CN108929705A

CN108929705A - Aligning agent for liquid crystal, liquid crystal orientation film and its manufacturing method, liquid crystal cell, polymer and diamines

Info

Publication number: CN108929705A
Application number: CN201810519099.4A
Authority: CN
Inventors: 村上拓也
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2017-05-29
Filing date: 2018-05-25
Publication date: 2018-12-04
Anticipated expiration: 2038-05-25
Also published as: CN108929705B; JP2018200439A; JP6897324B2

Abstract

The photoreactivity or rub resistance height of a kind of film obtained are provided, and can get liquid crystal aligning, AC image retention characteristic and voltage retention performance through balancing aligning agent for liquid crystal, liquid crystal orientation film and its manufacturing method, liquid crystal cell, polymer and the diamines of the liquid crystal cell improved well.Containing with the polymer (P) for selecting at least one of group composed by part-structure represented by part-structure represented by free style (1) and formula (2) in aligning agent for liquid crystal.(in formula (1) and formula (2), X¹For quadrivalent organic radical, X²There is the divalent organic base of specific structure for urea groups or oxalyl amido etc.；R⁵And R⁶For hydrogen atom or any monovalent organic radical of carbon number 1~6)

Description

Aligning agent for liquid crystal, liquid crystal orientation film and its manufacturing method, liquid crystal cell, polymer with And diamines

Technical field

The present invention relates to a kind of aligning agent for liquid crystal, liquid crystal orientation film and its manufacturing method, liquid crystal cell, polymer and two Amine.

Background technique

Liquid crystal cell utilizes extensively in TV or mobile device, various monitors etc..In liquid crystal cell, using as shape Tropism control is carried out to the liquid crystal molecule in liquid crystal cells at the liquid crystal orientation film in the organic film on substrate.As being had Have the method for the organic film of liquid crystal aligning restraint, in the past it has been known that there is：The organic film for using polymer composition to be formed is carried out The method of friction has the method for the monomolecular film of chain alkyl to the method for silica progress oblique evaporation, formation, to photosensitive Property organic film carry out light irradiation method (optical alignment method) etc..

Usually using rubbing manipulation due to easy and liquid crystal molecule orientation is good.In addition, optical alignment method can inhibit on one side The generation of electrostatic or dust assigns uniform liquid crystal aligning to photosensitive organic film on one side, and can carry out liquid crystal aligning Therefore the accurate control in direction has carried out various researchs in recent years (for example, referring to patent document 1).

In recent years, liquid crystal cell is in the LCD TV of arrogant picture to smart phone or tablet personal computer (tablet Personal computer) etc. the device (device) of the broad range of small-sized display device or with applying on the way, as liquid Crystal cell, it is desirable that further high performance.Based on such background, the display quality of liquid crystal cell it is further improvement compared with Before for it is more important, in order to realize it is described improvement and propose have various aligning agent for liquid crystal (for example, referring to 2~patent of patent document Document 4).

Disclosing in patent document 2, patent document 3 has a kind of aligning agent for liquid crystal, film surface when obtaining friction treatment It for the purpose of the liquid crystal orientation film of cutting or the generation few (rub resistance is excellent) scratched, and include use by (sulphur) urea bond, interval The diamines for the specific structure that object portion, concatenating group and 2 aminophenyl structures are constituted and the polyimide precursor or polyamides that obtain are sub- Amine.Disclosing in patent document 4 has：In order to improve aligning agent for liquid crystal storage stability and component of polymer albefaction and acquisition Even if initial characteristic is good and is exposed to the liquid crystal display element that voltage retention is also difficult to decrease after light irradiates for a long time, and A variety of different types of specific polyimide precursors or polyimides are applied in combination.

[existing technical literature]

[patent document]

[patent document 1] International Publication No. 2012/176822

No. 5333454 bulletins of [patent document 2] Japanese Patent No.

No. 5713010 bulletins of [patent document 3] Japanese Patent No.

[patent document 4] International Publication No. 2015/046373

Summary of the invention

[problem to be solved by the invention]

The good existing aligning agent for liquid crystal of rub resistance is mostly following situation：It is easy to produce the application with alternating voltage Image retention (hereinafter also referred to as " exchange (alternating current, AC) image retention ") or voltage retention reduce, i.e., AC is residual As characteristic or voltage retention are to accept or reject (trade-off) relationship.The AC image retention is since the direction of initial orientation is because of liquid crystal The long-time of element drive and deviate from the direction of the manufacture of liquid crystal cell originally and the image retention that generates.In addition, being taken using light In the case where method, compared with rubbing manipulation, the orientation restraint of liquid crystal molecule is simultaneously insufficient, exists and is easy to produce inclining for AC image retention To.In order to meet the requirement of further high performance in recent years, as aligning agent for liquid crystal, it is desirable that following aligning agent for liquid crystal： Using rubbing manipulation, goodization of the rub resistance of film and the AC image retention characteristic in liquid crystal cell and voltage can be made to protect Goodization of holdup is simultaneously deposited, and using optical alignment method, the photoreactivity of film is good, and can be substantially reduced AC image retention, And it can realize goodization of voltage retention.

The present invention is formed in view of the situation, the first purpose be to provide a kind of film obtained photoreactivity or Rub resistance is high, and can get liquid crystal aligning, AC image retention characteristic and voltage retention performance through balancing the liquid crystal improved well The aligning agent for liquid crystal of element.

[technical means to solve problem]

The present invention uses the following method in order to solve the problem.

<1>A kind of aligning agent for liquid crystal, part-structure and following formula represented by containing with being selected from by following formula (1) (2) polymer (P) of at least one of group composed by the part-structure represented by；

[changing 1]

(in formula (1) and formula (2), X¹For quadrivalent organic radical, X²For divalent organic base represented by following formula (3)；R¹And R² It is separately hydrogen atom or any monovalent organic radical of carbon number 1~6)

[changing 2]

(in formula (3), A¹And A²It is separately divalent aromatic ring group；Wherein, A¹And A²At least one contain for divalent Azacyclyl；R³And R⁵It is separately the divalent aliphatic hydrocarbon of carbon number 1~10, R⁴For the bivalent aliphatic of carbon number 1~10 Alkyl has oxygen atom, sulphur atom, "-COO- ", "-OCO- ", "-Si between the carbon-carbon bond of the aliphatic alkyl (R²¹R²²)-" or "-Si (R²¹R²²)-O-Si(R²³R²⁴)-”(R²¹~R²⁴It is separately hydrogen atom or the fat of carbon number 1~6 Race's alkyl) bilvalent radical；Y¹And Y²It is separately singly-bound, oxygen atom, sulphur atom, "-COO- ", "-OCO- ", "-NR⁶-”、 “-NR⁶- CO- " or "-CO-NR⁶-”(R⁶It, can be with adjacent R for hydrogen atom or any monovalent organic radical³Or R⁵It is bonded and forms ring knot Structure)；Z¹And Z²It is separately any one of the represented base of following formula (4)~formula (6) difference；N is 0 or 1；" * " indicates knot Close key)

[changing 3]

(in formula (4), R⁷For hydrogen atom or any monovalent organic radical, B¹For "-NR¹⁴-”、“*¹-CO-NR¹⁴", oxygen atom, " *¹- CO-O-”、“-NR¹⁴-CO-NR¹⁴" or " *¹-NR¹⁴-CO-O-”(R¹⁴For hydrogen atom or any monovalent organic radical, " *¹" indicate and carbonyl Associative key)；In formula (5), R⁸And R⁹It is separately hydrogen atom or any monovalent organic radical；In formula (6), R¹⁰~R¹³Independently Ground is hydrogen atom or any monovalent organic radical；" * " indicates associative key).

<2>A kind of liquid crystal orientation film is using described<1>Aligning agent for liquid crystal and formed.

<3>A kind of manufacturing method of liquid crystal orientation film comprising described in use<1>Aligning agent for liquid crystal form film and right The film implements photo-irradiation treatment and assigns the light orientation process of liquid crystal aligning ability.

<4>A kind of liquid crystal cell comprising described<2>Liquid crystal orientation film.

<5>A kind of polymer has represented by the part-structure being selected from by represented by the formula (1) and the formula (2) Part-structure composed by least one of group.

<6>A kind of diamines is indicated by following formula (12)；

[changing 4]

(in formula (12), A¹、A²、R³~R⁵、Y¹、Y²、Z¹、Z²And n respectively with the A in the formula (3)¹、A²、R³~R⁵、Y¹、 Y²、Z¹、Z²And n is identical meanings).

[The effect of invention]

According to the aligning agent for liquid crystal, photoreactivity or the good film of rub resistance can get.In addition, can get liquid crystal Orientation, AC image retention characteristic and voltage retention performance are through balancing the liquid crystal cell improved well.

Specific embodiment

Hereinafter, to the ingredient deployed in the aligning agent for liquid crystal of this announcement and the other compositions optionally and arbitrarily deployed It is illustrated.

《Polymer (P)》

The aligning agent for liquid crystal of this announcement contains the part-structure and the formula (2) having represented by being selected from by the formula (1) The polymer (P) of at least one of group composed by represented part-structure.In the formula (1) and formula (2), X¹For source From the quadrivalent organic radical of tetracarboxylic acid derivatives.Furthermore in this specification, " tetracarboxylic acid derivatives " are to include tetracarboxylic dianhydride, four The meaning of carboxylic acid diesters and tetracarboxylic acid acid diesters dihalide.

In the case where obtaining liquid crystal orientation film using light orientation processing, X¹Preferably with the tetravalence of cyclobutane ring structure Organic group.The cyclobutane ring structure preferably has at least one substituent group in the loop section of cyclobutane ring.As ring fourth Substituent group possessed by alkane ring, such as can enumerate：Halogen atom, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl etc..Replace The quantity of base is not particularly limited, and preferably 1~4.

In X¹In the case where for the quadrivalent organic radical with cyclobutane ring structure, preferably represented by following formula (11) Base.

