CN107338058A - Aligning agent for liquid crystal, liquid crystal orientation film and its manufacture method, liquid crystal cell, polymer and compound - Google Patents

Aligning agent for liquid crystal, liquid crystal orientation film and its manufacture method, liquid crystal cell, polymer and compound Download PDF

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Publication number
CN107338058A
CN107338058A CN201710260108.8A CN201710260108A CN107338058A CN 107338058 A CN107338058 A CN 107338058A CN 201710260108 A CN201710260108 A CN 201710260108A CN 107338058 A CN107338058 A CN 107338058A
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liquid crystal
formula
polymer
base
compound
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CN107338058B (en
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村上拓也
村主拓弥
须原辽
安池伸夫
樫下幸志
冈田敬
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JSR Corp
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
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    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
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    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
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    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

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Abstract

The present invention provides a kind of in the case of application optical alignment method, even if it can also obtain heat resistance without special processing after light irradiation is carried out to film well and show aligning agent for liquid crystal, liquid crystal orientation film and its manufacture method, liquid crystal cell, polymer and the compound of good liquid crystal aligning and the liquid crystal cell of image retention characteristic.Contain the polymer (P) with the part-structure represented by formula (1) in aligning agent for liquid crystal.(in formula (1), R1For the quadrivalent organic radical containing the cyclobutane ring structure can with substituent, R2For divalent organic base；X1And X2It is separately hydroxyl or any monovalent organic radical of carbon number 1~40；Wherein, X1And X2At least any one be any monovalent organic radical with reactive base).

Description

Aligning agent for liquid crystal, liquid crystal orientation film and its manufacture method, liquid crystal cell, polymer with And compound
Technical field
The present invention relates to a kind of aligning agent for liquid crystal, liquid crystal orientation film and its manufacture method, liquid crystal cell, polymer and change Compound.
Background technology
Liquid crystal cell is widely used in television set or mobile device, various monitors (monitor) etc..In addition, in liquid crystal Liquid crystal orientation film is used always in order to carry out tropism control to the liquid crystal molecule in liquid crystal cells in element.In the past, as obtaining There must be the method for the organic film of liquid crystal aligning restraint, it is known to：The method that is rubbed to organic film, oblique evaporation oxidation The method of silicon, the method for forming the monomolecular film with chain alkyl, the method (light that light irradiation is carried out to photosensitive organic film Alignment method) etc..
Optical alignment method can assign uniform liquid crystal while the generation of electrostatic or dust is suppressed to photosensitive organic film Orientation, and can also realize the accurate control in liquid crystal aligning direction, therefore, just promoting in recent years various researchs (referring for example to Patent document 1).Being disclosed in patent document 1 has herein below：The polyimides in main chain with cyclobutane ring structure will be contained The aligning agent for liquid crystal of precursor or polyimides is coated on substrate and calcined, and irradiates polarisation radioactive ray to the film obtained Afterwards, the organic solvent for making boiling point be 110 DEG C~180 DEG C contacts with film, and then the water solubility with 50 DEG C~105 DEG C of water or boiling point has After solvent contact, heated with more than 150 DEG C, be derived from liquid crystal orientation film.And announcement has herein below：Logical In the case of crossing the cleaning treatment for carrying out such a film and heating and assigning alignment capability to film using optical alignment method, altogether Face switch (In-Plane Switching, IPS) type of drive or fringing field switching (Fringe Field Switching, FFS the image retention caused by caused exchange driving) is suppressed in the liquid crystal display cells of type of drive.
[prior art literature]
[patent document]
[patent document 1] International Publication No. 2014/084362
The content of the invention
[inventing problem to be solved]
However, in the method described in patent document 1, due to the step of needing to clean film and heated, therefore have When manufacturing liquid crystal cell, number of steps becomes more, cost uprises or become numerous and diverse worry.In addition, in recent years, big picture and high-precision Thin liquid crystal TV set turns into main body, and smart mobile phone (smartphone) or tablet-type personal computer (personal Computer, PC) etc. the popularization of small-sized display terminal promoted, requirement and cost degradation to the High precision of liquid crystal panel Requirement further improve.Therefore, exploitation can be manufactured inexpensively liquid crystal aligning or image retention characteristic etc. and liquid crystal cell as far as possible The technology of the related good liquid crystal cell of various characteristics of display quality become than more important in the past.
At present, it is small-sized aobvious to smart mobile phone or plate PC etc. to can be applied to the liquid crystal TV set of arrogant picture for liquid crystal cell The broad range of device or purposes of showing device.In addition, with the multipurpose of liquid crystal cell, and load or be arranged at such as in-car Or the place of high temperature is likely to become as outdoor or with carrying out long-time driving than before, so as to assume harsher Used under hot environment.Therefore, require high to the reliability of heat resistance as liquid crystal cell.However, using containing in master Chain has the aligning agent for liquid crystal of the polyimides based polymer of cyclobutane ring structure and taken by light orientation processing to make liquid crystal In the case of film, there is following worry：Due to the caused analyte by the light irradiation to film, when growing in high temperature environments Micro bright point is easily produced during the liquid crystal cell that time exposure is obtained, to the less reliable of heat resistance.
The present invention be in view of the situation and formed, one of purpose is to provide a kind of feelings in application optical alignment method Under condition, even if can also obtain heat resistance without special processing after light irradiation is carried out to film well and show good The aligning agent for liquid crystal of liquid crystal aligning and the liquid crystal cell of image retention characteristic.
[technological means for solving problem]
Present inventor has carried out positive research to reach the problem of prior art as described above, as a result finds, leads to Cross and the polymer with specific part-structure is used in aligning film material, can solve the problem that the problem, so as to complete this Invention.Specifically, there is provided following means.
<1>A kind of aligning agent for liquid crystal, it contains the polymer (P) with the part-structure represented by following formula (1)；
[changing 1]
(in formula (1), R1For the quadrivalent organic radical containing the cyclobutane ring structure can with substituent, R2It is organic for divalence Base；X1And X2It is separately hydroxyl or any monovalent organic radical of carbon number 1~40；Wherein, X1And X2At least any one be with Any monovalent organic radical of reactive base).
<2>A kind of manufacture method of liquid crystal orientation film, described in its use<1>Aligning agent for liquid crystal and form film, to this Film carries out light irradiation and assigns liquid crystal aligning ability.
<3>A kind of liquid crystal orientation film, described in its use<1>Aligning agent for liquid crystal and formed.
<4>A kind of liquid crystal cell, it includes described<3>The liquid crystal orientation film of record.
<5>A kind of polymer, it has the part-structure represented by the formula (1).
<6>A kind of compound or its salt, it is represented by following formula (1-1) or following formula (1-2)；
[changing 2]
(in formula (1-1) and formula (1-2), X11And X12It is separately hydrogen atom or any monovalent organic radical of carbon number 1~40； Wherein, X11And X12At least any one be any monovalent organic radical with reactive base；R3It is separately hydrogen atom, fluorine original Son, chlorine atom, bromine atoms or can have substituent carbon number 1~10 univalent aliphatic series base；X is to select free hydroxyl, chlorine former One kind in the group that the respective represented structure of son, bromine atoms and following formula (4-1)~formula (4-6) is formed)
[changing 3]
(in formula (4-1)~formula (4-6), " * " represents associative key).
[The effect of invention]
According to the aligning agent for liquid crystal of the disclosure, even if special without cleaning or heating of film etc. after the irradiation of radioactive ray Processing, it is high and show good liquid crystal aligning and the liquid crystal cell of image retention characteristic can also to obtain heat resistance.That is, in profit In the case of assigning alignment capability to film with optical alignment method, step number that can be as few as possible obtain that heat resistance is high, image retention is few and The good liquid crystal cell of liquid crystal aligning.
Embodiment
Hereinafter, to the composition allocated in the aligning agent for liquid crystal of the disclosure and optionally and arbitrarily allocate other into Divide and illustrate.
《Polymer (P)》
The aligning agent for liquid crystal of the disclosure contains the polymer (P) with the part-structure represented by the formula (1).The formula (1) in, R1It is represented for the tetravalence base from the tetracarboxylic acid derivatives with cyclobutane ring structure, preferably following formula (r-1) Part-structure.That is, polymer (P) is preferably with the part-structure and following formula (1-B) institute table represented by following formula (1-A) The part-structure shown it is at least one.
[changing 4]
(in formula (r-1), R3It is separately hydrogen atom, fluorine atom, chlorine atom, bromine atoms or there can be substituent The univalent aliphatic series base of carbon number 1~10)
[changing 5]
(in formula (1-A) and formula (1-B), R2、X1And X2Implication respectively with the R in the formula (1)2、X1And X2It is identical.R3 Implication and the formula (r-1) in R3It is identical)
In the formula (r-1), R3The carbon number 1~10 with substituent univalent aliphatic series base be preferably carbon number 1~ 10 alkyl, containing fluoroalkyl, alkoxy, fluoroalkoxy or "-COOR20" (wherein, R20For the alkyl of carbon number 1~10, fluorine-containing Alkyl, alkoxy or fluoroalkoxy).In addition, 4 R in formula3Can it is mutually identical also can be different.
R2For the bilvalent radical from diamine compound, two one-levels of removal from existing known diamine compound can be enumerated Bilvalent radical that amino forms etc..
As X1And X2Carbon number 1~40 any monovalent organic radical, such as can enumerate：The monovalent hydrocarbon of carbon number 1~40, the hydrocarbon Methylene warp-O- ,-S- ,-CO- ,-COO- ,-the COS- ,-NR of base3-、-CO-NR3-、-Si(R3)2- (wherein, R3For hydrogen atom or The monovalent hydrocarbon of carbon number 1~12) ,-N=N- ,-SO2- wait monad radical A, monovalent hydrocarbon or monad radical A that substitution forms carbon former The hydrogen atom being bonded on son it is at least one through halogen atom (fluorine atom, chlorine atom, bromine atoms, iodine atom etc.), hydroxyl, alkane Epoxide, nitro, amino, sulfydryl, nitroso, alkyl tin groups, alkyl silane groups, alkoxysilane group, silanol group, sulfinic acid base, phosphino-, carboxylic The monad radical that the substitutions such as base, cyano group, sulfo group, acyl group form, monad radical with heterocycle etc..Wherein, X1And X2At least any one For any monovalent organic radical with reactive base.
Herein, " alkyl " refers to include chain alkyl, alicyclic type hydrocarbon and aromatic hydrocarbyl in this specification.So-called " chain Shape alkyl ", refer to the straight-chain alkyl and branch-like alkyl that only include chain structure for not including cyclic structure in main chain.Its In, can be that saturation is alternatively unsaturation.So-called " alicyclic type hydrocarbon ", refer to only comprising ester ring type hydrocarbon structure as ring structure without Alkyl comprising aromatic ring structure.Wherein, without only including ester ring type hydrocarbon structure, being also contained in one part has chain structure Person.So-called " aromatic hydrocarbyl ", refer to comprising alkyl aromatic ring structure as ring structure.Wherein, without only including aromatic rings Structure, also it can include chain structure or ester ring type hydrocarbon structure in one part." fatty group " refers to chain alkyl and ester ring type Alkyl.
X1And X2It is at least one possessed by reactive base be preferably heat, light, acid, alkali and free radical at least one In the presence of, reactive base forms the base of covalent bond each other and/or between maleimide compound.Reactive base is preferably Pass through at least hot and light at least one base to react.As the concrete example of reactive base, such as can enumerate：Following formula (5- 1) the respective represented structure of~formula (5-10), (methyl) acryloxy, styryl, ethenylphenyl, (methyl) propylene Amide groups, ethyleneoxy (CH2=CH-O-), the respective represented base etc. of following formula (p-1) and formula (p-2).Ethenylphenyl and Ethyleneoxy is one of the structure represented by following formula (5-1).
[changing 6]
(in formula (5-1)~formula (5-10), R41For that can have the bivalent aliphatic base of the carbon number 1~6 of substituent, R5Respectively It independently is hydrogen atom or there can be the univalent aliphatic series base of the carbon number 1~6 of substituent.Wherein, R41And R5In any two Fatty group can be bonded and form ring structure each other.Multiple R in formula (5-1), formula (5-9)5Can be mutually identical also different. " * " represents associative key)
[changing 7]
(in formula (p-1), X5For oxygen atom or-NH-." * " represents associative key)
In the formula (5-1), R41The bivalent aliphatic base of carbon number 1~6 be preferably alkane diyl or alkene diyl.As R41 The substituent that can have, such as halogen atom, alkoxy etc. can be enumerated.R5The univalent aliphatic series base of carbon number 1~6 be preferably alkane Base or alkenyl.
