CN1818020A

CN1818020A - Triazine ring based polymers for photoinduced liquid crystal alignment

Info

Publication number: CN1818020A
Application number: CN 200610056961
Authority: CN
Inventors: 申东天; 金珍栗; 朴奎淳; 金泰珉
Original assignee: LG Cable Ltd
Current assignee: LS Corp
Priority date: 2001-11-12
Filing date: 2002-11-11
Publication date: 2006-08-16
Also published as: CN1831086A

Abstract

Triazine ring based polymers for photoinduced liquid crystal alignment introduces photoactive groups for inducing, reinforcing, improving and preserving liquid crystal alignment, for example photoreactor such as cinnamate, coumarin, chalcone and maleimide, as a chain to have at least one photoactive group. One of the photoactive groups can experience Fries rearrangement which induces liquid crystal alignment, and other groups can experience photodimerization, photoisomerization, photocrosslinking or photodegradation to reinforce, change or preserve the generated alignment.

Description

The three pyridine ring based polyalcohols that are used for the photoinduction LCD alignment

The application be the applicant on November 11st, 2002 submit to, application number is 02803167.9 (international application no is PCT/KR02/02101), exercise question is divided an application for " being used for three pyridine ring based polyalcohols of photoinduction LCD alignment, the liquid crystal alignment layer that contains this polymkeric substance, the liquid crystal cell that uses this both alignment layers and manufacture method thereof ".

Technical field

The liquid crystal alignment layer that the present invention relates to be used for three pyridine ring based polyalcohols of photoinduction LCD alignment and contain this polymkeric substance; more specifically; relate to be used for the photoinduction LCD alignment have a chromophoric polymkeric substance of at least one photolytic activity; wherein in this main polymer chain, introduce the side chain of optical active group, also relate to the liquid crystal layer that uses this polymkeric substance with the LCD alignment of inducing and enhancing, raising and protection LCD alignment.

Background technology

Be used for of the LCD alignment agent of the polymkeric substance of photoinduction LCD alignment as the device of the optical characteristics of utilizing liquid crystal.Generally speaking, thus the polymkeric substance that is used for the photoinduction LCD alignment be meant by coated polymeric in substrate and subsequently in its surface irradiation ultraviolet radiation to form the material that anisotropy can the orientation liquid crystal thereon.

The liquid crystal cell that use is used for the polymkeric substance of photoinduction LCD alignment is used for various fields, comprises liquid-crystal display, loop expansion pipe, optics etc.Therefore, though following explanation concentrates on display element, should be appreciated that liquid crystal alignment layer is not limited in and be used for display element, and be applied to above-mentioned every field.

Flat pannel display (FPD) element that is applied to liquid crystal indicator replaces existing cathode ray tube (CRT) gradually, and this is because flat panel displaying element is frivolous and can amplify.In these FPD, liquid-crystal display (LCD) leads FPD market at present, because LCD has portable and advantage less energy-consumption.In addition, this LCD not only is applied to counter and notebook computer, and its application is also expanded to wall-hanging TV machine and high-definition television (HDTV).

In order to utilize liquid crystal cell to come display image, liquid crystal should be in upper edge, the interface pre-determined direction orientation between liquid crystal and the transparent conducting glass so that the liquid crystal between the transparent conducting glass by external electrical field switch.This LCD alignment degree is to determine the greatest factor of LCD picture quality.

Usually, known three kinds of exemplary process of liquid crystal being carried out orientation.First method is a rubbing manipulation shown in Figure 1, i.e. coated polymeric such as polyimide in substrate with friction drum its surface that rubs, are arranged the friction cloth with flocking nylon, polyester or rayon fiber subsequently around friction drum.Second method is the SiO deposition, promptly along inclined direction deposits SiO in substrate.The third method is the orientation method, is about to be used for the polymer-coated in substrate of photoinduction LCD alignment, and vertical subsequently or oblique illumination light is so that the photopolymer material generation photoresponse of coating, thereby forms anisotropy in its surface.

According to first method, when with friction drum friction polymer surface, produce minute dust or because the static guiding discharge, this can cause a lot of problems in the liquid crystal panel manufacturing processed.According to second method, be difficult to keep with respect to the deposition angles of substrate and the homogeneity of film thickness, and this process is scalable to big scale.According to the third method, have the weak excessively problem of physical attachment between photoinduction LCD alignment polymkeric substance and the liquid crystal, and because heating causes the orientation reduction, this makes this method can't drop into practical application.

Utilizing wherein, thereby the LCD alignment of the third method develops into by using rayed to induce the photopolymer photoresponse to come the orientation liquid crystal in coating surface formation anisotropy.This alignment method is to have the feature that overall process keeps cleaning to the noncontact treatment process on orientation surface and owing to not producing static, dust or other contaminant particle.Find to use the pyridine compound can realize light orientation (K.Ichimura et al.Langmuir, 4,1214,1988), various polymkeric substance such as poly maleimide (H.J.Choiet al. United States Patent (USP) 6,218,501) and polyolefine (R.H.Herr et al. United States Patent (USP) 6 have been developed thereafter, 201,087) as the light alignment materials.

Yet, for the light alignment method is dropped into practical application, need improve photochemical stability, thermostability and electrooptical property, and heavy dose of ultraviolet ray.Therefore, need the new light alignment materials of development to solve the problems referred to above.

Summary of the invention

The present invention relates to utilize light-struck noncontact LCD alignment method, this method can become LCD alignment a plurality of farmlands, thereby solves traditional contact-type rubbing manipulation and the sedimentary problem of traditional contact-type SiO.The purpose of this invention is to provide a kind of novel smooth alignment materials, it shows the excellent orientation characteristic that is used for liquid crystal, remarkable light and heat stability and improved photoelectric characteristic.

In other words, the invention provides the polymkeric substance that is used for the photoinduction LCD alignment, it has at least one photolytic activity chromophoric group, also will be used to induce the side chain with optical active group of orientation liquid crystal to introduce the orientation that polymer chain strengthens, improves and keep liquid crystal by utilizing triazine as main polymer chain.The Fries that liquid crystal induced orientation can take place in one of optical active group resets, and photodimerization, photoisomerization, photo-crosslinking or the photodegradation orientation to strengthen, to change or to keep being produced can take place in other group simultaneously.

In addition, another object of the present invention provides and uses the described liquid crystal alignment layer that is used for the polymkeric substance of photoinduction LCD alignment.

Other purpose of the present invention and advantage are as described below, and are better understood by following embodiment of the present invention.In addition, objects and advantages of the present invention can be achieved by method and the combination thereof that claims disclosed.

Description of drawings

In conjunction with the accompanying drawings, in the following detailed description these and other feature, aspect and the advantage of the preferred embodiment of the invention will be described more all sidedly.

Fig. 1 is the side elevational view of traditional alignment method of explanation liquid crystal alignment layer;

Fig. 2 is the perspective illustration that illustrates according to the alignment method of liquid crystal alignment layer of the present invention.

Embodiment

Hereinafter, describe the preferred embodiments of the invention with reference to the accompanying drawings in detail.

At first, the explanation of used term is not subjected to the restriction of general or lexical meaning in this specification sheets and the claim, but comprise implication consistent and notion with the technology of the present invention field, based on this, thereby the inventor can suitably limit the invention that the notion of term is described contriver oneself in the best way.

Therefore, structure in the specification sheets and accompanying drawing only are most preferred embodiment of the present invention, and not shown all aspects of the present invention.Thereby, should be appreciated that to have the various equivalents and the improvement project of replacing them.

The polymkeric substance that is used for the photoinduction LCD alignment provided by the invention comprises having the chromophoric polymkeric substance of at least one photolytic activity.

First embodiment

In the first embodiment, the general formula of this polymkeric substance is shown in Chemical formula 1.

Chemical formula 1

In Chemical formula 1, m+n=1, and m and n are respectively 0～1 real number.

In Chemical formula 1, R ₁Be to select one among the 1a-4a from following Chemical formula 2.

Chemical formula 2

In the 1a of Chemical formula 2, X selects one from following chemical formula 3.

In above-mentioned chemical formula 3, m and n are respectively 0～10 integers;

In addition, in the 1a of Chemical formula 2, Y selects one from following chemical formula 4.

Chemical formula 4

In above-mentioned chemical formula 4, Y1, Y2, Y3, Y4, Y5, Y6, Y7, Y8 and Y9 select one from following chemical formula 5.

Chemical formula 5

At this, m in the above-mentioned chemical formula 5 and n are respectively 0～10 integer, and A and B are selected from H, F, Cl, CN, CF respectively ₃Or CH ₃One of them.

In the 2a and 3a of Chemical formula 2, n is 0～10 integer, and a1, a2, a3, a4 and a5 select one from following chemical formula 6.

Chemical formula 6

At this, m in the above-mentioned chemical formula 6 and n are respectively 0～10 integer, and A and B are selected from H, F, Cl, CN, CF respectively ₃Or CH ₃One of them.

In the 4a of above-mentioned Chemical formula 2, Y selects one from following chemical formula 7.

Chemical formula 7

At this, the n in the above-mentioned chemical formula 7 is 0～10 integer.

In the 4a of Chemical formula 2, b1 and b2 select one from following chemical formula 8.

Chemical formula 8

At this, in the above-mentioned chemical formula 8, A is selected from H, F, CH respectively ₃, CF ₃Or CN one of them.

In above-mentioned Chemical formula 1, R ₂With R ₃Respectively based on a kind of amine that is selected from following chemical formula 9.

Chemical formula 9

At this, in the above-mentioned chemical formula 9, m and n are respectively 0～10 integers.

In addition, in above-mentioned Chemical formula 1, R ₄With R ₅Respectively based on a kind of carboxylic acid derivative that is selected from following Chemical formula 10 or a kind of carboxylic diacid acid anhydride.

Chemical formula 10

At this, in the above-mentioned Chemical formula 10, m and n are respectively 0～10 integers.

In the present invention, R ₂And R ₃Or R ₄And R ₅Can be by amide group or imide group or above-mentioned group mixing connection.

First embodiment of the present invention is described based on the formation of amido linkage.

In Chemical formula 1, connect R ₂And R ₃Or R ₄And R ₅Key be to set up by the forming of amido linkage that the reaction by amine and carboxylic acid obtains, it can be by following reaction formula 1 expression.