[changing 5]

(in formula (11), R³¹~R³³It is separately hydrogen atom, halogen atom, the alkyl of carbon number 1~6, carbon number 1~6 Halogenated alkyl, the alkoxy of carbon number 1~6, the alkylthio of carbon number 1~6, the alkenyl of carbon number 2~6, carbon number 2~6 alkynyl, Or "-COR³⁰”(R³⁰For the alkyl of carbon number 1~6, containing fluoroalkyl, alkoxy or fluoroalkoxy)；R³⁴For halogen atom, carbon number 1 ~6 alkyl, the halogenated alkyl of carbon number 1~6, the alkoxy of carbon number 1~6, the alkylthio of carbon number 1~6, carbon number 2~6 alkene The alkynyl or "-COR of base, carbon number 2~6³⁰"；Wherein, R³¹~R³⁴In the base of adjoining can be bonded each other and form ring structure； " * " indicates associative key)

In the formula (1) and formula (2), X²For divalent organic base represented by the formula (3).In the formula (3), A¹And A² It is separately divalent aromatic ring group.Herein, so-called " fragrant ring group " in this specification, to be substituted or being unsubstituted certainly The loop section of aromatic rings remove base made of 2 hydrogen atoms.As the aromatic rings, such as can enumerate：Phenyl ring, naphthalene nucleus, anthracene The aromatic series hydrocarbon ring such as ring；The nitrogenous heteroaromatics such as pyridine ring, pyridine ring, pyrimidine ring, pyridazine ring；The sulfur-containing aromatics such as thiphene ring Heterocycle etc..In the case where aromatic rings has substituent group, as the substituent group, such as the alkyl etc. of carbon number 1~6 can be enumerated.

As A¹And A²Preferred concrete example, such as following formula (a-1)~formula (a-11) represented base respectively can be enumerated Deng.

[change 61

A¹And A²At least one be to remove 2 hydrogen from the loop section of nitrogenous heteroaromatic for being substituted or being unsubstituted Bilvalent radical made of atom (hereinafter referred to as " divalent nitrogen heterocycle ").Heterocycle possessed by divalent nitrogen heterocycle is preferably Selected from one of group as composed by pyridine ring, pyridine ring, pyrimidine ring and pyridazine ring.The light reaction of polymer just can be improved Property aspect and can get the generation of micro bright point caused by the decomposition product generated as the light irradiation due to when the light orientation processing more For the aspect of few liquid crystal cell, preferably A¹And A²The two is divalent nitrogen heterocycle.Wherein, A¹And A²It is possessed to contain Azacyclo- is preferably pyridine ring.

About R³And R⁵, the divalent aliphatic hydrocarbon of carbon number 1~10 includes chain alkyl and alicyclic type hydrocarbon.Herein, this theory Straight-chain and branch-like so-called " chain alkyl " in bright book, refer to and be only made of chain structure not comprising cyclic structure Alkyl.Wherein, it is also unsaturated that chain alkyl, which can be saturation,.So-called " alicyclic type hydrocarbon " refers to only comprising ester ring type hydrocarbon Structure as ring structure, and be free of aromatic ring structure alkyl.Wherein, alicyclic type hydrocarbon is not necessarily required only by ester ring type hydrocarbon Structure is constituted, also comprising having the alkyl of chain structure in part of it.The aspect of the reduction effect of AC image retention just can be improved and Speech, R³And R⁵Preferably chain alkyl, more preferably straight-chain alkyl.About carbon number, in the liquid crystal orientation film using optical alignment method Manufacture in, with regard to promote using heating strand reorientation aspect for, be preferably set as 2 or more, using rub In the manufacture of the liquid crystal orientation film of alignment method, for promoting the aspect of extension of the strand using friction treatment, preferably It is set as 2 or more.

About R⁴, the concrete example and preference of the divalent aliphatic hydrocarbon of carbon number 1~10 can apply the R³And R⁵Say It is bright.R⁴Can have oxygen atom, sulphur former between the carbon-carbon bond of the divalent aliphatic hydrocarbon (preferably chain alkyl) of carbon number 1~10 Son, "-COO- ", "-OCO- ", "-Si (R²¹R²²)-" or "-Si (R²¹R²²）-O-Si(R²³R²⁴)-”(R²¹~R²⁴Separately For hydrogen atom or the aliphatic alkyl of carbon number 1~6).

Y¹And Y²It is separately singly-bound, oxygen atom, sulphur atom, "-COO- ", "-OCO- ", "-NR⁶-”、“-NR⁶- CO- " or "-CO-NR⁶-”(R⁶It, can be with adjacent R for hydrogen atom or any monovalent organic radical³Or R⁵It is bonded and forms ring structure).As R⁶Any monovalent organic radical, such as can enumerate：Alkyl, protecting group of carbon number 1~6 etc..Protecting group is preferably to be detached from using heat Base, such as can enumerate：Carbamate system protecting group, amide system protecting group, imide series protecting group, sulphonyl amine system protecting group Deng.In these, just using the high aspect of detachment of heat or in terms of reducing remaining quantity of the part of deprotection in film and Speech, protecting group is preferably tert-butoxycarbonyl.

In R⁶With adjacent R³Or R⁵In the case where being bonded and forming ring structure, as the ring structure, such as piperazine can be enumerated Piperazine ring, piperidine ring etc..

It is achieved with for the aspect of the higher polymer of photoreactivity, Y¹And Y²Preferably oxygen atom, sulphur atom or "- NR⁶", more preferably at least one is "-NR⁶", and then preferably Y¹And Y²It is "-NR⁶-".Just further increase polymer (P) for the viewpoint of photoreactivity, "-NR⁶" in R⁶The preferably alkyl of carbon number 1~6, the more preferably alkane of carbon number 1~3 Base.

For improving the viewpoint of photoreactivity of film obtained, preferably Y¹And Y²For oxygen atom, sulphur atom or "- NR⁶", and Y¹And Y²Relative to A¹And A²Possessed nitrogen-containing heterocycle and be adjacent to nitrogen-atoms in the nitrogenous heterocyclic ring Carbon atom bond.In the particularly preferably described formula (3), A¹And A²Possessed nitrogen-containing heterocycle is pyridine ring, Y¹And Y²Pyridine Bond position on ring relative to pyridine ring nitrogen-atoms and be ortho position, and relative to X²The formula (1) and described of bond Nitrogen-atoms in formula (2) and be contraposition structure.Specifically, base represented by the formula (3) is preferably following formula (3A) institute The base of expression.

[changing 7]

(in formula (3A), R³~R⁵、Y¹、Y²、Z¹、Z²And n is respectively identical meanings with the formula (3)；" * " indicates associative key)

Z¹And Z²It is appointing for the represented base of the formula (4)~formula (6) difference for the divalent functional group with hydrogen bond knot One.In the formula (4)~formula (6), the aspect and available voltage for just obtaining the more good liquid crystal orientation film of rub resistance are protected For the aspect of the higher liquid crystal cell of holdup, B¹Preferably "-NR¹³" or " *¹-CO-NR¹³-”。R⁷~R¹³Any monovalent organic radical Concrete example and preference can apply the R⁶Explanation.

As Z¹And Z²Preferred concrete example, following formula (z-1)~formula (z-10) represented base etc. respectively can be enumerated.

[changing 8]

(in formula, " * " indicates associative key)

The rub resistance of film obtained and the liquid crystal aligning of liquid crystal cell and electrical characteristics can be made more good For aspect, Z¹And Z²Base represented by the preferably described formula (4).Specifically, the particularly preferably described formula (z-1) or formula (z- 2) structure represented by.

N is 0 or 1, preferably 0.

Polymer (P) is at least one in the group as composed by polyamic acid, poly amic acid ester and polyimides Kind.Polymer (P) is with being originated from the part-structure of tetracarboxylic acid derivatives, have with divalent represented by the formula (3) with being originated from The part-structure of the diamine compound (hereinafter also referred to as " specific diamines ") of machine base.The synthetic method of such polymer (P) has no It is particularly limited to, can be obtained and the well-established law proper combination by organic chemistry.

In the case where polymer (P) is polyamic acid, the polyamic acid (hereinafter also referred to as " polyamic acid (P) ") Such as it can be by obtaining tetracarboxylic dianhydride and reaction with the diamine compound comprising specific diamines.

(tetracarboxylic dianhydride)

Tetracarboxylic dianhydride used in the synthesis of polyamic acid (P) is not particularly limited, such as can enumerate：Aliphatic tetracarboxylic acid Acid dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride etc..As the concrete example of these tetracarboxylic dianhydrides, aliphatic Tetracarboxylic dianhydride can for example enumerate：Ethylenediamine tetra-acetic acid dianhydride etc.；

Ester ring type tetracarboxylic dianhydride can for example enumerate：1,2,3,4- cyclobutane tetracarboxylic dianhydride has the formula (11) institute Tetracarboxylic dianhydride's (hereinafter also referred to as " replacing cyclobutane tetracarboxylic dianhydride ") of the base of expression, 2,3,5- tricarboxylic cyclopentyl second Acid dianhydride, 5- (2,5- dioxotetrahydro furans -3- base) -3a, 4,5,9b- tetrahydro naphtho- [1,2-c] furans -1,3- diketone, 5- (2,5- dioxotetrahydro furans -3- base) -8- methyl -3a, 4,5,9b- tetrahydro naphtho- [1,2-c] furans -1,3- diketone, 5- (2, 5- dioxotetrahydro -3- furyl) -3- methyl -3- cyclohexene -1,2- dicarboxylic anhydride, 3,5,6- tri- carboxyl -2- carboxymethyl groups drop Bornylane -2: 3,5: 6- dianhydride, 2, bicyclic [3.3.0] octane -2 of 4,6,8- tetracarboxylics：4,6：8- dianhydride, cyclopentanetetracarboxylic two Acid anhydride, pentamethylene tetracarboxylic dianhydride etc.；

Aromatic tetracarboxylic dianhydride can for example be enumerated：Pyromellitic acid anhydride, 4,4 '-(hexafluoroisopropyli,ene) two adjacent benzene two Formic anhydride, TOPOT 2,2′ p phenylenebis (trimellitic acid monoesters acid anhydride), ethylene glycol bis- (trimellitic anhydride esters), 1,3-PD are bis- (partially Benzenetricarboxylic acid acid anhydride ester), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides etc., furthermore, it is possible to use Japanese Patent Laid-Open 2010- The tetracarboxylic dianhydride recorded in No. 97188 bulletins.

