TWI304089B - Anisotropic films based on 1,8-naphthoylene-1',2'-benzimidazole sulfonates and lyotropic liquid crystal systems and methods for making - Google Patents

Description

1304089 (1) 发明 发明 发明 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 俄国 俄国 俄国 俄国 俄国 俄国 俄国 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 . TECHNICAL FIELD OF THE INVENTION The present invention relates to the field of organic chemistry, and more particularly to the synthesis of sulfonic acid-based derivatives (sulfonates), and the equivalent of jg as a substrate. Optically anisotropic film. [Prior Art] The advancement of modern technology is based on the creation of new materials and the development of reflective optical components based on these materials. In particular, the components required in the design of modern displays are optically anisotropic films with the best combination of properties for a given application. There are many types of polymeric materials that can be used in the manufacture of optically anisotropic films. The anisotropic optical properties of such films are derived from uniaxial stretching and modification with organic or inorganic (iodine) compounds. Polyvinyl alcohol (PVA) is commonly used as a base polymer, as in Liquid Grystalsi Applications and Use, B. Bahadur (ed), World Scientific? Singapore (l 9 90), Vol. l, p. 101-103. Said. However, the low thermal stability of PVA-based films limits their applicability. For this reason, there is a need for a new method of synthesizing an optically anisotropic film having improved properties. 5 - 1304089 · (2) Organic dichroic dyes can be used to synthesize opticals exhibiting excellent optical properties and operability. Anisotropic film. A film having such a compound as a substrate can be obtained by applying an aqueous solution of a liquid crystalline dye to the surface of a substrate, followed by evaporating a solvent such as water. The anisotropic properties are permeable to the pre-mechanical alignment of the surface of the substrate, as described, for example, in U.S. Patent No. 2,5,353,196, or by the use of an additional orientation, such as mechanical, electromagnetic, or the like. When the film material is in a liquid crystal state, it is applied thereto, and the film is imparted. This practice is explained in more detail in PCT Patent Publication No. WO 94/2 80 73. Although the liquid crystal properties of the dye solution have been known for a certain period of time, the thorough investigation of such systems has only recently begun. New research efforts have been motivated by the ability of some of these dyes to form M-color n n (C h r 〇 m ο n i c ) liquid crystal systems. The uniqueness of the chromonic system is the dye molecule, which is integrated into a supramolecular complex with a C〇lumil form, which is a structural element of the mesophase. The highly ordered structure of the dye molecules in such columns contributes to the use of such mesogens relative to the formation of strong dichroic targeting films. Various color copper systems, including organic dyes, molecular structures, phase diagrams, and molecular aggregation mechanisms have been previously reviewed (ie, Lydon, J.

Chromonies, in · Handbook of Liquid Crystals (Wiley - VCH, Wein-hein, 1 998), Vol. 2B, pp. 98 1 - 1 007). A particular feature of dye molecules that form a color ketone mesophase is that it contains a surrounding group that promotes the dyeing of such dyes. The main structural unit of all chromonic mesogenic phases is a stacked molecule of one column. The chromonic mesogenic phase of organic dyes is soluble -6 - 1304089. (3) Those who have a special structure and have the characteristics of specific phase diagrams and optical characteristics can be used to form liquid-directed liquid crystals (LLC). The system's dichroic dyes can give films with a high degree of optical anisotropy. These films exhibit the properties of an E-type polarizer, which is related to the optical absorption specificity of the chromone-based supramolecular complex. These membranes are represented in the form of a hysteresis (r e t a r d e r ) (phase shifting device) in the absorptive spectral region. The phase shifting properties of such anisotropic films are related to their eccentric birefringence, which is the refractive index measured along the direction in which the liquid crystal solution is applied to the substrate and the refractive index measured in the vertical direction. The difference between the two. These properties of the LLC system are the result of increasing interest in such materials. New methods for obtaining films based on such organic dyes are under development. Recent developments include optimization of membrane application conditions and identification and identification of new LLC compositions. In particular, the novel LLC compound used in the synthesis of the optically anisotropic film can be obtained by introducing a regulator, a stabilizer, a surfactant, and other additives into the known composition to improve the properties of the film. A more detailed discussion of these methods is contained in the Russian patent RU 2047643 and the published PCT patent application WO 9 9 / 3 1 5 3 5 . In recent years, there has been an increase in demand for optically anisotropic films having a characteristic of selectivity for different wavelengths. Because of the need for a film that has a maximum absorption of "variation" from infrared (IR) to ultraviolet (UV) over a broad spectral range, it is desirable to be able to form LLC phases and films that possess desirable properties. A wide variety of compounds. In this category, increased attention is focused on liquid crystal displays and remote communication lines - 7·1304089. (4) Birefringent film (hysteresis) materials. Other backgrounds for these topics Information can be seen in Yeh, P. Optical Waves in Layered Media, (John Wiley & Sons, New York, 1 998); and Gu, C. Optics in Liquid Crystal Displays (John Wiley & Sons, New York, 1 9 99) An ultrathin birefringent film can be obtained by forming an optically anisotropic layer through a liquid crystal system using an organic dye as a substrate. This method is described in P. L azarev and M. Paukshto, ''Thin Crystal Film Retarder s "( 2 000 ) ' Proceeding of the 7th International Display Workshop on Materials and Components (Kobe, Japan, November 29 December 1), pp. 1159-1160, which was dyed with Vat Red 14 Disulfonic acid ester is an optically anisotropic thin crystal of a thin sediment. The film comprises a mixture of cis- and trans-isomers of nabendazole naphthalenecarboxylate having the following structural formula

