Novel disperse azo dyes, their preparation and use

Abstract

The present invention relates to a compound of formula (1): The present invention relates to an azo dye of TIFF2026504705000022.tif57170, a dye mixture containing the azo dye, a method for producing the azo dye, specific uses of the azo dye, and semi-synthetic or synthetic hydrophobic fiber materials dyed or printed with the azo dye or the dye mixture.

Description

[Technical Field]

[0001] The present invention relates to azo disperse dyes based on 2-hydroxynaphthalene-3-carboxylic acid (BON) or derivatives of BON as coupling components, and to dye mixtures containing said azo dyes. The invention further relates to a process for producing such azo dyes, their use for dyeing or printing semi-synthetic and synthetic hydrophobic fiber materials, in particular textile materials, and semi-synthetic or synthetic hydrophobic fiber materials dyed or printed with said azo dyes or dye mixtures. [Background technology]

[0002] Azo dyes based on hydroxybenzoic acid as a coupling component have been known for a long time. These dyes have been investigated for various dyeing applications. Some salts of hydroxybenzoic acid monoazo dyes, such as copper or barium salts, are used as lakes, e.g., Pigment Red 64.

[0003] To date, BONO azo dyes have rarely been described for coloring synthetic textile materials. Relevant technical documents date back to the 1960s and 1970s. For example, as described in U.S. Patent No. 5,949,999, textile applications using BONO azo dyes in the free acid form or as alkali metal or alkaline earth metal salts have been limited to coloring polypropylene fibers, but these attempts have not been very successful.

[0004] Some azo dyes based on BONO acid have been described for dyeing polyester fibers. However, in this case, the BONO acid coupling component is used as an amide, as described, for example, in Patent Documents 2 and 3. These documents make little mention of dyeing polyester fibers with BONO acid azo dyes in the free acid form.

[0005] As an example, Non-Patent Document 1 describes a single azo dye synthesized by coupling 4-aminobenzanilide with BONO acid, but this dye is not suitable for practical use because it has poor build-up properties on polyester substrates. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] U.S. Patent No. 3,758,270 [Patent Document 2] German Patent Application Publication No. 2612964 [Patent Document 3] German Patent Application Publication No. 2643801 [Non-patent literature]

[0007] [Non-Patent Document 1] F. Urseanu et al. Revista de Chimie, 36 (6), 450-495 (1985) Summary of the Invention

[0008] Surprisingly, it has now been found that the novel azo dyes according to claim 1, in particular of formula (1), based on BONO acid (or a derivative of BONO acid) as coupling compound and diazo compounds of formula (2), show excellent results in terms of lightfastness and washfastness.

[0009] In particular, the present invention provides a compound of formula (1): [ka] (In the formula, R 1 represents hydrogen, halogen, nitro, cyano or C1-C4 alkoxy, preferably hydrogen, bromine or methoxy; D is a compound of the formula: [ka] (In the formula, n represents a number from 1 to 6, R 2 is unsubstituted or contains one or more C1 to C 12 Alkoxy groups, C1-C 12 Alkylcarbonyl group, C7-C 25 Aryl groups, C7-C 25 C1-C substituted with arylcarbonyl group, hydroxyl group, amino group, cyano group or halogen atom 12 Represents an alkyl chain, or is unsubstituted or has one or more C1-C 12 Alkoxy groups, C1-C 12 Alkylcarbonyl group, C7-C 25 C1-C substituted with arylcarbonyl group, hydroxyl group, amino group, cyano group or halogen atom 12 It may be substituted with an alkyl group, and may be —O—, —S—, or —NR 2 represents an aryl group, which may be interrupted one or more times by -, -COO- or -OOC- radicals, X represents a radical of hydrogen, halogen, preferably bromine or chlorine, nitro, C1-C6 alkyl, preferably methyl, or trifluoromethyl).

[0010] Preferably, R 1 represents hydrogen, bromine or methoxy.

