CN110121495A

CN110121495A - New polymers and diamine compound, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element

Info

Publication number: CN110121495A
Application number: CN201780080907.5A
Authority: CN
Inventors: 北浩; 结城达也
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2016-12-27
Filing date: 2017-12-26
Publication date: 2019-08-13
Also published as: JP6993618B2; JPWO2018124140A1; WO2018124140A1; CN117384076A; TW202342424A; KR20190097234A; CN117384077A; KR102516328B1; CN117384078A; TWI810169B; TW201833082A

Abstract

The manufacturing method of diamine compound shown in a kind of following formula (1), which comprises make P in bismaleimide compound shown in following formula (A) and following formula (B) compound represented¹For amino diamino compounds react, or with P in following formula (B) compound represented¹The process reacted for the nitro amino compound of nitro；Diamines shown in following formula (1) and polymer therefrom；Aligning agent for liquid crystal containing the polymer.R indicates hydrogen atom or 1 valence organic group, R¹Indicate hydrogen atom, C₁To C₅Optionally linear chain or branched chain alkyl, aryl, there are two R on identical maleimide ring¹It is optionally same or different to each other, there are two R¹C is formed optionally together₃To C₆Alkylidene, W¹Indicate singly-bound or divalent organic group, W²Indicate divalent organic group, Ar¹Indicate aromatic ring, L¹Indicate the alkylidene of carbon atom number 1 to 20.

Description

New polymers and diamine compound, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal watch Show element

Technical field

The present invention relates to the useful novel diamine compounds of the raw material as polymer used in liquid crystal orientation film (at this Diamines is also referred to as in specification), and the polymer obtained using the diamines.More particularly it relates to for example be applicable in Polyimides in electronic material and the diamines as its starting monomer.In addition, the invention further relates to use the diamines to obtain Polyamic acid, poly amic acid ester, polyimides, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element.

Background technique

In general, the characteristics of polyimide resin is due to its high mechanical strength, heat resistance, insulating properties, solvent resistance, extensive The electronic materials such as element, protection materials, insulating materials, colored filter in semiconductor are indicated as liquid crystal.In addition, recently, Polyimide resin is also expected to be used as the optic communications materials such as optical waveguide material.In recent years, field development is significant, correspondingly, It is required that material therefor has higher characteristic.That is, it is desirable to which these materials not only have excellent heat resistance, solvent resistant Property, and there is the multiple performance being consistent with purposes simultaneously.

However, for polyimides, be especially commonly used as the typical example of full aromatic polyimide resin by 1,2,4, 5- pyromellitic anhydride (PMDA) and 4, the polyimides (Kapton: trade name) of 4'- dioxy aniline (ODA) preparation, due to its shortage Dissolubility and cannot be used in the form of solution, therefore through being referred to as polyamic acid precursor, carry out heating bring it about it is de- Water reacts to obtain.

In addition, in the polyimides (hereinafter also referred to soluble polyimide) with solvent solubility, it is previous extensive The boiling of the amides systems such as the n-methyl-2-pyrrolidone (NMP) of the high-dissolvability used, gamma-butyrolacton or lactone system organic solvent Point is high.Therefore, in order to remove solvent, high temperature firing is inevitable.Liquid crystal indicate member arts, in recent years to use modeling Material substrate flexible liquid crystal indicate element research and development carrying out, carry out high temperature firing when, it may appear that element constitute at Divide rotten problem, therefore needs easy fired in recent years.

On the other hand, it there is also an issue, that is, the display deliquescent polyamic acid of high solvent cannot obtain sufficient liquid Brilliant characterization, and it is also easy to happen the volume change as caused by imidizate, so that one kind be needed to dissolve in low boiling The polyimides of the organic solvent class of point.As solution, it may be considered that a kind of utilization is conducive to organic solvent solubility The synthetic method of the tetracarboxylic dianhydride of ester ring type dicarboxylic anhydride.An example as this method, it is known that by using inclined benzene three Anhydride chloride, core hydrogenated trimellitic anhydride acyl chlorides manufacture various acid dianhydrides (for example, patent document 1) as raw material.However, right In diamines, as the example of above-mentioned acid dianhydride, it is to obtain the cheap raw material of polymer, and be up to the present still unaware of The method that resulting polymers various characteristics can be assigned.

In addition, all the time, liquid crystal indicates that element is widely used as the table of personal computer, mobile phone, television receiver etc. Show portion.The driving method of element is indicated as liquid crystal, it is known to the longitudinal electric fields mode such as TN mode, VA mode；IPS mode, side Boundary's electric field switches the Transverse electric-field types such as (Fringe Field Switching, hereinafter referred to as FFS) mode.

In general, only forming electrode in the side of substrate, and apply the cross of electric field on the direction with substrate-parallel Into Electric Field Mode, apply voltage with to the electrode being formed on upper and lower base plate to drive the longitudinal electric field mode phase of liquid crystal Than, it is known that it can obtain with wider viewing angle characteristic and be capable of the liquid crystal expression element of high quality expression.As making liquid crystal The method being orientated in a certain direction has one kind to form the polymeric membranes such as polyimides on substrate, uses cloth to wipe with and wipe its surface, i.e., The method for carrying out so-called brushing processing, corresponding brushing processing are industrially also widely used.

It as previous technical problem, can enumerate: keep high voltage holding ratio, from active matrix structure and by applying DC voltage component caused by charge accumulation.Charge generates liquid crystal aligning disorder, when liquid crystal indicates to accumulate in element with residual The form of shadow influences expression, significantly reduces the expression quality of liquid crystal cell.Alternatively, the case where being driven in the state of charge accumulation Under, after just driving, the control of liquid crystal molecule can not be normally carried out, and occur to flash (flicker) etc..

In addition, indicating that the expression quality of element can as key property required by liquid crystal orientation film to improve liquid crystal Enumerate ion concentration.When ion concentration is high, it is applied to the voltage decline of liquid crystal in a frame period, as a result brightness reduces, sometimes Will affect normal gray scale indicates.In addition, even if initial ion density is low, but when ion concentration is got higher after high temperature accelerated test There are also problems.Long-term reliability caused by this residual charge, ionic impurity reduces, ghost generation can reduce liquid crystal expression Quality, therefore become problem.

In order to meet above-mentioned requirements, the liquid crystal orientation film for being directed to polyimides system proposes various motions.Such as make It for the liquid crystal orientation film that the time until the ghost generated by DC voltage disappears is short, proposes: in addition to polyamic acid, containing acyl Except the polyamic acid of imine group, the liquid crystal orientation film of the aligning agent for liquid crystal of the tertiary amine containing specific structure is also used (specially Sharp document 2)；The liquid crystal orientation film of the aligning agent for liquid crystal containing soluble polyimide, the soluble polyimide are used The specific diamine compound with pyridine skeleton etc. has been used in the feed (for example, with reference to patent document 3).

Existing technical literature

Patent document

Patent document 1:WO2006/129771 pamphlet

Patent document 2: Japanese Unexamined Patent Publication 9-316200 bulletin

Patent document 3: Japanese Unexamined Patent Publication 10-104633 bulletin

Summary of the invention

Problems to be solved by the invention

It is an object of the present invention to which availability is high and can be easy to assign the manufacturer of the diamines of polymer various characteristics Method and the resulting diamines and thus obtained novel polymer.This polymer can be used for obtaining liquid crystal aligning Agent, liquid crystal orientation film, liquid crystal indicate element etc..

In addition, though brushing processing is widely used in industry as the method for making liquid crystal aligning, but according to being used Liquid crystal orientation film it is different, it may occur however that the differently- oriented directivity of brushing direction and liquid crystal is inconsistent, that is, showing for so-called twist angle occurs As.That is, the liquid crystal in Transverse electric-field type indicates in element, black expression can be shown in the state of no application voltage, but It is due to the phenomenon, it may appear that increase brightness in the state of no applied voltage, as a result indicate asking for contrast reduction Topic.

Therefore, the present invention also aims to provide a kind of aligning agent for liquid crystal that can obtain following liquid crystal orientation film: can Liquid crystal is indicated that the ion concentration in element inhibits low, and the charge of accumulation is quickly mitigated, is especially able to suppress brush Grind the problems in offset this transverse electric field driving method between direction and the differently- oriented directivity of liquid crystal.In turn, mesh of the invention Also reside in and a kind of liquid crystal comprising above-mentioned liquid crystal orientation film is provided indicates element.

The solution to the problem

In order to solve the above problems, the inventors of the present invention have made intensive studies, as a result, it has been found that by existing two amine compounds Object and cheap compound as raw material, so as to easily assign polymer various characteristics the polymer manufacturer Method has thus completed the present invention.The present invention is completed based on these opinions, and main idea is as follows.

1. a kind of manufacturing method of diamine compound shown in following formula (1), which comprises make following formula (A) institute P in the bismaleimide compound and following formula (B) compound represented shown¹It is reacted for the diamino compounds of amino, or Person and P in following formula (B) compound represented¹The process reacted for the nitro amino compound of nitro.

R indicates hydrogen atom or 1 valence organic group, R¹Indicate hydrogen atom, C₁To C₅Optionally linear chain or branched chain alkyl, Aryl, there are two R on identical maleimide ring¹It is optionally same or different to each other, there are two R¹Shape optionally together At C₃To C₆Alkylidene, W¹Indicate singly-bound or divalent organic group, W²Indicate divalent organic group, Ar¹Indicate aromatic ring, L¹Indicate carbon The alkylidene of atomicity 1 to 20.

2. a kind of diamines, with structure shown in following formula (1).

3. a kind of polymer is obtained as the diamines with structure shown in following formula (1).

4. a kind of aligning agent for liquid crystal contains the polymer obtained as the diamines with structure shown in following formula (1).

5. the aligning agent for liquid crystal according to 4, wherein Ar¹For 1,3- phenylene or 1,4- phenylene.

6. according to aligning agent for liquid crystal described in 4 or 5, wherein W¹For singly-bound.

7. the aligning agent for liquid crystal according to any one of 4 to 6, wherein the polymer is selected from including following formula (3) at least one kind of in the polyimide precursor of structural unit shown in and its acid imide compound, that is, polyimides.

X¹For the 4 valence organic groups from tetracarboxylic acid derivatives, Y¹It is organic for the divalent from the diamines comprising formula (1) structure Group, R⁴For hydrogen atom or the alkyl of carbon number 1~5.

8. the aligning agent for liquid crystal according to 7, wherein in the formula (3), X¹Structure be in following structures extremely It is a kind few.

9. according to aligning agent for liquid crystal described in 7 or 8, wherein relative to the entire infrastructure unit of polymer, the formula (3) Shown in structural unit be 10 moles of % or more.

10. a kind of liquid crystal orientation film is obtained using aligning agent for liquid crystal described in any one of 3 to 9.

11. a kind of liquid crystal indicates element, have 10 described in liquid crystal orientation film.

The effect of invention

Diamine compound according to the present invention, availability is high, and can easily assign resulting polymers various spies Property.In addition, being capable of providing one kind by using polymer of the invention, the aligning agent for liquid crystal of the invention containing the polymer Voltage retention and resistance to brushing are all high, and can rapidly mitigate the liquid crystal orientation film of the charge of accumulation and indicate special Property excellent liquid crystal indicate element.

Although still uncertain, why the above problem can solve through the invention, probably think as follows.Of the invention The structure of above-mentioned formula (1) contained in polymer has nitrogen-atoms.As a result, for example in liquid crystal orientation film, charge can be promoted Movement, and the mitigation of accumulated charge can be promoted.

Specific embodiment

The polymer that the diamines that aligning agent for liquid crystal of the invention contains the structure as shown in above-mentioned formula (1) obtains is (hereinafter, above-mentioned Structure shown in formula (1) is also referred to as specific structure, and the diamines with structure shown in above-mentioned formula (1) is also referred to as specific diamines, by having The polymer that the diamines of structure shown in above-mentioned formula (1) obtains is also referred to as particular polymers.).Hereinafter, being retouched in detail to each condition It states.

In above-mentioned formula (1), R indicates hydrogen atom or 1 valence organic group, R¹Indicate hydrogen atom, C₁To C₅Optionally straight chain or Alkyl, the aryl of branch, there are two R on identical maleimide ring¹It is optionally same or different to each other, there are two R¹Carbon number C is formed optionally together₃To C₆Alkylidene, W¹Indicate singly-bound or divalent organic group, W²Indicate divalent organic group, Ar¹ Indicate aromatic ring, L¹Indicate the alkylidene of carbon atom number 1 to 20.