In the formula (5-2)~formula (5-10), R41The bivalent aliphatic base of carbon number 1~6 be preferably alkane diyl.On R41The substituent that can have, the explanation of the formula (5-1) can be applied.R5The univalent aliphatic series base of carbon number 1~6 be preferably alkane Base.For the viewpoint of reactivity, the R in formula (5-5)5Particularly preferably hydrogen atom or methyl.
It is more excellent with regard to obtaining liquid crystal aligning, alternating current (Altemating Current, AC) image retention characteristic and heat resistance Liquid crystal cell viewpoint for, reactive base be preferably selected from by mentioned earlier described in formula (5-1)~formula (5-10) it is each At least one of group formed from represented structure and (methyl) acryloxy, more preferably it is selected from by the formula The group that (5-1), formula (5-2), the respective represented structure of formula (5-4)~formula (5-6) and (methyl) acryloxy are formed At least one of.In addition, " (methyl) acrylic " refers to acrylic and methacrylic acid group in this specification.
The reactive base of the illustration can directly be bonded to the carbonyl in formula (1), can be also bonded via bivalence linking base. As the bivalence linking base, such as can enumerate：Oxygen atom, carbon number 1~20 alkane diyl, have between the carbon-carbon bond of the alkane diyl There is-O- ,-CO- ,-COO- etc. bilvalent radical etc..
X1And X2At least any one be preferably selected from by following formula (2-1)~formula (2-10) each represented by structure and One kind in the group that (methyl) acryloxy is formed, more preferably it is selected from by following formula (2-1), formula (2-2), formula (2- 4) one kind in the group that the respective represented structure of~formula (2-6) and (methyl) acryloxy are formed.In addition, under State the R in formula (2-1)~formula (2-10)4And R5Explanation, the R in the formula (5-1)~formula (5-10) can be applied respectively41And R5 Explanation.
[changing 8]
(in formula (2-1)~formula (2-10), R4For that can have the bivalent aliphatic base of the carbon number 1~6 of substituent, R5It is only respectively It is on the spot hydrogen atom or the univalent aliphatic series base of the carbon number 1~6 can with substituent.Wherein, R4And R5In any two fat Fat race base can be bonded and form ring structure each other.Multiple R in formula (2-1), formula (2-9)5Can be mutually identical also different.“*” Represent associative key)
[synthesis of polymer (P)]
The method of synthetic polymer (P) is not particularly limited, and as preferable method, can be enumerated：Make to include the formula (1- And respective at least one four in represented compound (hereinafter also referred to as " specific acid derivative ") of the formula (1-2) 1) Carboxylic acid derivates and the method for diamine compound reaction.
In addition, " tetracarboxylic acid derivatives " form comprising four carboxyls possessed by tetrabasic carboxylic acid through dehydrating condensation in this specification Tetracarboxylic dianhydride and tetrabasic carboxylic acid possessed by least one of four carboxyls pass through "-COX3" (wherein, X3For halogen atom or carbon Any monovalent organic radical of number 1~40) substitute the compound formed.Specifically, in addition to tetracarboxylic dianhydride, such as can enumerate：Four One or two in four carboxyls possessed by carboxylic acid is through four possessed by esterification and the compound remaining as carboxyl, tetrabasic carboxylic acid One or two in individual carboxyl imports disengaging base through esterification and into remaining carboxyl (for example, halogen atom, the formula (4- 1) the respective represented structure etc. of~formula (4-6)) compound or its salt that forms etc..
On the formula (1-1), formula (1-2), R3Preference can apply the formula (r-1) explanation.X11And X12Extremely Any one is preferably selected from the structure represented by the formula (2-1)~formula (2-10) is respective and (methyl) acryloxy institute less One kind in the group of composition.In addition, in X11、X12In the case of the base without reactive base, X11、X12Preferably hydrogen is former The alkyl of son or carbon number 1~10.
X is preferably hydroxyl or chlorine atom.In addition, in the case where X is hydroxyl, specific acid dianhydride is tetracarboxylic acid acid diesters, in X In the case of for chlorine atom or bromine atoms, specific acid dianhydride is tetracarboxylic acid acid diesters dihalide.
[tetracarboxylic acid derivatives]
(specific acid derivative)
Specific acid derivative obtains such as using following methods：[1] make comprising four with cyclobutane ring structure (below, the tetracarboxylic dianhydride of carboxylic acid dianhydride (hereinafter also referred to as " specific tetracarboxylic dianhydride ") is with having the compound of reactive base Also referred to as " compound (E) containing reactive base ") reaction method；[2] tetracarboxylic dianhydride for including specific tetracarboxylic dianhydride is made Reacted with the compound (E) containing reactive base and obtain tetracarboxylic acid acid diesters, then, with the compound (example with the disengaging base Such as halogenating agent) reaction method.
Specific tetracarboxylic dianhydride
Specific tetracarboxylic dianhydride is then not particularly limited, specifically, by following formula as long as there is cyclobutane ring structure (4) it is represented.
[changing 9]
(in formula (4), A1For the quadrivalent organic radical with cyclobutane ring structure)
In the formula (4), A1Structure represented by preferably described formula (r-1).As the specific of specific tetracarboxylic dianhydride Example, such as can enumerate：1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1- methyl isophthalic acids, 2,3,4- cyclobutane tetracarboxylic dianhydrides, 1,3- bis- Methyl isophthalic acid, 2,3,4- cyclobutane tetracarboxylic dianhydrides, 1,2,3- trimethyls -1,2,3,4- cyclobutane tetracarboxylic dianhydrides, 1,2,3,4- Tetramethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydrides, 1- ethyls -1,2,3,4- cyclobutane tetracarboxylic dianhydrides, 1,3- diethyl -1, 2,3,4- cyclobutane tetracarboxylic dianhydrides, 1- ethyl -3- methyl isophthalic acids, 2,3,4- cyclobutane tetracarboxylic dianhydrides, following formula (T-1-1)~ Respective represented compound of formula (T-1-16) etc..
[changing 10]
Specific tetracarboxylic dianhydride is preferably 1 in these, 2,3,4- cyclobutane tetracarboxylic dianhydrides and 1,3- dimethyl -1,2, 3,4- cyclobutane tetracarboxylic dianhydrides, particularly preferably 1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydrides.In addition, conduct Specific tetracarboxylic dianhydride, the one kind that can be used alone or is used in combination of two or more.
Compound (E) containing reactive base
Compound (E) containing reactive base is as long as there is reactive base and the functional group reacted with acid dianhydride base, then It is not particularly limited, preferably the compound represented by following formula (3-1).
[changing 11]
(in formula (3-1), A2For reactive base, R11For singly-bound or the alkyl of (k+1) valency.K is 1~3 integer)
In the formula (3-1), as R11(k+1) valency alkyl, chain alkyl, alicyclic type hydrocarbon and aromatic series can be enumerated Alkyl.K is preferably 1, as R in this case11Concrete example, divalence chain alkyl can for example enumerate：Methylene, ethylidene, Glyceryl, fourth diyl, penta diyl, dihexyl, diyl in heptan, pungent diyl, nonyl diyl, last of the ten Heavenly stems diyl etc., these can be straight-chain For branch-like.In addition, as R11Divalence alicyclic type hydrocarbon, can enumerate：Cyclohexylidene ,-Rc-(CH2)n- (wherein, RcFor sub- ring Hexyl, n are 1~5 integer) etc., O divalent aromatic alkyl can for example be enumerated：Phenylene, biphenylene ,-Ph- (CH2)n- (its In, Ph is phenylene, and n is 1~5 integer) etc..
A2The explanation of reactive base and the explanation of preferred concrete example of the formula (1) can be applied.
As the concrete example of the compound represented by the formula (3-1), such as following formula (3-1-1)~formula (3- can be enumerated 1-16) respective represented compound etc..One kind or by two kinds in addition, the compound (E) containing reactive base can be used alone Combination of the above uses.
[changing 12]
Tetracarboxylic dianhydride and the reaction of the compound (E) containing reactive base
Tetracarboxylic dianhydride and the reaction of the compound (E) containing reactive base can optionally be carried out in organic solvent.Made As long as compound (E) of the organic solvent relative to tetracarboxylic dianhydride and containing reactive base is not active, then special limit is had no It is fixed, such as can enumerate：The ketone such as acetone, methyl ethyl ketone；The hydrocarbon such as hexane, heptane, toluene；The halogens such as chloroform, 1,2- dichloroethanes It is hydrocarbon；The ethers such as tetrahydrofuran, diethyl ether, the dioxane of Isosorbide-5-Nitrae-；Nitrile compounds such as acetonitrile, propionitrile etc..In addition, these organic solvents can It is used alone a kind of or is used in combination of two or more.
Relative to 1 mole of tetracarboxylic dianhydride, the use ratio of the compound (E) containing reactive base is usually 2 moles~100 Mole, preferably it is set to 2 moles~40 moles.Reaction temperature now can be according to the used compound containing reactive base (E) species and suitably set, be preferably set to -20 DEG C~150 DEG C, be more preferably set to 0 DEG C~100 DEG C.Reaction time is excellent Elect as 0.1 hour~24 hours, more preferably 0.5 hour~12 hours.In addition, reprecipitation can be optionally carried out after the reaction. Afterwards by the way that optionally the sediment obtained is cleaned and dried, target compound (tetracarboxylic acid acid diesters) can be obtained.
In methods described [2], make by the reaction and appropriate halogen such as the tetracarboxylic acid acid diesters obtained and thionyl chlorides In the case that agent is reacted, carried out preferably in organic solvent.On the bar such as organic solvent or reaction temperature, reaction time Part, tetracarboxylic dianhydride and the explanation of the reaction condition of the compound (E) containing reactive base can be applied.
Other acid derivatives
As synthetic polymer (P), as tetracarboxylic acid derivatives, specific acid derivative can be used only, also can and with specific Acid derivative and the tetracarboxylic acid derivatives different from specific acid derivative (hereinafter also referred to as " other acid derivatives ").It is used as it His acid derivative, such as can enumerate：Tetracarboxylic acid acid diesters without reactive base, the tetracarboxylic acid acid diesters two without reactive base Halide, the tetracarboxylic dianhydride (hereinafter also referred to as " other tetracarboxylic dianhydrides ") without cyclobutane ring structure are with containing reactivity The reaction product of the compound (E) of base, tetracarboxylic dianhydride etc..
Other described tetracarboxylic dianhydrides are not particularly limited.As concrete example, aliphatic tetracarboxylic dianhydride can for example enumerate： Ethylenediamine tetra-acetic acid dianhydride etc.；
Ester ring type tetracarboxylic dianhydride can for example enumerate：2,3,5- tricarboxylic cyclopentyl acetic acid dianhydrides, 5- (2,5- dioxos four Hydrogen furans -3- bases) -3a, 4,5,9b- tetrahydrochysene naphtho- [1,2-c] furans -1,3- diketone, 5- (2,5- dioxotetrahydro furans -3- Base) -8- methyl -3a, 4,5,9b- tetrahydrochysene naphtho- [1,2-c] furans -1,3- diketone, 5- (2,5- dioxotetrahydro -3- furans Base) -3- methyl -3- cyclohexene -1,2- dicarboxylic anhydride, 3,5,6- tri- carboxyl -2- carboxymethyl groups norbornanes -2：3,5：6- bis- Acid anhydride, 2, bicyclic [3.3.0] octane -2 of 4,6,8- tetracarboxylics：4,6：8- dianhydrides, cyclopentanetetracarboxylic's dianhydride, pentamethylene tetrabasic carboxylic acid two Acid anhydride etc.；Aromatic tetracarboxylic acid's dianhydride can for example be enumerated：Pyromellitic acid anhydride, 4,4 '-(hexafluoroisopropyli,ene) two O-phthalics Acid anhydrides, TOPOT 2,2′ p phenylenebis (trimellitic acid monoesters acid anhydride), ethylene glycol double (dehydration trimellitates), the double (dehydrations of 1,3-PD Trimellitate) etc.；In addition, the tetracarboxylic dianhydride described in Japanese Patent Laid-Open 2010-97188 publications can be used. In addition, as synthetic polymer (P), other tetracarboxylic dianhydrides, which can be used alone, one kind or to be used in combination of two or more.
