CN108885374A

CN108885374A - Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal expression element using it

Info

Publication number: CN108885374A
Application number: CN201780018862.9A
Authority: CN
Inventors: 相马早纪; 森本佳道; 石川和典; 南悟志; 石井秀则
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2016-01-22
Filing date: 2017-01-19
Publication date: 2018-11-23
Anticipated expiration: 2037-01-19
Also published as: TWI762464B; KR20180101576A; JPWO2017126627A1; JP6927050B2; WO2017126627A1; KR20240090617A; TW201736443A; CN108885374B; JP7173194B2; JP2021101023A

Abstract

It provides：Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal for the liquid crystal orientation film that available voltage retention is excellent, stored charge mitigation is fast, is not easy to cause flashing in driving indicate element.A kind of aligning agent for liquid crystal, contains：The polymer obtained as the diamines with structure shown in formula (1)；With organic solvent.(R₁Indicate that the organic group of hydrogen, fluorine atom, cyano, hydroxyl or monovalence, * indicate the position for being bonded to other groups.Replaced organic group of any hydrogen atom of phenyl ring optionally by monovalence.)

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 novel polymer Part.

Background technique

Liquid crystal indicates that element is widely used as the expressed portion of PC, mobile phone, smart phone, TV etc..Liquid Crystalline substance indicates that element for example has：It is held on the liquid crystal layer between device substrate and filter substrate, electric field is applied to liquid crystal layer Pixel electrode and common electrode, the alignment films of orientation of liquid crystal molecule for controlling liquid crystal layer, conversion supply pixel electrode Thin film transistor (TFT) (TFT) of electric signal etc..Driving method as liquid crystal molecule, it is known to longitudinal electricity such as TN mode, VA mode The Transverse electric-field types such as field type, IPS mode, FFS mode.It is known using only substrate it is unilateral formed electrode, to substrate Parallel direction apply alive Transverse electric-field type can be made into it is previous voltage applied to the electrode for being formed in upper and lower base plate and It compares the longitudinal electric field mode of liquid crystal drive with extensive angle of visibility characteristic and can be carried out the liquid crystal watch of high-quality expression Show element.

Although the liquid crystal cells angle of visibility excellent of Transverse electric-field type, the electrode section being formed in substrate Few, therefore, if voltage retention is low, not applying sufficient voltage to liquid crystal can make to indicate that contrast reduces.In addition, if The stability of liquid crystal aligning is small, then make liquid crystal for a long time drive when liquid crystal can not return to initial state, become contrast reduce, The reason of ghost, therefore, the stability of liquid crystal aligning, are important.In turn, electrostatic is easy to accumulate in liquid crystal cells, due to by The application of the positive and negative asymmetric voltage of driving and generation, charge are also accumulated in liquid crystal cells, and the charge that these have accumulated is with liquid The disorder of crystalline substance orientation, the mode of ghost impact expression, are substantially reduced the expression quality of liquid crystal cell.In addition, just After driving, due to backlight illumination to liquid crystal cells, thus charge accumulation, even if the driving of short time can also generate ghost, and The problems such as size of flashing (flickering) changes in generation driving.

It is excellent as voltage retention and reduce electricity when liquid crystal for such Transverse electric-field type indicates element The aligning agent for liquid crystal of lotus accumulation, discloses in patent document 1, the liquid crystal containing specific diamines and aliphatic tetracarboxylic acid derivatives takes To agent.However, indicating the high performance of element along with liquid crystal, characteristic required by liquid crystal orientation film also becomes harsh, with these The prior art, which is difficult to sufficiently meet, all requires characteristic.

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

Problem of the present invention is that providing：Can obtain voltage retention is excellent, mitigation of stored charge is fast, in driving not The aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal that flash the liquid crystal orientation film of (flickering) is easily caused to indicate element.

The solution to the problem

The inventors of the present invention have made intensive studies in order to solve the above problems, as a result, it has been found that：By in aligning agent for liquid crystal Specific structure is imported in contained polymer, various characteristics are improved simultaneously, complete the present invention.See the present invention is based on above-mentioned Solution, with following for main purport.

1. a kind of aligning agent for liquid crystal, which is characterized in that contain：It is obtained as the diamines with structure shown in following formula (1) Polymer；With organic solvent.

(R₁Indicate that the organic group of hydrogen, fluorine atom, cyano, hydroxyl or monovalence, * indicate the portion for being bonded to other groups Position.Replaced organic group of any hydrogen atom of phenyl ring optionally by monovalence.)

2. the aligning agent for liquid crystal according to aforementioned 1, wherein aforementioned polymer is selected from by as with previously described formula (1) Shown in structure diamines and tetracarboxylic dianhydride condensation polymer polyimide precursor and acyl as the polyimide precursor it is sub- At least one kind of polymer in the group of the polyimides composition of aminate.

3. the aligning agent for liquid crystal according to aforementioned 1 or 2, wherein above-mentioned diamines is indicated with formula below (2).

(R₁Definition and previously described formula (1) equally, R₂The structure of singly-bound or following formula (3) is each independently represented, n indicates 1 ~3 integer.Any hydrogen atom of phenyl ring is optionally replaced the organic group of 1 valence.)

(R₃It indicates singly-bound, be selected from-O- ,-COO- ,-OCO- ,-(CH₂)_l-、-O(CH₂)_m2 in O- ,-CONH- and-NHCO- The organic group (l, m indicate 1~5 integer) of valence, *₁Expression is bonded to the position of the phenyl ring in formula (2), *₂Expression is bonded to The position of amino in formula (2).)

4. the aligning agent for liquid crystal according to aforementioned 1~3, wherein aforementioned polyimide precursor is indicated with following formula (6).

(X₁For the organic group of 4 valences from tetracarboxylic acid derivatives, Y₁For the diamines from the structure comprising previously described formula (1) Divalent organic group, R₄For hydrogen atom or the alkyl of carbon number 1~5.)

5. the aligning agent for liquid crystal according to aforementioned 4, wherein in previously described formula (6), X₁Structure be selected from by aftermentioned formula (A-1) at least one kind of in the group of the structure composition of~formula (A-21).

6. the aligning agent for liquid crystal according to aforementioned 4 or 5, wherein containing relative to the whole contained in aligning agent for liquid crystal The polymer with structural unit shown in previously described formula (6) that polymer is 10 moles of % or more.

7. the aligning agent for liquid crystal according to aforementioned 4~6, wherein aforementioned organic solvents contain selected from by 4- hydroxyl -4- first It is at least one kind of in the group of base -2 pentanone and diethylene glycol diethyl ether composition.

8. a kind of liquid crystal orientation film is using obtained from 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 as with structure shown in following formula (1) diamines and tetracarboxylic dianhydride Condensation polymer polyimide precursor and acid imide compound as the polyimide precursor polyimides composition group in It is at least one kind of.

(R₁With * as described in aforementioned 1.)

12. the polymer according to aforementioned 11, wherein above-mentioned diamines is indicated with formula below (2).

(R₁、R₂It is recorded in n such as aforementioned 3.)