As R, the preferably straight chained alkyl of hydrogen atom or carbon number 1~3, more preferably hydrogen atom or methyl.In addition, R can To be to occur to be detached from reaction by heating and be replaced by the protecting group of hydrogen atom.For example, stablizing from the preservation of aligning agent for liquid crystal Property angle set out, R be do not depart from room temperature, the protecting group being preferably detached from by 80 DEG C or more of heating, more preferably The protecting group being detached from by 100 DEG C or more of heating.It as the example of this protecting group, can enumerate: 1,1- dimethyl -2- Chloroethoxycarbonyl, 1,1- dimethyl -2- cyanoethoxy carbonyl, tert-butoxycarbonyl, preferably tert-butoxycarbonyl.

As R¹, preferably hydrogen atom, methyl, ethyl, isopropyl, phenyl, more preferably hydrogen atom, methyl, phenyl.Separately Outside, as there are two R¹The C being formed together₃To C₆Alkylidene, preferably-(CH₂)₃-、-(CH₂)₄-、-(CH₂)₅, more Preferably-(CH₂)₄-.As W¹, preferably singly-bound, be selected from-O- ,-COO- ,-OCO- ,-(CH₂)_p-、-O(CH₂)_qO-、- The divalent organic group of CONH- ,-NHCO-, the natural number that p is 1 to 10, the natural number that q is 1 to 10.As Ar¹, preferably 1, 3- phenylene, 1,4- phenylene.

As L¹Carbon atom number 1 to 20 alkylidene, can be straight chain and be also possible to branch, can enumerate: by- (CH₂)_nThe alkylidene for the straight chain that (wherein, n is 1 to 20) indicates；1- methylmethane -1,1- diyl, 1- ethyl methane -1,1- two Base, 1- propylmethanediyl -1,1- diyl, 1- methyl ethane -1,2- diyl, 1- ethylethanaminium -1,2- diyl, 1- propyl ethane -1, 2- diyl, 1- methylpropane -1,3- diyl, 1- triethanol propane -1,3- diyl, 1- propyl propane -1,3- diyl, 2- methyl-prop Alkane -1,3- diyl, 2- triethanol propane -1,3- diyl, 2- propyl propane -1,3- diyl, 1- methybutane -1,4- diyl, 1- second Base butane -1,4- diyl, 1- propyl butane -1,4- diyl, 2- methybutane -1,4- diyl, 2- ethylbutane -1,4- diyl, 2- propyl butane -1,4- diyl, 1- methylpentane -1,5- diyl, 1- ethylpentane -1,5- diyl, 1- propyl pentane -1,5- two Base, 2- methylpentane -1,5- diyl, 2- ethylpentane -1,5- diyl, 2- propyl pentane -1,5- diyl, methylpentane -1 3-, 5- diyl, 3- ethylpentane -1,5- diyl, 3- propyl pentane -1,5- diyl, 1- methyl hexane -1,6- diyl, 1- ethyl hexyl Alkane -1,6- diyl, 2- methyl hexane -1,6- diyl, 2- ethyl hexane -1,6- diyl, 3- methyl hexane -1,6- diyl, 3- second Base hexane -1,6- diyl, 1- methyl heptane -1,7- diyl, 2- methyl heptane -1,7- diyl, 3- methyl heptane -1,7- diyl, 4- methyl heptane -1,7- diyl, 1- phenylmethane -1,1- diyl, 1- diphenylphosphino ethane -1,2- diyl, 1- phenyl-propane -1,3- bis- The branched alkylidenes such as base.Under conditions of oxygen atom or sulphur atom not adjacent to each other, the alkylidenes of these linear chain or branched chains can be with It is interrupted 1~5 time by oxygen atom or sulphur atom.

As divalent organic group W², such as following formula [W²- 1]~formula [W²- 197] shown in.

Wherein, from the angle for taking into account inhibition ion concentration and liquid crystal aligning stability, W²-7、W²-21、W²-25、W²-28、 W²-43、W²-56、W²-57、W²-58、W²-59、W²-60、W²-64、W²-65、W²-66、W²-69、W²-70、W²-73、W²-74、W²- 75、W²-76、W²- 77 be preferred.

Hereinafter, being illustrated to the aforementioned method for obtaining diamines.

Pairing is not particularly limited at the method for specific diamines of the invention, such as can be enumerated shown in following formula of sening as an envoy to (A) The method reacted with diamino compounds shown in following formula (B1) of bismaleimide compound.

R、R¹、L¹、Ar¹、W¹And W²Definition it is identical as above-mentioned formula (1).

Relative to 1 mole of formula (A) compound represented, the dosage of compound shown in formula (B1) is preferably 2 moles to 4 and rubs You, more preferably 2 moles to 2.5 moles.By formula (B1) compound represented excess, reaction can be made to go on smoothly, and And by-product can be inhibited.

This reaction preferably carries out in a solvent.For solvent, as long as the solvent not reacted with each raw material can use Without limiting.Aprotic polar organic solvent (DMF, DMSO, DMAc, NMP etc.) can be used for example；Ethers (Et₂O、i- Pr₂O, TBME, CPME, THF, dioxanes etc.)；Fat hydrocarbon (pentane, hexane, heptane, petroleum ether etc.)；Aromatic hydrocarbons (benzene, first Benzene, dimethylbenzene, mesitylene, chlorobenzene, dichloro-benzenes, nitrobenzene, tetrahydronaphthalene etc.)；Halogenated hydrocarbon (chloroform, methylene chloride, tetrachloro Change carbon, dichloroethanes etc.)；Lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate etc.)；Nitrile (acetonitrile, propionitrile, butyronitrile etc.) etc..

These solvents can be considered the easness etc. that reaction occurs and suitably be selected, and can be used alone, can also be with It is used in mixed way two or more.As needed, it is non-aqueous to make to be used as after solvent seasoning that suitable dehydrating agent, desiccant can be used Agent.The dosage (reaction density) of solvent is not particularly limited, but is 0.1~100 matter relative to bismaleimide compound Amount times.Preferably 0.5~30 mass times, more preferable 1~10 mass times.Reaction temperature is not particularly limited, but at -100 DEG C In the range of until the boiling point of solvent for use, preferably -50~150 DEG C.Reaction time is usually 0.05~350 hour, excellent It selects 0.5~100 hour.

As needed, this reaction can carry out in the presence of inorganic base, organic base.It, can as alkali used in reaction To use sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, saleratus, potassium phosphate, sodium carbonate, potassium carbonate, carbonic acid The inorganic bases such as lithium, cesium carbonate；The alkali such as tert-butoxy sodium, potassium t-butoxide, sodium hydride, hydrofining；Trimethylamine, triethylamine, 3 third The amine such as amine, tri-isopropyl amine, tri-n-butylamine, diisopropylethylamine, pyridine, quinoline, trimethylpyridine.Wherein, preferably triethylamine, pyrrole Pyridine, tert-butoxy sodium, potassium t-butoxide, sodium hydride, hydrofining etc..The dosage of alkali is not particularly limited, but relative to span Carry out imide compound, is 0.1~100 mass times, preferably 0~30 mass times, more preferably 0~10 mass times.

In addition, can be enumerated as the method for synthesizing specific diamines of the invention: carrying out span shown in following formula (A) Imide compound is reacted with amino nitro compound shown in following formula (B2), obtains dinitro shown in following formula (C) Close object, and the method restored.

The reaction condition of compound shown in compound shown in formula (B2) and formula (A) is with compound and formula shown in above-mentioned formula (B1) (A) subject to the reaction condition of compound shown in.

Hereinafter, to reduction-type (C) compound represented to preparation formula (1) indicate specific diamines when condition retouch It states.Catalyst used in reduction reaction is preferably the activated carbon supported metal for being used as commercially available product that can obtain, such as can be enumerated Out: palladium-active carbon, platinum-active carbon, rhodium-active carbon etc..In addition, palladium dydroxide, platinum oxide, Raney's nickel etc. can be not necessarily The metallic catalyst of activated carbon supported type.Usual widely used palladium-active carbon can obtain good as a result, being therefore preferred 's.In order to be more effectively carried out reduction reaction, reaction can be implemented under the coexisting of active carbon.At this point, used active carbon Amount be not particularly limited, it is more excellent but relative to dinitro compound shown in formula (C), the preferably range of 1~30 mass % It is selected as 10~20 mass %.Based on same reason (in order to be more effectively carried out reduction reaction), can implement under elevated pressure anti- It answers.In this case, it in order to avoid benzene nucleus reduction, is carried out in the pressure range in 20 air pressures.It is preferred that in 10 air pressures Range is reacted.

For solvent, as long as the solvent not reacted with each raw material can be used without limitation.It can be used for example Aprotic polar organic solvent (DMF, DMSO, DMAc, NMP etc.)；Ethers (Et₂O、i-Pr₂O, TBME, CPME, THF, dioxanes Deng)；Fat hydrocarbon (pentane, hexane, heptane, petroleum ether etc.)；Aromatic hydrocarbons (benzene,toluene,xylene, mesitylene, chlorobenzene, two Chlorobenzene, nitrobenzene, tetrahydronaphthalene etc.)；Halogenated hydrocarbon (chloroform, methylene chloride, carbon tetrachloride, dichloroethanes etc.)；Lower aliphatic Esters of gallic acid (methyl acetate, ethyl acetate, butyl acetate, methyl propionate etc.)；Nitrile (acetonitrile, propionitrile, butyronitrile etc.) etc..

These solvents can be considered the easness etc. that reaction occurs and suitably be selected, and can be used alone, can also be with It is used in mixed way two or more.As needed, it is non-aqueous to make to be used as after solvent seasoning that suitable dehydrating agent, desiccant can be used Agent.The dosage (reaction density) of solvent is not particularly limited, but relative to dinitro compound shown in above-mentioned formula (C), is 0.1~100 mass times.Preferably 0.5~30 mass times, more preferably 1~10 mass times.Reaction temperature is not particularly limited, But in the range of -100 DEG C until the boiling point of solvent for use, preferably -50~150 DEG C.Reaction time is usually 0.05 ~350 hours, preferably 0.5~100 hour.

It is desirable that importing 1 valence organic group as R, make R in dinitro compound shown in above-mentioned formula (C) The compound of hydrogen atom is reacted with the compound that can be reacted with amine.It (can be reacted with amine as this compound Compound), it can enumerate: carboxylic acid halides, acid anhydrides, isocyanates, epoxies, oxetanes class, aryl halide class, alkyl halide Compound class, further, it is possible to use alcohols as obtained from the hydroxyl that OMs, OTf, OTs etc. are detached from group substituted alcohols etc..

The method that 1 valence organic group is directed into NH base is not particularly limited, can enumerate and exist in alkali appropriate Under make carboxylic acid halides react method.Example as carboxylic acid halides can enumerate: chloroacetic chloride, propionyl chloride, methylchloroformate, chloro-carbonic acid second Ester, n-propyl chloroformate, isopropyl chlorocarbonate, butyl chloroformate, isobutyl chlorocarbonate, isobutylchloroformate, chloro-carbonic acid benzyl Base ester and chloro-carbonic acid -9- fluorenyl ester.As the example of alkali, alkali above-mentioned can be used.The reaction such as reaction dissolvent, reaction temperature Condition is recorded as standard with above-mentioned.

Acid anhydrides can also be made to react with NH base to import 1 valence organic group.Example as acid anhydrides can enumerate: acetic acid Acid anhydride, propionic andydride, two dimethyl carbonates, dicarbonic acid diethyl ester, di-tert-butyl dicarbonate, two dimethyl benzyls etc..It is anti-in order to promote It answers, catalyst can be added, pyridine, trimethylpyridine, N, N- dimethyl -4-aminopyridine etc. also can be used.It rubs relative to 1 R is the compound of hydrogen atom in dinitro compound shown in your above-mentioned formula (C), and catalytic amount is 0.0001 mole~1 mole. The reaction conditions such as reaction dissolvent, reaction temperature are recorded as standard with above-mentioned.

Isocyanates can also be made to react with NH base to import 1 valence organic group.As the example of isocyanates, It can enumerate: methyl isocyanate, ethyl isocyanate, propyl isocyanate, phenyl isocyanate etc..Reaction dissolvent, reaction temperature etc. Reaction condition is recorded as standard with above-mentioned.

Epoxide class, oxetane compound class can also be made to react with NH base to import 1 valence organic group. As epoxies, the example of oxetanes class, ethylene oxide, propylene oxide, 1,2- epoxy butane, oxa- ring fourth can be enumerated Alkane etc..The reaction conditions such as reaction dissolvent, reaction temperature are recorded as standard with above-mentioned.

