orientation film and display characteristic of raw flashing (flicker) are excellent indicates element.
It is unclear why to can solve above-mentioned technical problem through the invention, but substantially thinks as follows.It is considered that It is because of the conductive pyrrole ring of diamines shown in above-mentioned (1) possessed by the polymer contained in aligning agent for liquid crystal of the invention With the structure of phenyl ring conjugation, when using the liquid crystal orientation film formed by the aligning agent for liquid crystal, the charge that is applied when element drives It is easy movement, the mitigation of stored charge can be promoted.
Specific embodiment
The specific diamines > of <
Aligning agent for liquid crystal of the invention contains (also referred to as specific in the present invention by the diamines of the structure with following formula (1) Diamines.) obtained polymer.
In above-mentioned formula (1), R1、R2It is as defined above.Wherein, R1、R2It is preferred that with the alkyl of carbon number 1~3, alkenyl, Alkoxy, fluoro-alkyl, fluoro alkenyl or fluoroalkyl, particularly preferred hydrogen atom or methyl.In addition, * indicate with amino, take For the position of the bondings such as amino, other organic groups.
It is mobile from charge about the bonding position of 2 phenyl ring and pyrrole ring as shown in following formula (1-1) in specific diamines From the perspective of, preferably wherein at least one and be located at pyrrole ring on nitrogen-atoms beside carbon atom bonding.
Above-mentioned specific diamines can for example indicate by following formula (1-2), diamines shown in particularly preferred following formula (1-3), in turn Diamines shown in more preferable formula (1-4).In these chemical formulas, * indicates bonding position.
In formula (1-2)~formula (1-4), R1And R2Definition it is identical as the formula (1), Q1、Q2Be each independently singly-bound or Divalent organic group, i.e. Q1And Q2It can be mutually different structure.In addition, 2 Q in formula (1-4)2It can be mutually different Structure.Also, identical as above-mentioned formula (1), any hydrogen atom of phenyl ring is optionally replaced by 1 valence organic group.
As the preferred example of above-mentioned specific diamines, diamines shown in following formula (2), more preferably formula (2-1) can be enumerated Shown diamines.
In formula (2), R1And R2Definition it is identical as above-mentioned formula (1), R3Each independently represent the knot of singly-bound or following formula (3) Structure, n indicate 1~3 integer.Any hydrogen atom of phenyl ring is optionally replaced by 1 valence organic group.
(in formula (3), R4It indicates singly-bound, be selected from-O- ,-COO- ,-OCO- ,-(CH2)l-、-O(CH2)mO- ,-CONH- and- The divalent organic group (l, m indicate 1~5 integer) of NHCO-, *1Indicate the position being bonded with the phenyl ring in formula (2), *2Indicate with The position of amino bonded in formula (2).)
In formula (2) and formula (2-1), n indicates 1~3 integer.Preferably 1 or 2.
The specific example of diamines as above-mentioned formula (2), can enumerate following example, but not limited to this.Wherein, from accumulation From the perspective of the mitigation of charge, preferably (2-1-1), (2-1-2), (2-1-3), (2-1-4), (2-1-5), (2-1-8), (2- 1-9), (2-1-10), (2-1-11) or (2-1-12), particularly preferred (2-1-1), (2-1-2), (2-1-3), (2-1-4), (2- 1-5), (2-1-11) or (2-1-12).
The synthetic method > of the specific diamines of <
The synthetic method of the specific diamines of the present invention is not particularly limited, such as can enumerate two shown in synthesis following formula (1) Nitro compound, and then nitro is made to restore the method for being converted to amino.
(R1、R2And R3Indicate hydrogen or 1 valence organic group.)
The activated carbon supported metal that catalyst used in the reduction reaction can preferably be obtained with commercially available product, such as can enumerate Palladium-active carbon, platinum-active carbon, rhodium-active carbon etc. out.In addition, the catalyst is also possible to palladium dydroxide, platinum oxide, Raney's nickel Deng, it is not necessary to it is the metallic catalyst of activated carbon supported type.In particular, palladium-active carbon is available good as a result, therefore excellent Choosing.
In order to be more effectively carried out reduction reaction, it can also implement reaction under the coexisting of active carbon sometimes.At this point, using The amount of active carbon be not particularly limited, relative to dinitro compound, the preferably range of 1~30 mass %, more preferable 10~ 20 mass %.For the same reason, can also implement to react under elevated pressure sometimes.At this point, in order to avoid the reduction of benzene nucleus, preferably It carries out in the pressure range of most 20 air pressures, is more preferably carried out in the pressure range of most 10 air pressures.
As long as solvent is that the solvent not reacted with each raw material uses without limitation.It can be used for example non-proton Property polar organic solvent (DMF, DMSO, DMAc, NMP etc.)；Ethers (Et2O、i-Pr2O, TBME, CPME, THF, dioxanes etc.)； Aliphatic hydrocarbon (pentane, hexane, heptane, petroleum ether etc.)；It is aromatic hydrocarbon (benzene,toluene,xylene, mesitylene, chlorobenzene, Dichloro-benzenes, nitrobenzene, tetrahydronaphthalene etc.)；Halogen system hydro carbons (chloroform, methylene chloride, carbon tetrachloride, dichloroethanes etc.)；It is rudimentary Fatty acid ester (methyl acetate, ethyl acetate, butyl acetate, methyl propionate etc.)；Nitrile (acetonitrile, propionitrile, butyronitrile etc.) etc..This A little solvents can be considered reaction and difficulty etc. occur suitably to select, and can also be used in mixed way with two or more.Also it can according to need Using dehydrating agent appropriate, desiccant by solvent seasoning, used as nonaqueous solvents.
Relative to dinitro compound, dosage (reaction density) preferably 0.1~10 mass times of solvent, more preferable 0.5~ 30 mass times, particularly preferred 1~10 mass times.Reaction temperature is not particularly limited, for -100 DEG C of boilings to the solvent used certainly The range of point, preferably -50~150 DEG C.Reaction time is usually 0.05~350 hour, and preferably 0.5~100 hour.
On the other hand, the synthetic method of nitro compound (A-1) is not particularly limited, the amino in compound (A-1) When the position of substitution is 2 and 4, such as can be by making diamines shown in following formula (A-2) and the halogenated aryl with nitro exist In the presence of alkali, reacted in the presence of an additive as needed to obtain (X expression F, Cl, Br, I or OTf.)
In the above-mentioned halogenated aryl with nitro, if X is F or Cl, and NO2Base phase is 2 or 4 for X, then can be with In the presence of base, halogenated aryl is made to react to obtain compound (A-1) with aliphatic amine compound.About the alkali used, such as It can be used the inorganic bases such as sodium bicarbonate, saleratus, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, trimethylamine, The amines such as triethylamine, tripropyl amine (TPA), tri-isopropyl amine, tri-n-butylamine, diisopropylethylamine, pyridine, quinoline, trimethylpyridine, sodium hydride, Hydrofining etc..Reaction dissolvent, reaction temperature are according to the record in aforementioned.Product can use recrystallization, distillation, silica gel column chromatography Deng purifying.