Reaction formula 1

The R of above-mentioned Chemical formula 1 ₂And R ₃Be based on the amine of reaction formula 1, it selects one respectively from following Chemical formula 11.

Chemical formula 11

At this, in the above-mentioned Chemical formula 11, m and n are respectively 0 to 10 integer.

In addition, the R of above-mentioned Chemical formula 1 ₄And R ₅Based on the carboxylic acid of reaction formula 1, it is respectively to select one from following Chemical formula 12.

Chemical formula 12

At this, in the above-mentioned Chemical formula 12, m and n are respectively 0～10 integers.

In addition, be selected from the contained R of Chemical formula 1 ₁, R ₂, R ₃, R ₄And R ₅Substituting group in the phenyl ring that contains not only can have above-mentioned aligning structure, can also have an ortho position or a bit architecture or be selected from the neighbour,, the mixed structure of at least two kinds of structures in the aligning structure.

According to first embodiment of the invention, the polyamide polymer of above-mentioned Chemical formula 1 representative has at least one optical active group.In order to strengthen, to change or protecting the orientation that is produced, one of described optical active group can carry out photodegradation, and another group can carry out Fires to be reset, and other group can carry out light dimerization reaction, photoisomerization reaction or photo-crosslinking.

According to this embodiment, comprise LCD alignment agent by the polymkeric substance of Chemical formula 1 representative can be used to by the described polymkeric substance of coating in substrate and subsequently thereon irradiation ultraviolet radiation prepare the liquid crystal alignment layer that contains described polymkeric substance.Particularly, the polymkeric substance that is used for the photoinduction liquid crystal alignment layer can change the tilt angle of liquid crystal, and this angle is arranged consistent with the ultraviolet tilt angle that is shone.It is 0 ° that described polymkeric substance also makes the tilt angle of liquid crystal by change chemical structure or adjusting ultraviolet irradiation angle.

Thereby, the liquid-crystal display (LCD) that adopts this polymkeric substance that is used for the photoinduction LCD alignment to make can be applicable to various patterns, as STN (STN Super TN type), TN (stable twisted nematic), IPS (plane conversion type), VA (vertical orientation type) and VATN (vertical orientation stable twisted nematic).

In addition, utilize liquid crystal alignment layer and liquid crystal cell with LCD alignment can be used for various application, as loop expansion pipe or optics and LCD.

Hereinafter, the polymkeric substance of describing the photoinduction LCD alignment be used for first embodiment in detail prepares the method for liquid crystal alignment layer.

First method

The LCD alignment agent of the present embodiment polymkeric substance that contains the Chemical formula 1 representative of 1-20 weight % is dissolved in the organic solvent, makes its viscosity, subsequently it is coated on that to form 10-500nm in the substrate thick, thereby form both alignment layers with 1-100cps.

Described organic solvent is selected from chlorobenzene, N-methyl-pyrrolidone (NMP), N-ethyl-pyrrolidone (NEP), N, N-dimethyl-imidazolidone (DMI), N, N-dipropyl-imidazolidone (DPI), dimethyl-methane amide (DMF), dimethyl-ethanamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO), cyclopentanone, pimelinketone, ethylene dichloride, butyl glycol (butyl-cellusolve), gamma-butyrolactone (γ-butyroactone) and tetrahydrofuran (THF), or its mixture.

The LCD alignment agent that will be dissolved in organic solvent is coated in the substrate, makes the ito glass substrate be in the pre-determined thickness 10-500nm scope, so that form layers.At this moment, can use any possible traditional method carry out as spin coating and roll marks as described in coating process.

Second method

Derive from irradiation ultraviolet radiation on the alignment layer surface of LCD alignment agent of first method in coating, thereby make the liquid crystal alignment layer that contains described polymkeric substance.At this moment, in order to prepare liquid crystal alignment layer, to make the ultraviolet ray that utilizes the polarizer linear polarization or not adopting the unpolarized ultraviolet ray of polarizer to tilt or vertical irradiation.

Hereinafter, adopting more specifically, embodiment illustrates in greater detail first embodiment.Following examples are used for the exemplary illustration specific implementation of the present invention, it should be interpreted as restriction or retrain scope of the present invention.

Embodiment 1-1

Has the chromophoric polyamide polymer that is used for the photoinduction LCD alignment of laurate

(1) reformation triazine ring

27.1g 4 (2-tetrahydropyrans methoxyl group) bromobenzene is dissolved in the 250ml anhydrous tetrahydro furan in the three-necked flask that is filled with nitrogen, then, after the 3g magnesium of packing into, stirred 24 hours.This solution in-20 ℃ of reactions 12 hours, slowly drops to the 18.4g cyanuryl chloride in the 200ml anhydrous tetrahydro furan in being full of the three-necked flask of nitrogen simultaneously.

After the reaction, reaction soln at room temperature reduced pressure removes tetrahydrofuran (THF), is dissolved in the ethyl acetate subsequently.With this solution in alkaline solution mix and high degree of agitation with extracting impurities after, then this solution is at room temperature reduced pressure and removes ethyl acetate.

Remove residual solid phase material recrystallization in normal hexane behind the solvent, obtain 2-(4 (2-tetrahydropyrans methoxyl group) phenyl)-4,6-two chloro-1,3,5-three pyridines.

(2) hydroxy functional group is introduced three pyridine rings

The material that obtains in (1) with 34.0g embodiment 1-1 adds round-bottomed flask and subsequently it is dissolved in after the 300ml tetrahydrofuran (THF), with 0.3g pyridine-toluene-sulphonate is added in the flask and added 50ml ethanol sustained reaction 24 hours.

After the reaction, remove by underpressure distillation and to desolvate, once more residual solids is dissolved with methyl chloride subsequently, then in separating funnel, mix with twice of extracting impurities with distilled water.Calcium chloride added in the methyl chloride solution to remove anhydrate, remove by underpressure distillation once more subsequently and desolvate.This solid phase of recrystallization in the mixed solvent of methyl chloride and normal hexane obtains 2-(4-hydroxy phenyl)-4,6-two chloro-1,3,5-three pyridines.

(3) synthetic three pyridine rings with laurate side chain

Add the 25.6g three pyridine derivatives that derive from embodiment 1-1 (2) in the round-bottomed flask be full of nitrogen and by adding the 200ml tetrahydrofuran (THF) it is dissolved subsequently.The 15.2g triethylamine is being added this solution and subsequently solution temperature is being reduced to after-5 ℃, this solution of high degree of agitation and with the cinnamyl chloride solution reaction that slowly splashes into 12 hours, wherein cinnamyl chloride solution obtains by the 100ml anhydrous tetrahydro furan being added dilute in the 25g cinnamyl chloride.

After the reaction, to remove tetrahydrofuran (THF), this solution dissolves with methyl chloride subsequently with the reaction soln underpressure distillation, desolvates to remove by strainer and underpressure distillation subsequently that silica gel is housed.

At last, in the mixed solvent of 1: 1 methyl chloride and normal butane after the recrystallization, the described solution of filtration under diminished pressure.Vacuum-drying gained solid phase material is to obtain having the triazine of laurate side chain.

(4) synthetic three pyridine monomers with two amine functional groups

The 38.6g three pyridine derivatives that will obtain with the method for embodiment 1-1 (3) are packed at the bottom of the garden in the flask and are dissolved in the 400ml chloroform.32.8g 4-amino-phenol and 12g sodium hydroxide are dissolved in 300ml distilled water, dissolve the 3g palmityl trimethyl ammonium chloride therein, subsequently it is mixed with above-mentioned three pyridine derivative solutions and high degree of agitation and reaction 24 hours.After the reaction, separate the organic solution phase, and reacted solution moved into separating funnel and with distilled water wash three times with extracting impurities, remove with calcium chloride subsequently and anhydrate.This solution of underpressure distillation to be to remove the chloroform as organic solvent, subsequently recrystallization in the mixed solvent of methyl chloride and normal butane.

With precipitated crystal filtration under diminished pressure and vacuum-drying, obtain three pyridine monomers.

(5) be used for the polymerization of the polyamide polymer with laurate side chain of photoinduction LCD alignment

The 53.156g three pyridine monomers that the method for (4) that will be by embodiment 1-1 obtains are packed at the bottom of the garden that is full of nitrogen in the flask and are dissolved in the 400ml anhydrous tetrahydro furan, add the 20.238g triethylamine subsequently.The 20.3g terephthalyl chloride is dissolved in the 100ml anhydrous tetrahydro furan, slowly it is splashed into subsequently in the above-mentioned solution that is dissolved with three pyridine monomers and triethylamine, this solution of high degree of agitation also reacted 12 hours.

After the reaction, reaction soln is poured in the methyl alcohol, thus precipitation, filtration and vacuum-drying throw out.Dissolving gained throw out also precipitates in methyl alcohol subsequently in tetrahydrofuran (THF) once more, said process repeats twice, vacuum-drying throw out subsequently is to obtain the having synthesizing polyamides polymkeric substance that be used for LCD alignment of laurate photoinduction functional group by means of three pyridine rings.

(6) make liquid crystal display

Gained light orientation agent is dissolved in the mixing solutions of NMP and butyl glycol, and to have the density of 8 weight %, the filtering membrane through aperture 0.1 μ m filters to remove impurity particle subsequently.This solution is printed to thick about 300nm being coated with on the substrate of glass of transparency electrode, thereby is coated with lighting orientation agent, desolvate to remove about 1 hour of about 200 ℃ of down dry these substrate of glass subsequently.Subsequently, by with the ultraviolet ray of 500W mercury lamp with 20 ° at inclination angle, per 2 seconds～10 minutes once irradiatings to substrate of glass, and in described substrate, induce the photopolymerization or the photodegradative complex reaction of polymer chain of generation such as laurate group, make the liquid crystal alignment layer that contains polymkeric substance thus.The spacer that is of a size of 4-5 μ m is injected on two substrate of glass, subsequently substrate of glass is bonded into the unit interval with 4-5 μ m with epoxy adhesive.This unit under 130 ℃ through 1 hour process of setting, thereby make the epoxy adhesive sclerosis, make the wherein complete adherent of substrate of glass unit.Liquid crystal is packed in the unit of making, this unit carry out once 100-130 ℃ down heating then be cooled to the heat treatment process of room temperature in 1 hour.Subsequently, finally obtain liquid crystal display.