Aryl halide can also be made to react with NH base to import 1 in the presence of metallic catalyst, ligand and alkali Valence organic group.It as the example of aryl halide, can enumerate: iodobenzene, bromobenzene, chlorobenzene etc..As showing for metallic catalyst Example, can enumerate: acid chloride, palladium chloride, palladium chloride-acetonitrile complex compound, palladium-active carbon, bis- (dibenzalacetone) palladiums, three (dibenzalacetone) two palladium, bis- (acetonitrile) dichloro palladiums, bis- (benzonitrile) dichloro palladiums, CuCl, CuBr, CuI, CuCN etc., but it is unlimited In these.It as the example of ligand, can enumerate: triphenylphosphine, tri-o-tolyl phosphine, diphenyl methyl phosphine, pheiiyldimetliyl Bis- (diphenylphosphino) ethane of phosphine, 1,2-, bis- (diphenylphosphino) propane of 1,3-, bis- (diphenylphosphino) butane of 1,4-, 1,1'- Bis- (diphenylphosphino) ferrocene, Trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri-tert-butylphosphine etc., but not It is limited to these.As the example of alkali, aforementioned bases can be used.The reaction conditions such as reaction dissolvent, reaction temperature are recorded as with above-mentioned It is quasi-.

The hydroxyl for being detached from group substituted alcohols by OMs, OTf, OTs etc. can also be made to obtain in the presence of suitable alkali Alcohols reacted with NH base to import 1 valence organic group.As the example of alcohol, can enumerate: methanol, ethyl alcohol, 1- propyl alcohol etc., It is reacted, can be obtained by Oms, OTf, OTs etc. by these alcohol and mesyl chloride, trifluoromethanesulfchloride chloride, paratoluensulfonyl chloride etc. It is detached from the alcohol that group replaces.As the example of alkali, aforementioned bases can be used.It is more than the reaction conditions such as reaction dissolvent, reaction temperature It states subject to record.

Alkyl halide can also be made to react with NH base to import 1 valence organic group in the presence of suitable alkali.As The example of alkyl halide species can enumerate: methyl iodide, ethyl iodide, n-propyl iodide, methyl bromide, bromic ether, positive propyl bromo etc.. As the example of alkali, other than aforementioned bases, the metal alkoxides such as potassium tert-butoxide, sodium tert-butoxide can also be used.It is reaction dissolvent, anti- The reaction conditions such as temperature are answered to be recorded as standard with above-mentioned.

R is the compound of hydrogen atom, energy in dinitro compound shown in above-mentioned formula (C) relative to 1.0 molar equivalents The dosage of enough compounds reacted with above-mentioned amine can be set to 1.0~3.0 molar equivalents or so.Preferably 2.0~2.5 moles The range of equivalent.In addition, the compound that can be reacted with above-mentioned amine can be used alone or be applied in combination.

It should be noted that in the case where there is the isomers from asymmetric point in diamine compound shown in formula (1), In this application, Isomers and its mixture are all contained in diamines shown in formula (1).In addition, formula (1) in identical Malaysia There are two R on imide ring¹In the case where different from each other, each compound becomes R in diamine compound shown in formula (1)¹ The different isomers of the position of substitution.But in this application, this isomers and with the mixture of this isomers all include In the diamines shown in formula (1).

[manufacturing method of formula (A)]

The method of compound for synthesizing formula (A) is not particularly limited, for example, can enumerate send as an envoy to maleic anhydride with it is following The method of diamine reactant shown in formula (D).

Relative to diamine compound shown in 1 mole of formula (D), the dosage of maleic anhydride derivative is preferably 2 moles to 3 and rubs You, more preferably 2 moles to 2.5 moles.By using excessive maleic anhydride, reaction can be made to go on smoothly, and can be with Inhibit by-product.

This reaction preferably carries out in a solvent.The preparation condition phase of preferred solvent, reaction condition and above compound (1) Together.By above-mentioned each object reacted in obtained each stage can by distilling, weight column chromatographys such as crystal or silica gel etc. it is pure Change, can not also purify, but by reaction solution directly for next stage.

Polymer of the invention is the polymer obtained using above-mentioned diamines.Concrete example as the polymer can be enumerated Out: polyamic acid, poly amic acid ester, polyimides, polyureas, polyamide etc..As the polymer, from as aligning agent for liquid crystal It is more preferably sub- selected from the polyimide precursor containing structural unit shown in following formula (3) and its acyl from the perspective of use At least one of aminate, that is, polyimides.

In above-mentioned formula (3), X¹For the 4 valence organic groups from tetracarboxylic acid derivatives, Y¹For from including formula (1) structure The divalent organic group of diamines, R⁴For hydrogen atom or the alkyl of carbon number 1~5.From being easy to carry out the angle of imidizate by heating Degree sets out, R⁴Preferably hydrogen atom, methyl or ethyl.

<<<Diisocyanate component>>>

As by providing the Diisocyanate component of polyamide with diamine reactant shown in above-mentioned general formula (1), such as It can enumerate: aromatic diisocyanate, aliphatic diisocyanate etc..Preferred Diisocyanate component is that aromatic series two is different Cyanate, aliphatic diisocyanate.Here, aromatic diisocyanate refers to, diisocyanate ester structure (O=C=N-Q-N =C=O) group Q include the structure containing aromatic ring.In addition, aliphatic diisocyanate refers to, the base of the isocyanate structural Group Q is made of cyclic annular or non-annularity aliphatic structure.

As the concrete example of aromatic diisocyanate, can enumerate: adjacent phenylene diisocyanate, m-benzene diisocyanate, Paraphenylene diisocyanate, toluene di-isocyanate(TDI) class (such as Toluene-2,4-diisocyanate, 4- diisocyanate), 2- methoxybenzene -1,4- two are different Cyanate, dimethylbenzene -2,5- diisocyanate, 2,2'- bis- (4- diisocyanate root closes phenyl) propane, diphenyl methane -4,4'- Diisocyanate, diphenyl ether -4,4'- diisocyanate, diphenyl sulphone (DPS) -4,4'- diisocyanate, diphenyl sulphone (DPS) -3,3'- diisocyanate Ester, benzophenone-2,2'- diisocyanate.As aromatic diisocyanate, can preferably enumerate: m-benzene diisocyanate, Paraphenylene diisocyanate, Toluene-2,4-diisocyanate, 4- diisocyanate.

As the concrete example of aliphatic diisocyanate, can enumerate: isophorone diisocyanate, hexa-methylene two are different Cyanate, tetramethyl ethylidene diisocyanate etc..As aliphatic diisocyanate, it is different can preferably to enumerate isophorone two Cyanate.Wherein, from polymerisation reactivity, the angle of voltage retention, preferably isophorone diisocyanate and Toluene-2,4-diisocyanate, 4- diisocyanate；Further, from availability, polymerisation reactivity, voltage retention angle, more preferable isophorone Diisocyanate.

By providing the ingredient of polyimides (or polyimide precursor) with diamine reactant shown in above-mentioned general formula (1) i.e. Tetracarboxylic dianhydride is indicated by following formula (X)s.

X₁For the 4 valence organic groups from tetracarboxylic acid derivatives, its structure is not particularly limited.In addition, polyimides X in precursor¹Be according to polymer dissolubility in a solvent, aligning agent for liquid crystal coating, liquid crystal orientation film is made when liquid The degree of characteristic needed for brilliant orientation, voltage retention, accumulated charge etc. suitably carries out selection, and in same polymer In can be a kind, can also be mixed two or more.If enumerating X₁Concrete example, then can enumerate International Publication bulletin Formula (X-1)~(X-46) structure etc. of the record of page 13~14 of WO2015/119168.Hereinafter, showing preferred X₁Knot Structure, but the invention is not restricted to this.

In above structure, from the angle for further increasing resistance to brushing, particularly preferred (A-1), (A-2)；From into one The angle that step improves the mitigation speed of accumulated charge is set out, particularly preferred (A-4)；From further increasing liquid crystal aligning and accumulation The angle of the mitigation speed of charge is set out, particularly preferred (A-15)~(A-17) etc..

As for constituting through the dicarboxylic acid component's that provides polyamide with diamine reactant shown in above-mentioned general formula (1) The concrete example of monomeric compound can enumerate: terephthalic acid (TPA), M-phthalic acid, 2- methyl-m-phenylene dioctyl phthalate, 4- methyl- Phthalic acid, 5- methyl-m-phenylene dioctyl phthalate, 5- allyloxy M-phthalic acid, 5- allyloxy carbonyl M-phthalic acid, 5- alkynes Propoxyl group M-phthalic acid, 5- acetoxyl group M-phthalic acid, 5- benzamido M-phthalic acid, tetrafluoro M-phthalic acid, Methylterephthalic acid, tetrafluoro terephthalic acid (TPA), 2,6- naphthalenedicarboxylic acid, 1,6- naphthalenedicarboxylic acid, 2,6- anthracene dioctyl phthalate, 1,6- anthracene two Formic acid, 4,4'- dicarboxylate biphenyl, 3,4'- dicarboxylate biphenyl, 2,3'- dicarboxylate biphenyl, 2,4'- dicarboxylate biphenyl, 4,4'- bis- Carboxyl diphenyl ether, 3,4'- dicarboxydiphenyl ether, 2,3'- dicarboxydiphenyl ether, 2,4'- dicarboxydiphenyl ether, 3,3'- dicarboxyl Diphenyl ether, 3,3'- dimethyl -4,4'- dicarboxylate biphenyl, 4,4'- dimethyl -3,3'- dicarboxylate biphenyl, dimethyl -4 2,2'-, 4'- dicarboxylate biphenyl, 3,3'- dimethoxy-4 ', 4'- dicarboxylate biphenyl, 4,4'- dimethoxy -3,3'- dicarboxylate biphenyl, 2, 2'- dimethoxy-4 ', 4'- dicarboxylate biphenyl, 4,4'- benzophenonedicarboxylic acid, 3,4'- benzophenonedicarboxylic acid, 3,3'- dicarboxyl Base benzophenone, 4,4'- dicarboxyl diphenyl methane, 3,4'- dicarboxyl diphenyl methane, 3,3'- dicarboxyl diphenyl methane, 4,4'- dicarboxyl diphenyl amide, 3,4- dicarboxyl diphenyl amide, 4,4'- Dicarboxy diphenylsulfone, 3,4'- dicarboxyl hexichol Bis- (4- carboxyphenoxy) benzene of sulfone, 3,3'- Dicarboxy diphenylsulfone, 2,2'- dicarboxyl diphenyl propane, 1,4-, bis- (the 4- carboxylics of 1,3- Phenoxyl) benzene, N- [3 { (4- carboxyl phenyl) carbonylamino } phenyl] (4- carboxyl phenyl) formamide, N- [4 { (4- carboxyl benzene Base) carbonylamino } phenyl] (4- carboxyl phenyl) formamide, 4,4'- (4- carboxyphenoxy phenyl) methane, bis- (the 4- carboxylics of 4,4'- Phenoxyl) diphenyl sulphone (DPS), bis- [4- (4- carboxyphenoxy) phenyl] propane of 2,2'-, bis- (4- carboxyl phenyl) hexafluoropropane of 2,2-, Bis- [4- (4- carboxyphenoxy) phenyl] hexafluoropropane of 2,2'-, bis- (4- carboxyl phenyl) pentanes of 1,5-, bis- (the 4- carboxyl benzene of 1,4- Base) butane, bis- (4- carboxyl phenyl) propane of 1,3-, 4,4'- bis- (carboxyl phenyl) pentane -1,5- acid diesters, bis- (carboxyl of 4,4'- Phenyl) aromatic series such as hexane -1,6- acid diesters, 4,4'- bis- (carboxyl phenyl) heptane -1,7- acid diesters or contain aromatic two Carboxylic acid and their carboxylic acid halides and Arrcostab compound.

It can further enumerate: 1,3- dicarboxyl butylcyclohexane, 1,4- dicarboxyl butylcyclohexane, 1,2- dicarboxyl cyclobutane, 1, 3- dicarboxyl cyclobutane, bis- (4- carboxycyclohexyl) methane, bis- (4- carboxyl -3- methylcyclohexyl) methane, bis- (4- carboxy cyclohex Base) ester ring types dicarboxylic acids and their carboxylic acid halides and the Arrcostab compound such as ether, bis- (4- carboxyl -3- methylcyclohexyl) ethers, in addition Also the two or more mixtures in these can be used.

