CN103739523A

CN103739523A - Liquid crystal aligning agent

Info

Publication number: CN103739523A
Application number: CN201310611123.4A
Authority: CN
Inventors: 中原翔一; 南悟志
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2008-11-06
Filing date: 2009-11-05
Publication date: 2014-04-23
Anticipated expiration: 2029-11-05
Also published as: TW201030059A; CN102203662A; CN103739523B; KR101671659B1; WO2010053128A1; KR20110082589A; KR101613757B1; TWI477533B; CN104761471A; CN102203662B; JPWO2010053128A1; JP5733340B2; JP5333454B2; JP2013241412A; CN104761471B; KR20150138410A

Abstract

Provided is a liquid crystal aligning agent capable of forming a liquid crystal alignment film the surface of which is rarely scratched or abraded when rubbed, and which exhibits excellent liquid crystal aligning properties and enables the production of liquid crystal cells having high voltage holding ratios and low ion densities. The liquid crystal aligning agent contains either a polyimide precursor or a polyimide, said polyimide precursor and polyimide being substances obtained by reacting a diamine component with a tetracarboxylic acid derivative. The liquid crystal aligning agent is characterized in that the diamine component contains a diamine represented by formula (1) [wherein X is an oxygen atom or a sulfur atom; Y1 and Y2 are each independently a single bond, -O-, -S-, -OCO-, or -COO-; and R1 and R2 are each independently a C1-3 alkylene group].

Description

Aligning agent for liquid crystal

The divisional application of the application for a patent for invention that patent application of the present invention is that international application no is that PCT/JP2009/068915, international filing date are on November 5th, 2009, the application number that enters the China national stage is 200980144621.4, denomination of invention is " aligning agent for liquid crystal ".

Technical field

The present invention relates to the aligning agent for liquid crystal for the manufacture of liquid crystal orientation film.Be particularly related to the aligning agent for liquid crystal using in the liquid crystal orientation film of making through friction treatment operation.

Background technology

Liquid crystal orientation film is for controlling the differently-oriented directivity of liquid crystal molecule, to make its constant film in liquid crystal display device or the polarizer that uses polymerizable liquid crystal etc.

As the method for manufacturing easily liquid crystal orientation film, have on substrate, to form the polymeric membranes such as polyimide and implement, by the rub method of so-called friction treatment on this surface of cloth, nowadays still at industrial circle, to be widely used.

The problem that friction treatment exists the dust producing by the wearing and tearing of liquid crystal orientation film and the scar that results from liquid crystal orientation film can make display quality decline, therefore one of desired characteristic of liquid crystal orientation film is exactly rub resistance.

As obtaining the method that is difficult for the liquid crystal orientation film that produces frictional dissipation and friction scar, known method (for example, with reference to patent documentation 1,2) of adding various additives in polyimide or polyimide precursor.The good polyimide structures of wear-resisting wiping (for example, with reference to patent documentation 3,4) has in addition also been proposed.

In recent years, in the part purposes of liquid crystal display device, there is the trend of carrying out friction treatment by stronger friction.This is because by implementing strong friction treatment, can make the state of orientation of liquid crystal more even, and can obtain more firmly product.Therefore, the requirement of the wear-resisting wiping to liquid crystal orientation film is also more and more higher.

Patent documentation 1: Japanese patent laid-open 7-120769 communique

Patent documentation 2: Japanese patent laid-open 9-146100 communique

Patent documentation 3: Japanese Patent Laid-Open 2008-90297 communique

Patent documentation 4: Japanese patent laid-open 9-258229 communique

The announcement of invention

The object of this invention is to provide and can obtain the aligning agent for liquid crystal that is difficult for the good liquid crystal orientation film of wear-resisting wiping that produces frictional dissipation and friction scar.

The inventor has carried out conscientiously research for achieving the above object, found that the novel liquid crystal aligning agent that can obtain the good liquid crystal orientation film of wear-resisting wiping, and the present invention is the invention based on this discovery, has following technology contents.

1. aligning agent for liquid crystal, this treatment agent comprises any in polyimide precursor or the polyimide that two amine components is reacted and obtain with tetracarboxylic acid derivatives, it is characterized in that, and described two amine components comprise the diamines that following formula (1) represents;

In formula (1), X is Sauerstoffatom or sulphur atom, Y ¹and Y ²be independently respectively singly-bound ,-O-,-S-,-OCO-or-COO-, R ¹and R ²be the alkylidene group of carbon number 1～3 independently respectively.

2. the aligning agent for liquid crystal of recording in above-mentioned 1, wherein, in formula (1)-R ¹-Y ¹-and-R ²-Y ²-structure identical.

3. the aligning agent for liquid crystal of recording in above-mentioned 1 or 2, wherein, the Y in formula (1) ¹and Y ²for singly-bound.

4. the aligning agent for liquid crystal that any one is recorded in above-mentioned 1～3, wherein, the X in formula (1) is Sauerstoffatom.

5. the aligning agent for liquid crystal that any one is recorded in above-mentioned 1～4, wherein, described tetracarboxylic acid derivatives is tetracarboxylic dianhydride, tetracarboxylic acid list acid anhydride, tetracarboxylic acid, dicarboxylic acid dialkyl esters or dicarboxylic acid acyl chlorides dialkyl.

6. the aligning agent for liquid crystal that any one is recorded in above-mentioned 1～5, wherein, also wraps fluorinated tensio-active agent, silicone tensio-active agent or nonionic surfactant.

7. the aligning agent for liquid crystal that any one is recorded in above-mentioned 1～6, wherein, also comprises containing the compound of functional silanes or containing the compound of epoxy group(ing).

8. the aligning agent for liquid crystal that any one is recorded in above-mentioned 1～7, wherein, the solid component concentration in aligning agent for liquid crystal is 1～20 quality % with respect to aligning agent for liquid crystal total amount 100 quality %.

9. liquid crystal orientation film, is characterized in that, the aligning agent for liquid crystal of being recorded by any one in above-mentioned 1～8 obtains.

10. liquid crystal display device, is characterized in that, has above-mentioned 9 liquid crystal orientation films of recording.

Two aminophenyls or two amino-benzene oxygen alkyl urea that 11. following formulas (1-7), formula (1-8), formula (1-b) or formula (1-c) represent;

In formula (1-b), R ¹²and R ²²the alkylidene group of the carbon number 1～3 that expression carbon number differs from one another, in formula (1-c), R ¹³and R ²³be the alkylidene group of carbon number 1～3 independently respectively.

Two aminophenyls or two amino-benzene oxygen alkyl urea that 12. following formulas (1-9)～formula (1-11) represents.

The aligning agent for liquid crystal of the application of the invention, the scar on the film surface in the time of can obtaining friction treatment and wearing and tearing less, the good liquid crystal orientation film of orientation of liquid crystal.In addition, in the liquid crystal orientation film obtaining with aligning agent for liquid crystal of the present invention, because the voltage retention of liquid crystal structure cell is high, ion density is also low, so can make the liquid crystal display device of high-quality.

The best mode carrying out an invention

< specific diamine compound >

Aligning agent for liquid crystal of the present invention is characterised in that, comprises polyimide precursor or the polyimide such as polyamic acid, poly amic acid ester, as two amine components of its synthesis material, and the specific diamines that uses following formula (1) to represent.

In formula (1), being urea groups when X is Sauerstoffatom, is thioureido (sometimes urea groups and thioureido being referred to as to (sulphur) urea groups below) during for sulphur atom.

Sauerstoffatom and sulphur atom are the atom that electronegativity is high.In addition, on nitrogen-atoms, there are two to the high hydrogen atom of electronics.Therefore, two hydrogen atoms in the oxygen in (sulphur) urea groups or sulphur atom and other (sulphur) urea groups are by non covalent bond self aggregation comparatively securely.In the present invention, the preferred Sauerstoffatom of X in formula (1).Think that its reason is, if Sauerstoffatom and sulphur atom are compared, because be that Sauerstoffatom is higher aspect electronegativity, so compared with thiocarbamide structure, more easily self aggregation securely of urea structure.

In the present invention, in aligning agent for liquid crystal, in macromolecular chain, there is (sulphur) urea groups, should (sulphur) urea groups derive from the there is above formula specific diamines of ad hoc structure of (1).Therefore,, by thering is the electrostatic interaction between (sulphur) urea groups existing in the macromolecular chain of ad hoc structure, can improve wear-resisting wiping.In this, the present invention and passing through of conventionally adopting in liquid crystal orientation film field link with linking agent that to improve the method for wear-resisting wiping different between by macromolecular chain.

In formula (1), R ¹and R ²represent independently respectively the alkylidene group of carbon number 1～3, its structure can be any in straight or branched.

As its object lesson, can exemplify methylene radical, ethylidene, trimethylene, 1-methyl ethylidene, 2-methyl ethylidene.Wherein, from the orientation of liquid crystal and the angle of wear-resisting wiping, preferably there is the position and the sterically hindered little structure that rotate freely as much as possible, particularly, preferably methylene radical, ethylidene, trimethylene.

In formula (1), Y ¹and Y ²be independently respectively singly-bound ,-O-,-S-,-OCO-or-COO-.About Y ¹and Y ²structure, from the orientation of liquid crystal and the angle of wear-resisting wiping, also preferred soft as far as possible and sterically hindered little structure, preferably singly-bound ,-O-or-S-.

Forming the high film of film density, form more firmly aspect liquid crystal orientation film, the structure between (sulphur) urea groups and phenyl ring is better symmetrical centered by (sulphur) urea groups, is more preferably-R ¹-Y ¹-and-R ²-Y ²-structure identical.

In the specific diamines that formula (1) represents, the compound that preferably following formula (1-a)～formula (1-c) represents.

In formula (1-a), R ¹¹and R ²¹be the alkylidene group of the carbon number 1～3 that carbon number is equal.

In formula (1-b), R ¹²and R ²²the alkylidene group of the carbon number 1～3 differing from one another for carbon number.