Embodiment 1-2

A kind of have a chromophoric polyamide polymer that is used for the photoinduction LCD alignment of phenyl styryl ketone

(1) synthetic phenyl styryl ketone functional group

10g methoxyl group phenyl styryl ketone and 2.05g sodium cyanide are dissolved in the 100ml dimethyl sulfoxide (DMSO), with afterreaction 24 hours.After the reaction, reaction soln is stirred with extracting impurities with the chloroform mixing and with distilled water.Remove after the solution phase, this solution room temperature is reduced pressure to remove chloroform.With residual solid phase in methyl alcohol after the recrystallization, vacuum-drying solution, thereby obtain being used for the 4-hydroxy-benzalacetophenone of photoresponse.

(2) hydroxy functional group is introduced three pyridine rings

The 23.8g 4-hydroxy-benzalacetophenone that the method for (1) that will be by embodiment 1-2 obtains adds and is full of the round-bottomed flask of nitrogen and subsequently it is dissolved in the 240ml anhydrous tetrahydro furan.To also at room temperature react 6 hours in 2.4g sodium hydride (NaH) the adding solution.This solution is dissolved in the prepared solution of 200ml anhydrous tetrahydro furan in-5 ℃ of reactions 24 hours with passing through described in embodiment 1-1 (1) of slowly splashing into the 18.4g cyanuryl chloride under high degree of agitation.After the reaction, except that desolvating, once more residual solids is dissolved in chloroform subsequently by underpressure distillation.With this solution in separating funnel with distilled water wash three times with extracting impurities, remove with calcium chloride subsequently and anhydrate, this solution of underpressure distillation subsequently to be to remove chloroform, subsequently recrystallization in the mixed solvent of methyl chloride and normal hexane.This recrystallization material of filtration under diminished pressure and vacuum-drying is to obtain having three pyridine derivatives of phenyl styryl ketone functional group.

(3) synthetic three pyridine monomers with two amine functional groups

The three pyridine derivatives that the 38.6g that the method for (2) that will be by embodiment 1-2 obtains has a phenyl styryl ketone functional group are packed in the round-bottomed flask and are dissolved in the 300ml chloroform.32.8g 4-amino-phenol and 12g sodium hydroxide are dissolved in 300ml distilled water, dissolve the 3g palmityl trimethyl ammonium chloride therein, subsequently it is mixed with above-mentioned three pyridine derivative solutions and high degree of agitation and reaction 24 hours.After the reaction, separate the organic solution phase, and reacted solution moved into separating funnel and with distilled water wash three times with extracting impurities, remove with calcium chloride subsequently and anhydrate.This anhydrous solution of underpressure distillation to be to remove the chloroform as organic solvent, subsequently recrystallization in the mixed solvent of methyl chloride and normal butane.With precipitated crystal filtration under diminished pressure and vacuum-drying subsequently, obtain three pyridine monomers.

(4) be used for the polymerization with the chromophoric polyamide polymer of phenyl styryl ketone of photoinduction LCD alignment

The 53.156g three pyridine monomers that the method for (4) that will be by embodiment 1-1 obtains are packed at the bottom of the garden that is full of nitrogen in the flask and are dissolved in the 400ml anhydrous tetrahydro furan, add the 20.24g triethylamine subsequently.The 20.3g terephthalyl chloride is dissolved in the 100ml anhydrous tetrahydro furan, slowly it is splashed into subsequently in the above-mentioned solution that is dissolved with three pyridine monomers and triethylamine, this solution of high degree of agitation also reacted 12 hours.After the reaction, reaction soln is slowly poured in the methyl alcohol, thus precipitation, filtration and vacuum-drying throw out.Dissolving gained throw out and in methyl alcohol, precipitating subsequently in tetrahydrofuran (THF) once more, said process repeats twice, and vacuum-drying throw out subsequently is to obtain the having synthesizing polyamides polymkeric substance that be used for LCD alignment of phenyl styryl ketone functional group by means of three pyridine rings.

(5) make liquid crystal display

By the method for embodiment 1-1 (6), utilize the polyamide polymer that is used for the photoinduction LCD alignment that obtains by embodiment 1-2 (4) method to make liquid crystal display.

Embodiment 1-3

A kind of have a chromophoric polyamide polymer that is used for the photoinduction LCD alignment of tonka bean camphor

(1) introduces the tonka bean camphor chromophoric group

16.2g umbelliferone and 2.4g sodium hydride are packed at the bottom of the garden that is full of nitrogen in the flask, be dissolved in subsequently in the 160ml anhydrous tetrahydro furan.Afterwards, with this solution high degree of agitation and reacted 6 hours.With this solution high degree of agitation and with passing through described in embodiment 1-1 (1) of slowly splashing into the 18.4g cyanuryl chloride is dissolved in the prepared solution of 200ml anhydrous tetrahydro furan in-5 ℃ of reactions 24 hours.After the reaction, remove tetrahydrofuran (THF), once more residual solids is dissolved in chloroform subsequently by underpressure distillation.With this solution in separating funnel with distilled water wash three times with extracting impurities, remove with calcium chloride subsequently and anhydrate, this solution of underpressure distillation subsequently to be to remove chloroform, subsequently recrystallization in the mixed solvent of methyl chloride and normal hexane.This recrystallization material of filtration under diminished pressure and vacuum-drying is to obtain having three pyridine derivatives of tonka bean camphor functional group.

(2) synthetic three pyridine monomers with two amine functional groups

The three pyridine derivatives that the 31.1g that will obtain by the method for embodiment 1-3 (1) has a tonka bean camphor photoinduction functional group are packed in the round-bottomed flask and are dissolved in the 300ml chloroform.32.8g 4-amino-phenol and 12g sodium hydroxide are dissolved in 300ml distilled water, dissolve the 3g palmityl trimethyl ammonium chloride therein, subsequently it is mixed with above-mentioned three pyridine derivative solutions and intense reaction 24 hours.After the reaction, organic solution is separated and move into separating funnel with distilled water wash three times with extracting impurities.Subsequently, remove with calcium chloride and anhydrate.This anhydrous solution of underpressure distillation to be to remove the chloroform as organic solvent, subsequently recrystallization in the mixed solvent of methyl chloride and normal butane.With precipitated crystal filtration under diminished pressure and vacuum-drying subsequently, obtain three pyridine monomers.

(3) be used for the polymerization with the chromophoric polyamide polymer of tonka bean camphor of photoinduction LCD alignment

The 45.54g three pyridine monomers that will obtain by the method for embodiment 1-3 (2) are packed at the bottom of the garden that is full of nitrogen in the flask and are dissolved in the 400ml anhydrous tetrahydro furan, add the 20.24g triethylamine subsequently.The 20.3g terephthalyl chloride is dissolved in the 100ml anhydrous tetrahydro furan, slowly it is splashed into subsequently in the above-mentioned solution that is dissolved with three pyridine monomers and triethylamine, this solution of high degree of agitation also reacted 12 hours.After the reaction, reaction soln is slowly poured in the methyl alcohol, thus precipitation, filtration and vacuum-drying throw out.Dissolving gained throw out and in methyl alcohol, precipitating subsequently in tetrahydrofuran (THF) once more, said process repeats twice, and vacuum-drying throw out subsequently is to obtain the having synthesizing polyamides polymkeric substance that be used for LCD alignment of tonka bean camphor functional group by means of three pyridine rings.

(4) make liquid crystal display

By the method for embodiment 1-1 (6), utilize the polyamide polymer that is used for the photoinduction LCD alignment that obtains by embodiment 1-3 (3) method to make liquid crystal display.

EXPERIMENTAL EXAMPLE: the characteristic of measuring liquid crystal display

Photoelectric characteristic, thermostability, optical stability, residual DC and the VHR characteristic of the liquid crystal display that the method for measurement by embodiment 1-1 to 1-3 makes, it the results are shown in the table 1,2,3 and 4.

Test 1: tilt angle is with heat treated variation

As shown in table 1 below, the polymkeric substance that is used for the photoinduction LCD alignment of individual embodiment has as the thermostability of the fundamental characteristics of the polyimide that uses traditionally, optical transparence and excellent coating performance, and is the mechanical property of the peculiar excellence of polyamide polymer.Thereby, when utilization is made light orientation liquid crystal cells according to the polymkeric substance that is used for the photoinduction LCD alignment of present embodiment, can realize the multizone LCD alignment easily by simple procedure.In addition, because the very big improvement of orientation performance, for example even after needs pyritous sealing baking, still keep the tilt angle of liquid crystal, this unit need can be applicable to the liquid-crystal display at high definition and wide visual angle.

Table 1

		Embodiment 1-1	Embodiment 1-2	Embodiment 1-3
		Embodiment 1-1	Embodiment 1-2	Embodiment 1-3	Method		Rayed	Rayed	Rayed
Density		8 weight %	8 weight %	8 weight %	Method		Rayed	Rayed	Rayed
Density		8 weight %	8 weight %	8 weight %	Tilt angle	Room temperature	0-5°	0-3°	0-4°
After the thermal treatment	0-5°	0-3°	0-4°			Room temperature	0-5°	0-3°	0-4°
After the thermal treatment	0-5°	0-3°	0-4°	Contrast ratio		195	190	190

Annotate 1: adopt liquid crystal angle rotation mode to measure tilt angle.

Annotate 2: under 150 ℃ of sealing storing temperatures, heat-treated 3 minutes.

Test 2: thermostability

The thermostability of following measurement liquid crystal cells.After the initial tilt angle of measuring liquid crystal cells, survey and measure tilt angle under the room temperature with the variation of liquid crystal cells 150 ℃ of following thermal aging time.When the thermostability of orientation is unstable, the tilt angle time to time change, when stablizing, tilt angle is almost constant.Test result is shown in following table 2.As seen from Table 2, have very excellent thermostability according to the light orientation agent of present embodiment, thereby even in thermal ageing process for a long time the orientation and the tilt angle of liquid crystal also keep stable, satisfy the fundamental property of liquid-crystal display thus.