By the polymerization reaction with the diamine component comprising diamine compound shown in above-mentioned formula (1), to obtain the present invention Polymer when, well known synthetic method can be used.Usually using in organic solvent, make selected from diisocyanate at Point, the method reacted with diamine component of at least one of dicarboxylic acid component and tetracarboxylic acid sour component.Selected from Diisocyanate component, At least one of dicarboxylic acid component and tetracarboxylic acid sour component react with diamine component, relatively easy in organic solvent to carry out, And by-product is not generated, is advantageous in this regard.As selected from Diisocyanate component, dicarboxylic acid component and tetrabasic carboxylic acid Organic solvent used in the reacting of at least one of ingredient and diamine component, does not have as long as the polymer generated can dissolve There is special limitation.The specific examples are listed below.

Here, as workable organic solvent, can enumerate: n,N-Dimethylformamide, n,N-dimethylacetamide, N-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, N- methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, Dimethyl sulfone, gamma-butyrolacton, isopropanol, methoxy amylalcohol, cinene, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, Methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve second Acid esters, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, Propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethyl Diol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol list Ether, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3- methyl -3- first Oxygroup butylacetic acid ester, tripropylene glycol methyl ether, 3- methyl -3- methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, Pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, dioxanes, n-hexane, pentane, Normal octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, acetic acid second Ester, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionate, 3- second Oxygroup propionic acid Methylethyl, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, diethylene glycol dimethyl ether, 4- hydroxy-4-methyl-2-pentanone, 3- methoxyl group-N, N- dimethylpropionamide, 3- ethyoxyl-N, N- dimethylpropionamide, 3- butoxy-N, N- dimethylpropionamide etc..These can be used alone, can also be with It is used in mixed way.Further, since the moisture in organic solvent can become the reason of hindering polymerization reaction, therefore organic solvent preferably makes With the organic solvent dehydrated as far as possible.

In organic solvent, make selected from least one of Diisocyanate component, dicarboxylic acid component and tetracarboxylic acid sour component When reacting with diamine component, the following methods can be enumerated: (1) diamine component is dispersed or dissolved in organic solvent obtain it is molten Liquid stirs the solution, and will directly add selected from least one of Diisocyanate component, dicarboxylic acid component and tetracarboxylic acid sour component Add, or is dispersed or dissolved in the method in organic solvent and added；(2) conversely, Diisocyanate component, two will be selected from At least one of carboxylic acid composition and tetracarboxylic acid sour component, which are dispersed or dissolved in organic solvent, obtains solution, adds in the solution The method of diamine component；It (3) will be selected from least one of Diisocyanate component, dicarboxylic acid component and tetracarboxylic acid sour component and two The method etc. that amine component alternately adds, can be used any one of these methods.In addition, when selected from Diisocyanate component, It, can be to mix in advance when at least one of dicarboxylic acid component and tetracarboxylic acid sour component or diamine component are made of multiple compounds The state response of conjunction can also singly react in order, further, it is possible to make low-molecular weight made of individually reacting Hybrid reaction and form high molecular weight body.

For polymerization temperature at this time, -20 DEG C~150 DEG C of arbitrary temp can choose, preferably -5 DEG C~100 DEG C Range.In addition, reaction can carry out under any concentration, but when concentration is too low, it is difficult to obtain the polymer of high molecular weight；It is dense When spending high, the viscosity of reaction solution becomes excessively high, it is difficult to uniform stirring.Therefore, selected from Diisocyanate component, dicarboxylic acids at Point and at least one of tetracarboxylic acid sour component and total concentration of the diamine component in reaction solution be preferably 1~50 mass %, more Preferably 5~30 mass %.It can also be carried out in the reaction initial stage with high concentration, organic solvent is then added.

In the polymerization reaction of Inventive polymers, it is selected from Diisocyanate component, dicarboxylic acid component and tetracarboxylic acid sour component At least one of total mole number and the ratio of total mole number of diamine component be preferably 0.8~1.2.With conventional polycondensation reaction Equally, for the molar ratio closer to 1.0, the molecular weight of the polymer of generation is bigger.

When recycling the polymer of generation from the reaction solution of Inventive polymers, reaction solution is put into poor solvent Precipitate it.As the poor solvent for precipitating, can enumerate: methanol, acetone, hexane, butyl cellosolve, heptane, Methyl ethyl ketone, methylisobutylketone, ethyl alcohol, toluene, benzene, water etc..The polymer precipitated and putting into poor solvent can be After being recovered by filtration, air drying or heat drying are carried out under normal or reduced pressure.In addition, repeating 2 times~10 times makes to sink When the polymer recycled that forms sediment is re-dissolved in organic solvent and the operation of reprecipitation recycling, it is possible to reduce the impurity in polymer.Make For poor solvent at this time, such as can enumerate: alcohols, ketone, hydrocarbon etc. use 3 kinds or more the poor solvents in them When, purification efficiency further increases, thus is preferred.

In these polymer of the invention, polyureas is, for example, the polymer with repetitive unit shown in following formula [1].

(in formula [1], A₁For divalent organic group, A₂It is each independently containing following formula (A₂) shown in group divalent it is organic Group,

C₁And C₂It is optionally identical or different each other for hydrogen atom or the alkyl of carbon number 1~3.)

In above-mentioned formula [1], A₁And A₂It can be a kind of respectively and be the polymer with identical repetitive unit, in addition, A₁ And/or A₂It can be polymer that is a variety of and being the repetitive unit with different structure.In above-mentioned formula [1], A₁It is derived from as original The group of the Diisocyanate component of material.In addition, A₂It is derived from the group of the diamine component as raw material.It is according to the present invention excellent Embodiment is selected, as A₁, it is preferably derived from the group of the above-mentioned preferred Diisocyanate component enumerated.

Polyimide precursor is, for example, the polymer with repetitive unit shown in following formula [2].

In formula [2], A₃It is each independently 4 valence organic groups, A₂It is each independently comprising above-mentioned formula (A₂) shown in group Divalent organic group.R11 is the alkyl of hydrogen atom or carbon number 1~5, C₁~C₂It is each independently hydrogen atom or optionally has The alkynyl of the alkyl of the carbon number 1~10 of substituent group, the alkenyl of carbon number 2~10 or carbon number 2~10.

As R₁₁In abovementioned alkyl concrete example, can enumerate: methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl Base, sec-butyl, tert-butyl, n-pentyl etc..From being easy to carry out the angle of imidizate, R by heating₁₁Preferably hydrogen is former Son or methyl.

Polyamide is, for example, the polymer with repetitive unit shown in following formula [3].

In formula [3], A₄It is each independently the divalent organic group from dicarboxylic acids, A₂、C₁And C₂As described above.

It should be noted that when preparing polymer of the invention, Diisocyanate component, dicarboxylic acid component and tetrabasic carboxylic acid at 2 kinds or 3 kinds in point can simultaneously or sequentially react.For example, being obtained when reacting Diisocyanate component with tetracarboxylic acid sour component Polyureas polyamic acid is the polymerization with repetitive unit shown in repetitive unit shown in above-mentioned formula [1] and above-mentioned formula [2] Object.

Polyimide precursor comprising structural unit shown in formula (3) can wrap within the scope of the effect of the invention Containing at least one kind of in the structural unit shown in following formula (4) and its imidizate object, that is, polyimides.

In formula (4), X²For the 4 valence organic groups from tetracarboxylic acid derivatives, Y²For from main chain direction do not include formula (1) the divalent organic group of the diamines of structure, R¹⁴With the R in the formula (3)⁴Definition it is identical, R¹⁵Each independently represent hydrogen original The alkyl of son or carbon number 1~4.

As X²Concrete example, including preferable example, can enumerate with the X of formula (3)¹The identical structure of ones listed. In addition, the Y in polyimide precursor²It is derived from the divalent organic group of the diamines on main chain direction not comprising formula (1) structure, And its structure is not particularly limited.In addition, Y²It is the coating of the dissolubility, aligning agent for liquid crystal according to polymer in a solvent Property, the degree of characteristic needed for orientation, voltage retention, accumulated charge of liquid crystal etc. is suitably selected when liquid crystal orientation film is made It selects, and can be a kind in same polymer, can also be mixed two or more.

If enumerating Y²Concrete example, then can enumerate above-mentioned formula [W²- 1]~formula [W²- 152] group shown in.In addition, can It enumerates: the structure of the formula (2) of the record of page 4 of International Publication bulletin 2015/119168 and the formula of the record of page 8~12 (Y-1) structure of~(Y-97), (Y-101)~(Y-118)；From the formula of the record of page 6 of International Publication bulletin 2013/008906 (2) divalent organic group made of 2 amino of removal in；From the formula (1) of the record of page 8 of International Publication bulletin 2015/122413 Divalent organic group made of 2 amino of middle removal；The knot of the formula (3) of the record of page 8 of International Publication bulletin 2015/060360 Structure；It is organic from divalent made of 2 amino of removal in the formula (1) of the record of page 8 of Japanese Laid-Open Patent Publication 2012-173514 Group；Have from divalent made of 2 amino of removal in formula (A)~(F) of the record of page 9 of International Publication bulletin 2010/050523 Machine group etc..

The case where including the polyimide precursor of structural unit shown in formula (3) while including structural unit shown in formula (4) Under, relative to the total amount of formula (3) and formula (4), structural unit shown in formula (3) is preferably 10 moles of % or more, and more preferably 20 Mole % or more, particularly preferably 30 moles of % or more.

Polyimide precursor, that is, polyamic acid used in the present invention can be synthesized by method as shown below.Specifically For, it can be by reacting tetracarboxylic dianhydride and diamines with -20~150 DEG C, preferably 0~70 DEG C in presence of organic solvent 30 minutes~24 hours, preferably react 1~12 hour and synthesize.It is above-mentioned from the deliquescent angle of monomer and polymer Organic solvent used in reaction is preferably n,N-Dimethylformamide, n-methyl-2-pyrrolidone, gamma-butyrolacton etc., they It can be used a kind or be mixed with two or more.It is not easy to be precipitated and be easy to get the angle of high molecular weight body from polymer, The concentration of polymer is preferably 1~30 mass %, more preferably 5~20 mass %.

It, can be by being injected while reaction solution is sufficiently stirred for polyamic acid obtained from above-mentioned such operation Into poor solvent, polymer is made to be precipitated and recycle.In addition, passing through room temperature after being repeatedly precipitated and being cleaned with poor solvent Dry or heat drying, the polyamic acid powder that can be purified.Poor solvent is not particularly limited, can be enumerated: water, Methanol, ethyl alcohol, 2- propyl alcohol, hexane, butyl cellosolve, acetone, toluene etc., preferably water, methanol, ethyl alcohol, 2- propyl alcohol etc..

Polyimides used in the present invention can be manufactured by carrying out imidizate to foregoing polyamides acid.By polyamides It is easy in the case that amino acid manufactures polyimides, it is aforementioned to obtained from being reacted as diamine component with tetracarboxylic dianhydride The chemical imidization of catalyst is added in the solution of polyamic acid.Chemical imidization due to carrying out acyl Asia at a lower temperature Aminating reaction, the molecular weight that imidizate is not susceptible to polymer in the process are reduced, are therefore preferred.

Chemical imidization can be by the way that stirring is wanted to make in the presence of basic catalyst and acid anhydrides in organic solvent The polymer of its imidizate carries out.As organic solvent, solvent used when aforementioned polymeric reaction can be used.As alkali Property catalyst, can enumerate pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc..Wherein, pyridine have for make to react into Appropriate alkalinity for row, thus be preferred.In addition, acetic anhydride, trimellitic anhydride, equal benzene four can be enumerated as acid anhydrides Acid anhydrides etc., wherein when using acetic anhydride, be easy purifying after reaction, thus be preferred.

Temperature when carrying out imidization reaction is -20~140 DEG C, preferably 0~100 DEG C, the reaction time can with 1~ It carries out within 100 hours.The amount of basic catalyst is 0.5~30 times mole, preferably 2~20 times moles of polyamide acidic group, acid The amount of acid anhydride is 1~50 times mole, preferably 3~30 times moles of polyamide acidic group.The acid imide rate of resulting polymers can be with It is controlled by adjusting catalytic amount, temperature, reaction time.Due to being remained in the solution after the imidization reaction of polyamic acid There is added catalyst etc., it is therefore preferable that recycle obtained imide amination polymer by following means, and with organic Solvent is redissolved, so that aligning agent for liquid crystal of the invention be made.

It, can be by being injected while being sufficiently stirred for the solution of polyimides obtained from operating as described above In poor solvent, polymer is precipitated.It is precipitated and is cleaned with poor solvent for several times, then carried out air drying or heating is dry It is dry, it is hereby achieved that the polymer powder of purifying.Aforementioned poor solvent is not particularly limited, methanol, 2- third can be enumerated Alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl alcohol, toluene, benzene etc., preferably methanol, second Alcohol, 2- propyl alcohol, acetone etc..