13. the polymer according to aforementioned 11 or 12, wherein aforementioned polyimide precursor is indicated with following formula (6).

(X₁、Y₁And R₄It is recorded in such as aforementioned 4.)

14. the polymer according to aforementioned 13, wherein in previously described formula (6), X₁Structure be selected from by aftermentioned formula (A-1) at least one kind of in the group of the structure composition of~formula (A-21).

The effect of invention

By using aligning agent for liquid crystal of the invention, the mitigation that can provide stored charge is not easy to cause sudden strain of a muscle fastly, in driving The liquid crystal that the liquid crystal orientation film and characterization of bright (flickering) are excellent indicates element.It is above-mentioned by the way why the present application can solve Project is still uncertain, but approximately as thinking.

The conductive pyrroles's knot of the structure of above-mentioned (1) possessed by the polymer contained in aligning agent for liquid crystal of the invention Structure and conjugated structure as a result, for example in liquid crystal orientation film, can promote the movement of charge, can promote the mitigation of stored charge.

Specific embodiment

< has the amine > of specific structure

Aligning agent for liquid crystal of the invention contains：It is (also referred to as special in the present invention by the diamines of the structure with following formula (1) Determine diamines) obtained polymer (in the present invention, also referred to as particular polymers)；With organic solvent.

In above-mentioned formula (1), R₁Indicate the organic group of hydrogen, fluorine atom, cyano, hydroxyl or monovalence, * expression is bonded to it The position of his group.Its hydrogen atom of phenyl ring is arbitrarily replaced by the organic group of monovalence.

As the organic group of the monovalence in herein, can enumerate with carbon number be 1~10, preferably 1~3, alkyl, alkene Base, alkoxy, fluoro-alkyl, fluoro alkenyl or fluoroalkyl.Wherein, R₁It is preferred that hydrogen atom or methyl.

In the structure of above-mentioned formula (1), the phenyl ring aspect mobile from charge relative to the bonding position of pyrrole ring is as follows It states shown in formula (1-1) like that, the carbon atom adjacent with nitrogen-atoms preferably on pyrrole ring.

Above-mentioned specific diamines can for example use following formula (1-2) to indicate, diamines shown in particularly preferred following formula (1-3), In turn, diamines shown in more preferable formula (1-4).

In formula (1-2)~formula (1-4), R₁Definition and same, Q the case where previously described formula (1)₁、Q₂It is each independently singly-bound Or the organic group of divalent, it can be Q₁And Q₂Structure different from each other.In addition, 2 Q in formula (1-4)₂It can be for each other not Same structure.In turn, any hydrogen atom of phenyl ring and the case where above-mentioned formula (1) likewise it is possible to by the organic group institute of monovalence Replace.

As the preference of above-mentioned specific diamines, diamines shown in following formula (2), more preferable formula (2-1) institute can be enumerated The diamines shown.

R in above-mentioned formula (2) and formula (2-1)₁Definition and above-mentioned formula (1) it is same.2 R₂Each independently represent singly-bound Or the structure of following formula (3).It should be noted that in the same manner as with above-mentioned formula (1) the case where, any hydrogen atom optionally quilt of phenyl ring Replaced the organic group of monovalence.

In above-mentioned formula (3), R₃Indicate singly-bound, selected from by-O- ,-COO- ,-OCO- ,-(CH₂)_l-、-O(CH₂)_mO-、-CONH- With the organic group of the divalent in the group of-NHCO- composition, herein, l, m indicate 1~5 integer.Wherein, from the slow of stored charge The aspect of sum is set out, R₃It is preferred that singly-bound ,-O- ,-COO- ,-OCO- ,-CONH- or-NHCO-.In addition, *₁In expression and formula (2) The position of phenyl ring bonding, *₂Expression is bonded to the position of the amino in formula (2).

N in above-mentioned formula (2) and formula (2-1) indicates 1~3 integer.It is preferred that 1 or 2.

The concrete example of diamines as above-mentioned formula (2) can be exemplified hereinafter, but being not limited to these.Wherein, from accumulation electricity It sets out in terms of the mitigation of lotus, preferably (2-1-1), (2-1-2), (2-1-3), (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), (2-1-11) or (2-1-12).

The synthetic method > of the specific diamines of <

The method for synthesizing above-mentioned specific diamines is not particularly limited.For example, following method：It uses following formula (4) Shown in dinitro compound, the nitro being had is converted into amino by reduction reaction.

In formula (4), R₁Definition with it is same in above-mentioned formula (1)

The activated carbon supported metal that catalyst used in above-mentioned reduction reaction can preferably be obtained as commercially available product, such as can To enumerate palladium-active carbon, platinum-active carbon, rhodium-active carbon etc..Alternatively, it is also possible to use palladium dydroxide, platinum oxide, Raney's nickel Deng, may not be activated carbon supported type metallic catalyst.General widely used palladium-active carbon it is available good as a result, Therefore it is preferred that.

In order to be more effectively carried out reduction reaction, also implement reaction under the coexisting of active carbon sometimes.At this point, use The amount of active carbon is not particularly limited, relative to dinitro compound (4), preferably 1~30 mass %, more preferable 10~20 matter Measure %.According to same reason, also implement reaction under elevated pressure sometimes.Under above situation, in order to avoid the reduction of benzene nucleus, straight It is carried out in the pressure range of 20 air pressures.It is preferred that implementing reaction in the range of up to 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- matter Sub- property polar organic solvent (dimethylformamide, dimethyl sulfoxide, dimethyl acetic acid ester, n-methyl-2-pyrrolidone etc.)；Ether Class (diethyl ether, diisopropyl ether, t-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane etc.)；Aliphatic hydrocarbon (pentane, hexane, heptane, petroleum ether etc.)；Aromatic hydrocarbon (benzene,toluene,xylene, mesitylene, chlorobenzene, dichloro-benzenes, nitro Benzene, tetrahydronaphthalene etc.)；Halogen system hydro carbons (chloroform, methylene chloride, carbon tetrachloride, dichloroethanes etc.)；Lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate etc.)；Nitrile (acetonitrile, propionitrile, butyronitrile etc.) etc..These solvents can be with Using a kind or use two or more.Further, it is possible to use dehydrating agent appropriate, desiccant are using solvent seasoning as nonaqueous solvents It uses.

The dosage (reaction density) of solvent is not particularly limited, and is 0.1~100 mass relative to dinitro compound (4) Times.It is preferred that 0.5~30 mass times, further preferred 1~10 mass times.

Reaction temperature is not particularly limited, for -100 DEG C~boiling point of solvent that uses until range, preferably -50~ 150℃.Reaction time is usually 0.05~350 hour, preferably 0.5~100 hour.

[preparation method of the compound of formula (4)]

The method of the compound of a pairing accepted way of doing sth (4) is not particularly limited, for example, following method：Synthesize following formula (5) dinitro matrix shown in, and then protecting group R is imported to NH base₁。

Import R₁When, as long as the compound that can be reacted with amine.For example, carboxylic acid halides, acid anhydrides, isocyanic acid Esters, epoxy compound species, oxetanes class, halogenated aryl class, halogenated alkanes.Further, it is possible to use the hydroxyl of alcohol is taken On behalf of alcohols of leaving groups such as OMs (mesyl), OTf (trifyl), OTs (tosyl) etc..