In formula (1-c), R ¹³and R ²³be the alkylidene group of carbon number 1～3 independently respectively.

In formula (1), the amino binding site on phenyl ring is not particularly limited, from the angle of the orientation of liquid crystal, and preferably 3-aminophenyl structure or 4-aminophenyl structure, particularly preferably 4-aminophenyl structure.Particularly, as the example of formula (1), preferably any in following formula (1-1), formula (1-2) or formula (1-3), particularly preferably formula (1-1).

In formula (1-1), formula (1-2) and formula (1-3), Y ¹, Y ², R ¹and R ²definition identical with the definition in formula (1).

Below, as the object lesson of formula (1), announcement formula (1-4)～formula (1-15).

The compound of formula (1-7)～(1-11) is the novel cpd being provided first by the present invention, and obviously, using the polyimide precursor of this compound or polyimide is also novel cpd.The diamine compound in addition of formula (1-7)～(1-11) is known compound, but use the polyimide precursor of these diamine compounds or polyimide, is novel cpd.

The synthetic method > of < diamines

The diamines that formula (1) represents for example can as described belowly synthesize.The diamine compound that formula of the present invention (1) represents is by aniline skeleton, spacer part (R ¹, R ²), linking group (Y ¹, Y ²) and (sulphur) urea groups formation, its synthetic method is not particularly limited, for example can be synthetic by method as described below.

In formula (1), X is Sauerstoffatom or sulphur atom, Y ¹and Y ²be independently respectively singly-bound ,-O-,-S-,-OCO-or-COO-, R ¹and R ²be the alkylidene group of carbon number 1～3 independently respectively.In addition, the amino binding site on phenyl ring is not particularly limited.

The diamine compound that formula of the present invention (1) represents can obtain by the following method: and dinitro compound that synthetic corresponding formula (2) represents (in above formula (2), R ¹, R ², Y ¹, Y ²and the definition of X is identical with formula (1)), then nitroreduction is converted into amino.The method of reduction dinitro compound is not particularly limited, and conventionally has use palladium-carbon, platinum oxide, Raney nickel, iron, tin chloride, platinum black, rhodium-aluminum oxide or platinum sulfide carbon etc. as catalyzer, at ethyl acetate, toluene, tetrahydrofuran (THF), two

alkane, alcohol are in equal solvent, by the method for using the reaction of hydrogen, hydrazine, hydrogenchloride or ammonium chloride etc. to reduce.

The synthetic method of the dinitro compound that formula (2) represents is not particularly limited, can synthesize by any means, and as its object lesson, for example can be synthetic by the method shown in following reaction stream formula (3).

In reaction stream formula (3), the dinitro compound that formula (2) represents can be by making nitrobenzene compound (α), (α ') (β) react and synthesize under the existence of alkali in organic solvent with (sulfo-) carbonyl compound (general designation of carbonyl compound and thiocarbonyl compound).

Above-mentioned nitrobenzene compound (α), (α ') in, R ¹, R ², Y ¹and Y ²cotype (1), with NH ₂the amino representing can form hydrochloride (NH ₂the salt such as HCl).As its object lesson, can exemplify nitro-benzylamine or its hydrochloride, 2-(nitrophenyl) ethamine or its hydrochloride, 3-(nitrophenyl) propylamine or its hydrochloride etc.In addition, the position of substitution of the nitro on phenyl ring can suitably select to obtain the position of substitution of targeted diamine compound.Further, the compound shown in is here an example, is not particularly limited.

In (sulfo-) carbonyl compound (β), X cotype (1), Z is 1～divalent organic group.As (sulfo-) carbonyl compound (β), can exemplify for example phosgene, thiophosgene, diphenyl carbonate, thiocarbonic acid SOH diphenyl ester, two (nitrophenyl) esters of carbonic acid, two (nitrophenyl) esters of thiocarbonic acid SOH, methylcarbonate, thiocarbonic acid SOH dimethyl ester, diethyl carbonate, thiocarbonic acid SOH diethyl ester, ethylene carbonate, thiocarbonic acid SOH ethyl, 1,1 '-carbonyl is two-1H-imidazoles, 1, and 1 '-thiocarbonyl is two-1H-imidazoles etc.In addition, also can use oxycarbide (carbon monoxide or carbonic acid gas) to replace carbonyl compound (β).Further, the compound shown in is here an example, is not particularly limited.

In above-mentioned reaction stream formula (3), for obtaining the compound of structure symmetry centered by (sulphur) urea groups, can adopt identical nitrobenzene compound (α) and (α '), for obtaining asymmetrical compound, can after making nitrobenzene compound (α) and (sulfo-) carbonyl compound (β) with reaction with same mole, add again the nitrobenzene compound different with nitrobenzene compound (α) structure (α ').

As alkali, can exemplify the alkaline organic compounds such as such as triethylamine, diisopropylethylamine, DMAP (DMAP), the inorganic alkali compounds such as sodium hydroxide, salt of wormwood, the metal hydrides such as sodium hydride etc.Further, the compound shown in is here an example, is not particularly limited.

As organic solvent, the solvent that can be used alone and can not impact reaction, particularly has the aromatic series kind solvents such as toluene, dimethylbenzene, the aliphatic hydrocarbon such as hexane, heptane kind solvent, methylene dichloride, 1, the halogen solvents such as 2-ethylene dichloride, tetrahydrofuran (THF), Isosorbide-5-Nitrae-bis- the ether solvents such as alkane, the non-proton property polar solvents such as DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, methyl-sulphoxide, or also multiple above-mentioned solvent can be used.Their consumption is any amount.

Synthetic diamines the raw material of the polyimide precursors such as polyamic acid described later, poly amic acid ester or polyimide, also can be used as the raw material of polymeric amide or polyureas except can be used as mentioned above, and these polymkeric substance can be used as various electronic material starting material.

< polyimide precursor or polyimide >

The polyimide precursor that aligning agent for liquid crystal of the present invention comprises can obtain with reacting of tetracarboxylic acid derivatives as two amine components that must composition by comprising above-mentioned specific diamines.

The specific diamines that both can only represent for formula (1) for obtaining two amine components of polyimide precursor, also can and use with other diamines.

With other diamines used time, the ratio of the specific diamines that formula (1) represents can be to be worth arbitrarily, in order to obtain enough wear-resisting wipings, in whole two amine components (100 % by mole), this ratio is preferably more than 10 % by mole, preferably more than 30 % by mole, more preferably more than 50 % by mole.On the other hand, from the optimization of tilt angle with accumulate the angle of minimizing of electric charge etc., in whole two amine components, the ratio of specific two amine components is preferably below 90 % by mole.

Be not particularly limited with the specific diamines of formula (1) expression the diamines of use, available following formula (4) represents.

In above formula (4), R ⁵represent divalent organic group, R ³and R ⁴represent independently respectively the organic group of hydrogen atom or 1 valency.

As R ⁵object lesson, can exemplify following divalent organic group.

Two Q difference expression-COO-,-OCO-,-CONH-,-NHCO-,-CH independently in formula [B-112] and formula [B-113] ₂-,-O-,-CO-or-any in NH-.

In above formula (4), R ⁵part or all while being formula [B-80]～formula [B-101] etc., can increase the tilt angle of liquid crystal.

While making liquid crystal vertical-tropism, be better and use the diamines that meets following condition: and the above formula (4) of use in R ⁵there is any one structure in formula [B-80]～formula [B-101].Preferably whole 5～90 % by mole in diamines of the content of this diamines while using such diamines, more preferably 10～80 % by mole.On the other hand, when tilt angle is reduced, be better and use the diamines that meets following condition: the R in above formula (4) ⁵there is any one structure in formula [B-1]～formula [B-79] and [B-102]～formula [B-118].In addition, be better the R in formula (4) ³and R ⁴in at least one party be 1 valency organic group, be more preferably methyl.

The tetracarboxylic acid derivatives that reacts of specific two amine components that specific two amine components that represent with formula (1) or the formula (1) that comprises the diamines that above formula (4) represents represent is not particularly limited.Tetracarboxylic acid derivatives of the present invention can exemplify tetracarboxylic dianhydride, tetracarboxylic acid list acid anhydride, tetracarboxylic acid, dicarboxylic acid dialkyl esters (representing with following formula (5-d)), dicarboxylic acid acyl chlorides dialkyl (representing with following formula (5-e)) etc., as long as the compound that can react with diamines, be not limited to this.

Tetracarboxylic acid derivatives is with following formula (5-a)～(5-e) expression, R ⁷represent alkyl.As R ⁶object lesson, can exemplify following [A-1]～[A-47].

Wherein, R ⁶for formula [A-6], formula [A-16], formula [A-18]～formula [A-22], formula [A-25], formula [A-37] and formula [A-38] even the high polyimide of tetracarboxylic acid derivatives imide rate, the solvability in organic solvent is also high, so preferably.In addition, 10 of tetracarboxylic acid derivatives used % by mole above, preferably 20 % by mole be to there is the such alicyclic structure of formula [A-1]～formula [A-25] or the R of aliphatic structure above ⁶time, voltage retention improves, therefore preferred.Use R ⁶while being selected from the tetracarboxylic acid derivatives of formula [A-1], formula [A-16] and formula [A-19] in these alicyclic structures or aliphatic structure, can obtain the relaxation liquid crystal orientation film faster of electric charge.

On the other hand, if 10 % by mole of the total amount of tetracarboxylic acid derivatives used above, preferably 20 % by mole be aromatic tetracarboxylic acid's derivative above, can improve liquid crystal aligning, and can reduce and accumulate electric charge, therefore preferred.

The method that obtains polyimide precursor or polyimide as above-mentioned two amine components (below referred to as diamines) are reacted with tetracarboxylic acid derivatives composition (below referred to as tetracarboxylic acid derivatives), can obtain by known method.Below, as an example of the situation of using tetracarboxylic dianhydride example, describe.

