CN100334086C - Lyotropic liquid crystal systems based on perylenetetracarboxylic acid dibenzimidazole sulfoderivatives - Google Patents

Abstract

Sulfoderivatives of perylenetetracarboxylic acid dibenzimidazole are provided. These compounds form liquid crystal systems possessing high quality optical properties. The resulting liquid crystal systems are readily applicable onto a substrate to obtain optically isotropic or anisotropic, at least partially crystalline films applicable in various fields.

Description

Lytropic liquid crystals system based on Huangization perylene tetracarboxylic acid bisbenzimidazole

Related application

The application requires to submit on April 25th, 2003, sequence number is 60/465,657 U.S. Provisional Application No., and submit on November 14th, 2003, sequence number is 10/714, the right of priority of U.S.'s application for a patent for invention of 057, the disclosure of described application mode is by reference included in this specification sheets in full.

Technical field

The present invention relates in general to organic chemistry filed and optical anisotropy coatings art.More particularly, the present invention relates to based on the lytropic liquid crystals system of heterocycle sulfonic derivatives compound (sulfoderivativecompound) and preparation method based on the optical anisotropy coating of these compounds.

Background technology

Optical element more and more depends on has type material specific, accurate controllability.Particularly, a kind of essential element is can be with the combine optimization of optical signature with further feature in the modern visual display system, with a kind of optical anisotropic film of the requirement that adapts to a certain concrete equipment.

The multiple polymers material has been used to prepare optical anisotropic film.Film based on this material can obtain anisotropic optical property by uniaxial extension and with organic pigment (organic dye) or iodine modification.In many application, stock polymer is polyvinyl alcohol (PVA).This film is specified in monograph Liquid Crystals:Applications and Uses, B.Bahadur (editor), and World Scientific, Singapore-New York (1990), the 1st volume is in the 101st page.Yet, limited its application usually based on the low thermal stability of PVA film.Therefore, development of new material and synthetic method with the optical anisotropic film that improves characteristic are very useful.Particularly, higher thermotolerance, easier synthetic and more excellent one-tenth film are in demand.Organic dichroic dye is obtained unusual effect in preparation has the optical anisotropic film of the optical characteristics of improvement and performance characteristics.Can be by one deck liquid crystal (LC) aqueous dye solutions being coated stromal surface, then solvent (for example water) evaporation is obtained based on the film of this compound, described aqueous dye solutions comprises the supramolecule of being made up of dye molecule.The LC film that obtains obtains anisotropy by the following method: lower floor's stromal surface is carried out preliminary mechanical ordering, as United States Patent (USP) 2,553,961 is described, or apply exterior mechanical, electromagnetism or other dipole-dipole force to the LC of stromal surface coating subsequently, openly apply for as described in the WO 94/28073 as PCT.

In past 10 years, increasingly extensive for the research that above-mentioned LC dyestuff is used and the related system performance is carried out.Industrial application on liquid-crystal display (LCD) and the liquid-crystalline glasses window (glazing) has greatly excited recent research to these phenomenons.The dyestuff supramolecule can form lytropic liquid crystals (LLC) phase.This mutually in, dye molecule is piled into the super molecular complex of the big bodily form such as column, becomes the basic structural unit of intermediate phase.The high order of dye molecule makes that this intermediate phase can be in order to obtain oriented film with strong dichroism feature in the post.

The dye molecule that forms supramolecule LC intermediate phase generally includes and makes dyestuff have water miscible peripheral group (peripheral group).The organic pigment intermediate phase is characterised in that specific structure, phasor, optical property and solvability, as the Chromonics of J.Lydon in Handbook of LiquidCrystals (Wiley-VCH, Weinheim, 1998), the 2B volume is described in the 981st to 1007 page.

Utilization can form the dichroic dye of LLC system, can obtain to have highly optically anisotropic film.This film demonstrates the performance of the E type polarizer relevant with the optical absorption characteristics of super molecular complex, and is equivalent to polarizer (retarder) (phase shifter (phase-shifting device)) at the inapparent spectral region of absorption.The phase retardation performance of this anisotropic films is relevant with its birefringence (double refraction), that is, and and LLC solution coat different on the specific refractory power that records on the matrix direction and vertical direction.The film that is formed by the LLC system based on strong (fast light) dye molecule is characterised in that its high thermal stability and high-light-fastness.

The feasible concern for such material of the above-mentioned performance of LLC system increases day by day.Developed the method for preparation based on the film of this organic pigment.Recent improvement relates to the optimization of film coated condition and the evaluation (identification) of novel LLC system.Particularly, by properties-correcting agent, stablizer, tensio-active agent and other additive are introduced known dye to improve the characteristic of film, can obtain to be used for the novel LLC composition of optical anisotropic film synthetic, for example disclosed PCT application WO 94/28073 is described.

In recent years, for the demand sustainable growth with high optically anisotropic film, described film also has this characteristic of selectivity of improvement in different wavelength range.The special film of the film that the needs different positions that is that maximum absorption appears at infrared (IR) to the wide spectral range of ultraviolet (UV).Develop a big class and can form the compound that LLC reaches the film with desired properties mutually.Yet, knownly form solubilized stable to cause the quantity of dyestuff of intermediate phase still less relatively.

Bao Kuo perylene tetracarboxylic acid (PTCA) bisbenzimidazole (DBI) is at the disulfo derivative of interior multiple organic pigment, is important can form the water-soluble dichroic dye of stablizing the LLC phase.The PTCA DBI kind that can be used for preparing optical anisotropic film openly applies for describing to some extent among the WO94/28073 at PCT.Generally speaking, PTCA bisbenzimidazole and imide are characterised in that chemistry, thermodynamics and the photochemical stability of its excellence.These performances make such material cause more concern aspect the possible material of the optical anisotropic film that obtains to be used for LCD and other optical device.

The solvability of these dyestuffs in water and in some organic solvent is relatively poor usually, uses widely thereby hindered it.Be the solvability of Bao Zheng perylene dyestuff in organic solvent, suggestion is introduced multiple substituting group in the starting molecule.This substituent example comprises as R.A.Cormier and B.A.Gregg, Phys.Chem.101 (51), the the 11004th to 11006 page of (1997) described oxyethyl group, and as H.Quante H.Y.Geerts and K.Mullen, Chem.Mater.6 (2), the 495th to 500 page of (1997) described phenoxy group.The solvability of Gai Shan perylene dyestuff also can be utilized as I.K.Iverson, S.M.Casey, and W.Seo and S.-W.Tam-Chang, Langmuir18 (9), the 3510th to 5316 page of (2002) described amino, and openly apply for WO 94/28073 described sulfo group as PCT.At present, best effect obtains by utilizing the sulfo group substituted radical, and such substituting group guarantees sufficient solubleness of perylene dyestuff and stable LLC formation mutually.