As synthetic polymer (P), for fully obtaining the viewpoint of effect of the disclosure, relative to what is used in synthesis The total amount of tetracarboxylic acid derivatives, the use ratio of specific acid derivative are preferably to be set to 10 moles of more than %.More preferably 30 Mole more than %, and then preferably 50 moles of more than %.In addition, specific acid derivative and other acid derivatives can individually make With one kind, can also be used in combination of two or more.
[diamine compound]
There is no particular restriction for the diamine compound used in the synthesis of polymer (P), and various diamine compounds can be used.Make For its concrete example, aliphatic diamine can for example be enumerated：M-xylene diamine, 1,3- propane diamine, tetra-methylenedimine, hexa-methylene two Amine etc.；Ester ring type diamines can for example be enumerated：Isosorbide-5-Nitrae-diaminocyclohexane, 4,4 '-di-2-ethylhexylphosphine oxide (cyclo-hexylamine) etc.；
Aromatic diamine can for example be enumerated：Dodecyloxy diaminobenzene, hexadecane epoxide diaminobenzene, octadecane epoxide Diaminobenzene, cholesteric alkoxy diaminobenzene, cholesteric alkenyloxy group diaminobenzene, diaminobenzoic acid cholesteric Arrcostab, diaminourea Benzoic acid cholestene base ester, diaminobenzoic acid lanostane base ester, 3,6- double (4- aminobenzoics acyloxy) cholestane, 3,6- Double (4- amino-benzene oxygens) cholestane, 1,1- double (4- ((aminophenyl) methyl) phenyl) -4- butyl cyclohexanes, 2,5- diaminos Base-N, N- diallyl aniline, following formula (E-1).
[changing 13]
(in formula (E-1), XIAnd XIIIt is separately singly-bound ,-O- ,-COO- or-OCO-, RIFor the alkane two of carbon number 1~3 Base, RIIFor the alkane diyl of singly-bound or carbon number 1~3, the integer that a is 0 or 1, b are 0~2, c is 1~20 integer, and d is 0 or 1.Its In, become 0) during a and b differences
The side chain type diamines such as represented compound：
P-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diaminourea hexichol Base thioether, 4- aminophenyls -4 '-Aminobenzoate, 4,4 '-chrysoidine, 3,5- diaminobenzoic acids, 1,5- are double (4- amino-benzene oxygens) pentane, double [2- (4- aminophenyls) ethyl] hexane diacid, double (4- aminophenyls) amine, the double (4- of N, N- Aminophenyl) methyl amine, DAP, Isosorbide-5-Nitrae-bis--(4- aminophenyls)-piperazine, N, N '-bis- (4- aminophenyls)- Benzidine, 2,2 '-dimethyl -4,4 '-benzidine, 2,2 '-bis- (trifluoromethyl) -4,4 '-benzidine, 4,4 '-two Double [4- (4- amino-benzene oxygens) phenyl] propane of aminodiphenyl base ether, 2,2-, 4,4 '-(phenylenediisopropylidene) dianils, Isosorbide-5-Nitrae-bis- (4- amino-benzene oxygens) benzene, 4- (4- amino-benzene oxygens carbonyl) -1- (4- aminophenyls) piperidines, 4,4 '-[4,4 '-the third Alkane -1,3- diyl is double (piperidines-Isosorbide-5-Nitrae-diyl)] non-side chain type diamine such as diphenylamines；
Diaminourea organosiloxane can for example be enumerated：1,3- double (3- aminopropyls)-tetramethyl disiloxanes etc.；Except this with Outside, the diamines described in Japanese Patent Laid-Open 2010-97188 publications can be used.In addition, used in the synthesis of polymer (P) Diamine compound can be with the base with reactive base as substituent.
The diamine compound used in the synthesis of polymer (P) is preferably comprising the p-phenylenediamine in these, 4,4 '-diamino Base diphenyl methane and 4,4 '-diamino-diphenyl ethane at least any one.In addition, as synthetic polymer (P), two aminations Compound, which can be used alone, one kind or to be used in combination of two or more.
[reaction of tetracarboxylic acid derivatives and diamine compound]
The reaction of tetracarboxylic acid derivatives and diamine compound can be according to used tetracarboxylic acid derivatives and by organic chemistry Well-established law proper combination and carry out.
For example, in the case where tetracarboxylic acid derivatives are tetracarboxylic acid acid diesters, it is available to make tetracarboxylic acid acid diesters and two amine compounds Thing is preferably the method reacted in organic solvent, in the presence of appropriate dehydration catalyst.It is de- as what is used in reaction Water catalyst, such as can enumerate：Halogenation 4- (4,6- dimethoxys -1,3,5-triazines -2- bases) -4- methyl morpholines, carbonylic imidazole, Dicyclohexylcarbodiimide, phosphorus system condensing agent etc..Relative to 1 mole of tetracarboxylic acid acid diesters, the use ratio of these dehydration catalysts Example is preferably to be set to 2 moles~3 moles, is more preferably set to 2 moles~2.5 moles.
In addition, in the case where tetracarboxylic acid derivatives are tetracarboxylic acid acid diesters dihalide, it is available to make tetracarboxylic acid acid diesters two The method that halide preferably reacts with diamine compound in organic solvent, in the presence of appropriate alkali.As in reaction The alkali used, such as can enumerate：The tertiary amines such as pyridine, triethylamine；Sodium hydride, hydrofining, sodium hydroxide, potassium hydroxide, sodium, potassium Deng alkali metal class etc..Relative to 1 mole of diamine compound, the use ratio of alkali is preferably to be set to 2 moles~4 moles, more preferably To be set to 2 moles~3 moles.In addition, for the purpose for promoting reaction to carry out, tetracarboxylic acid acid diesters dihalide and diamine compound Reaction can carry out in the presence of a lewis acid.As lewis acid, such as lithium halides such as lithium chloride etc. can be enumerated.
In the reaction of tetracarboxylic acid derivatives and diamine compound, tetracarboxylic acid derivatives and diamine compound for reaction Use ratio is preferably relative to the equivalent of amino 1 of diamine compound, the possessed base related to reaction of tetracarboxylic acid derivatives “-COX4(X4For hydroxyl or depart from base) " turn into the ratio of the equivalent of 0.2 equivalent~2.Reaction temperature is preferably -30 DEG C~150 DEG C, Reaction time is preferably 0.1 hour~48 hours.
As the organic solvent used in reaction, such as can enumerate：Aprotic polar solvent, ketone, ester, ether, halogenated hydrocarbon, Hydrocarbon etc..In these organic solvents, it is preferable to use selected from the group being made up of aprotic polar solvent, (the first group has Machine solvent) one or more of, or the organic solvent selected from the first group more than one with selected from by ketone, ester, ether, halogenation The mixture of one or more of group's (organic solvent of the second group) that hydrocarbon and hydrocarbon are formed.In the latter case, phase The total amount of the organic solvent of organic solvent and the second group for the first group, the use ratio of the organic solvent of the second group Example is preferably below 50 mass %, more preferably below 40 mass %, and then preferably below 30 mass %.
Particularly preferred organic solvent is preferably that will be selected from by METHYLPYRROLIDONE, DMA, N, Dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, HMPA, metacresol, xylenol and halogen Change one or more of group that phenol is formed and be used as solvent, or the one of these organic solvents are used in the range of the ratio Plant the mixture above with other organic solvents.The usage amount (a) of organic solvent is preferably set to the conjunction of the monomer used in reaction Metering (b) becomes the mass % of 0.1 mass %~50 amount relative to the total amount (a+b) of reaction solution.
(end modified dose)
As synthetic polymer (P), by using tetracarboxylic acid derivatives and diamine compound and the end with feature base Terminal modified dose, as polymer (P), can obtain with the part-structure represented by the formula (1) and polymer ends with The polymer of feature base.In this case, polymer described later (Q) is set to contain with polymer (P) in the feelings of aligning agent for liquid crystal Under condition, it can further improve the coating of aligning agent for liquid crystal, for the aspect preferably.
As end modified dose, such as can enumerate：Monoester anhydride, single carbon acyl chlorides, monoamine compound, monoisocyanate compound Deng.As the end modified dose of feature having base, such as can enumerate：The reactive base, mercapto, the amino through protection Deng.
As such a end modified dose of concrete example, can enumerate：(methyl) acryloyl chloride, 2- furans phosgene, furfuryl group amine, 2- aminoothyl mercaptans, 3- amino propyl mercaptans, N- (tert-butoxycarbonyl)-EDA, N- (tert-butoxycarbonyl) -1, 3- diaminopropanes etc..In addition, end modified dose can be used alone and one kind or be used in combination of two or more.
In the synthesis, relative to total 100 molar parts of used diamine compound, end modified dose of use Ratio is preferably to be set to below 20 molar parts, is more preferably set to the molar part of 0.001 molar part~10.
Polymer (P) is comprising at least one of the respective represented compound of the formula (1-1) and the formula (1-2) The reaction product of tetracarboxylic acid derivatives and diamine compound.The reaction product can be only to have the structure from tetracarboxylic acid derivatives The polymer of unit and construction unit from diamine compound, also can and then have and the structure list from tetracarboxylic acid derivatives The different other parts structure of first and from diamine compound construction unit.As other parts structure, such as source can be enumerated From described end modified dose part-structure etc..
As more than, the reaction solution that will be formed as the polymer of poly amic acid ester (P) dissolving can be obtained.The reaction is molten Liquid can directly for aligning agent for liquid crystal preparation, also can be after by poly amic acid ester separation contained in reaction solution for liquid crystal The preparation of alignment agent.Poly amic acid ester can only have amic acid esters structure or amic acid structure and amic acid esters structure And the partial esterification thing deposited.In addition, the synthetic method of poly amic acid ester is not limited to described, such as it can also be used and make polyamic acid Method reacted with the alcohols with reactive base or halogenated alkyl etc. and obtain.
The polymer (P) obtained in this way is preferably when being made into the solution that concentration is 15 mass %, is had 20mPas~1,800mPas solution viscosity person, more preferably with 50mPas~1,500mPas solution viscosity Person.In addition, the solution viscosity (mPas) of polymer (P) is to use E type rotation viscometers, to using the good molten of polymer (P) Matchmaker's (such as gamma-butyrolacton, METHYLPYRROLIDONE etc.) and prepare concentration be 15 mass % polymer solution, 25 Value obtained by being measured at DEG C.
Polymer (P) is surveyed using gel permeation chromatography (gel permeation chromatography, GPC) The weight average molecular weight (Mw) of fixed polystyrene conversion is preferably 1,000~500,000, more preferably 2, and 000~300, 000.In addition, the molecule represented by the ratio for the number average molecular weight (Mn) that Mw and the polystyrene determined using GPC are converted Amount distribution (Mw/Mn) is preferably less than 7, and more preferably less than 5.By in such a molecular weight ranges, it can be ensured that liquid crystal cell Good orientation and stability.
Form the situation of film using the aligning agent for liquid crystal comprising polymer (P) by contrast, do not have with using only to include There is situation of the polymer of the part-structure represented by the formula (1) as the aligning agent for liquid crystal of component of polymer, having to press down Make by light orientation processing caused by analyte generation the advantages of.Speculate that its reason is：Think the cyclobutane ring in main chain Decomposed by the back reaction of [2+2], and carry out it is degraded, thus to film assign anisotropy, now pass through reaction Property base reaction and can make substantially caused by analyte combined with the composition in film, so as to reduce the generation of analyte.Its In, the content not carries out any restriction only to speculate to content of this disclosure.
《Other compositions》
<Polymer (Q)>
The aligning agent for liquid crystal of the disclosure can only contain polymer (P) and be used as component of polymer, also can contain polymer (P) with Selected from least one of the group being made up of polyamic acid and polyimides polymer (Q).Speculate using containing polymerization The aligning agent for liquid crystal of thing (P) and polymer (Q) and in the case of forming film on substrate, because surface energy it is different can make Polymer (P) is inclined to the outer layer for being present in film, thus can further improve liquid crystal aligning and AC image retention characteristics.
(polyamic acid)
Polyamic acid as polymer (Q) for example can be by making tetracarboxylic dianhydride be reacted with diamine compound to obtain. As the tetracarboxylic dianhydride and diamine compound used in reaction, the tetrabasic carboxylic acid two illustrated can be enumerated in polymer (P) explanation Acid anhydride and diamine compound etc..