It is reacted with carboxylic acid halides and imports R₁In the case where, preferably carry out in the presence of base.As the example of carboxylic acid halides, Ke Yiju Out 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 alkali, without spy as long as it can synthesize It does not limit, it is inorganic that potassium carbonate, sodium carbonate, cesium carbonate, sodium alkoxide, potassium alcoholate, sodium hydroxide, potassium hydroxide, sodium hydride etc. can be used Organic bases such as alkali, pyridine, dimethyl aminopyridine, trimethylamine, triethylamine, tri-n-butylamine etc..Reaction dissolvent, reaction temperature with it is aforementioned It is same in the reduction reaction of nitro compound (4).

R is imported with anhydride reaction₁In the case where, as the example of acid anhydrides, acetic anhydride, propionic andydride, two carbon can be enumerated Dimethyl phthalate, dicarbonic acid diethyl ester, di-tert-butyl dicarbonate, two dimethyl benzyls etc..As for promote reaction catalyst, Pyridine, trimethylpyridine, N, N- dimethyl -4-aminopyridine etc. can be used.Catalytic amount is relative to compound (5) 0.0001 mole~1 mole.Reaction dissolvent, reaction temperature with it is same in above-mentioned carboxylic acid halides.

It is reacted with isocyanates and imports R₁In the case where, as the example of isocyanates, it is different methyl can be enumerated Cyanate, ethyl isocyanate, n-propyl isocyanates, phenyl isocyanate etc..Reaction dissolvent, reaction temperature and above-mentioned carboxylic acid halides In situation it is same.

It is reacted with epoxy compound species, oxetane compound class and imports R₁In the case where, as epoxide The example of class, oxetanes class can enumerate ethylene oxide, propylene oxide, 1,2- epoxy butane, oxetanes etc..Instead Answer solvent, reaction temperature with it is same in above-mentioned carboxylic acid halides.

The alcohols that the hydroxyl of alcohol is substituted by the leaving groups such as OMs, OTf, OTs is set to react and import R₁In the case where, it is excellent Choosing carries out in the presence of base.As the example of above-mentioned alcohols, methanol, ethyl alcohol, 1- propyl alcohol etc. can be enumerated, make these alcohols with The reaction such as mesyl chloride, trifluoromethanesulfchloride chloride, paratoluensulfonyl chloride, leaves away so as to obtain being substituted by OMs, OTf, OTs etc. The alcohol of group.The example of alkali, reaction dissolvent, reaction temperature are same as the situation in above-mentioned carboxylic acid halides.

Alkyl halide is set to react and import R₁In the case where, preferably carry out in the presence of base.As the example of halogenated alkanes, Iodomethane, iodoethane, propyl iodide, bromomethane, bromoethane, n-propyl bromide etc. can be enumerated.As the example of alkali, preceding Stating can be used the metal alkoxides class such as potassium tert-butoxide, sodium tert-butoxide on the basis of alkali.Reaction dissolvent, reaction temperature and above-mentioned carboxylic acid halides In situation it is same.

[preparation method of the compound of formula (5)]

The method of the compound of a pairing accepted way of doing sth (5) is not particularly limited, and the position of substitution on the pyrrole ring of formula (5) is 2 In the case where 4, for example, making have the α-halogenatedketone of nitro and the ketone with nitro excellent as shown in following reaction equations 1 Choosing is reacted in the presence of base so as to obtain.In reaction equation 1, X indicates Br, I or OTf.

As the example of alkali used in above-mentioned reaction, exemplary alkali in aforementioned above-mentioned carboxylic acid halides can be used, reaction dissolvent, Reaction temperature is same as foregoing description.

In order to promote the speed in above-mentioned reaction, zinc chloride, sodium iodide, potassium iodide, tetrabutylammonium iodide etc. can be used.

On the other hand, in the case where being substituted by addition to 2 and 4 in the pyrrole ring of the compound of formula (5), make to correspond to Halogenated pyrrole and organometallic reagent carry out it is preferable to use the cross-coupling reactions of metallic catalyst, so as to obtain.

In reaction equation 2, X indicates Br, I or OTf.M indicates B (OH)₂Or 4,4,5,5- tetramethyl -1,3,2- dioxane penta Borine -2- base.

It is preferable to use metal complexs and ligand as catalyst for above-mentioned cross-coupling reaction (Suzuki-palace Pu reaction), but It is reacted in the case where no catalyst.As the example of metal complex, can enumerate acid chloride, palladium chloride, Palladium chloride-acetonitrile complex, palladium-active carbon, bis- (two benzal benzylacetones) palladiums, three (two benzal benzylacetones) two palladiums, bis- (acetonitriles) Dichloro palladium, bis- (benzonitrile) dichloro palladiums, CuCl, CuBr, CuI, CuCN etc..As the example of ligand, can enumerate triphenylphosphine, Bis- (diphenylphosphino) ethane of tri-o-tolyl phosphine, diphenyl methyl phosphine, phenyldimethylphosphine, 1,2-, the bis- (diphenylphosphines of 1,3- Base) propane, bis- (diphenylphosphino) butane of 1,4-, 1,1 '-bis- (diphenylphosphino) ferrocene, Trimethyl phosphite, phosphorous acid Triethyl, triphenyl phosphite, tri-tert-butylphosphine etc..

The dosage of above-mentioned metal complex can be so-called catalytic amount, relative to matrix be 20 moles of % or less be abundant , preferably 10 moles of % or less.

< polymer >

Aligning agent for liquid crystal of the invention is the polymer obtained using specific diamines.It, can be with as the concrete example of polymer Enumerate polyamic acid, poly amic acid ester, polyimides, polyureas, polyamide etc..Wherein, it is preferably selected from by with following formula (6) Shown in the polyimide precursor of structural unit and the polyimides composition of acid imide compound as the polyimide precursor At least one kind of polymer in group.

In above-mentioned formula (6), X₁For the organic group of 4 valences from tetracarboxylic acid derivatives.Y₁For from the knot comprising formula (1) The organic group of the divalent of the diamines of structure.R₄For hydrogen atom or the alkyl of carbon number 1~5.From the imidizate caused by heating It sets out in terms of easiness, R₄It is preferred that hydrogen atom, methyl or ethyl.

In above-mentioned formula (6), X₁For the organic group of 4 valences from tetracarboxylic acid derivatives.X₁In a solvent according to polymer The orientation of liquid crystal when dissolubility, the coating of aligning agent for liquid crystal, formation liquid crystal orientation film, voltage retention, stored charge Deng needed for characteristic degree and be suitable for selection, in same polymer can for a kind or two or more.

As X₁Concrete example, record in page 13~page 14 of International Publication bulletin 2015/119168, formula can be enumerated (X-1)~(X-46) structure etc..

It is described below to be used as preferred X₁Structure following (A-1)~(A-21).