In the case where assigning liquid crystal aligning ability to film using optical alignment method, in the combination with specific diamines, so that it may For the aspect for further increasing the photoreactivity of film, at synthesizing polyamides sour (P), it is preferable to use substitution cyclobutane Tetracarboxylic dianhydride.As the concrete example of substitution cyclobutane tetracarboxylic dianhydride, such as following formula (TA-1-1)~formula (TA- can be enumerated 1-6) respective represented compound etc..

[changing 9]

In the case where at synthesizing polyamides sour (P) using cyclobutane tetracarboxylic dianhydride is replaced, use ratio is with regard to abundant For the viewpoint for improving the photoreactivity of film, relative to the total amount of tetracarboxylic dianhydride used in synthesis, preferably it is set as 10 moles of % or more.More preferably 30 moles of % or more, and then preferably 50 moles of % or more.Furthermore at synthetic polymer (P) When, as tetracarboxylic dianhydride, the one kind that can be used alone or it is used in combination of two or more.

(diamine compound)

As specific diamines, compound represented by following formula (12) can be enumerated.

[changing 10]

(in formula (12), A¹、A²、R³~R⁵、Y¹、Y²、Z¹、Z²And n respectively with the A in the formula (3)¹、A²、R³~R⁵、Y¹、 Y²、Z¹、Z²And n is identical meanings)

A in the formula (12)¹、A²、R³~R⁵、Y¹、Y²、Z¹、Z²And the concrete example and preference of n can be respectively using described The explanation of formula (3).As the concrete example of specific diamines, such as can to enumerate following formula (d-1)~formula (d-22) respectively represented Compound etc..

[changing 11]

[changing 12]

[changing 13]

As specific diamines, in these, the respective represented compound of preferably described formula (d-1)~formula (d-8), especially The respective represented compound of the preferably described formula (d-1), formula (d-2), formula (d-5), formula (d-7) and formula (d-11).Furthermore it is special Determine diamines and can be used alone one kind or to be used in combination of two or more.

At synthesizing polyamides sour (P), as diamine compound, specific diamines can be used only, it can also be with specific diamines one With other diamines used other than specific diamines.

It as other diamines, is not particularly limited, such as can enumerate as long as not having base represented by the formula (3)： Aliphatic diamine, ester ring type diamines, aromatic diamine and diamino organosiloxane etc..As the concrete example of these diamines, rouge Fat race diamines can for example be enumerated：M-xylene diamine, ethylenediamine, 1,3- propane diamine, tetra-methylenedimine, hexamethylene diamine etc.； Ester ring type diamines can for example be enumerated：To cyclohexane diamine, 4,4 '-di-2-ethylhexylphosphine oxides (cyclo-hexylamine) etc.；

Aromatic diamine can for example be enumerated：Dodecyloxy diaminobenzene, hexadecane epoxide diaminobenzene, octadecane epoxide Diaminobenzene, cholesteric alkyl oxy diaminobenzene, cholesteryl oxygroup diaminobenzene, diaminobenzoic acid cholesteric alkyl ester, diamino Yl benzoic acid cholesterol ester, diaminobenzoic acid lanostane ester, 3,6- bis- (4- amino benzoyl oxygroup) cholestane, 3,6- Bis- (4- amino-benzene oxygen) cholestane, 1,1- bis- (4- ((aminophenyl) methyl) phenyl) -4- butyl cyclohexanes, 2,5- diamino Base-N, N- diallyl aniline, following formula (E-1)

[changing 14]

(in formula (E-1), X^IAnd X^IIIt is separately singly-bound ,-O- ,-COO- or-OCO-, R^IFor the alkane two of carbon number 1~3 Base, R^IIFor the alkane diyl of singly-bound or carbon number 1~3, a is 0 or 1, the integer that b is 0~2, the integer that c is 1~20, and d is 0 or 1；Its In, a and b will not be simultaneously for 0)

The side chain type diamines such as represented compound；

P-phenylenediamine, 4,4 '-diaminodiphenyl-methanes, 4,4- ethylene aniline, 4,4 '-diamino-diphenyl amine, 4,4 '-diamino diphenyl sulfides, 4- aminophenyl -4 '-Aminobenzoate, 4,4 '-chrysoidines, 3,5- diamino Bis- (4- amino-benzene oxygen) ethane of benzoic acid, 1,2-, 1,5- bis- (4- amino-benzene oxygen) pentanes, N, N '-two (4- aminophenyl)- N, N '-dimethyl-ethylenediamine, bis- [2- (4- aminophenyl) ethyl] adipic acids, bis- (4- aminophenyl) amine, N, bis- (the 4- amino of N- Phenyl) methylamine, Isosorbide-5-Nitrae-bis- (4- aminophenyl)-piperazines, N, N '-bis- (4- aminophenyl)-benzidine, 2,2 '-dimethyl -4, 4 '-benzidines, 2,2 '-bis- (trifluoromethyl) -4,4 '-benzidines, 4,4 '-diamino-diphenyl ethers, the bis- [4- of 2,2- (4- amino-benzene oxygen) phenyl] propane, 4, bis- (4- amino-benzene oxygen) benzene of 4 '-(phenylenediisopropylidene) dianils, Isosorbide-5-Nitrae-, 4- (4- amino-benzene oxygen carbonyl) -1- (4- aminophenyl) piperidines, 4,4 '-[bis- (piperidines-Isosorbide-5-Nitrae-of 4,4 '-propane -1,3- diyls Diyl)] non-side chain type diamines such as diphenylamines；

Diamino organosiloxane can for example enumerate bis- (3- aminopropyl)-tetramethyl disiloxanes of 1,3- etc., in addition, The diamine compound recorded in Japanese Patent Laid-Open 2010-97188 bulletin can be used.Furthermore it is sour (P) in synthesizing polyamides When, other diamines, which can be used alone, one kind or to be used in combination of two or more.

For sufficiently obtaining the viewpoint of effect of this announcement, two aminations that are used when relative to synthesizing polyamides sour (P) The total amount of object is closed, the use ratio of specific diamines is preferably set as 20 moles of % or more.More preferably 40 moles of % or more, into And preferably 60 moles of % or more.

Specific diamines can be obtained and the well-established law proper combination by organic chemistry.It, can the side of being listed below as its an example Method etc.：Synthesis replace the formula (12) in level-one amino and with nitro dinitro intermediate, then using it is appropriate also Original system carries out amination to the nitro of dinitro intermediate obtained.

The method for synthesizing dinitro intermediate can be suitable for selection according to target compound.For example, can enumerate：Make isocyanic acid Ester compounds react with amine compounds and obtain " H-Y¹-R³-(Z¹-R⁴)_n-Z²-R⁵-Y²After compound represented by-H ", make to be obtained Compound with have structure "-A-NO₂" (A A¹Or A²) halogen compounds reaction method；Make with structure "-R-Y- A-NO₂" (R R³Or R⁵, Y Y¹Or Y²) the method reacted with carbonyl dimidazoles of amine compounds；Make with structure "-R-Y-A- NO₂" the method reacted with oxalyl chloride (oxalyl chloride) of amine compounds；Make with structure "-R-Y-A-NO₂" amination Close the method that object is reacted with diisocyanate cpd；Make with structure "-R³-(Z¹-R⁴)_n-Z²-R⁵" oxychloride and tool There is structure "-A-NO₂" amine compounds reaction method etc..Wherein, the synthetic method of specific diamines is not limited to the side Method.

(synthesis of polyamic acid)

Polyamic acid (P) can by make it is described as tetracarboxylic dianhydride and diamine compound optionally with molecular weight regulator (for example, acid list acid anhydride, monoamine compound, monoisocyanate compound etc.) is reacted together and is obtained.Relative to diamine compound 1 equivalent of amino is preferably four for the tetracarboxylic dianhydride of synthetic reaction of polyamic acid (P) and the use ratio of diamine compound The anhydride group of carboxylic acid dianhydride is 0.2 equivalent~2 equivalents ratio.

The synthetic reaction of polyamic acid (P) preferably carries out in organic solvent.Reaction temperature at this time is preferably -20 DEG C ~150 DEG C, the reaction time is preferably 0.1 hour~24 hours.As organic solvent used in reaction, such as can enumerate：It is non- Protic polar solvent, phenol system solvent, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon etc..Particularly preferred organic solvent is that use is selected from By n-methyl-2-pyrrolidone, n,N-dimethylacetamide, n,N-Dimethylformamide, dimethyl sulfoxide, gamma-butyrolacton, four One or more of group composed by methylurea, hexamethylphosphoramide, metacresol, xylenol and halogenation phenol is as molten More than one of matchmaker or these organic solvents and other organic solvents (such as butyl cellosolve, diethylene glycol diethyl ether etc.) Mixture.The usage amount of organic solvent is preferably set as tetracarboxylic dianhydride and the total amount of diamine compound is molten relative to reaction The total amount of liquid and be 0.1 mass of mass %~50 % amount.Reaction solution made of dissolution polyamic acid (P) can be supplied directly to The preparation of aligning agent for liquid crystal is supplied to aligning agent for liquid crystal after can also separating polyamic acid contained in reaction solution (P) Preparation.

Poly amic acid ester as polymer (P) is with R in part-structure represented by the formula (1)¹And R²At least One is the polymer of the structural unit of any monovalent organic radical of carbon number 1~6.The poly amic acid ester is for example using following methods To obtain：[I] makes the polyamic acid (P) and esterifying agent (such as methanol or ethyl alcohol, n,N-Dimethylformamide diethyl of the acquisition Base acetal etc.) reaction method；[II] makes tetracarboxylic acid acid diesters with the diamine compound comprising specific diamines preferably organic molten In matchmaker and in dehydration catalyst appropriate (such as 4- (4,6- dimethoxys -1,3,5-triazines -2- base) -4- methyl morpholine halogen Compound, carbonylic imidazole, phosphorus system condensing agent etc.) in the presence of the method reacted；[III] make tetracarboxylic acid acid diesters dihalide with comprising The diamine compound of specific diamines is preferably in organic solvent and in alkali appropriate (such as the tertiary amines such as pyridine, triethylamine, hydrogen Change the alkali metal class of sodium, hydrofining, sodium hydroxide, potassium hydroxide, sodium, potassium etc.) in the presence of the method etc. reacted.