Table 2

	Embodiment 1-1	Embodiment 1-2	Embodiment 1-3
	Embodiment 1-1	Embodiment 1-2	Embodiment 1-3	Tilt angle	～5°	～4°	～4°
The thermal ageing temperature	150℃	150℃	150℃	Tilt angle	～5°	～4°	～4°
The thermal ageing temperature	150℃	150℃	150℃	Thermal aging time	48 hours	48 hours	48 hours
Tilt angle changes	Do not have	Do not have	Do not have	Thermal aging time	48 hours	48 hours	48 hours

Test 3: optical stability

Make liquid crystal cells and measure its optical stability according to embodiment 1-1,1-2 and 1-3.In order to measure optical stability, on a unitary surface, utilize polarizer to check the change of the orientation characteristic of irradiating surface and non-irradiating surface by naked eyes subsequently the UV-light in the certain limit and radiation of visible light.Measuring result is shown in the following table 3.When unit light stability is not enough, cause the variation of LCD alignment characteristic on the irradiating surface at least to the light of liquid crystal cells.Thereby the LCD alignment characteristic on the irradiating surface is different from non-irradiating surface and noticeable change or destroyed, and it is indeterminate to make LCD alignment mix.Thus, this unit that demonstrates the orientation characteristic variations can not be used as display unit.

Table 3

		Embodiment 1-1	Embodiment 1-2	Embodiment 1-3
		Embodiment 1-1	Embodiment 1-2	Embodiment 1-3	The rayed amount	0.5J/cm ²	No change	No change	No change
1J/cm ²	No change	No change	No change			0.5J/cm ²	No change	No change	No change
1J/cm ²	No change	No change	No change	2J/cm ²		No change	No change	No change
The illumination firing angle	90°	No change	No change	2J/cm ²		No change	No change	No change	No change
	90°	No change	No change	80°	No change	No change	No change		No change
	70°	No change	No change	80°	No change	No change	No change	No change

Test 4: residual DC and voltage retention (VHR)

The volts DS of rangeability for-10V～10V put on the two ends of liquid crystal cells and measure its electrostatic capacitance.Owing to the lagged value of electrostatic capacitance obtains residual DC.Liquid crystal cells is the TN structure sample, and thick 4-6 μ m prepares according to the described manufacture method of the foregoing description 1-1 to 1-3.Two electrodes of prepared liquid crystal cells are connected to LCD survey meter (being Fluke 6306) and write down under the 1kHz its electrostatic capacitance with the variation of volts DS from 0V-10V and 0V--10V.Obtaining electrostatic capacitance lags behind with the variation of voltage and uses it for the measurement residual DC.In order to obtain voltage retention (VHR), use have ± 1V in the pulse in 64 μ s time length, 60Hz cycle, measure the conservation rate of the voltage that initially applies subsequently.The results are shown in following table 4.By table 4 as seen, measuring result shows for all three unit all have the low residue DC of 20 ℃ of following 10-13mV and the high conservation rate of 98-99%.This expression is satisfied the fundamental property that can be used as liquid crystal indicator according to the light orientation agent of embodiment 1-1 to 1-3.

Table 4

		Embodiment 1-1	Embodiment 1-2	Embodiment 1-3
		Embodiment 1-1	Embodiment 1-2	Embodiment 1-3	R-DC	20℃	10mV	11mV	13mV
60℃	30mV	35mV	33mV			20℃	10mV	11mV	13mV
60℃	30mV	35mV	33mV	VHR		20℃	99％	99％	98％
60℃	98％	96％	97％			20℃	99％	99％	98％

Second embodiment

In second embodiment, the polymkeric substance general formula is shown in Chemical formula 13.

Chemical formula 13

At this, in Chemical formula 13, m+n=1, m and n are respectively the real number of 0-1.

In Chemical formula 13, R ₁Identical with in first embodiment.

Yet, in Chemical formula 13, connect R ₂And R ₃Or R ₄And R ₅Key be to form by the imide bond that the reaction by amine and carboxylic diacid acid anhydride obtains, they generally can be by 2 expressions of following reaction formula:

Reaction formula 2

The R of above-mentioned Chemical formula 13 ₂And R ₃Based on the amine of reaction formula 2, described amine is selected from one of following Chemical formula 14 respectively:

Chemical formula 14

At this, in the above-mentioned Chemical formula 14, m and n are respectively the integers of 0-10.

In addition, the R of above-mentioned Chemical formula 13 ₄And R ₅Based on the carboxylic diacid acid anhydride of reaction formula 2, described carboxylic diacid acid anhydride is selected from one of following Chemical formula 15.

Chemical formula 15

In addition, be selected from the contained R of Chemical formula 13 ₁, R ₂, R ₃, R ₄And R ₅Substituting group in the phenyl ring that contains not only can have above-mentioned aligning structure, can also have an ortho position or a bit architecture or be selected from the neighbour,, the mixed structure of at least two kinds of structures in the aligning structure.

According to this embodiment of the present invention, have at least one optical active group by the polyimide polymer of above-mentioned Chemical formula 13 representatives, identical with the situation of first embodiment.In order to strengthen, to change or protecting the orientation that is produced, one of described optical active group can carry out photodegradation, and another group can carry out Fires to be reset, and other group can carry out light dimerization reaction, photoisomerization reaction or photo-crosslinking.

According to this embodiment, comprise that the LCD alignment agent by the polymkeric substance of Chemical formula 13 representatives has and essentially identical performance of first embodiment and application.

In addition, utilize method that the polyimide polymer that is used for the photoinduction LCD alignment according to the present embodiment prepares liquid crystal alignment layer and to utilize the polyamide polymer that is used for the photoinduction LCD alignment according to first embodiment to prepare the method for liquid crystal alignment layer basic identical.

Hereinafter, utilizing more specifically, embodiment describes second embodiment in more detail.Following examples are used for exemplary illustration the specific embodiment of the present invention, and it should not be regarded as restriction or retrain scope of the present invention.

Embodiment 2-1

Has the chromophoric polyimide polymer that is used for the photoinduction LCD alignment of laurate

(1) reformation three pyridine rings

27.1g 4 (2-tetrahydropyrans methoxyl group) bromobenzene is dissolved in the 250ml anhydrous tetrahydro furan in the three-necked flask that is filled with nitrogen, then, after the 3g magnesium of packing into, reacted 24 hours.When slowly dripping the 18.4g cyanuryl chloride that is dissolved in the 200ml anhydrous tetrahydro furan, this solution was reacted 12 hours in being full of the three-necked flask of nitrogen in-20 ℃.

After the reaction, reaction soln at room temperature reduced pressure removes tetrahydrofuran (THF), is dissolved in the ethyl acetate subsequently.Mixing this solution also with alkaline solution, high degree of agitation then at room temperature reduces pressure this solution and removes ethyl acetate with after the extracting impurities.

(2) hydroxy functional group is introduced three pyridine rings

The material that obtains among the 34.0g embodiment 2-1 (1) is added round-bottomed flask and subsequently it is dissolved in after the 300ml tetrahydrofuran (THF), with 0.3g pyridine-toluene-sulphonate is added in the flask and added 50ml ethanol sustained reaction 24 hours.

(3) synthetic three pyridine rings with laurate side chain

The 25.6g three pyridine derivatives that will derive from embodiment 2-1 (2) add in the round-bottomed flask be full of nitrogen and by adding the 200ml tetrahydrofuran (THF) it are dissolved subsequently.The 15.2g triethylamine is being added this solution and subsequently solution temperature is being reduced to after-5 ℃, this solution of high degree of agitation and with the cinnamyl chloride solution reaction that slowly splashes into 12 hours, wherein cinnamyl chloride solution obtains by the 100ml anhydrous tetrahydro furan being added dilute in the 25g cinnamyl chloride.

At last, in the mixed solvent of 1: 1 methyl chloride and normal butane after the recrystallization, the described solution of filtration under diminished pressure.Vacuum-drying gained solid phase material is to obtain having three pyridines of laurate side chain.

(4) synthetic three pyridine monomers with two amine functional groups

The 38.6g three pyridine derivatives that will obtain with the method for embodiment 2-1 (3) are packed at the bottom of the garden in the flask and are dissolved in the 400ml chloroform.32.8g 4-amino-phenol and 12g sodium hydroxide are dissolved in 300ml distilled water, dissolve the 3g palmityl trimethyl ammonium chloride therein, subsequently it is mixed with above-mentioned three pyridine derivative solutions and high degree of agitation and reaction 24 hours.After the reaction, separate the organic solution phase, and reacted solution moved into separating funnel and with distilled water wash three times with extracting impurities, remove with calcium chloride subsequently and anhydrate.This solution of underpressure distillation to be to remove the chloroform as organic solvent, subsequently recrystallization in the mixed solvent of methyl chloride and normal butane.

(5) be used for the polymerization of the polyimide polymer with laurate side chain of photoinduction LCD alignment

The 53.156g three pyridine monomers that will obtain by the method for embodiment 2-1 (4) are packed at the bottom of the garden that is full of nitrogen in the flask and are dissolved in the 400ml N-Methyl pyrrolidone.With 21.8g 1,2,4,5-pyromellitic acid acid anhydride is dissolved in the 100ml N-Methyl pyrrolidone, it is slowly splashed into to be dissolved with in the monomeric above-mentioned solution of three pyridines subsequently, with above-mentioned solution high degree of agitation and reacted 24 hours.

After the reaction, reaction soln is slowly poured in the methyl alcohol into precipitation, filtration and vacuum-drying throw out.Dissolving gained throw out also precipitates in methyl alcohol subsequently in N-Methyl pyrrolidone once more, said process repeats twice, vacuum-drying throw out subsequently is to obtain the having synthesis of polyimides polymkeric substance that be used for LCD alignment of laurate photoinduction functional group by means of three pyridine rings.

(6) make liquid crystal display

Gained light orientation agent is dissolved in the mixing solutions of NMP and butyl glycol, makes its density with 8 weight %, the filtering membrane through aperture 0.1 μ m filters to remove impurity particle subsequently.This solution is printed to thick about 300nm being coated with on the substrate of glass of transparency electrode, thereby is coated with lighting orientation agent, desolvate to remove about 1 hour of about 200 ℃ of down dry these substrate of glass subsequently.Subsequently, by with the ultraviolet ray of 500W mercury lamp with 20 ° at inclination angle, per 2 seconds～10 minutes once irradiatings to substrate of glass, and in described substrate, induce the photopolymerization or the photodegradative complex reaction of polymer chain of generation such as laurate group, make the liquid crystal alignment layer that contains polymkeric substance thus.The spacer that is of a size of 4-5 μ m is injected on two substrate of glass, subsequently substrate of glass is bonded into the unit interval with 4-5 μ m with epoxy adhesive.This unit under 130 ℃ through 1 hour process of setting, thereby make the epoxy adhesive sclerosis, make the wherein complete adherent of substrate of glass unit.Liquid crystal is packed in the unit of making, this unit experience once 100-130 ℃ down heating then be cooled to the heat treatment process of room temperature in 1 hour.Subsequently, finally obtain liquid crystal display.

