CN100457755C - Perylenetetracarboxylic acid dibenzimidazole sulfoderivatives containing oxo-groups in the perylene core which form part of a para-quinoid system of bonds, lyotropic liquid crystal systems and anisotr - Google Patents
Perylenetetracarboxylic acid dibenzimidazole sulfoderivatives containing oxo-groups in the perylene core which form part of a para-quinoid system of bonds, lyotropic liquid crystal systems and anisotr Download PDFInfo
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Abstract
Anisotropic films based on sulfoderivatives of perylenetetracarboxylic acid dibenzimidazole (PTCA DBI) which contain oxo groups pendant to a perylene core. The oxo-groups, in combination with portions of the perylene core, form a quinoid system of bonds. The oxo substituted PTCA DBI sulfoderivatives form liquid crystal systems possessing high optical properties. Said liquid crystal systems can be applied onto various substrates to obtain optically isotropic or anisotropic, at least partially crystalline, films applicable in various fields.
Description
Related application
This patent application requires to be called in the name that on June 25th, 2003 submitted to the U.S. Provisional Patent Application 60/482 of " based on the lyotropic liquid crystal systems of the perylene tetracarboxylic acid bisbenzimidazole sulfonic derivatives of the oxygen base that comprises the paraquinones system that participates in bonding in perylene nuclear; relevant anisotropic membrane and their manufacture method ", 779 right of priority is hereby expressly incorporated by reference its full content.
Technical field
The present invention relates in general to organic chemistry and optical anisotropy paint field.More specifically, the present invention relates to the synthetic of heterocycle sulfo group derivative compound and based on the manufacturing of the optical anisotropy coating of this compound.
Background technology
The modern technologies progress need be special based on having, the development of the optical element of the novel material of may command performance.Especially, the necessary element in the contemporary optics indicating system is the optical anisotropic film with best combination of the optical characteristics that is used for specific device and other characteristics.
Known in the prior art have different polymer materialss to be used to make optical anisotropic film.Carry out modification by uniaxial extension with organic dye or iodine, make film obtain anisotropy optics performance based on these polymer materialss.In great majority were used, matrix polymer was polyvinyl alcohol (PVA).Monograph " Liquid Crystals:Applications andUses, B.Bahadur (ed.), World Scientific, Singapore-New York (1990), Vol.1 has described such film in p.101 in more detail.Yet, limited their application based on the low thermal stability of the film of PVA.Wish to find novel material and exploitation be used for synthetic have the characteristic of improvement, especially have higher heat impedance, be more convenient for synthesizing, have the method for the optical anisotropic film of better film forming properties.
Organic dichroic dyestuff is a class novel material, and it is in dominant position in the manufacturing of the optical anisotropic film with height optical characteristics and performance characteristics.Film based on these compounds is to contain supramolecular liquid crystal (LC) the water soluble dyestuffs solution of being made up of dye molecule by coating one deck on substrate surface, evaporates moisture subsequently and obtains.Resulting liquid crystal film or by as at United States Patent (USP) US 2,553, the substrate surface to below described in No. 961 carries out preliminary mechanical orientation, or by as at United States Patent (USP) the 5th, 739, No. 296 and the 6th, 174, subsequently on-chip liquid crystal coating is applied outside mechanical force, electric power, magnetic force or other dipole-dipole force and obtains anisotropic properties described in No. 394.The fundamental property of liquid crystalline dyes solution is known in the prior art.Yet, the development of upgrading was arranged in the past in 10 years for their application and the broad research of related system performance.Nearest research is subjected to the promotion of liquid-crystal display (LCD) and glass (glazing) industrial application to a great extent.The dyestuff supramolecule forms lytropic liquid crystals (LLC) phase.This mutually in, dye molecule produces the supramolecular complex of column form, the i.e. structural unit of intermediate phase.To make this intermediate phase can be used for obtaining with strong dichroic be the alignment films of characteristic to the high-sequentialization of dye molecule in post.
Another special property that forms the dye molecule of supramolecular liquid crystal intermediate phase is that the existence of group on every side makes these dye solubles in water.The organic dye intermediate phase is characterised in that specific structure, phasor, optical property and dissolving power.Referring to J.Lydon, Chromonics, Handbook of Liquid Crystals (Wiley-VCH, Weinheim, 1998), Vol.2B, pp.981-1007.
By using the dichroic dyestuff that can form the LLC system, might obtain to have highly optically anisotropic film.This film demonstrates the performance of E-type polaroid, and its characteristic with the optical absorption of supramolecular complex is relevant, and plays phase difference film (phase changer) effect in absorbing inapparent spectral region.The phase retardation performance of these anisotropic films (phase differential performance) is relevant with its double refraction, and double refraction is just different with the specific refractory power that records in vertical direction on the direction that LLC solution is applied to substrate.The film that is formed by the LLC system based on strong (fast light) dye molecule is characterised in that high heat stability and photostabilization.
The above performance of LLC system has been explained the reason to the attention rate increase of these materials.Developed a large amount of being used to and obtained novel method based on organic dye film, its development had both comprised the optimization of film applying condition, and seeking new LLC system also arranged.Especially, by properties-correcting agent, stablizer, tensio-active agent and other additive being incorporated in the known dyestuff, can obtain being used for the new LLC composition of synthesizing optical anisotropic films to improve the characteristic of film.Referring to United States Patent (USP) for example No. 5739296 and No. 6174394.
In recent years, the selectivity in different wavelength range is improved constantly increases for demand feature, that have highly optically anisotropic film.People need distinguish the interior film variable, that have different maximum absorption position of wide spectral range in ultraviolet (UV) district from infrared (IR).This make it possible to form LLC mutually and the kind of compound with film of desired properties enlarge to some extent.Yet the quantity of known dye that can form stable lyophily intermediate phase is still less.Very naturally, every kind of new liquid crystalline dyes all becomes the object of thorough research.
Can form stablize the LLC phase can be applicable to make among the water-soluble dichroic dyestuff of optical anisotropic film, the disulfo derivative of different organic dye has occupied important position, be included in United States Patent (USP) the 5th, 739, No. 296 and the 6th, 174, No. 394 Zhong Miao Shu De perylene tetracarboxylic acids (PTCA) bisbenzimidazoles (DBI).Because height chemical stability, thermostability and the photochemical stability of PTCA bisbenzimidazole and imide, these materials are widely used as different industrial dyestuff and pigment.These performances also can be explained the importance of these materials as the raising of the potential material of the optical anisotropic film that obtains to be used for LCD and other Optical devices.
The main difficulty that hinders above dyestuff to use is its poorly soluble in water and some organic solvents.In order to make dyestuff in organic solvent, have enough solubleness, different substituting groups is introduced molecule.This substituent example aerobic ethyl is (referring to R.A.Cormierand B.A.Gregg, Phys.Chem.101 (51), 11004-11006 (1997)) and phenoxy group (referring to H.Quante H.Y.Geerts, and K.Mullen, Chem.Mater.6 (2), 495-500 (1997)).The solubleness of perylene dyestuff also by amino (referring to I.K.Iverson, S.M.Casey, W.Seo, and S.-W.Tam-Chang, Langmuir 18 (9), 3510-5316 (2002)) and sulfo group (referring to United States Patent (USP) the 5th, 739, No. 296 and the 6th, 174, No. 394) and be improved.Obtained best result with sulfo group, enough solubleness Yi are provided for it Ji the formation of the stable LLC phase of perylene dyestuff.
