RU2137801C1 - Material for dichroic photopolarizers - Google Patents

Abstract

FIELD: organic chemistry, dyes. SUBSTANCE: invention relates to new materials used for dichroic photopolarizers making based on organic dyes. Polycyclic organic dyes are used as a film-forming component. These dyes are able to form lyotropic mesomorphic phase and used for additional use of modified addition also. For the latter low-volatile low- and high-molecular compounds containing different functional groups (OH, COOH, CONH₂, NH, CHO, CO and others) and different lacquers can be used. Obtained material is used as a base for making dichroic photopolarizers that exhibit yellow, red and gray color of high polarization indices (15, not less). EFFECT: improved quality and properties of material. 1 tbl

Description

 The invention relates to new materials for dichroic polarizers of light (DPS), based on organic dyes.

 Obtained on the basis of the claimed materials, DPS can be used where stringent conditions for the production and operation of products are assumed, for example, in the automotive industry for the manufacture of laminated glasses, in lighting equipment, in the manufacture of glasses for construction and architecture, that is, in areas where it is impossible to use traditional light polarizers based on polyvinyl alcohol films, colored in bulk by iodine or dichroic dyes and oriented by mechanical stretching in one m along the <1 US 5007942 A> because of their low thermal and radiation resistance, and high cost. DPS based on the claimed material can also be used in the manufacture of LCD displays and indicators.

 The closest in technical essence is the known material for DPS based on organic dyes, which are sulfonic acids of azo and polycyclic compounds of the formula or a mixture thereof, which are capable of forming a lyotropic liquid crystalline phase, which makes it possible to obtain stable lyotropic liquid crystals (VFA) based on them and compositions based on them.

 In addition to the dye, the known material may additionally contain low molecular weight water-miscible organic compounds, antioxidants and / or surfactants "2 WO 94/05493 A1".

 When applying the known material "2" to the surface of the substrate with simultaneous mechanical orientation and subsequent curing with solvent removal, a thin film of a molecularly ordered dye layer is formed - a polarizing coating (PP) that converts natural light into polarized.

 Obtained on the basis of the known material, DPSs have high thermal and light resistance and have fairly high polarization characteristics.

A feature of the known material for particle board is that the PP obtained on its basis is an ultrathin film of a molecularly oriented dye layer, the thickness of which is 0.2-1.5 μm. The small thickness of the PP leads to the fact that the scattering of light can have a significant effect on the polarization efficiency, due to the difference in the refractive indices of the dye, air, and substrate. For a dye film, the refractive index n _d > 1.5, for air n _d = 1.0.

 Light scattering is the main reason that the dyes used in the well-known `` 2 '' material do not allow DPSs of yellow, red, green, and gray colors with high polarization characteristics sufficient to be used in the manufacture of LCD displays and high-resolution indicators.

 The objective of the present invention is to provide a material on the basis of which it is possible to obtain DPS of yellow, red and gray colors with high polarization characteristics (Kd of at least 15).

 The problem is solved due to the use of organic dyes of type I-XXXIV or mixtures thereof, which are capable of forming a liquid crystal phase, as well as the additional use of a modifying additive in the material for DPS as a film-forming component.

Organic substances having a lower refractive index than the refractive index of an organic dye film (n _d <1.5) can be used as a modifying additive. It has been experimentally established that organic substances can be used as such substances, for which 1.42 <n _d <1.47, in particular:
low volatile low and high molecular weight compounds containing various functional groups (OH, COOH, CONH ₂ , NH, CHO, CO, etc.), for example, pentaerythritol, succinic aldehyde, hydroxycarboxylic acids, polyethylene glycol (PEG), polyacrylic acid (PAA ), polyacrylamide (PAA), polyethyleneimine (FDI), polyethylene polyamines, polypropylene glycol (PPG) and their copolymers, etc.,
- organosilicon polymers, including alkyl siliconates (alkyl: C1-C4),
- liquid crystalline polymers, for example hydroxyethyl and hydroxypropyl cellulose ethers, rigid chain LC polymers, for example, poly-p-benzamide and poly-p-phenylene terephthalimide.

 The material for dichroic light polarizers contains an organic dye of the formula I-XXXIV or a mixture thereof in an amount of 3.0-30.0 wt.%, A modifying additive in an amount of 0.1 - 20.0 wt.%, The solvent is the rest.

 The material may contain an antioxidant and / or inhibitor in an amount of 0.01 - 1.0 wt.%, As well as a surfactant in an amount of 0.1-10.0 wt.%. As a modifying additive, it is advisable to use alkylsiliconate or poly-p-phenylene terephthalimide.

 Antioxidants and inhibitors are added to ensure the chemical resistance of PP to the action of oxidizing agents, varnishes and adhesives.

 Surfactant is added to ensure the wettability of the surface of the substrate during the application of PP.

 The modifying additive provides mainly a decrease in light scattering, which leads to an increase in the efficiency of PP and to obtain on their basis DPS with high polarization characteristics (Kd above 15).

 The use of a modifying additive allows to obtain DPS with high polarization characteristics (Kd above 15) and based on dyes, which are used in the well-known material "2".

 A significant difference of the present invention is the use of dyes of type I-XXXIV or mixtures thereof in the claimed material, which are capable of forming a liquid crystal phase and in whose molecules the dipole moment vector of the optical transition determining the color of the PP lies in the plane of the substrate or makes a small angle with it its projection onto the substrate plane has a deviation from the perpendicular to the axis of macroscopic orientation, not exceeding 20 degrees, which ensures the achievement of a high dichroic ratio Niya.

расклинивающем отрыве одной поверхности от другой, между которыми распределен слой ЖК. Перечисленные способы ориентации ЖК могут осуществляться также одновременно с нанесением ЖК на поверхность подложки, в том числе по технологии "roll to roll". При этом также как и в случае известного материала ''2" могут быть использованы различные узлы нанесения в виде: щельевой фильеры, ракеля в форме невращающегося или катящегося цилиндра и т. д.The use of dyes I-XXXIV in the claimed material makes it possible to implement, as in the case of the known material "2", a method for orienting the LC based on mechanical ordering of the LC, which can be carried out by applying shear force or under the action of forces that cause strain strain on the meniscus formed by

proppant separation of one surface from another, between which the LC layer is distributed. The above methods of orienting the LC can also be carried out simultaneously with the application of the LC on the surface of the substrate, including the roll to roll technology. In this case, as well as in the case of the known material `` 2 '', various application units can be used in the form of: a slotted die, a doctor blade in the form of a non-rotating or rolling cylinder, etc.

 A significant difference of the claimed material is also the additional use of a modifying additive, which can significantly improve the polarization characteristics by reducing light scattering.

 It should be noted that the use of a modifying additive allows to obtain a more uniform and smooth PP, which improves the quality of the DPS based on the claimed material in comparison with the known material.

 Based on the proposed material, PP can be obtained on a solid flat, spherical or cylindrical, transparent or reflective surface of organic or inorganic glass, silicate glass with a sprayed semiconductor layer, silicon wafers with a sprayed layer of aluminum, etc. PP can also be applied to a flexible polymer film of polyethylene terephthalate, polycarbonate, cellulose triacetyl and other film materials.