X is if it is Br or I, NO2Base phase can be 2,3 or 4 for X, in metallic catalyst appropriate, match In the presence of body, alkali, using C-N cross-coupling reaction, also available dinitro matrix.As the example of metallic catalyst, can arrange Enumerate acid chloride, palladium chloride, palladium chloride-acetonitrile complex, palladium-active carbon, bis- (dibenzalacetone) palladiums, three (dibenzylidenes Acetone) two palladiums, bis- (acetonitrile) dichloro palladiums, bis- (benzonitrile) dichloro palladiums, CuCl, CuBr, CuI, CuCN etc., but it is not limited only to this. As the example of ligand, triphenylphosphine, three (o-tolyl) phosphines, diphenyl methyl phosphine, phenyldimethylphosphine, 1,2- can be enumerated Bis- (diphenylphosphino) propane of bis- (diphenylphosphino) ethane, 1,3-, bis- (diphenylphosphino) butane of 1,4-, 1,1 '-bis- (hexichol Base phosphino-) ferrocene, Trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri-tert-butylphosphine etc., but be not limited only to This.As the example of alkali, the alkali in aforementioned can be used.Reaction dissolvent, reaction temperature are according to the record in aforementioned.Product can be with It is purified with recrystallization, distillation, silica gel column chromatography etc..
In addition, the synthetic method of compound (A-2) is not particularly limited, such as synthesis following formula (A-3) institute can be enumerated Show diamines, and then in NH2R is introduced on base1、R3Method.
Introduce R1、R3When, as long as the compound that can be reacted with amine, such as carboxylic acid halides, acid anhydrides, isocyanide can be enumerated Esters of gallic acid, epoxies, oxetanes class, halogenated aryl class, halogenated alkanes.Further, it is possible to use the hydroxyl of alcohol is substituted by The alcohols etc. of the leaving groups such as OMs, OTf, OTs.
In NH2It introduces on base by R1、R3The method of 1 valence organic group of composition is not particularly limited, and can enumerate suitable Alkali in the presence of make carboxylic acid halides react method.As the example of carboxylic acid halides, can enumerate chloroacetic chloride, propionyl chloride, methylchloroformate, Ethyl chloroformate, n-propyl chloroformate, isopropyl chlorocarbonate, butyl chloroformate, isobutyl chlorocarbonate, isobutylchloroformate, Benzyl chloroformate, chloro-carbonic acid -9- fluorenes ester.As the example of alkali, the alkali in aforementioned can be used.Reaction dissolvent, reaction temperature according to According to the record in aforementioned.
It can also make NH2Base and anhydride reaction are to introduce R1、R3.As the example of acid anhydrides, acetic anhydride, third can be enumerated Acid anhydrides, two dimethyl carbonates, dicarbonic acid diethyl ester, di-tert-butyl dicarbonate, two dimethyl benzyls etc..In order to promote reaction can also To use catalyst, pyridine, trimethylpyridine, N, N- dimethyl -4-aminopyridine etc. can be used.Catalytic amount relative to (A-3) dosage, preferably 0.0001~1 mole.Reaction dissolvent, reaction temperature are according to the record in aforementioned.
It can also make NH2Base reacts to introduce R with isocyanates1.As the example of isocyanates, can enumerate Methyl isocyanate, ethyl isocyanate, n-propyl isocyanates, phenyl isocyanate etc..Reaction dissolvent and reaction temperature according to According to the record in aforementioned.
It can also make NH2Base reacts to introduce R with epoxy compound species, oxetane compound class1、R3.As ring The example of oxygen class, oxetanes class can enumerate ethylene oxide, propylene oxide, 1,2- epoxy butane, oxetanes etc.. Reaction dissolvent, reaction temperature are according to the record in aforementioned.
It can also make NH2Base is substituted by the leaving groups such as OMs, OTf, OTs with by the hydroxyl of alcohol in the presence of suitable alkali The alcohols reaction of group is to introduce R1、R3.As the example of alcohols, methanol, ethyl alcohol, 1- propyl alcohol etc. can be enumerated, by making these Alcohols and mesyl chloride, trifluoromethanesulfchloride chloride, paratoluensulfonyl chloride etc. react, available by leaving groups such as OMs, OTf, OTs The alcohol that group replaces.As the example of alkali, the alkali in aforementioned can be used.Reaction dissolvent, reaction temperature are according to the record in aforementioned.
It can also make NH2Base reacts to introduce R with alkyl halide in the presence of suitable alkali1、R3.As halogenated alkanes Example, iodomethane, iodoethane, propyl iodide, bromomethane, bromoethane, n-propyl bromide etc. can be enumerated.Example as alkali The metal alkoxides class such as potassium tert-butoxide, sodium tert-butoxide can be used in son in addition to aforementioned bases.Reaction dissolvent, reaction temperature are according to before Record in stating.
In addition, the synthetic method of compound (A-3) is not particularly limited, nitro shown in synthesis following formula (4) can be enumerated Compound, and then nitro possessed by the nitro compound is made to restore the method for being converted to amino.
Catalyst used in the reaction, solvent, temperature are according to the record in aforementioned.
In addition, the synthetic method of compound (A-4) is not particularly limited, it can be by acid condition, making following formula (5) Shown 1,4- dione compounds (A-5) carry out dehydrating condensation with primary amine to synthesize.
As example sour used in the reaction, acetic acid, p-methyl benzenesulfonic acid, p-methyl benzenesulfonic acid pyridine can be used Deng, but it is not limited only to this.Reaction dissolvent, reaction temperature are according to the record in aforementioned.
In addition, the synthetic method of compound (A-5) is not particularly limited, it can be by making to have shown in following formula (6) The α-halogenatedketone of nitro reacts to obtain with the ketone with nitro in the presence of base.
(X indicates Br, I or OTf.)
As the example of alkali used in the reaction, the alkali in aforementioned can be used.Reaction dissolvent, reaction temperature are according to before Record in stating.In order to promote reaction speed that additive can be used.As the additive, can be used zinc chloride, sodium iodide, Potassium iodide, tetrabutylammonium iodide etc., but it is not limited only to this.
< particular polymers >
Polymer of the invention is the polymer obtained using above-mentioned specific diamines.As specific example, can enumerate poly- Amic acid, poly amic acid ester, polyimides, polyureas, polyamide etc..Wherein, from the viewpoint of being used as aligning agent for liquid crystal, It is more preferably selected from the polyimide precursor and its acid imide compound i.e. polyimides containing structural unit shown in following formula (4) At least one kind of polymer (hereinafter also referred to as particular polymers.).
In above-mentioned formula (4), X1For the 4 valence organic groups from tetracarboxylic acid derivatives, Y1Have for the divalent from specific diamines Machine group.R5For hydrogen atom or the alkyl of carbon number 1~5.From the viewpoint of the difficulty of the imidizate caused by heating, R5 It is preferred that hydrogen atom, methyl or ethyl.
Above-mentioned X1Can according to the dissolubility of polymer in a solvent, aligning agent for liquid crystal coating, liquid crystal aligning is made The degree of characteristic needed for orientation, voltage retention, stored charge of liquid crystal when film etc. is suitably selected, in same polymerization It can be two or more in object.
If enumerating X1Specific example if, can enumerate and remember in International Publication bulletin 2015/119168 page 13~14 Formula (X-1)~(X-46) structure etc. of load.
It is described below to be used as preferred X1(A-1)~(A-21), but be not limited only to this.
Among the above, from the viewpoint of further increasing resistance to brushing, particularly preferred (A-1), (A-2), from stored charge Mitigation speed further increase from the perspective of, it is particularly preferred (A-4), from the mitigation speed of liquid crystal aligning and stored charge From the perspective of further increasing, particularly preferred (A-15)~(A-17) etc..