The standard method of synthetic disulfo derivative is as follows.The PTCA DBI and the oleum of manipulated variable are added in the volume chlorsulfonic acid.During reaction terminating, mixture variable color and dilute with water.With sedimentation and filtration, with salt acid elution and dry.With the water-soluble and purifying of water-soluble dibenzo Mi Zuo perylene tetracarboxylic disulfonic acid that obtains.The analysis of system structure shows that from a certain dye strength, the molten intermediate phase that causes of stable hexagon forms in given temperature range.Thereby, in enough narrow dye strength and temperature range, observe nematic phase.Determined that isotropic phase exists border and two-phase zone of transition in this system.

The multiple dye composite (also being called as " printing ink " (ink)) that is used to prepare based on the polarizer films of PTCA DBI sulfonic derivatives has obtained patent.An example of existing dyestuff has structural formula:

Wherein

Or

R is H, alkyl, halogen or alkoxyl group; Ar is for replacing or unsubstituted aryl.As U.S. Pat 5,739,296 is described, and this compound selectivity in about SPECTRAL REGION of 550 to 600nm absorbs.

Another kind of existing dye composite is based on the PTCA DBI of following formula

Wherein, R ₁Be H, 3 (4)-CH ₃, 3 (4)-C ₂H ₅, 3 (4)-Cl or 3 (4)-Br, and R ₂Be 4 (5)-SO ₃H.Of Russ P SU 1,598,430, this compound selectivity in about 550 to 600nm zones absorbs.

PCT openly applies for having narrated among the WO 94/28073 the LC blend (blend) of PTCA DBI sulfonic derivatives and multiple property-modifying additive, and wherein, introducing multiple property-modifying additive is in order to improve the characteristic of anisotropic films.A kind of this compound has following general formula:

Wherein

Or

And R is H, Br, Cl, OH, alkyl or alkoxyl group.

Narrated before this and had multiple substituent indanthrone disulfo derivative and have multiple organic cations composition.Use in the LLC system of interior multiple organic pigment sulfonic derivatives and the anisotropic films that obtains, also has the feature of performance and configuration aspects based on Bao Kuo perylene dyestuff.Particularly, I.K.Iverson, S.M.Casey, W.Seo and S.-W.Tam-Chang are at Controlling Molecular Orientation in Solid-Crystalline Phase, Langmuir18 (9) has studied the performance of the film that Shi Yong perylene dye-based LLC system obtains in the 3510th to 3516 page (2002).It is reported that all films that are studied all have the height optical anisotropy.

T.Fiske, L.Ignatov, P.Lazarev, V.Nazarov, M.PaukshtoMolecular Alignment in Crystal Polarizers and Retarders, Society for Information Display, Int.Symp.Digest of TechnicalPapers (Boston, MA, 19-24 day in May, 2002), reported the performance of using the anisotropic films that the LLC system based on the organic pigment sulfonic derivatives obtained according to recommend method in the 566th to 569 page.These films are verified to have partial crystallization structure at least.Optical anisotropic film can form on glass, plastics or other substrate material.Be used to form the blend of the violet dyestuff (Violet dye) of these optical anisotropic films for a kind of cis and trans-isomer(ide), as V.Nazarov, L.Ignatov, K.Kienskaya, ElectronicSpectra of Aqueous Solutions and Films Made of Liquid CrystalInk for Thin Film Polarizers, Mol.Mater.14 (2), the 153rd to 163 page (2001) are described.Because these films show high-quality optical characteristics, and dichroic ratio is near about 25 to 30, so can be used as polarizer, as Y.Bobrov, L.Blinov, L.Ignatov, G.King, V.Lazarev, Y.-D.Ma, V.Nazarov, E.Neburchilova, N.Ovchinnikova, S.Remizov, Environmental andOptical Testing of Optiva Thin Crystal FilmTM Polarizers, Proceedings of the 10 ^ThSID Symposium " Advanced displaytechnologies ", (Minsk, The Republic of BELARUS, 18-21 day in September, 2001), the 23rd to 30 page is described.PCT openly applies for having narrated among the WO 02/063,660 this film of preparation, comprises the method for the film with high-crystallinity.Therefore aforementioned PTCA DBI sulfonic derivatives can form the LLC phase.The anisotropic films of using this LLC system to obtain has excellent optical, also shows superperformance as polarizer.

One of shortcoming of aforementioned water-soluble PTC A DBI sulfonic derivatives is to be difficult to obtain to have reproducibility between for example criticizing and criticizing and on a collection of different substrates, and the relevant anisotropic films that has homogeneity on stromal surface.Existing film coated technical requirements is accurately selected to follow such as processing parameter such as concentration, temperature and strictness.Yet even become the full terms of film all accurately to satisfy, the random localized variation of coating area (regime) still may take place.This and LLC system are coated after the stromal surface, cause that by non-homogeneous microcosmic and macroscopical crystallisation process certain possibility that forms of misorientation (misorientation) district and microdefect is relevant during removal of solvents.In addition, be characterised in that based on the LLC system that has dyestuff now the possibility in uneven thickness of the coating that is coated with is higher, this also can reduce the reproducibility of thin film parameter.

Aforesaid drawbacks makes the formation of the film with useful optical characteristics complicated, makes the reproducibility deficiency of technology, and is requiring accurately to select most of technical parameter and strictness to follow from being applied to each stage of exsiccant.Therefore, need exploitation to avoid the compound and the film coated method of these defectives.

Summary of the invention

The invention provides the sulfonic derivatives of the PTCA DBI compound of no aforementioned shortcoming.The compound that is provided can easily and can repeatedly be coated on the multiple substrate material with membrane structure.Can improve solvability by replacing, described replacement generally is a desired location of some substituting group being introduced PTCA DBI sulfonic derivatives molecule along the molecule periphery.These substituting groups have improved the homogeneity of crystallization and drying process, thereby have improved the productive rate of the film with reproducibility feature.