Tetracarboxylic acid acid diesters used in [II] can be obtained by carrying out open loop to tetracarboxylic dianhydride using alcohols etc.. Tetracarboxylic acid acid diesters dihalide used in [III] can be by making the tetracarboxylic acid acid diesters obtained in this way and thionyl The chlorination reaction appropriate such as chlorine and obtain.

Poly amic acid ester can only have amic acid esters structure, can also be amic acid structure and amic acid esters structure and the portion deposited Divide carboxylate.Furthermore in the case where obtaining poly amic acid ester as a solution using the reaction, the solution can be straight The preparation for being supplied to aligning agent for liquid crystal is connect, liquid crystal is supplied to after poly amic acid ester contained in reaction solution can also being separated and takes To the preparation of agent.

Polyimides as polymer (P) is the polymer with part-structure represented by the formula (2).It is described poly- Acid imide imidizate can for example be obtained by carry out dehydration closed-loop to the polyamic acid (P) that synthesizes in this way and.It is poly- Acid imide can be for made of whole progress dehydration closed-loops to amic acid structure possessed by the polyamic acid (P) as its precursor Complete acid imide compound can also make amic acid structure and acid imide only to carry out dehydration closed-loop to a part of amic acid structure Ring structure and the part acid imide compound deposited.The polyimides is preferably that its acid imide rate is 40%~100%, more preferably It is 60%~90%.The acid imide rate is acyl of the quantity of imide ring structure expressed as a percentage relative to polyimides Total and shared ratio of the quantity of the quantity and imide ring structure of amino acid structure.Herein, a part of imide ring It can be different imide ring.

The dehydration closed-loop of polyamic acid (P) is preferably that benefit carries out with the following method：Polyamic acid is dissolved in organic solvent In, dehydrating agent and dehydration closed-loop catalyst are added in the solution and are optionally heated.As dehydrating agent, such as can make With acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride.Relative to 1 mole of amic acid structure of polyamic acid, the use of dehydrating agent Amount is preferably set as 0.01 mole~20 moles.As dehydration closed-loop catalyst, such as pyridine, collidine, diformazan can be used The tertiary amines such as pyridine, triethylamine.Relative to 1 mole of the dehydrating agent used, the usage amount of dehydration closed-loop catalyst is preferably set as 0.01 mole~10 moles.As the organic solvent used, can enumerate organic molten used in the synthesis as polyamic acid (P) Matchmaker and the organic solvent illustrated.The reaction temperature of dehydration closed-loop reaction is preferably 0 DEG C~180 DEG C, and the reaction time is preferably 1.0 small When~120 hours.The reaction solution containing polyimides so obtained can be supplied directly to the preparation of aligning agent for liquid crystal, can also The preparation of aligning agent for liquid crystal is supplied to after polyimides is separated.

About the solution viscosity of polymer (P), when the solution of 10 mass % of concentration is made, it is however preferred to have 10mPas The solution viscosity of~800mPas, more preferably with the solution viscosity of 15mPas~500mPas.Furthermore solution viscosity (mPas) for using E type rotational viscometer at 25 DEG C to good solvent (such as the gamma-butyrolacton, N- first for using polymer (P) Base -2-Pyrrolidone etc.) and the value that is measured of polymer solution of 10 mass % of concentration for preparing.

Polymer (P) is measured using gel permeation chromatography (Gel Penetration Chromatography, GPC) Polystyrene conversion weight average molecular weight (Mw) be preferably 1,000~500,000, more preferably 5,000~100, 000.The molecular weight distribution indicated with Mw and using the ratio of the number average molecular weight (Mn) of the polystyrene conversion of GPC measurement It (Mw/Mn) is preferably 15 hereinafter, more preferably 10 or less.Furthermore polymer contained in aligning agent for liquid crystal (P) can be only one Kind, or can be by two or more combinations.

《Other compositions》

The aligning agent for liquid crystal of this announcement contains the other compositions other than polymer (P).As the other compositions, such as It can enumerate：Any one its without part-structure represented by part-structure represented by the formula (1) and the formula (2) His polymer, in the molecule with compound, functional silanes compound, the antioxidant, metal chelating of at least one epoxy group Polymerisable compounds, hardening accelerator, interfacial agent, filler, dispersing agent, light sensitizer, acid producing agent, base generator, freedom Base producing agent etc..The allotment ratio of these ingredients can be suitable for according to each compound in the range of not undermining the effect of this announcement Selection.

Other polymers are the mesh for the reduced purpose for inhibiting voltage retention or the raising for realizing liquid crystal aligning And use.The main framing of other polymers is not particularly limited, such as can be enumerated polyamic acid, polyimides, polyamide Acid esters, polysiloxane, polyester, cellulose derivative, polyacetals, polystyrene derivative, poly- (styrene-phenyl Malaysia Acid imide) polymer as main framing such as derivative, poly- (methyl) acrylate.In these, other polymers are preferably selected At least one of group composed by free polyamic acid, poly amic acid ester and polyimides.

In the case where the aligning agent for liquid crystal of light orientation processing is made, it may be made as the polymer comprising non-photosensitive and make It for polymer (P) and include photosensitive polymer as other polymers person.In the situation, by containing polymer (P), compared with the case where being free of polymer (P), so that it may for the aspect for obtaining the liquid crystal cell for showing high voltage retention It is preferred that.

In the case where deploying other polymers to aligning agent for liquid crystal, allotment ratio is relative in aligning agent for liquid crystal Total polymerization object amount and the preferably 1 mass % of mass %~95, the more preferably 5 mass % of mass %~90, and then preferably 15 matter Measure the mass of %~80 %.

The aligning agent for liquid crystal of this announcement is the other compositions that with polymer (P) and optionally use preferably appropriate molten It is prepared by the form of liquid composition made of being dispersed or dissolved in matchmaker.

As the organic solvent used, such as can enumerate：N-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, 1, 2- dimethyl-2-imidazolinone, gamma-butyrolacton, butyrolactam, n,N-Dimethylformamide, n,N-dimethylacetamide, 4- hydroxy-4-methyl-2-pentanone, glycol monoethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxy Base propionic ester, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl Cellosolve), glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol It is monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, diisobutyl ketone, different Amyl propionic ester, isopentyl isobutyrate, isoamyl ether, ethylene carbonate, propylene carbonate etc..These organic solvents can be independent Using or be use mixing two or more.

(total quality of the ingredient other than the solvent of aligning agent for liquid crystal accounts for liquid crystal to solid component concentration in aligning agent for liquid crystal The ratio of the gross mass of alignment agent) it is to consider viscosity, volatility etc. and be suitable for selection, preferably 1 mass of mass %~10 %'s Range.That is, aligning agent for liquid crystal is preferably heated, by being coated on substrate surface in a manner of aftermentioned to be formed as liquid The film of brilliant alignment films or film as liquid crystal orientation film.At this point, the case where solid component concentration is less than 1 mass % Under, the film thickness of film becomes too small and is difficult to obtain good liquid crystal orientation film.It on the other hand, is more than 10 in solid component concentration In the case where quality %, the film thickness of film becomes excessive and exists and be difficult to obtain good liquid crystal orientation film, and aligning agent for liquid crystal Viscosity increase and coating decline tendency.

The content ratio of polymer (P) in aligning agent for liquid crystal relative in aligning agent for liquid crystal solid component (solvent with Outer ingredient) total 100 mass parts and it is more than preferably 10 mass parts, more than more preferably 20 mass parts, and then preferably It is more than 30 mass parts.

《Liquid crystal orientation film and liquid crystal cell》

The liquid crystal orientation film of this announcement can be formed using the aligning agent for liquid crystal prepared in this way.Particularly preferably originally The liquid crystal orientation film of announcement is manufactured using including the method for following light orientation process：It is formed and is applied using the aligning agent for liquid crystal Film simultaneously implements photo-irradiation treatment to the film and assigns liquid crystal aligning ability.

In addition, the liquid crystal cell of this announcement includes the liquid crystal orientation film formed using the aligning agent for liquid crystal of the explanation. The action mode of liquid crystal in liquid crystal cell is not particularly limited, for example, can be applied to twisted nematic (Twisted Nematic, TN) type, STN Super TN (Super TwistedNematic, STN) type, vertical orientation (Vertical Alignment, VA) Type (includes vertical orientation-multidomain vertical orientation (Vertical Alignment-Multi domain Vertical Alignment, VA-MVA) type, vertical orientation-pattern vertical orientation (Vertical Alignment-Patterned Vertical Alignment, VA-PVA) type etc.), coplanar switch type (In-Plane Switching, IPS type), fringing field cut Change (fringe field switching, FFS) type, optical compensation curved (Optically Compensated Bend, OCB) In the various modes such as type.Liquid crystal cell can for example be manufactured using including the method for 1~process of process 3 below.Make in process 1 It is different with the required action mode of substrate view.Each action mode is common in process 2 and process 3.

(process 1：The formation of film)

Firstly, the coating of liquid crystalline alignment agent on substrate, preferably heats coated face, is thus formed and applied on substrate Film.As substrate, such as can be used：The glass such as float glass, soda-lime glass；Comprising polyethylene terephthalate, gather to benzene two The transparent substrate of the plastics such as formic acid fourth diester, polyether sulfone, polycarbonate, poly- (ester ring type alkene).As its for being set to substrate The transparent conductive film of middle one side, can be used includes tin oxide (SnO₂) nesa (NESA) film (PPG register of company of U.S. trade mark), Include indium oxide-tin oxide (In₂O₃-SnO₂) tin indium oxide (Indium Tin Oxide, ITO) film etc..Manufacture TN type, In the case where STN type or VA type liquid crystal cell, the substrate of patterned transparent conductive film is provided with using two pieces.Another party It is led in the case where manufacturing IPS type or FFS type liquid crystal cell using being provided with comprising patterned for the transparent of interdigitated electrode structure in face The substrate of the electrode of electrolemma or metal film, the opposite substrate with not set electrode.As metal film, can be used for example comprising chromium The film of equal metals.Coating to the aligning agent for liquid crystal of substrate is that flexographic printing process, rotation are preferably utilized on electrode forming surface Rubbing method, roll-coater method or ink jet printing method and carry out.