[0011] Preferably, X represents hydrogen, methyl, chloro, or trifluoromethyl.

[0012] Preferably, n represents a number of 1 to 4.

[0013] n preferably represents 1, 2, 3 or 4, more preferably 1, 2 or 3, especially 1 or 2.

[0014] Preferably, R 2stands for methyl, ethyl, n-propyl, iso-propyl, n-butyl, n-pentyl, n-hexyl, 2-methoxy-ethyl, 2-ethoxy-ethyl, 2-(n-propoxy)-ethyl, 2-(n-butoxy)-ethyl, 2-ethoxy-iso-propyl, 2-(2-methoxyethoxy)ethyl, 2-(2-ethoxyethoxy)ethyl, benzyl, 2-phenylethyl, methoxy-carbonyl-methyl, ethoxy-carbonyl-methyl.

[0015] The present invention also relates to a process for preparing an azo dye of formula (1), in particular as defined above, which process comprises diazotizing an amine compound D-NH2 according to the general procedure, and then reacting the diazotized amine compound with an azo dye of formula: [ka] (In the formula, R 1 is defined above and is preferred) with a BON acid (2-hydroxynaphthalene-3-carboxylic acid) coupling component.

[0016] All definitions and preferred embodiments set out above for the azo dyes of formula (1) apply equally to the methods described herein.

[0017] The diazotization of the amine compound D-NH2 is carried out in a manner known per se, for example, using sodium nitrite in an acidic, e.g., hydrochloric or sulfuric acid-containing, aqueous medium. However, the diazotization can also be carried out using other diazotizing agents, for example, nitrosylsulfuric acid. During the diazotization, an additional acid, such as phosphoric acid, sulfuric acid, acetic acid, propionic acid, or hydrochloric acid, or a mixture of such acids, for example, a mixture of propionic acid and acetic acid, may be present in the reaction medium. The diazotization is advantageously carried out at a temperature of -10°C to 30°C, for example, -10°C to room temperature, in particular -5°C to 10°C.

[0018] The coupling reaction of the diazotized amine compound D-NH2 with the BONO acid coupling component of formula (3) is also effected in known manner, for example in an acidic, neutral or alkaline aqueous or aqueous-organic medium, preferably at temperatures between 0°C and 30°C, in particular below 20°C.

[0019] The BONO acid coupling components of formula (3) are known or can be prepared in a manner known per se, for example as described in US Pat. No. 1,503,984, US Pat. No. 1,947,819 and German Patent No. 561,425.

[0020] The present invention also relates to an azo dye obtained by the process described above.

[0021] The dyes of formula (1), especially as defined above, can be used advantageously in mixtures with other dyes to prepare mixed shades, for example reddish shades.

[0022] Accordingly, the present invention further provides that the dye of formula (1) is a dye of CI Disperse Red 050, CI Disperse Red 060, CI Disperse Red 072, CI Disperse Red 082, CI Disperse Red 86:1, CI Disperse Red 167, CI Disperse Red 277, CI Disperse Red 279, CI Disperse Red 302, CI Disperse Red 302:1, CI Disperse Red 342, CI Disperse Red 349, CI Disperse Red 356, CI Disperse Red 362, CI Disperse Red 376, CI Disperse Red 377, CI Disperse Red 378, CI Disperse Red 380, CI Disperse Red 383, CI Disperse Red 385, and / or formula: [ka] The present invention relates to a dye mixture, which is used in admixture with at least one further dye selected from the group consisting of the dyes

[0023] The amount of each dye in the dye mixture can vary over a wide range.

[0024] The dyes and dye mixtures according to the invention can be used for dyeing or printing semi-synthetic and especially synthetic hydrophobic fiber materials, more particularly textile materials. Textile materials made up of blends containing such semi-synthetic and / or synthetic hydrophobic fiber materials can likewise be dyed or printed using the dyes or dye mixtures according to the invention.