Embodiment 2-2

A kind of have a chromophoric polyimide polymer that is used for the photoinduction LCD alignment of phenyl styryl ketone

(1) synthetic phenyl styryl ketone functional group

(2) phenyl styryl ketone is introduced three pyridine rings

The 23.8g 4-hydroxy-benzalacetophenone adding that will obtain by the method for embodiment 2-2 (1) is full of the round-bottomed flask of nitrogen and subsequently it is dissolved in the 240ml anhydrous tetrahydro furan.To also at room temperature react 6 hours in 2.4g sodium hydride (NaH) the adding solution.This solution is dissolved in the prepared solution of 200ml anhydrous tetrahydro furan in-5 ℃ of reactions 24 hours with passing through described in embodiment 2-1 (1) of slowly splashing into the 18.4g cyanuryl chloride under high degree of agitation.After the reaction, except that desolvating, once more residual solids is dissolved in chloroform subsequently by underpressure distillation.With this solution in separating funnel with distilled water wash three times with extracting impurities, remove with calcium chloride subsequently and anhydrate, this solution of underpressure distillation subsequently to be to remove chloroform, subsequently recrystallization in the mixed solvent of methyl chloride and normal hexane.This recrystallization material of filtration under diminished pressure and vacuum-drying is to obtain having three pyridine derivatives of phenyl styryl ketone functional group.

(3) synthetic three pyridine monomers with two amine functional groups

The three pyridine derivatives that the 38.6g that will obtain by the method for embodiment 2-2 (2) has a phenyl styryl ketone functional group are packed in the round-bottomed flask and are dissolved in the 400ml chloroform.32.8g 4-amino-phenol and 12g sodium hydroxide are dissolved in 300ml distilled water, dissolve the 3g palmityl trimethyl ammonium chloride therein, subsequently it is mixed with above-mentioned three pyridine derivative solutions and high degree of agitation and reaction 24 hours.After the reaction, separate the organic solution phase, and reacted solution moved into separating funnel and with distilled water wash three times with extracting impurities, remove with calcium chloride subsequently and anhydrate.This anhydrous solution of underpressure distillation to be to remove the chloroform as organic solvent, subsequently recrystallization in the mixed solvent of methyl chloride and normal butane.With precipitated crystal filtration under diminished pressure and vacuum-drying subsequently, obtain three pyridine monomers.

(4) be used for the polymerization with the chromophoric polyimide polymer of phenyl styryl ketone of photoinduction LCD alignment

The 53.15g three pyridine monomers that will obtain by the method for embodiment 2-2 (3) are packed at the bottom of the garden that is full of nitrogen in the flask and are dissolved in the 400ml N-Methyl pyrrolidone.With 21.8g 1,2,4,5-pyromellitic acid acid anhydride is dissolved in the 100ml N-Methyl pyrrolidone, it is slowly splashed into to be dissolved with in the monomeric above-mentioned solution of three pyridines subsequently, with above-mentioned solution high degree of agitation and reacted 24 hours.After the reaction, reaction soln is slowly poured in the methyl alcohol, thus precipitation, filtration and vacuum-drying throw out.Dissolving gained throw out also precipitates in methyl alcohol subsequently in N-Methyl pyrrolidone once more, said process repeats twice, vacuum-drying throw out subsequently is to obtain the having synthesis of polyimides polymkeric substance that be used for LCD alignment of phenyl styryl ketone functional group by means of three pyridine rings.

(5) make liquid crystal display

By the method for embodiment 2-1 (6), utilize the polyimide polymer that is used for the photoinduction LCD alignment that obtains by embodiment 2-2 (4) method to make liquid crystal display.

Embodiment 2-3

A kind of have a chromophoric polyimide polymer that is used for the photoinduction LCD alignment of tonka bean camphor

(1) introduces the tonka bean camphor chromophoric group

16.2g umbelliferone and 2.4g sodium hydride are packed at the bottom of the garden that is full of nitrogen in the flask, be dissolved in subsequently in the 160ml anhydrous tetrahydro furan.Afterwards, with this solution high degree of agitation and reacted 6 hours.With this solution high degree of agitation and with passing through described in embodiment 2-1 (1) of slowly splashing into the 18.4g cyanuryl chloride is dissolved in the prepared solution of 200ml anhydrous tetrahydro furan in-5 ℃ of reactions 24 hours.After the reaction, remove tetrahydrofuran (THF), once more residual solids is dissolved in chloroform subsequently by underpressure distillation.With this solution in separating funnel with distilled water wash three times with extracting impurities, remove with calcium chloride subsequently and anhydrate, this solution of underpressure distillation subsequently to be to remove chloroform, subsequently recrystallization in the mixed solvent of methyl chloride and normal hexane.This recrystallization material of filtration under diminished pressure and vacuum-drying obtains having three pyridine derivatives of tonka bean camphor functional group.

(2) synthetic three pyridine monomers with two amine functional groups

The three pyridine derivatives that the 31.1g that will obtain by the method for embodiment 2-3 (1) has a tonka bean camphor photoinduction functional group are packed in the round-bottomed flask and are dissolved in the 300ml chloroform.32.8g 4-amino-phenol and 12g sodium hydroxide are dissolved in 300ml distilled water, dissolve the 3g palmityl trimethyl ammonium chloride therein, subsequently it is mixed with above-mentioned three pyridine derivative solutions and intense reaction 24 hours.After the reaction, organic solution is separated and move into separating funnel with distilled water wash three times with extracting impurities.Subsequently, remove with calcium chloride and anhydrate.This anhydrous solution of underpressure distillation to be to remove the chloroform as organic solvent, subsequently recrystallization in the mixed solvent of methyl chloride and normal butane.With precipitated crystal filtration under diminished pressure and vacuum-drying subsequently, obtain three pyridine monomers.

(3) be used for the polymerization with the chromophoric polyimide polymer of tonka bean camphor of photoinduction LCD alignment

The 45.54g three pyridine monomers that will obtain by the method for embodiment 2-3 (2) are packed at the bottom of the garden that is full of nitrogen in the flask and are dissolved in 400ml 400ml N-Methyl pyrrolidone.With 21.8g 1,2,4,5-pyromellitic acid acid anhydride is dissolved in the 100ml N-Methyl pyrrolidone, it is slowly splashed into to be dissolved with in the monomeric above-mentioned solution of three pyridines subsequently, with above-mentioned solution high degree of agitation and reacted 24 hours.After the reaction, reaction soln is slowly poured in the methyl alcohol, thus precipitation, filtration and vacuum-drying throw out.Dissolving gained throw out also precipitates in methyl alcohol subsequently in N-Methyl pyrrolidone once more, said process repeats twice, vacuum-drying throw out subsequently is to obtain the having synthesis of polyimides polymkeric substance that be used for LCD alignment of tonka bean camphor functional group by means of three pyridine rings.

(4) make liquid crystal display

By the method for embodiment 2-1 (6), utilize the polyamide polymer that is used for the photoinduction LCD alignment that obtains by embodiment 2-3 (3) method to make liquid crystal display.

EXPERIMENTAL EXAMPLE: the characteristic of measuring liquid crystal display

Photoelectric characteristic, thermostability, optical stability, residual DC and the VHR characteristic of the liquid crystal display that the method for measurement by embodiment 2-1 to 2-3 makes, it the results are shown in the table 5,6,7 and 8.

Test 1: tilt angle is with heat treated variation

As shown in table 5 below, the polymkeric substance that is used for the photoinduction LCD alignment of individual embodiment has as the thermostability of the fundamental characteristics of the polyimide that uses traditionally, optical transparence and excellent coating performance.In addition, owing to have functional group, so the advantage of this polymkeric substance is to compare with traditional polyimide alignment agent, reduced the required rayed amount of orientation.Thereby, when utilization is made light orientation liquid crystal cells according to the polymkeric substance that is used for the photoinduction LCD alignment of present embodiment, can realize the multizone LCD alignment easily by simple procedure.In addition, because the very big improvement of orientation performance, for example even after needs pyritous sealing baking, still keep the tilt angle of liquid crystal, this unit need can be applicable to the liquid-crystal display at high definition and wide visual angle.

Table 5

		Embodiment 2-1	Embodiment 2-2	Embodiment 2-3
		Embodiment 2-1	Embodiment 2-2	Embodiment 2-3	Method		Rayed	Rayed	Rayed
Density		8 weight %	8 weight %	8 weight %	Method		Rayed	Rayed	Rayed
Density		8 weight %	8 weight %	8 weight %	Tilt angle	Room temperature	0-4°	0-4°	0-4°
After the thermal treatment	0-4°	0-3°	0-4°			Room temperature	0-4°	0-4°	0-4°
After the thermal treatment	0-4°	0-3°	0-4°	Contrast ratio		195	190	190

Annotate 1: adopt liquid crystal angle rotation mode to measure tilt angle.

Test 2: thermostability

The thermostability of following measurement liquid crystal cells.After the initial tilt angle of measuring liquid crystal cells, at room temperature measure tilt angle with the variation of liquid crystal cells 200 ℃ of following thermal aging time.When the thermostability of orientation is unstable, the tilt angle time to time change, when stablizing, tilt angle is almost constant.Test result is shown in following table 6.As seen from Table 6, have very excellent thermostability according to the light orientation agent of present embodiment, thereby even in thermal ageing process for a long time the orientation and the tilt angle of liquid crystal also keep stable, satisfy the fundamental property of liquid-crystal display thus.