In above structure, from the aspect of resistance to brushing further improved, particularly preferably (A-1) or (A-2), from The aspect of the mitigation speed of stored charge further improved is set out, particularly preferred (A-4), from liquid crystal aligning and accumulation electricity The aspect of the mitigation speed of lotus further improved is set out, particularly preferred (A-15)~(A-17) etc..

In formula (6), Y₁It can enumerate from structure obtained from 2 amino of exclusion in the diamines of previously described formula (2).Wherein, Y₁More It is preferred that from above-mentioned formula (2-1-1), (2-1-2), (2-1-3), (2-1-5), (2-1-8), (2-1-9), (2-1-10), (2-1- 11) structure obtained from 2 amino, is excluded in the structure of (2-1-12), particularly preferably from (2-1-1), (2-1-2), (2-1- 3) structure obtained from 2 amino, is excluded in the structure of (2-1-11), (2-1-12).

< other polymers (structural unit) >

Aligning agent for liquid crystal of the invention can wrap in addition to the polyimide precursor of the structural unit with above-mentioned formula (6) Contain：Selected from sub- as the polyimide precursor with structural unit shown in following formula (7) and the acyl as the polyimide precursor At least one kind of polymer in the group of the polyimides composition of aminate.

In formula (7), X₂For the organic group of 4 valences from tetracarboxylic acid derivatives.Y₂For from the structure for not having formula (1) Diamines divalent organic group.R₄It is identical as the definition in previously described formula (6).R₅Indicate the alkyl of hydrogen atom or carbon number 1~4. Additionally, it is preferred that 2 R₅At least one of be hydrogen atom.

As X₂Concrete example, also include preference, the X with formula (6)₁In it is exemplary identical.In addition, Y₂According to polymer The coating of dissolubility, aligning agent for liquid crystal in a solvent, liquid crystal when forming liquid crystal orientation film orientation, voltage keep The characteristics such as rate, stored charge and select, can for a kind or two or more.

If showing Y₂Concrete example, then can enumerate the formula recorded in page 4 of International Publication bulletin 2015/119168 (2) structure recorded in structure and page 8~page 12, formula (Y-1)~(Y-97), (Y-101)~(Y-118)；From international public affairs Open organic group record in page 6 of bulletin 2013/008906, divalent obtained from 2 amino of removal in formula (2)；From state The organic group of divalent obtained from 2 amino of removal in the formula (1) recorded in page 8 of border Publication 2015/122413；State The structure for the formula (3) recorded in page 8 of border Publication 2015/060360；From Japanese Laid-Open Patent Publication 2012-173514's The organic group of divalent obtained from 2 amino of removal in the formula (1) recorded in page 8；From International Publication bulletin 2010-050523 Page 9 in formula (A)~(F) that records divalent obtained from 2 amino of removal organic group etc..

Preferred Y described below₂Structure, but the present invention is not limited to these.

Among the above, from the aspect of resistance to brushing further improved, particularly preferred (B-28), (B-29) etc., from The aspect of liquid crystal aligning further improved is set out, particularly preferred (B-1)~(B-3) etc., from the mitigation speed of stored charge The aspect of degree further improved is set out, particularly preferred (B-14)~(B-18), (B-27) etc., from voltage retention into one It sets out in terms of the raising of step, preferably (B-26) etc..

Aligning agent for liquid crystal of the invention includes the polyimide precursor of the structural unit with formula (6) and has formula (7) In the case where the polyimide precursor of structural unit, total of the structural unit of formula (6) relative to formula (6) and formula (7), preferably 10 Mole % or more, more preferable 20 moles of % or more, particularly preferred 30 moles of % or more.

The molecular weight of the polyimide precursor of above-mentioned formula (6) and formula (7) with Weight-average molecular meter, preferably 2000~ 500000, more preferable 5000~300000, further preferred 10000~100000.

As the polyimides of the group with divalent shown in formula (1) on main chain, can enumerate makes aforementioned polyimides Polyimides obtained from precursor closed loop.In the polyimides, the closed loop rate (also referred to as acid imide rate) of amide acidic group may not Be necessary for 100%, can depending on the application, purpose and arbitrarily adjust.

As the method for making polyimide precursor imidizate, can enumerate：Add the solution of polyimide precursor directly The hot-imide of heat；Or, adding the catalysis imidizate of catalyst in the solution of polyimide precursor.

< aligning agent for liquid crystal >

It is (specific poly- that aligning agent for liquid crystal of the invention contains the polymer obtained as the diamines with structure shown in formula (1) Close object), the particular polymers of different structure of more than two kinds can be contained.It, can also be in addition, on the basis of particular polymers The polymer of group containing other polymers, i.e. without divalent shown in formula (1).As other polymers, can enumerate Polyamic acid, polyimides, poly amic acid ester, polyester, polyamide, polyureas, polysiloxane, cellulose derivative, bunching Aldehyde, polystyrene or derivatives thereof, poly- (styrene-phenyl maleimide) derivative, poly- (methyl) acrylate etc..This hair In the case that bright aligning agent for liquid crystal contains other polymers, particular polymers are preferred relative to the ratio of whole component of polymer 5 mass % or more, for example, 5~95 mass %.

Aligning agent for liquid crystal generally takes the form of coating fluid from forming uniform film aspect.Liquid of the invention Brilliant alignment agent is preferably also the coating fluid containing aforementioned polymer ingredient and the organic solvent for dissolving the component of polymer.At this point, The concentration of polymer in aligning agent for liquid crystal can think that the thickness of film to be formed is suitable for change by setting.From wishing shape It sets out in terms of at uniform and flawless film, preferably 1 mass % or more, from the storage stability aspect of solution, It is preferably set to 10 mass % or less.The concentration of particularly preferred polymer is 2~8 mass %.

The organic solvent contained in aligning agent for liquid crystal is as long as the solvent to dissolve component of polymer equably without spy It does not limit.If enumerating its concrete example, n,N-Dimethylformamide, n,N-dimethylacetamide, N- methyl -2- can be enumerated Pyrrolidones, N- ethyl-2-pyrrolidone, dimethyl sulfoxide, gamma-butyrolacton, 1,3- dimethyl-2-imidazolidinone, methyl ethyl ketone, ring Hexanone, cyclopentanone etc..Wherein, it is preferable to use n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone or gamma-butyrolacton.

In addition, the organic solvent contained in aligning agent for liquid crystal of the invention, on the basis of above-mentioned solvent, can combine makes The solvent of the surface smoothness of coating, film when with raising coating of liquid crystalline alignment agent.It is following to enumerate above-mentioned organic solvent Concrete example, but not limited thereto.