The tetracarboxylic acid derivatives using in the manufacture of aligning agent for liquid crystal of the present invention and the polymerisation process of diamines are not particularly limited.Generally can be by mixing in organic solvent and carrying out polyreaction and make polyamic acid.In addition,, by make the hydroxy-acid group esterification of polyamic acid with known esterifying agent, can obtain poly amic acid ester.By making thus obtained polyamic acid and poly amic acid ester cyclodehydration, can be made into polyimide.

The method that tetracarboxylic acid derivatives and two amine components are mixed in organic solvent can exemplify and stir the solution that makes diamines be dispersed or dissolved in organic solvent and to obtain, and directly adds therein tetracarboxylic acid derivatives composition or makes tetracarboxylic acid derivatives composition be dispersed or dissolved in the method for adding again after organic solvent; The method of adding diamines in the solution obtaining tetracarboxylic acid derivatives is dispersed or dissolved in to organic solvent; Alternately add the method for tetracarboxylic acid derivatives and diamines etc.In addition, when at least one party in tetracarboxylic acid derivatives composition and diamines is comprised of multiple compounds, the state that can in advance these Multiple components be mixed carries out polyreaction, also can carry out successively respectively polyreaction.

Temperature when tetracarboxylic acid derivatives and diamines carry out polyreaction in organic solvent is generally 0～150 ℃, and preferably 5～100 ℃, more preferably 10～80 ℃.The higher polyreaction of temperature completes sooner, if but too high, sometimes cannot obtain the polymkeric substance of high molecular.In addition, polyreaction can be carried out with blanking concentration arbitrarily, if but blanking concentration is too low, be difficult to obtain the polymkeric substance of high molecular, if blanking excessive concentration, the viscosity of reaction solution is too high, is difficult to stir uniformly, therefore be better 1～50 quality %, be more preferably 5～30 quality %.Can carry out with high density at the polyreaction initial stage, and then append organic solvent.Here said blanking concentration refers to the concentration of the total mass of tetracarboxylic dianhydride's composition and two amine components.

While carrying out above-mentioned reaction, organic solvent used, as long as can dissolve the polyamic acid and the poly amic acid ester (being sometimes called polyamic acid (ester) below) that generate, is not particularly limited.As object lesson, can exemplify DMF, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-methyl caprolactam, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolactone etc.These solvents can be used alone, but also also mix together.Further, even the solvent of insoluble solution polyamic acid (ester), in the scope that can not separate out at the polyamic acid (ester) generating, also can be used with above-mentioned solvent.

In addition, the moisture in organic solvent hinders polyreaction, and can make polyamic acid (ester) hydrolysis generating, and therefore organic solvent is preferably used the organic solvent through farthest dehydrating.

For the ratio that obtains the polyreaction of polyamic acid tetracarboxylic acid derivatives used and diamines, with preferably 1:0.8～1:1.2 of molar ratio computing, the molecular weight that this mol ratio more approaches the polyamic acid that 1:1 obtains is larger.If the molecular weight of polyamic acid (ester) is too small, the painting film strength obtaining thus may be not enough, on the contrary, if the molecular weight of polyamic acid (ester) is excessive, the viscosity of the aligning agent for liquid crystal making thus may be too high, operability when film forms and the lack of homogeneity of film.Therefore, the weight-average molecular weight of polyamic acid (ester) used preferably 2000～500000 in aligning agent for liquid crystal of the present invention, more preferably 5000～300000.

In the present invention, for obtaining polyamic acid, use tetracarboxylic acid derivatives and diamines, as diamines, the diamines that uses the specific diamines of above formula (1) expression and the above formula (4) of use as required to represent.During diamines that use formula (4) represents, in the tetracarboxylic acid derivatives preferably using, the R in above formula (5-a)～formula (5-e) ⁶for formula [A-1], formula [A-2], formula [A-16], formula [A-18], formula [A-19], formula [A-25], formula [A-26], formula [A-27], formula [A-32], formula [A-35], formula [A-38] or formula [A-47], as with the diamines of the above formula (4) of specific diamines use, preferably use R wherein ⁵for formula [B-6], formula [B-7], formula [B-8], formula [B-16], formula [B-17], formula [B-20], formula [B-21], formula [B-29], formula [B-30], formula [B-32], formula [B-33], formula [B-40], formula [B-44], formula [B-45], formula [B-48], formula [B-56], formula [B-57], formula [B-58], formula [B-61], formula [B-62], formula [B-63], formula [B-76], formula [B-80], formula [B-82], formula [B-83], formula [B-84], formula [B-85], formula [B-86], formula [B-87], formula [B-93], formula [B-104], formula [B-114], the diamines of formula [B-115] or formula [B-118].Wherein, as tetracarboxylic acid derivatives, the R in above formula (5-a) ⁶preferred formula [A-1], formula [A-2], formula [A-16], formula [A-18], formula [A-19], formula [A-25], formula [A-26], formula [A-27] or formula [A-32], as the diamines of formula (4), R wherein ⁵preferred formula [B-7], formula [B-8], formula [B-17], formula [B-20], formula [B-21], formula [B-29], formula [B-30], formula [B-32], formula [B-61], formula [B-76], formula [B-80], formula [B-82], formula [B-83], formula [B-84], formula [B-85], formula [B-104], formula [B-114], formula [B-115] or formula [B-118].

The polyamic acid obtaining as mentioned above also can represent with the repeating unit of following formula (6), and poly amic acid ester also can represent with following formula (7).

In above formula (6), (7), R ^a, R ^b, R ^cfor deriving from the group of the diamines that above formula (1) or formula (4) represent, during diamines that use formula (1) represents, R ^aand R ^bfor hydrogen, R ^cfor-phenylene-Y ¹-NH-CX-HN-R ²-Y ²-phenylene-, use formula (4) represent diamines time, R ^afor R ³, R ^bfor R ⁴, R ^cfor R ⁵.R ⁶r in the tetracarboxylic acid derivatives representing with above formula (5-a)～(5-e) ⁶implication identical.R in formula (7) is the group that derives from used esterifying agent.

The polyamic acid obtaining as mentioned above or poly amic acid ester both can be directly used in aligning agent for liquid crystal of the present invention, also can make its cyclodehydration and use after becoming polyimide.But, according to the difference of the structure of polyamic acid (ester), because imidization reaction becomes insolublely, be difficult to use in aligning agent for liquid crystal sometimes.Now, can not make the whole imidizations of amido acid (ester) base in polyamic acid (ester), but can keep carrying out imidization in suitable deliquescent scope.

The normally direct hot-imide of the solution heating to polyamic acid or add the chemical imidization of catalyzer in the solution of polyamic acid (ester) of the imidization reaction that makes polyamic acid (ester) cyclodehydration, the chemical imidization that carries out imidization reaction at lower temperature is difficult for occurring the molecular weight reduction of gained polyimide, therefore preferred.

Chemical imidization can be undertaken by stir polyamic acid (ester) under the existence of basic catalyst and acid anhydrides in organic solvent.Temperature of reaction is now-20～250 ℃, and preferably 0～180 ℃, the reaction times can carry out 1～100 hour.The amount of basic catalyst is 0.5～30 mole times of polyamic acid (ester), is better 2～20 moles times, and the amount of acid anhydrides is 1～50 mole times of polyamic acid (ester), is better 3～30 moles times.If the amount of basic catalyst and acid anhydrides is less, reaction cannot fully be carried out, if too much, reaction is difficult to remove completely after finishing.

Imidization basic catalyst used can exemplify pyridine, triethylamine, Trimethylamine 99, Tributylamine, trioctylamine etc.Wherein preferred pyridine, because it has the suitable alkalescence that the reaction of making is carried out.

In addition, as acid anhydrides, can exemplify diacetyl oxide, trimellitic acid 1,2-anhydride, pyromellitic dianhydride etc., wherein, while using diacetyl oxide, be easy to the purifying after reaction finishes, therefore preferred.Solvent used when organic solvent can be used above-mentioned polyamic acid polyreaction.Imide rate based on chemical imidization can be by regulating catalytic amount and temperature of reaction, reaction times to control.

In the polyimide solution obtaining as mentioned above, because the catalyzer adding remains in solution, therefore for for aligning agent for liquid crystal of the present invention, be better that this polyimide solution is put in the Weak solvent in stirring, after polyimide precipitation is reclaimed, use.During the precipitation of polyimide reclaims, Weak solvent used is not particularly limited, and can exemplify methyl alcohol, acetone, hexane, ethylene glycol butyl ether, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene etc.By putting into the polyimide precipitating in Weak solvent, can after filtering, cleaning and reclaim, under normal pressure or reduced pressure, carry out normal temperature or heat drying, thereby make powder.If again by this powder dissolution in good solvent and repeat the operation of 2～10 reprecipitations, also can purifying polyimide.In the time of cannot thoroughly removing impurity by primary sedimentation reclaimer operation, be better repeatedly to carry out this purification procedures.Weak solvent when repeatedly carrying out purification procedures, because purification efficiency further improves, so be better that such as 3 kinds of above Weak solvents such as alcohols, ketone, hydro carbons are mixed or used successively.

In addition, polyamic acid (ester) also can be precipitated and be reclaimed and purifying by same operation.While containing the polymerization of polyamic acid solvent used in not wanting to make aligning agent for liquid crystal, or while wanting to remove unreacted monomer component in reaction soln and impurity, can carry out this precipitation recovery and purifying.

The imide rate of the polyimide that aligning agent for liquid crystal of the present invention comprises is not particularly limited.The solvability that can consider polyimide is set as arbitrary value.The molecular weight of the polyimide that aligning agent for liquid crystal of the present invention comprises is not particularly limited, if but the molecular weight of polyimide is too small, gained painting film strength may be not enough, on the contrary, if the molecular weight of polyimide is excessive, the viscosity of the aligning agent for liquid crystal making may be too high, operability when film forms and the lack of homogeneity of film.Therefore, the weight-average molecular weight of polyimide used preferably 2000～500000 in aligning agent for liquid crystal of the present invention, more preferably 5000～300000.