The standard step that obtains the disulfo derivative is as follows.The PTCA DBI and the oleum that in the chlorsulfonic acid of certain volume, add calculated amount.In case reaction terminating, mixture are colored and dilute with water.Throw out is filtered, clean with hydrochloric acid, dry then, obtain water miscible dibenzo Mi Zuo perylene tetracarboxylic acid disulfonic acid, be dissolved in the water it and purification.The analysis of system architecture demonstrated from certain dye strength begun, in given temperature range, formed six side's lyophily intermediate phase.Thereby, in dye strength that is rather narrow and temperature range, observe nematic phase.Border and two-phase zone of transition that isotropic phase exists in this system, have been determined.
There has been patent to describe to be used to the different dyes composition (printing ink) that obtains based on the polarizing coating of PTCA DBI sulfonic derivatives.Especially, known dyestuff with following structural formula:
Wherein
Perhaps
R=H, alkyl, halogen or alkoxyl group; And Ar is that replace or unsubstituted aryl.At United States Patent (USP) the 5th, 739, this dyestuff has been described in No. 296, it is optionally in the 550-600nm zone.
Other the dyestuff based on PTCA DBI has following formula:
R wherein
1=H, 3 (4)-CH
3, 3 (4)-C
2H
5, 3 (4)-Cl, 3 (4)-Br; And R
2=4 (5)-SO
3H.At United States Patent (USP) the 1st, 598, this dyestuff has been described in No. 430, it also is optionally in the 550-600nm zone.
At United States Patent (USP) the 5th, 739, No. 296 and the 6th, 174, the LC mixture of PTCADBI sulfonic derivatives has been described in No. 394, wherein introduced different property-modifying additives to improve the characteristic of anisotropic membrane.At United States Patent (USP) the 5th, 739, No. 296 and the 6th, 174, the indanthrone disulfo derivative of having described to have different substituents in No. 394.In disclosed patent application EP 961138, described and had different organic cations compositions.
Use is based on different organic dye (Bao Kuo perylene dyestuffs) the anisotropic films that obtains of the LLC system of sulfonic derivatives characterized in its performance and configuration aspects.Especially, after deliberation use the performance of the film that base obtains in the LLC of perylene dyestuff system.Referring to I.K.Iverson, S.M.Casey, W.Seo, and S.-W.Tam-Chang, Controlling Molecular Orientation in Solid-Crystalline Phase, Langmuir 18 (9), 3510-5316 (2002).Report the optical anisotropy that all films all have height.
Reported the performance of using the anisotropic films that obtains based on the LLC system of the sulfonic derivatives of organic dye.Referring to T.Fiske, L.Ignatov, P.Lazarev, V.Nazarov, M.Paukshto, Molecular Alignment in Crystal Polarizers andRetarders, Society for Information Display, Int.Symp.Digest ofTechnical Papers (Boston, MA, May 19-24,2002), p.566-569.Determined that these films have to small part crystallographic structure.Optical anisotropic film can obtain on the substrate of glass, plastics or any other material.The purple dye that is used to form these anisotropic membranes has been represented the mixture of cis-trans-isomer.Referring to V.Nazarov, L.Ignatov, K.Kienskaya, Electronic Spectra of Aqueous Solutions andFilms Made of Liquid Crystal Ink for Thin Film Polarizers, Mol.Mater.14 (2), 153-163 (2001).These films have the height optical characteristics that the dichroic ratio reaches 25-30, can be used as polaroid.Referring to Y.Bobrov, L.Blinov, L.Ignatov, G.King, V.Lazarev, Y.-D.Ma, V.Nazarov, E.Neburchilova, N.Ovchinnikova, S.Remizov, Environmental and Optical Testing ofOptiva Thin Crystal Film
TMPolarizers, Proceedings of the 10
ThSIDSymposium " Advanced display technologies ", (Minsk, Republic ofBelarus, September 18-21,2001), p.23-30.
In the open text WO 02/063,660 of PCT, described and be used to obtain these films method of (comprising film) with highly crystalline degree.
All aforementioned PTCA DBI sulfonic derivativess can both form the LLC phase.The anisotropic membrane that uses this LLC system to obtain has the optical characteristics of height, and demonstrates the superperformance as polaroid.
Yet one of main drawback of known water-soluble PTC ADBI sulfonic derivatives is: the anisotropic films with reproducibility (from a collection of to another batch and with on the substrates of different a collection of) and homogeneous (on substrate surface) performance that is difficult to obtain to be correlated with.Present thin film applied technology requires accurately to select and the strict processing parameter (concentration, temperature etc.) of carrying out.Yet even under the situation that strictly observes all film formation conditions, the partially scrambling that occurs at random in the coating structure is still possible.This certain probability with the formation of misorientation district and microdefect is relevant, and the formation of misorientation district and microdefect is because after being applied to the LLC system on the substrate surface, in removing the process of desolvating due to microcosmic and macroscopical crystallisation process unbalanced.In addition, the LLC system based on known dye is characterised in that: the coat-thickness that is applied in possibility heterogeneous is higher, and it has also reduced the circulation ratio of film parameter.Aforementioned disadvantages makes the formation of the film with height optical characteristics complicated, and this technology can not fully be reappeared, and need all accurately select the also strict most technical parameter of carrying out from being applied to each stage of exsiccant.
Summary of the invention
Disclosedly the invention provides new Shui Rong perylenetetracarboxyacid acid bisbenzimidazole (PTCADBI) sulfonic derivatives and based on the optical element of these compounds.Have been found that when with some substituting groups when certain position is incorporated into PTCA DBI sulfonic derivatives, it has improved the homogeneity of crystallization and drying process, thereby but has improved formed productive rate with film of reproducing characteristic.
Particularly, in a specific embodiment, disclosed PTCA DBI sulfonic derivatives, it contains the oxygen base of side direction Lian Jie Dao perylene nuclear, and this oxygen base is comprised in the quinone system of bonding.This oxo PTCA DBI sulfonic derivatives can form stable LLC intermediate phase.
Can use oxo PTCA DBI sulfonic derivatives to obtain the film of anisotropic partial crystallization at least, and have reproducible height optical characteristics.Therefore, disclosed another specific embodiment of the present invention is based on the formation of the anisotropic films of oxo PTCA DBI sulfonic derivatives, and this anisotropic films can be used as polarizing coating.The present invention has enlarged the kind that can absorb and can form the compound of the stable LLC phase with the stability that increases in visible spectrum range.
Thereby, the invention provides new organic compound, the LLC of this compound has the stability that increases in very wide concentration, temperature and pH value scope.And, the invention provides new organic compound, it has simplified the film forming process, and allows to use and can apply these layers by the commercial equipment that obtains, and it has guaranteed that the film that forms has the parameter circulation ratio.
Description of drawings
Fig. 1 is the synoptic diagram that PTCA DBI is changed into the sulfo group compound of the oxygen base on the Bao Han Zai perylene nuclear by oxidation.Oxygen base on Gai perylene nuclear constitutes the part of the paraquinoid system of bonding.