For example, ethyl alcohol, isopropanol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1- amylalcohol, 2- amylalcohol, 3- 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, butyl oxide, two hexyl ethers, dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, second Dibutyl ether, 1,2- butoxy ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4- hydroxy-4-methyl-2-pentanone, Diethylene glycol Methyl ether, dibutyl ethylene glycol ether, 2 pentanone, propione, methyl-n-butyl ketone, 2-HEPTANONE, 4- heptanone, 3- ethyoxyl fourth Yl acetate, 1- methyl amyl acetic acid esters, 2- ethyl-butyl acetic acid esters, 2- ethylhexyl acetate, ethylene glycol acetate, second Glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethyl alcohol, ethylene glycol monobutyl ether, ethylene glycol list Isoamyl ether, ethylene glycol monohexylether, 2- (hexyloxy) ethyl alcohol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- (fourth oxygen Base oxethyl) propyl alcohol, propylene glycol methyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropyl Glycol dimethyl ether, Tripropylene glycol monomethyl Ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol monobutyl ether Acetic acid esters, ethylene glycol acetate, ethylene acetate, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether acetic acid Ester, 2- (2- ethoxy ethoxy) ethylhexoate, diethylene glycol acetic acid esters, triethylene glycol, triethylene glycol monomethyl ether, three second two Alcohol list ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycolmethyletheracetate list ether, acetone Sour methyl esters, ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-propionic acid Methylethyl, 3- methoxypropionate, 3- second Oxygroup propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, methyl lactate, ethyl lactate, cream Sour n-propyl, n-butyl lactate, isoamyl lactate, solvent shown in following formula [D-1]~[D-3] 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, it is preferable to use 1- hexanol, cyclohexanol, 1,2- ethylene glycol, 1,2-PD, propylene glycol monobutyl ether, diethyl two Diethylene glycol diethyl ether, 4- hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether or dimethyl ether.The type of such solvent and Content is suitable for selection according to apparatus for coating, application conditions, coating environment of aligning agent for liquid crystal etc..

Aligning agent for liquid crystal of the invention can be added containing the ingredient in addition to component of polymer and organic solvent.As this The addition ingredient of sample can enumerate adaptation for improving liquid crystal orientation film and substrate, liquid crystal orientation film and sealing material The closely sealed auxiliary agent of adaptation, the crosslinking agent for improving liquid crystal aligning film strength, the dielectric for adjusting liquid crystal orientation film are normal Number, the dielectric of resistance, conductive materials etc..The concrete example that ingredients are added as these can enumerate International Publication bulletin the Substance disclosed in No. 015/060357 paragraphs of page 53 paragraph 0116 of page 0105~55.

< liquid crystal orientation film >

Liquid crystal orientation film of the invention is obtained by foregoing liquid crystal alignment agent.If enumerating to obtain the side of liquid crystal orientation film An example of method can then enumerate following method：The aligning agent for liquid crystal of coating fluid form is coated on substrate and drying, is burnt At for gained film brushing facture or light orientation position logos implementation orientation process.

As the substrate of coating of liquid crystalline alignment agent, it is not particularly limited as long as the high substrate of the transparency, with glass base Plate, silicon nitride board could be used with plastic bases such as acrylic substrate, polycarbonate substrate etc..At this point, if using It is formed with the substrate of ITO electrode for making liquid crystal drive etc., then conforms to the principle of simplicity to set out in terms of chemical industry skill preferably.In addition, for anti- The liquid crystal of emitting indicates element, if being only unilateral substrate, the opaque substance such as silicon wafer, electrode at this time can be used The material of the meeting reflected light such as aluminium can be used.

The coating method of aligning agent for liquid crystal is not particularly limited, and industrially generally silk-screen printing, hectographic printing, soft version print Brush, ink-jet method etc..As other coating methods, there are infusion process, rolling method, slot coated method, spin-coating method, spray coating method etc., it can To use them according to purpose.

After aligning agent for liquid crystal is coated on substrate, it can use hot plate, thermal cycle type baking oven or IR (infrared ray) type and dry The heating meanss such as case make solvent evaporate and be burnt into.Drying, firing process after being coated with aligning agent for liquid crystal of the invention can choose Arbitrary temperature and time.Generally for the contained solvent of abundant removal, can enumerate：1~10 is burnt at 50~120 DEG C Minute, later, 5~120 minutes conditions are burnt at 150~300 DEG C.

When the thickness of liquid crystal orientation film after firing is excessively thin, liquid crystal indicates that the reliability of element reduces sometimes, it is therefore preferable that 5~300nm, more preferable 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 member Part indicates that the liquid crystal orientation film of element is useful especially as the liquid crystal of FFS mode.

< liquid crystal indicates element >

Liquid crystal of the invention indicates that element can be by obtaining the subsidiary liquid crystal orientation film obtained by above-mentioned aligning agent for liquid crystal After substrate, benefit makes liquid crystal cells by known method, and is obtained using the liquid crystal cells.

As an example of liquid crystal cells production method, it is illustrated so that the liquid crystal of passive-matrix structure indicates element as an example. It should be explained that, or each pixel portion for constituting image expression is provided with TFT (ThinFilm Transistor, film Transistor) etc. the active matrix structure of conversion elements element.

Specifically, preparing transparent glass substrate of electrode, common electrode is set on one substrate, on another substrate It is arranged segment electrode (segment electrode).ITO electrode can be for example made in these electrodes, and being patterned to can be real Existing desired image indicates.Then, insulating film is set on each substrate to cover common electrode and segment electrode.Insulating film such as may be used Be made by sol-gel method formed by SiO₂-TiO₂The film of composition.Then, under the foregoing conditions, formed on each substrate Liquid crystal orientation film.

Then, the specified position configuration on a substrate in 2 substrates for being formed with liquid crystal orientation film is for example ultraviolet The sealing material of line curability, in turn, in liquid crystal alignment film surface after defined multiple position configuration liquid crystal, with liquid crystal orientation film Opposite mode, makes another substrate sticking and crimps, thus after liquid crystal is sprawled before liquid crystal orientation film, to the whole of substrate Ultraviolet light is irradiated in face, sealing material is solidified, to obtain liquid crystal cells.

Alternatively, after forming liquid crystal orientation film on substrate, when specified position on one substrate configures sealing material, if Setting can be from the opening portion of external filling liquid crystal, after making substrate sticking, by being set to the opening portion of sealing material to liquid crystal cells The opening portion is then sealed with bonding agent, obtains liquid crystal cells by interior injection liquid crystal material.The injection of liquid crystal material can be Vacuum impregnation, or utilize the method for capillarity in an atmosphere.

In any of the above-described method, in order to ensure the space of filling liquid crystal material in liquid crystal cells, it is preferably to using at one Columnar protrusion is set on substrate, or spreads spacer on one substrate, or is mixed into spacer in sealing material, or by it The schemes such as combine.

As above-mentioned liquid crystal material, nematic crystal and smectic crystal can be enumerated, wherein preferred nematic crystal, Any one of positive type liquid crystal material, negative type liquid crystal material can be used.Then, the setting of polarizing film is carried out.Specifically, it is preferable that A pair of of polarizing film is pasted on the face with liquid crystal layer opposite side of 2 substrates.

It should be noted that liquid crystal orientation film of the invention and liquid crystal indicate that as long as element uses liquid crystal aligning of the invention Agent is just not limited to above-mentioned record, can be the substance made of other well known gimmicks.Liquid crystal watch is obtained by aligning agent for liquid crystal Show the process until element e.g., as disclosed in Japanese Unexamined Patent Publication 2015-135393 paragraph page 0074~19 of paragraph of page 17 0081 etc..