For the synthetic reaction of polyamic acid tetracarboxylic dianhydride and diamine compound use ratio be preferably relative to The equivalent of amino 1 of diamine compound, the anhydride group of tetracarboxylic dianhydride turn into the ratio of the equivalent of 0.2 equivalent~2, more preferably turned into The ratio of the equivalent of 0.3 equivalent~1.2.The synthetic reaction of polyamic acid is preferably to be carried out in organic solvent.Reaction temperature now Degree is preferably -20 DEG C~150 DEG C, and the reaction time is preferably 0.1 hour~24 hours.Containing polyamic acid as polymer (Q) in the case of, the effect as caused by polymer (P) allotment can be obtained, and can further improve printing, with regard to the side For face preferably.
(polyimides)
Polyimides as polymer (Q) can for example be closed by the way that the polyamic acid synthesized as described is carried out into dehydration Ring, and be subject to imidizate and obtain.Polyimides can be using amic acid knot possessed by the polyamic acid as its precursor Structure all carries out complete acid imide compound obtained by dehydration closed-loop or is only dehydrated a part for amic acid structure Closed loop and the part acid imide compound for making amic acid structure and imide ring structure and depositing.Used in the preparation of aligning agent for liquid crystal The acid imide rate of polyimides is preferably more than 20%, and more preferably 30%~99%, and then preferably 40%~99%.Should Acid imide rate is to represent quantity of the quantity of imide ring structure relative to the amic acid structure of polyimides with percentage With the quantity of imide ring structure it is total for shared ratio.Herein, a part of of imide ring can be different acid imide Ring.
The dehydration closed-loop of polyamic acid is preferably using the method heated to polyamic acid or utilized polyamic acid It is dissolved in organic solvent, dehydrating agent and dehydration closed-loop catalyst, the method optionally heated is added in the solution Come carry out.In described, method described later is preferably utilized.
In the method that dehydrating agent and dehydration closed-loop catalyst are added into the solution of polyamic acid, as dehydrating agent, such as The acid anhydrides such as acetic anhydride, propionic andydride, TFAA can be used.Relative to 1 mole of the amic acid structure of polyamic acid, dehydrating agent Usage amount is preferably to be set to 0.01 mole~20 moles.As dehydration closed-loop catalyst, such as can be used：Pyridine, collidine (collidine), the tertiary amine such as two picolins (lutidine), triethylamine.Relative to used 1 mole of dehydrating agent, dehydration The usage amount of ring-closing catalyst is preferably to be set to 0.01 mole~10 moles.It is organic molten as what is used in dehydration closed-loop reaction Matchmaker, the compound used can be enumerated in the reaction as tetracarboxylic acid acid diesters and diamines and the organic solvent illustrated.Dehydration closed-loop is anti- The reaction temperature answered is preferably 0 DEG C~180 DEG C, and the reaction time is preferably 1.0 hours~120 hours.Make containing polyimides In the case of for polymer (Q), the effect as caused by polymer (P) allotment can be obtained, and can further improve electric spy Property, for the aspect preferably.
Polymer (Q) is preferably when being made into the solution that concentration is 15 mass %, has 20mPas~1, 800mPas solution viscosity person, more preferably with 50mPas~1,500mpas solution viscosity person.In addition, polymerization The solution viscosity (mPas) of thing (Q) is to use E type rotation viscometers, to good solvent (such as γ-fourth using polymer (Q) Lactone, METHYLPYRROLIDONE etc.) and the concentration of preparation is 15 mass % polymer solution, is measured at 25 DEG C Obtained by value.
The weight average molecular weight (Mw) of the polystyrene determined using GPC the conversion of polymer (Q) is preferably 1,000 ~500,000, more preferably 2,000~300,000.In addition, the quantity of polystyrene conversions of the Mw with being determined using GPC is put down Molecular weight distribution (Mw/Mn) represented by the ratio of average molecular weight (Mn) is preferably less than 7, and more preferably less than 5.
In the case where the aligning agent for liquid crystal of the disclosure contains polymer (Q), relative to polymer (P) and polymer (Q) Total 100 mass parts, the content ratio of polymer (P) is preferably to be set to more than 3 mass parts, is more preferably set to 5 mass parts ~95 mass parts, and then be preferably to be set to the mass parts of 10 mass parts~90, particularly preferably it is set to the mass parts of 15 mass parts~85. In addition, polymer (P) and polymer (Q) be able to can be also used in combination of two or more individually using one kind.
The aligning agent for liquid crystal of the disclosure is containing the composition beyond polymer (Q) as other compositions.As other compositions, Such as it can enumerate：Polymer (hereinafter referred to as " other polymers ") beyond polymer (P) and polymer (Q), have in intramolecular There are the compound (hereinafter referred to as " compound containing epoxy radicals "), functional silanes compound, photopolymerization of at least one epoxy radicals Property compound, antioxidant, metal complex compounds, hardening accelerator, crosslinking agent, imidizate accelerator, surfactant, Filler, dispersant, light sensitizer, acid producing agent, alkali producing agent, free-radical generating agent etc..The aligning agent for liquid crystal of the disclosure is excellent Elect as containing polymer (P) with being selected from by functional silanes compound, acid producing agent, alkali producing agent and free-radical generating agent institute group Into at least one of group.
(other polymers)
Other polymers can be used for improving solution properties or electrical characteristic.As the other polymers, such as can enumerate： With polysiloxane, polyester, polyamide, cellulose derivative, polyacetals, polystyrene derivative, poly- (styrene-phenyl Maleimide) derivative, poly- (methyl) acrylate etc. be polymer of main framing etc..Relative to being adjusted in aligning agent for liquid crystal Total 100 mass parts for the polymer matched somebody with somebody, the allotment ratio of other polymers are preferably to be set to below 50 mass parts, more preferably It is set to below 30 mass parts, and then is preferably to be set to below 20 mass parts.
(compound containing epoxy radicals)
Compound containing epoxy radicals can be used for the adherence or electrical characteristic with substrate surface for improving liquid crystal orientation film.Make For such a compound containing epoxy radicals, such as can enumerate：Ethylene glycol diglycidylether, propylene glycol diglycidylether, 1,6- Hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, N, N, N ', N '-four glycidyl group-isophthalic diformazan Amine, 1,3- couples of (N, N- diglycidyl amino methyl) hexamethylenes, N, N, N ', N '-four glycidyl group -4,4 '-diaminourea Diphenyl methane, N, N, N ', N '-four (2- hydroxyethyls) ethylenediamine, N, N- diglycidyl-benzyl amine, N, N- bis- shrink Glyceryl-aminomethyl cyclohexane, N, N- diglycidyls-cyclo-hexylamine etc..In addition, as the chemical combination containing epoxy radicals The example of thing, the polysiloxane containing epoxy radicals described in International Publication No. 2009/096598 can be used.Ring will contained In the case that the compound of epoxide is added in aligning agent for liquid crystal, relative to the total of polymer contained in aligning agent for liquid crystal 100 mass parts, the allotment ratio are preferably to be set to below 50 mass parts, are more preferably set to the mass parts of 0.1 mass parts~30.
(functional silanes compound)
Functional silanes compound can be used for the purpose of the raising of the printing of aligning agent for liquid crystal.As such a function Property silane compound, such as can enumerate：3- TSL 8330s, APTES, N- (2- ammonia Base ethyl) -3- TSL 8330s, 3- ureidopropyltriethoxysilanes, N- ethoxy carbonyl -3- aminopropyls Trimethoxy silane, 10- trimethoxy silanes base-Isosorbide-5-Nitrae, the azepine decane of 7- tri-, N- benzyl -3- aminopropyl trimethoxy silicon Alkane, N- phenyl -3- TSL 8330s, 3- glycidoxypropyls diethoxy silane, 2- shrink sweet Oily epoxide ethyl trimethoxy silane, 3- glycidoxypropyltrimewasxysilanes etc..By functionality silane compound In the case of added in aligning agent for liquid crystal, relative to total 100 mass parts of polymer, the allotment ratio is preferably 5 matter Measure below part, the mass parts of more preferably 0.02 mass parts~3, the mass parts of and then preferably 0.1 mass parts~2.
(acid producing agent)
As acid producing agent, can suitably be selected in known compound from as by heat or light producing the compound of acid Select to use.Specifically, as thermal acid generator, such as can enumerate：Diphenyl iodine fluoroform sulphonate, double (4- tert-butyl groups Phenyl) salt compounded of iodine such as iodine fluoroform sulphonate etc., as light acid producing agent, such as can enumerate：Triphenylsulfonium triflate sulfonate etc. Sulfonium salt；The thiophane salt such as 1- (4- n-butoxy naphthalene -1- bases) thiophane fluoroform sulphonate；N- (trifluoro methylsulfonyls Epoxide) the N- sulfonyloxyimide compounds such as bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides etc..Produced by acid In the case that agent is added in aligning agent for liquid crystal, relative to total 100 mass parts of polymer, the allotment ratio is preferably 50 Below mass parts, the mass parts of more preferably 0.1 mass parts~30.
(alkali producing agent)
As alkali producing agent, can suitably be selected in known compound from as by heat or light producing the compound of alkali Select to use.Specifically, such as it can be used imidazoles system thermokalite producing agent；Adjacent nitro Benzylcarbamate system, α, alpha, alpha-dimethyl Base -3,5- Dimethoxybenzylamino formic acid esters system, the light alkali producing agent etc. of acyloxy imido base system.Added by alkali producing agent In the case of into aligning agent for liquid crystal, relative to total 100 mass parts of polymer, the allotment ratio is preferably 50 mass parts Hereinafter, the mass parts of more preferably 0.1 mass parts~30.
(free-radical generating agent)
As free-radical generating agent, the compound of free radical can be produced and known compound from as by heat or light In suitable selection use.Specifically, as hot radical producing agent, such as can enumerate：TBHP, peroxidating The peroxide such as tert-butyl acetate；Azobis isobutyronitrile (azobisisobutyronitrile, AIBN), 2,2 '-azo are double (different Butyronitrile) etc. azo-compound；Redox series initiators etc.；As optical free radical producing agent, such as can enumerate：Acetophenone, 1- Hydroxycyclohexylphenylketone, fluorenes, triphenylamine, 3- methyl acetophenones, 4,4 '-dimethoxy-benzophenone, 2- benzyl -2- diformazans Base amino -1- (4- morpholino phenyls)-butanone-Isosorbide-5-Nitrae-(2- hydroxyl-oxethyls) phenyl-(2- hydroxyl -2- propyl group) ketone etc..To In the case that free-radical generating agent is added in aligning agent for liquid crystal, relative to total 100 mass parts of polymer, the allotment ratio Example is preferably the mass parts of more preferably 0.1 mass parts~30 below 50 mass parts.
<Solvent>
The other compositions that the aligning agent for liquid crystal of the disclosure is with polymer (P) and optionally and used be preferably it is scattered or The form of the composition of the liquid formed in appropriate solvent is dissolved in prepare.
As used organic solvent, such as can enumerate：METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones, 1,2- dimethyl -2- imidazolidinones, butyl- butyrolactone, butyrolactam, DMF, N, N- dimethylacetamides Amine, 4- hydroxy-4-methyl-2-pentanones, glycol monoethyl ether, butyl lactate, butyl acetate, methoxy methyl propionate, ethyoxyl Ethyl propionate, 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 Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, DIBK, third Isoamyl valerate, isoamyl isobutyrate, isoamyl ether, ethylene carbonate, propylene carbonate etc..These can be used alone or by two Kind use mixed above.
(total quality of the composition beyond the solvent of aligning agent for liquid crystal is in liquid crystal for solid component concentration in aligning agent for liquid crystal Shared ratio in the gross mass of alignment agent) it is to consider viscosity, volatility etc. and suitably select, the matter of preferably 1 mass %~10 Measure % scope.That is, as described below, aligning agent for liquid crystal is coated on substrate surface, is preferably heated, is consequently formed Film as liquid crystal orientation film or the film as liquid crystal orientation film.Now, in solid component concentration less than 1 mass %'s In the case of, the thickness of film becomes too small and is difficult to obtain good liquid crystal orientation film.On the other hand, surpass in solid component concentration In the case of crossing 10 mass %, the thickness of film becomes too much and is difficult to obtain good liquid crystal orientation film, in addition, there is liquid crystal to take Increase and the tendency of coating decline to the viscosity of agent.