After coating of liquid crystalline alignment agent, the purpose of for the sagging for preventing be coated with aligning agent for liquid crystal, preferably implement It preheats (prebake conditions).Prebake conditions temperature is preferably 30 DEG C~200 DEG C, and the prebake conditions time is preferably 0.25 minute~10 minutes. Thereafter, for the purpose that solvent is completely removed to and optionally carried out to amic acid structure present in polymer hot-imide And implement calcining (rear baking) process.Calcination temperature (rear baking temperature) at this time is preferably 80 DEG C~300 DEG C, post-bake times Preferably 5 minutes~200 minutes.The film thickness of the film formed in this way is preferably 0.001 μm~1 μm.By liquid crystal aligning After agent is coated on substrate, organic solvent is removed, liquid crystal orientation film or the film as liquid crystal orientation film is consequently formed.

(process 2：Orientation process)

Manufacturing TN type, STN type, IPS type or in the case where FFS type liquid crystal cell, implement to being formed in the process 1 The processing (orientation process) of film imparting liquid crystal aligning ability.The alignment capability of liquid crystal molecule is imparted to film and forms as a result, For liquid crystal orientation film.It is high with regard to the photo sensitivity of polymer (P) as orientation process, even and if film can also be made for few light exposure For showing anisotropic aspect, it is preferable to using carrying out light irradiation to the film formed on substrate and assigned to film Give the light orientation processing of liquid crystal aligning ability.It on the other hand, can be by institute in the case where manufacturing the liquid crystal cell of vertical orientating type It states the film formed in process 1 and is directly used as liquid crystal orientation film, orientation process can also be implemented to the film.

Light irradiation in light orientation processing is carried out using following method：Film after post-bake process is irradiated Method, the method that the film after prebake conditions process and before post-bake process is irradiated, in prebake conditions process and rear Roaster The method etc. that film is irradiated in the heating process of film in at least either of sequence.In light orientation processing, as right The radiation of film irradiation, such as the ultraviolet light and luminous ray of the light of the wavelength comprising 150nm~800nm can be used.It is preferred that For the ultraviolet light of the light of the wavelength comprising 200nm~400nm.It can be linear polarization in the case where radiation is polarisation For part polarisation.In addition, irradiation can hang down from real estate in the case where the radiation used is linear polarization or part polarisation Straight direction carries out, and can carry out from inclined direction, or can also carry out these combinations.Irradiating the radiation of non-polarized In the case of, direction of illumination is set as inclined direction.

As the light source used, such as Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halide lamp, argon can be used Resonance lamp, xenon lamp, excimer laser etc..The exposure of radiation is preferably 400J/m²~20,000J/m², more preferably 1, 000J/m²~5,000J/m².In order to improve reactivity, the light irradiation to film can be carried out while heating to film.

It, can be below at 120 DEG C or more and 280 DEG C to the film for implementing photo-irradiation treatment when manufacturing liquid crystal orientation film It is heated in temperature range.Utilize such heat treatment, so that it may obtain liquid crystal aligning be further improved (heating take again To), the liquid crystal cell that is further reduced of AC image retention in terms of for preferably.The heating is toasted after being, can also be and rear baking Bake the heat treatment for separating and carrying out after rear baking.For promoting the viewpoint of reorientation of the strand using heating, add Hot temperature is preferably set as 140 DEG C or more, is more preferably set as 150 DEG C~250 DEG C.Heating time is preferably 5 minutes~200 points Clock, more preferably 10 minutes~60 minutes.

It, can be in turn comprising having the film for implementing photo-irradiation treatment contact water, water solubility when manufacturing liquid crystal orientation film The Contact operation of the mixed solvent of machine solvent or water and water-soluble organic solvent.By carrying out such Contact operation, can by because Light orientation processing and the decomposition product generated is removed from film, so that it may inhibit the generation of micro bright point in liquid crystal cell obtained It is suitable for for aspect.Herein, it as water-soluble organic solvent, such as can enumerate：Methanol, ethyl alcohol, 1- propyl alcohol, isopropanol, 1- first Oxygroup -2- propanol acetate, butyl cellosolve, ethyl lactate, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclopentanone.This In a little organic solvents, solvent used in Contact operation is preferably water, isopropanol and these mixture.

As the contact method of film and solvent, such as can enumerate：Spraying (spray) processing, spray process, at dipping Reason, covering liquid processing etc., but it is not limited to these.The time of contact of film and solvent is not particularly limited, and for example, 5 seconds~15 Minute.The heat treatment of film can be carried out after Contact operation.

(process 3：Liquid crystal cells are constructed)

Prepare two pieces of substrates for being formed with liquid crystal orientation film in this way, configures liquid between two pieces of oppositely disposed substrates Thus crystalline substance manufactures liquid crystal cells.In order to manufacture liquid crystal cells, such as can enumerate：(1) in a manner of keeping liquid crystal orientation film opposite every Gap (spacer) two pieces of substrates are oppositely disposed, and the peripheral portion of two pieces of substrates is bonded using sealant, liquid crystal is infused Enter in the cell gap for being filled in and being divided by substrate surface and sealant, later will seal the method for injection hole sealing, (2) Agent is coated on the specified position on the one of substrate for being formed with liquid crystal orientation film, and then the regulation in liquid crystal alignment film surface After liquid crystal is added dropwise in several places, another piece of substrate is bonded in such a way that liquid crystal orientation film is opposite, and liquid crystal is made to be spread in substrate Method (liquid crystal drip-injection (one drop filling, ODF) mode) in whole face etc..Preferably for manufactured liquid crystal list Member, and then heat the temperature until the liquid crystal acquirement isotropic phase used, it is slowly cooled to room temperature later, thus by liquid Flow orientation removal when crystalline substance filling.

As sealant, such as the epoxy resin etc. of the alumina balls containing curing agent and as spacer can be used.Make For spacer, light spacer (photo spacer), pearl spacer (beads spacer) etc. can be used.As liquid crystal, can arrange Nematic liquid crystal and disc-like liquid crystal are lifted, wherein preferably nematic liquid crystal, such as can be used：Schiff bases (Schiffbase) be liquid crystal, Azoxy (azoxy) is liquid crystal, biphenyl system liquid crystal, cyclohexylbenzene system liquid crystal, ester system liquid crystal, terphenyl system liquid crystal, biphenyl Butylcyclohexane system liquid crystal, liquid crystal, dioxane system of pyrimidine system liquid crystal, double-octane system liquid crystal, cubane (cubane) are liquid crystal etc.. It is used in addition, can be added in these liquid crystal such as cholesteric crystal, chiral auxiliary, ferroelectric liquid crystal.

Then, polarizer is bonded if necessary in the outer surface of liquid crystal cells.As polarizer, it can enumerate and utilize acetic acid fibre It ties up plain protective film clamping and is referred to as polarizer or the polarizer comprising H film itself made of the light polarizing film of " H film ", " H Film " is to absorb iodine while making polyvinyl alcohol extend and be orientated.Liquid crystal cell is obtained as a result,.

Furthermore according to the aligning agent for liquid crystal containing polymer (P), the photoreactivity or rub resistance of film are good and can It is not true to obtain the reasons why liquid crystal aligning, AC image retention characteristic and voltage retention performance are through balancing the liquid crystal cell improved well It is fixed, but be speculated as polymer (P) and light is being carried out to film using possessed nitrogen-containing heterocycle in the structural unit for being originated from diamines Light reaction is improved by Photo-induced electron transfer from diamine skeleton to acid anhydrides skeleton when irradiation (electronics transfer increases sense reaction) Property.Thus, thus it is speculated that can be improved the liquid crystal of liquid crystal cell obtained orientation degree of order, it can be achieved that AC image retention reduction.In addition, Utilize hydrogen bond knot functional group (Z possessed by polymer (P)¹、Z²) and play intermolecular interaction, thus speculating can get The high film of rub resistance, and can get the high liquid crystal cell of voltage retention.

The liquid crystal cell of this announcement can be effectively applied in various uses, such as can be used for clock and watch, portable game machine (portable game), word processor (word processor), notebook-PC (note type Personal computer), it is auto-navigation system (car navigation system), video camera (camcorder), personal Digital assistants (Personal Digital Assistant, PDA), digital camera (digital camera), mobile phone, The various display devices or light modulation film etc. such as smart phone, various monitors, LCD TV, information display.In addition, using this The aligning agent for liquid crystal of announcement and the liquid crystal cell formed can also be applied in phase difference film.

[embodiment]

Hereinafter, being more specifically illustrated using embodiment, but the present invention is not limited to these embodiments.

The structure of main compound used in following example and abbreviation are as described below.

(tetracarboxylic dianhydride)

TA-1：(1R, 2R, 3S, 4S) -1,3- dimethylcyclobutane -1,2,3,4- tetracarboxylic dianhydrides

TA-2：1,2,3,4- cyclobutane tetracarboxylic dianhydride

TA-3：2,3,5- tricarboxylic cyclopentyl acetic acid dianhydrides

TA-4：Bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydrides

TA-5：Pyromellitic acid anhydride

TA-6: 4,4 '-two O-phthalic acid dianhydrides

[changing 15]

(specific diamines)

DA-1：Bis- (2- ((5- amino -2- pyridyl group) (methyl) amino) ethyl) ureas of N, N ' -

DA-2：Bis- (2- ((5- amino -2- pyridyl group) oxygroup) ethyl) ureas of N, N ' -

DA-3：Bis- (2- ((5- amino -2- pyridyl group) (methyl) amino) ethyl) oxamides of N, N ' -

DA-4：Bis- (2- ((5- amino -2- pyridyl group) oxygroup) ethyl) oxamides of N, N ' -

DA-5: 5- amino -2- pyridyl group -6- (3- (6- ((5- amino -2- pyridyl group) amino) -6- oxo-hexyl) uride Base) caproamide

Bis- (the 3- (2- ((5- amino -2- pyridyl group) (methyl) amino) ethyl) of DA-6: 1,1 '-(hexane -1,6- diyl) Urea)

(other diamines)

DB-1：P-phenylenediamine

DB-2：N, N '-(4- aminophenyl) urea

DB-3：N, N '-two (5- amino -2- pyridyl group)-N, N '-dimethyl-ethylenediamine

DB-4：Bis- (4- aminophenyl) esters of adipic acid

DB-5：Bis- (2- ((4- aminophenyl) (methyl) amino) ethyl) ureas of N, N '-

[changing 16]

(solvent)

NMP：N-methyl-2-pyrrolidone

BC：Butyl cellosolve

DMAc：N,N-dimethylacetamide

[synthesis example 1]

2- chloroethyl amine hydrochloride (11.60g, 0.10mol), 2- chlorine are put into the three-necked flask for including nitrogen ingress pipe Ethyl isocyanate (10.55g, 0.10mol) and methylene chloride 100mL.Under ice cooling, 4 be added dropwise triethylamine (11.13g, 0.11mol), it and is stirred at room temperature 24 hours.After reaction, water 100mL is injected to reaction solution and be stirred, to outstanding Floating solution is filtered.After precipitate obtained is stirred and cleaned in water 100mL, it is dried in vacuo, thus to obtain Bis- (2- chloroethyl) ureas (16.7g, yield 90%) of N represented by following formula (DA-1-a), N '-.