Embodiment

Embodiment etc. is enumerated to the present invention below to be specifically described.It should be noted that the present invention is not limited to these Embodiment.The abbreviation of compound used in below and the method for evaluating characteristics are as described below.

In above-mentioned formula, Boc is group shown in following formula.

< organic solvent >

NMP：N-methyl-2-pyrrolidone, GBL：Gamma-butyrolacton,

BCS：Butyl cellosolve

< additive >

LS-4668：3- epoxy propoxy propyl triethoxysilane

< crosslinking agent >

(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)

The molecular weight determination > of < polyimide precursor and polyimides

Utilize room temperature gel permeation chromatography (GPC) device (GPC-101) (Showa Denko K. K's system) and column (KD- 803, KD-805) (Shodex corporation), such as following measurement.

Column temperature：50℃

Eluent：N, (as additive, lithium bromide monohydrate (LiBrH2O) is N '-dimethyl formamide 30mmol/L (liter), phosphoric acid anhydrous crystal (orthophosphoric acid) are 30mmol/L, tetrahydrofuran (THF) is 10ml/L)

Flow velocity：1.0ml/ minute

Standard curve making standard sample：TSK standard polyethylene oxide (molecular weight；About 900000,150000, 100000 and 30000, TOSOH Co., Ltd's system) and polyethylene glycol (molecular weight；About 12000,4000 and 1000, Polymer Laboratories Ltd. system).

< viscosimetric analysis >

The viscosity of polyamic acid solution uses E type viscosimeter TVE-22H (Toki Sangyo Co., Ltd.'s system), at 25 DEG C of temperature Under, be measured at sample size 1.1mL, cone rotor TE-1 (1 ° 34 ', R24)

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.Later, 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 used It is dry after (200g), pure water (300g) and methanol (200g) cleaning, obtain coarse crystal.Make gained coarse crystal complete at 60 DEG C It after being dissolved in tetrahydrofuran (1340g), is added ethyl alcohol (1340g), stirs 1 hour at 5 DEG C.The crystal of precipitation is subtracted Press filtration, it is dry after being cleaned with ethyl alcohol (200g), obtain the powder crystal (receipts amount 63g, yield 45%) of compound (1).

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), is warming up to 120 DEG C, stirs 3 hours under reflux.Terminated with HPLC (high performance liquid chromatography) confirmation reaction Afterwards, reaction solution is added in cold water (4000g), stirs 1 hour.The crystal of precipitation is filtered under diminished pressure, with acetonitrile (100g) It is dry after carrying out repulped cleaning, obtain the powder crystal (receipts amount 53g, yield 78%) of compound (2).

1H-NMR(DMSO-d₆)：11.8 (1H, br), 8.30-8.26 (4H, m), 8.11-8.07 (4H, m), 7.04 (2H, s)

By the powder crystal (22g, 72.4mmol) of compound (2), 5 mass % palladium carbons (Pd/C) (50% is water type), spy Property egression active carbon (2.0g) and dioxane (220g) mixture under hydrogen pressurized conditions, at 80 DEG C stirring it is 8 small When.After reaction, it by after catalyst filtration, is concentrated, is added 2- propyl alcohol (300g), stirred 1 hour at 5 DEG C.It will analysis Crystal out is filtered under diminished pressure, dry after being cleaned with methanol (50g), obtains powder crystal (receipts amount 13g, the yield of DA-1 69%).

1H-NMR(DMSO-d₆)：10.6 (1H, s), 7.39-7.35 (4H, m), 6.57-6.53 (4H, m), 6.19 (2H, S), 5.01 (4H, s)

[synthesis example 1]

DA-1 (2.49g, 10.0mmol) is added in the four-hole boiling flask of the 100ml with agitating device and with nitrogen ingress pipe Afterwards, NMP29.0g is added, is stirred and makes it dissolve when being sent into nitrogen.While the solution is stirred, side addition CA-2 (0.98g, 5.0mmol) and after NMP 3.6g (additional quantity 1 in table 1), stirred 1 hour under the conditions of 25 DEG C.Later, CA-1 is added (0.87g, 4.0mmol) after NMP3.6g (additional quantity 2 in table 1) is added, and then is stirred 12 hours under the conditions of 50 DEG C, thus Obtain the polyamic acid solution (PAA-A1) of 12 mass % of resin solid content concentration.The viscosity of the polyamic acid solution is 300mPa·s。

[synthesis example 2~16]

Using shown in table 1, tetracarboxylic dianhydride's ingredient, diamine component and NMP amount, respectively become and react temperature shown in table 1 Degree, in addition to this, implements in the same manner as synthesis example 1, to obtain the polyamides with solid component concentration shown in table 1 and viscosity Amino acid solution (PAA-A2)~(PAA-A9) and polyamic acid solution (PAA-B1)~((PAA-B7).

[table 1]

[synthesis example 17]

In the four-hole boiling flask of the 200ml with agitating device and with nitrogen ingress pipe be added DA-6 (4.03g, 16.5mmol), after DA-7 (3.59g, 9.0mmol) and DA-8 (2.50g, 4.5mmol), NMP 102.1g is added, nitrogen is sent on side Gas side, which is stirred, to be made it dissolve.CA-4 (4.37g, 19.5mmol) and NMP 12.8g is added when stirring the solution, at 40 DEG C Under the conditions of stir 3 hours.Later, it after CA-2 (1.71g, 8.7mmol) and NMP 12.8g being added under the conditions of 25 DEG C, and then stirs It mixes 12 hours, to obtain the polyamic acid solution of 15 mass % of resin solid content concentration.The viscosity of the polyamic acid solution For 820mPas.

Polyamic acid solution 80.0g is separated and recovered, after NMP 70.0g is added, acetic anhydride 6.8g and pyridine 1.8g is added, It is reacted 3 hours at 50 DEG C.The reaction solution is injected in methanol 555.0g, and the sediment of generation is filtered out.By the sediment It is cleaned with methanol, is dried under reduced pressure to obtain the powder of polyimides at 60 DEG C.The acid imide rate of the polyimides is 75%.NMP586.7g is added in gained polyimide powder 80.0g, stirs 20 hours and makes it dissolve at 50 DEG C, thus To polyimide solution (SPI-B8).

[synthesis example 18]

In the four-hole boiling flask of the 100ml with agitating device and with nitrogen ingress pipe be added DA-6 (2.20g, 9.0mmol), After DA-13 (1.62g, 15.0mmol) and DA-14 (2.45g, 6.0mmol), NMP 81.8g is added, is carried out when being sent into nitrogen It stirs to dissolve.It is added when stirring the solution CA-4 (6.52g, 29.10mmol), after NMP 9.1g is added, in 40 DEG C of items It is stirred 24 hours under part, to obtain the polyamic acid solution (PAA-B9) of 12 mass % of resin solid content concentration.The polyamides The viscosity of amino acid solution is 386mPas.