Anti-isomer cis-isomer

A B uses this technique to control the direction of the crystal axis in the film during application and crystallization on the substrate. The resulting film having a size of 5 x 7 · 5 cm on a glass plate has a uniform composition and a high crystal sequence and has a dichroic ratio Kd equal to 28 characteristics. These films can be used in polarizers and hysteresis. As shown in Figure 1, the oriented 1304089 (5) film with Vat Red 14 dye as the substrate exhibits a high degree of optical anisotropy, as shown by the large difference in refractive index between ordinary and extraordinary rays: n. One ne = 0.6 - 〇.8 (1 = 5 5 0 - 7 0 Onm ). The use of such a membrane as a retarder is limited to the green spectral range in which the dye does not absorb light. A thin birefringent film that transmits light in the visible light range can also be made of chromoglycate disodium salt (DSCG), which is a compound having the following structural formula:

C The oriented film of this compound has a small degree of optical anisotropy. The refractive index difference 値 is about 0.1 - 0.13. However, since the thickness of the DSCG layer can vary within a wide range of limits, a satisfactory phase shift can be achieved even with such a relatively low defect. The main disadvantage of the D S C G films is their temporal instability, which can be manifested by the gradual recrystallization and the reduction in the degree of optical anisotropy. Various compositions based on water-soluble organic dyes can also be used to obtain optically anisotropic films according to the techniques described above in PCT Publication Nos. WO 94/2 8073 and WO 9 9/31535, however, common to such materials The disadvantage is high absorbance in the visible spectrum. This property significantly limits the synthesis of these dyes for transparent birefringent films. SUMMARY OF THE INVENTION In one embodiment of the present invention, 1 -9 - 1304089 . 8 - anthranilyl- 1 ', 2'-benzimidazolylsulfonic acid derivative having the general structural formula D is proposed.

In the compound, 11 is an integer in the range of 1 to 4, m is an integer in the range of 0 to 4; z is an integer in the range of 0 to 6, and integers of m, η and z satisfy the equation rn + z + nS 1 〇. X and γ are individually selected from the group consisting of the lower jaw U and are: CHs, C2H5, 〇CH3, 〇C2H5, Cl, Br, 〇H and NH2. M is a counter ion and j is the number of different counter ions (Μ) in a single molecule of the 1,8-naphthoquinone-fluorene, 2·-benzimidazolesulfonate derivative. In another embodiment of the present invention, there is proposed a 1,8-naphthoquinone-indole, 2'-benzimidazolylsulfonic acid derivative, wherein the structural formula is selected from the group consisting of structures I-VIII. Wherein X and γ are individually selected from the group consisting of CH3, C2H5, OCHh, CM, Br, 〇H or Guan 2:

An integer within the circumference, where m is an integer in the range of 0 to 3, and z is an integer in the range of 0 to 4, where m is 璧 in the range of 1fe〇 to 4 and z is in the range of 0 to 4. Integer 1304089 (7)

Wherein m is an integer in the range of 0 to 2, and z is an integer in the range of 0 to 4

And z is an integer in the range of 0 to 4

Wherein m is an integer in the range of 0 to 3, and z is an integer in the range of 0 to 4, wherein m is an integer in the range of 0 to 3, and z is an integer in the range of 0 to 4

Wherein m is an integer in the range of 0 to 2, and z is an integer in the range of 0 to 4

Wherein m is an integer in the range of 0 to 2, and z is an integer in the range of 0 to 4

In another embodiment of the present invention, a liquid crystal liquid crystal system is proposed, wherein the LLC is derived from the 1,8-naphthoquinone- 1 ', 2'-benzimidazole sulfonic acid group of the foregoing specific examples. Formed by matter. In still another embodiment of the present invention, an optically anisotropic film is proposed. The film comprises an additional 1,8-naphthoquinone-fluorene, 2f-benzimidazolylsulfonic acid derivative according to the foregoing specific examples. In another embodiment of the invention, a method of forming an optically anisotropic film is provided. In this method, a liquid crystal system according to one of the specific examples described herein is deposited on a substrate. Apply a certain force and dry the film -11 - 1304089 (8). [Embodiment]