< aligning agent for liquid crystal >

Aligning agent for liquid crystal of the present invention comprises any in polyimide precursor or the polyimide obtaining as mentioned above, conventionally makes these polymer dissolution make coating fluid in organic solvent.The polymkeric substance that aligning agent for liquid crystal of the present invention comprises, except described polyimide precursor or polyimide, also can comprise the polymkeric substance with other structure.The organic solvent that aligning agent for liquid crystal of the present invention comprises, as long as can dissolve the polymkeric substance comprising, is not particularly limited.

As the object lesson of organic solvent, can exemplify N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl pyrrolidone, NVP, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolactone, 1,3-dimethyl-imidazolinone etc.These can use one kind or two or more mixing to use.

In addition, even solvent that cannot dissolve polymer while using separately, as long as in the scope that can not separate out at polymkeric substance, can mix with aligning agent for liquid crystal of the present invention.Particularly known to mixing ethyl cellosolve, ethylene glycol butyl ether, ethyl carbitol, diethylene glycol monobutyl ether, ethyl carbitol acetic ester, ethylene glycol, 1-methoxy-2-propanol, 1-oxyethyl group-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, propylene-glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic ester, propylene glycol-1-monoethyl ether-2-acetic ester, dipropylene glycol, 2-(2-oxyethyl group propoxy-) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactates etc. have the solvent of low surface tension, painting film uniformity on substrate improves.Therefore, these solvents can one or more mix use.

In aligning agent for liquid crystal of the present invention, also preferably use the solvent with low surface tension, its consumption is better 5～80 quality % of whole solvents of comprising of aligning agent for liquid crystal, is more preferably 20～60 quality %.

In aligning agent for liquid crystal of the present invention, except above-mentioned polymkeric substance and organic solvent, also can comprise various additives.

As improving the homogeneity of thickness or the additive of surface smoothness, can exemplify fluorine class tensio-active agent, silicone tensio-active agent, nonionic surfactant etc.

More specifically, for example can exemplify エ Off トップ EF301, EF303, EF352 (illuminating product Co., Ltd. (トーケ system プロダクツ society) system), メガ Off ァッ Network F171, F173, R-30 (large Japanese ink Co., Ltd. (large Japanese イ Application キ society) system), Off ロラー De FC430, FC431 (Sumitomo 3M Co., Ltd. (Sumitomo スリーエ system society) system), アサヒガー De AG710, サー Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd (Asahi Glass society) system) etc.The usage ratio of these tensio-active agents, with respect to component of polymer 100 mass parts that comprise in aligning agent for liquid crystal, is better 0.01～2 mass parts, is more preferably 0.01～1 mass parts.

As the additive of adaptation that improves liquid crystal orientation film and substrate, can exemplify containing the compound of functional silanes, containing the compound of epoxy group(ing) etc.

For example, can exemplify 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (the oxyethylene group)-3-TSL 8330 of N-, two (the oxyethylene group)-APTESs of N-, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidylether, 1,3,5,6-four glycidyl group-2,4-hexylene glycol, N, N, N ', N ' ,-four glycidyl group-m-xylene diamine, two (N, the N-diglycidyl amino methyl) hexanaphthenes of 1,3-, N, N, N ', N ' ,-four glycidyl group-4, 4 '-diaminodiphenyl-methane etc.

While adding these compounds, with respect to component of polymer 100 mass parts that comprise in aligning agent for liquid crystal, its content is better 0.1～30 mass parts, is more preferably 1～20 mass parts.If less than 0.1 mass parts cannot be expected the effect that adaptation improves, if more than 30 mass parts, the orientation variation of liquid crystal sometimes.

In aligning agent for liquid crystal of the present invention, except above-mentioned, not damaging in the scope of effect of the present invention, dielectric medium or conducting material that the electrical characteristic such as the specific inductivity of change liquid crystal orientation film or electroconductibility are object can be added, the hardness of the film while forming liquid crystal orientation film or the cross-linked compound that density is object etc. can also be added to improve.

The concentration of the solids component in aligning agent for liquid crystal of the present invention can be according to the target film thickness appropriate change of liquid crystal orientation film, owing to forming flawless film, and can obtain the suitable thickness as liquid crystal orientation film, be better therefore 1～20 quality %, is more preferably 2～10 quality %.

Aligning agent for liquid crystal of the present invention is being coated on substrate and after burning till, and can carry out the orientation process such as friction treatment or rayed, or in vertical orientated purposes etc. without orientation process and as liquid crystal orientation film.At this moment, substrate used limits without special as long as the high substrate of the transparency, can use the plastic bases such as glass substrate and vinylformic acid substrate, polycarbonate substrate etc., from the angle that production technique is simplified, preferably use the substrate being formed with for the ITO electrode of liquid crystal drive etc.In addition, in reflection type liquid crystal display element, can use the opaque materials such as silicon wafer, but only limit to one-sided substrate, electrode now also can be used the light reflecting materials such as aluminium.

The coating process of aligning agent for liquid crystal is not particularly limited, and industrial circle adopts the method being coated with by silk screen printing, offset printing, flexographic printing, ink-jet etc. conventionally.As other coating process, also have dip coating, rolling method, slot coated, spin-coating method etc., can use these methods according to object.

The burning till of substrate that has been coated with aligning agent for liquid crystal can be carried out under the arbitrary temp of 100～350 ℃ of temperature, and preferably temperature is 150～300 ℃, and preferred temperature is 180～250 ℃.While comprising polyamic acid or poly amic acid ester in aligning agent for liquid crystal, the transformation efficiency transforming to imide changes with this firing temperature, but liquid crystal aligning agent of the present invention is without 100% imidization.Therefore, firing time can be set as random time, if but firing time is too short, and, sometimes because the impact of remaining solvent shows badly, be therefore better 5～60 minutes, be more preferably 10～40 minutes.

When the thickness of the film after burning till is blocked up, unfavorable aspect the power consumption of liquid crystal display device, cross when thin, the reliability of liquid crystal display device reduces sometimes, is therefore better 5～300nm, is more preferably 10～100nm.While making liquid crystal horizontal alignment or tilted alignment, by friction or polarisation uviolizing etc., the film after burning till is processed.

Liquid crystal display device of the present invention is to be obtained after the substrate with liquid crystal orientation film by aligning agent for liquid crystal of the present invention by aforesaid method, by known method, manufactures the liquid crystal display device that liquid crystal structure cell forms.

If exemplify an example of manufacturing liquid crystal structure cell, can illustrate following method: a pair of substrate of preparing to be formed with liquid crystal orientation film, on the liquid crystal orientation film of a substrate, scatter spacer, make liquid crystal aligning face become interior rear flank another baseplate-laminating, the method for liquid crystal sealing is injected in decompression; Or drip liquid crystal on the liquid crystal aligning face that is scattered with spacer after, the method that baseplate-laminating is sealed etc.The thickness of spacer is now better 1～30 μ m, is more preferably 2～10 μ m.

As mentioned above, use aligning agent for liquid crystal of the present invention and the reliability of the liquid crystal display device that makes is good, can perform well in the LCD TV of giant-screen and high-resolution etc.

Embodiment

The present invention will be described in more detail below to exemplify embodiment, but the present invention is not limited by this.

Abbreviation used in following embodiment and comparative example is as described below.

BABU:1, two (4-aminobenzyl) ureas of 3-

BAPU:1, two (the 4-amino-benzene ethyl) ureas of 3-

DA-3:1, two (3-aminobenzyl) ureas of 3-

DA-4:1-(4-aminobenzyl)-3-(4-amino-benzene ethyl) urea

DA-5:1, two (2-(4-amino-benzene oxygen) ethyl) ureas of 3-

DA-6:1, two (3-(4-amino-benzene oxygen) propyl group) ureas of 3-

DA-7:1,5 '-bis-(4-amino-benzene oxygen) pentane

CBDA:1,2,3,4-tetramethylene tetracarboxylic dianhydride

PMDA: pyromellitic acid anhydride

BODA: dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride.

CA-4:1,3-dicarbapentaborane methoxyl group-2, two (chloroformyl) tetramethylene of 4-

CA-5:2,5-dicarbapentaborane methoxyl group terephthalic acid diacid chloride

P-PDA: Ursol D

In synthesis example, ¹h-NMR refers to the nuclear magnetic resonance spectrum of hydrogen atom in molecule.

[synthesis example 1]

Synthesizing of two (the 4-amino-benzene ethyl) ureas [BAPU] of 1,3-

Under room temperature, in the four-hole boiling flask of nitrogen replacement, adding 2-(4-nitrophenyl) ethylamine hydrochloride [C] (52.50g, 259mmol), two (4-nitrophenyl) esters [D] (37.53g, 123mmol) of carbonic acid and THF (tetrahydrofuran (THF)) (1877g), add therein triethylamine (74.90g, 740mmol) and 4-N, N-dimethyl aminopyridine (3.01g, 24.7mmol), stirs with mechanical stirrer.By HPLC (high performance liquid chromatography), follow the tracks of reaction, after reaction finishes, reaction soln is joined in pure water (9L), carry out the stirring of 30 minutes.Then filter, with pure water (1L) cleaning, obtain the crude product of white solid.After this gained white solid is disperseed to clean with ultrasonic unit in methyl alcohol (488g), filter, be dried, obtain the dinitro compound [E] (must measure 42.3g, yield 96%) of white solid.

¹H-NMR(400MHz,DMSO-d6,δppm):8.11-8.08(4H,m),7.43-7.40(4H,m),5.89(2H,t),3.24-3.19(4H,q),2.76(4H,t).

By compound [E] (42.32g, 118mmol), 5% palladium carbon (5%Pd/C) (4.23g) and Isosorbide-5-Nitrae-bis- the mixture of alkane (2031g), with after nitrogen replacement, is replaced again with hydrogen, under the existence of hydrogen, under room temperature, stirs.By HPLC, follow the tracks of reaction, after reaction finishes, with diatomite (Celite) filtering catalyst.Then under reduced pressure steam the solvent except filtrate, obtain the crude product of white solid.In gained crude product, add 2-propyl alcohol (85g), after disperseing to clean with ultrasonic unit, filter, be dried, obtain the diamino compounds [BAPU] (must measure 31.9g, yield 91%) of white solid.