[0025] The amounts of the individual dyes in the dye mixture can vary over a wide range.The dyed products obtained according to the method of the present invention are characterized by a uniform shade and very good practical fastness properties, especially good lightfastness, heat fixation fastness, pleat fastness, chlorine fastness, and wet fastness, such as water fastness, sweat fastness, and washing fastness.The finished dyed products are further characterized by very good rubbing fastness.The good overall fastness properties of the dyed products and their excellent clarity should be particularly emphasized.

[0026] Semi-synthetic fiber materials that come into consideration are, in particular, cellulose 2.5 acetate and cellulose triacetate.

[0027] Synthetic hydrophobic fibre materials consist in particular exclusively of fibres based on linear aromatic polyesters, such as polyesters of terephthalic acid with glycols, in particular ethylene glycol, or condensation products of terephthalic acid with 1,4-bis(hydroxymethyl)cyclohexane; polycarbonates, such as the polycarbonate of α,α-dimethyl-4,4-dihydroxy-diphenylmethane with phosgene; and polyvinyl chloride or polyamide.

[0028] The dyes and dye mixtures according to the invention are applied to textile materials according to known dyeing methods. For example, polyester textile materials are dyed from aqueous dispersions in the presence of conventional anionic or nonionic dispersants and, optionally, conventional swelling agents (carriers) by the exhaust process at temperatures between 80°C and 140°C. 2.5 Cellulose acetate is preferably dyed at temperatures between 65°C and 85°C, and cellulose triacetate at temperatures between 65°C and 115°C.

[0029] The dyes and dye mixtures according to the invention do not dye wool and cotton which are simultaneously present in the dye liquor, or dye such materials only slightly (very good dye resistance), and can therefore also be satisfactorily used for dyeing polyester / wool and polyester / cellulosic fibre blend fabrics.

[0030] The dyes and dye mixtures according to the invention are suitable for dyeing by the thermosol process, the exhaust process and the printing process, in which the textile materials may be in various processed forms, for example in the form of fibres, yarns or nonwovens, wovens or knits.

[0031] The dyes and dye mixtures according to the invention can be advantageously converted into dye preparations before use. To this end, the dyes are milled to an average particle size of 0.1 to 10 microns. Milling can be carried out in the presence of a dispersant. For example, the dried dyes can be milled with a dispersant or kneaded with a dispersant to form a paste, which is then vacuum-dried or spray-dried. After adding water, the resulting preparations can be used to prepare printing pastes and dye liquors.

[0032] For printing, conventional thickeners are used, for example modified or unmodified natural products such as alginates, British gum, gum arabic, crystal gum, locust bean powder, tragacanth, carboxymethylcellulose, hydroxyethylcellulose, starch, or synthetic products such as polyacrylamide, polyacrylic acid or its copolymers, or polyvinyl alcohol.

[0033] The dyes and dye mixtures according to the present invention are also suitable as colorants for use in recording systems. Such recording systems are, for example, commercially available inkjet printers for printing paper or textiles, or writing instruments such as fountain pens or ballpoint pens, in particular inkjet printers. For this purpose, the dyes according to the present invention are first made into a form suitable for use in the recording system. A suitable form is, for example, an aqueous ink containing the dyes according to the present invention as colorants. The ink can be prepared in a conventional manner by mixing the individual components, if necessary in combination with suitable dispersing agents, in the desired amount of water.

[0034] The dyes and dye mixtures according to the invention impart to the above-mentioned materials, especially polyester materials, a uniform shade and very good practical fastness properties, such as in particular good lightfastness, heat fixation fastness, pleat fastness, chlorine fastness, and wet fastness properties, such as water fastness, sweat fastness, and wash fastness. The finished dyeings are further characterized by very good rub fastness. The good overall fastness properties of the dyeings and their excellent clarity should be particularly emphasized.

[0035] Furthermore, the dyes and dye mixtures according to the invention are also well suited for dyeing hydrophobic fibre materials from supercritical CO2.