 Typical equipment, including printing equipment, using various application methods, for example, intaglio printing, flexographic printing, etc., can be used for applying PP.

 The use of organic dyes I-XXXIV in the proposed material also allows you to implement the technology of layer-by-layer application of PP. Moreover, the subsequent PP layer of the same dye or another can be applied directly to the previous one, or to an intermediate layer of transparent material. Moreover, the direction of the polarization axis of the second layer relative to the direction of the polarization axis of the first layer can be an angle from 0 to 90 degrees.

 It should be noted that the technology of layer-by-layer deposition allows to obtain both color and gray DPS with very high polarization characteristics.

 The use of the claimed material allows to obtain DPS, which consist of a set of polarizing elements that differ in the direction of the polarization vector in the plane of the substrate and / or color, and the polarizing elements can be made in a layered version, where each layer can also have its own color and direction of the polarization vector. Such traffic police are of great interest for advertising, protection of trademarks, for the manufacture of various consumer goods (booklets, postcards, etc.). For the manufacture of this kind of DPS during the formation of PP, the direction of the orienting action varies at an angle from 0 to 90 degrees relative to the movement of the substrate.

 The application of the proposed material also allows the use of various adhesives to obtain various kinds of laminated structures, for example, triplex glasses or multilayer films, which is of interest to the automotive industry and architecture.

 All this makes it possible to produce DPS of various purposes on the basis of the claimed material. The high polarization characteristics of PP allow the use of DPS based on the proposed material for LCD displays and indicators.

 The foregoing is illustrated by the following examples.

 Example 1

 1.1. Synthesis of a dye of formula I, R = H, n = 2.

5 g of the Dye of the distillation golden yellow LC is dissolved in 50 ml of 45-50% oleum, heated to 80 ^o C and kept at this temperature for 7 hours. At the end of the exposure, the reaction mass is diluted with 170 ml of water, 40 g of sodium chloride are added. The resulting suspension is heated to 80 ^o C and maintained at this temperature for 10 minutes, after which it is filtered while hot. The precipitate is squeezed out and washed with a 13% sodium chloride solution until there is no sulfate anion. The precipitate is dried, boiled with 30 ml of 16% hydrochloric acid and filtered. The resulting precipitate was washed with 10% hydrochloric acid, then with isopropyl alcohol and dried. Get 5.06 g of the dye of the formula I, n = 2. Found%: S 11.69, 11.88. C ₂₄ H ₁₂ O ₈ S ₂ + 4H ₂ O. Calculated%: S 11.37
Similarly, by sulfonation of the anthantrone, a dye of formula IV, n = 2, is obtained. Found%: S 13.12, 13.56. C ₂₃ H ₁₁ O ₈ S ₂ . Calculated%: S 13.37.

Similarly, sulfonation of the isovialontron gives a dye of formula IX, n = 3. Found%: S 12.58, 13.23. C ₃₄ H ₁₆ O ₁₁ S ₃ + 3H ₂ O. Calculated%: S 12.82
Similarly, by sulfonation of a vialontron, a dye of the formula X is obtained, n = 4. Found%: S 14.80, 14.95. C ₃₄ H ₁₆ O ₁₄ S ₄ + 4H ₂ O. Calculated%: S 15.09.

Similarly, by sulfonation of VAT gray C, a dye of formula XIII, n = 4, is obtained. Found%: S 11.78, 11.80. C ₄₅ H ₂₁ N ₃ O ₁₆ S ₄ + 4H ₂ O. Calculated%: S 12.09.

 1.2. The manufacture of lyotropic liquid crystal dye.

 a) 2.5 g of a Dye, for example, formula I, n 2, free from mineral impurities, is dissolved by heating in 7.5 ml of distilled water, after which the solution is cooled to room temperature and adjusted to pH with a base solution, for example ammonia or alkali 5-6. The presence of a liquid crystal * phase was detected when a sample was observed under a polarizing microscope equipped with two crossed polarizers.

 0.25 g of surfactant Triton X-100, 0.05 g of hydroquinone, 1.0 g of polyethylene glycol are added to the obtained VFA, and mixed. The resulting composition is used to form PP on the surface of the substrate.

 b) 2.5 g of Dye 1, n = 2, free from mineral impurities, dissolved in a mixture of 75 ml of water and 25 ml of isopropyl alcohol, 10% ammonia solution is added to the resulting solution to a pH of 5-6, then it is filtered off from mechanical impurities and concentrated by removing the solvent to a mass of 10 g. Receive 10 g of VFA.

 c) upon receipt of liquid crystals based on dyes of a polymer structure of type XXII-XXXIV, the following solvents can be used as solvents: sulfuric acid of various concentrations, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone.

 1.3. Production of dichroic light polarizers.

 1.3.1. Application of PP on a film of polyethylene terephthalate (PET).

 1.3.1.1. Application by slotted die.

(All experiments on the application of PP are carried out at 20-25 ^o C and relative humidity of 70%).

 A PET film with a thickness of 50 μm, a width of 120 mm and a length of 1000 mm is laid between a pressure cylinder having a diameter of 40 mm and a length of 200 mm, and a die. The die has a volume of 5 ml, its gap is 300 microns wide and 100 mm long. The working surface of the die, especially its edge, is carefully polished and has no scratches. The PET film is pressed against the surface of the die with a force of about 10 Newtons; LC is poured into the die (to improve wettability in the LC surfactant can be added, the concentration of surfactant is 0.2%), the film is stretched at a speed of 150 mm / sec. An oriented dye layer forms on the film surface; after drying, it has a transmission of To = 40% and a Kd value of 15.6 at the absorption maximum.

 1.3.1.2. Application with a squeegee in the form of a non-rotating cylinder. A PET film is passed between two steel cylinders with a diameter of 20 mm and a length of 1000 mm. The surface of the cylinders is carefully polished. The thickness of the PP is set by gaskets located at the edges of the cylinder and having a thickness of 60 μm. 2 ml of LC is applied in the form of a strip 5-10 mm wide on the surface of the film immediately in front of the cylinder. Then the film is pulled between the cylinders at a speed of 150 mm / sec. After drying, the PP has the following parameters: transmission - To = 38% and Kd = 15.

 1.3.1.3. Application by rolling cylinder.

 A cylinder with a diameter of 20 mm and a length of 200 mm is placed on a flat surface without the ability to move along it, but with the possibility of rotation around its axis. At the edges of the cylinder, gaskets 10 microns thick are fixed. One end of the film is passed between the cylinder and a flat surface, about 1 ml of LC is applied to the film in front of the cylinder, and then the film is stretched at a speed of 150 mm / sec. In this case, the rolling cylinder distributes the LC in a uniform layer. After drying, the PP has the following parameters: To = 45%, Kd = 17.0.