Fig. 2 illustrates by 1-hydroxyl PTCA and begins from the process of the synthetic PTCA DBI sulfonic derivatives of PTCA hydroxy derivatives, and this PTCA DBI sulfonic derivatives contains at the oxygen base that forms on the paraquinones Bu Fen De perylene nuclear.
Embodiment
(1)
Definition
As employed at this paper, following term has following implication:
" sulfonated " and " sulfonic derivatives " is meant and has one or more sulfo group substituting groups.
" sulfo group " is meant-SO
3 -Or-SO
3The H substituting group.
“ perylene tetracarboxylic acid bisbenzimidazole ", be abbreviated as PTCA DBI, be meant following structure (A) or one of (B):
Wherein each R can be identical or different substituting group, and can form bridge (structure) with adjacent R group, and wherein x and y are 1 to 4 integers.
The oxygen base " be meant=O.
" perylene nuclear " be meant and appear at, for example in the PTCA DBI with lower section (I):
Wherein each R can be identical or different substituting group, and can form bridge (structure) with adjacent R group.
" paraquinones " or " in conjunction with the paraquinoid system of (bonding) " is meant with lower section (m) or one of (n):
(2) (explanation) described
PTCA DBI sulfonic derivatives of the present invention comprises the oxygen base of side direction Lian Jie Dao perylene nuclear.Oxygen Ji is with perylene nuclear part forms the paraquinones system of bonding.Oxo PTCA DBI sulfonic derivatives comprises, for example, and any among the general structure I to VII that below provides.
Oxo PTCA DBI sulfonic derivatives can be by any known method synthetic cis or trans-isomer(ide).Especially, as shown in Figure 1, oxo PTCA DBI sulfonic derivatives can obtain by the sulfonation of PTCA DBI under the different condition.
In addition, oxo PTCA DBI sulfonic derivatives can by the PTCA hydroxy derivatives through with O-Phenylene Diamine or with the condensation of ortho-diaminobenzene sulfonic acid, with after oxidation, and in some specific embodiments, further obtain through sulfonation.Fig. 2 has provided from the path of the PTCA hydroxy derivatives synthesizing oxo PTCA DBI compound of known structure with schematic form.
Alternatively optional, independent oxo PTCA DBI sulfonic derivatives can pass through the fractionation of its mixture and obtain.
The mixture of oxo PTCA DBI sulfonic derivatives can pass through the isomerization of pure compound and obtain.
As long as follow certain previously selected condition, just can synthesize these oxos PTCADBI sulfonic derivatives, comprise the oxo PTCADBI sulfonic derivatives of the general structure I to VII that hereinafter lists.In order to obtain target compound, as long as determine that the starting point concentration and the synthetic processing condition of reactant are just enough.Most important parameter is starting point concentration, temperature of reaction and the reaction times of reactant.These parameters decision synthetic result, productive rate and different oxo PTCA DBI sulfonic derivatives (for example Formula I-VII) and the ratio of isomer in reaction mass thereof.
Another aspect of the present invention is to have developed new organic compound, and its solution is characterised in that best hydrophilic hydrophobic balance.This balance advantageously influences the size of the supramolecular complex that forms and shape and the degree of molecular assembly in this mixture in this system.These performance provisions and are studied the needed solubleness of compound and guarantee high stability based on the LLC phase of this compound simultaneously.Thus, improved the reproducibility of film parameter and simplified production technique, reason is to select to become so not strict with the requirement of the best-of-breed technology condition that maintains the different production phases.In addition, improved the optical characteristics of new film, because the planar molecule of oxo PTCA DBI sulfonic derivatives is more even with respect to the orientation of substrate.The orientation better on of the moment of dipole of transition of electron (being arranged in planes of molecules) by the determined direction of outside orientation factor.
Use water-soluble oxo PTCA DBI sulfonic derivatives disclosed by the invention can reach above purpose, this oxo PTCA DBI sulfonic derivatives is the original compound of before not reporting in the literature.By using with disclosed structural formula as the compound of feature, based on the liquid crystal system of this compound and use the optical anisotropic film of this system's manufacturing can guarantee this technique effect.
Use sulfonated cis or the anti-formula perylene tetracarboxylic acid bisbenzimidazole derivative that contains the aerobic base in perylene nuclear by making, purpose of the present invention is guaranteed, this oxygen base is examined the paraquinones system that part forms bonding with perylene.Comprise one of following general structure I-VII as illustrative compound:
A wherein
1And A
2Be respectively identical or different segment (fragment), it comprises following general structure:
X wherein
1, X
3, X
4, X
5, X
6, X
7And X
8Be independently be selected from comprise-H ,-OH ,-SO
3Substituting group in the group of H makes substituent X
6And X
7Can interact and form bridge (base) Z; Wherein Z be selected from series-O-,-SO
2-and-SO
2The bridge of-O-(base); Wherein each Y be independently be selected from series-H ,-Cl ,-F ,-Br, alkyl ,-OH ,-alkoxyl group ,-NO
2With-NH
2Substituting group, wherein n is 0,1 and 2 integer, so that pulsating at least one sulfo group that comprises one of at least of A1 and A2; Wherein p is 0,1,2,3 and 4 integer, and wherein each M is counter ion; Wherein j is the quantity of counter ion in the dye molecule, if one or more counter ion belong to several molecule, then j can be a mark; And wherein when n＞1, can comprise different counter ion M.
All compounds of Formula I-VII can both form stable LLC phase, can form separately, can form with other compound of this group again, can also with other can form LLC mutually dichroic dyestuff and/or mix formation with other material that in visible-range, does not absorb (colourless) or weak absorption and can form the LLC phase.Remove desolvate after, LLC forms anisotropic, the film of partially crystalline at least with reproducible height optical characteristics mutually.
The greatest optical that oxo PTCA DBI sulfonic derivatives demonstrates in the aqueous solution in the range of wavelengths of 530-600nm absorbs.Do not compare with replacing molecule, introduce substituting group, for example Cl, F, Br, alkyl and alkoxyl group obviously do not change absorption band.Introducing amino and hydroxyl makes absorption band widen and change the feature of absorption spectrum.By changing number and the substituent number and the character of the sulfo group in oxo PTCA DBI sulfonic derivatives, might control the hydrophilic-hydrophobic balance that is formed on the molecule aggregates in the LLC solution, and change the viscosity of solution.No matter pointed substituent number and type among the structural formulas I-VI I can reach technique effect of the present invention.
In structural formulas I-VI I, counter ion M can be from H
+, NH
4 +, K
+, Li
+, Na
+, Cs
+, Ca
++, Sr
++, Mg
++, Ba
++, Co
++, Mn
++, Zn
++, Cu
+++, Pb
++, Fe
++, Ni
++, Al
+++, Ce
+++, La
+++Different positively charged ions and these cationic combinations Deng series.
Oxo PTCA DBI sulfonic derivatives can form stable lyotropic liquid crystal systems.Liquid crystal solution (system) comprises the independent oxo PTCA DBI sulfonic derivatives of structural formulas I-VI I and the mixture of these compounds, and it can prepare by any traditional method.