¹H-NMR(400MHz,DMSO-d6,δppm):6.85-6.82(4H,m),6.51-6.48(4H,m),5.78(2H,t),4.83(4H,s),3.14-3.09(4H,m),2.50-2.45(4H,m).

[synthesis example 2]

Synthesizing of two (4-aminobenzyl) ureas [BABU] of 1,3-

Under room temperature, in the four-hole boiling flask of nitrogen replacement, adding 4-nitro benzyl amine hydrochlorate [F] (25.00g, 133mmol), two (4-nitrophenyl) esters [D] (19.20g, 63.1mmol) of carbonic acid and THF (750g), add therein triethylamine (38.32g, 379mmol) and 4-N, N-dimethyl aminopyridine (1.54g, 12.6mmol), stirs with mechanical stirrer.By HPLC, follow the tracks of reaction, after reaction finishes, reaction soln is joined in pure water (4.5L), carry out the stirring of 30 minutes.Then filter, with pure water (500mL) cleaning, obtain the crude product of ivory buff solid state.After this gained ivory buff solid is disperseed to clean with ultrasonic unit in methyl alcohol (300g), filter, be dried, obtain the dinitro compound [G] (must measure 19.01g, yield 91%) of ivory buff solid state.

¹H-NMR(400MHz,DMSO-d6,δppm):8.22-8.19(4H,m),7.53-7.50(4H,m),6.82(2H,t),4.36(4H,d).

By compound [G] (16.00g, 48.4mmol), 5% palladium carbon (5%Pd/C) (1.60g) and Isosorbide-5-Nitrae-bis- the mixture of alkane (800g), with after nitrogen replacement, is replaced again with hydrogen, under the existence of hydrogen, under room temperature, stirs.By HPLC, follow the tracks of reaction, after reaction finishes, use diatomite filtration catalyzer.Then under reduced pressure steam the solvent except filtrate, obtain the crude product of white solid.In gained crude product, add 2-propyl alcohol (128g), after disperseing to clean with ultrasonic unit, filter, be dried, obtain the diamino compounds [BABU] (must measure 12.19g, yield 93%) of white-yellowish solid shape.

¹H-NMR(400MHz,DMSO-d6,δppm):6.92-6.88(4H,m),6.51-6.48(4H,m),6.03(2H,t),4.91(4H,s),4.02(4H,d).

[synthesis example 3]

Synthesizing of two (3-aminobenzyl) ureas [DA-3] of 1,3-

Under room temperature, in the four-hole boiling flask of nitrogen replacement, adding 3-nitro benzyl amine hydrochlorate [H] (10.00g, 53.0mmol), two (4-nitrophenyl) esters [D] (7.68g, 25.3mmol) of carbonic acid and THF (384g), add therein triethylamine (15.33g, 152mmol) and 4-N, N-dimethyl aminopyridine (0.62g, 5.05mmol), stirs.By HPLC, follow the tracks of reaction, after reaction finishes, reaction soln is joined in pure water (2.3L), carry out the stirring of 30 minutes.Then filter, with pure water (500mL) cleaning, obtain the crude product of tea white solid.After this gained white solid is disperseed to clean with ultrasonic unit in 2-propyl alcohol (50g), filter, be dried, obtain the dinitro compound [I] (must measure 7.04g, yield 84%) of white solid.

¹H-NMR(400MHz,DMSO-d6,δppm):8.06-8.05(4H,m),7.68(2H,d),7.56-7.55(2H,m),6.84(2H,t),4.32(4H,d).

By compound [I] (7.04g, 21.3mmol), 5% palladium carbon (5%Pd/C) (0.7g) and Isosorbide-5-Nitrae-bis-

the mixture of alkane (350g), with after nitrogen replacement, is replaced again with hydrogen, under the existence of hydrogen, under room temperature, stirs.By HPLC, follow the tracks of reaction, after reaction finishes, use diatomite filtration catalyzer.Then under reduced pressure filtrate is carried out to solvent steaming and remove, obtain the crude product of tea white solid.In gained crude product, add 2-propyl alcohol (60g), after disperseing to clean with ultrasonic unit, filter, be dried, obtain the diamino compounds [DA-3] (must measure 4.04g, yield 81%) of tea white solid.

¹H-NMR(400MHz,DMSO-d6,δppm):6.93(2H,t),6.46-6.45(2H,m),6.42-6.34(4H,m),6.20(2H,t),5.01(4H,s),4.07(4H,d).

[synthesis example 4]

Synthesizing of 1-(4-aminobenzyl)-3-(4-amino-benzene ethyl) urea [DA-4]

Under room temperature, add 4-nitro benzyl amine hydrochlorate [F] (50.00g, 265mmol), pyridine (20.97g, 265mmol) and methylene dichloride (750g) in the four-hole boiling flask of nitrogen replacement, solution is cooled to below 10 degree.Add therein after methylene dichloride (150g) solution of chloroformic acid 4-nitro phenyl ester [J] (53.43g, 265mmol), temperature of reaction is risen to 23 ℃, stir and carry out reflux after 1 hour.After reaction finishes, reaction soln is cooled to room temperature, adds methylene dichloride (500g) and be diluted to the aqueous hydrochloric acid (1000g) of 10 quality %, filter.Under room temperature, stir filtrate, by the solid filtering of separating out.Clean this solid with methyl alcohol (200g), dry, obtain the compound [K] (must measure 33.26g, yield 40%) of white solid.On the other hand, after adding saturated sodium bicarbonate aqueous solution (500g) to clean in filtrate, then use saturated aqueous common salt (500g) to clean organic layer, use dried over mgso.Then filter, steaming desolventizes, and obtains white crude product.By this methyl alcohol (200g) recrystallization for crude product, obtain the compound [K] (must measure 16.6g, yield 20%) of white solid.

¹H-NMR(400MHz,CDCl ₃,δppm):8.8.28-8.24(4H,m),7.55-7.53(2H,m),7.37-7.34(2H,m),5.64(1H,t),4.59(2H,d).

Under room temperature, in the four-hole boiling flask of nitrogen replacement, adding 2-(4-nitrophenyl) ethylamine hydrochloride [C] (30.29g, 150mmol), compound [K] (45.18g, 142mmol) and THF (2260g), add therein triethylamine (43.23g, 427mmol) and 4-N, N-dimethyl aminopyridine (1.74g, 14.2mmol), reacts.By HPLC, follow the tracks of reaction, after reaction finishes, reaction soln is joined in pure water (10L), carry out the stirring of 30 minutes.Then filter, with pure water (2L) cleaning, obtain the crude product of white solid.After this gained white solid is cleaned with 2-propyl alcohol (300g), filter, be dried, obtain the dinitro compound [L] (must measure 43.9g, yield 90%) of white solid.

¹H-NMR(400MHz,DMSO-d6,δppm):8.19-8.14(4H,m),7.52-7.44(4H,m),6.62(1H,t),6.12(1H,t),4.31(2H,d),3.33(2H,m),2.86(2H,t).

By compound [L] (50.00g, 145mmol), 5% palladium carbon (5%Pd/C) (5.0g) and Isosorbide-5-Nitrae-bis-

the mixture of alkane (1000g), with after nitrogen replacement, is replaced again with hydrogen, under the existence of hydrogen, under room temperature, stirs.By HPLC, follow the tracks of reaction, after reaction finishes, use diatomite filtration catalyzer.Then under reduced pressure filtrate is carried out to solvent steaming and remove, obtain the crude product of tea white solid.In this crude product, add 2-propyl alcohol (330g), after disperseing to clean with ultrasonic unit, filter, be dried, obtain the diamino compounds [DA-4] (must measure 37.0g, yield 90%) of peach white solid.

¹H-NMR(400MHz,DMSO-d6,δppm):6.90-6.87(2H,m),6.84-6.82(2H,m),6.51-6.47(4H,m),6.08(1H,t),5.73(1H,t),4.9(2H,s),4.84(2H,s),3.99(2H,d),3.15-3.10(2H,m),2.51-2.46(2H,m).

[synthesis example 5]

Synthesizing of two (2-(4-amino-benzene oxygen) ethyl) ureas [DA-5] of 1,3-

Synthesizing of the compound [P] of employing reaction process A

Under room temperature, nitrogen atmosphere, in four-hole boiling flask, add 4-nitrophenols (27.69g, 199mmol), salt of wormwood (55.01g, 398mmol) and N, dinethylformamide (being denoted as DMF below) (140g), is heated to 65 ℃.Drip therein DMF (140g) solution of N-(2-bromotrifluoromethane) phthalic imidine (50.57g, 199mmol).After reaction finishes, reaction soln is joined in frozen water (2240g), obtain yellow solid.After being filtered, washing, by dry, make white-yellowish solid, obtain compound [O] (must measure 44.2g, yield 71%).

¹H-NMR(400MHz,CDCl ₃,δppm):8.19-8.16(2H,m),7.90-7.87(2H,m),7.77-7.74(2H,m),6.96-6.94(2H,m),4.33(2H,t),4.14(2H,t).

In ethanol (930g) solution of the compound [O] (40.00g, 128mmol) under room temperature, nitrogen atmosphere in four-hole boiling flask, add hydrazine monohydrate (81.00g, 1.28mol), then carry out reflux.After reaction finishes, with distilled water (930g), dissolve after the solid of separating out, with 1,2-ethylene dichloride (500g), carry out 4 times and extract.Merge after organic layer, carry out 2 washings (500g), with after dried over mgso, filter, steaming desolventizes, and with the form of yellow solid, obtains compound [P] (must measure 16.5g, yield 51%).

¹H-NMR(400MHz,CDCl ₃,δppm):8.22-8.20(2H,m),6.99-6.96(2H,m),4.09(2H,t),3.15(2H,t),1.26(2H,brs).