Polyimide precursor, that is, poly amic acid ester used in the present invention can by (i) as follows, (ii) or (iii) manufacturing method manufactures.

(i) when being manufactured by polyamic acid

Poly amic acid ester can be manufactured by being esterified to the aforementioned polyamic acid manufactured like that.Specifically, can By reacting polyamic acid at -20 DEG C~150 DEG C, preferably 0 DEG C~50 DEG C with esterifying agent in presence of organic solvent 30 minutes~24 hours, preferably react 1~4 hour and manufacture.

As esterifying agent, it is preferably able to the substance being readily removable by purifying, can be enumerated: N, N- dimethyl formyl Amine dimethylacetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N, N- dimethyl Formamide di neo-pentyl butyl acetal, N,N-dimethylformamide di-t-butyl acetal, 1- methyl -3- p-methylphenyl triazenes, 1- ethyl -3- p-methylphenyl triazenes, 1- propyl -3- p-methylphenyl triazenes, 4- (4,6- dimethoxy -1,3,5- triazine -2- Base) -4- methyl morpholine hydrochloride etc..The additive amount of esterifying agent is relative to 1 mole of repetitive unit of polyamic acid preferably 2~6 Molar equivalent.

It as organic solvent, such as can enumerate: n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone or γ-fourth Lactone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide or 1,3- dimethyl-2-imidazolidinone.In addition, In the case where the solvent solubility of polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4- hydroxyl -4- first can be used Solvent shown in base -2 pentanone or following formula [D-1]~formula [D-3].

In formula [D-1], D¹The alkyl for indicating carbon number 1~3, in formula [D-2], D²Indicate the alkyl of carbon number 1~3, formula [D-3] In, D³Indicate the alkyl of carbon number 1~4.These solvents can be used alone, and can also be used in mixed way.In turn, even can not make The solvent of polyimide precursor dissolution, as long as also may be combined in the range of the polyimide precursor of generation will not be precipitated It is used in aforementioned solvents.It hinders polymerization reaction in addition, the moisture in solvent can become, even make the polyimide precursor water generated The reason of solution, therefore, solvent, use after preferably dehydrating.

From the deliquescent angle of polymer, solvent used in above-mentioned reaction is preferably N, N- dimethyl formyl Amine, n-methyl-2-pyrrolidone or gamma-butyrolacton, they can be used a kind or are mixed with two or more.From being not susceptible to gather It closes the precipitation of object and is easy to get the angle of high molecular weight body and set out, concentration when manufacture is preferably 1~30 mass %, more preferably For 5~20 mass %.

(ii) by tetracarboxylic acid acid diesters diacid chloride with diamines when reacting to manufacture

Poly amic acid ester can be manufactured by tetracarboxylic acid acid diesters diacid chloride and diamines.Specifically, can by alkali and Tetracarboxylic acid acid diesters diacid chloride is set to react 30 at -20 DEG C~150 DEG C, preferably 0 DEG C~50 DEG C with diamines in the presence of organic solvent Minute~24 hours reacts 1~4 hour preferably to manufacture.Pyridine, triethylamine, 4-dimethylaminopyridine can be used in the alkali Deng, in order to carry out with making reacting balance, preferably pyridine.For the additive amount of alkali, the amount that Cong Qiwei is easily removed, and be easy to obtain The angle of sub- amount body of securing satisfactory grades is set out, and is 2~4 times moles preferably with respect to tetracarboxylic acid acid diesters diacid chloride.

From the deliquescent angle of monomer and polymer, solvent used in above-mentioned reaction is preferably N- methyl -2- Pyrrolidones or gamma-butyrolacton, they can be used a kind or are mixed with two or more.From the precipitation for being not susceptible to polymer and The angle for being easy to get high molecular weight body is set out, polymer concentration when manufacture be preferably 1~30 mass %, more preferably 5~ 20 mass %.In addition, the hydrolysis of tetracarboxylic acid acid diesters diacid chloride in order to prevent, solvent used in the manufacture of poly amic acid ester is excellent Choosing is dehydrated as much as possible, and being mixed into for outside air is prevented preferably in nitrogen atmosphere.

(iii) when being manufactured by tetracarboxylic acid acid diesters and diamines

Poly amic acid ester can be manufactured by the way that tetracarboxylic acid acid diesters are carried out polycondensation with diamines.Specifically, can pass through Make tetracarboxylic acid acid diesters and diamines at 0 DEG C~150 DEG C, preferably 0 DEG C~100 DEG C in the presence of condensing agent, alkali and organic solvent It reacts 30 minutes~24 hours, react 3~15 hours preferably to manufacture.

Triphenyl phosphite, dicyclohexylcarbodiimide, 1- ethyl -3- (3- dimethylamino can be used in aforementioned condensation agent Propyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-cyanuro 1,3,5 methyl morpholine, O- (benzo three Azoles -1- base)-N, N, N ', N '-tetramethylurea tetrafluoroborate, O- (benzotriazole -1- base)-N, N, N ', N '-tetramethylurea six Fluorophosphate, (2,3- dihydro -2- thioketones -3- benzoxazolyl) phosphonic acid diphenyl ester etc..The additive amount of condensing agent is relative to tetracarboxylic acid Acid diesters are preferably 2~3 times moles.

The tertiary amines such as pyridine, triethylamine can be used in the alkali.For the additive amount of alkali, the amount that Cong Qiwei is easily removed, and The angle for being easy to get high molecular weight body is set out, and is 2~4 times moles preferably with respect to diamine component.In addition, in above-mentioned reaction, By addition lewis acid as additive, reaction can be promoted effectively.As lewis acid, preferably lithium chloride, lithium bromide Equal lithium halides.Lewis acidic additive amount is preferably 0~1.0 times mole relative to diamine component.

Among the manufacturing method of above-mentioned 3 kinds of poly amic acid esters, in order to obtain the poly amic acid ester of high molecular weight, especially It is preferred that the manufacturing method of above-mentioned (1) or above-mentioned (2).Solution for the poly amic acid ester obtained in the manner described above passes through on one side It is sufficiently stirred and is injected into poor solvent on one side, so as to so that polymer is precipitated.It is precipitated for several times and clear with poor solvent It washes, air drying or heat drying is then carried out, it is hereby achieved that purified poly amic acid ester powder.Do not have to poor solvent It is particularly limited to, water, methanol, ethyl alcohol, hexane, butyl cellosolve, acetone, toluene etc. can be enumerated.

In order to prepare polymer of the invention, in above-mentioned manufacturing method, can be used two shown in formula (1) as diamines Amine.In addition, the diamines in addition to the diamines shown in formula (1) also can be used as diamines at this time.It, can if enumerating its concrete example It enumerates in above-mentioned formula [W²- 1] to [W²- 197] diamines of 2 amino is bonded on group shown in.In addition, can enumerate The diamines of 2 amino is bonded in the structure of the formula (2) of the record of page 4 of International Publication bulletin 2015/119168 and in state The structure of formula (Y-1)~(Y-97), (Y-101)~(Y-118) that page 8~12 of border Publication 2015/119168 is recorded On be bonded with the diamines of 2 amino；The diamines of the formula (2) of the record of page 6 of International Publication bulletin 2013/008906；It is international public Open the diamines of the formula (1) of the record of page 8 of bulletin 2015/122413；In the note of page 8 of International Publication bulletin 2015/060360 The diamines of 2 amino is bonded in the structure of the formula (3) of load；The record of page 8 of Japanese Laid-Open Patent Publication 2012-173514 The diamines of formula (1)；Formula (A)~(F) diamines etc. of the record of page 9 of International Publication bulletin 2010/050523.

The polymer of the invention obtained in this way may be used as coating, in addition to this can be also used for insulating film, The purposes such as film substrate, liquid crystal orientation film, protective film.

Polymer of the invention is used as in the case where aligning agent for liquid crystal, for polymer, that is, polyimides of the invention The molecular weight of precursor or polyimides is examined in the case where obtaining liquid crystal orientation film by the aligning agent for liquid crystal containing the polymer Consider its film (liquid crystal orientation film) intensity, formed film when workability and film uniformity, utilize GPC (gel Permeation chromatography；Gel Permeation Chromatography) method measurement weight average molecular weight be preferably 2000~500000, More preferably 5000~300000, further preferably 10000~100000.

Aligning agent for liquid crystal of the invention contains the polymer (specific aggregation obtained as the diamines with structure shown in formula (1) Object), in the range of can obtain the effect that the present invention records, two or more specific aggregation with different structure can be contained Object.In addition, removing specific aggregation beyond the region of objective existence, it can also contain other polymers, i.e. the diamines as not having divalent group shown in formula (1) obtains The polymer arrived.As the type of other polymers, can enumerate: polyamic acid, poly amic acid ester, polyester, gathers polyimides Amide, polyureas, polysiloxane, cellulose derivative, polyacetals, polystyrene or derivatives thereof, poly- (styrene-phenyl Maleimide) derivative, poly- (methyl) acrylate etc..The case where aligning agent for liquid crystal of the invention contains other polymers Under, relative to all component of polymer, the ratio of particular polymers is preferably 5 mass % or more, can be arranged as an example therein Enumerate 5~95 mass %.

Aligning agent for liquid crystal is used to prepare liquid crystal orientation film, from the angle for forming uniform film, generallys use coating The form of liquid.In aligning agent for liquid crystal of the invention, preferably also containing aforementioned polymer ingredient and the component of polymer is dissolved The coating fluid of organic solvent.At this point, the concentration of the polymer in aligning agent for liquid crystal can be according to the thickness for thinking film to be formed Setting and be suitable for change, from the viewpoint of forming uniform and flawless film, preferably 1 mass % or more, from solution Storage stability from the perspective of, be preferably set to 10 mass % or less.The concentration of particularly preferred polymer is 2~8 matter Measure %.

Organic solvent contained in aligning agent for liquid crystal, without special as long as the solvent for making component of polymer uniform dissolution It limits.If enumerating its concrete example, it can enumerate: n,N-Dimethylformamide, n,N-dimethylacetamide, N- methyl -2- pyrrole Pyrrolidone, N- ethyl-2-pyrrolidone, dimethyl sulfoxide, gamma-butyrolacton, 1,3- dimethyl-2-imidazolidinone, methyl ethyl ketone, hexamethylene Ketone, cyclopentanone etc..Wherein, it is preferable to use n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone or gamma-butyrolacton.

In addition, the organic solvent contained in aligning agent for liquid crystal is usually using mixed solvent, the mixed solvent is in addition to above-mentioned Except such solvent, the surface smoothness of coating when improving coating of liquid crystalline alignment agent and/or film has also been applied in combination Solvent, it is also preferred that using this mixed solvent in aligning agent for liquid crystal of the invention.The organic solvent being applied in combination is enumerated below Concrete example, but be not limited to these examples.

For example, ethyl alcohol, isopropanol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1- amylalcohol, 2- amylalcohol, 3- Amylalcohol, 2-methyl-1-butene alcohol, isoamyl alcohol, tert-pentyl alcohol, 3- methyl -2- butanol, neopentyl alcohol, 1- hexanol, 2- methyl-1-pentene alcohol, 2- Methyl -2- amylalcohol, 2- ethyl-n-butyl alcohol, 1-heptanol, 2- enanthol, 3- enanthol, 1- octanol, sec-n-octyl alcohol, 2- ethyl -1- hexanol, ring Hexanol, 1 methyl cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 1,2- ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,5- pentanediol, 2- methyl -2,4-PD, 2- second Base -1,3- hexylene glycol, dipropyl ether, butyl oxide, two hexyl ethers, dioxanes, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol two Butyl ether, 1,2- butoxy ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4- hydroxy-4-methyl-2-pentanone, diethyl two Alcohol ethyl methyl ether, dibutyl ethylene glycol ether, 2 pentanone, propione, methyl-n-butyl ketone, 2-HEPTANONE, 4- heptanone, acetic acid 3- Ethoxybutyl, 1- methyl amyl acetic acid esters, 2- ethyl-butyl acetic acid esters, 2- ethylhexyl acetate, ethylene glycol acetate, ethylene glycol diethyl Acid esters, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethyl alcohol, ethylene glycol monobutyl ether, ethylene glycol list isoamyl ether, Ethylene glycol monohexylether, 2- (hexyloxy) ethyl alcohol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- (butoxy ethoxy Base) propyl alcohol, propylene glycol methyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol two Methyl ether, Tripropylene glycol monomethyl Ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol monomethyl ether acetate, Ethylene glycol acetate, ethylene acetate, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate, acetic acid 2- (2- ethoxy ethoxy) ethyl ester, diethylene glycol acetic acid esters, triethylene glycol, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, Ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-propionic acid Methylethyl, 3- methoxypropionate, 3- ethoxy-c Acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, methyl lactate, ethyl lactate, lactic acid positive third Ester, n-butyl lactate, isoamyl lactate, solvent shown in following formula [D-1]~[D-3] etc..