 1.3.1.4. Application at break of two films.

 Two cylinders with a diameter of 20 mm and a length of 200 mm are fixed motionless on a table at a height of 150 mm from its surface and at a distance of 110 microns from one another. The ends of two films with a thickness of 50 μm are passed between the cylinders at a distance of 150 mm. 0.5 ml of LC is applied in the intermediate space between the cylinders on the surface of both films. Then both films are simultaneously pulled down with simultaneous dilution at a speed of 50 mm / sec. After drying, the PP has: To = 45%, Kd = 16.8.

 1.3.2. Application of PP on a hard surface.

 1.3.2.1. Application with a squeegee in the form of a non-rotating cylinder. A glass plate with a size of 100 per 100 square mm and a thickness of 2 mm is thoroughly washed and dried. On the edge of the plate is applied in the form of a strip of 1 ml of LC. The plate is fixed on a table that can move in a straight line. A squeegee with a diameter of 20 mm and a length of 200 mm is pressed against the plate. The thickness of the formed layer is set by two gaskets with a thickness of 10 μm, mounted on the cylinder at a distance of 80 mm from each other. A table with a fixed plate moves at a speed of 100 mm / sec relative to the stationary cylinder. After drying, the PP has the following parameters: To = 43% Kd = 16.0.

 1.3.2.2. Application by rolling cylinder.

 The glass plate with the applied LCD is fixed on a movable table in the same way as in example 1.3.2.1. Two gaskets 10 microns thick and 5 microns wide are fixed along the longitudinal edges of the plate. A cylinder that can rotate around its axis, with a diameter of 20 mm and a length of 200 mm is placed on the edge of the plate. The table moves at a speed of 200 mm / s relative to the cylinder so that the cylinder rolls over the surface of the plate. In this case, the LCD is evenly distributed and oriented on the surface of the plate. After drying, the PP has the following parameters: To = 45%, Kd = 15.0.

 1.3.2.3. Application upon separation of the film from the surface of a solid plate.

 On the prepared plate with gaskets 10 μm thick fixed on the longitudinal edges, 0.3 ml of LC is applied. Then the plate is coated with a PET film 80 mm wide, 100 mm long and 2 microns thick. LCD is distributed along the surface of the plate using a roller, after which the film is torn off, starting from one of the edges at a speed of 50 mm / sec. After drying, the PP has the following parameters: To = 44%, Kd = 16.2.

 Example 2. Synthesis of a dye of the formula I, R = H, n = 3.

5 g of the Dye of a still golden yellow LC was dissolved in 50 ml of 20-45% oleum, 0.03 g of mercury sulfate was added and heated to 115 ^° C. The reaction mass was kept at 110-120 ^° C for 8 hours. At the end of the exposure, the reaction mass is diluted with water to a sulfuric acid concentration of 50% and 25 g of sodium chloride are added. The resulting suspension is heated to 80 ^o C and filtered. The precipitate is washed with a 12% solution of sodium chloride, then with 16% hydrochloric acid, after which it is washed with isopropyl alcohol and dried. Obtain 5.4 g of the dye of the formula 1, n = 3. Found%: S 14.89, 15.03. C ₂₄ H ₁₂ O ₁₁ S ₃ + 3H ₂ O. Calculated%: S 15.36.

Similarly, by sulphonation of a vat golden yellow KX, a dye of formula I is obtained, R = Br, n = 2. Found%: Br 23.44, 23.68; S 9.00, 9.12. C ₂₄ H ₁₀ Br ₂ O ₈ S ₂ + 2H ₂ O. Calculated%: Br 23.32; S 9.33.

In a similar manner, a dye of formula I is obtained, R = anthraquinonyl-1-amino, n = 4. Found%: N 2.40, 2.54; S 10.78, 10.81. C ₅₂ H ₂₈ N ₂ O ₁₈ S ₄ + 4H ₂ O. Calculated%: N 2.39; S 10.96.

Similarly, by sulphonation of a pure yellow 4K cubic dye, a dye of formula II is obtained, n = 4. Found%: S 12.97, 12.68: N 2.56, 2.64. C ₄₂ H ₁₈ N ₂ O ₁₈ S ₄ . Calculated%: S 13.25; N, 2.90.

Similarly, by sulfonation of cubic gray 2C, a dye of the formula IV is obtained, R = anthraquinonyl-1-amino, n = 4. Found%: N 2.36, 2.61: S 10.98. 11 a.m. C ₅₀ H ₂₄ N ₂ O ₁₈ S ₄ + 4H ₂ O. Calculated%: N 2.46; S 11.23.

Similarly, by sulfonation of a cubic dark green W, a dye of the formula XII, R = a), n = 3 is obtained. Found%: S 12.24, 12.57; N, 1.80, 2.01. C ₃₁ H ₁₅ NO ₁₂ S ₃ + 3H ₂ O. Calculated%: S 12.94; N 1.88.

Similarly, by sulfonation of a 9-bromo derivative of a vat dark green W, a dye of formula XII, R = b), n = 2, is obtained. Found%: S 7.98, 8.12; Br 9.55, 9.60; N 1.45, 1.67. C ₃₁ H ₁₄ BrNO ₉ S ₂ + 4H ₂ O. Calculated%: S 8.44; Br 9.73; N 1.70.

Similarly, sulphonation of VAT 23 produces a dye of formula XII, R = c), n = 4. Found% S 11.57, 11.88. C ₄₅ H ₂₂ N ₂ O ₁₇ S ₄ + 4H ₂ O. Calculated%: S 12.08.

 Example 3. The synthesis of the dye of the formula III, R = H, n = 2.

5 g of Diphaloalkarbazole are dissolved in a mixture of 10 ml of 20% oleum and 20 ml of chlorosulfonic acid and heated at 85-90 ^o C for 10-12 hours. At the end of the exposure, the reaction mass is cooled and diluted with water to obtain 50% sulfuric acid. The precipitate formed is filtered off, washed with 16% hydrochloric acid and dried. The precipitate is then dissolved in 150 ml of water at a pH of 6 and 100 ml of isopropyl alcohol is added. The precipitate formed is filtered off, washed with a 1: 1 water-isopropanol mixture and dried. Obtain 5.8 g of dye III, R = H, n = 2. Found%: S 9.34, 9.65; N, 2.00. 2.35. C ₂₈ H ₁₃ NO ₁₀ S ₂ + 4H ₂ O. Calculated%: S 9.73; N 2.12.

Similarly, the dye of formula III, R = NHCOPh, n = 3, is obtained by sulfonation of 4,5'-dibenzoylaminodiphthaloalkarbazole. Found%: S 10.36, 10.55; N, 4.07, 4.26. C ₄₂ H ₂₃ N ₃ O ₁₅ S ₃ + 3H ₂ O. Calculated%: S 10.94; N, 4.38.

Similarly, the dye of formula III, R = NHCOPh, n = 4, is obtained by sulfonation of 5,5'-dibenzoylaminodiphthaloalkarbazole. Found%: S 11.87, 11.98: N 3.98, 4.11. C ₄₂ H ₂₃ N ₃ O ₁₈ S ₄ . Calculated%: S 12.13; 4.26.