Add up to 100 mass parts relative to the solid constituent (composition beyond solvent) in aligning agent for liquid crystal, the disclosure The content ratio of polymer (P) in aligning agent for liquid crystal is preferably more than 3 mass parts, more preferably more than 5 mass parts, Jin Eryou Elect as more than 10 mass parts.
《Liquid crystal orientation film and liquid crystal cell》
The liquid crystal orientation film of the disclosure is formed using the aligning agent for liquid crystal prepared as described.In addition, the liquid of the disclosure Crystal cell possesses the liquid crystal orientation film formed using the aligning agent for liquid crystal of the middle explanation.The running of liquid crystal in liquid crystal cell Pattern is not particularly limited, such as can be applied to twisted nematic (Twisted Nemafic, TN) type, STN Super TN (Super Twisted Nematic, STN) type, vertical orientated (Vertical Alignment, VA) type (hang down comprising vertical orientated-multiple domain Straight orientation (Vertical Alignment-Multi-domain Vertical Alignment, VA-MVA) type, it is vertical orientated- Vertical orientated (Vertical Alignment-Patterned Vertical Alignment, VA-PVA) type of pattern etc.), altogether Face switching (In-Plane Switching, IPS) type, fringing field switching (fringe field switching, FFS) type, light The various patterns such as compensated bend (Optically Compensated Bend, OCB) type.Liquid crystal cell is for example available to be included The method of following step 1~step 3 manufactures.Step 1 uses different substrates according to required operating mode.Step 2 And step 3 is common in each operating mode.
(step 1：The formation of film)
The coating of liquid crystalline alignment agent first on substrate, is preferably heated to coated face, is thus formed and applied on substrate Film.As substrate, such as can be used：The glass such as float glass (float glass), soda-lime glass (soda glass)；Comprising poly- The plastics such as PETP, polybutylene terephthalate, polyether sulfone, makrolon, poly- (ester ring type alkene) it is saturating Bright substrate.As the nesa coating for the one side for being arranged at substrate, it can be used and include 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..It is patterned using being provided with the case of manufacture TN types, STN types or VA type liquid crystal cells Two pieces of substrates of nesa coating.On the other hand, in the case of manufacture IPS types or FFS type liquid crystal cells, using being provided with The substrate of electrode comprising the patterned nesa coating for interdigitated electrode structure or metal film, be not provided with electrode to base Plate.As metal film, such as the film for including the metals such as chromium can be used.Coating towards the aligning agent for liquid crystal on substrate is in electrode shape Into on face, carried out preferably by lithographic methods, spin-coating method, roll coater method or ink jet printing method.
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 pre- Heat (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.So Afterwards, solvent is removed completely, it is real optionally for the purpose of carrying out hot-imide to amic acid structure present in polymer Apply calcining (rear baking) step.Calcining heat (rear baking temperature) now is preferably 80 DEG C~300 DEG C, and post-bake times are preferred For 5 minutes~200 minutes.The thickness of the film formed in this way is preferably 0.001 μm~1 μm.By being coated with substrate After aligning agent for liquid crystal, organic solvent is removed to form liquid crystal orientation film or the film as liquid crystal orientation film.
(step 2：Orientation process)
In the case of manufacture TN types, STN types, IPS types or FFS type liquid crystal cells, the painting to being formed in the step 1 Film is implemented to assign the processing (orientation process) of liquid crystal aligning ability.Thus, the alignment capability of liquid crystal molecule is imparted on film And turn into liquid crystal orientation film.As orientation process, can enumerate：The fiber such as nylon, artificial silk, cotton is included using being wound with The roller of cloth, film is rubbed towards fixed-direction, the friction treatment of liquid crystal aligning ability is thus assigned to film；To being formed at Film on substrate carries out light irradiation and light orientation processing of liquid crystal aligning ability etc. is assigned to film.Particularly, polymer (P) Photo sensitivity it is high, even if can also make film show anisotropy with few light exposure, therefore preferably apply optical alignment method. On the other hand, in the case where manufacturing vertical alignment-type liquid crystal element, the film formed in the step 1 can be directly used as liquid Brilliant alignment films, but orientation process can also be implemented to the film.
Light irradiation in light orientation processing can be carried out using following methods：Film after rear baking procedure is irradiated Method；The method being irradiated to the film after pre-bake step and before rear baking procedure；In pre-bake step and rear baking At least in any one of step, method being irradiated in the heating process of film to film etc..In light orientation processing, as The radioactive ray being irradiated to film, such as the ultraviolet and luminous ray of the light comprising wavelength 150nm~800nm can be used. The preferably ultraviolet of the light comprising wavelength 200nm~400nm.Can be linear polarization in the case where radioactive ray are polarisation It can be part polarisation.In addition, in the case where used radioactive ray are linear polarization or part polarisation, can be from vertical direction Real estate is irradiated, real estate can be also irradiated from incline direction, or these can be also combined to carry out. In the case of the radioactive ray of irradiation non-polarized, the direction of irradiation is set to incline direction.
As used light source, such as can be used：Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halide lamp, Argon resonance lamp, xenon lamp, PRK etc..The exposure of radioactive ray is preferably 400J/m2~50,000J/m2, more preferably 1, 000J/m2~20,000J/m2., can be while carrying out heating to film while carrying out the illumination to film in order to improve reactivity Penetrate.
After the light irradiation assigned for alignment capability, it can carry out for example using water, organic solvent (for example, methanol, 1- first Epoxide -2- propanol acetates, butyl cellosolve, ethyl lactate etc.) or these mixture substrate surface is cleaned Processing or the processing heated to substrate.In the case where the aligning agent for liquid crystal using the disclosure forms film, even if Do not implement such a cleaning treatment or heating, can obtain the good liquid crystal cell of display performance yet, and can realize that cost is reduced, For the aspect preferably.
(step 3：Liquid crystal cells are constructed)
By preparing two pieces of substrates formed with liquid crystal orientation film in this way, match somebody with somebody between two pieces of oppositely disposed substrates Liquid crystal is put to manufacture liquid crystal cells.When manufacturing liquid crystal cells, such as following methods can be enumerated：(1) with liquid crystal orientation film to Mode, it is across gap (sept) that two pieces of substrates are oppositely disposed, the periphery of two pieces of substrates is bonded using sealant, After injecting filling liquid crystal in substrate surface and the cell gap divided by sealant, by the method for hand-hole sealing；(2) in shape Sealant is coated with into the predetermined portion on one of substrate of liquid crystal orientation film, and then as defined on liquid crystal aligning film surface After liquid crystal is added dropwise in several positions, by liquid crystal orientation film to being bonded another piece of substrate in a manner of, and by liquid crystal in the whole of substrate Method (instil (One Drop Fill, ODF) mode) spread out on individual face etc..Preferably manufactured liquid crystal cells are entered And untill liquid crystal used in being heated to takes the temperature of isotropic phase, thus then slow cooling removes liquid crystal untill room temperature Flow orientation during filling.
As sealant, such as usable epoxy resin of alumina balls containing curing agent and as sept etc.. As sept, light spacer (photospacer), pearl sept (beads spacer) etc. can be used., can as liquid crystal Nematic liquid crystal (nematic liquid crystal) and smectic liquid crystal (smectic liquid crystal) are enumerated, wherein Preferably nematic liquid crystal, such as can be used：Schiff bases (Schiffbase) are that liquid crystal, azoxy (azoxy) are liquid crystal, biphenyl Be liquid crystal, cyclohexylbenzene system liquid crystal, ester system liquid crystal, terphenyl (terphenyl) be liquid crystal, biphenyl butylcyclohexane system liquid crystal, Liquid crystal, dioxanes system of pyrimidine system liquid crystal, double-octane system liquid crystal, cubane (cubane) are liquid crystal etc..Alternatively, it is also possible at this Such as cholesteric crystal (cholesteric liquid crystal), chiral agent, ferroelectric liquid crystal are added in a little liquid crystal (ferroelectric liquid crystal) etc. is used.
Then, it is bonded Polarizer if necessary in the outer surface of liquid crystal cells and liquid crystal cell is made., can as Polarizer Enumerate：With the clamping of cellulose acetate diaphragm be referred to as Polarizer that the light polarizing film of " H films " forms or comprising H films itself Polarizer, " the H films " are to make polyvinyl alcohol extension orientation while making it absorb the film that iodine forms.
The liquid crystal cell of the disclosure can be effectively applied to various uses, such as can be used in：Clock and watch, portable game Machine, word processor (word processor), notes type personal computer (note type personal computer), Auto-navigation system (car navigation system), video camera (camcorder), personal digital assistant (Personal Digital Assistant, PDA), digital camera (digital camera), mobile phone, smart mobile phone, various monitors, liquid The various display devices or light modulation film etc. such as brilliant television set, information display (information display).In addition, may be used also The liquid crystal cell that aligning agent for liquid crystal using the disclosure is formed is applied to phase retardation film.
[embodiment]
Hereinafter, the present invention is further specifically described by embodiment, but the present invention is not limited to these realities Apply example.
In following example, the molecular weight of polymer is determined using following methods.
[molecular weight of polymer]
The number average molecular weight of polystyrene conversion is determined using the gel permeation chromatography (GPC) under the conditions of following (Mn) and weight average molecular weight (Mw), and molecular weight distribution (Mw/Mn) is obtained.
Determine device：Eastern Cao's (Tosoh) (stock) manufacture, HLC-8020
Tubing string：Eastern Cao's (stock) manufacture, TSK guardcolumn α, TSK gel α-M and TSK gel α -2500 are connected and connected Connect and use
Deploy solvent：It is molten dissolved with lithium bromide monohydrate 9.4g and phosphatase 11 .7g relative to dimethylformamide 3L Liquid
Temperature：35℃
Flow velocity：1.0mL/min
The structure of the main compound used in following example and contracted notation are as described below.
(tetracarboxylic dianhydride)
TA-1：1,2,3,4- butane tetracarboxylic acid dianhydride
TA-2：1,2,3,4- cyclobutane tetracarboxylic dianhydride
TA-3：(1R, 2R, 3S, 4S) -1,3- dimethylcyclobutanes -1,2,3,4- tetracarboxylic dianhydrides
TA-4：Anti-form-1,2,3,4- pentamethylene tetracarboxylic dianhydrides
TA-5：2,3,5- tricarboxylic cyclopentyl acetic acid dianhydrides
TA-6：Pyromellitic acid anhydride
[changing 14]
(diamines)
DA-1：P-phenylenediamine
DA-2：4,4 '-diaminodiphenyl-methane
DA-3：4,4 '-second diphenylamines
DA-4：2,2 '-dimethyl -4,4 '-benzidine
DA-5：N- (tert-butoxycarbonyl) -2,5- diaminourea benzyl amine
DA-6：4- amino-N- (4- aminophenyls)-N- (tert-butoxycarbonyl) benzamide
DA-7：4,4 '-diamino-diphenyl amine
DA-8：4,4 '-diamino-N 4, N4 '-bis- (4- aminophenyls)-N4, N4 '-dimethyl diphenyl
DA-9：N-2- (4- aminophenylethyls)-N- methyl amines
DA-10：6,6 '-(piperazine-Isosorbide-5-Nitrae-diyl)-bis- (pyridine -3- amine)
DA-11：Isosorbide-5-Nitrae-sub- phenoxy group-bis- (PABA ester)
DA-12：4- aminophenyls -3- (4- aminophenyls) -2- methacrylates
[changing 15]
(end modified dose)
EC-1：Methacrylic chloride
EC-2：2- furans phosgenes
EC-3：Furfuryl group amine
EC-4：2- aminoothyl mercaptans
EC-5：N- (tert-butoxycarbonyl)-EDA
[changing 16]
(imidizate accelerator)
I-1：3- (2- hydroxy phenyls)-N- (pyridin-3-yl methyl) propionamide
I-2：N- α-(9- fluorenylmethoxycarbonyl groups)-N- (tert-butoxycarbonyl)-L-Histidine
(functional silanes compound)
s-1：3- glycidoxypropyl diethoxy silanes
(compound containing epoxy radicals)
CL-1：N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenyl-methane
CL-2：N, N, N ', N '-four (2- hydroxyethyls) ethylenediamine
(dehydration catalyst)
DMT-MM：Chlorination 4- (4,6- dimethoxys -1,3,5-triazines -2- bases) -4- methyl morpholines
(solvent)
NMP：METHYLPYRROLIDONE
γBL：Gamma-butyrolacton
BC：Butyl cellosolve
[embodiment 1a]
22.42g is put into the three-necked flask for the 200mL for possessing nitrogen ingress pipe, backflow cooling tube and thermometer TA-3, the 100mL of (100mmol) tetrahydrofuran, 0.79g (10.0mmol) pyridine, are stirred and make under nitrogen flowing It suspends.Beta-methyl allyl alcohol 15.14g (210mmol) is added into the suspension, is stirred at room temperature 2 hours.And then Reacted 8 hours at 60 DEG C and obtain the solution of water white transparency.The reaction solution is concentrated under reduced pressure at 60 DEG C, and then carried out Vacuum drying, so as to obtain the mixed of the compound represented by the compound and following formula (DE-1b) represented by following formula (DE-1a) Compound (hereinafter referred to as DE-1a/b) 36.84g.