Then, N, bis- (2- chloroethyl) ureas of N '-are put into the three-necked flask for including return pipe and nitrogen ingress pipe It is small to stir 48 at 40 DEG C for (14.80g, 0.08mol), ethyl alcohol (100mL) and 40% aqueous solution of methylamine (124g, 1.6mol) When.The dissolution of raw material with reaction, obtains colorless and transparent reaction solution.After reaction, cooling in ice bath to reaction solution Lower addition potassium hydroxide (8.98g, 0.16mol) is neutralized, and is concentrated under reduced pressure.Ethyl alcohol is added to concentrate obtained And extract, it is filtered after removing insoluble salt, is concentrated under reduced pressure, it is represented thus to obtain following formula (DA-1-b) N, the crude product (15.0g) of bis- (2- (methylamino) ethyl) ureas of N '-.

[changing 17]

[synthesis example 2]

N, bis- (2- (methylamino) ethyl) ureas of N '-are put into the three-necked flask for including return pipe and nitrogen ingress pipe (6.97g, 40mmol), triethylamine (16.7mL, 120mmol) and DMAc (80mL).The fluoro- 5- nitro pyrrole of 2- is added dropwise under a nitrogen Pyridine (11.37g, 80mmol) is stirred 12 hours at 60 DEG C.After reaction, reaction solution is filtered and is depressurized Concentration.Precipitate obtained is recrystallized using ethyl acetate, and is dried in vacuo, thus to obtain following formula (DA- Nitro-body intermediate product (12.24g, yield 78%) represented by 1-c).

Then, nitro-body intermediate product (2.09g, 5.0mmol), 5% palladium carbon are put into the autoclave of 100mL (0.21g) and ethyl alcohol (30mL) is blown into hydrogen until 0.4MPa, is stirred 12 hours at 50 DEG C.After reaction, to reaction Solution carries out diatomite filtering and is concentrated under reduced pressure.Precipitate obtained is cleaned using ethyl alcohol, and carries out vacuum It is dry, thus to obtain diamines represented by following formula (DA-1) (1.60g, yield 65%).

[changing 18]

[synthesis example 3]

O- represented by following formula (DA-2-b) (5- nitro -2- pyridyl group) ethyl alcohol is synthesized according to synthesis flow below Amine.

[changing 19]

[synthesis example 4]

O- (5- nitro -2- pyridyl group) second is put into the three-necked flask for including return pipe, thermometer and nitrogen ingress pipe Hydramine (1.10g, 6.0mmol), carbonyl dimidazoles (0.58g, 3.6mmol) and DMAc (30mL), it is small to be stirred at room temperature 24 When.After reaction, it is concentrated under reduced pressure, precipitate obtained is recrystallized using ethyl acetate, and carry out vacuum It is dry, thus to obtain nitro-body intermediate product represented by following formula (DA-2-c) (0.91g, yield 77%).

Then, nitro-body intermediate product (1.57g, 4.0mmol), 5% palladium carbon are put into the autoclave of 100mL (0.16g) and ethyl alcohol (30mL) is blown into hydrogen until 0.4MPa, is stirred 12 hours at 50 DEG C.After reaction, to reaction Solution carries out diatomite filtering and is concentrated under reduced pressure.Precipitate obtained is cleaned using ethyl alcohol, and carries out vacuum It is dry, thus to obtain diamines represented by following formula (DA-2) (1.00g, yield 63%).

[changing 20]

[synthesis example 5]

(5- nitro -2- the pyridine of N- methyl-N- represented by following formula (DA-3-b) is synthesized according to synthesis flow below Base) ethylenediamine.

[changing 21]

[synthesis example 6]

N- methyl-N- (5- nitro -2- pyrrole is put into the three-necked flask for including return pipe, thermometer and nitrogen ingress pipe Piperidinyl) ethylenediamine (1.18g, 6.0mmol), triethylamine (0.91g, 9.0mmol) and DMAc (30mL), under ice cooling, 4 into Row stirring.It is added dropwise oxalyl chloride (0.38g, 3.0mmol), and is stirred at room temperature 8 hours.After reaction, it is concentrated under reduced pressure, Precipitate obtained is recrystallized using ethyl acetate, and is dried in vacuo, thus to obtain following formula (DA-3-c) Represented nitro-body intermediate product (1.11g, yield 83%).

Then, nitro-body intermediate product (1.79g, 4.0mmol), 5% palladium carbon are put into the autoclave of 100mL (0.18g) and ethyl alcohol (30mL) is blown into hydrogen until 0.4MPa, is stirred 12 hours at 50 DEG C.After reaction, to reaction Solution carries out diatomite filtering and is concentrated under reduced pressure.Precipitate obtained is cleaned using ethyl alcohol, and carries out vacuum It is dry, thus to obtain diamines represented by following formula (DA-3) (0.74g, yield 48%).

[changing 22]

[synthesis example 7]

Diamines represented by the formula (DA-4) is synthesized according to synthesis flow below.

[changing 23]

[synthesis example 8]

Diamines represented by the formula (DA-5) is synthesized according to synthesis flow below.

[changing 24]

[synthesis example 9]

Diamines represented by the formula (DA-6) is synthesized according to synthesis flow below.

[changing 25]

[synthesis example 10]

Diamines represented by the formula (DB-5) is synthesized according to synthesis flow below.

[changing 26]

[synthesis example 11]

It is dissolved in 60 molar part of diamines (DA-1) and 40 molar part of diamines (DB-1) in NMP, the four of 0.95 equivalent of addition Carboxylic acid dianhydride (TA-1) carries out the solution for reacting and obtaining polyamic acid for 6 hours at room temperature.Phase is added to solution obtained For polyamic acid carboxyl and be 0.8 equivalent 1- methyl piperidine and acetic anhydride, heating stirring 3 hours at 60 DEG C.To institute Reduced pressure and the dilution using NMP is repeated in the solution of acquisition, and obtaining has the knot of part represented by following formula (PI-1) 15 mass % solution of the polyimides (PI-1) of structure.Measure polyimides (P1-1)¹H- nuclear magnetic resonance (¹H-Nuclear Magnetic Resonance,¹H-NMR) spectrum (DMSO-d⁶, 400MHz), it utilizes aromatic protons (δ 6.4ppm~9.0ppm) With the integral ratio of backbone amide proton (δ 9.8ppm~10.3ppm), acetyl group terminal amide proton (δ 59.6ppm~9.8ppm) To calculate acid imide rate, as a result, acid imide rate is 70%.

[changing 27]

[12~synthesis example of synthesis example 17]

Type and molar ratio to tetracarboxylic dianhydride and diamine compound are changed as recorded in following table 1 respectively, In addition to this, it is carried out similarly respectively with synthesis example 11 and obtains polyimides (PI-2~PI-7).Furthermore about in table 1 Numerical value is 100 molar part of total amount indicated relative to tetracarboxylic dianhydride used in synthesis for tetracarboxylic dianhydride The use ratio (molar part) of each compound for diamine compound is indicated relative to two amination used in synthesis Close the use ratio (molar part) of each compound of 100 molar part of total amount of object.

[synthesis example 18]

It is dissolved in diamines (DA-1) in NMP, adds the tetracarboxylic dianhydride (TA-5) of 0.95 equivalent, carry out 6 at room temperature Hour reacts and obtains the 15 mass % solution with the polyamic acid (PA-1) of part-structure represented by following formula (PA-1).

[changing 28]

[19~synthesis example of synthesis example 27]

Type and molar ratio to tetracarboxylic dianhydride and diamine compound are changed as recorded in following table 1 respectively, In addition to this, it is carried out similarly respectively with synthesis example 18 and obtains polyamic acid (PA-2~PA-10).

[table 1]

[embodiment 1：Light orientation FFS type liquid crystal display element]

(1) preparation of aligning agent for liquid crystal

Using the polyimides (PI-1) obtained in synthesis example 11 solution and be diluted using NMP and BC, consolidate The solution that body constituent concentration is 4.0 mass %, solvent ratio of components is NMP: BC=80: 20 (mass ratioes).Utilize 0.2 μm of aperture Filter is filtered the solution, thus prepares aligning agent for liquid crystal (R-1).

(2) formation of the liquid crystal orientation film of optical alignment method is utilized

It is coated in such a way that film thickness is 0.1 μm using the aligning agent for liquid crystal (R-1) prepared in rotator (1) by described in Single side is sequentially laminated with the glass substrate of plate electrode, insulating layer and comb-like electrode, the opposite glass base with not set electrode On the respective face of plate, drying (prebake conditions) in 1 minute is carried out using 80 DEG C of heating plates, to form film.Use Hg-Xe lamp Ultraviolet light 2,000J/m of the self-reference substrate normal direction to bright line of the film coated surface irradiation comprising the 254nm through linear polarization² And carry out light orientation processing.The film for implementing light orientation processing 230 DEG C of nitrogen displacement have been subjected in library It is heated 30 minutes in baking oven and is heat-treated (rear baking), to form liquid crystal orientation film.