The liquid crystal solution (system) of the independent oxo PTCA DBI sulfonic derivatives of general structure I-VII and the mixture of these compounds can be applied on the substrate surface, and be orientated with any known method, for example at United States Patent (USP) the 5th, 739, No. 296, the 6th, 174, No. 394 and the 6th, method described in 563, No. 640 is hereby expressly incorporated by reference its whole disclosures.According to disclosed content in the aforementioned patent, desirable orientation can provide by for example applying mechanical shearing stress or electric field or magnetic field.In order to make substrate wettingly and make the rheological property optimization of liquid crystal system better, can make solution modification by adding plastifying water-soluble polymers and/or negatively charged ion or nonionogenic tenside.In addition, this system can comprise water miscible low molecular weight additives.All additives of selecting must not destroy the orientation performance of liquid crystal system.Subsequently, from alignment films, remove and desolvate, make to form optically anisotropic polycrystal film with 0.2 to 1.2 micron thickness.
Compare with the film that for example obtains according to film disclosed by the invention, it is characterized in that from a collection of to another batch, with a collection of different films and in the raising of the lip-deep reproducibility of a film from disulfo PTCA DBI.
Therefore, oxo PTCA DBI sulfonic derivatives disclosed by the invention can form the lytropic liquid crystals phase, and can be used to obtain to have the anisotropic films of highly reproducible optical characteristics.
Oxo PTCA DBI sulfonic derivatives disclosed by the invention can form optical isotropy film or optical anisotropic film.
Oxo PTCA DBI sulfonic derivatives disclosed by the invention can be formed up to the crystalline film of small part, and this film demonstrates along the spacing in the crystal of one of optical axis and roughly exists
Extremely
Scope in.This spacing is easy to use standard method, and for example X-ray diffraction fixes.
Oxo PTCA DBI sulfonic derivatives disclosed by the invention can form the film of polarising and/or double refraction (double refraction).
Oxo PTCA DBI sulfonic derivatives disclosed by the invention can be the part of optical isotropy or optically anisotropic, polarising and/or composition phase retardation and/or birefringent film.The material of this optical isotropy or optical anisotropic film can comprise: at least two kind compounds of Formula I to the VII, and/or at least two kinds of mixtures with Formula I compound that comprises at least two kinds of different substituents of at least a chemical formula to the VII.
Liquid crystal system (being sometimes referred to as " aqueous ink composition ") by a kind of water-based obtains technique effect of the present invention equally, and this liquid crystal system comprises the mixture of a kind of or at least two kinds of these compounds in the oxo PTCA DBI sulfonic derivatives that is selected from structural formula I to VII disclosed by the invention.Liquid crystal system disclosed by the invention is based on the mixture of water or water and organic solvent, this organic solvent easily and water with any mixed or with have can with the limited blended character of water.Disclosed by the invention separately or the content of blended oxo PTCADBI sulfonic derivatives in disclosed liquid crystal system between 3 to 40 quality %, change, most typical is to change between 7 to 20 quality %.Liquid crystal system disclosed by the invention can also comprise to the tensio-active agent of 5 quality % and/or softening agent.
According to required performance, the specific content of oxo PTCA DBI sulfonic derivatives in liquid crystal system disclosed by the invention can change in following scope:
The compound of-Formula I and/or V, from 0 to 99 quality %, best is in 0-70 quality % scope;
The compound of-Formulae II and/or VI, from 0 to 99 quality %, best is in 0-50 quality % scope;
The compound of-Formula I V and/or VII, from 0 to 50 quality %, best is in 0-20 quality % scope;
The compound of-Formulae II I, from 0 to 99 quality %, best is in 0-20 quality % scope;
Liquid crystal system disclosed by the invention can comprise in addition at least aly can participate in water-soluble organic dye or the colourless organic compound that lytropic liquid crystals forms mutually.
Liquid crystal system disclosed by the invention can comprise and is selected from Formula I to two or more compounds of VII and/or be selected from Formula I two or more compounds that comprise at least two kinds of different substituents one of to the VII.
Can also obtain the technique effect of disclosure invention by following anisotropic films: perhaps contain the single anisotropic films that has the oxo PTCA DBI sulfonic derivatives of general structure I-VII or contain the mixture of these compounds.Optical anisotropic film can comprise different organic dye or some leucocompound in addition.Can be according to optical anisotropic film of the present invention by liquid crystal system is applied on the substrate, subsequently by orientation effect and dry obtaining.This anisotropic films is partially crystalline at least.
Mould material according to the present invention comprises that at least two kinds of compounds that are selected from different chemical formula I to VII and/or two kinds have the compound that in the lump comprise at least two kind different substituents of Formula I to the VII.
Fig. 1 and Fig. 2 show possible preparation method.Can reach by sulfonation method (Fig. 1) and by condensation and prepare compound disclosed by the invention with rear oxidation (Fig. 2).The experimental result that below provides is some embodiment of two kinds of preparation methods.These embodiment are illustrative purposes rather than in order to limit protection scope of the present invention for example just.
Embodiment 1: isomeric DBI PTCA dioxo-disulfonic acid synthetic
The condensation of step (stage) 1a. monohydroxy PTCADA and O-Phenylene Diamine
Monohydroxy PTCADA and 1.6 gram O-Phenylene Diamines the suspension in 30ml ethylene glycol of 1 gram by currently known methods (referring to J.Org.Chem, USSR, 1972, VIII, 369) preparation was heated 10 hours at 90 ℃.By filtering separation precipitation and use washing with alcohol.Obtain the compound that 1.3 grams have following structural formula:
Mass spectrum (VISION 2000, negative reflective-mode (negative reflection mode)): m/z, 551.7; Molar mass, 552.54.
Synthesizing of the isomeric DBI PTCA of step 1b. dioxo-disulphonic acid mixtures
In 50 ℃ of products (1 gram) sulfonation 2 hours in the oleum of 5ml 50% with stage 1a, then with reaction mass earlier with sulfuric acid again dilute with water to obtain 55% sulfuric acid (solution).By the filtering separation precipitation, wash with acetate again.Obtain the compound that 1.1 grams have following structural formula:
Mass spectrum (VISION 2000, negative reflective-mode): m/z, 726.2; Molar mass, 726.65.
The preparation of the single DBI PTCA dioxo of step 1c.-disulfonic acid isomers
To be dissolved in the 20ml sulfuric acid from the mixture (1 gram) of the isomers of stage 1b, and dilute with water is to obtain 65% sulfuric acid (solution).By filtering, and wash with acetate with precipitate and separate.Obtain the compound that 0.5 gram has following structural formula:
Mass spectrum (VISION 2000, negative reflective-mode): m/z, 726.5; Molar mass, 726.65; Ultimate analysis records (%): C, 59.13; 59; 48; H, 1.87; 1.90; N, 7.51; 7.38; S, 8.66; 9.07; Be C
36H
14N
4O
10S
2To C
36H
14N
4O
10S
2Analytical calculation (%): C, 59.50; H, 1.94; N, 7.71; O, 22.02; S, 8.83; IR spectrum (FSM-1201 Fourier transformation infrared spectrometer, film is on KRS-5 window (sheet)) (υ, cm
-1): 1229.0,1179.7 (sulfo groups), 1073.6,1033.2 (sulfo groups), 1670.6 (carbonyls); Electronic absorption spectroscopy (Ocean PC2000, the aqueous solution) (λ max, nm): 325,375,540.