< other structures unit >
Other than the structural unit shown in formula (4), above-mentioned polyimide precursor can also have structure shown in following formula (5) Unit.
In formula (5), X2Definition it is identical as the definition in the formula (4).As X2Specific example, can enumerate including The X of formula (4) including preference1In the example enumerated.R4It is identical as the definition in the formula (4).It is preferred that 2 R4In extremely Few one is hydrogen atom.
In addition, Y2For from the divalent organic group in diamines of the main chain direction without containing structure shown in above-mentioned formula (1), Structure is not particularly limited.Y2Can according to the dissolubility of polymer in a solvent, aligning agent for liquid crystal coating, liquid crystal is made The degree of characteristic needed for orientation, voltage retention, stored charge of liquid crystal when alignment films etc. is suitably selected, same It can be mixed in polymer and deposit two or more
If enumerating Y2Specific example if, formula described in International Publication bulletin 2015/119168 page 4 can be enumerated (2) structure of formula (Y-1)~(Y-97) described in structure and page 8~12, (Y-101)~(Y-118)；International Publication is public It reports and removes the divalent organic group that 2 amino obtain from formula (2) described in page 2013/008906 the 6th；International Publication bulletin 2015/ The divalent organic group that 2 amino of removal obtain from formula (1) described in page 122413 the 8th；International Publication bulletin 2015/ The structure of formula (3) described in page 060360 the 8th；Described in Japanese Laid-Open Patent Publication 2012-173514 page 8 from formula (1) Remove the divalent organic group that 2 amino obtain；Described in International Publication bulletin 2010-050523 page 9 from formula (A)~(F) Remove the divalent organic group etc. that 2 amino obtain.
Preferred Y described below2Structure, but the present invention is not limited only to this.
In above structure, from the viewpoint of further increasing resistance to brushing, particularly preferred (B-28), (B-29) etc., from From the perspective of liquid crystal aligning further increases, particularly preferred (B-1)~(B-3) etc., from the mitigation speed of stored charge into From the perspective of one step improves, particularly preferred (B-14)~(B-18) and (B-27) etc. is further increased from voltage retention Viewpoint is set out, preferably (B-26) etc..
Above-mentioned polyimide precursor is other than containing structural unit shown in formula (4) also containing structural unit shown in formula (5) When, structural unit shown in formula (4) is preferably 10 moles of % or more relative to the total amount of formula (4) and formula (5), and more preferably 20 rub You are % or more, particularly preferably 30 moles of % or more.
The molecular weight of polyimide precursor used in the present invention is more excellent with Weight-average molecular meter preferably 2000~500000 Select 5000~300000, further preferred 10000~100000.
< polyimides >
Polyimides in particular polymers is obtained by polyimide precursor closed loop shown in formula (4), formula (5).This When acid imide rate be not necessarily 100%, can depending on the application, purpose arbitrarily adjusts.
As the method for making polyimide precursor imidizate, known method can be used.It is molten in polyimide precursor It is easy that the chemical imidization of basic catalyst is added in liquid.Chemical imidization is to carry out acyl Asia at a lower temperature Aminating reaction is not susceptible to the molecular weight and molecular weight of polymer during imidizate, thus preferably.
Chemical imidization can be stirred by by polyimide precursor in organic solvent, in the presence of basic catalyst It mixes to carry out.As organic solvent, the solvent used when polymerization reaction above-mentioned can be used.As basic catalyst, can arrange Enumerate pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc..Wherein, triethylamine fills for reacting due to having Point alkalinity and it is preferred that.
Temperature when carrying out imidization reaction is -20 DEG C~140 DEG C, preferably 0 DEG C~100 DEG C, can be preferably with reaction 1~100 hour time carried out.The amount of basic catalyst is 0.5~30 mole times of amic acid ester group, and preferably 2~20 rub You are again.The acid imide rate of obtained polymer can be controlled by adjusting catalytic amount, temperature, reaction time etc..
It is preferably logical due to remaining the catalyst etc. of addition in the solution after polyimide precursor imidization reaction Means as described below are crossed, obtained imide amination polymer is recycled, is redissolved with organic solvent, form liquid of the invention Brilliant alignment agent.
It is injected into poor solvent while that is, the solution of the polyimides obtained as described above is by being sufficiently stirred, it can So that polymer is precipitated.It is precipitated several times, after being washed with poor solvent, carries out room temperature or heat drying, available process The polyimide powder of purifying.
Poor solvent is not particularly limited, methanol, acetone, hexane, butyl cellosolve, heptane, methyl can be enumerated Ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl alcohol, toluene, benzene etc..
< aligning agent for liquid crystal >
Aligning agent for liquid crystal of the invention contains particular polymers, can also be in the limit for playing effect of the present invention Contain two or more different particular polymers of structure.In addition, other polymer can also be contained other than particular polymers. As the type of other polymer, polyamic acid can be enumerated, polyimides, poly amic acid ester, polyester, polyamide, polyureas, gathered Organosiloxane, cellulose derivative, polyacetals, polystyrene or derivatives thereof, poly- (styrene-phenyl maleimide) spread out Biological, poly- (methyl) acrylate etc..Alternatively, it is also possible to containing polyimide precursor shown in above-mentioned formula (5) and selected from keeping this poly- The polyimides etc. in polyimides that imide precursor imidizate obtains.
When aligning agent for liquid crystal of the invention contains other polymer, particular polymers relative to whole component of polymer Ratio preferably 5 mass % or more, can more preferably enumerate 5~95 mass %.
Aligning agent for liquid crystal is for making liquid crystal orientation film, general using coating from the viewpoint of forming uniform film The form of liquid.Aligning agent for liquid crystal of the invention preferably also contains component of polymer above-mentioned and can dissolve the component of polymer The coating fluid of organic solvent.At this point, the concentration of the polymer in aligning agent for liquid crystal can according to film to be formed thickness Setting and suitably change.From the viewpoint of forming uniform and flawless film, preferably 1 mass % or more, from solution Storage stability from the perspective of, be preferably set to 10 mass % or less.The concentration of particularly preferred polymer is 2~8 matter Measure %.
The organic solvent contained in aligning agent for liquid crystal is then no special if the organic solvent of component of polymer energy uniform dissolution It does not limit.If if enumerating its concrete example, n,N-Dimethylformamide, n,N-dimethylacetamide, N- methyl-can be enumerated 2-Pyrrolidone, N- ethyl-2-pyrrolidone, dimethyl sulfoxide, gamma-butyrolacton, 1,3- dimethyl-2-imidazolinone, methyl Ethyl ketone, cyclohexanone, cyclopentanone etc..Wherein, preferably n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone or γ-Ding Nei Ester.
In addition, being generally used on the basis of above-mentioned solvent for the organic solvent contained in aligning agent for liquid crystal and using energy Mixed solvent made of the solvent of the surface smoothness of coating, film when raising coating of liquid crystalline alignment agent, liquid of the invention It is also preferred that using such mixed solvent in brilliant alignment agent.The specific example for the organic solvent being listed below, but be not limited to These examples.