Synthesizing of the compound [P] of employing reaction process B

In room temperature, stream of nitrogen gas, in four-hole boiling flask, add 1,2-glycol dimethyl ether (being denoted as DME below) (150g), add therein 60% sodium hydride (16.24g, 372mmol).Then slowly drip DME (50g) solution of 2-thanomin (22.73g, 372mmol).Then drip DME (50g) solution of the fluoro-4-oil of mirbane of 1-(50.00g, 354mmol).After reaction finishes, reaction soln is joined in distilled water (1250g), with methylene dichloride (400g), carry out 3 times and extract.Merge organic layer, with after dried over mgso, filter, steaming desolventizes, and with the form of yellow solid, obtains compound [P] (must measure 46.1g, yield 71%).

Under room temperature, in the four-hole boiling flask of nitrogen replacement, adding two (4-nitrophenyl) esters [D] (7.95g, 26.1mmol) of carbonic acid, triethylamine (15.87g, 157mmol), DMAP (0.64g, 5.23mmol) and THF (280g) and stirring.THF (40g) solution that adds therein compound [P] (10.00g, 54.9mmol), then reacts.By HPLC, follow the tracks of reaction, after reaction finishes, reaction soln is joined in pure water (1.9L), carry out the stirring of 30 minutes.Then filter, with pure water (500mL) cleaning, obtain the crude product of yellow solid shape.After gained crude product is cleaned with 2-propyl alcohol (60g), be dried, obtain the dinitro compound [Q] (must measure 6.98g, yield 68%) of yellow solid shape.

¹H-NMR(400MHz,CDCl ₃,δppm):8.21-8.18(4H,m),6.97-6.93(4H,m),4.83(2H,t),4.15(4H,q),3.68(4H,q).

To add have compound [Q] (6.73g, 17.2mmol), 5% palladium carbon (5%Pd/C) (0.67g) and Isosorbide-5-Nitrae-bis-

in the four-hole boiling flask of the mixture of alkane (337g), with after nitrogen replacement, with hydrogen, again replace, under the existence of hydrogen, under room temperature, stir.By HPLC, follow the tracks of reaction, after reaction finishes, use diatomite filtration catalyzer.Then under reduced pressure filtrate is carried out to solvent steaming and remove, obtain the crude product of light yellow solid shape.In this crude product, add 2-propyl alcohol (48g), after disperseing to clean with ultrasonic unit, filter, be dried, obtain the diamino compounds [DA-5] (must measure 3.43g, yield 60%) of peach white solid.

¹H-NMR(400MHz,DMSO-d6,δppm):6.67-6.63(4H,m),6.51-6.48(4H,m),6.18(2H,t),4.60(4H,brs),3.79(4H,t),3.30(4H,q).

[synthesis example 6]

Synthesizing of two (3-(4-amino-benzene oxygen) propyl group) ureas [DA-6] of 3-

Synthesizing of the compound [T] of employing reaction process C

Under room temperature, nitrogen atmosphere, in four-hole boiling flask, add 4-nitrophenols (25.79g, 185mmol), salt of wormwood (49.70g, 185mmol) and DMF (130g), be heated to 65 ℃.Drip therein DMF (130g) solution of N-(3-bromopropyl) phthalic imidine (49.7g, 185mmol).After reaction finishes, reaction soln is joined in frozen water (2080g), obtain yellow solid.After being filtered, washing, by dry, make white-yellowish solid, obtain compound [S] (must measure 59.5g, yield 98%).

¹H-NMR(400MHz,CDCl ₃,δppm):8.8.17-8.15(2H,m),7.89-7.84(2H,m),7.76-7.73(2H,m),6.86-6.84(2H,m),4.13(2H,t),3.93(2H,t),?2.27-2.20(2H,m).

In ethanol (908g) solution of the compound [S] (60.50g, 185mmol) under room temperature, nitrogen atmosphere in four-hole boiling flask, add hydrazine monohydrate (116.0g, 1.85mol), then carry out reflux.After reaction finishes, with distilled water (908g), dissolve after the solid of separating out, with 1,2-ethylene dichloride (500g), carry out 4 times and extract.Merge after organic layer, carry out 2 washings (500g), use dried over mgso.Then filter, steaming desolventizes, and with the form of glassy yellow oily matter, obtains compound [T] (must measure 36.0g, yield 99%).

¹H-NMR(400MHz,CDCl ₃,δppm):8.20-8.17(2H,m),6.98-6.94(2H,m),4.18-4.15(2H,m),3.40-3.37(2H,m),2.20-2.14(2H,m),2.03-2.20(2H,m).

Synthesizing of the compound [T] of employing reaction process D

In room temperature, stream of nitrogen gas, in four-hole boiling flask, add 1,2-glycol dimethyl ether (being denoted as DME below) (188g), add therein 60% sodium hydride (14.52g, 333mmol).Then slowly drip DME (94g) solution of 3-amino-1-propyl alcohol (25.00g, 333mmol).Then drip DME (94g) solution of the fluoro-4-oil of mirbane of 1-(46.96g, 333mmol).After reaction finishes, reaction soln is joined in distilled water (564g), with methylene dichloride (500g), carry out 3 times and extract.Merge organic layer, with filtering after dried over mgso, steaming desolventizes, and with the form of yellow oil, obtains compound [T] (must measure 60.72g, yield 93%).

Under room temperature, in the four-hole boiling flask of nitrogen replacement, adding compound [T] (60.72g, 310mmol), two (4-nitrophenyl) esters [D] (35.87g, 118mmol) of carbonic acid, triethylamine (47.72g, 472mmol), DMAP (1.44g, 11.8mmol) and THF (720g) and stirring.By HPLC, follow the tracks of reaction, after reaction finishes, reaction soln is joined in pure water (4.3L), carry out the stirring of 30 minutes.Then filter, with pure water (1L) cleaning, obtain the crude product of yellow solid shape.After gained crude product is cleaned with 2-propyl alcohol (400g), be dried, obtain the dinitro compound [U] (must measure 38.1g, yield 77%) of yellow solid shape.

¹H-NMR(400MHz,DMSO-d6,δppm):8.18-8.14(4H,m),7.11-7.08(4H,?m),5.96(2H,t),4.07(4H,5),3.11(4H,q),1.84-1.78(4H,m).

To add have compound [U] (26.00g, 62.1mmol), 5% palladium carbon (5%Pd/C) (2.6g) and Isosorbide-5-Nitrae-bis-

in the four-hole boiling flask of the mixture of alkane (160g)/ethanol (160g), with after nitrogen replacement, with hydrogen, again replace, under the existence of hydrogen, under room temperature, stir.By HPLC, follow the tracks of reaction, after reaction finishes, in order to dissolve separated out solid, carry out after nitrogen replacement, add acetonitrile (1500g) and DMF (150g), heating is dissolved it completely.Then use diatomite filtration catalyzer.Then under reduced pressure filtrate is carried out to solvent steaming and remove, obtain the crude product of tea white solid.In this crude product, add 2-propyl alcohol (160g), with ultrasonic unit, disperse to clean.Then filter, be dried, obtain the diamino compounds [DA-6] (must measure 17.7g, yield 79%) of tea white solid.

¹H-NMR(400MHz,DMSO-d6,δppm):6.65-6.61(4H,m),6.51-6.47(4H,m),5.90(2H,t),4.58(4H,s),3.81(4H,t),3.13-3.08(4H,m),1.77-1.70(4H,m).

[embodiment 1]

In the 50ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add the BAPU of 0.60g (2.0mmol) and the p-PDA of 1.95g (18.0mmol), add the METHYLPYRROLIDONE of 30g, supplying nitrogen stirs and makes its dissolving on one side on one side.Stir this two amine aqueous solution while add the CBDA of 3.70g (18.9mmol), add again METHYLPYRROLIDONE, make solid component concentration reach 12 quality %, under nitrogen atmosphere, in stirring at room 4 hours, obtain polyamic acid (P1) solution.By E type viscometer ((East Machine industry society of Toki Sangyo Co., Ltd.) system) confirmed the viscosity of this polyamic acid solution at 25 ℃, result is 316mPas.

In this polyamic acid solution of 16.24g, add the METHYLPYRROLIDONE of 9.94g and the ethylene glycol butyl ether of 6.54g, the concentration that obtains P1 is the aligning agent for liquid crystal of 6.0 quality %.

(wear-resisting wiping)

After being filtered with 1.0 μ m filters, aligning agent for liquid crystal obtained above is spun on the glass substrate with transparency electrode, and dry after 5 minutes on the hot-plate of 80 ℃, burn till 30 minutes in 230 ℃, obtain the polyimide film of thickness 100nm.With artificial silk cloth to this polyimide film rub (roller footpath 120mm, rotating speed 1000rpm, translational speed 20mm/sec, the amount of being pressed into 0.4mm).By the condition of surface on this film surface of confocal laser microscopic examination, with the multiples of 10 times, observe and have or not abrasive dust and scar.The results are shown in table 2.

(manufacture of liquid crystal structure cell)

After being filtered with 1.0 μ m filters, aligning agent for liquid crystal obtained above is spun on the glass substrate with transparency electrode, and dry after 5 minutes on the hot-plate of 80 ℃, burn till 30 minutes in 230 ℃, obtain the polyimide film of thickness 100nm.This polyimide film is rubbed after (roller footpath 120mm, rotating speed 300rpm, translational speed 20mm/sec, the amount of being pressed into 0.2mm) with artificial silk cloth, in pure water, carries out the ultrasonic irradiation of 1 minute, in 80 ℃ dry 10 minutes.Prepare 2 substrates with above-mentioned liquid crystal orientation film, after the spacer of 6 μ m being set on the liquid crystal aligning face of a substrate, with the antiparallel condition of frictional direction of 2 substrates by 2 substrate in combination, sealing around, but leave liquid crystal injecting port, making structure cell interval (cell gap) is the negative crystal born of the same parents of 6 μ m.To vacuum in this structure cell, inject liquid crystal (MLC-2041, Merck & Co., Inc.'s system) at normal temperatures, by inlet sealing, make antiparallel type liquid crystal structure cell.