DETAILED DESCRIPTION OF THE INVENTION A The present invention proposes novel chemical compounds belonging to the class of 1,8-naphthoquinone--1,2,monobenzimidazole sulfonic acid derivatives (sulfonates) and their Synthetic methods. These compounds are capable of forming a stable LLC phase, and they have a potential potential as a material for forming an optically anisotropic, at least partially crystalline film. The present invention aims to increase the electromagnetic spectrum. A class of compounds that do not absorb or only weakly absorb light in the visible light range. The compounds of the present invention are capable of forming stable LLC phases with increased stability. These materials can be used to obtain optically anisotropic, at least partially crystalline films. It possesses high optical properties _ and it avoids the disadvantages of previously obtained films. In one embodiment of the invention, a weakly absorptive (micro-dark) film is proposed which can be used as a polarizer and phase shift (hysteresis) In addition, the synthesis method of the compounds and the preparation method of the film are also disclosed. Some of the aryl-benzimidazole-based compounds, that is, 1,8-naphthoquinone-1, 2, benzene. Imidazole , having a 7-electron conjugated system, the formation of which is different from that of naphthalene tetracarboxylic acid or tetracarboxylic acid benzimidazole. Therefore, the present invention, 1,8-naphthoquinone- 1', 2 · Benzimidazoles do not absorb light in the UV and near-visible light-spectral regions. In particular, unsubstituted anthracene, 8-exetylene-mercapto-1, -' 2'-benzimidazole exhibits at λ = A maximum absorption of 80 nm. Another embodiment of the present invention provides for the synthesis of novel organic compounds capable of forming an LLC phase having increased stability at a wide concentration, temperature -12 - 1304089 (9), and pH 値 range. The method can simplify the film formation process, facilitate the application of standard equipment for the layers, and aid in the manufacture of films having reproducible parameters. In yet another aspect of the invention, novel organic compounds are proposed. The compounds form a solution having the characteristics of an optimal hydrophilic-hydrophobic balance which can advantageously affect the size and shape of the supramolecular complexes formed in such systems, as well as molecular ordering procedures in such complexes. In addition to this feature In addition to the stability of the LLC phase with these compounds as the substrate, it also provides the necessary solubility of the compound under consideration. This in turn improves the reproducibility of the membrane parameters and simplifies the manufacturing process because of the choice The requirements for maintaining the optimum technical conditions at each stage of production have been reduced. The optical properties of films based on such compounds are further enhanced by the 1,8-naphthoquinone-based group: The 2'-benzimidazolylsulfonic acid derivative molecules have the following characteristics: their plane and electronic transition dipole moments (in the planes) have an increased uniformity with respect to the direction of the external orientation factor. The 1,8-naphthoquinone-indenyl, 2'-benzimidazolesulfonic acid-derivative-the water-soluble compound of the present invention is novel with respect to the previously disclosed material for forming an anisotropic film. Improvements. The compounds according to the invention disclosed can generally be described by the following structural formula D: 1304089 (10)

Wherein h is an integer in the range of 1 to 4, m is an integer in the range from 〇 to 4; ζ is an integer in the range of 0 to 6, and m + z + nq〇; X and Υ are individually selected From among the following groups: CH3, C2H5, OCH3, 〇C2H5, Cl, Br, 〇H or NH2; Μ is a counterion; and j is the number of different counterions in a single molecule, where When the counter ion is shared by several molecules (for η > 1, it can contain different counter ions), it can be a fraction. The compounds of Formula D include a wide variety of structures which may vary in number and position, for example, of sulfonic acid groups and other substituents. The following structures I - VIII are all examples of the invention, 2'-benzimidazole sulfonate. These examples are not intended to limit the scope of any aspect of the invention by way of an exemplary more specific example of the formula D 1,8 - —naphthylmethyl.

Y2

LIJ where m is an integer in the range of 〇 to 3, and z is an integer in the range of 0 to 4, where m is an integer in the range of 〇 to 4, and z is a number in the range of 0 to 4 - 14304 (11)

And ζ is an integer in the range of 0 to 4, where m is an integer in the range of 0 to 2, and ζ is an integer in the range of 0 to 4.

Where m is an integer in the range 0 to 3, and ζ is an integer in the range of 0 to 4

Where m is an integer in the range 0 to 3, and ζ is an integer in the range of 0 to 4

Where m is an integer in the range 0 to 2, and ζ is an integer in the range of 0 to 4