Such as ethyl alcohol, isopropanol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1- amylalcohol, 2- amylalcohol, 3- can be enumerated Amylalcohol, 2-methyl-1-butene alcohol, isoamyl alcohol, tert-pentyl alcohol, 3- methyl -2- butanol, neopentyl alcohol, 1- hexanol, 2- methyl-1-pentene alcohol, 2- Methyl -2- amylalcohol, 2- ethyl-n-butyl alcohol, 1-heptanol, 2- enanthol, 3- enanthol, 1- octanol, sec-n-octyl alcohol, 2- ethyl -1- hexanol, ring Hexanol, 1 methyl cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 1,2- ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,5- pentanediol, 2- methyl -2,4-PD, 2- second Base -1,3- hexylene glycol, dipropyl ether, dibutyl ethers, hexyl ether, dioxanes, ethylene glycol dimethyl ether, ethylene glycol diethyl Ether, ethylene glycol dibutyl ethers, 1,2- butoxy ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4- hydroxy-4-methyl- 2 pentanone, diethylene glycol (DEG) methyl ethyl ether, diethylene glycol dibutyl ether, 2 pentanone, propione, methyl-n-butyl ketone, 2-HEPTANONE, 4- heptanone, 3- Ethoxybutyl acetic acid esters, 1- methyl amyl acetic acid esters, 2- ethyl-butyl acetic acid esters, 2- ethylhexyl acetate, ethylene glycol list Acetic acid esters, ethylene acetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethyl alcohol, ethylene glycol monobutyl Ether, ethylene glycol list isoamyl ether, ethylene glycol mono hexyl ether, 2- (hexyloxy) ethyl alcohol, furfuryl alcohol, diethylene glycol (DEG), propylene glycol, propylene glycol list Butyl ether, 1- (Butoxyethoxy) propyl alcohol, propylene glycol monomethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, two Propylene glycol monoethyl, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol single methyl ether acetic acid esters, ethylene glycol Single monoethyl ether acetate, ethylene glycol monobutyl ether acetic acid esters, ethylene glycol acetate, ethylene acetate, diglycol monotertiary second Base ether acetic acid ester, diethylene glycol monobutyl ehter acetic acid esters, 2- (2- ethoxy ethoxy) ethylhexoate, diethylene glycol (DEG) acetic acid esters, three Glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid are just Butyl ester, propyleneglycolmethyletheracetate list ethylether, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-propionic acid first Base ethyl ester, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl Acid butyl ester, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate, following formula [D-1]~[D-3] Shown solvent etc..
In formula [D-1], D1The alkyl for indicating carbon number 1~3, in formula [D-2], D2Indicate the alkyl of carbon number 1~3, formula [D-3] In, D3Indicate the alkyl of carbon number 1~4.Wherein, preferably 1- hexanol, cyclohexanol, 1,2- ethylene glycol, 1,2-PD, propylene glycol list Butyl ether, diethylene glycol diethyl ether, 4- hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether. The type and content of such solvent can suitably be selected according to apparatus for coating, application conditions, coating environment of aligning agent for liquid crystal etc. It selects.
Aligning agent for liquid crystal of the invention can also be added containing the ingredient in addition to component of polymer and organic solvent.As Such additional ingredient can enumerate adaptation, liquid crystal orientation film and sealing material for improving liquid crystal orientation film and substrate Adaptation closely sealed auxiliary agent；For improving the crosslinking agent of liquid crystal aligning film-strength；Dielectric for adjusting liquid crystal orientation film is normal Number, the dielectric of resistance, conductive materials etc..These specific examples for adding ingredient are such as related to each known document of aligning agent for liquid crystal Disclosed in like that, if column are given one example, page 53 of International Publication bulletin 20,15/,060,357 the can be enumerated [0105] ingredient disclosed in [0116] section of section~55th page etc..
< liquid crystal orientation film >
Liquid crystal orientation film of the invention is obtained by the aligning agent for liquid crystal of aforementioned present invention.If enumerating by aligning agent for liquid crystal An example for obtaining the method for liquid crystal orientation film, can enumerate and the aligning agent for liquid crystal of coating fluid form is applied on substrate, Drying roasts and obtains film, implements the method for orientation process to the film by brushing facture or light orientation position logos.
As the substrate of coating of liquid crystalline alignment agent, it is not particularly limited, can be used as long as the high substrate of the transparency Glass substrate, silicon nitride board, and the plastic bases such as acrylic compounds substrate, polycarbonate substrate also can be used etc..At this point, If the use of the substrate of the ITO electrode being formed with for driving liquid crystal etc. being preferred from the viewpoint of simplifying technique.In addition, The liquid crystal of reflection-type indicates in element, the opaque substrate such as Silicon Wafer also can be used if being only unilateral substrate, at this time Electrode the materials of the reflected lights such as aluminium also can be used.
The coating method of aligning agent for liquid crystal is not particularly limited, industrially, silk-screen printing, hectographic printing, soft version Printing, ink-jet method etc. are common.As other coating methods, there is infusion process, rolling method, slot coated method, spin-coating method, is sprayed Method etc. can use these methods according to purpose.
On substrate after coating of liquid crystalline alignment agent, added by heating plate, thermal cycle type baking oven, IR (infrared ray) type baking oven etc. Hot cell evaporation solvent is simultaneously burnt into.Drying, firing process after coating of liquid crystalline alignment agent can choose arbitrary temperature and time. Sufficiently removed generally for by contained solvent, can enumerate and be burnt into 1~10 minute at 50~120 DEG C, then 150~ 5~120 minutes conditions are burnt at 300 DEG C.
The thickness of liquid crystal orientation film after firing is not particularly limited, liquid crystal indicates the reliability of element if excessively thin It is likely to decrease, therefore preferably 5~300nm, more preferably 10~200nm.
The liquid crystal that liquid crystal orientation film of the invention is suitable as the Transverse electric-field types such as IPS mode, FFS mode indicates element Liquid crystal orientation film, particularly suitable as FFS mode liquid crystal indicate element liquid crystal orientation film.
< liquid crystal indicates element >
Liquid crystal of the invention indicates that element is to obtain the base with the liquid crystal orientation film obtained by above-mentioned aligning agent for liquid crystal After plate, liquid crystal cells are made by known method, form element using the liquid crystal cells.
As an example of liquid crystal cells production method, said so that the liquid crystal of passive-matrix structure indicates element as an example It is bright.It should be noted that or being provided with TFT (Thin Film constituting each pixel portion that image is shown Transistor, thin film transistor (TFT)) etc. the active matrix structure of conversion elements liquid crystal indicate element.
Specifically, preparing the substrate of transparent glass system, common electrode is set on a substrate, another substrate it Upper setting segment electrode.These electrodes can be for example ITO electrode, and carry out being patterned so as to can be realized desired figure As display.Then, insulating film is set in a manner of covering common electrode and segment electrode on each substrate.Insulating film such as may be used Think through sol-gel method formation by SiO2-TiO2The film of formation.Then, under the conditions of above-mentioned, on each substrate Form liquid crystal orientation film.
Then, for example ultra-violet solidified sealing material is configured into the base in the two substrates for being formed with liquid crystal orientation film Specified position on plate, further after several specified positions configuration liquid crystal in liquid crystal alignment film surface, by with liquid crystal aligning The opposite form of film crimps the fitting of another substrate, spreads over liquid crystal in liquid crystal orientation film entire surface, then to substrate Entire surface irradiation ultraviolet light solidify sealing material, thus obtain liquid crystal cells.
Alternatively, specified position on a substrate configures as liquid crystal orientation film subsequent process is formed on substrate When sealing material, preset can from the opening portion of external filling liquid crystal, in the case where not configuring liquid crystal adhesive substrates it Afterwards, liquid crystal material is injected in liquid crystal cells by the opening portion of setting on the sealing material, then seals this with bonding agent and opens Oral area is to obtain liquid crystal cells.Vacuum impregnation can be used in the injection of liquid crystal material, also can be used and utilizes in an atmosphere The method of capillarity.