Similarly, by sulfonation of 1,4,5,8-naphthalene tetracarboxylic acid hydroxyphenylimide methylbenzimidazole (NTCC), a dye of the formula V is obtained, R = OH, R ′ = CH ₃ , n = 3. Found%; N, 5.33, 5.60; S 12.00, 12.23. C ₂₇ H ₁₅ N ₃ O ₁₃ S ₃ + 3H ₂ O. Calculated%: N 5.68; S 12.99.

Similarly, by sulfonation of chlorobenzimidazole NTCC with butylphenylimide, a dye of formula V is obtained, R = C ₄ H ₉ , R ′ = Cl, n = 2. Found%: Cl 4.68, 5.12: N 5.33, 5.60; S 8.90, 9.23. C ₃₀ H ₂₀ ClN ₃ O ₉ S ₂ + 2H ₂ O. Calculated%: Cl 5.06; N, 5.99; S 9.12.

Similarly, by sulfonation of methylbenzimidazole ethoxyphenylimide NTCC, a dye of the formula V is obtained, R = C ₂ H ₅ O, R ′ = CH ₃ , n = 3. Found%: N 5.00, 5.32; S 11.90, 12.45. C ₂₉ H ₁₉ N ₃ O ₁₃ S ₃ + 3H ₂ O. Calculated%: N 5.48; S 12.52.

Similarly, by sulfonation of methylbenzimidazole NTCC bromophenylimide, a dye of formula V is obtained, R = Br, R ′ = CH ₃ , n = 2. Found%: Br 10.77, 10.98; N, 5.45, 5.71: S 9.56, 9.79. C ₂₇ H ₁₅ BrN ₃ O ₉ S ₂ + 2H ₂ O. Calculated%: Br 11.36; N, 5.97; S 9.09.

Similarly, by sulfonation of methylbenzimidazole 3,4,9,10-perylenetetracarboxylic acid hydroxyphenylimide (PTCC), a dye of formula VI is obtained, R = OH, R ′ = CH ₃ , n = 3. Found%: N 5.54, 5.76; S 11.87, 12.00. C ₃₁ H ₁₉ N ₃ O ₁₃ S ₃ + 3H ₂ O. Calculated%: N 5.32; S 12.14.

Similarly, by sulfonation of chlorobenzimidazole PTCC butylphenylimide, a dye of formula VI is obtained, R ₄ H ₉ , R ′ = Cl, n = 2. Found%: Cl 4.32, 4.40; N, 5.34; 5.39; S 8.90, 9.34. C ₃₄ H ₂₄ ClN ₃ O ₉ S ₂ + 2H ₂ O. Calculated%: Cl 4.71: N 5.57; S 8.49.

Similarly, by sulfonation of the benzimidazole methoxyphenylimide of 3,4,9,10-antanthronetetracarboxylic acid (AATCC), a dye of the formula VII is obtained, R ′ = CH ₃ O, R ′ = H, n = 3. Found%: N 4.59, 4.76; S 10.45, 10.51. C ₃₉ H ₁₇ N ₃ O ₁₅ S ₃ + 3H ₂ ). Calculated%: N 4.75; S 10.85.

Similarly, by sulphonation of methylphenylimide bromobenzimidazole AATCC, a dye of formula VII is obtained, R = CH ₃ , R ′ = Br, n = 2. Found%: Br 8.56, 8.70; N, 4.33, 4.50; S 7.69, 7.90. C ₃₉ H ₁₆ BrN ₃ O ₁₁ S ₂ + 2H ₂ O. Calculated%: Br 9.07; N, 4.76; S 7.26.

Similarly, by sulfonation of a dihydroxyisoviolantrone, a dye of formula IX is obtained, R = OH, n = 2. Found%: S 8.98, 9.08. C ₃₄ H ₁₆ O ₁₆ S ₂ + 2H ₂ O. Calculated%: S 9.37.

Similarly, by dimethoxyisoviolantrone sulfonation, a dye of formula IX is obtained, R = CH ₃ , n = 2. Found%: S 9.65, 9.49. C ₃₆ H ₁₈ O ₁₀ S ₂ + 2H ₂ O. Calculated%: S 9.03.

Similarly, by dimethoxyviolantrone sulfonation, a dye of the formula X is obtained, R = CH ₃ , n = 2. Found%: S 9.75, 9.60. C ₃₆ H ₁₈ O ₁₀ S ₂ + 2H ₂ O. Calculated%: S 9.03.

Similarly, by sulfonation of dianilino dichloropyreninquinone, a dye of the formula XI, R = H, n = 2 is obtained. Found%: S 9.88, 9.95. C ₂₈ H ₁₈ Cl ₂ N ₂ O ₈ S ₂ + 2H ₂ O. Calculated%: S 9.42.

Similarly, by sulfonation of di (4-chloroanilino) - dichloropyreninquinone, a dye of the formula XI, R = 4-Cl, n = 2 is obtained. Found%: S 8.78, 8.90. C ₂₈ H ₁₆ Cl ₄ N ₂ O ₈ S ₂ + 2H ₂ O. Calculated%: S 8.55.

Similarly, sulphonation of a cubic gray C gives a dye of formula XIII, n = 3. Found%: S 10.97, 11.21. C ₄₅ H ₂₁ N ₃ O ₁₃ S ₃ . Calculated%: S 10.60.

 Example 4. The synthesis of the dye of the formula V, R = R '= H, n = 2.

10 g of benzimidazole phenylimide NTCC is dissolved in 50 ml of 10% oleum and heated at 80-85 ^o C for 4 hours. At the end of the exposure, the reaction mass is cooled and diluted with 100 ml of water. The precipitate formed is filtered off, washed with concentrated hydrochloric acid until there is no sulfate anion in the wash water, squeezed and dried. 12.45 g of dye V, R = R ′ = H, n = 2, is obtained. Found%: N 6.98, 7.10: S 11.67, 11.73. C ₂₆ H ₁₃ N ₃ O ₉ S ₂ + 2H ₂ O. Calculated%: N 7.30; S 11.13.

Similarly, by sulfonation of methoxyphenylimide with benzimidazole NTCC, a dye of the formula V is obtained, R = CH ₃ O, R ′ = H, n = 2. Found%: N 6.33, 6.40; S 10.34, 10.50. C ₂₇ H ₁₅ N ₃ O ₁₀ S ₂ + 2H ₂ O. Calculated%: N 6.55; S 9.98.

Similarly, a dye of the formula V is obtained, R = NHPh, R '= H, n = 4. Found%: N 5.89, 6.10; S 13.90, 14.11. C ₃₂ H ₁₈ N ₄ O ₁₅ S ₄ + 4H ₂ O. Calculated%: N 6.24; S 14.25.

In a similar manner, a dye of formula V is obtained, R = OC ₆ H ₅ , R ′ = CH ₃ , n = 3. Found% N 4.78, 5.10; S 11.45, 11.63. C ₃₃ H ₁₉ N ₃ O ₁₃ S ₃ + 3H ₂ O. Calculated%: N 5.15; S 11.78.