After water was diluted to mother liquor sulfuric acid concentration and is 45%, another kind of isomer promptly was precipitated out.Still by filtering, wash with acetate then its separation.Obtain the compound that 0.4 gram has following structural formula:
Mass spectrum (VISION 2000, negative reflective-mode): m/z, 726.5; Molar mass, 726.65; Electronic absorption spectroscopy (Ocean PC2000, the aqueous solution) (λ max, nm): 325,355,375,550.
Embodiment 2: isomeric DBI PTCA dioxo-sulfone-disulfonic acid synthetic
Synthesizing of the isomeric DBI PTCA of step 2a. dioxo-sulfone-disulphonic acid mixtures
At 65 ℃, with the product of stage 1a (1 gram) sulfonation 12 hours in 65% oleum of 5ml, then with reaction mass earlier with sulfuric acid again dilute with water to obtain 45% sulfuric acid (solution).By filtering, wash with acetate again precipitate and separate.Obtain the compound that 1.4 grams have following structural formula:
Mass spectrum (VISION 2000, negative reflective-mode): m/z, 789.2; Molar mass, 788.7; Electronic absorption spectroscopy (Ocean PC2000, the aqueous solution) (λ max, nm): 325,375,550,590.
The preparation of the single DBI PTCA of step 2b. dioxo-sulfone-disulfonic acid trans-isomer(ide)
Will from the isomer mixture of stage 2a (1 gram) be dissolved in the 20ml sulfuric acid and dilute with water to obtain 65% sulfuric acid (solution).By filtering, wash with acetate again precipitate and separate.Obtain the compound that 0.5 gram has following structural formula:
Mass spectrum (VISION 2000, negative reflective-mode): m/z, 789.2; Molar mass, 788.7; Ultimate analysis records (%): C, 54.22; 54; 45; H, 1.44; 1.46; N, 7.01; 7.19; S, 12.32; 12.10; Be C
36H
14N
4O
10S
3To C
36H
14N
4O
10S
3Analytical calculation (%): C, 54.82; H, 1.53; N, 7.10; O, 24.34; S, 12.20; IR spectrum (FSM-1201 Fourier transformation infrared spectrometer, film is on KRS-5 window (sheet)) (υ, cm
-1): 1228.9,1179.4 (sulfo groups), 1074.0,1027.0 (sulfo groups), 1324.0 (sulfones), 1699.6 (carbonyls); Electronic absorption spectroscopy (Ocean PC2000, the aqueous solution) (λ max, nm): 325,375,540,600.
The preparation of the single DBI PTCA of step 2c. dioxo-sulfone-disulfonic acid cis-isomeride
After water was diluted to mother liquor sulfuric acid concentration and is 45%, another isomers was precipitated out.Still by filtering, wash with acetate then its separation.Obtain the compound that 0.4 gram has following structural formula:
Mass spectrum (VISION 2000, negative reflective-mode): m/z, 789.2; Molar mass, 788.7; Electronic absorption spectroscopy (Ocean PC2000, the aqueous solution) (λ max, nm): 325,355,375,550,580.
Embodiment 3: from the synthetic isomeric DBI PTCA dioxo of DBI PTCA disulfonic acid-
Sulfone-disulfonic acid
The condensation of step 3a. monohydroxy PTCADA and ortho-diaminobenzene sulfonic acid
Mixture in the aqueous pyridine of 30ml 70% was 90 ℃ of heating 8 hours with 1 gram monohydroxy PTCADA and 1.5 gram ortho-diaminobenzene sulfonic acid.By filtering, and wash with aqueous ethanolic solution with precipitate and separate.Obtain the 1.2 grams compound identical with following structural formula:
Mass spectrum (VISION 2000, negative reflective-mode): m/z, 711.4; Molar mass, 712.67.
Step 3b. oleum oxidation and sulfonation PTCADBI monohydroxy derivative
Heating is 8 hours in 65% oleum of 50 ℃ of mixtures with monohydroxy PTCADBI (1 gram) at 30ml.Then, with reaction mass earlier with sulfuric acid again dilute with water to obtain 55% sulfuric acid (solution).By filtering, and wash with acetate with precipitate and separate.Obtain the similar compound of product that 1.4 grams and embodiment 2a obtain, it has following structural formula:
Embodiment 4: trans-DBI PTCA dioxo-disulfonic acid synthetic
50 ℃ with trans-DBI PTCA (1 gram) sulfonation 3 hours in the oleum of 100ml 55%, then, with reaction mass earlier with sulfuric acid again dilute with water to obtain 65% sulfuric acid (solution).By filtering, and wash with acetate with precipitate and separate.Obtain 0.9 gram and have and the identical compound of embodiment 1c product structure, it is corresponding to following structural formula:
Embodiment 5: trans-DBI PTCA dioxo-sulfone-disulfonic acid synthetic
Step 5a. is trans-sulfonation of DBI PTCA dioxo-disulfonic acid
In 65 ℃ of products (1 gram) sulfonation 10 hours in the oleum of 50ml 65% with embodiment 4, then, with reaction mass earlier with sulfuric acid again dilute with water to obtain 45% sulfuric acid.By filtering, and wash with acetate with precipitate and separate.Obtain 1 gram and the identical compound of embodiment 2b product structure, it is corresponding to following structural formula:
Step 5b. is trans-sulfonation of DBI PTCA
60-55 ℃ with trans-DBI PTCA (1 gram) sulfonation 12 hours in the oleum of 100ml 65%, then, with reaction mass earlier with sulfuric acid again dilute with water to obtain 65% sulfuric acid.By filtering, and wash with acetate with precipitate and separate.Obtain the identical compound of product structure that obtains among 1.2 grams and the embodiment 5a.
Embodiment 6: cis-DBI PTCA dioxo-disulfonic acid synthetic
50-55 ℃ with cis-DBI PTCA (1 gram) sulfonation 3 hours in the oleum of 30ml 50%, then, with reaction mass earlier with sulfuric acid again dilute with water to obtain 55% sulfuric acid.By filtering, and wash with acetate with precipitate and separate.Obtain 1.2 grams and the corresponding compound of product that is obtained by embodiment 1c, its structural formula is as follows:
Embodiment 7: cis-DBI PTCA dioxo-sulfone-disulfonic acid synthetic
Step 7a. is suitable-sulfonation of DBI PTCA dioxo-disulfonic acid
In 65 ℃ of products (1 gram) sulfonation 10 hours in the oleum of 50ml 65% with embodiment 6, then, with reaction mass with sulfuric acid and dilute with water to obtain 45% sulfuric acid.By filtering, and wash with acetate with precipitate and separate.Obtain 1 gram and have the compound of following structural formula, it is corresponding to the product that obtains from embodiment 2b:
The sulfonation of step 7b cis-DBI PTCA
60-55 ℃ with cis-DBI PTCA (1 gram) sulfonation 12 hours in the oleum of 50ml 65%, then, with reaction mass with sulfuric acid and dilute with water to obtain 65% sulfuric acid.By filtering, and wash with acetate with precipitate and separate.Obtain 1.3 grams corresponding to a kind of compound in the product that from embodiment 7a, obtains.