In one embodiment of the invention, provide a kind of sulfonic derivatives compound.The structural formula of this sulfonic derivatives compound is to have a kind of Huangization perylene tetracarboxylic acid bisbenzimidazole (PTCA DBI) that is selected from one of following structural formula:

X wherein ₁, X ₂, X ₃, X ₄, X ₅, X ₆, X ₇And X ₈For independently be selected from-H ,-OH and-SO ₃The peripheral substituting group of H need make at least one peripheral substituting group not be H; M is one or more counter ion (counter ion), and j is the counter ion number that links to each other with a molecule; Z ₁And Z ₂For independently be selected from-O-,-SO ₂-,-SO ₂The bridging substituting group (bridgingsubstituent) of-O-; A ₁And A ₂For having the fragment of following structural formula

Y be one or morely independently be selected from-H ,-Cl ,-F ,-Br ,-OH ,-NO ₂And-NH ₂The fragment substituting group; N is selected from 0,1 and 2 integer; P is selected from 0,1,2,3 and 4 integer.

In other optional embodiment, the invention provides the lytropic liquid crystals system and the anisotropic films that comprise one or more these compounds.

Description of drawings

By reading summary of the invention and claims, and with reference to the following drawings, other goal of the invention of the present invention and advantage will be apparent:

Accompanying drawing 1 is mechanism figure, Shuos the possible sulfonated products of Ming perylene tetracarboxylic acid bisbenzimidazole.

Accompanying drawing 2 is mechanism figure, and reverse synthetic (countersynthesis) of two sulfones is described.

Accompanying drawing 3 is mechanism figure, and the reverse synthetic of disultone is described.

Embodiment

The present invention is the water-soluble sulfonic derivatives of Ti Gong perylene tetracarboxylic acid bisbenzimidazole (PTCA DBI) generally, and preparation is based on the anisotropic films of these compounds and the method for optical element.The present invention also provides the synthetic method that can form the sulfonation PTCA DBI derivative of stablizing the LLC intermediate phase.In addition, also provide the method for preparation based on the anisotropic films of the partial crystallization at least of these compounds.These films have the optical property and the performance characteristics of special needs.

Described and other advantage of the present invention can be obtained by the sulfonic derivatives of the perylene tetracarboxylic acid bisbenzimidazole with one of following structural formula (PTCA DBI):

X wherein ₁, X ₂, X ₃, X ₄, X ₅, X ₆, X ₇And X ₈For be selected from-H ,-OH and-SO ₃The peripheral substituting group of H need make at least one be different from H by the periphery substituting group; M is one or more counter ion, and j is the counter ion number that links to each other with this dye molecule.Belong to a plurality of molecules as one or more these counter ion, then counter ion are counted j and be can be decimal.In structural formula I-III, A ₁And A ₂For having the fragment of following structural formula:

At A ₁And A ₂In the fragment, Y is for being selected from H, Cl, F, Br, alkyl, OH, alkoxyl group, NO ₂And NH ₂Substituting group; P is selected from 0,1,2,3 and 4 integer; N is selected from 0,1 and 2 integer.Advantageously select the n value so that A ₁Or A ₂In the fragment at least one comprises at least one sulfo group.When the n value greater than 1 the time, for each SO ₃ ^-Functional group, a plurality of counter ion M can be different.In III, one or more these counter ion M can comprise, for example one or more H that are selected from structural formula I ⁺, NH ₄ ⁺, K ⁺, Li ⁺, Na ⁺, Cs ⁺, Ca ⁺⁺, Sr ⁺⁺, Mg ⁺⁺, Ba ⁺⁺, Co ⁺⁺, Mn ⁺⁺, Zn ⁺⁺, Cu ⁺⁺, Pb ⁺⁺, Fe ⁺⁺, Ni ⁺⁺, Al ⁺⁺⁺, Ce ⁺⁺⁺, La ⁺⁺⁺Deng positively charged ion and these cationic combinations.

Shown in structural formula II and III, the substituent X among the structural formula I ₂And X ₃And/or X ₆And X ₇Can be respectively by bridged group Z ₁And/or Z ₂Replace.In these structural formulas, Z ₁And Z ₂Independently be selected from-O-,-SO ₂-and-SO ₂-O-.In an alternative embodiment of the present invention, substituent X ₂And X ₃And/or X ₆And X ₇Can interact and form bridging (bridge) Z ₁And/or Z ₂, sealing constitutes other heterocyclic system, for example furans, sulfone and sultone.

The present invention also provides other novel cpd, and described compound absorbs also at visible region can form stability-enhanced stable LLC phase.These stable LLC can be used for forming the anisotropic films of the partial crystallization at least that reproducibility height and optical characteristics optimize mutually.There are not many shortcomings of above-mentioned existing film in film of the present invention.

Another embodiment of the invention provides new organic compound, and its LLC has advantages of higher stability in wide concentration, temperature and pH value scope.These compounds have been simplified the made membrane method, allow to use multiple commercially available equipment to be coated with coating, and help to have the manufacturing of the film of high reproducibility parameter.

The perylene tetracarboxylic acid benzoglyoxaline of the present invention of favourable structural formula I, II or III can be by method known to those skilled in the art synthetic cis or trans-isomer(ide).Particularly, PCTA DBI sulfonic derivatives of the present invention can obtain by sulfonation PCTA DBI under different condition, as shown in Figure 1.On the basis of understanding organic synthesis technology and instruction provided by the invention, those skilled in the art can easily synthesize these compounds.

In addition, by with the O-Phenylene Diamine condensation after sulfonation, or by with the condensation of sulfonation O-Phenylene Diamine, also can obtain sulfonic derivatives of the present invention from corresponding PTCA derivative.Fig. 2 and Fig. 3 schematically show the synthesis path that generates PTCA DBI sulfonic derivatives two sulfones and disultone from the PTCA derivative of known structure.

Perhaps, simplification compound of the present invention can obtain by the mixture of these compounds of fractionation.Otherwise the mixture of sulfonic derivatives can obtain by the isomerization of pure compound.

Structural formula I De perylene tetracarboxylic acid benzoglyoxaline sulfonic derivatives is easy to synthesize under some preselected conditions.Determine reactant initial concentration and synthetic technology condition, can obtain target compound.Most important parameter is initial action substrate concentration, temperature and reaction times.These parameters have determined the ratio of various PTCA DBI sulfonic derivativess of synthetic result, product yield, reactant (reaction mass) Chinese style I to III and the ratio of their isomer.