(3) manufacture of liquid crystal display element

For having a pair of of substrate of the liquid crystal orientation film made in (2), in the face for being formed with liquid crystal orientation film Edge remains liquid crystal injecting port, after the epoxy resin solid screen painting coating for the alumina balls for being put into 5.5 μm of diameter, Substrate is overlapped and is crimped in such a way that the projecting direction of polarisation axial direction real estate when light irradiates becomes antiparallel, at 150 DEG C Under last 1 hour and make solid thermmohardening.Then, nematic liquid crystal (Merck is filled from liquid crystal injecting port between a pair of of substrate (Merck) company manufactures, MLC-7028) after, liquid crystal injecting port is sealed using epoxy solid.In turn, in order to by liquid crystal Flow orientation removal when injection, is slowly cooled to room temperature after heating at 120 DEG C to it.Secondly, in the outside of substrate Two sides is bonded polarizer and manufactures FFS type liquid crystal display element.

(4) evaluation of photoreactivity

It is coated on quartz base plate using the aligning agent for liquid crystal (R-1) prepared in rotator (1) by described in, utilizes 80 DEG C After heating plate carries out drying in 1 minute, carry out carrying out drying in 30 minutes, shape in 230 DEG C of baking oven of nitrogen displacement in library At 0.1 μm of film of average film thickness.Using Hg-Xe lamp self-reference substrate normal direction to film coated surface irradiation comprising inclined through straight line The ultraviolet light 1,000J/m of the bright line of the 254nm of light².According to from the substituted maleimide amine compounds generated by photodegradation Absorption evaluate photoreactivity.Specifically, measuring the illumination in the maximum absorption wavelength in the region of 220nm~250nm The absorbance of film after penetrating, and calculate the increase for the absorbance of the film before the light irradiation in the wavelength Rate.The situation that the increment rate of absorbance is 20% or more is set as " excellent ", is 10% or more and small by the increment rate of absorbance " good " is set as in 20% the case where, by the increment rate of absorbance less than 10% the case where is set as " bad ".As a result, the implementation It is the evaluation of " excellent " in example.

(5) evaluation of liquid crystal aligning

For the liquid crystal display element manufactured in (3), the voltage of 5V is led with 50 times of multiplying power observations using microscope The presence or absence of abnormal domain (domain) when on-off opens (ONOFF) (apply and release) in light and shade variation.It, will not about evaluation The case where observing abnormal domain is set as orientation degree of order " good ", it will be observed that the case where abnormal domain is set as " bad ".As a result, institute State the evaluation in embodiment for " good ".

(6) evaluation of AC image retention characteristic

In addition to substrate outside two sides be bonded polarizer in terms of other than, carry out with (3) identical operation, from And make FFS type liquid crystal cells.For the FFS type liquid crystal cells, after alternating voltage 10V driving 30 hours, using The device of polarizer and analyzer is configured between light source and light quantity detector to measure minimum phase represented by following numerical expressions (2) To transmitance (%).

Minimum relative permeability (%)=(β-B₀)/(B₁₀₀-B₀)×100...(2)

(in numerical expression (2), B₀It for blank (blank), and is the transmission of the light under cross Nicols (crossednicols) Amount；B₁₀₀It for blank, and is the transit dose of the light under parallel Nicolle (parallel nicols)；β be cross Nicols under Liquid crystal cells are clamped between polarizer and analyzer and become the smallest smooth transit dose)

The black level of dark state is indicated by the minimum relative permeability of liquid crystal cells, in FFS type liquid crystal cells, dark shape The smaller then contrast (contrast) of black level under state is more excellent.Minimum relative permeability is set as " excellent less than 0.2% It is good ", it is set as " good " more than and less than 0.5% by 0.2%, is set as "available" more than and less than 1.0% for 0.5%, it will 1.0% or more person is set as " bad ".As a result, being the evaluation of " excellent " in the embodiment.

(7) evaluation of voltage retention

With the application time of 60 microseconds, 167 milliseconds of span, after the voltage that the liquid crystal cells of the manufacture are applied with 5V, Measure the voltage retention from applying and releasing after 167 milliseconds.Voltage retention is set as " excellent " for 99.5% or more, it will 99.0% is set as " good " more than and less than 99.5%, is set as "available" more than and less than 99.0% for 98.0%, will be less than 98.0% is set as " bad ".As a result, being the evaluation of " excellent " in the embodiment.Furthermore it is filled as the measurement of voltage retention It sets, the model name " VHR-1 " manufactured using Dongyang Te Kenika (Toyo Technica) (stock) company.

[2~embodiment of embodiment 4,1~comparative example of comparative example 2, reference example 1]

In the embodiment 1, it is as described in Table 2 to polymer contained in aligning agent for liquid crystal as change, remove this In addition, it carries out similarly to Example 1 and prepares aligning agent for liquid crystal and form liquid crystal orientation film using optical alignment method, and manufacture FFS type liquid crystal display element and liquid crystal cells carry out various evaluations.It shows the results of the evaluation in following table 2.

[embodiment 5：Friction orientation FFS type liquid crystal display element]

(1) preparation of aligning agent for liquid crystal

Using the polyamic acid (PA-1) obtained in synthesis example 18 solution and be diluted using NMP and BC, consolidate The solution that body constituent concentration is 4.0 mass %, solvent ratio of components is NMP: BC=80: 20 (mass ratioes).Utilize 0.2 μm of aperture Filter is filtered the solution, thus prepares aligning agent for liquid crystal (R-5).

(2) formation of the liquid crystal orientation film of rubbing manipulation is utilized

It is coated on using the aligning agent for liquid crystal (R-5) prepared in rotator (1) by described in and is sequentially laminated with plate in single side On the respective face of the opposite glass substrate of electrode, the glass substrate of insulating layer and comb-like electrode and not set electrode, utilize After 80 DEG C of heating plate carries out drying in 1 minute, carry out carrying out doing for 30 minutes in 230 DEG C of baking oven of nitrogen displacement in library It is dry, to form 0.1 μm of average film thickness of film.For the film coated surface, the roller with the cloth for being wound with nylon is used Friction machine, friction treatment is carried out with roller revolution 1000rpm, platform movement speed 25mm/ seconds, hair indentation length 0.4mm.It is right It is described implement friction orientation processing film carry out 1 minute ultrasonic cleaning in ultrapure water after, in 100 DEG C of baking oven into Row drying in 10 minutes, to form liquid crystal orientation film.

(3) manufacture of liquid crystal display element

(4) evaluation (evaluation of the foreign matter amount generated by friction treatment) of rub resistance

It is coated on using the aligning agent for liquid crystal (R-5) prepared in rotator (1) by described in the transparent electricity comprising ito film On the transparent electrode face of the glass substrate of pole, after carrying out drying in 1 minute using 80 DEG C of heating plates, nitrogen has been carried out in library Drying in 30 minutes is carried out in 230 DEG C of baking oven of displacement, forms 0.1 μm of average film thickness of film.For the film coated surface, make With the friction machine of the roller with the cloth for being wound with cotton, it is pressed into roller revolution 1000rpm, platform movement speed 25mm/ second, hair Length 0.4mm carries out 5 friction treatments, and substrate is used in the foreign matter amount evaluation of acquisition.Using optical microscopy to foreign matter amount obtained Evaluation is observed with the foreign matter on substrate, is counted to the foreign matter number in 500 μm of 500 μ m of regions.By 500 μ ms Less than 5 persons of foreign matter number in 500 μm of region are set as " excellent ", 5 more than and less than 10 persons are set as "available", by 10 The above person is set as " bad ".As a result, be in the embodiment and do not confirm foreign matter " excellent " evaluation.

(5) evaluation of liquid crystal aligning

The evaluation of liquid crystal aligning is carried out similarly with (5) of embodiment 1.As a result, being " good " in the embodiment Evaluation.

(6) evaluation of AC image retention characteristic

The evaluation of AC image retention characteristic is carried out similarly with (6) of embodiment 1.As a result, being " excellent " in the embodiment Evaluation.

(7) evaluation of voltage retention

The evaluation of voltage retention is carried out similarly with (7) of embodiment 1.As a result, being " excellent " in the embodiment Evaluation.

[6~embodiment of embodiment 8, comparative example 3]

In the embodiment 5, it is as described in Table 2 to polymer contained in aligning agent for liquid crystal as change, remove this In addition, it carries out similarly to Example 5 and prepares aligning agent for liquid crystal and form liquid crystal orientation film using rubbing manipulation, and manufacture FFS type liquid crystal display element and liquid crystal cells carry out various evaluations.It shows the results of the evaluation in following table 2.

[9~embodiment of embodiment 12, comparative example 4]

In the embodiment 1, it is as described in Table 2 to polymer contained in aligning agent for liquid crystal as change, remove this In addition, it carries out similarly to Example 1 and prepares aligning agent for liquid crystal and form liquid crystal orientation film using optical alignment method, and manufacture FFS type liquid crystal display element and liquid crystal cells carry out various evaluations.It shows the results of the evaluation in following table 2.Furthermore embodiment 9 In~embodiment 12 and comparative example 4, make two kinds of polymer (polymer 1 and polymer 2) with polymer 1: polymer 2=40: 60 The allotment ratio of (solid component reduced mass ratio) contains in aligning agent for liquid crystal.9~embodiment of embodiment 12 and comparative example 4 In, polymer 1 is photosensitive polymer, and polymer 2 is the polymer of non-photosensitive.

[table 2]

As shown in table 2, the photoreactivity or resistance to of the aligning agent for liquid crystal of 1~embodiment of embodiment 12 comprising polymer (P) Frictional property is evaluated as " excellent ", and AC image retention characteristic and voltage retention are evaluated as " excellent " or " good ", and achieve The balance of various characteristics.In contrast, the rub resistance of the aligning agent for liquid crystal of 1~comparative example of comparative example 4 without polymer (P) At least either of property, AC image retention characteristic and voltage retention is poorer than embodiment.In addition, though reference example 1 is without bad evaluation, Photoreactivity and AC image retention characteristic are poorer than embodiment.