[synthesis example 19]

In the four-hole boiling flask of the 200ml with agitating device and with nitrogen ingress pipe be added DA-1 (2.62g, 10.5mmol), after DA-2 (1.39g, 7.0mmol) and DA-3 (3.49g, 17.5mmol), NMP70.0g is added, nitrogen is sent on side It is made it dissolve while being stirred.While the solution is stirred, after CA-2 (1.70g, 8.7mmol) and NMP 9.5g is added in side, 25 It is stirred 1 hour under the conditions of DEG C.Later, CA-3 (6.57g, 26.3mmol) is added, after NMP 9.5g is added, and then in 50 DEG C of conditions Lower stirring 12 hours, to obtain the polyamic acid solution (PAA-A10) of 12 mass % of resin solid content concentration.The polyamide The viscosity of acid solution is 375mPas.

[synthesis example 20]

In the four-hole boiling flask of the 100ml with agitating device and with nitrogen ingress pipe be added DA-1 (1.12g, 4.5mmol), After DA-2 (0.59g, 3.0mmol) and DA-3 (1.49g, 7.5mmol), NMP is added：GBL=1：1 mixed solvent 31.0g, while sending Enter nitrogen side and be stirred to make it dissolve.While the solution is stirred, CA-2 (1.15g, 5.9mmol) and NMP is added in side：GBL= 1：After 1 mixed solvent 10.0g, stirred 1 hour under the conditions of 25 DEG C.Later, CA-5 (2.60g, 8.8mmol) is added, is added NMP：GBL=1：It after 1 mixed solvent 10.0g, and then is stirred 12 hours under the conditions of 50 DEG C, so that it is dense to obtain resin solid content Spend the polyamic acid solution (PAA-A12) of 12 mass %.The viscosity of the polyamic acid solution is 200mPas.

[Examples 1 to 2 2] and [comparative example 1~6]

By polyimide solution obtained in polyamic acid solution obtained in synthesis example 1~16,18 and synthesis example 17 with As shown in following table 2-1 and table 2-2, the mode of the ratio of polymer 1 and polymer 2 carry out being obtained by mixing solution, For acquired solution, NMP, GBL is added while stirring in the way of becoming and form shown in table 2-1 and table 2-2, BCS, includes The nmp solution of 1 weight % of LS-4668 and nmp solution comprising 3 weight % of AD-1, and then be stirred at room temperature 2 hours, from And obtain the aligning agent for liquid crystal of Examples 1 to 22 and comparative example 1~6.

[table 2-1]

[table 2-2]

< indicates the production > of element based on the liquid crystal of brushing method

Prepare having a size of 30mm × 35mm and with a thickness of the electroded glass substrate of 0.7mm.On substrate, as the 1st Layer, forms for structure paired electrode and has the IZO electrode of solid shape pattern.At the 1st layer on electrode, as the 2nd layer, 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 layer insulation Film and function.On the 2nd layer of SiN film, as the 3rd layer, the comb teeth-shaped pixel electricity for forming IZO film figure is configured Pole, to form the 1st pixel and the 2nd pixel the two pixels.The size of each pixel is：Vertical 10mm and horizontal about 5mm.At this point, 1st layer with the 3rd layer of pixel electrode because of the effect of the 2nd layer of SiN film is in be electrically insulated to electrode.

The pixel electrode of 3rd floor have Japanese Unexamined Patent Publication 2014-77845 bulletin in record it is shown in Fig. 3, arrangement it is multiple " < " shape electrode element that center portion bends and the comb teeth-shaped shape constituted.The width of the width direction of each electrode element 3 μm, between electrode element between be divided into 6 μm.Form what the pixel electrode of each pixel was bent by arranging multiple center portions " < " shape electrode element and constitute, therefore the shape of each pixel not instead of oblong-shaped, have in the same manner as electrode element Shape that center portion bends, " < " similar to runic.Also, each pixel is using the bending part in the center as boundary's quilt Segmentation up and down, the 2nd region with the 1st region and downside on the upside of bending part.

When comparing the 1st region and 2 region of each pixel, the formation direction of the electrode element of their pixel electrode is constituted It is different.That is, using the brushing direction of aftermentioned liquid crystal orientation film as when benchmark, in the 1st region of pixel ,+10 ° of angle is presented The mode of degree (clockwise) forms the electrode element of pixel electrode, (suitable with the angle for being presented -10 ° in the 2nd region of pixel Hour hands) mode form the electrode element of pixel electrode.In addition, the 1st region of each pixel is constituted as follows with the 2nd region：Pass through In pixel electrode and to applying voltage between electrode and the liquid crystal that induces, spinning movement (plane conversion) in real estate side To opposite direction each other.

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 opposite substrate and has height for the glass substrate of 4 μm of column spacer.Then exist Drying after five minutes, is burnt into 20 minutes with 230 DEG C, the polyimides of film thickness 60nm is obtained on each substrate in 80 DEG C of heating plate Film.On the polyimides film surface, in roller diameter 120mm, roller revolving speed 500rpm, platform movement speed 30mm/ seconds, the indentation of brushing cloth Under conditions of pressure 0.3mm, after implementing brushing processing using rayon cloth, 1 minute ultrasonic irradiation is carried out, in pure water with 80 DEG C dry 10 minutes.

Using above-mentioned 2 with liquid crystal orientation film kind substrate, antiparallel mode is become with respective brushing direction and is combined, it is residual Liquid crystal injecting port is stayed, surrounding is sealed, 3.8 μm of dummy cell is divided between production unit.The vacuum in the dummy cell at normal temperature After injecting liquid crystal (MERCK CORPORATION system, MLC-3019), inlet is sealed, the liquid crystal list of antiparallel orientations is formed Member.Gained liquid crystal cells, which constitute FFS mode liquid crystal, indicates element.Later, liquid crystal cells are heated 1 hour with 120 DEG C, places one Following each evaluations are used for after Dinner.

The evaluation > of < ghost cancellation time

The evaluation of ghost is carried out using following optics system etc..That is, being set to the liquid crystal cells made with polarizing axis Between 2 polarizing films configured as orthogonal mode, LED backlight is lighted in the state of without voltage is applied, with transmitted light Brightness becomes least way, adjusts the arrangement angles of liquid crystal cells.Then, while the liquid crystal cells are applied with the friendship of frequency 30Hz Galvanic electricity flanging measures V-T curve (voltage-transmission rate curve), calculates relative transmittance as 23% alternating voltage as driving Voltage.

In ghost evaluation, side applies relative transmittance and drives liquid crystal cells as the alternating voltage of 23% frequency 30Hz, Side applies the DC voltage of 1V simultaneously, drives 30 minutes.Later, make to apply DC voltage value 0V, only stop applying direct current Pressure further drives 15 minutes in this state.

In ghost evaluation, from passing through 30 minutes at the time of starting to apply DC voltage, relative transmittance is reduced to 30% Time below quantizes.Relative transmittance within 5 minutes is reduced in 30% situation below and is defined as "○", such as Fruit is then to be defined as " △ " within 6~30 minutes to be evaluated.Relative transmittance needs 30 minutes until being reduced to 30% or less In the case where above, it is denoted as that ghost can not be eliminated, is defined as "×" and is evaluated.Moreover, ghost evaluation according to the method described above It is carried out under the conditions of the temperature for the state that the temperature of liquid crystal cells is 23 DEG C.