Another embodiment of the invention provides organic compound, and its solution is characterised in that to have the hydrophilic-hydrophobic balance of the best for the formation of LLC system.This balance affects the size and the shape of the super molecular complex that forms in this system valuably, and the degree of order of molecule in these title complexs.These performances have improved the required solubleness of The compounds of this invention, have also improved the stability based on the LLC phase of these compounds.Thereby the reproducibility that has improved thin film parameter has thus also greatly been simplified the manufacture method of film.In each manufacturing stage, select and the requirement of keeping the best-of-breed technology condition becomes so strict.In addition, the optical characteristics of the film that is obtained also is improved.The planar molecule of PTCA DBI sulfonic derivatives orientation for stromal surface is more consistent, and this makes the moment of dipole (be usually located at planes of molecules in) of transition of electron better along the determined direction proper alignment of outside orientation factor (alined).

Use disclosed water-soluble cpds, promptly sulfonation PCTA DBI derivative can solve above-mentioned task, and described derivative is a new compound not on the books in the literature.The optical anisotropic film that compound with these structures is easy to form the lytropic liquid crystals system and has desired properties.

The sulfonated derivative of perylene tetracarboxylic acid bisbenzimidazole can advantageously comprise at least a in the structural formula more specifically shown below.These exemplary molecular structures limit the scope of the invention never by any way, each structure all belongs to a kind of in the aforesaid compound kind, particularly, the furan derivatives that belongs to sulfonic derivatives, hydroxyl-sulfo group compound, sulfone, sultone, two sulfones, disultone, sulfone-sultone and the PTCA DBI of oxy-compound.

In above-mentioned structural formula I, II and III, M is counter ion, and j is the counter ion number in this dye molecule.Belong to a plurality of molecules as these counter ion, then counter ion are counted j and be can be decimal.Similarly, as described above, A ₁And A ₂For having the fragment of following structural formula:

Wherein Y for be selected from-H ,-Cl ,-F ,-Br ,-alkyl ,-OH ,-alkoxyl group ,-NO ₂And-NH ₂Substituting group; P is selected from 0,1,2,3 and 4 integer; N is selected from 0,1 and 2 integer.Advantageously select the n value so that A ₁Or A ₂In the fragment at least one comprises at least one sulfo group.When the n value greater than 1 the time, for each SO ₃ ^-Functional group, a plurality of counter ion M can be different.

Generally speaking, the compound of formula I, II and III both may be separately formed stablizes the LLC phase, also can mix back formation with following substances and stablize LLC mutually, described material comprises other material that this is organized other compound, can form other dichroic dye of LLC phase and not have absorption (colourless) or faint absorption is arranged and can form the LLC phase usually in visible-range.After removing solvent, this LLC forms the anisotropic films of the high partial crystallization at least of optical characteristics reproducibility mutually.Common unsettled U.S. Patent application 6,563, among 640 (the application attorney docket A-72221/AJT/MDV), be described in detail and formed method and the system of stablizing the LLC phase, and the optical anisotropic film of the partial crystallization at least that makes thus, the disclosure of described patent application is included in this specification sheets by reference.

Aqueous solution Zhong De perylene tetracarboxylic acid bisbenzimidazole sulfonic derivatives shows maximum light absorption usually in about range of wavelengths of 550 to 700nm.Compare with unsubstituted molecule,, significantly do not change absorption band such as substituent introducings such as Cl, F, Br, alkyl and alkoxyl groups.Yet the introducing of amino and hydroxyl makes absorption band broaden usually, and changes the feature of absorption spectrum.By changing quantity and the substituent quantity and the characteristic of sulfo group in the PTCA DBI derivative, the hydrophilic-hydrophobic balance of the molecule aggregates that forms in the may command LLC solution, and can change the viscosity of solution.

In another embodiment of the invention, provide a kind of preparation method who can be used as the anisotropic films of polarization film.De perylene tetracarboxylic acid benzoglyoxaline sulfonic derivatives of the present invention can form stable lytropic liquid crystals system.On the basis of the instruction that this specification sheets provided, those skilled in the art can prepare the liquid crystal solution (system) of Dan Yi perylene tetracarboxylic acid benzoglyoxaline sulfonic derivatives of structural formula I, II or III and the mixture of this compound.

The liquid crystal solution (system) of the Dan Yi perylene tetracarboxylic acid benzoglyoxaline sulfonic derivatives of structural formula I, II and III and the mixture of this compound, can be by currently known methods, for example the PCT method described in WO 94/28073 and the WO 00/25155 of openly applying for is coated stromal surface and orientation, and the content of described open text is included in this specification sheets by reference.Required orientation can be passed through, and for example, the mode that applies shear-stress or gravity field, electromagnetic field provides.For improving the rheological property of matrix wettability and optimization liquid crystal system, can pass through, for example, add water-soluble plasticized polymer and/or negatively charged ion or nonionic surface active agent solution is carried out modification.This system can further comprise one or more water-soluble low molecular weight additives.Advantageously select whole additives, not destroy the arrangement performance of liquid crystal system.Subsequently solvent is removed from the film that has been orientated, thus the polycrystalline optical anisotropic film of formation thickness 0.2 to 1.2 μ m.

Compare with the film that is obtained by disulfo PTCA DBI, the feature of film of the present invention is usually: for batch with batch between, reach between same batch the different films on the surface with a slice film, the reproducibility of its parameter improves about 10%.

Therefore, the PTCA DBI sulfonic derivatives of structural formula I of the present invention, II or III can form the lytropic liquid crystals phase, and can be used for obtaining the anisotropic films of high optical reproduction.These compounds also can be used for obtaining the isotropy film.The lytropic liquid crystals system can be coated on the matrix, so that it avoids any outside orientation effect.Can reach this purpose by method coating of liquid crystalline system such as spraying, offset printing and silk screen printing.After removing solvent, the polycrystal film that matrix is promptly had optical anisotropy domain structure (domain structure) covers.

Perylene tetracarboxylic acid benzoglyoxaline sulfonic derivatives can be formed up to small part crystalline film and/or polarization film and/or birefringent film.Zhe Xie perylene tetracarboxylic acid benzoglyoxaline sulfonic derivatives can be used for making in optical isotropy or anisotropic polarization film and/or phase retardation film and/or the birefringent film.The material of optical isotropy or anisotropic films can comprise at least two kinds of compounds that are selected from general formula I, II and III.Perhaps, this film can comprise at least two kinds of concrete compounds with at least a structure among formula I, II and the III, and included X ₁To X ₈Substituting group has two differences at least.

The present invention also comprises the aqueous fluid crystal system that can be described as " aqueous ink composition ", this liquid crystal system comprise structural formula I, II or III the simplification compound of the public perylene tetracarboxylic acid benzoglyoxaline sulfonic derivatives of opening, or the mixture of at least two kinds of these compounds.