In formula [D-1], D¹The alkyl for indicating carbon number 1~3, in formula [D-2], D²Indicate the alkyl of carbon number 1~3, formula [D-3] In, D³Indicate the alkyl of carbon number 1~4.

Wherein, it is preferable to use 1- hexanol, cyclohexanol, 1,2- ethylene glycol, 1,2-PD, propylene glycol monobutyl ether, diethyl two Diethylene glycol diethyl ether, 4- hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether or dimethyl ether.The type of this solvent and contain Amount is suitably selected according to apparatus for coating, application conditions, coating environment of aligning agent for liquid crystal etc..

Aligning agent for liquid crystal of the invention can within the scope of the effect of the invention in addition containing except polymer at Divide and the ingredient except organic solvent.It as this supplementary element, can enumerate: for improving the close of liquid crystal orientation film and substrate The closely sealed auxiliary agent of conjunction property, the adaptation of liquid crystal orientation film and sealing material；For improving the crosslinking agent of liquid crystal aligning film strength； Dielectric or conductive materials etc. for adjusting the dielectric constant of liquid crystal orientation film, resistance.As the specific of these supplementary elements Example, discloses various concrete examples in the known document about aligning agent for liquid crystal, if enumerating wherein an example, can enumerate open public affairs Ingredient disclosed in the 0105th section of page 53~the 0116th section of page 55 of report 2015/060357 etc..

Liquid crystal orientation film of the invention is the film obtained by the aligning agent for liquid crystal.Liquid is obtained by aligning agent for liquid crystal if enumerating An example of the method for brilliant alignment films can be enumerated for the aligning agent for liquid crystal of coating fluid form to be coated on substrate and do Film obtained from dry, firing, the method handled by brushing facture or light orientation position logos.It is orientated as coating of liquid crystalline The substrate of agent is not particularly limited as long as the high substrate of the transparency, in addition to glass substrate, silicon nitride board, can also make With plastic bases such as acrylic compounds substrate, polycarbonate substrate etc..At this point, the angle for the chemical industry sequence that conforms to the principle of simplicity is set out, it is preferable to use shape At the substrate having for driving ITO electrode of liquid crystal etc..In addition, being indicated in element in reflective liquid crystal, if only single sided substrate If, the opaque articles such as Silicon Wafer also can be used, the material of the meeting reflected light such as aluminium also can be used in electrode in this case Material.

The coating method of aligning agent for liquid crystal is not particularly limited, industrial usual way is silk-screen printing, hectograph Printing, flexographic printing, ink ejecting method etc..As other coating methods, there are infusion process, rolling method, slot coated method, spin coating Method, spray coating method etc. can use these methods according to purpose.After aligning agent for liquid crystal is applied on substrate, pass through heating The heating devices such as plate, thermal cycle type baking oven, IR (infrared ray) type baking oven, by solvent evaporation, firing.After coating of liquid crystalline alignment agent In dry, firing process, arbitrary temperature and time can choose.In general, can be enumerated to sufficiently remove contained solvent Out: being burnt at 50~120 DEG C 1~10 minute, 5~120 minutes conditions are then burnt at 150~300 DEG C.

Coating thickness after firing is not particularly limited, but it is excessively thin when, liquid crystal indicate element reliability sometimes It reduces, therefore preferably 5~300nm, more preferably 10~200nm.Liquid crystal orientation film of the invention is suitable as IPS type, FFS The liquid crystal of the Transverse electric-field types such as type indicates the liquid crystal orientation film of element, and the liquid crystal particularly suitable as FFS type indicates element Liquid crystal orientation film.

Liquid crystal of the invention indicates that element obtains as follows: obtaining with the liquid crystal obtained by above-mentioned aligning agent for liquid crystal After the substrate of alignment films, liquid crystal cells are prepared by known method, element is made using the liquid crystal cells.As liquid crystal cells One example of preparation method, is illustrated so that the liquid crystal of passive-matrix structure indicates element as an example.It should be noted that can also Think that each pixel portion for constituting image expression, which is provided with TFT (thin film transistor (TFT) (Thin Film Transistor)) etc., to be opened The liquid crystal for closing the active matrix structure of element indicates element.

Specifically, common electrode is arranged on one substrate, in another base firstly, prepare transparent glass substrate of electrode Segment electrode is set on plate.These electrodes can for example form ITO electrode, the shape in a manner of it can carry out desired image and indicate At pattern.Then, on each substrate, insulating film is set in a manner of covering common electrode and segment electrode.Insulating film such as can be with Using the SiO by being formed by sol-gel method₂-TiO₂The film of formation.Then, under the above conditions, formed on each substrate Liquid crystal orientation film.Then, it is configured for example at the specified position on the plate base in 2 plate bases for being formed with liquid crystal orientation film Ultra-violet solidified sealing material, further, in liquid crystal aligning film surface as defined in liquid crystal is configured at multiple positions.It connects Get off, by pasting another plate base in liquid crystal orientation film mode facing with each other and crimping, makes liquid crystal in liquid crystal orientation film Then whole surface expansion obtains liquid crystal cells with the whole surface of ultraviolet light irradiation substrate to make sealing material solidify.

Alternatively, matching at the specified position on a plate base as liquid crystal orientation film subsequent process is formed on substrate When setting sealing material, presetting can be from the opening portion of external filling liquid crystal.Then, it is pasted in the case where not configuring liquid crystal After substrate, liquid crystal material is injected into liquid crystal cells by the opening portion of setting on the sealing material, it is then close with bonding agent The opening portion is sealed to obtain liquid crystal cells.Vacuum impregnation can be used in the injection of liquid crystal material, also can be used in atmosphere The middle method using capillarity.

In any of the above-described method, in order to ensure the space of the filling liquid crystal material in liquid crystal cells, preferably take as follows Means: being arranged columnar protrusions on a plate base, perhaps spreads spacer on a plate base or is mixed into sealing material Spacer, or by these combine etc..It as above-mentioned liquid crystal material, can enumerate: nematic liquid crystal and smectic liquid crystal, wherein It is preferred that nematic liquid crystal, also can be used any one of positive type liquid crystal material, negative type liquid crystal material.Then, polarizing film is carried out Setting.Specifically, it is preferable that pasting a pair of of polarizing film on 2 plate bases and surface that liquid crystal layer is opposite side.

It should be noted that as long as liquid crystal orientation film of the invention and liquid crystal indicate that element uses liquid crystal aligning of the invention Agent is then not limited to above description, is also possible to through the manufacture of method well known to other.For from aligning agent for liquid crystal to obtaining liquid The process that crystalline substance indicates element, for example, in addition to page 17 of Japanese Unexamined Patent Publication 2015-135393 (Japanese Patent Publication) the The 0081st section of 0074 section~page 19 is disclosed, and is also disclosed in many other documents.

Embodiment

Enumerating embodiment below, the present invention will be described in more detail, but the present invention is not restricted to these.The present embodiment It is as follows with the shorthand notation of compound used in comparative example, the method for evaluating characteristics.

NMP:N- N-methyl-2-2-pyrrolidone N

BCS: butyl cellosolve

GBL: gamma-butyrolacton

DA-1-1: following formula DA-1-1 compound represented

DA-1-2: following formula DA-1-2 compound represented

DA-1-3: following formula DA-1-3 compound represented

DA-1-4: following formula DA-1-4 compound represented

DA-1-5: following formula DA-1-5 compound represented

DA-1-6: following formula DA-1-6 compound represented

DA-1-7: following formula DA-1-7 compound represented

DA-1-8: following formula DA-1-8 compound represented

DA-1-9: following formula DA-1-9 compound represented

DA-1-10: following formula DA-1-10 compound represented

(embodiment A1: the synthesis of specific diamines)

(DA-1-1) synthesis

N is added in flask, N'- (1,4- phenylene) dimaleimide 8g (29.8mmol) and tetrahydrofuran are (following Referred to as THF) 160g, then it is cooled with ice.4- (2- methylaminoethyl) aniline 9.801g is added into the mixture (65.2mmol).Then, it after being gradually restored to room temperature, is stirred at room temperature 1 day.Confirmation after reaction, is depressurized and is distilled Remove THF.Methanol 140g is added into gained residue and stirs.Filtering gained precipitate.Filtrate is added to 140g first In alcohol, stirs and filter again, obtain crystal.Gained crystal is dry at 50 DEG C, obtain target compound (DA-1-1) 12.44g (yield 73%, HPLC area percentage: 99.1%).

1H-NMR (CDCl3, δ ppm): 7.35 (s, 4H), 6.88 (d, 4H), 6.49 (d, 4H), 4.82 (brs, 4H), 4.19 (dd、2H)、2.89-2.98(m、2H)、2.53-2.80(m、10H)

(embodiment A2: the synthesis of specific diamines)

(DA-1-2) synthesis

N, N '-(Isosorbide-5-Nitrae-phenylene) dimaleimide 1.00g (3.73mmol) and THF10g are added in flask, then It is cooled with ice.3- amino methyl aniline 1.00g (8.19mmol) is added into the mixture.Then, it is being gradually restored to room temperature Afterwards, it is stirred at room temperature 1 day.Confirmation after reaction, depressurizes and distills removal THF.Isopropanol is added into gained residue (hereinafter referred to as IPA) is simultaneously stirred, and obtains crystal.Filtering gained crystal, the filtered crystal is dry at 50 DEG C, obtain mesh Mark compound (DA-1-2) 0.55g (yield 29%).

1H-NMR (d6-DMSO, δ ppm): 7.40 (s, 4H), 6.93-6.99 (m, 2H), 6.58-6.61 (m, 2H), 6.49- 6.53(m、2H)、6.42-6.47(m、2H)、4.99(brs、4H)、3.71-3.90(m、6H)、3.00-3.08(m、2H)、2.87 (brs、2H)、2.56-2.63(m、2H)

(embodiment A3: the synthesis of specific diamines)

(DA-1-3) synthesis

N, N '-(Isosorbide-5-Nitrae-phenylene) dimaleimide 1.00g (3.73mmol) and THF10g are added in flask, then It is cooled with ice.3- ((methylamino) methyl) aniline 1.30g (9.51mmol) is added into the mixture.Then, it is being gradually recovered To after room temperature, it is stirred at room temperature 1 day.Confirmation after reaction, depressurizes and distills removal THF.It is added into gained residue IPA 100g is simultaneously stirred, and obtains crystal.Filtering gained crystal, the filtered crystal is dry at 50 DEG C, obtain targeted Close object (DA-1-3) 1.21g (yield 60%).

1H-NMR (d6-DMSO, δ ppm): 7.40 (s, 4H), 6.94-6.99 (m, 2H), 6.57-6.60 (m, 2H), 6.44- 6.50(m、4H)、5.00(brs、4H)、4.12-4.18(m、2H)、3.62(dd、4H)、2.79-2.98(m、4H)、2.27(s、 6H)

(embodiment A4: the synthesis of specific diamines)

(DA-1-4) synthesis

N, N '-(1,3- phenylene) dimaleimide 1.00g (3.73mmol) and THF 10g are added in flask, so After be cooled with ice.3- ((methylamino) methyl) aniline 1.12g (8.22mmol) is added into the mixture.Then, gradually extensive It answers to after room temperature, is stirred at room temperature 3 hours.Confirmation after reaction, IPA 100g is added into reaction mixture and stirs, Obtain crystal.Filtering gained crystal, the filtered crystal is dry at 50 DEG C, obtain target compound (DA-1-4) 1.63g (yield 80%).

1H-NMR (d6-DMSO, δ ppm): 7.58-7.63 (m, 1H), 7.32-7.46 (m, 2H), 7.22-7.25 (m, 1H), 6.94-6.99(m、2H)、6.57-6.60(m、2H)、6.44-6.49(m、4H)、5.00(brs、4H)、4.12-4.17(m、2H)、 3.61(dd、4H)、2.77-2.96(m、4H)、2.26(s、6H)

(embodiment A5: the synthesis of specific diamines)

(DA-1-5) synthesis

N, N '-(1,3- phenylene) dimaleimide 1.00g (3.73mmol) and THF 10g are added in flask, so After be cooled with ice.2- (4- aminophenyl) ethamine 1.12g (8.22mmol) is added into the mixture.Then, it is being gradually recovered To after room temperature, an evening is stirred at room temperature.Confirmation after reaction, IPA 100g is added into reaction mixture and stirs, obtains To crystal.Filtering gained crystal, the filtered crystal is dry at 50 DEG C, obtain target compound (DA-1-5) 0.57g (yield 38%).