Embodiment 8: by oxo-disulfonic acid of the synthetic isomeric PTCA DBI of dihydroxyl PTCA
Step 8a.2, the condensation of 8-dihydroxyl PTCADA and O-Phenylene Diamine
1.5 suspension that restrain dihydroxyl PTCADA and 3 gram O-Phenylene Diamines in 30ml acetate were seethed with excitement 8 hours.By filtering, and use washing with alcohol with precipitate and separate.Obtain the compound that 1.8 grams have following structural formula:
Mass spectrum (VISION 2000, negative reflective-mode): m/z, 567.4; Molar mass, 568.5; Ultimate analysis records (%): C, 75.82; 75; 91; H, 2.94; 2.65; N, 9.61; 9.49; Be C
36H
14N
4O
10S
3To C
36H
16N
4O
10Analytical calculation (%): C, 76.05; H, 2.84; N, 9.85; O, 11.6.
The sulfonation of step 8b. dihydroxyl PTCADA and O-Phenylene Diamine condensation product
In 100 ℃ of products (1 gram) sulfonation 12 hours in the oleum of 5ml 4% with step 1a, then with reaction mass with the dilution of 20ml water.By filtering, and wash with acetate with precipitate and separate.Obtain the compound that 1 gram has following structural formula:
Mass spectrum (VISION 2000, negative reflective-mode): m/z, 729.0; Molar mass, 728.6.
Step 8c. oleum oxidation dihydroxyl PTCADBI disulfonic acid
Join in the oleum of 20ml 80% and stirred 12 hours at 20 ℃ of products with step 8b (1 gram), then, it is 50% that reaction mass is diluted to sulfuric acid concentration.By filtering, and wash with acetate with precipitate and separate.Obtain the compound that 0.8 gram has following structural formula:
Mass spectrum (VISION 2000, negative reflective-mode): m/z, 758.4; Molar mass, 758.6; Ultimate analysis records (%): C, 56.62; 56; 84; H, 1.94; 1.72; N, 7.34; 7.32; S, 8.32; 8.40; Be C
36H
14N
4O
10S
2To C
36H
14N
4O
10S
2Analytical calculation (%): C, 56.99; H, 1.86; N, 7.39; O, 25.31; S, 8.45; IR spectrum (FSM-1201 Fourier transformation infrared spectrometer, film is on KRS-5 window (sheet)) (υ, cm
-1): 1230.4,1180.5 (sulfo groups), 1074.0,1030.5 (sulfo groups), 1700.9 (carbonyls); Electronic absorption spectroscopy (Ocean PC2000, the aqueous solution) (λ max, nm): 560.
Step 8d.1, the condensation of 12-dihydroxyl PTCADA and O-Phenylene Diamine
Make 1.5 grams 1,12-dihydroxyl PTCADA and the suspension boiling of 3 gram O-Phenylene Diamines in 30ml acetate 8 hours.By filtering, and wash with acetate with precipitate and separate.Obtain the compound that 1.8 grams have following structural formula:
Mass spectrum (VISION 2000, negative reflective-mode): m/z, 567.4; Molar mass, 568.5.
Step 8e. oleum oxidation dihydroxyl PTCADBI disulfonic acid
Stirred 12 hours in the oleum of 10ml 80% at 20 ℃ of products with step 8d (1 gram), then, it is 50% that reaction mass is diluted to sulfuric acid concentration.By filtering, and wash with acetate with precipitate and separate.Obtain the compound that 0.8 gram has following structural formula:
Mass spectrum (VISION 2000, negative reflective-mode): m/z, 758.4; Molar mass, 758.6; Ultimate analysis records (%): C, 56.54; 56; 77; H, 1.80; 1.74; N, 7.25; 7.30; S, 8.24; 8.36 be C
36H
14N
4O
10S
2To C
36H
14N
4O
12S
2Analytical calculation (%): C, 56.99; H, 1.86; N, 7.39; O, 25.31; S, 8.45; IR spectrum (FSM-1201 Fourier transformation infrared spectrometer, film is on KRS-5 window (sheet)) (υ, cm
-1): 1230.4,1180.5 (sulfo groups), 1074.0,1030.5 (sulfo groups), 1700.9 (carbonyls); Electronic absorption spectroscopy (Ocean PC2000, the aqueous solution) (λ max, nm): 560.
The sulfonation of step 8j. dihydroxyl PTCADA and O-Phenylene Diamine condensation product
To be diluted to 50% oleum at the reaction mass of the step 8e in 80% oleum, and 50 ℃ of heating 10 hours, then with the dilution of 200ml water.By filtering, and wash with acetate with precipitate and separate.Obtain the compound that 1.4 grams have following structural formula:
Mass spectrum (VISION 2000, negative reflective-mode): m/z, 819.8; Molar mass, 818.7; Ultimate analysis records (%): C, 52.77; 52; 80; H, 1.04; 1.26; N, 6.51; 6.49; S, 11.62; 11.40 be C
36H
14N
4O
10S
3To C
36H
14N
4O
10S
3Analytical calculation (%): C, 52.81; H, 1.23; N, 6.84; O, 27.36; S, 11.75; IR spectrum (FSM-1201 Fourier transformation infrared spectrometer, film is on KRS-5 window (sheet)) (υ, cm
-1): 1230.4,1180.5 (sulfo groups), 1074.0,1030.5 (sulfo groups), 1330.0 (sulfones), 1700.6 (carbonyls); Electronic absorption spectroscopy (Ocean PC2000, the aqueous solution) (λ max, nm): 560,675.
Embodiment 9: by the synthetic PTCA DBI furan derivatives of sulfonation PTCA DBI
Synthesizing of step 9a. cis-PTCA DBI furans disulfonic acid
Joined from the product of step 8d (5.0 gram) in the oleum of 35ml 10% and 60 ℃ of sulfonation 5 hours in batches.In order with the reaction mass dilution, elder generation is diluted to monohydrate with 92% aqueous sulfuric acid then, and being diluted with water to sulfuric acid concentration again is 65%.By the filtering separation precipitation, in acetate, suspend three times, dry then, obtain the compound that 6.5 grams have following structural formula:
Mass spectrum (VISION 2000, negative reflective-mode): m/z, 709.4; Molar mass, 710.65; Ultimate analysis records: C, 60.66; 60.10; H, 2.09; 2.27; N, 7.39; 7.32; S, 9.51; 9.41 be C
36H
14N
4O
9S
2To C
36H
14N
4O
9S
2Analytical calculation (%): C, 60.84; H, 1.99; N, 7.88; O, 20.26; S, 9.02; Electronic absorption spectroscopy (Ocean PC2000, the aqueous solution) (λ max, nm): 325,355,375,600.
Step 9b. oleum sulfonation cis-PTCA DBI furans disulfonic acid
Join in the oleum of 30ml 50% at 50 ℃ of products with step 9a (1 gram), and stirred 8 hours under this temperature, then, it is 65% that reaction mass is diluted to sulfuric acid concentration.By filtering, and wash with acetate with precipitate and separate.Obtain the compound that 0.4 gram has following structural formula:
It is 40% that water is diluted to sulfuric acid concentration with mother liquor.By filtering, and wash with acetate with precipitate and separate.Obtain the compound that 0.4 gram has following structural formula.