Liquid crystal system of the present invention is usually based on the mixture of water or water and organic solvent, described organic solvent or can arbitrary proportion and water miscible, perhaps limit compatibility (limited miscibility) feature is arranged with glassware for drinking water.

In the liquid crystal system of the present invention, the concentration of perylene tetracarboxylic acid benzoglyoxaline sulfonic derivatives or its mixture is usually in the scope of about 3 quality % to 40 quality %.Advantageously, this concentration is in the scope of about 7 quality % to 20 quality %.This liquid crystal system can further comprise tensio-active agent and/or the softening agent that is up to 5 quality %.

In the liquid crystal system of the present invention, the concentration of a single perylene tetracarboxylic acid benzoglyoxaline sulfonic derivatives can be according to the required performance variation of film, and is as described below.In one embodiment, the concentration of compound of Formula I is in the scope of about 0 quality % to 99 quality %.Perhaps, these compound concentrations are in the scope of about 0 quality % to 50 quality %.The compound concentrations of general formula I I is in the scope of about 0 quality % to 99 quality %.Perhaps, these compound concentrations are in the scope of about 0 quality % to 70 quality %.The compound concentrations of general formula III is in the scope of about 0 quality % to 50 quality %.Perhaps, these compound concentrations are in the scope of about 0 quality % to 20 quality %.Liquid crystal system of the present invention also can comprise at least a water-soluble organic pigment or the colourless organic compound that lytropic liquid crystals forms mutually that participate in.

This liquid crystal system also can further comprise the compound of at least two kinds of general formula Is, II or III, and/or at least two kinds of compounds with at least a structure among formula I, II and the III, and this compound comprises at least two different substituting groups.

Plurality of advantages of the present invention also can provide by obtaining a kind of optical anisotropic film, and described film can comprise the Dan Yi perylene tetracarboxylic acid bisbenzimidazole sulfonic derivatives of structural formula I, II or III, or its mixture.Optical anisotropic film of the present invention also can further comprise a kind of different organic pigment or certain leucocompound.These anisotropic films are partial crystallization at least usually.

Optical anisotropic film of the present invention can obtain by the following method: the liquid crystal system is coated on the matrix, is orientated effect and dry then.

Experimental example

The method according to this invention and system have been carried out repeatedly experiment.These experiments are not to limit the scope of the invention by any way only in order to illustrate.

Embodiment 1

Following isomery disulphonic acid mixtures by the synthetic PTCA DBI sulfone of PTCA sulfone.

The condensation of single sulfone of stage 1a.PTCADA (monosulfone) and O-Phenylene Diamine.

40ml acetate and 1.5g O-Phenylene Diamine are added in the suspension of the single sulfone of 2g PTCA dianhydride (PTCADA) in 50ml 4%NaOH solution.The reacting by heating mixture also keeps boiling 5 hours.With the sedimentation and filtration that forms, and use washing with alcohol.This method obtains 2.1g following structural formula compound.

Mass spectrum (VISION 2000) locates to record molion (negative polarity) at 598.8 (m/z), and calculating molecular weight is 598.59.

The sulfonation of single sulfone of stage 1b.PTCADA and O-Phenylene Diamine condensation product.

Under 100 ℃, with the sulfonation 10 hours in the oleum of 6ml 4% of the product (1.5g) of stage 1a.Use 10ml water diluting reaction thing then.Sedimentation and filtration separates and washs with acetate.This method obtains the compound of the following structural formula of 1.8g

The condensation of single sulfone of stage 1c.PTCADA and sulfonation O-Phenylene Diamine.

1.0g sulfonation O-Phenylene Diamine is added in the suspension of the single sulfone of 1g PTCADA in 30ml acetate and 10ml DMF.Mixture boiling 8 hours.The sedimentation and filtration separation is also used the alcoholic acid solution washing.This method obtains 2g and the identical compound of stage 1b product structure formula.

Mass spectrum (VISION2000) locates to record molion (negative polarity) at 759.2 (m/z), and calculating molecular weight is 758.72.

Embodiment 2

Following by sulfonation anti--PTCA DBI synthetic anti--disulfonic acid of PTCA DBI sulfone.

Anti--PTCA DBI (5.3g) is added in the oleum of 25ml 35% in batches 90 ℃ of following sulfonation 8 hours.Diluting reaction thing in the following order then: be diluted to mono-hydrate with 92% aqueous sulfuric acid earlier, water is diluted to 55% with sulfuric acid concentration again.Sedimentation and filtration separates, and resuspending is three times in acetate, and the dry compound that obtains the following structural formula of 7.1g

Its mass spectrum (VISION 2000) is as follows: molion (negative polarity) is at the 758.4m/z place, and calculating molecular weight is 758.For C ₃₆H ₁₄N ₄O ₁₀S ₃, ultimate analysis records (%): C56.72,56.80; H 1.94; 1.66; N 7.31,7.39; S 12.32,12.40.Calculated value (%) is: C 56.99; H 1.86; N 7.38; O 21.09; S 12.68.Infrared spectra (IR-fourier spectrometer FSM-1201, KRS-5 window) peak position is in 1229.4,1179.7 (sulfo groups), 1074.0,1030.5 (sulfo groups), 132 4.7 (sulfones), 1699.6 (carbonyls).The λ of the electronic spectrum of sample (Ocean PC 2000 spectrographs, the aqueous solution) _Max=600nm and 675nm.

Embodiment 3

The following mixture that synthesizes the isomery disulfonic acid of PTCA DBI sultone by the PTCA sultone.

The condensation of single sultone of stage 3a.PTCADA (monosultone) and O-Phenylene Diamine.

The 1.5g O-Phenylene Diamine is added in the suspension of the single sultone of 2g PTCADA in 20ml acetate and 20ml DMF mixture.Reactant heating 2 hours.The sedimentation and filtration that forms separated and use washing with alcohol.This method obtains the compound of the following structural formula of 2.4g

The sulfonation of single sultone of stage 3b.PTCADA and O-Phenylene Diamine condensation product.

Under 100 ℃, with the sulfonation 8 hours in the oleum of 5ml 4% of the product (1g) of stage 3a.Use 10ml water diluting reaction thing then.Sedimentation and filtration separates and washs with acetate.Obtain the compound of the following structural formula of 1.1g

The condensation of single sultone of stage 3c.PTCADA and sulfonation O-Phenylene Diamine.

1.5g sulfonation O-Phenylene Diamine is added in the suspension of the single sultone (1g) of PTCADA in 30ml acetate.Mixture boiling 8 hours.The sedimentation and filtration that forms is separated, and use the alcoholic acid solution washing.Obtain the 1.8g compound identical with the product structure formula of stage 3b.