Wherein m is an integer in the range of 0 to 2, and ζ is an integer in the range of 0 to 4. For structures I - VIII, X and Y are individually selected from the group consisting of: CH3, C2H5 , 〇CH3, 〇C2H5, (:1, Br, 〇H or NH2; Μ is a counter ion; and" is the number of counter ions contained in the dye molecule, which may be when the anti-ion is shared by several molecules Fraction (when the number of sulfonic acid groups is greater than 1 (n> 1 ), the different counterionic compounds I-VIII and other compounds of the invention may be formed to form a stable LLC phase either individually or in combination with other materials. Wherein the other substance comprises other compounds of the invention, other dichroic dyes, and various organic compounds which are not -15-1304089. (12) color (or weakly absorbing light in the visible range). After solvent removal, such LLC The phase may form an anisotropic, at least partially crystalline film having high optical properties. In structures I and II, the counterion ruthenium comprises one or more cations selected from the group consisting of Η+, ΝΗ4+, Κ+, , Na+, Cs+, Ca2+, Sr2+, Mg2+, Ba2+, Co2+, Mn2+, zn2+, Cu2+, Pb2+, Fe2+, Ni2+, Al3+, La3+, etc., and combinations of such cations. The present invention is a naphthylbenzimidazole sulfonic acid derivative in an aqueous solution. The range (around 380 nm) exhibits maximum optical absorption. The introduction of substituents such as ethyl, methyl, chlorine, and bromine does not significantly shift the absorption band, while the introduction of amine groups and hydroxyl groups results in absorption bands. Widening and changing the characteristics of the spectrum. By variation, the number of sulfonic acid groups contained in the molecule of 1,8-naphthoquinone-1,1 -benzimidazole is the number of substituents and 'traits, Controlling the hydrophilic-hydrophobic balance of the aggregates formed in the liquid crystal solution and changing the viscosity of the solution. However, the desirable aspects of the present invention can also be achieved by other combinations of the foregoing parameters and substituents. The chemical compound of the structural formula disclosed herein, the liquid crystalline liquid crystal system of the substrate of such a compound, and the related optical anisotropic film are obtained. * All of the foregoing 1,8-extension The indole-benzimidazole acid-expanding derivative can form a stable LLC phase. In the present invention, 8-arylene naphthyl-methyl-1,2'-benzimidazolesulfonic acid-derived The materials are preferably used for the production of optically isotropic films or anisotropic films. The 1,8-naphthomethyl-1,2'-benzimidazolylsulfonic acid derivative of the present invention can also be advantageously used.制备-16- 1304089 (13) Manufacture at least a portion of the crystalline film. The 1,8-naphthoquinone-1,2-benzimidazolylsulfonic acid derivative described herein also has a polarizing film and/or The application of birefringent films. The 1,8-naphthoquinone-11,2'-benzimidazolylsulfonic acid derivative of the present invention enters an optically isotropic or anisotropic, polarizing and/or birefringent film. The optically isotropic or anisotropic film of the present invention comprises at least two compounds having at least one of Formulas I-VIII and containing at least two different substituents. In another embodiment, the invention particularly provides an aqueous liquid crystal system (sometimes referred to as a water-based ink composition) comprising individual Formulas D of the above Formula D or, more particularly, according to any of Structural Formulas I - V111 Invention 1,8 - anthrapenyl- 1 ',2'-benzimidazolylsulfonic acid derivative or a mixture of such compounds. In another embodiment, the liquid crystal system of the present invention is based on a mixture of water and an organic solvent which is miscible with water in any ratio or which is characterized by limited miscibility with water. In this specific example, the 1,8-naphthoquinone-indenyl, 2-benzimidazolesulfonic acid-based derivative, individually or in a mixture, has a concentration in the liquid crystal system of about 3 Up to 30% by mass. Alternatively, the concentration is in the range of from about 7 to 15% by mass. The liquid crystal system of this embodiment further includes up to about 5% by mass of a surfactant and/or a plasticizer. In this liquid crystal system, the concentration of 1,8-naphthoquinone-oxime, 2,benzimidazolesulfonic acid derivative can be within the following range, depending on the desired properties: • has structure I and Π Monosulfonate derivative, mass concentration -17-1304089 (14) in the range of about 〇 to 99% by mass, or in the concentration range of about 50 to 99% by mass; • double with structure III and IV a sulfonic acid derivative having a mass concentration in the range of from about 0 to 99% by mass, or in a concentration range of from about 50 to 99% by mass; • a trisulfonate derivative having the structures VI and V11, The mass concentration is in the range of about 0 to 30% by mass, or in the concentration range of about 10 to 20% by mass; • The tetrasulfonate derivative having the structure V 111 has a mass concentration of about 0 to 20 mass. Within the range of %, or within a concentration range of about 5 to 10% by mass. The liquid crystal system may further comprise at least one water-soluble organic dye or a colorless organic compound capable of participating in the formation of the L L C phase. Alternatively, the liquid crystal system may further comprise at least two compounds constituting the formula I-V 111 and/or at least two compounds having at least one I - V III structure having at least two substituents. In another embodiment of the present invention, there is provided an optically isotropic film comprising an individual 1,8-naphthoquinone- 1', 2^-benzimidazolesulfonic acid derivative or a compound thereof mixture. Such an optically anisotropic film may further comprise a different organic dye or a colorless compound. Exemplary organic dyes and colorless compounds capable of forming a mixed liquid crystal system together with 1,8-naphthoquinone-1,2-benzimidazolesulfonic acid-based derivatives include, but are not limited to, chromoglycate disodium salt: 1304089 · (15)

NaOOC G

0 COONa. Phenonthrophenazine sulfonate derivative: s〇3h

Q naphthalene tetracarboxylic acid dibenzimidazole sulfonic acid derivative: (S〇3H)i.4

Terpenic acid dibenzimidazole sulfonic acid derivative:

Indanthrone sulfonic acid derivative

A wide variety of these compounds are available. The choice of a particular additive for a given LLC system can be determined by the skilled artisan based on the teachings herein and the desirable optical properties of the anisotropic film, the rheological properties of the liquid crystal system, etc., as determined by routine experimentation. . The compound or the compounds should be selected such that the introduction of the compound does not cause cracking of the liquid crystal system. Optical polarization techniques can be used to monitor the effect of the selected additive to determine its suitability for use in the LLCs of the present invention in -19-1304089 (16). The optically anisotropic film of the present invention can be obtained by depositing a liquid crystal system on a substrate, and further applying orientation and drying. In this specific example, the anisotropic film is at least partially crystallized. The film material comprises at least two compounds of structure I-VIII, and/or at least two compounds having one of structures J-VIII, each having at least two different substituents. The 1,8-naphthomethyl-1,2,-benzimidazolylsulfonic acid derivative of the present invention as shown in Structure D is more particularly shown in the slacks I-VIII of the general structural formula. It can be synthesized in a variety of ways, including known and novel methods. The sulfonic acid derivative of the present invention having the general formula X is such that i ' 8 - anthranilyl-methane, 2'-benzimidazole or a derivative thereof IX is used in various concentrations of sulfonic acid or fuming sulfuric acid. Different temperatures/times are formed according to the results of sulfonation according to the following procedure:

Where n = l , 2 , 3 , 4 ; m = 0 , 1 , 2 , 3 , 4 ; and z = 0, 1 , 2 , 3 ' 4 such that m + z + n <10; and X and Y are It is selected from the group consisting of: CH3, C2H5, OCHs, 〇C2H5, Cl, Br, 〇H and NH". The general formula X sulfonate can also be via the corresponding derivative XI. Hydrolyzed or may be formed as a result of sulfonation of compound XI with chlorosulfonic acid. • 20- 1304089 (17), as in D. Tocksteinova, J. Slosar, J. Urbanek, and J.