Herein, the result of embodiment is investigated, then about photoreactivity, 1~embodiment of embodiment 4, embodiment 9~ Embodiment 12 is " good " or " excellent ".These situations are speculated as：There is pyridine ring and electron donating property base to make in polymer (P) For the part-structure from diamines, therefore using from the part-structure of diamines is originated to replacing the Photoinduced Electron of cyclobutane ring to turn (electronics transfer increases sense reaction) is moved to promote the photodegradation using inverse [2+2] reaction for replacing cyclobutane ring.

About rub resistance, 5~embodiment of embodiment 8 is " excellent ".These situations are speculated as：Tool in polymer (P) Have hydrogen bond knot functional group (urea bond, oxalyl amine key), therefore the toughness of the liquid crystal orientation film raising using intermolecular interaction, As a result the cutting of film caused by friction treatment is inhibited, and foreign matter number is reduced.In addition, about voltage retention, embodiment 1~implementation Example 12 is " good " or " excellent ".These situations are speculated as：There is hydrogen bond knot functional group (urea bond or grass in polymer (P) Amido bond), thus using intermolecular interaction and transport properties of molecules is inhibited, as a result dielectric polarization is inhibited and voltage Conservation rate improves.

Comprising photosensitive polymer 1 in 9~embodiment of embodiment 12 of the polymer 2 of non-photosensitive, such as according to The comparison of comparative example 2 and it is clear as, the reduction of voltage retention caused by polymer 1 is inhibited.In addition, embodiment 9~reality It applies in example 12, in the same manner as the comparative example 2 for only including photosensitive polymer 1, the evaluation of liquid crystal aligning and AC image retention characteristic For " excellent ".These situations are speculated as：The polymer (P) of non-photosensitive contained in 9~embodiment of embodiment 12 has hydrogen bond Knot property functional group (urea bond, oxalyl amine key) and basic group (pyridine ring), thus be it is highly polar, with it is opposite be low polar poly- The layer separation property for closing object 1 improves, and photosensitive polymer 1 is locally present in the interface of liquid crystal orientation film, thus can show good Good liquid crystal aligning.On the other hand, thus it is speculated that be：The polymer 2 of non-photosensitive contained in comparative example 4 does not simultaneously have pyridine Ring, therefore acid is easy to produce between basic pyridinium ring contained in the carboxylic acid contained in polymer 2 and photosensitive polymer 1 The intermiscibility of alkali interaction, polymer 1 and polymer 2 improves, and the polymer 2 of non-photosensitive is easy to be present in liquid crystal orientation film Interface, liquid crystal aligning reduce.Furthermore the investigation only speculates after all, does not appoint to the content of this announcement What is limited.

It is learnt by the above content：According to the aligning agent for liquid crystal of this announcement comprising polymer (P), the light of liquid crystal orientation film Reactivity or rub resistance are good, and can get AC image retention characteristic and the good liquid crystal cell of voltage retention.

Claims

1. a kind of aligning agent for liquid crystal, it is characterised in that：Containing having selected from by part-structure represented by following formula (1) and following The polymer (P) of at least one of group composed by part-structure represented by formula (2)；

In formula (1) and formula (2), X¹For quadrivalent organic radical, X²For divalent organic base represented by following formula (3)；R¹And R²It is only respectively It is on the spot hydrogen atom or any monovalent organic radical of carbon number 1~6,

In formula (3), A¹And A²It is separately divalent aromatic ring group；Wherein, A¹And A²At least one be divalent nitrogen-containing heterocycle Base；R³And R⁵It is separately the divalent aliphatic hydrocarbon of carbon number 1~10, R⁴For carbon number 1~10 divalent aliphatic hydrocarbon or There is oxygen atom, sulphur atom ,-COO- ,-OCO- ,-Si (R between the carbon-carbon bond of the aliphatic alkyl²¹R²²）Or-Si (R²¹R²²）-O-Si(R²³R²⁴)-bilvalent radical, wherein R²¹~R²⁴It is separately hydrogen atom or the aliphatic hydrocarbon of carbon number 1~6 Base；Y¹And Y²It is separately singly-bound, oxygen atom, sulphur atom ,-COO- ,-OCO- ,-NR⁶-、-NR⁶- CO- or-CO-NR⁶, Middle R⁶It, can be with adjacent R for hydrogen atom or any monovalent organic radical³Or R⁵It is bonded and forms ring structure；Z¹And Z²Under being separately State any one of base represented by formula (4)~formula (6) difference；N is 0 or 1；* associative key is indicated,

In formula (4), R⁷For hydrogen atom or any monovalent organic radical, B¹For-NR¹⁴-、*¹-CO-NR¹⁴, oxygen atom, *¹-CO-O-、-NR¹⁴- CO-NR¹⁴Or *¹-NR¹⁴- CO-O-, wherein R¹⁴For hydrogen atom or any monovalent organic radical, *¹Indicate the associative key with carbonyl；Formula (5) In, R⁸And R⁹It is separately hydrogen atom or any monovalent organic radical；In formula (6), R¹⁰~R¹³It is separately hydrogen atom or one Valence organic group；* associative key is indicated.

2. aligning agent for liquid crystal according to claim 1, it is characterised in that：The A¹And A²It is separately nitrogenous for divalent Heterocycle.

3. aligning agent for liquid crystal according to claim 2, it is characterised in that：The Y¹And Y²It is separately oxygen atom, sulphur Atom or-NR⁶,

The Y¹And Y²Relative to the A¹And A²Possessed nitrogen-containing heterocycle and be adjacent to nitrogen in the nitrogenous heterocyclic ring The carbon atom of atom is bonded.

4. aligning agent for liquid crystal according to any one of claim 1 to 3, it is characterised in that：The X¹For following formula (11) institute The quadrivalent organic radical of expression；

In formula (11), R³¹~R³³It is separately the halogenation of hydrogen atom, halogen atom, the alkyl of carbon number 1~6, carbon number 1~6 Alkyl, the alkoxy of carbon number 1~6, the alkylthio of carbon number 1~6, the alkenyl of carbon number 2~6, carbon number 2~6 alkynyl or- COR³⁰, wherein R³⁰For the alkyl of carbon number 1~6, containing fluoroalkyl, alkoxy or fluoroalkoxy；R³⁴For halogen atom, carbon number 1~ 6 alkyl, the halogenated alkyl of carbon number 1~6, the alkoxy of carbon number 1~6, the alkylthio of carbon number 1~6, carbon number 2~6 alkene The alkynyl or-COR of base, carbon number 2~6³⁰；Wherein, R³¹~R³⁴In the base of adjoining can be bonded each other and form ring structure；* table Show associative key.

5. a kind of liquid crystal orientation film, it is characterised in that：Use aligning agent for liquid crystal according to any one of claim 1 to 4 And it is formed.

6. a kind of manufacturing method of liquid crystal orientation film, it is characterised in that：Including using according to claim 1 to any one of 4 institutes The aligning agent for liquid crystal stated forms film and assigns the light orientation work of liquid crystal aligning ability to film implementation photo-irradiation treatment Sequence.

7. the manufacturing method of liquid crystal orientation film according to claim 6, it is characterised in that：It and then include described to implementing The heating process that the film of photo-irradiation treatment is heated within the scope of 120 DEG C or more and 280 DEG C or less of temperature.

8. a kind of liquid crystal cell, it is characterised in that：Including liquid crystal orientation film according to claim 5.

9. a kind of polymer, it is characterised in that：Part-structure and following formula (2) institute represented by with being selected from by following formula (1) At least one of group composed by the part-structure of expression；

In formula (3), A¹And A²It is separately divalent aromatic ring group；Wherein, A¹And A²At least one be divalent nitrogen-containing heterocycle Base；R³And R⁵It is separately the divalent aliphatic hydrocarbon of carbon number 1~10, R⁴For carbon number 1~10 divalent aliphatic hydrocarbon or There is oxygen atom, sulphur atom ,-COO- ,-OCO- ,-Si (R between the carbon-carbon bond of the aliphatic alkyl²¹R²²)-or-Si (R²¹R²²）-O-Si(R²³R²⁴)-bilvalent radical, wherein R²¹~R²⁴It is separately hydrogen atom or the aliphatic hydrocarbon of carbon number 1~6 Base；Y¹And Y²It is separately singly-bound, oxygen atom, sulphur atom ,-COO- ,-OCO- ,-NR⁶-、-NR⁶- CO- or-CO-NR⁶, Middle R⁶It, can be with adjacent R for hydrogen atom or any monovalent organic radical³Or R⁵It is bonded and forms ring structure；Z¹And Z²Under being separately State any one of base represented by formula (4)~formula (6) difference；N is 0 or 1；* associative key is indicated,

In formula (4), R⁷For hydrogen atom or any monovalent organic radical, B¹For-NR¹⁴-、*¹-CO-NR¹⁴, oxygen atom, *¹-CO-O-、-NR¹⁴- CO-NR¹⁴Or *¹-NR¹⁴- CO-O-, wherein R¹⁴For hydrogen atom or any monovalent organic radical；In formula (5), R⁸And R⁹It is separately hydrogen Atom or any monovalent organic radical；In formula (6), R¹⁰~R¹³It is separately hydrogen atom or any monovalent organic radical；* associative key is indicated.

10. a kind of diamines, it is characterised in that：It is indicated by following formula (12)；

In formula (12), A¹And A²It is separately divalent aromatic ring group；Wherein, A¹And A²At least one be divalent nitrogen-containing heterocycle Base；R³And R⁵It is separately the divalent aliphatic hydrocarbon of carbon number 1~10, R⁴For carbon number 1~10 divalent aliphatic hydrocarbon or There is oxygen atom, sulphur atom ,-COO- ,-OCO- ,-Si (R between the carbon-carbon bond of the aliphatic alkyl²¹R²²)-or-Si (R²¹R²²)-O-Si(R²³R²⁴)-bilvalent radical, wherein R²¹~R²⁴It is separately hydrogen atom or the aliphatic hydrocarbon of carbon number 1~6 Base；Y¹And Y²It is separately singly-bound, oxygen atom, sulphur atom ,-COO- ,-OCO- ,-NR⁶-、-NR⁶- CO- or-CO-NR⁶, Middle R⁶It, can be with adjacent R for hydrogen atom or any monovalent organic radical³Or R⁵It is bonded and forms ring structure；Z¹And Z²Under being separately State any one of base represented by formula (4)~formula (6) difference；N is 0 or 1,