Similarly, by sulfonation of the benzimidazole PTAC phenylimide, a dye of formula VI is obtained, R = R ′ = H. n = 2. Found%: N 5.87, 5.90; S 9.99, 10.12. C ₃₀ H ₁₇ N ₃ O ₉ S ₂ + 2H ₂ O. Calculated%: N 6.33; S 9.65.

Similarly, by sulfonation of the benzimidazole PTCC methoxyphenylimide, a dye of formula VI is obtained, R = CH ₃ O, R ′ = H, n = 2. Found%: N 5.34, 5.60; S 9.45, 9.63. C ₃₁ H ₁₉ N ₃ O ₁₀ S ₂ + 2H ₂ O. Calculated%: N 5.91; S 9.00.

Similarly, a dye of formula VI is obtained, R = NHPh, R ′ = H, n = 4. Found%: N 5.46, 5.66; S 13.00, 13.47. C ₃₆ H ₂₂ N ₄ O ₁₅ S ₄ + 4H ₂ O. Calculated%: N 5.89; S 13.47.

Similarly, by sulfonation of ethoxyphenylimide bromobenzimidazole PTCC, a dye of formula VI is obtained, R = C ₂ H ₅ O, R ′ = Br, n = 2. Found%: Br 9.78, 9.90; N, 4.98, 5.12; S 8.23, 8.45. C ₃₂ H ₂₀ BrN ₃ O ₁₀ S ₂ + 2H ₂ O. Calculated%: Br 10.18; N, 5.34; S 8.14.

Similarly, by sulphonation of benzimidazole AATCC phenylimide, a dye of formula VII is obtained, R = R ′ = H, n = 2. Found%: N 4.87, 4.90; S 8.45, 8.64. C ₃₈ H ₁₅ N ₃ O ₁₁ S ₂ + 2H ₂ O. Calculated%: N 5.32; S 8.11.

Similarly, by sulfonation of chlorobenzimidazole ethoxyphenylimide AATCC, a colorant of formula VII is obtained, R = C ₂ H ₅ O. R '= Cl, n = 2. Found%: Cl 3.67, 3.90; N, 4.34, 4.51. C ₄₀ H ₁₈ ClN ₃ O ₁₂ S ₂ + 2H ₂ O. Calculated%: Cl 4.08; N, 4.83; S 7.36.

Similarly, a dye of the formula VII is obtained, R = OPh, R ′ = CH ₃ , n = 3. Found%: N 3.99, 4.27; S 9.45, 9.81. C ₄₅ H ₂₁ N ₃ O ₁₅ S ₃ + 3H ₂ O. Calculated%: N 4.23; S 9.67.

Example 5. The synthesis of the dye of the formula VIII, R = CH ₃ O.

10 g of Dimethoxythioindigo are dissolved in 50 ml of 18-25% oleum and incubated at room temperature for 15-18 hours until a water-soluble sample. At the end of the exposure, the reaction mass is diluted with water to obtain 50% sulfuric acid, 25 g of sodium chloride are added, heated to 50 ^o C and filtered. The precipitate is washed with a 15% solution of sodium chloride, then with 16% hydrochloric acid until no sulfate anion is present and dried. The resulting precipitate is boiled with 100 ml of ethyl alcohol and filtered hot, then washed with 20 ml of alcohol and dried. 12.4 g of a dye of formula V are obtained, R = CH ₃ O. Found%: S 21.77, 21.89. C ₁₈ H ₁₂ O ₁₀ S ₄ + 4H ₂ O. Calculated%: S 21.81.

Similarly, by sulfonation of thioindigo orange KX, a dye of formula V, R = C ₂ H ₅ O is obtained. Found%: S 20.34, 20.42. C ₂₀ H ₁₆ O ₁₀ S ₄ + 4H ₂ O. Calculated%: S 20.82.

Similarly, by sulfonation of thioindigo pink 2C, a dye of formula V, R = Cl, is obtained. Found%: S 22.26, 22.44; Cl 12.09, 12.23. C ₁₆ H ₆ Cl ₂ O ₈ S ₄ + 2H ₂ O. Calculated%: S 22.86; Cl 12.64.

Similarly, sulfonation of dianisidino-dichloropyreninquinone gives a dye of formula VIII, R = CH ₃ O, n = 2. Found%: S 8.33, 8.50; Cl 10.05, 10.10; N, 3.60, 3.68. C ₃₀ H ₂₂ Cl ₂ N ₂ O ₁₀ S ₂ + 2H ₂ O. Calculated%: S 8.65; Cl 9.58; N, 3.78.

Similarly, by sulfonation of the corresponding substituted diphenylamino-dichloropyrenequinone, dyes of the formula VIII are obtained, where R = CH ₃ , C ₂ H ₅ O.

Similarly, by sulfonation of the corresponding derivatives of 6-arylaminopyrimidantrons, dyes of the formula XIV are obtained: R = Ph, R '= CH ₃ , X = H, n = 2. Found%: N 6.66, 6.89; S 10.78, 10.90. C ₂₆ H ₁₉ N ₃ O ₇ S ₂ + 2H ₂ O. Calculated%: N 7.04; S 10.72. R = H, R '= NHC ₆ H ₅ , X = Br, n = 2. Found%: Br 11.78, 11.90; N, 7.98, 8.30; S 8.97, 9.20. C ₂₆ H ₁₇ BrN ₄ O ₇ S ₂ + 2H ₂ O. Calculated%: Br 11.82; N, 8.27; S 9.45. R = C ₆ H ₅ , R '= OC ₆ H ₅ , X = H, n = 3. Found%: N 5.01, 5.33; S 11.90. 12.25. C ₃₂ H ₂₁ N ₃ O ₁₁ S ₃ + 3H ₂ O. Calculated%: N 5.43; S 12.42. R = ClC ₆ H ₄ , R '= OC ₆ H ₅ , X = SO ₃ H, n = 2. Found%: Cl 4.00, 4.34; N, 4.90, 5.11; S 11.78, 11.98. C ₃₂ H ₂₀ ClN ₃ O ₁₁ S ₃ + 3H ₂ O. Calculated%: Cl 4.39; N 5.20; S 11.89.

 Example 6. The synthesis of dyes of the formula XV is carried out according to the known method "3" from the corresponding derivatives of 1-amino-4-6romanthraquinone.

Example 7. The synthesis of the dye of the formula XVI, R '= R "= CH ₃ , n = 2, Y = CH ₃ SO ₄ .

 3.08 g of 1,4-diaminoantraquinone-2,3-dicarboxylic anhydride, 1.32 g of dimethylaminoethylamine in 30 ml of acetic acid are heated to boiling and kept at boiling for 4 hours. At the end of the exposure, the reaction mass is cooled, the precipitate is filtered off, washed with alcohol and dried. Obtain 3.6 g of 1,4-diaminoantraquinone-2,3-dicarboxylic acid dimethylaminoethylimide.

 The resulting imide is suspended in 100 ml of chlorobenzene and 0.5 ml of dimethyl sulfate in 10 ml of chlorobenzene is added at room temperature, stirred for 5 hours and left overnight. The precipitate is filtered off, washed with benzene, petroleum ether and dried. 4.85 g of dye are obtained.