Chur achek, Microchi m. Acta 11, 193 (1979), or sulfonated with chlorosulfonic acid and fuming sulfuric acid in various concentrations. The sulfonation of 1,8-naphthomethyl-1,2'-benzimidazole and derivatives thereof can be carried out in a sulfonating agent medium or an organic solvent. Further, 1,8-naphthoquinone-indenyl, 2-benzimidazolesulfonic acid-based derivative X can be condensed by using naphthalic anhydride or its derivative XII with o-phenylenediamine or derivative XIII Synthesis, but with the proviso that at least one starting compound contains one or several sulfonic acid groups:

〇^x〇ss^O

XIII

Wherein 111 = 0, 1, 2, 3, 4, and 2: =0, 1, 2, 3, 4, such that 111 + 2 ^ 7 ; and X and Y are individually selected from the group consisting of : CHs, C2H5, 〇CH3, OC2H5, Cl, Br, 〇H and NH2. 1 , 8 — Streptavidin- 1 ·, 2'-benzimidazolylsulfonic acid derivative can also be obtained by separating the mixture from the solution by fractional separation. A 1,8-naphthoquinone- 1 ',2 · -benzimidazolylsulfonic acid derivative mixture can also be obtained via isomerization, for example

Iv xv When the compounds of the invention or a mixture thereof are dissolved in water, their molecules form an anisometric (rod-like) aggregate -21 - 1304089 (18) which is deposited in a stack of coins. Each of the aggregates in such solutions represents a molecular micelle with an electric double layer, while the bulk solution represents a highly dispersed (gel-like) lyophilic liquid. As the concentration of the solution (i.e., the concentration of the molecular group) increases, the anisometric aggregates exhibit natural ordering (self-ordering), resulting in the formation of a liquid-type mesophase. As a result, the system becomes liquid crystal. ' The solution typically becomes a liquid crystal system at a concentration ranging from about 3 to 50% by mass, depending on the 1,8-naphthoquinone-1,2,monobenzimidazolesulfonic acid derivative. Special types and proportions. The liquid crystal state can be easily confirmed by the general method φ, for example, by means of a polarizing microscope. Individual liquid crystal systems (solutions) of the present invention may be coated on a substrate, as well as the structure D and more particularly the structure I-VIII, or a mixture of such compounds. The surface of the material and the method previously described, for example, as disclosed in P c T publication \ν Ο 9 4 / 2 8 0 7 3 and W Ο _ 〇〇 /2 5 1 5 5, are oriented. For example, the orientation can be achieved by applying a shear stress or a gravitational field or an electromagnetic field. In order to enhance the wettability of the substrate and to optimize the rheological quality of the liquid crystal system, the solution may be modified, for example, by adding a plasticizing additive such as a water-soluble polymer, and/or an anionic or nonionic surfactant. The system may also contain low molecular weight water soluble additives. All additives have been desirably selected so as not to disturb the orientation of the liquid crystal solution. Subsequent removal of the solvent from the oriented film results in an optically anisotropic polycrystalline film having a thickness in the range of about 0.2 to 1 .2 microns. In the visible > spectral range (about 380-900 nm), the difference between the refractive index measured in the orientation direction and the refractive index measured in the vertical direction appears in the range of about 0.1 - 0.8. Inside. These defects are only achieved in previously known hysteresis at film thicknesses greater than -22 - 1304089 · (19) of about 200 microns. The birefringent film according to the disclosed invention achieves a higher efficiency of 100-200 times or more than the previously uncovered film. Therefore, the present invention has 1,8-naphthoquinone- 1', 2 · The benzimidazole sulfonic acid derivative can form the LLC phase and is indeed micro-colored (absorbable in the range of visible light), an anisotropic film with high optical properties. Figure 1-3 shows Some of the advantages of the present invention. Fig. 1 shows the spectral correlation of the anisotropy degree of a film of a naphthoquinone #benzimidazolylsulfonic acid derivative. Figure 2 shows (a) 1,8-naphthoquinone-I1,2'-benzimidazole-3,6'-disulfonic acid and (b) 1,8-naphthoquinone-yl-anthracene, 2. Electron absorption spectrum of benzimidazole-6'-amino-3-sulfonic acid. Figure 3 