In above-mentioned any means, in order to ensure the space of the filling liquid crystal material in liquid crystal cells, preferably take as follows Means: being arranged columnar protrusion on a substrate, between perhaps spreading spacer on a substrate or being mixed into sealing material Parting, or by they combine etc..
As above-mentioned liquid crystal material, nematic crystal and smectic crystal can be enumerated, wherein it is preferred that nematic crystal, it can To use any one of positive type liquid crystal material, negative type liquid crystal material.Then, the setting of polarizing film is carried out.Specifically, it is preferable that In a pair of of polarizing film of face stickup with liquid crystal layer opposite side of 2 substrates.
It should be noted that as long as liquid crystal orientation film of the invention and liquid crystal indicate element using liquid crystal aligning of the invention Agent is not just limited by above-mentioned record, can also be made of other well known method.Such as Japanese Unexamined Patent Publication 2015-135393 The 0074th section of page 17 of bulletin~the 0081st section etc. of page 19 discloses until obtaining liquid crystal by aligning agent for liquid crystal indicates element Process.
Embodiment
Embodiment etc. is exemplified below out the present invention is specifically described.It should be noted that the present invention explain not by The restriction of these embodiments.
The abbreviation and evaluating characteristics of following raw material are as described below.
< organic solvent >
NMP:N- N-methyl-2-2-pyrrolidone N,
NEP:N- ethyl-2-pyrrolidone
GBL: gamma-butyrolacton, BCS: butyl cellosolve
PB: glycol monobutyl ether
DME: dipropylene glycol dimethyl ether
DAA:4- hydroxy-4-methyl-2-pentanone
DEDG: diethylene glycol diethyl ether
DIBK:2,6- valerone,
DIPE: Di Iso Propyl Ether,
DIBC:2,6- 2,6-dimethyl-4-heptanol,
Pd/C: palladium carbon,
DMSO: dimethyl sulfoxide, THF: tetrahydrofuran
< additive >
LS-4668:3- epoxy propoxy propyl triethoxysilane
< crosslinking agent >
It should be noted that Boc and Fmoc indicate that following shown groups, Me indicate methyl in specification.
(1The measurement of H-NMR)
Device: Varian NMR system 400NB (400MHz) (Varian corporation) and JMTC-500/54/SS (500MHz) (JEOL corporation)
Measure solvent: CDCl3(deuterated chloroform), DMSO-d6(deuterated dimethyl sulfoxide)
Primary standard substance: TMS (tetramethylsilane) (δ: 0.0ppm,1) and CDCl H3(δ: 77.0ppm,13C)
(measurement of acid imide rate)
Polyimide powder 20mg is added to NMR sample cell (NMR standard sample pipe, φ 5 (wasteland's scientific company system)), It adds deuterated dimethyl sulfoxide (DMSO-d6,0.05%TMS (tetramethylsilane) melange) (0.53ml), applying ultrasonic wave makes It is completely dissolved.NMR measuring machine (JNW-ECA500) (JEOL DATUM LTD. system) measurement 500MHz's is utilized for the solution Proton NMR.Acid imide rate is found out as follows: the proton for being originated from the structure not changed before and after imidizate is determined as benchmark Proton, the proton of the NH base from amic acid occurred using the peak accumulated value of the proton and near 9.5ppm~10.0ppm Peak accumulated value, is found out using the following formula.
Acid imide rate (%)=(1- α x/y) × 100
In above-mentioned formula, x is for peak accumulated value, the α that proton peak accumulated value, the y of the NH base from amic acid are benchmark proton Number ratio of the reference proton relative to 1 NH matrix of amic acid in the case where polyamic acid (acid imide rate is 0%).
The synthesis > of < diamine compound (DA-1)
Zinc chloride (120.3g, 882mmol) is added in the four-hole boiling flask of 3L (liter), 100 DEG C are warming up to, with oil pump vacuum It is 1 hour dry.Then, in a nitrogen atmosphere, at room temperature, sequentially add toluene (460g), diethylamine (45.0g, 615mmol), the bromo- 4- nitro-acetophenone (100.0g, 410mmol) of the tert-butyl alcohol (46.4g, 626mmol), 2- and 4- nitrobenzene second Ketone (104.2g, 631mmol) is stirred at room temperature 3 days.After reaction with HPLC (high performance liquid chromatography) confirmation, it is added 5% Aqueous sulfuric acid (400g), is neutralized, and is stirred at room temperature 1 hour.The crystal of precipitation is filtered under diminished pressure, toluene is successively used After (200g), pure water (300g), methanol (200g) are washed, it is dried, obtains coarse crystal.Make gained coarse-grain at 60 DEG C It after body is dissolved completely in tetrahydrofuran (1340g), is added ethyl alcohol (1340g), stirs 1 hour at 5 DEG C.By the crystal of precipitation It is filtered under diminished pressure, after being washed with ethyl alcohol (200g), is dried, obtain powder crystal (1) (yield 63g, yield 45%).
1H-NMR(DMSO-d6): 8.40-8.36 (4H, m), 8.28-8.24 (4H, m), 3.53 (4H, s)
In the four-hole boiling flask of 2L put into compound (1) (65.8g, 200mmol), ammonium acetate (84.5g, 1100mmol), And acetic acid (855g), 120 DEG C are warming up to, is stirred 3 hours under reflux.Terminated with HPLC (high performance liquid chromatography) confirmation reaction Afterwards, reaction solution is added in cold water (4000g), is stirred 1 hour.The crystal of precipitation is filtered under diminished pressure, with acetonitrile (100g) into Row after plasm scouring, is dried again, obtains powder crystal (2) (yield 53g, yield 78%).
1H-NMR(DMSO-d6): 11.8 (1H, br), 8.30-8.26 (4H, m), 8.11-8.07 (4H, m), 7.04 (2H, s)
In the four-hole boiling flask of 1L put into compound (2) (41.3g, 134mmol), potassium carbonate (27.8g, 201mmol) and Dimethylformamide (540g) instills methyl iodide (38.1g, 268mmol) at room temperature, stirs 24 hours.With HPLC (efficient liquid Phase chromatography) confirm after reaction, reaction solution is added in cold water (4300g), is stirred 1 hour.The crystal of precipitation is depressurized Filtering, after being washed with 2- propyl alcohol (100g), is dried, obtains powder crystal (3) (yield 41.1g, yield 90%).
1H-NMR(DMSO-d6): 8.34-8.33 (4H, m), 7.86-7.81 (4H, m), 6.67 (2H, s), 3.73 (3H, s)
Under the conditions of pressurized with hydrogen, by compound (3) (40g, 124mmol), 5 mass %Pd/C (50% is water type), spy The mixture of grade egression active carbon (4.0g) and dioxanes (400g) stirs 8 hours at 80 DEG C.After reaction, filtration catalytic Then agent is concentrated, be added 2- propyl alcohol (400g), is stirred 1 hour at 5 DEG C.The crystal of precipitation is filtered under diminished pressure, with 2- third It after alcohol (100g) is washed, is dried, obtains powder crystal (4) (yield 17g, yield 52%).