In a similar manner, a dye of formula XVI, R ′ = C ₂ H ₅ , R ″ = CH ₃ , Y = CH ₃ SO ₄ or Cl, is prepared using 3-diethylaminopropylamine.

 The synthesis of azo dyes of the formula XVII is carried out according to a standard procedure, for example, “4”, by azo coupling of the corresponding diazonium salts with phenylaminoethylalkyl dimethylammonium salts, which are obtained by the method of “5”.

 The synthesis of dyes of the formula XVIII is carried out according to the standard method "4".

 The synthesis of dyes of the formula XIX is carried out according to the known method "6".

 The azo dyes of formula XX are prepared in a known manner (7).

 Example 8. Synthesis of a dye of the formula XXPa, R '= H, Y = H, n = 30.

39.4 g (0.1 mol) of 1,1'-binaphthyl-4,4 'dianhydride, 5,5'-tetracarboxylic acid (BTCC), 12.96 g (0.12 mol) of para-phenylenedimamine and 8.2 g of sodium acetate in 300 ml of dimethylacetamide (DMMA ) or dimethyl sulfoxide (DMSO) is heated at 100-120 ^o C for 12 hours. At the end of the exposure, the reaction mass is poured onto a mixture of 1000 ml of water and 100 ml of concentrated hydrochloric acid, the precipitate formed is filtered off, washed with water and dried. 45.2 g (95.8%) of dye are obtained. Mass-average molecular weight M.M. = 14000.

 In this example and in all subsequent ones, the MM values determined by the sedimentation method and the corresponding average values of the number of links n are given. As a rule, the range of distribution by mass for all dyes corresponds to the range by number of links from 20 to 300.

 Example 9

 Dye XXIIb, R '= COOH, Y = H. n = 40 is obtained in a similar manner by condensation of 1,1'-binaphthyl-4.4'5,5'8,8'-hexacarboxylic acid dianhydride (BGCC) with para-phenylenediamine, M.M. = 21600.

 Example 10

Analogously to example 8, dye XXIIb is obtained, R '= NO ₂ , Y = H, n = 50 by condensation of 8,8'-dinitro-BTCC dianhydride with benzidine in acetic acid, M.M. = 27800.

 Example 11

Synthesis of dye XXIIc, R '= SO ₃ H, X = O, Y = H, n = 60.

5.54 g (0.01 mol) of 8.8'-disulfonic acid BTCC, 2.38 g (0.012 mol) of 4,4'-diaminodiphenyl ether and 0.82 g of sodium acetate in 100 ml of water are heated at 100-105 ^o C for 10 hours, then the reaction mass is cooled, acidified to pH 1.0 and filtered. The precipitate is squeezed and washed with water until neutral. 7.02 g (93.8%) of the dye are obtained, M.M. = 43100.

 Example 12

Analogously to example 11, the dye XXIIb, R '= SO ₃ H, X = CH = CH, Y = SO ₃ H, n = 75 is obtained by condensation of 8,8'-disulfonic acid BTCC with 4,4'-diaminostilbene-2,2' -disulfonic acid, M.M. = 66700.

 Example 13

Analogously to example 10, dye XXIIb, R '= COOH, Y = COOH n-70 is obtained by condensation of BGCC dianhydride with benzidine-3,3'-dicarboxylic acid, M.M. = 50300
Example 14

Analogously to example 10, the dye XXIIb, R'-COOH, Y = CH ₃ O n = 60 is obtained by condensation of the BGCC dianhydride with dianisidine, M.M. = 41400
Example 15

Analogously to example 8, dye XXIIb, R '= COOH, X = CONH, Y = H, n = 80 is obtained by condensation of BGCC dianhydride with 4,4'-diaminobenzanilide, M.M. = 53900
Example 16

Analogously to example 10, the dye XXIIb, R '= H, Y = CH ₃ n = 85 is obtained by condensation of BTCC dianhydride with 3,3'-tolidine, M.M. = 48500
Example 17

Analogously to example 11, the dye XXIIb, R ′ = SO ₃ H, X = NH, Y = H and SO ₃ H, n = 60, is obtained by reacting 8,8′-disulfonic acid BTCC with 4,4′-diaminodiphenylamine-2-sulfonic acid, M.M. = 47800
Example 18
Analogously to example 8, the dye XXIIb, R '= COOH, X = NHCONH, Y = H is obtained by condensation of BGCC dianhydride with 4,4'-diaminodiphenylurea.

 Example 19

Synthesis of dyes of the formula XXIII (general procedure). R '= H, n = 90
0.01 mol of 8.8'-disubstituted BTCC dianhydride, 0.01 mol of tetraminodiphenyl ether and 0.8 g of sodium acetate in 100 ml of dimethyl sulfoxide are heated at 100-110 ^° C for 10-15 hours. At the end of the reaction (control by TLC on plates with a fixed layer of silica gel), the reaction mass is poured into a mixture of 1000 ml of water and 100 ml of concentrated hydrochloric acid. The precipitate is filtered off, washed with water and dried. Yield 85-90%, M.M. = 61400
Example 20. The synthesis of dyes of formula XXIV (General procedure), R = -C ₆ H ₄ -, n = 120
0.01 mol of 1,4,5,8-naphthalene-tetracarboxylic acid dianhydride (NTCC) and 0.01 mol of p-phenylenediamine in 100 ml of polyphosphoric acid are heated at 200 ^° C. for 25 hours. Then the reaction mass is cooled to 70-90 ^o C and poured into a thin stream of 500 g of crushed ice. The precipitate is filtered off, washed with water and dried. Yield 90-95%. M.M. = 40600
Example 21

Analogously to example 19, the dye XXV, Y = H, n = 130, M.M. = 55400 is obtained by condensation of the NTCC dianhydride with tetraaminodiphenyl ether.
Example 22

Synthesis of dye XXV, Y = SO ₃ H, n = 150
5.0 g of Dye XXV, Y = H is dissolved in 50 ml of 20% oleum, heated to 85-90 ^o C and kept at this temperature for 5 hours to obtain a water-soluble sample. At the end of the exposure, the reaction mass is cooled to room temperature and, with ice cooling, 90 ml of water are pinned so that the temperature of the reaction mass does not exceed 35-40 ^° C. Then it is stirred for 30 minutes, then it is filtered and washed first with 55% sulfuric acid, then 40%. Then the precipitate is washed with 15% hydrochloric acid and dried. 6.46 g (93.8%) of dye are obtained. M.M. = 88000
Example 23

 Synthesis of dyes of the general formula XXVI (standard procedure).