1H-NMR (d6-DMSO, δ ppm): 7.56-7.61 (m, 1H), 7.29-7.32 (m, 2H), 7.21-7.23 (m, 1H), 6.84(d、4H)、6.49(d、4H)、4.82(brs、4H)、3.86-3.93(m、2H)、3.16(brs、2H)、3.01-3.09(m、 2H)、2.90-2.99(m、2H)、2.70-2.80(m、2H)、2.50-2.59(m、6H)

(embodiment A6: the synthesis of specific diamines)

(DA-1-6) synthesis

N, N '-(1,3- phenylene) dimaleimide 1.00g (3.73mmol) and THF 10g are added in flask, so After be cooled with ice.4- (2- methylaminoethyl) aniline 1.23g (8.19mmol) is added into the mixture.Then, gradually After being restored to room temperature, an evening is stirred at room temperature.Confirmation after reaction, IPA 200g is added into reaction mixture and stirs It mixes, obtains crystal.Filtering gained crystal, the filtered crystal is dry at 50 DEG C, obtain target compound (DA-1-6) 1.50g (yield 71%).

1H-NMR (d6-DMSO, δ ppm): 7.57-7.62 (m, 1H), 7.30-7.33 (m, 2H), 7.19-7.21 (m, 1H), 6.87(d、4H)、6.48(d、4H)、4.82(brs、4H)、4.15-4.21(m、2H)、2.86-2.96(m、2H)、2.66-2.78 (m、6H)、2.52-2.60(m、4H)、2.35(s、6H)

(embodiment A7: the synthesis of specific diamines)

(DA-1-7) synthesis

Bis- [3- ethyl -5- methyl -4- (maleimide -1- base) phenyl] methane 2.00g are added in flask (4.52mmol) and THF 20g, is then cooled with ice.3- amino methyl aniline 1.21g is added into the mixture (9.90mmol).Then, after being gradually restored to room temperature, an evening is stirred at room temperature.Confirmation after reaction, is mixed to reaction Hexane 300g is added in object and stirs, obtains crystal.Filtering gained crystal, the filtered crystal is dry at 50 DEG C, it obtains To target compound (DA-1-7) 2.85g (yield 92%).

1H-NMR(d6-DMSO、δppm)7.04-7.12(m、4H)、6.93-6.98(m、2H)、6.56-6.58(m、2H)、 6.42-6.52(m、4H)、4.98(brs、4H)、3.93-3.99(m、2H)、3.91(s、2H)、3.73(dd、4H)、3.09-3.18 (m、2H)、2.87(brs、2H)、2.66-2.74(m、2H)、2.36(q、2H)、2.30(q、2H)、2.02(s、3H)、1.97(s、 3H)、1.03(t、3H)、0.99(t、3H)

(embodiment A8: the synthesis of specific diamines)

(DA-1-8) synthesis

Bis- [3- ethyl -5- methyl -4- (maleimide -1- base) phenyl] methane 1.00g are added in flask (2.26mmol) and THF 10g, is then cooled with ice.3- ((methylamino) methyl) aniline 0.68g is added into the mixture (4.99mmol).Then, it after being gradually restored to room temperature, is stirred at room temperature 3 days.Confirmation after reaction, is mixed to reaction IPA 150g is added in object and stirs, obtains crystal.Filtering gained crystal, the filtered crystal is dry at 50 DEG C, it obtains To target compound (DA-1-8) 1.62g (yield 41%).

1H-NMR(d6-DMSO、δppm)7.05-7.12(m、4H)、6.94-6.98(m、2H)、6.56-6.58(m、2H)、 6.44-6.49(m、4H)、5.01(brs、4H)、4.29-4.34(m、2H)、3.91(s、2H)、3.63(dd、4H)、2.94-3.11 (m、4H)、2.26-2.36(m、4H)、2.27(s、3H)、2.01(s、3H)、1.97(s、3H)、1.04(t、3H)、1.02(t、3H)

(embodiment A9: the synthesis of specific diamines)

(DA-1-9) synthesis

Bis- [4- (4- maleimide -1- phenoxyl) phenyl] the propane 10.0g of 2,2- are added in flask (17.5mmol) and THF 100g, is then cooled with ice.4- (2- methylaminoethyl) aniline 5.79g is added into the mixture (38.5mmol).Then, it after being gradually restored to room temperature, is stirred at room temperature 3 days.Confirmation after reaction, is steamed under reduced pressure It evaporates except solvent.IPA300g is added into gained residue and stirs.Filtering gained precipitate.It is added in gained filtrate Ethyl alcohol 100g stirs and filters again, obtains crystal.Gained crystal is dry at 70 DEG C, obtain target compound (DA-1- 9) 13.8g (yield 90%).

1H-NMR(CDCl3、δppm)7.17-7.23(m、8H)、7.03-7.07(m、4H)、6.93-7.00(m、8H)、 6.59-6.63(m、4H)、4.01-4.06(m、2H)、3.57(brs、4H)、2.89-2.98(m、2H)、2.66-2.84(m、 10H)、2.47(s、6H)、1.68(s、6H)

(embodiment A10: the synthesis of specific diamines)

(DA-1-10) synthesis

A) bis- (4- amino-benzene oxygen) the propane 10g (38.7mmol) of 1,3- and 1- methyl -2- pyrrolidines are added in flask Ketone (hereinafter referred to as NMP) 80g, is then cooled with ice.Maleic anhydride 8.35g (85.2mmol) is added into the mixture.Then, After being gradually restored to room temperature, it is stirred at room temperature 1 day.P-methyl benzenesulfonic acid monohydrate 1g and right is added into reaction mixture After dimethylbenzene 250g, water is removed using Dean-Stark device under reflux on one side, is reacted 6 hours on one side.Confirmation reaction terminates Afterwards, distillation removes solvent under reduced pressure.By gained residue chloroform-silica gel chromatography, the target of yellow crystals is obtained Object DA-1-10a 11.2g (yield 69%).

1H-NMR(CDCl3、δppm)7.20-7.25(m、4H)、6.96-7.01(m、4H)、6.83(s、4H)、4.18(t、 4H)、2.24-2.32(m、2H)

B) DA-1-10a 1.00g (2.39mmol) and THF 10g are added in flask, is then cooled with ice.To the mixing 4- (2- methylaminoethyl) aniline 0.79g (5.26mmol) is added in object.Then, after being gradually restored to room temperature, in room temperature Lower stirring 3 days.After reaction, distillation removes solvent under reduced pressure for confirmation.IPA 30g is added into gained residue and stirs It mixes, obtains crystal.Filtering gained crystal, the filtered crystal is dry at 45 DEG C, obtain the targeted of light yellow crystal Close object (DA-1-10) 1.53g (yield 89%).

1H-NMR(CDCl3、δppm)7.12-7.18(m、4H)、6.94-7.01(m、8H)、6.60-6.65(m、4H)、 4.12-4.19(m、4H)、4.01-4.07(m、2H)、3.58(brs、4H)、2.88-2.98(m、2H)、2.63-2.86(m、 10H)、2.48(s、6H)、2.22-2.30(m、2H)

The Production Example of the polymer described below for having used diamines of the invention.Shorthand notation is as follows.

DA-1-1: following formula DA-1-1 compound represented

DA-2: following formula DA-2 compound represented

DA-3: following formula DA-3 compound represented

DA-4: following formula DA-4 compound represented

CA-1: following formula CA-1 compound represented

CA-2: following formula CA-2 compound represented

[viscosimetric analysis]

For the viscosity of polyamic acid solution, using E type viscosimeter TVE-22H (Toki Sangyo Co., Ltd.'s manufacture) with sample Product amount 1.1ml, cone rotor TE-1 (1 ° 34 ', R24) are measured.

[embodiment PAA-1]

After DA-1-1 (3.98g, 7mmol) is added in the 50ml four-hole boiling flask with agitating device and nitrogen ingress pipe, add Enter NMP 31.0g, is stirred to dissolve while supplying nitrogen.CA-1 is added while being stirred to the diamine solution After (0.61g, 2.8mmol), CA-2 (0.74g, 3.8mmol), NMP 8.1g, further stirred 12 hours under the conditions of 50 DEG C, To obtain polyamic acid solution (PAA-1).Viscosity at 25 DEG C of the polyamic acid solution is 300mPas.

[embodiment PAA-2]

After DA-1-1 (2.27g, 4mmol) is added in the 50ml four-hole boiling flask with agitating device and nitrogen ingress pipe, add Enter NMP 18.2g, is stirred to dissolve while supplying nitrogen.CA-1 is added while being stirred to the diamine solution After (0.82g, 3.8mmol), NMP 5.5g, further stirred 12 hours under the conditions of 50 DEG C, to obtain polyamic acid solution (PAA-2).Viscosity at 25 DEG C of the polyamic acid solution is 225mPas.

[embodiment PAA-3]

DA-1-1 (0.68g, 1.2mmol), DA- are added in the 50ml four-hole boiling flask with agitating device and nitrogen ingress pipe After 2 (1.37g, 4.8mmol), NMP 19.4g is added, is stirred to dissolve while supplying nitrogen.It is molten to the diamines on one side After liquid is stirred addition CA-1 (1.24g, 5.7mmol) on one side, NMP 4.8g is added, is then further stirred at room temperature It mixes 12 hours, to obtain polyamic acid solution (PAA-3).Viscosity at 25 DEG C of the polyamic acid solution is 240mPas.

[embodiment PAA-4]

DA-3 (4.78g, 24mmol), DA-4 are added in the 100ml four-hole boiling flask with agitating device and nitrogen ingress pipe After (1.18g, 6mmol), NMP 52.7g is added, is stirred to dissolve while supplying nitrogen.On one side to the diamine solution into After row stirring adds CA-2 (5.64g, 28.8mmol) on one side, NMP 13.2g is added, is then further stirred at room temperature 12 hours, to obtain polyamic acid solution (PAA-4).Viscosity at 25 DEG C of the polyamic acid solution is 550mPas.

[embodiment 1]

Divide and take the polyamic acid solution obtained in embodiment PAA-1 (PAA-1) 7.5g, adds NMP while stirring 6.6g, BCS 5.0g, 3- aminopropyl triethoxysilane comprising 1 weight % nmp solution 0.9g, further stir at room temperature It mixes 2 hours, obtains aligning agent for liquid crystal (Q-1).

[embodiment 2]

Divide and take the polyamic acid solution obtained in embodiment PAA-2 (PAA-2) 7.5g, adds NMP while stirring 6.6g, BCS 5.0g, 3- aminopropyl triethoxysilane comprising 1 weight % nmp solution 0.9g, further stir at room temperature It mixes 2 hours, obtains aligning agent for liquid crystal (Q-2).

[embodiment 3]

Divide and take the polyamic acid solution obtained in embodiment PAA-3 (PAA-3) 7.5g, adds NMP while stirring 6.6g, BCS 5.0g, 3- aminopropyl triethoxysilane comprising 1 weight % nmp solution 0.9g, further stir at room temperature It mixes 2 hours, obtains aligning agent for liquid crystal (Q-3).

[embodiment 4]

Divide and take the polyamic acid solution obtained in embodiment PAA-2 (PAA-2) 1.5g, is added thereto in embodiment Polyamic acid solution obtained in PAA-4 (PAA-4) 4.8g adds NMP 7.8g, BCS 5.0g, comprising 1 while stirring The nmp solution 0.9g of the 3- aminopropyl triethoxysilane of weight % is further stirred at room temperature 2 hours, obtains liquid crystal and take To agent (Q-4).

[embodiment 5]

Divide and take the polyamic acid solution obtained in embodiment PAA-3 (PAA-3) 1.5g, is added thereto in embodiment Polyamic acid solution obtained in PAA-4 (PAA-4) 4.8g adds NMP 7.8g, BCS 5.0g, comprising 1 while stirring The nmp solution 0.9g of the 3- aminopropyl triethoxysilane of weight % is further stirred at room temperature 2 hours, obtains liquid crystal and take To agent (Q-5).

[embodiment 6]

After DA-1-1 (5.69g, 10mmol) is added in the 100ml four-hole boiling flask with agitating device and nitrogen ingress pipe, NMP 57.46g is added, is stirred to dissolve while supplying nitrogen.It is added while being stirred to the diamine solution After CA-2 (1.82g, 9.30mmol), NMP 8.26g, further stir 12 hours at room temperature, to obtain polyamide Acid solution (PAA-5).It is added while stirring into 376g methanol polyamic acid solution (PAA-5).Obtained solid is filtered, is used The cleaning of 75g methanol.Further, after stirring solid in 376g methanol, filter solid is crossed, is cleaned with 75g methanol.Obtained solid is true Sky is dry, obtains polyamic acid 6.65g (yield 88%).