1H-NMR(DMSO-d6): 7.11-7.08 (4H, m), 6.63-6.59 (4H, m), 5.96 (2H, s), 5.15 (4H, S), 3.43 (3H, s)
Compound (4) (27.4g, 104mmol) and THF (270g) are put into the four-hole boiling flask of 1L, in ice-cold lower instillation Trifluoroacetic anhydride (46.5g, 220mmol) stirs 1 hour.After reaction with HPLC (high performance liquid chromatography) confirmation, it carries out dense Contracting dry solidification.Into obtained solid, THF (600g), potassium carbonate (45.1g, 326mmol) is added, instills methyl at room temperature Iodine (45.8g, 324mmol) stirs 22 hours at 40 DEG C.After reaction, passed through with HPLC (high performance liquid chromatography) confirmation It is filtered under diminished pressure desalination, carries out concentrate drying solidification.
Be added into obtained solid N-Methyl pyrrolidone (200g), pure water (30g) and potassium hydroxide (20.8g, 315mmol), it is stirred 30 minutes at 60 DEG C.After reaction, reaction solution is added to HPLC (high performance liquid chromatography) confirmation In cold water (1200g), stir 1 hour.The crystal of precipitation is filtered under diminished pressure, after being washed with 2- propyl alcohol (100g), is done It is dry, obtain powder crystal (5) (yield 22.9g, yield 76%).
1H-NMR(DMSO-d6): 7.20-7.17 (4H, m), 6.60-6.57 (4H, m), 5.99 (2H, s), 5.73 (2H, Q), 3.45 (3H, s), 2.70 (6H, d)
Sodium hydride (19.7g, 494mmol) and N-Methyl pyrrolidone (20g) are added in the four-hole boiling flask of 1L, carries out ice It is cold.Under nitrogen flowing, compound (5) (22.9g, 78.7mmol) and N-Methyl pyrrolidone (115g) are slowly instilled thereto After solution, the solution of 4- fluoronitrobenzene (44.4g, 315mmol) and N-Methyl pyrrolidone (44g) are then instilled, at room temperature Stirring 24 hours.
After reaction, reaction solution is added in cold water (1800g) with HPLC (high performance liquid chromatography) confirmation, stirring 1 Hour.It after carrying out plasm scouring again to gained coarse crystal with tetrahydrofuran (450g), is filtered under diminished pressure, is carried out with methanol (100g) Washing, is dried, obtains powder crystal (6) (yield 22.7g, yield 54%).
1H-NMR(DMSO-d6): 8.09 (4H, d), 7.64 (4H, d), 7.42 (4H, d), 6.87 (4H, d), 6.37 (2H, S), 3.69 (3H, s), 3.44 (6H, s),
Under the conditions of pressurized with hydrogen, by compound (6) (22.7g, 42.6mmol), 5 mass %Pd/C (50% is water type), The mixture of characteristic egression active carbon (2.0g) and dioxanes (230g) stirs 8 hours at 80 DEG C.After reaction, filtering is urged Then agent is concentrated, be added 2- propyl alcohol (300g), is stirred 1 hour at 5 DEG C.The crystal of precipitation is filtered under diminished pressure, 2- is used It after propyl alcohol (100g) is washed, is dried, obtains powder crystal (DA-1) (yield 17.4g, yield 86%).
1H-NMR(DMSO-d6): 7.20 (4H, d), 6.89 (4H, d), 6.67-6.59 (8H, m), 6.02 (2H, s), 5.06 (4H, s), 3.46 (3H, s), 3.17 (6H, s),
[synthesis example 1]
DA-1 (1.99g, 4.2mmol) is added in the four-hole boiling flask of the 100ml with agitating device and with nitrogen introducing tube Afterwards, the mixed solvent 20.0g of NMP:GBL=1:1 (mass ratio) is added, is stirred and makes it dissolve when being sent into nitrogen.While stirring The solution is mixed, CA-1 (0.61g, 2.8mmol), CA-2 (0.73g, 3.7mmol) and NMP:GBL=1:1 mixed solvent is added in side After 8.0g, is further stirred 12 hours at 50 DEG C, thus obtain polyamic acid solution (PAA-A1).
[synthesis example 2~6]
It is in addition to this, real in the same manner as synthesis example 1 respectively using diamine component, tetracarboxylic acid sour component and solvent shown in table 1 It applies, thus obtains polyamic acid solution (PAA-A2) and polyamic acid solution (PAA-B1)~(PAA-B4).
[table 1]
[synthesis example 7]
In the four-hole boiling flask of the 200ml with agitating device and with nitrogen introducing tube be added DA-6 (4.03g, 16.5mmol), after DA-7 (3.59g, 9.0mmol) and DA-8 (2.51g, 4.5mmol), NMP74.0g is added, nitrogen is sent on side It is made it dissolve while being stirred.CA-4 (4.37g, 19.5mmol) and NMP9.0g is added when stirring the solution, in 40 DEG C of items It is stirred 3 hours under part.Later, after CA-2 (1.71g, 8.7mmol) and NMP9.0g being added under the conditions of 25 DEG C, it is small that 12 are stirred for When, thus obtain polyamic acid solution.
Divide and take the 80.0g polyamic acid solution, after NMP20.0g is added, acetic anhydride 6.8g and pyridine 1.8g is added, 50 It is reacted 3 hours at DEG C.The reaction solution is put into 434.4g methanol while stirring, the sediment of precipitation is filtered out.Use methanol The sediment is washed, is dried under reduced pressure at 60 DEG C, the powder of polyimides is obtained.The acid imide of the polyimides Rate is 75%.NMP80.0g is added in gained polyimide powder 20.0g, stirs 20 hours and makes it dissolve at 70 DEG C, Thus polyimide solution (SPI-B5) is obtained.
[synthesis example 8]
DA-5 (68.5g, 280mmol) is measured in the four-hole boiling flask of the 1000mL with agitating device and with nitrogen introducing tube And DA-8 (23.9g, 70mmol), NMP 586g is added, is stirred and makes it dissolve when being sent into nitrogen.When stirring the solution Be added CA-4 (74.5g, 332mmol), and then be added NMP so that solid component concentration be 18 mass %, be stirred at room temperature 24 Hour, obtain polyamic acid solution.
Polyamic acid solution 200g is measured, NMP 100g is added, is stirred 30 minutes.Add in gained polyamic acid solution Enter acetic anhydride 21.78g and pyridine 2.81g, is reacted 3 hours at 60 DEG C.Gained reaction solution is put into 624.2g first while stirring In alcohol, the sediment of precipitation is filtered out.The sediment is washed with methanol, is dried under reduced pressure, is gathered at 60 DEG C Imido powder.The acid imide rate of the polyimides is 68%.NMP is added in gained polyimide powder 32.7g 239.8g stirs 20 hours at 70 DEG C and makes it dissolve, thus obtains polyimide solution (SPI-B6).
[embodiment 1~12] and [comparative example 1~7]
When stirring polyimide solution obtained in polyamic acid solution obtained in synthesis example 1~6 and synthesis example 7,8 Solvent and additive is added, to be formed namely to shown in table 2 and table 3, and then is stirred at room temperature 2 hours, thus obtains To the aligning agent for liquid crystal of embodiment 1~12 and comparative example 1~7.
It should be noted that ※ 1, the ※ 2 in table 2,3 indicate to contain (addition) relative to whole 100 mass parts of polymer It measures (mass parts), ※ 3 indicates the dosage (mass parts) of the solvent relative to 100 mass parts of aligning agent for liquid crystal.