To a solution of 3.6 g of a dye of the formula XXII, R '= COOH, R = -C ₆ H ₄ -, n = 120 in 300 ml of a 2% sodium hydroxide solution, 9.0 g of sodium dithionite are added, heated to 80-85 ^o C and maintained at this temperature for 30 minutes. Then, air is blown through the obtained violet solution until a red precipitate forms, which is filtered off, washed with water and dried. The yield of XXVI dyes (R = C ₆ H ₄ -, n = 120) is 65-80%, M.M. = 55900
Example 24

Synthesis of dye XXVII, Y = H, n = 160
To a solution of 5.2 g of dye XXIII, R '= COOH in 500 ml of a 2% sodium hydroxide solution, 2.5 g of sodium hydroxymethyl sulfinate are added, heated to 96-98 ^° C and kept at this temperature for 30 minutes. Then, air is blown through the obtained blue-violet reaction mass until the excess of the reducing agent disappears and a blue precipitate forms, which is filtered off, washed with water and dried. Obtain 3.9 g (88%) of the dye. M.M. = 93100
Example 25

Synthesis of dye XXVII, Y = SO ₃ H, n = 95
2.5 g of dye XXVII, Y = H is dissolved in 10 ml of 20% oleum, 5 ml of chlorosulfonic acid is added, heated to 85-90 ^o C and kept at this temperature for 8-10 hours to obtain a water-soluble sample. At the end of the exposure, the reaction mass is cooled and 30 ml of water are added dropwise at a temperature not exceeding 40 ^° C., stirred for 30 minutes at room temperature and filtered. The precipitate is filtered off, squeezed, washed with 20% hydrochloric acid until there are no sulfate anions (sample with barium chloride) and dried. Obtain 2.8 g (88%) of the dye. M.M. = 70500
Example 26

 Synthesis of dyes of the formula XXVIII, Y = H (general procedure).

0.01 mol of the Dye of formulas XXII, R '= COOH R = -C ₆ H ₄ NHCO-, n = 120 is dissolved in 100 ml of 95-98% sulfuric acid and heated to 120-125 ^o C, and then kept at this temperature for 2-3 hours. At the end of the exposure, the reaction mass is cooled and diluted with 500 ml of water, the precipitate formed is filtered off, washed with water and dried. Yield 95-97%. M.M. = 67700
Example 27

Analogously to example 25, by sulfonation of dye XXIX, Y = H n = 130, dye XXIX, Y = SO ₃ H, n = 130, M.M = 93900 is obtained
Example 28

Synthesis of dyes of formula XXX (general procedure R = -C ₆ H ₄ -, R '= OH, M = NH $\genfrac{}{}{0ex}{}{\text{+}}{\text{4}}$ n = 170
a) Diazotization of p-phenylenediamine.

0.05 mol of p-phenylenediamine is dissolved in a mixture of 100 ml of water and 30 ml of 30% hydrochloric acid. The resulting solution was cooled with ice to 0 ^° C. and 0.1 mol of sodium nitrite was added as a 30% solution, after which it was stirred for 1 hour.

 b) The combination.

1-2 hours before the combination, a solution of the azo component is prepared by dissolving 0.05 mol of Ash or chromotropic acid in 100 ml of water in the presence of soda. The resulting solution at a temperature of 6-8 ^o C is poured for 1 hour to a solution of the diazocompound, and then stirred for 1-2 hours. Then the reaction mass is alkalinized by adding 10 ml of a 40% sodium hydroxide solution, 10 g of soda and ice are added to a temperature of 2-4 ^° C. and stirred for 4-6 hours. At the end of the reaction, a mixture of 150 ml of isopropanol and 100 ml of a saturated solution of ammonium bicarbonate is added to the reaction mixture, incubated for 3-5 hours, the precipitate formed is filtered off and washed with 100 ml of a saturated solution of ammonium bicarbonate. The dye is dried at a temperature of 80-100 ^o C. M.M. = 78200
Example 29

Synthesis of dyes of the formula XXXI, A = a, b, c (general procedure) R = -C ₆ H ₄ -, n = 180
0.01 mol of Corresponding dichlorantraquinone, 0.01 mol of p-phenylenediamine, 1.0 g of copper acetate in 25 ml of nitrobenzene is heated at 170 -180 ^o C for 15 hours, then the reaction mass is cooled, the precipitate formed is filtered off, washed with 25 ml of ethanol, squeezed and boiled with 100 ml of 5% hydrochloric acid at the boil. The suspension is cooled and filtered. The precipitate is washed with water until neutral and dried. The dye yield is 88-95%. M.M. = 50400
Example 30

Synthesis of dyes of the formula XXXI, A = d (general procedure) R = -C ₆ H ₄ -, n = 160
0.01 mol of 2,7-dibromantantrone, 0.01 p-phenylenediamine, 1.0 g of copper oxide, 1.5 g of soda are loaded into 30 ml of nitrobenzene, heated at 200-205 ^o C for 12-18 hours, then the reaction mass is cooled, the precipitate is filtered off, washed with 3 portions of 10 ml of acetic acid, squeezed and boiled with 100 ml of 5% hydrochloric acid. The suspension is cooled and the precipitate is filtered off, washed with water and dried. The yield of dye is 85-95%. M.M. = 63000
Example 31

Analogously to example 30, by the condensation of 3,9-dibromobenzantrone with p-phenylenediamine, dyes of the formula XXXI, A = e, are obtained. R = C ₆ H ₄ , n = 120, M.M. = 40100
Example 32

Analogously to example 30, dyes of the formula XXXI, A = f, are obtained by condensation of tetrachloropyrenequinone with 4,4'-diaminostilbene. R = C ₆ H ₄ CH = CHC ₆ H ₄ , n = 105, M.M. = 53000
Example 33

Analogously to example 30, dyes of dibromindigo with 4,4'-diaminostilbene were obtained by dyes of the formula XXXI, A = g. R = C ₆ H ₄ CH = CHC ₆ H ₄ , n = 110, M.M. = 51500.

 Example 34

Translation of polymer dyes of formulas XXII-XXXI in a water-soluble form (general method):
Method A.

2.5 g of a polymer dye type XXII-XXIV is dissolved in 20 ml of monohydrate and heated to 50 ^o C, kept at this temperature for 5-15 hours to obtain a water-soluble sample. At the end of the reaction, sulfomass is diluted with 40 ml of water, the precipitate is filtered off, washed with 17.5% hydrochloric acid, then with 5% hydrochloric acid until sulfate anions are absent in the wire (barium chloride sample). For purification, dyes are reprecipitated from water with a mixture of isopropanol and a saturated solution of ammonium bicarbonate.

Method B:
2.5 g of Polymer dye type XXV-XXIX, dissolved in 10 ml of 10-20% oleum, add 10 ml of chlorosulfonic acid and heated at 70-80 ^o C for 7-8 hours to obtain a water-soluble sample. At the end of the reaction, the sulfomass is diluted with 50 ml of water, the precipitate formed is filtered off, washed first with concentrated hydrochloric acid, then with 17.5% and 5% hydrochloric acid until there are no sulfate anions in the promoter. For purification, dyes are reprecipitated and water with a mixture of isopropanol and a saturated solution of ammonium bicarbonate.