(liquid crystal aligning)

By the state of orientation of the above-mentioned liquid crystal structure cell of polarized light microscope observing, results verification is flawless uniform orientation.

(tilt angle)

For above-mentioned liquid crystal structure cell, use determinator (TBA107, autroNic-MELCHERS GmbH company system) based on rotating crystal method to measure the tilt angle of the liquid crystal after 30 minutes in 110 ℃ of heating.

(voltage retention)

The liquid crystal structure cell similarly making with above-mentioned (manufacture of liquid crystal structure cell) is applied to the voltage 60 μ s of 4V, measure the voltage after 16.67ms, calculate by this variation with respect to initial value, set it as voltage retention.During mensuration, the temperature of liquid crystal structure cell is made as to 90 ℃, under differing temps, measures respectively.

(ion density)

Using the liquid crystal structure cell similarly making with above-mentioned (manufacture of liquid crystal structure cell), with the (East Yang テ of Toyo Corp. Network ニカ society) the 6254 type liquid crystal evaluation of physical property devices of making carry out the mensuration of ion density.During mensuration, apply the choppy sea of 10V, 0.01Hz, by trilateral trial and error method, calculate the area suitable with ion density of gained waveform, set it as ion density.During mensuration, the temperature of liquid crystal structure cell is made as to 60 ℃ and measures.

[embodiment 2]

In the 50ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add the BAPU of 2.39g (8.0mmol) and the p-PDA of 0.87g (8.0mmol), add the METHYLPYRROLIDONE of 30g, supplying nitrogen stirs and makes its dissolving on one side on one side.Stir this two amine aqueous solution while add the CBDA of 2.92g (14.9mmol), add again METHYLPYRROLIDONE, make solid component concentration reach 12 quality %, under nitrogen atmosphere, in stirring at room 2 hours, obtain polyamic acid (P2) solution.With E type viscometer (Toki Sangyo Co., Ltd.'s system), confirmed the viscosity of this polyamic acid solution at 25 ℃, result is 281mPas.

In this polyamic acid solution of 16.12g, add the METHYLPYRROLIDONE of 9.61g and the ethylene glycol butyl ether of 6.43g, the concentration that obtains P2 is the aligning agent for liquid crystal of 6.0 quality %.

[embodiment 3]

In the 50ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add the BAPU of 2.68g (9.0mmol) and the METHYLPYRROLIDONE of 30g, supplying nitrogen stirs and makes its dissolving on one side on one side.Stir this two amine aqueous solution while add the CBDA of 1.69g (8.6mmol), add again METHYLPYRROLIDONE, make solid component concentration reach 12 quality %, under nitrogen atmosphere, in stirring at room 6 hours, obtain polyamic acid (P3) solution.With E type viscometer (Toki Sangyo Co., Ltd.'s system), confirmed the viscosity of this polyamic acid solution at 25 ℃, result is 206mPas.

In this polyamic acid solution of 14.65g, add the METHYLPYRROLIDONE of 5.10g and the ethylene glycol butyl ether of 4.94g, the concentration that obtains P3 is the aligning agent for liquid crystal of 6.0 quality %.

[embodiment 4]

In the 50ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add the BABU of 2.62g (9.7mmol) and the METHYLPYRROLIDONE of 25g, supplying nitrogen stirs and makes its dissolving on one side on one side.Stir this two amine aqueous solution while add the CBDA of 1.85g (9.4mmol), add again METHYLPYRROLIDONE, make solid component concentration reach 10 quality %, under nitrogen atmosphere, in stirring at room 2 hours, obtain polyamic acid (P4) solution.With E type viscometer (Toki Sangyo Co., Ltd.'s system), confirmed the viscosity of this polyamic acid solution at 25 ℃, result is 173mPas.

In this polyamic acid solution of 13.90g, add the METHYLPYRROLIDONE of 5.10g and the ethylene glycol butyl ether of 4.75g, the concentration that obtains P4 is the aligning agent for liquid crystal of 6.0 quality %.

[embodiment 5]

In the 50ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add the BAPU of 2.54g (8.5mmol) and the METHYLPYRROLIDONE of 30g, supplying nitrogen stirs and makes its dissolving on one side on one side.Stir this two amine aqueous solution while add the PMDA of 1.69g (7.7mmol), add again METHYLPYRROLIDONE, make solid component concentration reach 10 quality %, under nitrogen atmosphere, in stirring at room 4 hours, obtain polyamic acid (P5) solution.With E type viscometer (Toki Sangyo Co., Ltd.'s system), confirmed the viscosity of this polyamic acid solution at 25 ℃, result is 138.6mPas.

In this polyamic acid solution of 15.13g, add the METHYLPYRROLIDONE of 5.64g and the ethylene glycol butyl ether of 4.94g, the concentration that obtains P5 is the aligning agent for liquid crystal of 6.0 quality %.

[embodiment 6]

In the 50ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add the BABU of 2.43g (9.0mmol) and the METHYLPYRROLIDONE of 30g, supplying nitrogen stirs and makes its dissolving on one side on one side.Stir this two amine aqueous solution while add the PMDA of 1.88g (8.6mmol), add again METHYLPYRROLIDONE, make solid component concentration reach 10 quality %, under nitrogen atmosphere, in stirring at room 3 hours, obtain polyamic acid (P6) solution.With E type viscometer (Toki Sangyo Co., Ltd.'s system), confirmed the viscosity of this polyamic acid solution at 25 ℃, result is 276mPas.

In this polyamic acid solution of 10.75g, add the METHYLPYRROLIDONE of 8.56g and the ethylene glycol butyl ether of 4.83g, the concentration that obtains P6 is the aligning agent for liquid crystal of 4.5 quality %.

[embodiment 7]

In the 50ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add the BAPU of 3.58g (12.0mmol) and the METHYLPYRROLIDONE of 30g, supplying nitrogen stirs and makes its dissolving on one side on one side.Stir this two amine aqueous solution while add the BODA of 2.86g (11.4mmol), add again METHYLPYRROLIDONE, make solid component concentration reach 12 quality %, under nitrogen atmosphere, in 50 ℃ of stirrings 28 hours, obtain polyamic acid (P7) solution.With E type viscometer (Toki Sangyo Co., Ltd.'s system), confirmed the viscosity of this polyamic acid solution at 25 ℃, result is 630mPas.

In this polyamic acid solution of 12.22g, add the METHYLPYRROLIDONE of 12.80g and the ethylene glycol butyl ether of 6.32g, the concentration that obtains P7 is the aligning agent for liquid crystal of 6.0 quality %.

[embodiment 8]

In the 50ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add the BABU of 3.24g (12.0mmol) and the METHYLPYRROLIDONE of 25g, supplying nitrogen stirs and makes its dissolving on one side on one side.Stir this two amine aqueous solution while add the BODA of 2.99g (11.9mmol), add again METHYLPYRROLIDONE, make solid component concentration reach 15 quality %, under nitrogen atmosphere, in 50 ℃ of stirrings 24 hours, obtain polyamic acid (P8) solution.With E type viscometer (Toki Sangyo Co., Ltd.'s system), confirmed the viscosity of this polyamic acid solution at 25 ℃, result is 498mPas.

In this polyamic acid solution of 9.95g, add the METHYLPYRROLIDONE of 12.0g and the ethylene glycol butyl ether of 5.50g, the concentration that obtains P8 is the aligning agent for liquid crystal of 6.0 quality %.

[embodiment 9]

In the 50ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add the DA-3 of 2.31g (8.54mmol) and the METHYLPYRROLIDONE of 24.3g, supplying nitrogen stirs and makes its dissolving on one side on one side.Stir this two amine aqueous solution while add the CBDA of 1.66g (8.46mmol), add again METHYLPYRROLIDONE, make solid component concentration reach 10 quality %, under nitrogen atmosphere, in stirring at room 4 hours, obtain polyamic acid (P9) solution.With E type viscometer (Toki Sangyo Co., Ltd.'s system), confirmed the viscosity of this polyamic acid solution at 25 ℃, result is 155mPas.

In this polyamic acid solution of 16.80g, add the METHYLPYRROLIDONE of 7.57g and the ethylene glycol butyl ether of 6.09g, the concentration that obtains P9 is the aligning agent for liquid crystal of 6.0 quality %.

[embodiment 10]

In the 50ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add the DA-4 of 2.84g (9.98mmol) and the METHYLPYRROLIDONE of 29.5g, supplying nitrogen stirs and makes its dissolving on one side on one side.Stir this two amine aqueous solution while add the CBDA of 1.66g (9.53mmol), add again METHYLPYRROLIDONE, make solid component concentration reach 10 quality %, under nitrogen atmosphere, in stirring at room 4 hours, obtain polyamic acid (P10) solution.With E type viscometer (Toki Sangyo Co., Ltd.'s system), confirmed the viscosity of this polyamic acid solution at 25 ℃, result is 206mPas.

In this polyamic acid solution of 17.12g, add the METHYLPYRROLIDONE of 7.75g and the ethylene glycol butyl ether of 6.22g, the concentration that obtains P10 is the aligning agent for liquid crystal of 5.5 quality %.

[embodiment 11]

In the 50ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add the DA-6 of 3.40g (9.48mmol) and the METHYLPYRROLIDONE of 29.5g, supplying nitrogen stirs and makes its dissolving on one side on one side.Stir this two amine aqueous solution while add the CBDA of 1.76g (8.97mmol), add again METHYLPYRROLIDONE, make solid component concentration reach 10 quality %, under nitrogen atmosphere, in stirring at room 4 hours, obtain polyamic acid (P11) solution.With E type viscometer (Toki Sangyo Co., Ltd.'s system), confirmed the viscosity of this polyamic acid solution at 25 ℃, result is 150mPas.