[table 2]
[table 3]
< indicates the production > of element based on the liquid crystal of brushing method
Prepare having a size of long 30mm × wide 35mm and with a thickness of the electroded substrate of 0.7mm.On substrate, as the 1st Layer is formd for constituting opposite electrode and having the IZO electrode of solid shape pattern.On the 1st layer of opposite electrode, as 2 layers, form SiN (silicon nitride) film to form a film using CVD method.The film thickness of 2nd layer of SiN film is 500nm, is used as interlayer Insulating film and function.On the 2nd layer of SiN film, as the 3rd layer, the comb teeth-shaped picture for forming IZO film figure is configured Plain electrode, to form the 1st pixel and the 2nd pixel the two pixels.The size of each pixel is vertical 10mm, horizontal about 5mm.At this point, 1st layer of opposite electrode is in be electrically insulated with the 3rd layer of pixel electrode because of the effect of the 2nd layer of SiN film.
The comb that " く word " shape electrode member that there are 3rd layer of pixel electrode multiple center portions to bend is arranged to make up Tooth shape (referring to Fig. 3 of Japanese Unexamined Patent Publication 2014-77845 bulletin).The width of the width direction of each electrode member is 3 μm, 6 μm are divided between electrode member.Form " く word " shape electrode that the pixel electrode of each pixel is bent by multiple center portions Element arrangements are constituted, therefore the shape of each pixel not instead of oblong-shaped, are had in the same manner as electrode member in center portion Shape bend, " く word " similar to runic.Also, each pixel is divided up and down by boundary of the bending part in the center It cuts, the 2nd region with the 1st region and downside on the upside of bending part.
If the 1st region of each pixel and the 2nd region are compared, the electrode member of their pixel electrode is constituted It is different to form direction.That is, using the brushing direction of aftermentioned liquid crystal orientation film as benchmark in the case where, the 1st region of pixel with The mode for the angle (clockwise) that the electrode member of pixel electrode is+10 ° is formed, and the 2nd region of pixel is with the electricity of pixel electrode The mode for the angle (clockwise) that pole element is -10 ° is formed.In addition, the 1st region of each pixel and the 2nd region are to pass through pixel Voltage between electrode and opposite electrode applies and the side of the spinning movement (converting in face) in real estate of the liquid crystal of induction It is constituted to the mode for being mutual reverse direction.
Then, with after the filter filtering gained aligning agent for liquid crystal in 1.0 μm of aperture, it is spun on above-mentioned electroded base respectively Plate and it is overleaf formed with ito film as counter substrate and has height on the glass substrate of 4 μm of column spacer.Then Drying after five minutes, is burnt into 20 minutes at 230 DEG C, the polyamides of film thickness 60nm is obtained on each substrate in 80 DEG C of heating plate Imines film.On the polyimides film surface, in roller diameter 120mm, roller revolving speed 500rpm, platform movement speed 30mm/ seconds, brushing cloth It is pressed under conditions of pressure 0.3mm, after implementing brushing processing using rayon cloth, 1 minute ultrasonic irradiation is carried out in pure water, It is 10 minutes dry at 80 DEG C.
Using above-mentioned 2 with liquid crystal orientation film kind substrate, is combined, reserved in a manner of antiparallel with respective brushing direction Liquid crystal injecting port seals surrounding, and 3.8 μm of dummy cell is divided between production unit.The vacuum impregnating in the dummy cell at normal temperature After entering liquid crystal (Merck & Co., Inc.'s system, MLC-3019), inlet is sealed, the liquid crystal cells of antiparallel orientations are formed.Gained liquid crystal Unit, which constitutes FFS mode liquid crystal, indicates element.Later, liquid crystal cells are heated 1 hour at 120 DEG C, is used for after placing a Dinner Evaluation.
The evaluation > of < ghost cancellation time
The liquid crystal cells made are set to be become between 2 polarizing films that orthogonal mode configures with polarization axle, Without LED backlight is lighted in the state of application voltage, the arrangement angles for adjusting liquid crystal cells become the brightness of transmitted light most It is small.Then, while the liquid crystal cells are applied with the alternating voltage of frequency 30Hz, side measures V-T curve (voltage-transmission rate curve), The alternating voltage that relative transmittance is 23% is calculated as driving voltage.
In ghost evaluation, the alternating voltage that side applies the frequency 30Hz that relative transmittance is 23% drives liquid crystal cells, side Apply the DC voltage of 1V simultaneously, drives 30 minutes.Later, make to apply DC voltage value 0V, only stop applying DC voltage, It further drives 15 minutes in this state.
In ghost evaluation, to by until 30 minutes, relative transmittance is reduced from start to apply DC voltage at the time of It quantizes to 30% time below.It is reduced to 30% or less situation to be evaluated as relative transmittance within 5 minutes "○", if it is being then evaluated as " △ " within 6~30 minutes.Relative transmittance needed until being reduced to 30% or less 30 minutes with In the case where upper, it is denoted as that ghost can not be eliminated, is evaluated as "×".Moreover, ghost according to the method described above is evaluated in liquid crystal cells Temperature be 23 DEG C state temperature under the conditions of carry out.
< just starts the evaluation > of the flashing variation occurred after driving
The liquid crystal cells made are set to be become between 2 polarizing films that orthogonal mode configures with polarization axle, Without LED backlight is lighted in the state of application voltage, the arrangement angles for adjusting liquid crystal cells become the brightness of transmitted light most It is small.Then, while the liquid crystal cells are applied with the alternating voltage of frequency 30Hz, side measures V-T curve (voltage-transmission rate curve), The alternating voltage that relative transmittance is 23% is calculated as driving voltage.
In the measurement of flicker level, temporarily extinguishes the LED backlight lighted and light LED again after shading is placed 72 hours Backlight applies the alternating voltage for the frequency 30Hz that relative transmittance is 23% while starting to light backlight, makes liquid crystal Unit drives 60 minutes, tracking flashing amplitude.Flashing amplitude be will transmit through 2 polarizing films and its between liquid crystal cells LED The transmitted light of backlight is converted by the data collection/data logger connected by photodiode with I-V switching amplifier What unit 34970A (Agilent Technologies corporation) was read.Flicker level is calculated by following mathematical expressions.
Flicker level (%)={ flashing amplitude/(2 × z) } × 100
In above-mentioned formula, the brightness when alternating voltage that z is the frequency 30Hz that will be 23% by relative transmittance drives is used The value that data collection/data logger converting unit 34970A is read.
Evaluation for flicker level, from LED backlight and application alternating voltage start time is lighted to by 60 minutes Until, the case where flicker level is maintained less than 3%, defines and is evaluated as "○".Flicker level in 60 minutes is reached 3% Above situation defines and is evaluated as "×".
The evaluation of flicker level according to the method described above be liquid crystal cells temperature be 23 DEG C state temperature condition Lower progress.
< evaluation result >
For using the liquid crystal of each aligning agent for liquid crystal of above-described embodiment 1,2,4,5 and comparative example 1~4,6,7 to indicate member Part, by the ghost implemented among the above eliminate the time and just start driving after occur flashing variation evaluation result is shown in table 4 ~table 6.
It should be noted that ※ 1 indicates each polymer phase for the content of whole 100 mass parts of polymer in table 4~6 (mass parts).
[table 4]
[table 5]
[table 6]
By 4~table of table 6 it is found that indicating element, stored charge using the liquid crystal of the aligning agent for liquid crystal of embodiment 1,2,4,5 Mitigation it is fast, and be less likely to occur just to start the flashing occurred after driving variation.