Method B:
2.5 g of the Polymer dye of the formula XXXI-XXXII is dissolved in 20 ml of 20-25% oleum, heated at 85-90 ^o C for 10-12 hours until a water-soluble sample is formed. At the end of the reaction, the mass is diluted with 50 ml of water, the precipitate is filtered off, washed with concentrated hydrochloric acid, then with 17 and 5% hydrochloric acid until there are no sulfate anions in the wash water. For cleaning, dyes are reprecipitated from water with a mixture of isopropanol and a saturated solution of ammonium carbonate.

 Example 35

Synthesis of dyes of the formula XXXIII, Ro = H, X = NH, R = C ₆ H ₄ , A = a, n = 145
To 3.5 g of 1-amino-4- (4'-aminophenyl) aminoanthraquinone in 25 ml of o-dichlorobenzene, 1.35 g of acrylic acid chloride was added and heated at 85-90 ^° C for 3 hours. At the end of the exposure, the reaction mass is cooled, 25 ml of petroleum ether are added and stirred at room temperature for 30 minutes. The precipitate formed is filtered off, washed with petroleum ether and dried. The obtained acyl derivative was dissolved in 30 ml of dimethylformamide, 0.025 g of ammonium persulfate was added, then nitrogen was added to the reaction mass with stirring for 30 minutes, and heated at 80 ^° C for 4 hours. The resulting mass was diluted with 300 ml of water, the precipitate was filtered off, washed with water, methanol and dried. The yield of dye was 4.6 g (98%). M.M. = 66600
Example 36

Analogously to example 33 receive the dye XXXIII, Ro = CH ₃ , X = O, R = C ₆ H ₄ C ₆ H ₄ A = e, M = NH ₄ , n = 80, M.M. = 63400
Example 37

Analogously to example 33, dye XXXIII is obtained, Ro = H, X = NH, R = (CH ₂ ) ₃ , A = c, n = 85, M.M. = 35500
Example 38

Analogously to example 33, dyes XXXIII, Ro = CH ₃ , X = NH, R = C ₆ H ₄ OC ₆ H ₄ A = d, R ₃ = H or Br, z = H are obtained. n = 95, M.M. = 53000
Example 39

Synthesis of dyes of the formula XXXIII, Ro = CH ₃ , X = NH, R = C ₆ H ₄ (General procedure), A = b, M = H, n = 105
To a solution of 0.01 mol of 1-amino-4- (p-aminophenyl) aminoantraquinone-2-sulfonic acid in 25 ml of dimethyl sulfoxide, 1.5 g of methacrylic acid chloride was added and heated at 45-50 ^° C for 2 hours. At the end of the exposure, the reaction mass is poured onto 300 ml of a 1% hydrochloric acid solution, the precipitate formed is filtered off, washed with water and dried. The obtained monomeric dye is stirred in a stream of nitrogen in 30 ml of distilled water, 0.1 g of potassium persulfate in 4 ml of distilled water is added, after which the reaction mass is heated at 80 ^° C for 2 hours. To the resulting reaction mass add 70 ml of acetone, the precipitated precipitate is filtered off, washed with acetone, petroleum ether and dried. The dye yield is quantitative. M.M. = 49700
Example 40

Analogously to example 39, dyes of the formula XXXIII are obtained, X = NH, R ₀ = CH ₃ , R = C ₆ H ₄ CH = CHC ₆ H ₄ A = d), R ₃ and z = SO ₃ H. n = 85, M. M. = 62200
Example 41

 Analogously to example 30, dyes of the formula XXXII are synthesized by the joint polycondensation of NTAC, PTAC dianhydrides and dihalo derivatives of polycyclic compounds with aromatic diamines. As a solvent, quinoline can be used.

 Example 42

 Analogously to example 37, by co-polymerization of two or three monomeric dyes, dyes of the formula XXXIV are synthesized.

 The characteristics obtained on the basis of the claimed material PP are presented in the Table, from which it follows that the claimed material allows to obtain DPS of yellow, red, green and, very importantly, gray colors with high polarization characteristics (dichroic ratio is greater than 15).

 Thus, as can be seen from the presented Table, the claimed material can improve the polarization characteristics of DPS (Kd above 15) compared with the prototype - Kd 7-12. This allows the use of DPS based on the claimed material not only in the automotive industry and architecture, but also in the manufacture of devices for recording and displaying information on high-resolution liquid crystals.

Claims (4)

A material for dichroic light polarizers, including as a film-forming component an organic dye capable of forming a liquid crystalline phase, and a solvent, characterized in that as a film-forming component it contains an organic dye of the formula I-XXXIV or a mixture thereof

M - cation, n = 2 - 4

R = H, NHCOPh

R, M, n = 2 - 4

R, R '= H, Hal, Alk, OAlk, OPh, ArNH
M is a cation, n = 2 - 4

R = H, OH, OCH ₃
M is a cation, n = 2 - 4

R = H, OH, OCH ₃
M is a cation, n = 2 - 4

M - cation

X = O, CH ₂ , NH, CONH, CH = CH;
Y = H, CH ₃ , CH ₃ O, COOM, SO ₃ M;
R '= H, NO ₂ , COOM, SO ₃ M;
M - cation, n = 20 - 300

R '= H, NO ₂ , COOM, SO ₃ M;
M - cation, n = 20 - 300

Y = H, CH ₃ , CH ₃ O, COOM, SO ₃ M;
X = O, CH ₂ , NH, CONH, CH = CH;
M - cation, n = 20 - 300

Y = H, SO ₃ M; M - cation
n = 20 - 300

X = O, CH ₂ , NH, CONH, CH = CH;
Y = H, CH ₃ , CH ₃ O, COOM, SO ₃ M;
M is a cation; n = 20 - 300

Y = H, SO ₃ M; M is a cation; n = 20 - 300

X = O, CH ₂ , NH, CONH, CH = CH;
Y = H, CH ₃ , CH ₃ O, COOM, SO ₃ M;
M - cation, n = 20 - 300

Y = H, SO ₃ M;
M is a cation; n = 20 - 300

X = O, CH ₂ , NH, CONH, CH = CH;
Y = X, CH ₃ , CH ₃ O, COOM, SO ₃ M;
M is a cation; n = 20-300; R ', R''= OH, NH ₂

and additionally, a modifying additive selected from the group of low-volatile colorless organic compounds containing OH, CO, COOH, NH, CONH ₂ , CHO groups with a refractive index of nd = 1.41 - 1.47, in the following ratio, wt.%:
Organic dye of the formula I-XXXIV or a mixture thereof - 3.0 - 30.0
A modifying additive selected from a number of non-volatile colorless organic compounds containing OH, CO, COOH, NH, CONH ₂ , CHO groups with a refractive index of nd = 1.41 - 1.47 - 0.1 - 20.0
Solvent - Other
2. The material according to claim 1, characterized in that it contains an antioxidant and / or inhibitor in an amount of 0.01 to 1.0 wt.%.  3. The material according to claims 1 and 2, characterized in that it contains a surfactant in an amount of 0.1 to 10.0 wt.%.  4. The material according to claims 1 to 3, characterized in that it contains alkyl siliconate as a modifying additive.  5. The material according to claims 1 to 3, characterized in that it contains poly-p-phenylene terephthalimide as a modifying additive.

Images