Mass spectrum (VISION 2000) records the negative polarity molion and locates at 773.1 (m/z), and calculating molecular weight is 774.7.The λ of the electron absorption power spectrum of sample (Ocean PC2000 spectrograph, the aqueous solution) _Max=590nm.

Embodiment 4

Following disulfonic acid by sulfonation PTCA DBI synthesizing cis PTCA DBI sultone.

Cis PTCA DBI (5.3g) is added in the oleum of 25ml 10% in batches, 190 to 200 ℃ of following sulfonation 8 hours.Diluting reaction thing in the following order then: be diluted to mono-hydrate with 92% aqueous sulfuric acid earlier, water is diluted to 60% with sulfuric acid concentration again.The sedimentation and filtration that forms is separated, and resuspending is three times in acetate, and drying obtains the compound of the following structural formula of 6.8g

Mass spectrum (VISION 2000) locates to record the negative polarity molion at 772.4 (m/z), and calculating molecular weight is 774.1.For C ₃₆H ₁₄N ₄O ₁₁S ₃, ultimate analysis records (%): C 55.51,55.58; H 1.64,1.71; N 7.00,7.11; S 12.65,12.58.Calculated value is (%): C 55.81; H 1.82; N 7.23; O 22.72; S 12.42.Infrared spectra (IR-fourier spectrometer FSM-1201, KRS-5 window) peak position is in 1237.7,1179.7 (sulfo groups), 1074.0,1030.5 (sulfo groups), 1431.4 (sultone), 1712.3 (carbonyls).The λ of sample electronic spectrum (Ocean PC 2000 spectrographs, the aqueous solution) _Max=580nm and 660nm.

Embodiment 5

Following disulphonic acid mixtures by the synthetic PTCA DBI disultone of PTCA disultone.

The condensation of stage 5a.PTCADA disultone and O-Phenylene Diamine.

The acetic acid suspension that makes 1g PTCADA disultone and 1g O-Phenylene Diamine be dissolved in 30ml was boiled 5 hours.The sedimentation and filtration that forms separated and use washing with alcohol.This method obtains the compound of the following structural formula of 1.1g

The sulfonation of stage 5b.PTCADA disultone and O-Phenylene Diamine condensation product.

Under 100 ℃, with the sulfonation 6 hours in 4% oleum 5ml of the product (1g) of stage 5a.Use 10ml water diluting reaction thing then.Sedimentation and filtration separates and washs with acetate.Obtain the compound of the following structural formula of 1.1g

The condensation of stage 5c.PTCADA disultone and sulfonation O-Phenylene Diamine.

1g sulfonation O-Phenylene Diamine is added in the acetic acid suspension of PTCADA disultone (0.5g).Mixture boiled 4 hours.The sedimentation and filtration that forms is separated, and use the alcoholic acid solution washing.Obtain the 0.6g compound identical with the product structure formula of stage 5b.

Mass spectrum (VISION 2000) locates to record molion (negative polarity) at 851.4 (m/z), and calculating molecular weight is 852.76.For C ₃₆H ₁₂N ₄O ₁₄S ₄, ultimate analysis records (%): C 50.72,50.63; H 1.28,1.33; N 6.47,6.01; S 14.74,14.81.Calculated value is (%): C 50.70; H 1.42; N 6.57; O 26.27; S 15.04.Infrared spectra (IR-fourier spectrometer FSM-1201, KRS-5 window) peak position is in 1237.7,1179.7 (sulfo groups), 1074.0,1030.5 (sulfo groups), 1431.4 (sultone), 1712.3 (carbonyls).The λ of the electronic spectrum of sample (Ocead PC 2000 spectrographs, the aqueous solution) _Max=580nm and 660nm.

Embodiment 6

The following mixture that synthesizes the isomery hydroxyl sulfoacid of PTCA DBI by hydroxyl-PTCA.

The condensation of stage 6a. monohydroxy-PTCADA and O-Phenylene Diamine.

1g monohydroxy-PTCADA and the suspension of 1.6g O-Phenylene Diamine in 30ml acetate were boiled 8 hours.The sedimentation and filtration that forms is separated, and use washing with alcohol.Obtain the compound of the following structural formula of 1.3g

The sulfonation of stage 6b. monohydroxy-PTCADA and O-Phenylene Diamine condensation product.

Under 100 ℃, with the product (1g) of stage 6a in the oleum of 5ml 4% in sulfonation 12 hours.Use the water diluting reaction thing of 20ml then.Sedimentation and filtration separates and washs with acetate.Obtain the compound of the following structural formula of 1.2g

The condensation of stage 6c. monohydroxy-PTCADA and sulfonation O-Phenylene Diamine.

Make monohydroxy-PTCADA (1g) and the mixture boiled of 1.5g sulfonation O-Phenylene Diamine in 30ml acetate 8 hours.The sedimentation and filtration separation is also used the alcoholic acid solution washing.Obtain the 1.2g compound identical with the product structure formula of stage 6b.

Mass spectrum (VISION 2000) is as follows: the negative polarity molion is at the 711.5m/z place, and calculating molecular weight is 712.67.

Embodiment 7

Following by sulfonation PTCA DBI synthetic anti--PTCA DBI dihydroxyl sulfonic acid.

Will anti--PTCA DBI (5.3g) add in the oleum of 20ml 10% in batches and stirred 8 hours, the concentration with oleum increases to 30% subsequently, and continues sulfonation 10 hours down in 120 ℃.Diluting reaction thing in the following order then: be diluted to mono-hydrate with 92% aqueous sulfuric acid earlier, water is with vitriolic concentration dilution to 75% again.The sedimentation and filtration that forms is separated, and resuspending is three times in acetate, and the dry compound that obtains the following structural formula of 6.0g

Mass spectrum (VISION 2000) locates to record the negative polarity molion at 727.9 (m/z), and calculating molecular weight is 728.67.For C ₃₆H ₁₆N ₄O ₁₀S ₂, ultimate analysis records (%): C 59.17,60.12; H 2.27,2.30; N 7.20,7.35; S 9.12,9.24.Calculated value is (%): C 59.34; H 2.21; N 7.69; O 21.96; S 8.80.Infrared spectra (IR-fourier spectrometer FSM-1201, KRS-5 window) peak position is in 1237.7,1179.7 (sulfo groups), 1074.0,1030.5 (sulfo groups), 896 (hydroxyls), 1710.0 (carbonyls).The λ of the electronic spectrum of sample (Ocean PC 2000 spectrographs, the aqueous solution) _Max=720nm.