Table 6

	Embodiment 2-1	Embodiment 2-2	Embodiment 2-3
	Embodiment 2-1	Embodiment 2-2	Embodiment 2-3	Tilt angle	～4°	～3°	～4°
The thermal ageing temperature	200℃	200℃	200℃	Tilt angle	～4°	～3°	～4°
The thermal ageing temperature	200℃	200℃	200℃	Thermal aging time	48 hours	48 hours	48 hours
Tilt angle changes	Do not have	Do not have	Do not have	Thermal aging time	48 hours	48 hours	48 hours

Test 3: optical stability

Make liquid crystal cells and measure its optical stability according to embodiment 2-1,2-2 and 2-3.In order to measure optical stability, on a unitary surface, utilize polarizer to check the change of the orientation characteristic of irradiating surface and non-irradiating surface by naked eyes subsequently the UV-light in the certain limit and radiation of visible light.Measuring result is shown in the following table 7.When unitary light stability was not enough, the light that exposes to liquid crystal cells caused the variation of LCD alignment characteristic on the irradiating surface.Thereby the LCD alignment characteristic on the irradiating surface is different from non-irradiating surface and noticeable change or destroyed, and it is indeterminate to make LCD alignment mix.Thus, this unit that demonstrates the orientation characteristic variations can not be used as display unit.

Table 7

		Embodiment 2-1	Embodiment 2-2	Embodiment 2-3
		Embodiment 2-1	Embodiment 2-2	Embodiment 2-3	The rayed amount	0.5J/cm ²	No change	No change	No change
1J/cm ²	No change	No change	No change			0.5J/cm ²	No change	No change	No change
1J/cm ²	No change	No change	No change	2J/cm ²		No change	No change	No change
The illumination firing angle	90°	No change	No change	2J/cm ²		No change	No change	No change	No change
	90°	No change	No change	80°	No change	No change	No change		No change
	70°	No change	No change	80°	No change	No change	No change	No change

Test 4: residual DC and voltage retention (VHR)

The volts DS of rangeability for-10V～10V put on the two ends of liquid crystal cells and measure its electrostatic capacitance.Owing to the lagged value of electrostatic capacitance obtains residual DC.Liquid crystal cells is the TN structure sample, and thick 4-6 μ m prepares according to the described manufacture method of the foregoing description 2-1 to 2-3.Two electrodes of prepared liquid crystal cells are connected to LCD survey meter (being Fluke 6306) and write down under the 1kHz its electrostatic capacitance with the variation of volts DS from 0V-10V and 0V--10V.Obtaining electrostatic capacitance lags behind with the variation of voltage and uses it for the measurement residual DC.In order to obtain voltage retention (VHR), use have ± 1V in the pulse in 64 μ s time length, 60Hz cycle, measure the conservation rate of the voltage that initially applies subsequently.The results are shown in following table 8.By table 8 as seen, measuring result shows for all three unit all have the low residue DC of 20 ℃ of following 10-13mV and the high conservation rate of 98-99%.This expression is satisfied the fundamental property that can be used as liquid crystal indicator according to the light orientation agent of embodiment 2-1 to 2-3.

Table 8

		Embodiment 2-1	Embodiment 2-2	Embodiment 2-3
		Embodiment 2-1	Embodiment 2-2	Embodiment 2-3	R-DC	20℃	8mV	10mV	10mV
60℃	25mV	30mV	32mV			20℃	8mV	10mV	10mV
60℃	25mV	30mV	32mV	VHR		20℃	99％	99％	98％
60℃	99％	98％	97％			20℃	99％	99％	98％

The 3rd embodiment

In the 3rd embodiment, the general formula of polymkeric substance is shown in Chemical formula 16.

Chemical formula 16

At this, in Chemical formula 16, m+n=1, and m and n are respectively the real number of 0-1.

In Chemical formula 16, R ₁With the R in first and second embodiments ₁Identical.

In Chemical formula 16, connect R ₂, R ₃And R ₄Key be to form by the amido linkage that obtains by amine and carboxylic acid reaction, it generally can be by 1 expression of following reaction formula:

Reaction formula 1

In Chemical formula 16, connect R ₂, R ₃And R ₅Key be to form by the imide bond that obtains by amine and carboxylic diacid anhydride reactant, they generally can be by 2 expressions of following reaction formula:

Reaction formula 2

Thereby, as the imide of the key of Chemical formula 16 and amido linkage be by respectively by the amine of above-mentioned reaction formula 1 and 2 representatives and arbitrarily the reaction between carboxylic acid and the carboxylic diacid acid anhydride obtain.

The R of above-mentioned Chemical formula 16 ₂And R ₃Based on the amine of reaction formula 1 and 2, described amine is selected from one of them of Chemical formula 14 respectively.

The R of above-mentioned Chemical formula 16 ₄Based on the carboxylic acid of reaction formula 1, this carboxylic acid is selected from one of them of Chemical formula 12.

The R of above-mentioned Chemical formula 16 ₅Based on the carboxylic diacid acid anhydride of reaction formula 2, this carboxylic diacid acid anhydride is selected from one of them of Chemical formula 15.

In addition, be selected from the contained R of Chemical formula 16 ₁, R ₂, R ₃, R ₄And R ₅Substituting group in the phenyl ring that contains not only can have above-mentioned aligning structure, can also have an ortho position or a bit architecture or be selected from the neighbour,, the mixed structure of at least two kinds of structures in the aligning structure.

According to this embodiment of the present invention, have at least one optical active group by poly-(amide-imide) multipolymers of above-mentioned Chemical formula 16 representatives, identical with the situation of first and second embodiments.In order to strengthen, to change or protecting the orientation that is produced, one of described optical active group can carry out photodegradation, and another group can carry out Fires to be reset, and other group can carry out light dimerization reaction, photoisomerization reaction or photo-crosslinking.

In addition, use polyamide ligand under the situation of agent and polyimide alignment agent, this poly-(amide-imide) multipolymer can be used as the isolating compatilizer of inhibitory phase together.

According to the present embodiment, comprise that the LCD alignment agent by the polymkeric substance of Chemical formula 16 representatives has and essentially identical performance of first embodiment and application.

In addition, utilize according to the present embodiment be used for the photoinduction LCD alignment poly-(amide-imide) copolymer liquid crystal alignment layer method with utilize the polyamide polymer that is used for the photoinduction LCD alignment according to first embodiment to prepare the method for liquid crystal alignment layer and to utilize the polyimide polymer that is used for the photoinduction LCD alignment according to second embodiment to prepare the method for liquid crystal alignment layer basic identical.

Hereinafter, utilizing more specifically, embodiment describes the 3rd embodiment in more detail.Following examples are used for exemplary illustration the specific embodiment of the present invention, and it should not be regarded as restriction or retrain scope of the present invention.

Embodiment 3-1

Has chromophoric poly-(amide-imide) multipolymer that is used for the photoinduction LCD alignment of laurate

(1) reformation three pyridine rings

(2) hydroxy functional group is introduced three pyridine rings

The material that obtains among the 34.0g embodiment 3-1 (1) is added round-bottomed flask and subsequently it is dissolved in after the 300ml tetrahydrofuran (THF), with 0.3g pyridine-toluene-sulphonate is added in the flask and added 50ml ethanol sustained reaction 24 hours.

(3) synthetic three pyridine rings with laurate side chain

The 25.6g three pyridine derivatives that will derive from embodiment 3-1 (2) add in the round-bottomed flask be full of nitrogen and by adding the 200ml tetrahydrofuran (THF) it are dissolved subsequently.The 15.2g triethylamine is being added this solution and subsequently solution temperature is being reduced to after-5 ℃, this solution of high degree of agitation and with the cinnamyl chloride solution reaction that slowly splashes into 12 hours, wherein cinnamyl chloride solution obtains by the 100ml anhydrous tetrahydro furan being added dilute in the 25g cinnamyl chloride.

(4) synthetic three pyridine monomers with two amine functional groups

The 38.6g three pyridine derivatives that will obtain with the method for embodiment 3-1 (3) are packed at the bottom of the garden in the flask and are dissolved in the 400ml chloroform.32.8g 4-amino-phenol and 12g sodium hydroxide are dissolved in 300ml distilled water, dissolve the 3g palmityl trimethyl ammonium chloride therein, subsequently it is mixed with above-mentioned three pyridine derivative solutions and high degree of agitation and reaction 24 hours.After the reaction, separate the organic solution phase, and reacted solution moved into separating funnel and with distilled water wash three times with extracting impurities, remove with calcium chloride subsequently and anhydrate.This solution of underpressure distillation to be to remove the chloroform as organic solvent, subsequently recrystallization in the mixed solvent of methyl chloride and normal butane.

(5) be used for the polymerization of poly-(amide-imide) multipolymer of photoinduction LCD alignment with laurate side chain

The 53.156g three pyridine monomers that will obtain by the method for embodiment 3-1 (4) are packed at the bottom of the garden that is full of nitrogen in the flask and are dissolved in the 400ml N-Methyl pyrrolidone.In this solution, add the 10.12g triethylamine.

The 10.15g p-phthaloyl chloride is dissolved in after the 100ml anhydrous tetrahydro furan, when it slowly being dropped to the solution that is dissolved with above-mentioned three pyridine monomers and triethylamine, with above-mentioned solution high degree of agitation and reacted 6 hours.After this, with 10.9g 1,2,4,5-pyromellitic acid acid anhydride is dissolved in the 100ml N-Methyl pyrrolidone, it slowly being splashed into above-mentioned solution simultaneously, reacts 6 hours subsequently again.

After the reaction, reaction soln is slowly poured in the methyl alcohol into precipitation, filtration and vacuum-drying throw out.Dissolving gained throw out also precipitates in methyl alcohol subsequently in N-Methyl pyrrolidone once more, said process repeats twice, the vacuum-drying throw out gathers (amide-imide) multipolymer to obtain having laurate photoinduction functional group by means of the synthesizing of LCD alignment that be used for of three pyridine rings subsequently.

(6) make liquid crystal display

Gained light orientation agent is dissolved in the mixing solutions of NMP and butyl glycol, and to have the density of 8 weight %, the filtering membrane through aperture 0.1 μ m filters to remove impurity particle subsequently.This solution is printed to thick about 300nm being coated with on the substrate of glass of transparency electrode, thereby is coated with lighting orientation agent, desolvate to remove about 1 hour of about 200 ℃ of down dry these substrate of glass subsequently.Subsequently, by with the ultraviolet ray of 500W mercury lamp with 20 ° at inclination angle, per 2 seconds～10 minutes once irradiatings to substrate of glass, and in described substrate, induce the photopolymerization or the photodegradative complex reaction of polymer chain of generation such as laurate group, make the liquid crystal alignment layer that contains polymkeric substance thus.The spacer that is of a size of 4-5 μ m is injected on two substrate of glass, subsequently substrate of glass is bonded into the unit interval with 4-5 μ m with epoxy adhesive.This unit under 130 ℃ through 1 hour process of setting, thereby make the epoxy adhesive sclerosis, make the wherein complete adherent of substrate of glass unit.Liquid crystal is packed in the unit of making, this unit experience once 100-130 ℃ down heating then be cooled to the heat treatment process of room temperature in 1 hour.Subsequently, finally obtain liquid crystal display.