[changing 17]
[embodiment 2a]
It is put into 18.42g's (50.0mmol) into the eggplant type flask for the 100mL for possessing nitrogen ingress pipe and the cooling tube that flows back DE-1a/b, 100mL toluene, stirred 30 minutes at 80 DEG C.Then, room temperature is cooled to when stirring, and then in room temperature Lower stirring 30 minutes.The suspension obtained is filtered, cleaned 2 times with toluene 5mL.Solid at 60 DEG C to being obtained It is dried in vacuo, obtains the DE-1a 15.47g (42.0mmol, yield 84%) of white powder.
[embodiment 3a]
14.74g is put into the three-necked flask for the 500mL for possessing nitrogen ingress pipe, backflow cooling tube and thermometer DE-1a, the 80mL of (40.0mmol) heptane, 0.032g (0.40mmol) pyridine, are carried out under nitrogen flowing and at 75 DEG C Stirring.Spend 20 minutes and thionyl chloride 14.28g (120mmol) is slowly added dropwise, and confirm the bubbling of the progress with reaction.Drop After adding end, it is set to be reacted 2 hours at 75 DEG C and obtain the solution of water white transparency.The reaction solution is subtracted at 60 DEG C Pressure, which is concentrated and distilled, removes superfluous thionyl chloride.Heptane 80mL is added into the liquid obtained and is stirred at room temperature Mix, separated out insoluble component is removed by filtering.The filtrate is concentrated under reduced pressure at 60 DEG C, and then under vacuo simultaneously Dried 4 hours at 60 DEG C, so as to obtain the compound 15.89g represented by the following formula of colourless transparent liquid (DC-1a) (39.2mmol, yield 98%).
[changing 18]
[embodiment 4a]
Beta-methyl allyl alcohol 15.14g (210mmol) is changed to furfuryl alcohol 20.60g (210mmol), in addition, Obtained in a manner of with embodiment 1a identicals represented by the compound and following formula (DE-2b) represented by following formula (DE-2a) Mixture (hereinafter referred to as DE-2a/b) 42.04g of compound.
[changing 19]
[embodiment 5a]
9.81g is put into the three-necked flask for the 100mL for possessing nitrogen ingress pipe, backflow cooling tube and thermometer TA-2, the 50mL of (50mmol) tetrahydrofuran, 0.40g (5.0mmol) pyridine, it is stirred under nitrogen flowing and makes it outstanding It is floating.2-hydroxyethyl methacrylate 13.66g (105mmol) is added into the suspension, is stirred at room temperature 2 hours.And then Reacted 24 hours at 40 DEG C and obtain the solution of water white transparency.The reaction solution is concentrated under reduced pressure at 40 DEG C, and then It is dried in vacuo, so as to obtain the compound represented by following formula (DE-3a) and the compound represented by following formula (DE-3b) Mixture (hereinafter referred to as DE-3a/b) 22.82g.
[changing 20]
[embodiment 6a]
Beta-methyl allyl alcohol 15.14g (210mmol) is changed to propargyl ethanol 11.77g (210mmol), except this with Outside, obtained in a manner of with embodiment 1a identicals represented by the compound and following formula (DE-4b) represented by following formula (DE-4a) Compound mixture (hereinafter referred to as DE-4a/b) 33.63g.
[changing 21]
[embodiment 7a]
Beta-methyl allyl alcohol 15.14g (210mmol) is changed to hydroxypropanone- 15.56g (210mmol), except this with Outside, obtained in a manner of with embodiment 1a identicals represented by the compound and following formula (DE-5b) represented by following formula (DE-5a) Compound mixture (hereinafter referred to as DE-5a/b) 37.23g.
[changing 22]
[embodiment 8a]
2-hydroxyethyl methacrylate 13.66g (105mmol) is changed to glycerine 1,2- carbonic esters 12.40g (105mmol), in addition, the compound represented by following formula (DE-6a) is obtained in a manner of with embodiment 5a identicals with State mixture (hereinafter referred to as DE-6a/b) 21.61g of the compound represented by formula (DE-6b).
[changing 23]
[synthesis example 9]
9.81g is put into the three-necked flask for the 100mL for possessing nitrogen ingress pipe, backflow cooling tube and thermometer The 1S of (50mmol), 2S, 4R, 5R- cyclopentanetetracarboxylics dianhydride, 50mL tetrahydrofuran, 0.40g (5.0mmol) pyridine, It is stirred under nitrogen stream and makes its suspension.Methanol 6.4g (200mmol) is added into the suspension, it is small to be stirred at room temperature 24 When and obtain the solution of water white transparency.The reaction solution is concentrated under reduced pressure at 60 DEG C, and then is dried in vacuo, so as to Obtain mixture (following, the title of the compound represented by following formula (DE-7a) and the compound represented by following formula (DE-7b) For DE-7a/b) 14.41g.
[changing 24]
[synthesis example 10]
Following formula (DE-8a) institute is synthesized according to the method described in the embodiment 4 of International Publication No. 2010/092989 The compound of expression.It is in addition, following to synthesize according to the method described in the embodiment 47 of International Publication No. 2010/092989 Compound represented by formula (DC-8a).
[changing 25]
[synthesis example 11]
1.63g is put into the eggplant type flask for the 50mL for possessing nitrogen ingress pipe, backflow cooling tube and thermometer 3, the 4- dihydrocoumarin of (11.0mmol), 1.08g (10.0mmol) 3- (amino methyl) pyridine, 10mL tetrahydrofuran, It is heated to reflux under nitrogen flowing and at 80 DEG C 3 hours.Heptane 40ml is added into the reaction solution and is separated out product and is gone forward side by side Row filtering.The solid obtained is cleaned using heptane, is dried under reduced pressure and is obtained 3- (2- hydroxy phenyls)-N- (pyridine -3- Ylmethyl) propionamide 2.51g (9.8mmol).
[changing 26]
[synthesis example 12]
N- (tert-butoxy carbonyls are synthesized according to the method described in the synthesis example 7 of International Publication No. 2011/115118 Base) -2,5- diaminourea benzyl amine.
[embodiment 1]
3.54g (9.6mmol) DE-1a/ is put into the three-necked flask for the 50mL for possessing nitrogen ingress pipe and thermometer B, 1.08g (10.0mmol) DA-1,31.0g NMP, 0.51g (5.0mmol) triethylamine, is cooled to about 10 DEG C, and add 8.30g (30.0mmol) DMT-MM as triazine system dehydrating condensation agent, under nitrogen flowing and react 24 hours at room temperature. The polymeric solution obtained is diluted using NMP, is slowly injected into methanol when stirring and makes its solidification.Recovery Solid through precipitation, and stirring and washing is repeated twice in methyl alcohol, it is dried in vacuo at 60 DEG C, so as to obtain white powder Poly amic acid ester (PAE-1).The number average molecular weight Mn of the polymer is 11,000, molecular weight distribution mw/mn 3.0.
[embodiment 2]
DE-1a/b is changed to DE-1a 3.54g (9.6mmol), in addition, obtained in the same manner as example 1 Obtain poly amic acid ester (PAE-2).The number average molecular weight Mn of the polymer is 12,000, molecular weight distribution mw/mn 4.1.
[embodiment 3]
DE-1a/b is changed to DE-1a 2.83g (7.68mmol) and DE-7a/b 0.553g (1.92mmol), except this with Outside, poly amic acid ester (PAE-3) is obtained in the same manner as example 1.The number average molecular weight Mn of the polymer is 21, 000, molecular weight distribution mw/mn 3.5.
[embodiment 4]
Be put into the three-necked flask for the 50mL for possessing nitrogen ingress pipe and thermometer 1.03g (9.5mmol) DA-1, 0.106g (0.50mmol) DA-3,20.0g NMP, it is cooled to about 10 DEG C and prepares diamine solution.Added into the solution DC-1a 3.89g (9.6mmol) are made to be dissolved in the acyl chlorides prepared in pyridine 1.90g (21.6mmol) and γ BL 20.0g in advance Solution, under nitrogen flowing and react 4 hours at room temperature.0.209g (2.0mmol) EC-1 is added into the polymeric solution, is entered And react 4 hours.The polymeric solution obtained is diluted using γ BL, deionized water is slowly injected into when stirring In and make its solidification.The solid through precipitation is reclaimed, and stirring and washing is repeated twice in isopropanol, vacuum is carried out at 60 DEG C and is done It is dry, so as to obtain the poly amic acid ester of white powder (PAE-4).The number average molecular weight Mn of the polymer is 8,000, molecule Amount distribution Mw/Mn is 2.1.
[embodiment 5]
Be put into the three-necked flask for the 50mL for possessing nitrogen ingress pipe and thermometer 0.973g (9.0mmol) DA-1, 0.327g (1.0mmol) DA-6,20.0g NMP, it is cooled to about 10 DEG C and prepares diamine solution.Added into the solution DC-1a 3.89g (9.6mmol) are made to be dissolved in the acyl chlorides prepared in pyridine 1.90g (21.6mmol) and γ BL 20.0g in advance Solution, under nitrogen flowing and react 4 hours at room temperature.0.261g (2.0mmol) EC-2 is added into the polymeric solution, is entered And react 4 hours.The polymeric solution obtained is diluted using γ BL, deionized water is slowly injected into when stirring In and make its solidification.The solid through precipitation is reclaimed, and stirring and washing is repeated twice in isopropanol, vacuum is carried out at 60 DEG C and is done It is dry, so as to obtain the poly amic acid ester of white powder (PAE-5).The number average molecular weight Mn of the polymer is 25,000, point Son amount distribution Mw/Mn is 4.5.
[embodiment 6]
4.04g (9.6mmol) DE-2a/ is put into the three-necked flask for the 50mL for possessing nitrogen ingress pipe and thermometer B, 0.995g (9.2mmol) DA-1,0.078g (0.8mmol) EC-3,31.0g NMP, 0.51g (5.0mmol) three second Amine, it is cooled to about 10 DEG C and adds 8.30g (30.0mmol) DMT-MM, under nitrogen flowing and reacts 24 hours at room temperature. The polymeric solution obtained is diluted using NMP, is slowly injected into methanol when stirring and makes its solidification.Recovery Solid through precipitation, and stirring and washing is repeated twice in methyl alcohol, it is dried in vacuo at 60 DEG C, so as to obtain white powder Poly amic acid ester (PAE-6).The number average molecular weight Mn of the polymer is 15,000, molecular weight distribution mw/mn 3.2.
[embodiment 7]
2.19g (4.8mmol) DE-3a/ is put into the three-necked flask for the 50mL for possessing nitrogen ingress pipe and thermometer B, 1.38g (4.8mmol) DE-8a, 1.08g (10.0mmol) DA-1,31.0g NMP, 0.51g (5.0mmol) three second Amine, it is cooled to about 10 DEG C and adds 8.30g (30.0mmol) DMT-MM, under nitrogen flowing and reacts 24 hours at room temperature. The polymeric solution obtained is diluted using NMP, is slowly injected into methanol when stirring and makes its solidification.Recovery Solid through precipitation, and stirring and washing is repeated twice in methyl alcohol, it is dried in vacuo at 60 DEG C, so as to obtain white powder Poly amic acid ester (PAE-7).The number average molecular weight Mn of the polymer is 18,000, molecular weight distribution mw/mn 1.8.