Embodiment 8

The following mixture that synthesizes the isomery dihydroxyl disulfonic acid of PTCA DBI by dihydroxyl-PTCA.

The condensation of stage 8a. dihydroxyl-PTCADA and O-Phenylene Diamine.

Suspension in 30ml acetate boiled 8 hours with 1.5g dihydroxyl-PTCADA and 3g O-Phenylene Diamine.The sedimentation and filtration that forms is separated, and use washing with alcohol.This method obtains the compound of the following structural formula of 1.8g

The sulfonation of stage 8b. dihydroxyl-PTCADA and O-Phenylene Diamine condensation product.

Under 100 ℃, with the sulfonation 12 hours in the oleum of 5ml 4% of the product (1g) of stage 8a.Use 20ml water diluting reaction thing then.Sedimentation and filtration separates and washs with acetate.This method obtains the compound of the following structural formula of 1g

The condensation of stage 8c. dihydroxyl-PTCADA and sulfonation O-Phenylene Diamine.

The mixture that 1.5g sulfonation O-Phenylene Diamine in dihydroxyl-PTCADA (1g) and the 40ml acetate is formed seethed with excitement 8 hours.Sedimentation and filtration separates, and uses the alcoholic acid solution washing.Obtain the 1.1g compound identical with the product structure formula of stage 8b.

Mass spectrum (VISION 2000) is as follows: the negative polarity molion is at the 727.5m/z place, and calculating molecular weight is 728.67.

Embodiment 9

Following by sulfonation PTCA DBI synthetic suitable-PTCA DBI furans disulfonic acid.

Suitable-PTCA DBI (5.0g) is added in the oleum of 25ml 45% in batches, and in 60 ℃ of following sulfonation 5 hours.Diluting reaction thing in the following order then: be diluted to mono-hydrate with 92% aqueous sulfuric acid earlier, water is diluted to 65% with sulfuric acid concentration again.The sedimentation and filtration that forms is separated, and resuspending is three times in acetate, and the dry compound that obtains the following structural formula of 6.5g

Mass spectrum (VISION 2000) is as follows: the negative polarity molion is located at 709.4 (m/z), and calculating molecular weight is 710.65.For C ₃₆H ₁₄N ₄O ₉S ₂, ultimate analysis records (%): C 60.66,60.10; H 2.09,2.27; N 7.39,7.32; S 9.51,9.41.Calculated value is (%): C 60.84; H 1.99; N 7.88; O 20.26; S 9.02.The λ of the electronic spectrum of sample (OceanPC 2000 spectrographs, the aqueous solution) _Max=600nm.

Can be synthetic corresponding to other derivative of structural formula I, II and III by similar method, for example by sulfonation PTCA DBI isomer or mixture, by sulfonation behind the corresponding PTCA derivative of condensation, synthesize by these PTCA derivatives of condensation and sulfonation O-Phenylene Diamine or by the method that is equal to.

Embodiment 10

Be prepared as follows a kind of liquid-crystal composition and film of the PTCA of comprising DBI dihydroxyl disulfonic acid, and measure the optical characteristics of this film.

10g PTCA DBI dihydroxyl disulfonic acid (embodiment 7) is dissolved in down at 20 ℃ and makes solution in the 79.9ml deionized water,, promptly obtain the liquid crystal solution of 100g 10% with ammonia this solution that neutralizes by stirring.With No. 3 wheats rods (Meyer rod No.3) with the linear velocity of 25mm/s with this solution coat on quartz glass plate.This method is implemented for 65% time in 20 ℃ of temperature, relative humidity, dry under the same conditions afterwards this film.

This film characterizes with transmitted spectrum, adopts the Cary-500 spectrophotometer measurement, and wavelength region is 190 to 800nm, uses along film coated direction (T _Par) and perpendicular to solution coat direction (T _Per) the polarising light beam.At the wavelength X=650nm place corresponding to maximum absorption, dichroic ratio K _d=log (T _Par)/log (T _Per) equal 35; When film was transmitted as 35%, contrast ratio was C/R=200.

Embodiment 11

Be prepared as follows a kind of liquid-crystal composition and film of mixture of the PTCA of comprising DBI sulfonic derivatives, and measure the optical characteristics of this film.

Under 20 ℃, be dissolved in the 79.9ml deionized water and make solution by stirring mixture 10g with PTCA DBI sulfonic derivatives, with ammonia this solution that neutralizes, described mixture comprises 20% sulfone (embodiment 2), 25% sultone (embodiment 4) and 55% hydroxyl sulfoacid (embodiment 6b).The solution that 0.1g sodium alkyl benzene sulfonate (sulfonol) is dissolved in the 10ml water adds in the above-mentioned solution.Mixture fully stirs, and obtains 10% liquid crystal solution 100g.With No. 3 wheats rod with the linear velocity of 25mm/s with this solution coat on quartz glass plate.This method is implemented for 65% time in 20 ℃ of temperature, relative humidity, dry under the same conditions afterwards this film.

This film characterizes with transmitted spectrum, adopts the Cary-500 spectrophotometer measurement, and wavelength region is 190 to 800nm, uses along film coated direction (T _Par) and perpendicular to solution coat direction (T _Per) the polarising light beam.At the wavelength X=650nm place corresponding to maximum absorption, dichroic ratio K _d=log (T _Par)/log (T _Per) equal 32; When film was transmitted as 35%, contrast ratio was C/R=200.

Embodiment 12

Prepare the liquid-crystal composition and the film of the mixture of a kind of PTCA DBI disulfo derivative and indanthrone derivative, and measure the optical characteristics of this film.

Under 20 ℃, be dissolved in the 79.9ml deionized water and make solution by stirring mixture with 10g PTCA DBI sulfone disulfonic acid (embodiment 2,40 quality %) and indanthrone trisulfonic acid (60 quality %), with ammonia this solution that neutralizes.The solution that the 0.1g sodium alkyl benzene sulfonate is dissolved in the 10ml water adds in the above-mentioned solution.Mixture fully stirs, and obtains the liquid crystal solution of 100g 10%.With No. 3 wheats rod with the linear velocity of 25mm/s with this solution coat on quartz glass plate.This method is implemented for 65% time in 20 ℃ of temperature, relative humidity, dry under the same conditions afterwards this film.

This film characterizes with transmitted spectrum, adopts the Cary-500 spectrophotometer measurement, and wavelength region is 190 to 800nm, uses along film coated direction (T _Par) and perpendicular to solution coat direction (T _Per) the polarising light beam.At the wavelength X=650nm place corresponding to maximum absorption, dichroic ratio K _d=log (T _Par)/log (T _Per) equal 30; When film was transmitted as 35%, contrast ratio was K _d=250.