Mass spectrum (VISION 2000, negative reflective-mode): m/z, 772.0740.6; Molar mass, 772.7; Ultimate analysis records (%): C, 55.56; 55.5958.72; 58,10; H, 1.49; 1.431.54; 1.56; N, 6.98; 6.83; 7.31; 7.39; S, 13.00,13.16,8.33; 8.46 be C
36H
14N
4O
10S
3To C
36H
14N
4O
10S
3Analytical calculation (%): C, 55.96 58.38; H, 1.571.63; N, 7.257.5; O, 22.78 23.76; S, 12.4 58.66; IR spectrum (FSM-1201 Fourier transformation infrared spectrometer, film is on KRS-5 window (sheet)) (υ, cm
-1): 1230.0,1182.2 (sulfo groups), 1072.0,1030.5 (sulfo groups), 1324.0 (sulfones), 1700.0 (carbonyls); Electronic absorption spectroscopy (OceanPC2000, the aqueous solution) (λ max, nm): to first part is 325,375,540 and be 325,355,375,535 to second section.
Can be synthetic corresponding to structure I to other derivative of VII by similar step, or the sulfonation by PTCA DBI isomer or mixture, or the condensation sulfonation subsequently by corresponding PTCA derivative, or the condensation by PTCA derivative and ortho-diaminobenzene sulfonic acid.
Embodiment 10: liquid-crystal composition that obtains and PTCA DBI dioxo disulfonic acid thin
Film, and measure the optical characteristics of this film
Prepare 10 gram PTCA DBI dioxo disulfonic acid (embodiment 1, the solution of step c) in the 79.9ml deionized water, and with the ammonia neutralization, to obtain the liquid crystal solution of 100 grams 10% by stirring down at 20 ℃.With the linear velocity of No. 3 mayers (Meyer) rod this solution is coated on the quartz glass plate with 25mm/s.This process is to be that 20 ℃ and relative humidity are to carry out under 65% the condition in temperature, afterwards dry this film under identical condition.
This film is to characterize by the transmitted spectrum that the Cary-500 spectrophotometer records between wavelength region 190 to 800nm, and employed light beam is polarized along the direction (Tpar) of film coating with the perpendicular direction (Tper) of solution coating direction.At the wavelength X=540nm place of corresponding maximum absorption, dichroic ratio Kd=log (Tper)/log (Tpar) equals 32; In the film transmissivity is 35% o'clock, and contrast gradient (CR) is 170.
Embodiment 11: liquid-crystal composition that obtains and PTCA DBI dioxo-and four oxos-
The film of the mixture of disulfo derivative, and measure the optical characteristics of this film
Prepare 10 grams and comprise dioxo-disulfo derivative (embodiment 1 by stirring down at 20 ℃, mass ratio is 30%), dioxo-sulfone-disulfo derivative (embodiment 2b, mass ratio is 30%), four oxos-disulfo derivative (embodiment 8e, mass ratio is 20%, embodiment 8j, mass ratio is 20%) the solution of mixture in the 79.9ml deionized water of PTCA DBI sulfonic derivatives, and neutralize with ammonia.In this solution, add the solution of 0.1 gram sulfonol (a kind of anion surfactant) in 10ml water, and this mixture is fully stirred to obtain the liquid crystal solution of 100 grams 10%.With the linear velocity of No. 3 mayers (Meyer) rod this solution is coated on the quartz glass plate with 25mm/s.This process is to be that 20 ℃ and relative humidity are to carry out under 65% the condition in temperature, afterwards dry this film under identical condition.
This film is to characterize by the transmitted spectrum that the Cary-500 spectrophotometer records in wavelength region 190 to 800nm, and employed light beam is polarized along the direction (Tpar) of film coating with the perpendicular direction (Tper) of solution coating direction.At the wavelength X=540nm place of corresponding maximum absorption, dichroic ratio Kd=log (Tper)/log (Tpar) equals 28; In the film transmissivity is 36% o'clock, and contrast gradient (CR) is 150.
Embodiment 12: the liquid-crystal composition that obtains and PTCA DBI dioxo-disulfo spread out
The film of the mixture of biology and dioxo-sulfone-disulfo derivative and indanthrone derivative,
And measure the optical characteristics of this film
Dioxo-(embodiment 1 for the disulfo derivative to prepare 10 gram PTCA DBI by stirring under 20 ℃, mass ratio is 20%), dioxo-sulfone-disulfo derivative (embodiment 2b, mass ratio is 20%) with the solution of mixture in the 79.9ml deionized water of indanthrone trisulfonic acid (mass ratio is 60 quality %), and neutralize with ammonia.In this solution, add the solution of 0.1 gram sulfonol in 10ml water, this mixture is fully stirred to obtain the liquid crystal solution of 100 grams 10%.With the linear velocity of No. 3 mayers (Meyer) rod this solution is coated on the quartz glass plate with 25mm/s.This process is to be that 20 ℃ and relative humidity are to carry out under 65% the condition in temperature, afterwards dry this film under identical condition.
This film is to characterize by the transmitted spectrum that the Cary-500 spectrophotometer records in wavelength region 190 to 800nm, and employed light beam is polarized along the direction (Tpar) of film coating with the perpendicular direction (Tper) of solution coating direction.At the wavelength X=650nm place of corresponding maximum absorption, dichroic ratio Kd=log (Tper)/log (Tpar) equals 35; In the film transmissivity is 36% o'clock, and contrast gradient (CR) is 250.
Embodiment 13: the liquid-crystal composition that obtains and PTCA DBI dioxo-sulfone-disulfo
The film of the mixture of derivative and indanthrone and naphthalene tetracarboxylic acid derivative, and measure this film
Optical characteristics
(it comprises PTCA DBI dioxo-sulfone-disulfo derivative (embodiment 2b to prepare 10 gram mixtures by stirring under 20 ℃, mass ratio is 40%), indanthrone trisulfonic acid (mass ratio is 40%) and NTCA DBI disulfonic acid (mass ratio is 20%)) solution in the 79.9ml deionized water, and neutralize with ammonia.In this solution, add the solution of 0.1 gram sulfonol in 10ml water, this mixture is fully stirred to obtain the liquid crystal solution of 100 grams 10%.With the linear velocity of No. 3 mayers (Meyer) rod this solution is coated on the quartz glass plate with 25mm/s.This step is to be that 20 ℃ and relative humidity are to carry out under 65% the condition in temperature, afterwards dry this film under identical condition.
This film is to characterize by the transmitted spectrum that the Cary-500 spectrophotometer records in wavelength region 190 to 800nm, and employed light beam is polarized along the direction (Tpar) of film coating with the perpendicular direction (Tper) of solution coating direction.At the wavelength X=650nm place of corresponding maximum absorption, dichroic ratio Kd=log (Tper)/log (Tpar) equals 34; In the film transmissivity is 35% o'clock, and contrast gradient (CR) is 200.
All compounds with structural formula I to VII feature have all provided stable lyotropic liquid crystal systems, and this lyotropic liquid crystal systems can be used in the optical anisotropic film that obtains to have height performance characteristic and height reproducibility.Above embodiment is exemplary, and should not be interpreted as is limiting the scope of the invention.