shows the plot of (a) refractive index and (b) absorption coefficient versus wavelength for 1,8-naphthoquinone-indenyl, 2·-benzimidazole-6,sulfonic acid membrane . EXPERIMENTAL · The present invention 1,8 - anthrapenyl-1,2,monobenzimidazolylsulfonylsulfonyl hydrazine I# is intended to be exemplified by the following examples. Are these examples? » Η is used for the purpose of hearing and is not intended to limit the scope of the invention in any way. Example 1 - sulfonation of 1'8-naphthoquinone-anthracene|,2,monobenzimidazole, 丨'8-naphthoquinone-anthracene, 2•monobenzimidazole-6, The sulfonate -23- 1304089·, (20) was carried out as follows. A mixture of 5 · 0 g of 1,8-naphthoquinone-1', 2'-benzimidazole and 30 ml of 10% fuming sulfuric acid was stirred for 1.5 hours. The reaction mass was then diluted with water to give a 70% aqueous solution of sulfuric acid. The precipitate was filtered off, washed with hydrochloric acid until it was free from S-42- ions, and dried at 100 °C. The yield of 1,8-naphthoquinone- 1 ·, 2 · benzimidazole-6'-sulfonic acid was 5.7 g (88%). Sample analysis revealed the following data: • 4 NMR spectra (Bruker AC-300) in DMSO, · 5 ppm 7.7 8 (single line, 2 Η), 7 · 9 5 (multiple lines, 2 Η), 8 · 3 9 (double line, 1 Η ) , 8 · 5 5 (double line, 1 Η ) , 8 · 7 8 (multiple line, 3 Η ) 0 • mass spectrum (VISION 2000, negative reflection mode): measured 値: m/z = 347.8 : Calculated 値, 350.35. • IR spectrum (FSM – 1201 Fourier transform spectrometer) in the film on the KRS-5 window (^?, cm-1): 653,1 070, 1 234 (SChH), 1731.2 (C = 0). Φ • Atomic absorption spectroscopy (Ocean PC 2000 spectrophotometer) in aqueous solution (^max, nm): 380 • Elemental analysis 'Measurement 値 (%): C 6 1.6 1 ' 6 1. 6 0 ; 2 · 6 7 , 2.76; N7.97, 8.12; S9.3 2,9·41; CI8H1()N2〇4S. The calculated enthalpy is C61.71; H2.88; N8.00; 〇18·27; S9.15. #Example 2 Through the 1,8-naphthoquinone-indenyl, the sulfonation of 2'-benzimidazole into -24- 1304089.. (21) Line 1,8-streptylene-methyl-1, The synthesis of 2,-benzimidazole-3,6-disulfonic acid was carried out as follows. A mixture of 3.0 g of 1,8-naphthoquinone- 1 '' 21-benzimidazole and 32 ml of 20% fuming sulfuric acid was stirred at 50 ° C 5 ° C for 4 hours. The reactant mass was then diluted with water to give a 5 2 % aqueous solution of sulfuric acid. The precipitate was filtered off, washed with hydrochloric acid to free of S.sub.42- ions, and dried at 100 °C. The yield of 1,8-streptazinyl-1,2·-benzoimidazole-3,6-disulfonic acid was 4,3 g (90%). • 4 NMR spectra (Bruker AC-3 00) in DMSO, φ (5ppm 7.82 (single line, 2Η), 7.97 (multiple line, 1H), 8.64 (double line, 2H), 8.78 (double line, 2H) , 9.03 (single line, 1H) 〇 sample analysis reveals the following data: ' • Mass Spectrometry (VISION 2000, Negative Reflection Mode): Measured 値: · m/z = 428.8: Calculated 値, 430.4 1. • IR Spectrum (FSM - 1201 Fourier transform spectrometer) in the film on the KRS-5 window (7?, cm-1): 65 3,1 070,1 234 (SChH) #,1731.2 (C=〇)cm-1. Absorption spectrum (Ocean PC 2000 spectrophotometer) in aqueous solution (in..., nm): 380 _ • Elemental analysis, measurement 値 (%): C5 0.11, 50.08; 112.05, 2.24; N6.46, 6.62; S 14.50 , 14.63; CI8HI〇N2〇7S2. Calculation · 値 is C50.23; H2.34; N, 6.51; 026.02; S14.90. ^ Example 3 -25- 1304089, (22) through 1,8-extension The sulfonation of naphthyl-methyl ketone-1, 2'-benzopyrene 13 is carried out by 1,8-naphthoquinone-based oxime, and 2'-benzo-pyrene is a 3,6,6--trisulphonate The acid synthesis was carried out as follows: 1.5 g 1 , a mixture of 8-naphthoquinone-anthracene, 2·-benzimidazole and 10 ml of 20% fuming sulfuric acid was stirred at 4 115-120 ° C for 14 hours, then cooled on ice. Dilute the reaction mass at 1 7-20 ° C (maintained on ice) and allow the mixture to stand for 24 hours. The sediment was filtered off, washed with hydrochloric acid, and dried at 1 ° C until constant weight. The yield of 1,8-naphthoquinone-based, 2'-benzopyrene D-sodium- 3,6,6-trisulfonic acid was 1.1 g (40%). Sample analysis revealed the following data: • ^ NMR spectrum (Bruker AC-300) in DMSO, 5 ppm 7.82 (single line, 2H), 8.62 (single line, 1H), 8.77 (double line, 2H), 8.90 (double line, 1H), 9.00 (Unique, 1H). • Mass Spectrometry (VISION 2000, Negative Reflection Mode): Measured 値: m / z = 5 0 6.1 : Calculated 値, 5 1 0.4 8. • IR Spectrum (FSM – 1201 Fourier Transform Spectrometer ) in the film on the KRS-5 window (7?, cm_]): 