Embodiment 3-2

A kind of have chromophoric poly-(amide-imide) multipolymer that is used for the photoinduction LCD alignment of phenyl styryl ketone

(1) synthetic phenyl styryl ketone chromophoric group

(2) phenyl styryl ketone functional group is introduced three pyridine rings

The 23.8g 4-hydroxy-benzalacetophenone adding that will obtain by the method for embodiment 3-2 (1) is full of the round-bottomed flask of nitrogen and subsequently it is dissolved in the 240ml anhydrous tetrahydro furan.To also at room temperature react 6 hours in 2.4g sodium hydride (NaH) the adding solution.This solution is dissolved in the prepared solution of 200ml anhydrous tetrahydro furan in-5 ℃ of reactions 24 hours with passing through described in embodiment 3-1 (1) of slowly splashing into the 18.4g cyanuryl chloride under high degree of agitation.After the reaction, except that desolvating, once more residual solids is dissolved in chloroform subsequently by underpressure distillation.With this solution in separating funnel with distilled water wash three times with extracting impurities, remove with calcium chloride subsequently and anhydrate, this solution of underpressure distillation subsequently to be to remove chloroform, subsequently recrystallization in the mixed solvent of methyl chloride and normal hexane.This recrystallization material of filtration under diminished pressure and vacuum-drying is to obtain having three pyridine derivatives of phenyl styryl ketone functional group.

(3) synthetic three pyridine monomers with two amine functional groups

The three pyridine derivatives that the 38.6g that will obtain by the method for embodiment 3-2 (2) has a phenyl styryl ketone functional group are packed in the round-bottomed flask and are dissolved in the 400ml chloroform.32.8g 4-amino-phenol and 12g sodium hydroxide are dissolved in 300ml distilled water, dissolve the 3g palmityl trimethyl ammonium chloride therein, subsequently it is mixed with above-mentioned three pyridine derivative solutions and high degree of agitation and reaction 24 hours.After the reaction, separate the organic solution phase, and reacted solution moved into separating funnel and with distilled water wash three times with extracting impurities, remove with calcium chloride subsequently and anhydrate.This anhydrous solution of underpressure distillation to be to remove the chloroform as organic solvent, subsequently recrystallization in the mixed solvent of methyl chloride and normal butane.With precipitated crystal filtration under diminished pressure and vacuum-drying subsequently, obtain three pyridine monomers.

(4) be used for the polymerization with chromophoric poly-(amide-imide) multipolymer of phenyl styryl ketone of photoinduction LCD alignment

The 53.15g three pyridine monomers that will obtain by the method for embodiment 3-2 (3) are packed at the bottom of the garden that is full of nitrogen in the flask and are dissolved in the 400ml anhydrous tetrahydro furan.In this solution, add the 10.12g triethylamine.The 10.15g p-phthaloyl chloride is dissolved in after the 100ml anhydrous tetrahydro furan, when it slowly being dropped to the solution that is dissolved with above-mentioned three pyridine monomers and triethylamine, with above-mentioned solution high degree of agitation and reacted 24 hours.After this, with 10.9g 1,2,4,5-pyromellitic acid acid anhydride is dissolved in the 100ml N-Methyl pyrrolidone, it slowly being splashed into above-mentioned solution simultaneously, reacts 6 hours subsequently again.After the reaction, reaction soln is slowly poured in the methyl alcohol, thus precipitation, filtration and vacuum-drying throw out.Dissolving gained throw out also precipitates in methyl alcohol subsequently in N-Methyl pyrrolidone once more, said process repeats twice, the vacuum-drying throw out gathers (amide-imide) multipolymer to obtain having phenyl styryl ketone functional group by means of the synthesizing of LCD alignment that be used for of three pyridine rings subsequently.

(5) make liquid crystal display

By the method for embodiment 3-1 (6), utilize poly-(amide-imide) multipolymer that is used for the photoinduction LCD alignment that obtains by embodiment 3-2 (4) method to make liquid crystal display.

Embodiment 3-3

A kind of have chromophoric poly-(amide-imide) multipolymer that is used for the photoinduction LCD alignment of tonka bean camphor

(1) introduces the tonka bean camphor chromophoric group

16.2g umbelliferone and 2.4g sodium hydride are packed at the bottom of the garden that is full of nitrogen in the flask, be dissolved in subsequently in the 160ml anhydrous tetrahydro furan.Afterwards, with this solution high degree of agitation and reacted 6 hours.With this solution high degree of agitation and with passing through described in embodiment 3-1 (1) of slowly splashing into the 18.4g cyanuryl chloride is dissolved in the prepared solution of 200ml anhydrous tetrahydro furan in-5 ℃ of reactions 24 hours.After the reaction, remove tetrahydrofuran (THF), once more residual solids is dissolved in chloroform subsequently by underpressure distillation.With this solution in separating funnel with distilled water wash three times with extracting impurities, remove with calcium chloride subsequently and anhydrate, this solution of underpressure distillation subsequently to be to remove chloroform, subsequently recrystallization in the mixed solvent of methyl chloride and normal hexane.Filtration under diminished pressure and vacuum-drying at the recrystallization material to have three pyridine derivatives of tonka bean camphor functional group.

(2) synthetic three pyridine monomers with two amine functional groups

The three pyridine derivatives that the 31.1g that will obtain by the method for embodiment 3-3 (1) has a tonka bean camphor photoinduction functional group are packed in the round-bottomed flask and are dissolved in the 300ml chloroform.32.8g 4-amino-phenol and 12g sodium hydroxide are dissolved in 300ml distilled water, dissolve the 3g palmityl trimethyl ammonium chloride therein, subsequently it is mixed with above-mentioned three pyridine derivative solutions and intense reaction 24 hours.After the reaction, organic solution is separated and move into separating funnel with distilled water wash three times with extracting impurities.Subsequently, remove with calcium chloride and anhydrate.This anhydrous solution of underpressure distillation to be to remove the chloroform as organic solvent, subsequently recrystallization in the mixed solvent of methyl chloride and normal butane.With precipitated crystal filtration under diminished pressure and vacuum-drying subsequently, obtain three pyridine monomers.

(3) be used for the polymerization with chromophoric poly-(amide-imide) multipolymer of tonka bean camphor of photoinduction LCD alignment

The 45.54g three pyridine monomers that will obtain by the method for embodiment 3-3 (2) are packed at the bottom of the garden that is full of nitrogen in the flask and are dissolved in the 400ml anhydrous tetrahydro furan.In this solution, add the 10.12g triethylamine.The 10.15g p-phthaloyl chloride is dissolved in after the 100ml anhydrous tetrahydro furan, when it slowly being dropped to the solution that is dissolved with above-mentioned three pyridine monomers and triethylamine, with above-mentioned solution high degree of agitation and reacted 24 hours.After this, with 10.9g 1,2,4,5-pyromellitic acid acid anhydride is dissolved in the 100ml N-Methyl pyrrolidone, it slowly being splashed into above-mentioned solution simultaneously, reacts 6 hours subsequently again.After the reaction, reaction soln is slowly poured in the methyl alcohol, thus precipitation, filtration and vacuum-drying throw out.Dissolving gained throw out also precipitates in methyl alcohol subsequently in N-Methyl pyrrolidone once more, said process repeats twice, the vacuum-drying throw out gathers (amide-imide) multipolymer to obtain having tonka bean camphor functional group by means of the synthesizing of LCD alignment that be used for of three pyridine rings subsequently.

(4) make liquid crystal display

By the method for embodiment 3-1 (6), utilize the polyamide polymer that is used for the photoinduction LCD alignment that obtains by embodiment 3-3 (3) method to make liquid crystal display.

EXPERIMENTAL EXAMPLE: the characteristic of measuring liquid crystal display

Photoelectric characteristic, thermostability, optical stability, residual DC and the VHR characteristic of the liquid crystal display that the method for measurement by embodiment 3-1 to 3-3 makes, it the results are shown in the table 9,10,11 and 12.

Test 1: tilt angle is with heat treated variation

As shown in table 9 below, the polymkeric substance that is used for the photoinduction LCD alignment of each embodiment has as the thermostability of the fundamental characteristics of the polyimide that uses traditionally, optical transparence and excellent coating performance.When having excellent properties again, with LCD alignment agent and polyimide copolymerization.In addition, owing to have functional group, so the advantage of this polymkeric substance is to compare with traditional polyimide alignment agent, reduced the required rayed amount of orientation.Thereby, when utilization is made light orientation liquid crystal cells according to the polymkeric substance that is used for the photoinduction LCD alignment of present embodiment, can realize the multizone LCD alignment easily by simple procedure.In addition, because the very big improvement of orientation performance, for example even after needs pyritous sealing baking, still keep the tilt angle of liquid crystal, this unit need can be applicable to the liquid-crystal display at high definition and wide visual angle.

Table 9

		Embodiment 3-1	Embodiment 3-2	Embodiment 3-3
		Embodiment 3-1	Embodiment 3-2	Embodiment 3-3	Method		Rayed	Rayed	Rayed
Density		8 weight %	8 weight %	8 weight %	Method		Rayed	Rayed	Rayed
Density		8 weight %	8 weight %	8 weight %	Tilt angle	Room temperature	0-3°	0-5°	0-6°
After the thermal treatment	0-3°	0-5°	0-6°			Room temperature	0-3°	0-5°	0-6°
After the thermal treatment	0-3°	0-5°	0-6°	Contrast ratio		196	194	193

Annotate 1: adopt liquid crystal angle rotation mode to measure tilt angle.