< indicates the production > of element based on the liquid crystal of optical alignment method
After filtering aligning agent for liquid crystal with 1.0 μm of the filter in aperture, it is spun on the above-mentioned electroded base prepared respectively Plate and it is overleaf formed with ito film as counter substrate and has height for the glass substrate of 4 μm of column spacer.Then, It is dry in 80 DEG C of heating plate to be burnt into 30 minutes with 230 DEG C after five minutes, the film of film thickness 100nm is formed, on each substrate Obtain polyimide film.The purple of the wavelength 254nm of the linear polarization of extinction ratio 26:1 is irradiated by polarizing film to the coated surface Outside line 250mJ/cm2。
The substrate is impregnated 5 minutes in 25 DEG C EL (ethyl lactate) solution, 1 point is then impregnated in 25 DEG C of pure water Zhong Hou heats 30 minutes in 230 DEG C of heating plate, obtains the substrate with liquid crystal orientation film.Using above-mentioned 2 substrates as one Group, the printing and sealing agent on substrate paste another 1 substrate face-to-face and in a manner of differently- oriented directivity becomes 0 ° by liquid crystal alignment film surface After conjunction, make sealant cures, makes dummy cell.By the MLC- for injecting negative type liquid crystal in decompression injection normal direction dummy cell 7026-100 (Merck & Co., Inc.'s system), inlet is sealed, and obtains FFS driving liquid crystal cells.Later, by gained liquid crystal cells with 110 DEG C are heated 1 hour, are used for each evaluation after placing a Dinner.
The evaluation > of < ghost cancellation time
In the same manner as the case where liquid crystal based on brushing method indicates element, use what is made among the above based on optical alignment method Liquid crystal indicates that optics system of element etc. carries out the evaluation of ghost.
< just drive after flicker level evaluation >
In the same manner as the case where liquid crystal based on brushing method indicates element, use what is made among the above based on optical alignment method Liquid crystal indicates the optics system etc. of element, carries out the evaluation of ghost.
< evaluation result >
It, will be above-mentioned for using the liquid crystal of aligning agent for liquid crystal obtained in above-described embodiment 12 and comparative example 7 to indicate element The result of evaluation of flicker level after the ghost of middle implementation eliminates the evaluation of time and just drives is shown in table 7.It needs to illustrate , in table 7, ※ 1 indicates each polymer phase for the content (mass parts) of whole 100 mass parts of polymer.
[table 7]
As shown in Table 7, element is indicated using the liquid crystal of the aligning agent for liquid crystal of embodiment 12, the mitigation of stored charge is fast, And the flashing for just starting to occur after driving variation is less likely to occur.
Industrial availability
The longitudinal electric fields sides such as TN mode, VA mode are widely used in using the aligning agent for liquid crystal of new polymers of the invention The liquid crystal of the Transverse electric-field types such as formula, particularly IPS mode, FFS mode indicates element.
It should be noted that by Japanese patent application 2016-191765 specification filed on September 29th, 2016, The full content of claims and abstract introduces so far, is introduced into as specification disclosure of the invention.

Claims (15)

1. a kind of aligning agent for liquid crystal, which is characterized in that contain the polymerization obtained as the diamines with structure shown in following formula (1) Object and organic solvent,
In formula (1), R1、R2For hydrogen atom or 1 valence organic group, any hydrogen atom of phenyl ring is optionally replaced by 1 valence organic group, * Indicate bonding position.
2. aligning agent for liquid crystal according to claim 1, wherein the polymer is selected from by polyimide precursor and its acyl At least one kind of polymer in imines compound, that is, polyimides composition group, the polyimide precursor is with the formula (1) institute Show the diamines of structure and the condensation polymer of tetracarboxylic dianhydride.
3. aligning agent for liquid crystal according to claim 1 or 2, wherein the diamines by following formula (2) indicate,
In formula (2), R1And R2Definition it is identical as the formula (1), R3Each independently represent the structure of singly-bound or following formula (3), n Indicate that 1~3 integer, any hydrogen atom of phenyl ring are optionally replaced by 1 valence organic group,
In formula (3), R4It indicates singly-bound, be selected from-O- ,-COO- ,-OCO- ,-(CH2)l-、-O(CH2)mO- ,-CONH- and-NHCO-'s Divalent organic group, l, m indicate 1~5 integer, *1Indicate the position being bonded with the phenyl ring in formula (2), *2In expression and formula (2) Amino bonded position.
4. aligning agent for liquid crystal according to claims 1 to 3, wherein the polyimide precursor has shown in following formula (4) Structure,
In formula (4), X1For the 4 valence organic groups from tetracarboxylic acid derivatives, Y1Have for the divalent from diamines shown in the formula (1) Machine group, R5For hydrogen atom or the alkyl of carbon number 1~5.
5. aligning agent for liquid crystal according to claim 4, wherein in the formula (4), X1For selected from by following (A-1)~(A- It is 21) at least one kind of in the group of structure composition,
6. aligning agent for liquid crystal according to claim 4 or 5, wherein relative to the whole polymerization contained in aligning agent for liquid crystal Object, the polymer with structural unit shown in the formula (4) containing 10 moles of % or more.
7. aligning agent for liquid crystal described according to claim 1~any one of 6, wherein the organic solvent contains selected from by 4- It is at least one kind of in the group of hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether composition.
8. a kind of liquid crystal orientation film is obtained using aligning agent for liquid crystal according to any one of claims 1 to 7.
9. a kind of liquid crystal indicates element, has liquid crystal orientation film according to any one of claims 8.
10. liquid crystal according to claim 9 indicates element, wherein liquid crystal indicates that element is transverse electric field driving method.
11. a kind of polymer, in the group being made of polyimide precursor and its acid imide compound, that is, polyimides It is at least one kind of, the polyimide precursor be with the diamines of structure shown in following formula (1) and the condensation polymer of tetracarboxylic dianhydride,
In formula (1), R1、R2For hydrogen atom or 1 valence organic group, any hydrogen atom of phenyl ring is optionally replaced by 1 valence organic group, * Indicate bonding position.
12. polymer according to claim 11, wherein the diamines by following formula (2) indicate,
In formula (2), R1And R2Definition it is identical as the formula (1), R3There is structure shown in singly-bound or following formula (3) each independently, N indicates that 1~3 integer, any hydrogen atom of phenyl ring are optionally replaced by 1 valence organic group,
In formula (3), R4It indicates singly-bound, be selected from-O- ,-COO- ,-OCO- ,-(CH2)l-、-O(CH2)mO- ,-CONH- and-NHCO-'s Divalent organic group, l, m indicate 1~5 integer, *1Indicate the position being bonded with the phenyl ring in formula (2), *2In expression and formula (2) Amino bonded position.
13. polymer according to claim 11 or 12, wherein the polyimide precursor by following formula (4) indicate,
In formula (4), X1For the 4 valence organic groups from tetracarboxylic acid derivatives, Y1Have for the divalent from diamines shown in the formula (1) Machine group, R5For hydrogen atom or the alkyl of carbon number 1~5.
14. polymer according to claim 13, wherein in the formula (6), X1For selected from by following (A-1)~(A-21) It is at least one kind of in the group of shown structure composition,
15. a kind of diamines is indicated by following formula (2),
In formula (2), R1And R2Definition it is identical as above-mentioned formula (1), R3There is structure shown in singly-bound or following formula (3) each independently, N indicates that 1~3 integer, any hydrogen atom of phenyl ring are optionally replaced by 1 valence organic group.
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