[embodiment 8]
3.23g (9.6mmol) DE-4a/ is put into the three-necked flask for the 50mL for possessing nitrogen ingress pipe and thermometer B, 0.995g (9.2mmol) DA-1,0.062g (0.8mmol) EC-4,31.0g NMP, 0.51g (5.0mmol) three second Amine, it is cooled to about 10 DEG C and adds 8.30g (30.0mmol) DMT-MM, under nitrogen flowing and reacts 24 hours at room temperature. The polymeric solution obtained is diluted using NMP, is slowly injected into methanol when stirring and makes its solidification.Recovery Solid through precipitation, and stirring and washing is repeated twice in methyl alcohol, it is dried in vacuo at 60 DEG C, so as to obtain white powder Poly amic acid ester (PAE-8).The number average molecular weight Mn of the polymer is 12,000, molecular weight distribution mw/mn 3.3.
[embodiment 9]
3.57g (9.6mmol) DE-5a/ is put into the three-necked flask for the 50mL for possessing nitrogen ingress pipe and thermometer B, 0.796g (7.36mmol) DA-1,0.437g (1.84mmol) DA-5,0.128g (0.80mmol) EC-5,31.0g NMP, 0.51g (5.0mmol) triethylamine, be cooled to about 10 DEG C and add 8.30g (30.0mmol) DMT-MM, in nitrogen Flow down and react 24 hours at room temperature.The polymeric solution obtained is diluted using NMP, slowly noted when stirring Enter into methanol and make its solidification.The solid through precipitation is reclaimed, and is repeated twice stirring and washing in methyl alcohol, is carried out at 60 DEG C Vacuum drying, so as to obtain the poly amic acid ester of white powder (PAE-9).The number average molecular weight Mn of the polymer is 12, 000, molecular weight distribution mw/mn 3.5.
[embodiment 10]
2.08g (4.8mmol) DE-6a/ is put into the three-necked flask for the 50mL for possessing nitrogen ingress pipe and thermometer B, 1.38g (4.8mmol) DE-8a, 0.796g (7.36mmol) DA-1,0.437g (1.84mmol) DA-5,0.128g EC-5, the 31.0g of (0.80mmol) NMP, 0.51g (5.0mmol) triethylamine, it is cooled to about 10 DEG C and adds 8.30g The DMT-MM of (30.0mmol), under nitrogen flowing and react 24 hours at room temperature.The polymeric solution obtained is entered using NMP Row dilution, is slowly injected into methanol when stirring and makes its solidification.The solid through precipitation is reclaimed, and is repeated in methyl alcohol Stirring and washing twice, it is dried in vacuo at 60 DEG C, so as to obtain the poly amic acid ester of white powder (PAE-10).The polymerization The number average molecular weight Mn of thing is 20,000, molecular weight distribution mw/mn 3.0.
[synthesis example 13]
Be put into the three-necked flask for the 50mL for possessing nitrogen ingress pipe and thermometer 1.08g (10.0mmol) DA-1, 16.0g NMP, it is cooled to about 10 DEG C and prepares diamine solution.Being added into the solution makes DC-8a 3.12g (9.6mmol) The solution of acid chloride prepared in pyridine 1.90g (21.6mmol) and γ BL 16.0g is dissolved in advance, under nitrogen flowing and in room The lower reaction of temperature 4 hours.The polymeric solution obtained is diluted using γ BL, disengaging is slowly injected into when stirring Make its solidification in water.The solid through precipitation is reclaimed, and stirring and washing is repeated twice in isopropanol, vacuum is carried out at 60 DEG C Dry, so as to obtain the poly amic acid ester of white powder (PAE-11).The number average molecular weight Mn of the polymer is 19,000, Molecular weight distribution mw/mn is 1.5.
[synthesis example 14]
The DA-1 of TA-3 as 100 molar parts of tetracarboxylic dianhydride, 100 molar parts as diamines is dissolved to NMP In, reaction in 6 hours is carried out at room temperature and obtains the solution of the polyamic acid (PAA-1) containing 20 mass %.
[synthesis example 15]
The DA-4 of TA-2 as 100 molar parts of tetracarboxylic dianhydride, 100 molar parts as diamines is dissolved to NMP In, reaction in 6 hours is carried out at room temperature and obtains the solution of the polyamic acid (PAA-2) containing 20 mass %.
[synthesis example 16]
The DA-7 of TA-1 as 100 molar parts of tetracarboxylic dianhydride, 100 molar parts as diamines is dissolved to NMP In, reaction in 6 hours is carried out at room temperature and obtains the solution of the polyamic acid (PAA-3) containing 20 mass %.
[synthesis example 17]
Using the TA-4 as 100 molar parts of tetracarboxylic dianhydride, the DA-2 of 80 molar parts as diamines and 20 molar parts DA-8 be dissolved in NMP, carry out reactions in 6 hours at room temperature and obtain the polyamic acid (PAA-4) containing 20 mass % Solution.
The species of the compound used in the synthesis of polymer and allotment ratio are shown in table 1 below.In addition, following tables In 1, " mol ratio " represents the use ratio (mol ratio) (Table 3 below is also identical) of each compound used in synthesis.
[table 1]
[embodiment 11：Light orientation FFS types liquid crystal display cells]
(1) preparation of aligning agent for liquid crystal
The polymer (PAE-1) obtained in embodiment 1 as polymer is dissolved in comprising gamma-butyrolacton (GBL), N- N-methyl-2-2-pyrrolidone N (N-methyl-2-pyrrolidone, NMP) and butyl cellosolve (butyl cellosolve, BC) Mixed solvent (GBL: NMP: BC=80: 10: 10 (mass ratio)) in, be made solid component concentration be 4.0 mass % solution. The solution is filtered by using 0.2 μm of the filter in aperture to prepare aligning agent for liquid crystal (R-1).
(2) evaluation of coating
The aligning agent for liquid crystal (R-1) of the preparation is coated on glass substrate using spin coater, utilizes 80 DEG C of heating After plate carries out 1 minute prebake conditions, it is (rear to dry to carry out heating in 30 minutes using 230 DEG C of the baking oven to having carried out nitrogen displacement in storehouse It is roasting), it is consequently formed the film of 0.1 μm of average film thickness.Observe the film using the microscope of 100 times and 10 times of multiplying power and investigate The presence or absence of thickness inequality and pin hole.On evaluation, thickness is not observed not even if the microscope using 100 times is observed yet The situation of both equal and pin holes is evaluated as coating " good ", and the microscope using 100 times is observed into thickness inequality and pin hole At least one but do not observe that thickness is uneven and the situation of pin hole both sides is evaluated as coating "available" using 10 times of microscope, It will clearly observe that thickness is uneven and the situation of at least one of pin hole is evaluated as coating " bad " using 10 times of microscope. In the present embodiment, both thickness inequality and pin hole are not observed yet using 100 times of microscope, coating is " good ".
(3) measure of the acid imide rate of the component of polymer in film
For the film obtained in (2), the 1360cm in being determined according to FT-IR-1Neighbouring absorption be (imide Absorption from C-N stretching vibrations) absorbance α 1 and 1500cm-1(aromatic rings is derived from C=C stretching vibrations for neighbouring absorption Absorption) absorbance α 2, and calculate acid imide rate (%) using following numerical expressions (4).
Acid imide rate (%)={ (α 1230℃/α2230℃)/(α1300℃/α2300℃)}×100…(4)
(in numerical expression (4), α 1230℃And α 2230℃For the measurement result of the film obtained in (2), α 1300℃And α 2300℃For The measurement result of the film after heating in 90 minutes has been carried out using 300 DEG C of the baking oven to having carried out nitrogen displacement in storehouse.Wherein, Using the acid imide rate of 300 DEG C of films heated as 100%)
Its result is that the acid imide rate of the film is 30%.
(4) adhesion
The adhesion of the film formed by aligning agent for liquid crystal and substrate is carried out using the film of manufacture in (2) Evaluation.First, otch is cut to film using the sept at equal intervals with guiding element and using cutter, so as in 1cm × 1cm In the range of form the grid pattern of 10 × 10.Untill the depth of each otch is formed as the centre of arrival film.Then, exist After touching adhesive tape in a manner of covering the entire surface of the grid pattern, the adhesive tape is peeled off.Pass through orthogonal Nico Under ear visually come observe peel off after grid pattern notch and evaluate adhesion.Evaluation is carried out as follows：Will be along cutting The part of mouth line and the cross section of the grid pattern situation unconfirmed to stripping are evaluated as adhesion " ◎ ", will be in the part It was observed that the situation that the number for the grid eye peeled off is less than 15% relative to the overall number of grid pattern is evaluated as adhesion "○", adhesion " △ " is evaluated as less than 20% situation by 15%, more than 20% situation is evaluated as "×".Its As a result it is that the adhesion of the film is " △ ".
(5) manufacture of the liquid crystal display cells of optical alignment method is utilized
Using spin coater in a manner of thickness turns into 0.1 μm, the aligning agent for liquid crystal (R-1) of the preparation is coated on successively Be laminated with one side plate electrode, insulating barrier and comb-like electrode glass substrate, be not provided with electrode to glass base On the respective face of plate, dried 1 minute using 80 DEG C of heating plates and dried 1 hour and formed using 200 DEG C of cleaning oven Film.Ultraviolet using Hg-Xe lamps and from substrate normal direction to the polarisation of bright line of the film coated surface irradiation comprising 254nm 500mJ/cm2, so as to form liquid crystal orientation film.Secondly, on having carried out a pair of substrates of the photo-irradiation treatment, liquid crystal is reserved Inlet and the epoxy resin solid silk-screen printing for the alumina balls for being put into 5.5 μm of diameter is coated on to form liquid crystal aligning The edge in the face of film, then the projecting direction to real estate of polarizing axis when light irradiation turn into antiparallel in a manner of by substrate Overlap and crimp, spend 1 hour at 150 DEG C and make solid thermmohardening.Then, from liquid crystal injecting port between a pair of substrates After filling nematic liquid crystal (Merck ＆ Co., Inc. manufactures, MLC-7028), liquid crystal injecting port is sealed with epoxy solid.And then it is Flow orientation during liquid crystal injection is removed, after being heated to 150 DEG C is slowly cooled down to room temperature.Secondly, Polarizer is pasted The liquid crystal display cells of transverse electric field (FFS) mode are made together in the outside two sides of substrate.
(6) evaluation of liquid crystal aligning
For the liquid crystal display cells of manufacture in (5), observed again by 5V voltage with multiplying power 50 using microscope The presence or absence of abnormal area of light and shade change during on-off (ONOFF) (apply and release).On evaluation, will not observe Situation to abnormal area is evaluated as liquid crystal aligning " good ", it will be observed that the situation of abnormal area is evaluated as liquid crystal aligning " bad ".Its result is to be evaluated as in this embodiment " good ".
(7) the contrast evaluation (evaluation of AC image retention characteristics) after stress is driven
Except in addition in terms of the outside two sides of substrate fitting Polarizer, progress is operated and made with (5) identical Make FFS type liquid crystal cells.For the FFS type liquid crystal cells, after being driven 30 hours with alternating voltage 10V, using in light source and light The device of polarization element and analyzer is configured between amount detector, it is minimum relatively saturating represented by following numerical expressions (2) to determine Cross rate (%).
Minimum relative permeability (%)=(β-B0)/(B100-B0) × 100 ... (2)
(in numerical expression (2), B0 is to utilize the light transmission capacity under the cross Nicols of blank.B100 is the parallel Buddhist nun using blank Light transmission capacity under section's ear.β turns into clamp liquid crystal display cells under cross Nicols, between polarization element and analyzer Minimum light transmission capacity)
Black level under dark state is the minimum relative permeability expression by liquid crystal display cells, in FFS type liquid crystal displays In element, the black level under dark state is smaller and contrast is more excellent.Minimum relative permeability is evaluated as AC less than 1.0% Image retention characteristic " ◎ ", "○" is evaluated as less than 1.5% by 1.0%, by 1.5% less than 2.0% evaluations For " △ ", more than 2.0% person is evaluated as "×".Its result is to be evaluated as in this embodiment " △ ".