Test 2: thermostability

The thermostability of following measurement liquid crystal cells.After the initial tilt angle of measuring liquid crystal cells, at room temperature measure tilt angle with the variation of liquid crystal cells 200 ℃ of following thermal aging time.When the thermostability of orientation is unstable, the tilt angle time to time change, when stablizing, tilt angle is almost constant.Test result is shown in following table 10.As seen from Table 10, have very excellent thermostability according to the light orientation agent of present embodiment, thereby even in thermal ageing process for a long time the orientation and the tilt angle of liquid crystal also keep stable, satisfy the fundamental property of liquid-crystal display thus.

Table 10

	Embodiment 3-1	Embodiment 3-2	Embodiment 3-3
	Embodiment 3-1	Embodiment 3-2	Embodiment 3-3	Tilt angle	～3°	～5°	～6°
The thermal ageing temperature	150℃	150℃	150℃	Tilt angle	～3°	～5°	～6°
The thermal ageing temperature	150℃	150℃	150℃	Thermal aging time	48 hours	48 hours	48 hours
Tilt angle changes	Do not have	Do not have	Do not have	Thermal aging time	48 hours	48 hours	48 hours

Test 3: optical stability

Make liquid crystal cells and measure its optical stability according to embodiment 3-1,3-2 and 3-3.In order to measure optical stability, on a unitary surface, utilize polarizer to check the change of the orientation characteristic of irradiating surface and non-irradiating surface by naked eyes subsequently the UV-light in the certain limit and radiation of visible light.Measuring result is shown in the following table 11.When unitary light stability was not enough, the light that exposes to liquid crystal cells caused the variation of LCD alignment characteristic on the irradiating surface.Thereby the LCD alignment characteristic on the irradiating surface is different from non-irradiating surface and noticeable change or destroyed, and it is indeterminate to make LCD alignment mix.Thus, this unit that demonstrates the orientation characteristic variations can not be used as display unit.

Table 11

		Embodiment 3-1	Embodiment 3-2	Embodiment 3-3
		Embodiment 3-1	Embodiment 3-2	Embodiment 3-3	The rayed amount	0.5J/cm ²	No change	No change	No change
1J/cm ²	No change	No change	No change			0.5J/cm ²	No change	No change	No change
1J/cm ²	No change	No change	No change	2J/cm ²		No change	No change	No change
The illumination firing angle	90°	No change	No change	2J/cm ²		No change	No change	No change	No change
	90°	No change	No change	80°	No change	No change	No change		No change
	70°	No change	No change	80°	No change	No change	No change	No change

Test 4: residual DC and voltage retention (VHR)

The volts DS of rangeability for-10V～10V put on the two ends of liquid crystal cells and measure its electrostatic capacitance.Owing to the lagged value of electrostatic capacitance obtains residual DC.Liquid crystal cells is the TN structure sample, and thick 4-6 μ m prepares according to the described manufacture method of the foregoing description 3-1 to 3-3.Two electrodes of prepared liquid crystal cells are connected to LCD survey meter (being Fluke 6306) and write down under the 1kHz its electrostatic capacitance with the variation of volts DS from 0V-10V and 0V--10V.Obtaining electrostatic capacitance lags behind with the variation of voltage and uses it for the measurement residual DC.In order to obtain voltage retention (VHR), use have ± 1V in the pulse in 64 μ s time length, 60Hz cycle, measure the conservation rate of the voltage that initially applies subsequently.The results are shown in following table 12.By table 12 as seen, measuring result shows for all three unit all have the low residue DC of 20 ℃ of following 10-13mV and the high conservation rate of 98-99%.This expression is satisfied the fundamental property that can be used as liquid crystal indicator according to the light orientation agent of embodiment 3-1 to 3-3.

Table 12

		Embodiment 3-1	Embodiment 3-2	Embodiment 3-3
		Embodiment 3-1	Embodiment 3-2	Embodiment 3-3	R-DC	20℃	9mV	12mV	12mV
60℃	26mV	28mV	30mV			20℃	9mV	12mV	12mV
60℃	26mV	28mV	30mV	VHR		20℃	99％	99％	99％
60℃	99％	98％	97％			20℃	99％	99％	99％

Commercial viability

As mentioned above, the invention provides the polymeric amide that the photoinduction LCD alignment is used, polyimide and poly-(amide-imide) polymkeric substance and the both alignment layers of utilizing this polymkeric substance, wherein utilize three pyridine derivatives to introduce photoreactive groups such as the laurate that is used for photopolymerization and photolysis as main chain, tonka bean camphor, cinnamophenone and maleimide, the low temperature stability that weak physical bond power thereby the present invention can overcome between liquid crystal and both alignment layers is caused, weak orientation capability problems, and keep optical stability in the unit manufacturing processed again, the problems referred to above are present in employing hydrocarbon polymer such as traditional orientation agent of polyolefine as main chain.In addition, not only can have optical transparence and chemical resistance according to polymkeric substance of the present invention, also have excellent mechanical property and thermotolerance, this is that polymeric amide, polyimide and poly-(amide-imide) polymkeric substance are peculiar.Thereby the liquid crystal display device that adopts photoinduction LCD alignment according to the present invention to make with polymkeric substance can be realized high-quality display.

Those skilled in the art can easily change the present invention, should be appreciated that these variations and change are included in this

Within the scope of invention.

Claims

1. LCD alignment agent, it contains by three represented pyridine ring based polyalcohols of following Formula I:

Formula I

At this, m that represents in the Formula I and n are respectively 0～1 real number, and m+n=1,

Wherein, the R that represents in the Formula I ₁Be to select one from following Chemical formula 1 a to 4a:

The X that represents among the wherein above-mentioned Chemical formula 1 a selects one from the represented material of following chemical formula:

-((CH ₂) _nO) _m- -O((CH ₂) _nO) _m-

Respectively 0～10 integer at the represented m of this above-mentioned chemical formula and n;

Wherein the represented Y of Chemical formula 1 a selects one from the represented material of following chemical formula:

Wherein be selected from one of represented material of following chemical formula corresponding to the above-mentioned chemical formula of the material that is elected to be the represented Y of Chemical formula 1 a represented Y1, Y2, Y3, Y4, Y5, Y6, Y7, Y8 and Y9:

-A -(CA ₂) _nCA ₃ -O(CA ₂) _nCA ₃ -(O(CA ₂) _m) _nCA ₃ -O(CA ₂) _nOCA ₃ -(O(CA ₂) _m) _nOCA ₃

At this, m that above-mentioned chemical formula is represented and n are respectively 0 to 10 integer, and

At this, A that above-mentioned chemical formula is represented and B are selected from H, F, Cl, CN, CF respectively ₃Or CH ₃One of them;

Wherein, the represented n of above-mentioned Chemical formula 2 a and 3a is 0～10 integer, and a1, a2, a3, a4 and a5 are selected from one of material of following chemical formulation respectively:

The represented Y of wherein above-mentioned chemical formula 4a is selected from one of represented material of following chemical formula:

At this, the represented n of above-mentioned chemical formula is 0～10 integer;

B1 that wherein above-mentioned chemical formula 4a is represented and b2 are selected from one of represented material of following chemical formula respectively:

-A

At this, the represented A of above-mentioned chemical formula is selected from H, F, CH respectively ₃, CF ₃Or CN one of them;

Wherein, the represented R of Formula I ₂With R ₃Based on amine, described amine is selected from one of represented material of following chemical formula respectively:

-(CH ₂) _n-NH ₂ -O(CH ₂) _n-NH ₂

At this, m that above-mentioned chemical formula is represented and n are respectively 0～10 integers,

Wherein, the represented R of above-mentioned Formula I ₄With R ₅Respectively based on one of them of carboxylic acid derivative that is selected from the represented material of following chemical formula or carboxylic diacid acid anhydride,

At this, m that above-mentioned chemical formula is represented and n are respectively 0～10 integers.

Wherein, the represented connection R of Formula I ₂And R ₃Or R ₄And R ₅Key formed by the amido linkage that the reaction by amine and carboxylic acid obtains, it can be represented by following reaction formula I:

Reaction formula I

Wherein, the represented R of Formula I ₂And R ₃Based on the carboxylic acid among the reaction formula I, it is selected from one of represented material of following chemical formula:

Wherein, represented m of above-mentioned chemical formula and n are respectively 0～10 integers.

2. the LCD alignment agent described in the claim 1 or 2, the wherein contained R that is selected from the Formula I ₁, R ₂, R ₃, R ₄And R ₅Substituting group in contained phenyl ring have the aligning structure of being selected from, ortho position structure, a bit architecture or contain a kind of single structure of the mixed structure of two kinds of said structures at least.

3. liquid crystal alignment layer that contains polymkeric substance, thus described liquid crystal alignment layer be by the photoinduction LCD alignment agent that claim 1 limited is coated on form in the substrate both alignment layers and subsequently thereon irradiation ultraviolet radiation prepare.

4. liquid crystal cell, it has directivity by the liquid crystal alignment layer that coating contains polymkeric substance, thus described liquid crystal alignment layer be by the photoinduction LCD alignment agent that claim 1 limited is coated in the substrate form both alignment layers and subsequently thereon irradiation ultraviolet radiation prepare.

5. liquid crystal cell as claimed in claim 4, wherein this liquid crystal cell is used as one of them of liquid-crystal display, loop expansion pipe and optical element.

6. liquid crystal cell as claimed in claim 5, wherein this liquid-crystal display has drive pattern, and this drive pattern is selected from STN Super TN type STN, stable twisted nematic TN, plane conversion type IPS, vertical orientation type VA and vertical orientation stable twisted nematic VATN.

7. method for preparing the liquid crystal alignment layer that contains polymkeric substance, this method may further comprise the steps:

By in organic solvent, dissolve 1～20 weight % by the LCD alignment agent that claim 1 limited, make its viscosity with 1～100cps, the described LCD alignment agent of coating in substrate subsequently, coating thickness is 10～500nm, thereby forms both alignment layers; With

Tilt or the vertical irradiation ultraviolet ray at alignment layer surface, described ultraviolet ray is by the polarizer polarization or do not use polarizer and polarization not.

8. the method for preparing liquid crystal alignment layer as claimed in claim 7, wherein said organic solvent is selected from chlorobenzene, N-Methyl pyrrolidone, N-ethyl pyrrolidone, N, N-methylimidazole alkane ketone, N, N-dipropyl imidazolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), cyclopentanone, pimelinketone, ethylene dichloride, butyl glycol, gamma-butyrolactone and tetrahydrofuran (THF), or the mixture of above material.