[embodiment 7]

Solid 3g and NMP 34.5g obtained in embodiment 6 is added in 50ml four-hole boiling flask, is heated to 60 DEG C.To this Acetic anhydride 1.20g (11.8mmol) and pyridine 0.31g (3.92mmol) are added in solution, are stirred 5 hours at 60 DEG C.It is cooling anti- After answering solution, it is added while stirring into 150g methanol.Filter obtained solid.Solid is further added to 150g methanol Middle stirring and after cleaning, filtering.Carry out 3 methanol stirring and washings.Obtained solid vacuum decompression is dry, obtain polyimides 2.49g (yield 83%).

Hereinafter, an example of the usage scenario as polymer of the invention, evaluation when to for aligning agent for liquid crystal As a result it is illustrated.

[production that liquid crystal cells are used in ion concentration measurement]

Filter aligning agent for liquid crystal with 1.0 μm of filters, then using spin-coating method be coated on electroded substrate (having a size of Horizontal 30mm × vertical 40mm, the glass substrate with a thickness of 1.1mm, electrode are width 10mm × length 40mm rectangle, thickness 35nm ITO electrode) on.Drying after five minutes, be burnt within 20 minutes with 230 DEG C of IR formula baking oven, forms film on 50 DEG C of hot plate Thickness is the film of 100nm, obtains the substrate with liquid crystal orientation film.The liquid crystal is taken with rayon cloth (lucky river chemical industry YA-20R) Brushing (roller diameter: 120mm, roller revolving speed: 1000rpm, movement speed: 20mm/sec is pressed into length: 0.4mm) is carried out to film, so Ultrasonic irradiation 1 minute is carried out in pure water afterwards to be cleaned, removes water droplet by blowing, it is then 15 points dry at 80 DEG C Clock is to obtain the substrate with liquid crystal orientation film.

Prepare 2 above-mentioned substrates with liquid crystal orientation film, is spread between 4 μm in wherein 1 liquid crystal aligning film surface Parting, then, from top printing and sealing material, by another plate base using brushing direction as opposite direction and the opposite side of film surface After formula fitting, solidify sealing material, to make dummy cell.By injecting liquid crystal MLC- in decompression injection normal direction dummy cell 3019 (manufactures of MERCK company) seal inlet, obtain liquid crystal cells.Then, gained liquid crystal cells are small with 110 DEG C of heating 1 When, an evening is placed at 23 DEG C, obtains ion concentration measurement liquid crystal cells.

[ion concentration measurement]

Liquid crystal cells by method production described in above-mentioned [production of ion concentration measurement liquid crystal cells] are carried out The measurement of ion concentration.In ion concentration measurement, the triangle for applying voltage ± 10V, frequency 0.01Hz to liquid crystal cells is measured Ion concentration when wave.It is carried out at a temperature of 60 DEG C of measurement.For measuring device, using by Toyo Technology Co., Ltd. the 6256 type liquid crystal evaluation of physical property devices manufactured.

[production of liquid crystal expression element]

Firstly, preparing electroded substrate.Substrate is having a size of 30mm × 35mm, with a thickness of the glass substrate of 0.7mm.? On substrate, as the 1st layer, the IZO electrode of solid shape pattern is formd for structure paired electrode and had.At the 1st layer to electricity On extremely, as the 2nd layer, SiN (silicon nitride) film to form a film using CVD method is formd.The film thickness of 2nd layer of SiN film is 500nm is functioned as interlayer dielectric.On the 2nd layer of SiN film, as the 3rd layer, configure IZO film figure And the comb teeth-shaped pixel electrode formed, to form the 1st pixel and the 2nd pixel the two pixels.The size of each pixel is vertical 10mm, horizontal about 5mm.At this point, the 1st layer to electrode and the 3rd layer of pixel electrode due to the effect of the 2nd layer of SiN film and in electricity Insulation.

3rd layer of pixel electrode is identical as the figure recorded in Japanese Unexamined Patent Publication 2014-77845 (Japanese Laid-Open Patent Publication), The comb teeth-shaped shape constituted with " く " font electrode element that the multiple center portions of arrangement bend.Each electrode element The width of width direction is 3 μm, between electrode element between be divided into 6 μm.The pixel electrode of each pixel is formed by arranging in multiple Centre " く " font electrode element for bending of part and constitute, therefore the shape of each pixel not instead of oblong-shaped, have with Shape that electrode element similarly bends in center portion, being similar to runic " く " word.Also, each pixel is with the center Bending part be that boundary is divided up and down, the 2nd region with the 1st region and downside on the upside of bending part.

When comparing the 1st region and 2 region of each pixel, the formation direction of the electrode element of their pixel electrode is constituted It is different.That is, when using the brushing direction of aftermentioned liquid crystal orientation film as benchmark, in the 1st region of pixel, to be in+10 ° of angle The mode of (clockwise) forms the electrode element of pixel electrode, in the 2nd region of pixel, to be in -10 ° of angle (clockwise) Mode form the electrode element of pixel electrode.That is, the 1st region of each pixel is constituted as follows with the 2nd region: by pixel electricity Pole with to applying voltage between electrode and the direction of the spinning movement (plane switching) of the liquid crystal that induces in real estate phase each other Opposite direction.

Next, then spin application is upper in what is prepared respectively with 1.0 μm of filter filtering gained aligning agent for liquid crystal It states electroded substrate and is overleaf formed with ito film and with the column spacer for being highly 4 μm as counter substrate On glass substrate.Then, drying after five minutes, is burnt into 20 minutes at 230 DEG C, is made film thickness 60nm's on 80 DEG C of hot plate Film obtains polyimide film on each substrate.It is carried out with rayon cloth on the polyimide film with defined brushing direction Brushing (roller diameter: 120mm, roller revolving speed: 500rpm, movement speed 30mm/sec, intrusion 0.3mm), then in pure water into It is row ultrasonic irradiation 1 minute, 10 minutes dry at 80 DEG C.

Then, using above-mentioned 2 with liquid crystal orientation film kind substrate, by their modes antiparallel with respective brushing direction Combination, leaves liquid crystal injecting port and seals surrounding, the dummy cell that production unit gap is 3.8 μm.It is single to the sky at normal temperature In member after vacuum injection liquid crystal (manufacture of MLC-3019, MERCK company), inlet is sealed, the liquid crystal list of antiparallel orientations is made Member.Gained liquid crystal cells, which constitute FFS mode liquid crystal, indicates element.Then, gained liquid crystal cells are heated 1 hour at 120 DEG C, Each evaluation is used for after placing an evening.

[estimation of stability of liquid crystal aligning]

Using the liquid crystal cells, applies frequency 30Hz under 60 DEG C of isoperibol and the alternating voltage 168 of 10VPP is small When.Then, make the pixel electrode of liquid crystal cells and to short-circuit condition is between electrode, place one at room temperature with the state It.After placement, liquid crystal cells are set between 2 polarizing films configured in the orthogonal mode of polarization axle, voltage is not being applied In the state of light backlight, with the arrangement angles of the brightness least way of transmitted light adjustment liquid crystal cells.Then, liquid crystal will be made Rotation angle when the most dark angle in 2nd region of unit from the 1st pixel is rotated to the most dark angle in the 1st region is as angle delta And it calculates.Similarly the 2nd region and the 1st region are compared in 2nd pixel, calculate same angle delta.Then by the 1st The average value of the angle delta value of pixel and the 2nd pixel as liquid crystal cells angle delta and calculate.The angle delta of the liquid crystal cells Value less than 0.15 ° in the case where be defined as " good ", the value of angle delta is defined as " bad " Lai Jinhang in the case of being greater than 0.15 ° Evaluation.

[relaxation properties of accumulated charge]

Above-mentioned liquid crystal cells are set between 2 polarizing films configured in the orthogonal mode of polarization axle, keep pixel electric Pole and to electric pole short circuit at same potential in the state of, from the lower section irradiation LED backlight of 2 polarizing films, adjust liquid crystal cells Angle, so that the brightness of the LED backlight transmitted light measured on 2 polarizing films is minimum.Then, frequency is being applied to the liquid crystal cells While the rectangular wave of rate 30Hz, measure 23 DEG C at a temperature of V-T characteristic (voltage-transmission rate characteristic), calculate it is relatively saturating The rate of penetrating reaches 23% alternating voltage.Since the alternating voltage is equivalent to the region big relative to the brightness change of voltage, It is convenient to pass through luminance evaluation accumulated charge.

Then, applying alternating voltage and the frequency for reaching 23% as relative transmittance is rectangular wave 5 minutes of 30Hz, Then the DC voltage of superposition+1.0V and drive 30 minutes.Then, DC voltage is cut off, only applies be used as Relative Transmission again Rate reaches 23% alternating voltage and frequency is rectangular wave 30 minutes of 30Hz.Since the mitigation of the charge of accumulation is faster, superposition The charge accumulation to liquid crystal cells when DC voltage is also faster, therefore utilizes the Relative Transmission after being just superimposed DC voltage The relaxation properties that time needed for rate is down to 23% in the state of being 30% or more evaluates accumulated charge.The time is shorter, stores The relaxation properties of accumulated charge are the better.

Using aligning agent for liquid crystal Q-1~Q-5 of Examples 1 to 5, the stability of ion concentration measurement, liquid crystal aligning is carried out The evaluation of the relaxation properties of evaluation and accumulated charge.Show the result in table 1.

[table 1]

Industrial availability

Diamines of the invention is cheap, for the polymer obtained by the diamines, can easily assign its various characteristics.Cause This, expects that it is used for the fields such as coating, electronic material, such as the practicability as liquid crystal orientation film etc..

In addition, liquid crystal orientation film of the invention, especially in IPS driving method, the FFS driving method for needing brushing to handle Liquid crystal indicate element in, can by liquid crystal indicate element in ion concentration inhibit in reduced levels, while make accumulation electricity Lotus quickly mitigates.Further, due to being able to suppress the offset of the differently- oriented directivity in brushing direction and liquid crystal, ghost can be obtained The excellent expression performance of characteristic, contrast.Therefore, the liquid crystal especially suitable for IPS driving method, FFS driving method indicates member Liquid crystal orientation film used in part, multi-functional mobile phone (smart phone), tablet-type personal computer, LCD TV etc..

Claims

1. a kind of manufacturing method of diamine compound shown in following formula (1), which comprises make shown in following formula (A) P in bismaleimide compound and following formula (B) compound represented¹It is reacted for the diamino compounds of amino, Huo Zheyu P in following formula (B) compound represented¹For nitro nitro amino compound react process,

Wherein, R indicates hydrogen atom or 1 valence organic group, R¹Indicate hydrogen atom, C₁To C₅Optionally linear chain or branched chain alkyl, Aryl, there are two R on identical maleimide ring¹It is optionally same or different to each other, there are two R¹Shape optionally together At C₃To C₆Alkylidene, W¹Indicate singly-bound or divalent organic group, W²Indicate divalent organic group, Ar¹Indicate aromatic ring, L¹Indicate carbon The alkylidene of atomicity 1 to 20.

2. a kind of diamines, with structure shown in following formula (1),

3. a kind of polymer is obtained as the diamines with structure shown in following formula (1),

4. a kind of aligning agent for liquid crystal contains the polymer obtained as the diamines with structure shown in following formula (1),

5. aligning agent for liquid crystal according to claim 4, wherein Ar¹For 1,3- phenylene or 1,4- phenylene.

6. aligning agent for liquid crystal according to claim 4 or 5, wherein W¹For singly-bound.

7. the aligning agent for liquid crystal according to any one of claim 4 to 6, wherein the polymer is selected from comprising under State structural unit shown in formula (3) polyimide precursor and its acid imide compound i.e. polyimides in it is at least one kind of,

Wherein, X¹For the 4 valence organic groups from tetracarboxylic acid derivatives, Y¹Have for the divalent from the diamines comprising formula (1) structure Machine group, R⁴For hydrogen atom or the alkyl of carbon number 1~5.

8. aligning agent for liquid crystal according to claim 7, wherein in the formula (3), X¹Structure be in following structures It is at least one kind of,

9. aligning agent for liquid crystal according to claim 7 or 8, wherein relative to the entire infrastructure unit of polymer, the formula (3) structural unit shown in is 10 moles of % or more.

10. a kind of liquid crystal orientation film is obtained using aligning agent for liquid crystal described in any one of claim 3 to 9.

11. a kind of liquid crystal indicates element, has liquid crystal orientation film described in any one of claim 10.