(8) micro bright point observation (heat-resisting reliability test)
The evaluation of micro bright point is to carry out in the following manner, i.e. except not being bonded Polarizer on the outside two sides of substrate Aspect beyond, will carry out with (5) identical operation and manufacture liquid crystal cells in 100 DEG C of thermostat take care of 21 Day, then utilize the presence or absence of micro bright point in micro- sem observation liquid crystal cells.And understand：By using being handled with light orientation In the case that light irradiation and the analyte that generates are residued in film, pass through the member of long-time exposure liquid crystal display in high temperature environments Part, analyte are oozed out into film surface, slowly crystallize in liquid crystal and observed in the form of micro bright point.In addition, observation area Domain is 680 μm of 680 μ m, and is observed again with microscope multiplying power 100.On evaluation, the feelings of micro bright point will not be observed Condition is evaluated as "○", it will be observed that the quantity of micro bright point is that 1 point or 2 points of situation is evaluated as " △ ", it will be observed that small bright The quantity of point is that more than 3 points and less than 5 points of situation is evaluated as "×", it will be observed that micro bright point is that more than 6 points of situation is commented Valency is " ×× ".Its result is to be evaluated as "○" in this embodiment.
[12~embodiment of embodiment 22,1~comparative example of comparative example 3]
In the embodiment 11, except changing polymer contained in aligning agent for liquid crystal and addition as described in Table 2 Beyond the species and allotment ratio of agent, aligning agent for liquid crystal is prepared in a manner of with the identical of embodiment 11, and manufacture FFS type liquid crystal Display element or liquid crystal cells and carry out various evaluations.Evaluation result is shown in table 2 below.In addition, aligning agent for liquid crystal in table 2 In polymer 1 and the allotment ratio of polymer 2 be to be represented by the mass parts of solid constituent conversion, additive 1 and additive 2 Mass parts when allotment ratio by the solid constituent quality of polymer 1 and polymer 2 total by being set to 100 mass parts represent.
[table 2]
In 11~embodiment of embodiment 22, coating and adhesion and the liquid crystal display of aligning agent for liquid crystal are achieved The balance of the liquid crystal aligning of element, AC image retentions characteristic and heat resistance.Particularly in 14~embodiment of embodiment 18, embodiment 20th, in embodiment 21, for the result of the characteristic " good ", " ◎ " or "○", the balancing good of various characteristics.In addition, It is that AC image retentions characteristic for the evaluation of "○" is slightly worse result in embodiment 19, embodiment 22, but on coating or liquid crystal Orientation, heat resistance, then it is good result in the same manner as other embodiment.In contrast, 1~comparative example of comparative example 3 be The result poor compared with embodiment in multiple assessment items.
In addition, if high acid imide is shown to 12~embodiment of embodiment 22 compared with comparative example 1, in embodiment Rate, AC image retention characteristics become good.Think that its reason is：Perhaps uprised by acid imide rate, the phase interaction with liquid crystal With raising, so as to improve liquid crystal aligning.
In addition, it can be seen from the result of comparative example 1, light decomposability is low in polyamic acid, the exposure of equal polarisation ultraviolet Liquid crystal aligning becomes bad under light quantity.
And then, it is believed that by 14~embodiment of embodiment 18,20~embodiment of embodiment 22, the contrast with comparative example 3, contain In the aligning agent for liquid crystal for having the poly amic acid ester modified end and polyamic acid, from poly amic acid ester and polyamic acid The minute asperities of phase separation be inhibited, and coating becomes good.
It can be seen from 11~embodiment of embodiment 22 above with the result of 1~comparative example of comparative example 3, according to containing in side Chain has the aligning agent for liquid crystal of the poly amic acid ester of reactive base, even if without in flushing membrane after light orientation processing The cleaning treatment of analyte, heat resistance (particularly long-term heat resistance) are also good.In 14~embodiment of embodiment 18, teaching Long-term heat resistance is especially excellent, and suppresses the diffusion of the light analyte of material and/or crystallization the reason for as micro bright point.
[18~synthesis example of synthesis example 22]
In addition to the species and amount of tetracarboxylic dianhydride and diamine compound is changed as shown in table 3, with the phase of synthesis example 14 Same mode obtains the solution containing polyamic acid (PAA-5~PAA-9).
[embodiment 23]
Be put into the three-necked flask for the 50mL for possessing nitrogen ingress pipe and thermometer 1.08g (10.0mmol) DA-1, 20.0g NMP, it is cooled to about 10 DEG C and prepares diamine solution.Being added into the solution makes DC-1a 3.89g (9.6mmol) The solution of acid chloride prepared in pyridine 1.90g (21.6mmol) and γ BL 20.0g is dissolved in advance, under nitrogen flowing and in room The lower reaction of temperature 4 hours.The polymeric solution obtained is diluted using γ BL, disengaging is slowly injected into when stirring Make its solidification in water.The solid through precipitation is reclaimed, and stirring and washing is repeated twice in isopropanol, vacuum is carried out at 60 DEG C Dry, so as to obtain the poly amic acid ester of white powder (PAE-12).The number average molecular weight Mn of the polymer is 20,000, Molecular weight distribution mw/mn is 3.20.
[24~embodiment of embodiment 27]
In addition to species and amount that tetracarboxylic acid derivatives and diamine compound are changed as described in Table 3, with implementation The identical mode of example 23 obtains poly amic acid ester (PAE-13~PAE-16).The number average molecular weight Mn of polymer (PAE-13) For 22,000, molecular weight distribution mw/mn 3.90, the number average molecular weight Mn of polymer (PAE-14) is 30,000, molecule Amount distribution Mw/Mn is 4.10.The number average molecular weight Mn of polymer (PAE-15) is 11,000, and molecular weight distribution mw/mn is 3.00, the number average molecular weight Mn of polymer (PAE-16) is 10,000, molecular weight distribution mw/mn 2.90.
[embodiment 28]
In the method described in the synthesis example 4 of International Publication No. 2015/152174 as reference, and using following methods come Synthesizing polyamides acid esters-polyamic acid copolymer (PAE-17).
Into the three-necked flask for the 100mL for possessing nitrogen ingress pipe and thermometer add 3.50g (9.5mmol) DE-1a, 55.4g NMP is simultaneously stirred and is made its dissolving.Then, 2.11g (20.9mmol) triethylamine, 2.05g (19.0mmol) is added DA-1 is simultaneously stirred and is made its dissolving.The solution is cooled to about 10 DEG C, and adds 7.28g (19.0mmol) (2,3- dihydro -2- Thio -3- benzoxazolyls) phosphonic acids diphenyl, and then 11.9g NMP is added, react under nitrogen flowing and at room temperature 12 Hour.Then, diphenyl phoshate 0.95g (3.80mmol) and 2.00g (8.93mmol) TA-3 is added, and then is added 11.9g NMP, under nitrogen flowing and react 12 hours at room temperature.When stirring by the polymeric solution obtained slowly It is injected into methanol (600g) and makes its solidification.The solid through precipitation is reclaimed, and after being repeated twice stirring and washing in methyl alcohol, It is dried in vacuo at 60 DEG C, so as to obtain poly amic acid ester-polyamic acid copolymer (PAE-17) powder.The polymer Number average molecular weight Mn is 20,000, molecular weight distribution mw/mn 3.50.
[table 3]
[29~embodiment of embodiment 41]
In the embodiment 11, except changing polymer contained in aligning agent for liquid crystal and addition as described in Table 4 Beyond the species of agent, aligning agent for liquid crystal is prepared in a manner of with the identical of embodiment 11, and manufacture FFS types liquid crystal display cells or Liquid crystal cells and carry out various evaluations.Evaluation result is shown in table 4 below.
[table 4]
It is special on the liquid crystal aligning in the coating and adhesion and liquid crystal display cells of aligning agent for liquid crystal, AC image retentions Property and heat resistance, in 29~embodiment of embodiment 41, are the result of " good ", " ◎ " or "○", and achieve various The balance of characteristic.Wherein, the liquid crystal aligning of embodiment 31 and AC image retention characteristics are especially good, and the adhesion of embodiment 41 is special Well.
In addition, the heat resistance of 29~embodiment of embodiment 37 is especially excellent, even if so that the ratio of polymer 1 is few and is 10 parts Composition also show that good liquid crystal aligning and AC image retention characteristics.Think that its reason is：The poly amic acid ester of polymer 1 Hydrophobicity it is high, promotion separates with the layer of the polyamic acid of polymer 2, is easily inclined to so as to be derived from the polyimides of polymer 1 It is present in alignment films top layer.Additionally, it is believed that if the ratio of polymer 1 is few, the yield of light analyte tails off, therefore can reduce The pollution of calcining furnace, and the light analyte residued in alignment films tails off, thus under exposure to hot environment in the case of, it is micro- The generation of sparklet is lacked, so as to which heat resistance improves.

Claims (11)

  1. A kind of 1. aligning agent for liquid crystal, it is characterised in that：Contain the polymer (P) with the part-structure represented by following formula (1)；
    In formula (1), R1For the quadrivalent organic radical containing the cyclobutane ring structure can with substituent, R2For divalent organic base；X1And X2It is separately hydroxyl or any monovalent organic radical of carbon number 1~40；Wherein, X1And X2At least any one be with reactivity Any monovalent organic radical of base.
  2. 2. aligning agent for liquid crystal according to claim 1, it is characterised in that：In the formula (1), X1And X2At least any one For selected from by following formula (2-1)~formula (2-10) each represented by structure and the group that is formed of (methyl) acryloxy in One kind；
    In formula (2-1)~formula (2-10), R4For that can have the bivalent aliphatic base of the carbon number 1~6 of substituent, R5Separately For hydrogen atom or the univalent aliphatic series base of the carbon number 1~6 can with substituent；Wherein, R4And R5In any two aliphatic Base can be bonded and form ring structure each other；Multiple R in formula (2-1), formula (2-9)5Can be mutually identical also different；" * " is represented Associative key.
  3. 3. aligning agent for liquid crystal according to claim 1 or 2, it is characterised in that：The polymer (P) is to include following formula (1-1) and following formula (1-2) each at least one tetracarboxylic acid derivatives of represented compound and diamine compound it is anti- Answer product；
    In formula (1-1) and formula (1-2), X11And X12It is separately hydrogen atom or any monovalent organic radical of carbon number 1~40；Wherein, X11And X12At least any one be any monovalent organic radical with reactive base；R3It is separately hydrogen atom, fluorine atom, chlorine original Sub, bromine atoms can the univalent aliphatic series base with the carbon number 1~10 of substituent；X is to select free hydroxyl, chlorine atom, bromine former One kind in the group that son and the respective represented structure of following formula (4-1)~formula (4-6) are formed；
    In formula (4-1)~formula (4-6), " * " represents associative key.
  4. 4. aligning agent for liquid crystal according to claim 1 or 2, it is characterised in that：Also contain represented without the formula (1) Part-structure polymer.
  5. 5. aligning agent for liquid crystal according to claim 4, it is characterised in that：Without the part knot represented by the formula (1) The polymer of structure is the polymer selected from least one of the group being made up of polyamic acid and polyimides.
  6. 6. aligning agent for liquid crystal according to claim 1 or 2, it is characterised in that：Containing selected from by functional silanes compound, At least one of group that acid producing agent, alkali producing agent and free-radical generating agent are formed.
  7. A kind of 7. liquid crystal orientation film, it is characterised in that：Use aligning agent for liquid crystal according to any one of claim 1 to 6 And formed.
  8. A kind of 8. manufacture method of liquid crystal orientation film, it is characterised in that：Using according to any one of claim 1 to 6 Aligning agent for liquid crystal and form film, to the film carry out light irradiation and assign liquid crystal aligning ability.
  9. A kind of 9. liquid crystal cell, it is characterised in that：Including liquid crystal orientation film according to claim 7.
  10. A kind of 10. polymer, it is characterised in that：With the part-structure represented by following formula (1)；
    In formula (1), R1For the quadrivalent organic radical containing the cyclobutane ring structure can with substituent, R2For divalent organic base；X1And X2It is separately hydroxyl or any monovalent organic radical of carbon number 1~40；Wherein, X1And X2At least any one be with reactivity Any monovalent organic radical of base.
  11. A kind of 11. compound or its salt, it is characterised in that：Represented by following formula (1-1) or following formula (1-2)；
    In formula (1-1) and formula (1-2), X11And X12It is separately hydrogen atom or any monovalent organic radical of carbon number 1~40；Wherein, X11And X12At least any one be any monovalent organic radical with reactive base；R3It is separately hydrogen atom, fluorine atom, chlorine original Sub, bromine atoms can the univalent aliphatic series base with the carbon number 1~10 of substituent；X is to select free hydroxyl, chlorine atom, bromine former One kind in the group that son and the respective represented structure of following formula (4-1)~formula (4-6) are formed；
    In formula (4-1)~formula (4-6), " * " represents associative key.
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