653,1070, 1234 (SChH), 173 1 · 2 (C = 〇). • Atomic Absorption Spectroscopy (Ocean PC 2000 Spectrophotometer) in 'Aqueous Solution (λ ma X, nm): 380 • Elemental Analysis, Measurement 値 (%): C 4 2 · 1 5, 4 2.4 6 ; Η 2.1 3 , 2·06 ; Ν 5.22, 5·37 ; S19.01, 19.16 ; C] 8H 丨〇 N2 〇 1 〇 S3. Calculated - C42.35; H1.97; N5.49; 03 1.34; S18.84. -26- 1304089 (23) Example 4 Synthesis of 1,8-Benimidazole- 6-sulfonic acid by the condensation of o-phenylenediamine with 3-sulfonic acid phthalic anhydride . A mixture of 2.3 g of 3-sulfonic acid anhydride and 1.4 g of o-phenylenediamine in 50' ml of acetic acid was boiled for 8 hours and then cooled to 15 t. Filter out the 'precipitate, wash with acetic acid and cool to 15 ° C, then dry and 2.3 g of isomer 1,8 -naphthoquinone-based, 2'-benzopyrene D sit a 3-sulfonic acid And a mixture of 1,8-naphthoquinone-1',2-benzimidazole-6-sulfonic acid. A similar procedure can be used to obtain other 1,8-naphthomethyl-1,2'-benzimidazolylsulfonic acid derivatives containing various substituents. Example 5 The synthesis of the liquid crystal composition, the application of the optically anisotropic film, and the measurement of the optical properties of the film were carried out as follows. Add 5.3 to a solution prepared by stirring 1 2 g of 1,8-naphthoquinone-based plant, 2'-benzopyrene D, and 6'-mineral acid in 65.0 g of deionized water at 20 t. Milliliter of 25% ammonia was stirred and the mixture was stirred until completely dissolved. To this solution, 10 g of a 1% aqueous solution of SUlf〇n〇l was added and the mixture was thoroughly stirred to obtain 92 g of a 13% liquid crystal solution. This solution was coated on a glass plate at a rate of 25 mm/sec using a Meyer rod. The procedure was carried out at 20 ° C and 65% relative temperature, after which the film was also dried under the same conditions. ~ The optical properties of the film were investigated by measuring the transmission spectrum of the sample at 400 to 800 nm (Cary 500 Spectrophotometer) along the direction of film coating and perpendicular to the polarized beam. These measurements are also 30 compared to the normal of the plane -27- 1304089 _ (24). Implemented from the perspective. Using these measurements, the refractive index (η.') and the absorption coefficient (k, ke ) along the film coating direction and the vertical direction were calculated. The calculation method is contained elsewhere (P. Lazarev, Ν·Ovchinnikova, and M. Paukshto, Submicron Film Retardation Coating, SID'01 DIGEST (San Jose, California, June 200 1 ), Vol. XXXII, p. 57 1]. The calculation results for the 1,8-naphthoquinone-11,2-benzimidazole-6'-sulfonic acid film are shown in Fig. 3. The film has optical anisotropy and exhibits good phase shift properties, as shown in Figure 3a, with high polarization characteristics in the wavelength range of 380-45 nm and above the entire 500 nm Very low absorption in the visible light range. A liquid directional liquid crystal system and a corresponding film were also obtained using all of the other compounds described above. These films also have high optical properties and thus support the technical results of the disclosed invention. The foregoing description of the specific embodiments and embodiments of the invention are intended to They are not intended to be exhaustive or to limit the invention to the obvious form disclosed, and it is obvious that many modifications, specific examples, and variations are intended to cover the invention as disclosed herein. The scope is defined by the scope of the appended claims and their equivalents. BRIEF DESCRIPTION OF THE DRAWINGS Other objects and advantages of the present invention will become apparent after reading the detailed description of the invention and the appended claims. As a graph, the spectral correlation of the degree of anisotropy of the naphthoquinone-benzimidazolesulfonic acid-based derivative film of the present invention is plotted. Figure 2 is a graph showing the (a) 1,8-naphthoquinone-yl-1,2'-benzimidazole-3,6'-disulfonic acid and (b) 1,8 of the present invention. - an electron absorption spectrum of a stretched, naphthyl-based 1', 2'-benzotriene- 6'-monoamino-3-mineral acid'. Figure 3 is a graph showing the (a) refractive index and (b) absorption coefficient of the 1,8-naphthoquinone- 1', 2'-benzimidazole-6'-sulfonic acid film of the present invention. Relative to the wavelength. -29-