In this polyamic acid solution of 18.88g, add the METHYLPYRROLIDONE of 5.26g and the ethylene glycol butyl ether of 6.03g, the concentration that obtains P11 is the aligning agent for liquid crystal of 6.0 quality %.

[embodiment 12]

In the 50ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add the DA-5 of 0.53g (1.6mmol) and the p-PDA of 1.56g (14.4mmol), add the METHYLPYRROLIDONE of 30.9g, supplying nitrogen stirs and makes its dissolving on one side on one side again.Stir this two amine aqueous solution while add the CBDA of 2.82g (15.4mmol), add again METHYLPYRROLIDONE, make solid component concentration reach 10 quality %, under nitrogen atmosphere, in stirring at room 4 hours, obtain polyamic acid (P12) solution.With E type viscometer (Toki Sangyo Co., Ltd.'s system), confirmed the viscosity of this polyamic acid solution at 25 ℃, result is 160mPas.

In this polyamic acid solution of 18.41g, add the METHYLPYRROLIDONE of 6.03g and the ethylene glycol butyl ether of 6.11g, the concentration that obtains P12 is the aligning agent for liquid crystal of 6.0 quality %.

[embodiment 13]

In the 1000ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add the DA-7 of 7.00g (24.44mmol) and the BAPU of 3.13g (10.48mmol), will in flask, use nitrogen replacement.Then, add 359.90g dehydration METHYLPYRROLIDONE and 6.63g pyridine with syringe, in 25 ℃, by magnetic stirrer, BAPU and DA-7 are dissolved completely.Then by reaction solution water-cooled, by magnetic stirrer, add the CA-4 of 9.34g (31.44mmol) on one side on one side.Use funnel to add with the time of 30 seconds.Then, with the dehydration METHYLPYRROLIDONE of 10.00g, clean and add funnel used, to carrying out nitrogen replacement in reaction vessel, under water-cooled, continue to stir 3 hours.Then, under the condition that the methyl alcohol of 5 times of weight of reaction soln is stirred, successively inject on a small quantity wherein reaction soln, continue to stir 1 hour.Then, by filtration and the methyl alcohol of precipitate and 5 times of weight together with stir after 1 hour, filtered and recycled precipitate.Then, carry out same operation with the methyl alcohol of 5 times of weight, in 100 ℃ under reduced pressure by dry 24 hours of gained precipitate, obtain the poly amic acid ester (P13) of 14.59g.2.26g in gained solid matter is dissolved in completely to the METHYLPYRROLIDONE of 20.36g.Then, add the METHYLPYRROLIDONE of 2.12g and the ethylene glycol butyl ether of 10.60g in this solution, the concentration that obtains P13 is the aligning agent for liquid crystal of 6.0 quality %.

[embodiment 14]

In the 300ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add the DA-7 of 4.00g (13.97mmol) and the BAPU of 1.78g (5.99mmol), will in flask, use nitrogen replacement.Then, add 202.93g dehydration METHYLPYRROLIDONE and 3.79g pyridine with syringe, in 25 ℃, by magnetic stirrer, BAPU and DA-7 are dissolved completely.Then by reaction solution water-cooled, by magnetic stirrer, add the CA-5 of 1.27g (3.99mmol) and the CA-4 of 4.15g (13.96mmol) on one side on one side.Use funnel to add with the time of 30 seconds.Then, with the dehydration METHYLPYRROLIDONE of 10.00g, clean and add funnel used, to carrying out nitrogen replacement in reaction vessel, under water-cooled, continue to stir 3 hours.Then, under the condition that the methyl alcohol of 5 times of weight of reaction soln is stirred, successively inject on a small quantity wherein reaction soln, continue to stir 1 hour.Then, by filtration and the methyl alcohol of precipitate and 5 times of weight together with stir after 1 hour, filtered and recycled precipitate.Then, then carry out same operation with the methyl alcohol of 5 times of weight, in 100 ℃ under reduced pressure by dry 24 hours of gained precipitate, obtain the poly amic acid ester (P14) of 8.87g.2.27g in gained solid matter is dissolved in completely to the METHYLPYRROLIDONE of 20.45g.Then, add the METHYLPYRROLIDONE of 2.13g and the ethylene glycol butyl ether of 10.65g in this solution, the concentration that obtains P14 is the aligning agent for liquid crystal of 6.0 quality %.

[comparative example 1]

In the 50ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add the p-PDA of 2.17g (20.0mmol), then add the METHYLPYRROLIDONE of 25g, supplying nitrogen stirs and makes its dissolving on one side on one side.Stir this two amine aqueous solution while add 1,2,3 of 3.77g (19.2mmol), 4-tetramethylene tetracarboxylic dianhydride, then add METHYLPYRROLIDONE, make solid component concentration reach 12 quality %, in stirring at room 4 hours, obtain polyamic acid solution.With E type viscometer (Toki Sangyo Co., Ltd.'s system), confirmed the viscosity of this polyamic acid solution at 25 ℃, result is 602.3mPas.

The gained polyamic acid solution of 7.89g is sub-packed in the 50ml Erlenmeyer flask that stirrer is housed, add the METHYLPYRROLIDONE of 6.29g and the ethylene glycol butyl ether of 3.55g, by magnetic stirrer 30 minutes, obtain the aligning agent for liquid crystal of polyamic acid concentration 5.5 quality %.

[comparative example 2]

In the 1000ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add the DA-7 of 10.00g (34.92mmol), will in flask, use nitrogen replacement.Then, add 304g dehydration METHYLPYRROLIDONE and 6.1g pyridine with syringe, in 25 ℃, by magnetic stirrer, DA-7 is dissolved completely.Then by reaction solution water-cooled, by magnetic stirrer, add the CA-4 of 9.34g (31.43mmol) on one side on one side.Use funnel to add with the time of 30 seconds.Then, with the dehydration METHYLPYRROLIDONE of 20g, clean and add funnel used, to carrying out nitrogen replacement in reaction vessel, under water-cooled, continue to stir 3 hours.Then, under the condition that the distilled water of 5 times of weight of reaction soln is stirred, successively inject on a small quantity wherein reaction soln, continue to stir 1 hour.Then, by filtration and the distilled water of precipitate and 5 times of weight together with stir after 1 hour, filtered and recycled precipitate.Then, then carry out same operation with the ethanol of 5 times of weight, in 100 ℃ under reduced pressure by dry 24 hours of gained precipitate, obtain the solid matter of 14.82g.3.99g in gained solid matter is dissolved in completely to the METHYLPYRROLIDONE of 35.90g.Then, add the METHYLPYRROLIDONE of 6.91g and the ethylene glycol butyl ether of 19.36g in this solution, the concentration that obtains poly amic acid ester is the aligning agent for liquid crystal of 5.5 quality %.

[comparative example 3]

In the 1000ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add the DA-7 of 7.00g (24.44mmol), will in flask, use nitrogen replacement.Then, add 249.3g dehydration METHYLPYRROLIDONE and 4.6g pyridine with syringe, in 25 ℃, by magnetic stirrer, DA-7 is dissolved completely.Then by reaction solution water-cooled, by magnetic stirrer, add the CA-5 of 1.56g (4.88mmol) and the CA-4 of 6.08g (17.12mmol) on one side on one side.Use funnel to add with the time of 30 seconds.Then, with the dehydration METHYLPYRROLIDONE of 10g, clean and add funnel used, to carrying out nitrogen replacement in reaction vessel, under water-cooled, continue to stir 3 hours.Then, under the condition that the methyl alcohol of 5 times of weight of reaction soln is stirred, successively inject on a small quantity wherein reaction soln, continue to stir 1 hour.Then, by filtration and the methyl alcohol of precipitate and 5 times of weight together with stir after 1 hour, filtered and recycled precipitate.Then, then carry out same operation with the methyl alcohol of 5 times of weight, in 100 ℃ under reduced pressure by dry 24 hours of gained precipitate, obtain the solid matter of 11.15g.10.06g in gained solid matter is dissolved in completely to the METHYLPYRROLIDONE of 90.54g.Then, add the METHYLPYRROLIDONE of 5.63g and the ethylene glycol butyl ether of 44.97g in this solution, the concentration that obtains poly amic acid ester is the aligning agent for liquid crystal of 6.0 quality %.

In table 1, gather the viscosity of the consumption, the contracting contracted notation (P1 etc.) of gained polyamic acid and the METHYLPYRROLIDONE solution of this polyamic acid that show starting material (diamines etc.) used in embodiment 1～14 and comparative example 1～3.The unmarked contracting contracted notation of the polyamic acid of comparative example 1～3 and poly amic acid ester (representing by blank column in table 1).

In table 1, "-" represents viscosity undetermined.

With the aligning agent for liquid crystal obtaining in embodiment 2～embodiment 4, embodiment 7～embodiment 13, comparative example 1 and comparative example 2, manufacture liquid crystal structure cell similarly to Example 1, measure wear-resisting wiping, liquid crystal aligning, tilt angle, voltage retention and ion density.For embodiment 5, embodiment 6, embodiment 14 and comparative example 3, use method similarly to Example 1 to measure wear-resisting wiping and liquid crystal aligning.Acquired results is shown in table 2.

[table 1]

[table 2]

The possibility of utilizing in industry

The aligning agent for liquid crystal of the application of the invention, can obtain that wear-resisting wiping is good, the orientation of liquid crystal is also good and need the liquid crystal orientation film of strong friction treatment.In addition, the voltage retention of the liquid crystal structure cell of liquid crystal orientation film of the present invention is high, and ion density is also low, therefore can be used as the vertical orientated liquid crystal display device without friction treatment, also can be used as the liquid crystal display device of light orientation.

Here quote the full content of specification sheets, claims and specification digest of No. 2008-285860, the Japanese patent application of filing an application on November 6th, 2008 as the announcement of specification sheets of the present invention.

Claims

1. following formula (1-7), formula (1-8), formula (1-b) or formula (1-c) represent two aminophenyls or two amino-benzene oxygen alkyl urea;

2. following formula (1-9)～formula (1-11) represents two aminophenyls or two amino-benzene oxygen alkyl urea.