Embodiment 13

Prepare a kind of liquid-crystal composition and film that contains a kind of mixture, described mixture is the mixture of PTCA DBI disulfo derivative, indanthrone derivative and naphthalene tetracarboxylic acid derivative, and measures the optical characteristics of this film.

Under 20 ℃, make solution by stirring the 10g mixture is dissolved in the 79.9ml deionized water, with ammonia this solution that neutralizes, described mixture comprises PTCA DBI sulfone disulfonic acid, and (embodiment 2,10 quality %), PTCA DBI dihydroxyl disulfonic acid (embodiment 8b, 30 quality %), PTCA DBI monohydroxy disulfonic acid (embodiment 6b, 10 quality %), indanthrone trisulfonic acid (40 quality %) and NTCA DBI disulfonic acid (10 quality %).The solution of 0.1g sodium alkyl benzene sulfonate in 10ml water is added in the above-mentioned solution.Mixture fully stirs, and obtains the liquid crystal solution of 100g 10%.With No. 3 wheats rod with the linear velocity of 25mm/s with this solution coat on quartz glass plate.This method is implemented for 65% time in 20 ℃ of temperature, relative humidity, dry under the same conditions afterwards this film.

This film characterizes with transmitted spectrum, adopts the Cary-500 spectrophotometer measurement, and wavelength region is 190 to 800nm, uses along film coated direction (T _Par) and perpendicular to solution coat direction (T _Per) the polarising light beam.At the wavelength X=650nm place corresponding to maximum absorption, dichroic ratio K _d=log (T _Par)/log (T _Per) equal 34; When film was transmitted as 35%, contrast ratio was C/R=300.

Except that the compound of above clearly record, all general formula Is, II and III compound all can provide stable lytropic liquid crystals system, and described liquid crystal system can be used for obtaining to have the optical anisotropic film of premium properties and high reproducibility.

The specific embodiments of the present invention of aforementioned proposition and embodiment only reach descriptive purpose presented for purpose of illustration, though above-mentioned some embodiment describes the present invention, can not be interpreted as limitation of the present invention.Described embodiment is also non exhaustive, and the also non-the present invention of planning only is limited to disclosed form, obviously, according to above instruction multiple improvement project, embodiment and variation scheme can be arranged.The present invention cover by this specification sheets claims and the disclosed general field of equivalent thereof.

Claims (19)

1. sulfonic derivatives compound comprises:

Has a kind of Huangization perylene tetracarboxylic acid bisbenzimidazole (PTCADBI) that is selected from one of following structural formula

I II III

X wherein ₁, X ₂, X ₃, X ₄, X ₅, X ₆, X ₇And X ₈For independently be selected from-H ,-OH and-SO ₃The peripheral substituting group of H, need make at least one should the periphery substituting group not be H;

M is one or more counter ion, and j is the counter ion number that links to each other with a molecule;

Z ₁And Z ₂For independently be selected from-O-,-SO ₂-and-SO ₂The bridging substituting group of-O-;

A ₁And A ₂For having the fragment of following structural formula

Y be one or morely independently be selected from-H ,-Cl ,-F ,-Br ,-OH ,-NO ₂And-NH ₂The fragment substituting group;

N is selected from 0,1 and 2 integer; And

P is selected from 0,1,2,3 and 4 integer.

2. the sulfonic derivatives of claim 1, wherein segment A ₁Or A ₂In at least one comprise at least one sulfo group.

3. the sulfonic derivatives of claim 1, wherein one or more these counter ion are common by the sulfonic derivatives molecule more than.

4. the sulfonic derivatives of claim 1, wherein one or more these counter ion M independently are selected from H ⁺, NH ₄ ⁺, K ⁺, Li ⁺, Na ⁺, Cs ⁺, Ca ⁺⁺, Sr ⁺⁺, Mg ⁺⁺, Ba ⁺⁺, Co ⁺⁺, Mn ⁺⁺, Zn ⁺⁺, Cu ⁺⁺, Pb ⁺⁺, Fe ⁺⁺, Ni ⁺⁺, Al ⁺⁺⁺, Ce ⁺⁺⁺And La ⁺⁺⁺

5. the sulfonic derivatives compound of claim 1, wherein the structural formula of Huangization perylene tetracarboxylic acid bisbenzimidazole (PTCA DBI) is selected from one of the following

6. lytropic liquid crystals (LLC) system that comprises each described sulfonic derivatives compound at least a claim 1 to 5.

7. the LLC system of claim 6, wherein the LLC system is based on water.

8. the LLC system of claim 6, wherein the LLC system based on a kind of water and with the mixture of the miscible organic solvent of water.

9. the LLC system of claim 6, wherein the PTCA DBI sulfonic derivatives in the LLC system is in the concentration range of 3 quality % to 40 quality %.

10. the LLC system of claim 6 further comprises the tensio-active agent that is up to 5 quality %.

11. the LLC system of claim 6 further comprises the softening agent that is up to 5 quality %.

12. the LLC system of claim 6 comprises at least a following sulfonic derivatives:

Concentration range is at the structural formula I sulfonic derivatives of 0 quality % to 99 quality %;

Concentration range is at the structural formula II sulfonic derivatives of 0 quality % to 99 quality %; And

Concentration range is at the structural formula II I sulfonic derivatives of 0 quality % to 50 quality %.

13. the LLC system of claim 6 comprises at least a following sulfonic derivatives:

Concentration range is at the structural formula I sulfonic derivatives of 0 quality % to 50 quality %;

Concentration range is at the structural formula II sulfonic derivatives of 0 quality % to 70 quality %; And

Concentration range is at the structural formula II I sulfonic derivatives of 0 quality % to 2,0 quality %.

14. the LLC system of claim 6 further comprises at least a water-soluble organic pigment or a kind of organic compound, this organic pigment or organic compound can participate in forming the LLC system of the sulfonic derivatives that contains at least a structural formula I, II and III.

15. an optical anisotropic film forms by each lytropic liquid crystals system of deposition claim 6 to 14.

16. the optical anisotropic film of claim 15, wherein this film partial crystallization at least.

17. the optical anisotropic film of claim 16, wherein the spacing along one of optical axis is about 3.1  to 3.7  in the crystal.

18. the optical anisotropic film of claim 15, wherein this film is a polarization film.

19. the optical anisotropic film of claim 15, wherein this film is a polarizer.

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