< just drive after flicker level evaluation >

The liquid crystal cells made are set to be become between 2 polarizing films that orthogonal mode configures with polarizing axis, Without LED backlight is lighted in the state of application voltage, least way is become with the brightness of transmitted light, adjusts matching for liquid crystal cells Angle setting degree.Then, while the liquid crystal cells are applied with the alternating voltage of frequency 30Hz, side measures V-T curve, and (voltage-transmission rate is bent Line), relative transmittance is calculated as 23% alternating voltage 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 is lighted with backlight and starts simultaneously to apply the alternating voltage that relative transmittance becomes 23% frequency 30Hz, makes liquid Brilliant unit drives 60 minutes, tracking flashing amplitude.For flashing amplitude, connected with by photodiode and I-V conversion amplifier The data collection connect/data logger converting unit 34970A (Agilent technologies corporation), which is read, passes through 2 The transmitted light of the LED backlight of polarizing film and the liquid crystal cells between it.Flicker level is calculated with mathematical expression below.

Flicker level (%)={ flashing amplitude/(2 × z) } × 100

In above-mentioned formula, z is to read relative transmittance with data collection/data logger converting unit 34970A to become 23% Frequency 30Hz alternating voltage under drive when brightness value.

For flicker level, since LED backlight light and alternating voltage application at the time of by 60 minutes Until, the case where flicker level is maintained at less than 3%, is evaluated as "○".The situation that flicker level reaches 3% or more in 60 minutes is commented Valence is "×".

Moreover, the temperature strip for the state that the evaluation of flicker level according to the method described above is 23 DEG C in the temperature of liquid crystal cells It is carried out under part.

< evaluation result >

It, will be upper for using the liquid crystal of each aligning agent for liquid crystal of above-described embodiment 1~22 and the Comparative Examples 1 to 5 to indicate element The result of the evaluation of flicker level after stating the evaluation of the ghost cancellation time of implementation and just driving is shown in table 3.

[table 3]

< 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 opposite substrate and has height for the glass substrate of 4 μm of column spacer.At 80 DEG C Heating plate on it is dry be burnt into 30 minutes with 230 DEG C after five minutes, form the film of film thickness 100nm, gathered on each substrate Acid imide film.Extinction ratio 26 is irradiated by polarizing film to the coated surface：The ultraviolet light of the wavelength 254nm of 1 linear polarization 300mJ/cm².The substrate is heated 30 minutes on 230 DEG C of hot plate, obtains the substrate with liquid crystal orientation film.By above-mentioned 2 Substrate is as one group, the printing and sealing agent on substrate, make another 1 substrate with liquid crystal alignment film surface face-to-face and differently- oriented directivity become After 0 ° of mode bonds, make sealant cures, makes dummy cell.By injecting negative type liquid crystal in decompression injection normal direction dummy cell MLC-7026-100 (MERCK CORPORATION system), inlet is sealed, obtain FFS driving liquid crystal cells.Later, will Gained liquid crystal cells are heated 1 hour with 110 DEG C, are used for following each evaluations 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.

It should be noted that in ghost evaluation, the case where indicating element from the liquid crystal based on brushing method, is different, from starting to apply By 30 minutes at the time of adding DC voltage, it is reduced to for 23% time quantize relative transmittance.Within 5 minutes Relative transmittance is defined as "○", if it is being then defined as " △ " within 6~30 minutes in the case where being reduced to 23%.Relatively thoroughly The rate of penetrating needs 30 minutes or more until being reduced to 23% in the case that, it is denoted as that ghost can not be eliminated, is defined as "×".

< 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 19 and comparative example 6 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 4.

[table 4]

If above-mentioned table 3 and table 4 can be determined that, member is indicated by using the liquid crystal of the aligning agent for liquid crystal of the embodiment of the present invention Part, the mitigation of stored charge it is fast and be not easy to cause just start driving after caused flashing be displaced.

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 novel polymer 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 No. 2016-010996 and 2016 6 filed on January 22nd, 2016 The full content of Japanese patent application 2016-110237 specification, claims and abstract is introduced to filed in the moon 1 This, is introduced into as specification disclosure of the invention.

Claims

1. a kind of aligning agent for liquid crystal, which is characterized in that contain：It is obtained as the diamines with structure shown in following formula (1) poly- Close object；With, organic solvent,

R₁Indicate that the organic group of hydrogen, fluorine atom, cyano, hydroxyl or monovalence, * indicate the position for being bonded to other groups, phenyl ring Organic group of any hydrogen atom optionally by monovalence replaced.

2. aligning agent for liquid crystal according to claim 1, wherein the polymer is selected from by as with the formula (1) Shown in structure diamines and tetracarboxylic dianhydride condensation polymer polyimide precursor and acyl as the polyimide precursor it is sub- At least one kind of polymer in the group of the polyimides composition of aminate.

3. aligning agent for liquid crystal according to claim 1 or 2, wherein diamines formula below (2) expression,

R₁Definition and the formula (1) equally, 2 R₂The structure of singly-bound or following formula (3) is each independently represented, n indicates 1~3 Integer, any hydrogen atom of phenyl ring optionally replaced the organic group of 1 valence,

R₃It indicates singly-bound, be selected from-O- ,-COO- ,-OCO- ,-(CH₂)_l-、-O(CH₂)_mDivalent in O- ,-CONH- and-NHCO- Organic group, l, m indicate 1~5 integer, *₁Expression is bonded to the position of the phenyl ring in formula (2), *₂Expression is bonded to formula (2) In amino position.

4. aligning agent for liquid crystal described in any one of claim 1 to 3, wherein the polyimide precursor has following Structural unit shown in formula (6),

X₁For the organic group of 4 valences from tetracarboxylic acid derivatives, Y₁For the divalent of the diamines from the structure comprising the formula (1) Organic group, R₄For hydrogen atom or the alkyl of carbon number 1~5.

5. aligning agent for liquid crystal according to claim 4, wherein in the formula (6), X₁For selected from by following formulas (A-1)~ It is at least one kind of in the group of the structure composition of formula (A-21),

6. aligning agent for liquid crystal according to claim 4 or 5, wherein containing relative to the whole contained in aligning agent for liquid crystal The polymer with structural unit shown in the formula (6) that polymer is 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 by 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, for selected from as with the diamines of structure shown in following formula (1) and the contracting of tetracarboxylic dianhydride In the group of the polyimide precursor of polymers and the polyimides composition of the acid imide compound as the polyimide precursor at least 1 kind,

R₁It is defined in * such as claim 1.

12. polymer according to claim 11, wherein diamines formula below (2) expression,

R₁、R₂It is defined in n such as claim 3.

13. polymer according to claim 11 or 12, wherein polyimide precursor following formula (6) expression,

X₁、Y₁And R₄As defined in claim 4.

14. polymer according to claim 13, wherein in the formula (6), X₁For selected from the formula as described in claim 5 (A-1) at least one kind of in the group of the structure composition of~formula (A-21).