Claims (1)

130408' Patent Application No. 92117454 Patent Application Revision Chinese Patent Application Revision Amendment Aug. 20, 1997, Republic of China 1 · A liquid-directed liquid crystal system containing at least one 1,8-naphthoquinone having the following general formula醯基Γ, 2'-benzimidazole sulfonate derivative Wherein η is an integer in the range of 1 to 4, m is an integer in the range of 0 to 4; z is an integer in the range of 0 to 6, and 値 of πι, η and z satisfy the equation m + z + nS10; And X and Y are individually selected from CH3, C2H5, OCH3, OC2H5, Cl, Br, OH or NH2; and M is a counterion; and j is in the 1,8-naphthoquinone-based, 2' - the number of different counterions (M) in a single molecule of the benzimidazole sulfonic acid derivative. 2. The liquid-directed liquid crystal system according to claim 1, wherein the structural formula is selected from the group consisting of structures I-VIII. Wherein m is an integer in the range of 0 to 3, and z is an integer in the range of 0 to 4, wherein m is an integer in the range of 0 to 4, and z is an integer in the range of 0 to 4 1304089· Where m is an integer in the range 0 to 2, and ζ is an integer in the range 0 to 4 Wherein m is an integer in the range of 0 to 4, and ζ is an integer in the range of 0 to 4 Wherein m is an integer in the range of 0 to 3, and ζ is an integer in the range of 0 to 4 Wherein m is an integer in the range of 0 to 3, and ζ is an integer in the range of 0 to 4 Wherein m is an integer in the range of 0 to 2, wherein m is an integer in the range of 0 to 2, and ζ is an integer in the range of 0 to 4 and ζ is an integer in the range of 0 to 4, wherein X and The Y system is individually selected from the group consisting of CH3, C2H5, OCH3, OC2H5, Cl, Br, OH or NH2. 3. The liquid directional liquid crystal system according to claim 1 or 2, wherein the counter ion (M) is shared by a plurality of molecules; and the number (j) of the counter ions is a fraction. 4. The liquid-directed liquid crystal system of claim 3, wherein η >1; and Mj are more than one counter ion. 5. The liquid crystal liquid crystal system of claim 1 or 2, -2- 1304089 wherein the 1,8-naphthoquinone-indenyl group and the 2'-benzimidazolesulfonic acid group derivative form a stable Liquid directional liquid crystal system. 6. The liquid-directed liquid crystal system of claim 1, which contains an individual 1,8-naphthoquinone- 1 ', 2'-benzimidazole sulfonate derivative. 7. The liquid crystalline liquid crystal system of claim 1, which comprises a mixture of the 1,8-naphthoquinone- 1'' 2'-benzimidazolesulfonic acid derivative. 8. The liquid-directed liquid crystal system of claim 6, further comprising a mixture of water and an organic solvent miscible with water in any ratio. 9. The liquid-directed liquid crystal system of claim 6 Further, it includes a mixture of water and an organic solvent which is characterized by a limited miscibility with water. 10. The liquid-directed liquid crystal system according to claim 6, wherein the concentration of the 1,8-naphthoquinone-based, 2f-benzimidazolesulfonic acid derivative is from about 3% by mass to 40%. Within the range of mass %. 11. The liquid-directed liquid crystal system according to claim 6, wherein the concentration of the 1,8-naphthoquinone-based, 2f-benzimidazolesulfonic acid derivative is from about 7 mass% to 15 Within the range of mass %. 12. The liquid-directed liquid crystal system of claim 6, further comprising up to about 5% by mass of a surfactant. 13. The liquid-directed liquid crystal system of claim 6, further comprising up to about 5% by mass of a plasticizer. 1304089. The liquid crystal liquid crystal system of claim 6, which further comprises at least one other water-soluble organic dye. The liquid crystal liquid crystal system of claim 6, further comprising a second organic compound capable of reacting with at least one 1,8-naphthoquinone- 1 ', 2 The monobenzimidazole sulfonic acid group derivative participates in the formation of the liquid crystal phase. The liquid permeable liquid crystal system of claim 1, which comprises at least two compounds having at least one structure selected from the group consisting of structure I to structure VIII and having at least two different substituents. 1 7 · a liquid-directed liquid crystal system comprising one or more 1,8-naphthoquinone- 1',2'-benzimidazolylsulfonic acid derivatives as described in claim 2 a mixture wherein: the concentration of each individual 1,8-naphthoquinone-indenyl, 2,monobenzimidazolesulfonic acid derivative in the mixture is determined by one or more desired properties of the mixture, And the mixture thereof comprises: one or more monosulfonic acid derivatives of structures I and II in a concentration ranging from about 〇/❹ to 99% by mass; one or more disulfonic acids of structures III and IV a base derivative in a concentration ranging from about 0% by mass to 99% by mass; one or more trisulfonate derivatives of structures VI and VII in a concentration ranging from about 0% by mass to 30% by mass And a tetrasulfonate derivative of one or more structures V111 in a concentration ranging from about 0% by mass to 20% by mass. 1 8 · The liquid directional liquid crystal system of claim 17 of the patent application, the mixture of -4- 1304089 comprising: one or more monosulfonate derivatives of structures I and 11 having a concentration of about 50 Within the range of % by mass to 99% by mass; one or more disulfonate derivatives of structures III and IV have a concentration ranging from about 50% by mass to 99% by mass; one or more structures The trisulfonate derivative of VI and V11 has a concentration in the range of about 1% by mass to 20% by mass; and the tetrasulfonate derivative of one or more structures V111 has a concentration of about 5 The mass% is within the range of 10% by mass. An optically anisotropic film comprising an individual 1,8-naphthoquinone- 1', 2'-benzimidazolylsulfonic acid derivative as described in claim 1 or 2 of the patent application. . 20. An optically anisotropic film according to claim 19, which comprises two or more 1,8-naphthoquinone- 1',2,monobenzimidazolesulfonate derivatives. An optically anisotropic film according to claim 19, which comprises a mixture of the 1,8-naphthoquinone-1', 2'-benzimidazolesulfonic acid group derivatives. An optically anisotropic film according to claim 19, wherein the film further comprises at least one other organic compound. An optically anisotropic film, wherein the film is formed by: depositing a liquid crystal system according to claim 6 of the patent application on a substrate; -5 - 1304089 applying a certain force; and The film was dried. An optically anisotropic film according to claim 23, wherein the film is at least partially crystallized. An optically anisotropic film according to claim 19, which comprises at least two compounds having at least one structure selected from the structures of structures I to VIII and having at least two different substituents. 2 6. An optically anisotropic film according to claim 21, which comprises at least two compounds selected from the group consisting of I to VIII. An optically anisotropic film according to claim 20, wherein the film is a retarder film. 28. An optically anisotropic film according to claim 20, wherein the film is polarized. 29. A method of forming an optically anisotropic film comprising the steps of: applying a direct force on a substrate deposited on a substrate as in claim 6; and drying the film. 9