Claims (15)
1. a sulfonation oxygen is for perylene tetracarboxylic acid bisbenzimidazole compound, and it contains side direction and connects the oxygen base that connects perylene nuclear, and wherein this oxygen base is examined the combination that segment forms the paraquinoid system with this perylene,
Wherein said compound is following structure I to one of IV or V to VII:
A wherein
1And A
2Independently for having the identical or different segment of following structural formula
X wherein
1, X
3, X
4, X
5, X
6, X
7And X
8Be independently be selected from-H ,-OH and-SO
3The substituting group of H,
Wherein Z be selected from-O-,-SO
2-and-O-SO
2-divalent abutment,
Wherein each Y be independently be selected from-H ,-Cl ,-F ,-Br ,-OH ,-NO
2And NH
2Substituting group,
Wherein n is selected from 0,1 and 2 integer, and A
1And A
2At least comprise a sulfo group,
Wherein p is selected from 0,1,2,3 and 4 integer,
Wherein each M is counter ion, is selected from H
+, NH
4 +, K
+, Li
+, Na
+, Cs
+, Ca
++, Sr
++, Mg
++, Ba
++, Co
++, Mn
++, Zn
++, Cu
+++, Pb
++, Fe
++, Ni
++, Al
+++, Ce
+++, La
+++In different positively charged ions, and when n＞1, each M can be identical or different, and
Wherein j be in this molecule with SO
3 -The number of the counter ion that combine, and if these counter ion it can be a mark when total by several molecule.
2. lyotropic liquid crystal systems, it comprise at least a at the sulfonation oxygen described in the aforementioned claim 1 for perylene tetracarboxylic acid bisbenzimidazole compound.
3. lyotropic liquid crystal systems according to claim 2, wherein this system is a water-based.
4. lyotropic liquid crystal systems according to claim 2, wherein this system comprises water and organic solvent that can be miscible with water.
5. according to each described lyotropic liquid crystal systems in the claim 2 to 4, the range of the wherein said sulfonation Yang Dai perylene tetracarboxylic acid mass content of bisbenzimidazole compound in this liquid crystal system between 3 to 40%.
6. according to each described lyotropic liquid crystal systems in the claim 2 to 4, further comprise reaching 5% tensio-active agent in mass.
7. according to each described lyotropic liquid crystal systems in the claim 2 to 4, further comprise reaching 5% softening agent in mass.
8. according to each described lyotropic liquid crystal systems in the claim 2 to 4,
Wherein the combination of compounds of the compound of structural formula I or V or I and V is to be that 0 to 99% concentration range exists in mass,
Wherein the combination of compounds of the compound of structural formula II or VI or II and VI is to be that 0 to 99% concentration range exists in mass,
Wherein the combination of compounds of the compound of structural formula IV or VII or IV and VII is that 0 to 50% concentration range exists in mass, and
Wherein the compound of structural formula II I is that 0 to 99% concentration range exists in mass.
9. lyotropic liquid crystal systems according to claim 8, wherein
Wherein the combination of compounds of the compound of structural formula I or V or I and V is that 0 to 70% concentration range exists in mass;
Wherein the combination of compounds of the compound of structural formula II or VI or II and VI is to be that 0 to 50% concentration range exists in mass;
Wherein the combination of compounds of the compound of structural formula IV or VII or IV and VII is that 0 to 20% concentration range exists in mass;
Wherein the compound of structural formula II I is that 0 to 50% concentration range exists in mass.
10. according to the described lyotropic liquid crystal systems of arbitrary claim in the claim 2 to 4, further comprise at least a other sulfonation Yang Dai perylene tetracarboxylic acid bisbenzimidazole compound that contains arbitrary structure among the following structure VIII to X:
A wherein
1And A
2Independently for having the identical or different segment of following structural formula
X wherein
1, X
2, X
3, X
4, X
5, X
6, X
7And X
8Be independently be selected from-H ,-OH and-SO
3The substituting group of H, these substituting groups at least one be not-H and substituent X
2, X
3And/or X
6, X
7Can interact to form abutment Z
1And/or Z
2,
Z wherein
1And/or Z
2Be be selected from-O-,-SO
2-and-SO
2The abutment of-O-,
Wherein each Y be independently be selected from-H ,-Cl ,-F ,-Br ,-OH ,-NO
2With-NH
2Substituting group,
Wherein n is selected from 0,1 and 2 integer, and A
1And A
2At least comprise a sulfo group,
Wherein p is selected from 0,1,2,3 and 4 integer,
Wherein each M is counter ion, is selected from H
+, NH
4 +, K
+, Li
+, Na
+, Cs
+, Ca
++, Sr
++, Mg
++, Ba
++, Co
++, Mn
++, Zn
++, Cu
+++, Pb
++, Fe
++, Ni
++, Al
+++, Ce
+++, La
+++In different positively charged ions, and when n＞1, each M can be identical or different, and
Wherein j be in this molecule with SO
3 -The number of the counter ion that combine is if it can be a mark to these counter ion when total by several molecule.
11. an optical anisotropic film, wherein said film are by being applied to each described lyotropic liquid crystal systems in the aforementioned claim 2 to 10 on the substrate, subsequently by orientation effect and dry formation.
12. optical anisotropic film according to claim 11, wherein said film are partially crystallines at least.
13. optical anisotropic film according to claim 12, wherein the spacing along one of optical axis is 3.1 in described crystallization
To 3.7
Scope.
14. according to each described optical anisotropic film in the claim 11 to 13, wherein said film is a polarising.
15. according to each described optical anisotropic film in the claim 11 to 13, wherein said film is a phase difference film.
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| KR20100132028A (en) * | 2008-03-07 | 2010-12-16 | 닛토덴코 가부시키가이샤 | Lyotropic chromophoric compounds, liquid crystal systems and optically anisotropic films |
| JP6367828B2 (en) * | 2013-01-11 | 2018-08-01 | フィリップス ライティング ホールディング ビー ヴィ | Horticulture lighting device and method for stimulating plant growth and plant biorhythm |
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|---|---|---|---|---|
| DE3145711A1 (en) * | 1981-11-19 | 1983-05-26 | Basf Ag, 6700 Ludwigshafen | Insoluble compounds as colorants for liquid-crystal mixtures |
| US5739296A (en) * | 1993-05-21 | 1998-04-14 | Russian Technology Group | Method and materials for thermostable and lightfast dichroic light polarizers |
| EP1158320A2 (en) * | 1994-11-18 | 2001-11-28 | Optiva, Inc. | Dichroic light polarizers |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3145711A1 (en) * | 1981-11-19 | 1983-05-26 | Basf Ag, 6700 Ludwigshafen | Insoluble compounds as colorants for liquid-crystal mixtures |
| US5739296A (en) * | 1993-05-21 | 1998-04-14 | Russian Technology Group | Method and materials for thermostable and lightfast dichroic light polarizers |
| EP1158320A2 (en) * | 1994-11-18 | 2001-11-28 | Optiva, Inc. | Dichroic light polarizers |
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| CN102816571A (en) * | 2011-06-10 | 2012-12-12 | 日东电工株式会社 | Coating liquid, optical anisotropic film and image display device |
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