[0036] The present invention relates to the above-mentioned use of the dyes and dye mixtures according to the invention, as well as to a process for dyeing or printing semi-synthetic or synthetic hydrophobic fiber materials, in particular synthetic hydrophobic fiber materials, more particularly textile materials, in which the dyes according to the invention are applied to or incorporated into said materials, said hydrophobic fiber materials being preferably textile polyester materials.

[0037] In the inkjet printing process, individual ink droplets are controlled and ejected from a nozzle onto a substrate. For this purpose, the continuous inkjet and drop-on-demand methods are mainly used. In the continuous inkjet method, droplets are continuously generated, and droplets not required for the printing operation are discharged into a receiver and reused. In contrast, in the drop-on-demand method, droplets are generated as needed and used for printing. That is, droplets are generated only when needed for the printing operation. Droplet generation can be achieved, for example, by a piezo inkjet head or by thermal energy (bubble jet). Piezo inkjet head printing and continuous inkjet printing are preferred.

[0038] The present invention also relates to hydrophobic fibre materials, preferably polyester textile materials, dyed or printed by the above process.

[0039] The dyes according to the invention are additionally suitable for modern reproduction processes, such as thermal transfer printing.

[0040] A further aspect of the present invention is therefore the use of a dye of formula (1) as defined above or a dye mixture as defined above in the dyeing or printing of semi-synthetic or synthetic hydrophobic fibre materials, in particular synthetic hydrophobic fibre materials, more particularly textile polyester materials, and a further aspect of the present invention is semi-synthetic or synthetic hydrophobic fibre materials, in particular textile polyester materials, dyed or printed with a dye of formula (1) as defined above or a dye mixture as defined above.

[0041] The following examples are intended to illustrate the invention. Unless otherwise specified, parts are parts by weight and percentages are percentages by weight. Temperatures are in degrees Celsius. Parts by weight relate to parts by volume in the same way that grams relate to cubic centimeters. DETAILED DESCRIPTION OF THE INVENTION [Example]

[0042] I. Manufacturing example I.1 Precursor synthesis: I.1.1 Synthesis of the diazotization component for dye (100) [ka] The synthesis of the diazotization component for dye (100) begins with 4-phenylbutanoic acid, which can be obtained by Friedel-Crafts acylation as described in J. Cai et al. Bioorg. Med. Chem. 23 (2015) pp. 657-667 or WO 2019202607, followed by Clemmensen reduction as described by L. M. Elmore J. Am. Chem. Soc. 1936, 58, 8, pp. 1438-1442.

[0043] In the first step, 4-phenylbutanoic acid is nitrated. [ka] To 75.0 g of deionized water, 50.0 g of 4-phenylbutyric acid is added. After cooling to 0°C, 485.0 g of sulfuric acid (95%) is added dropwise, followed by 33.0 g of nitric acid (65%) at 0°C to 12°C. 170.0 g of water is then added, raising the temperature to 32°C. After adding an additional 200 g of water, the reaction mixture is stirred overnight at low temperature. The precipitated crystals are filtered off and washed with water until neutral. Purification (removal of the ortho isomer) is carried out by column filtration (toluene / ethanol 2:1). Yield: 40.2 g (pale yellow solid) of 4-(4-nitrophenyl)butanoic acid. 1 H-NMR (CDCl3, 400 MHz): δ = 8.18, 7.38 (AA'BB', 4H, aromatic H), 2.82 (t, 2H, CH2), 2.44 (t, 2H, CH2), 2.03 (m, 2H, CH2).

[0044] The second step involves the reduction of 4-(4-nitrophenyl)butanoic acid to 4-(4-nitrophenyl)butanoic acid. [ka] To 500 mL of methanol was added 50.70 g of 4-(4-nitrophenyl)butyric acid, followed by 4.10 g of sodium bicarbonate and 2.55 g of palladium (5% on carbon). 15.7 L of hydrogen (1 bar pressure) was added over 2 hours. After the reaction was complete, the reaction mixture was filtered from the catalyst and the filtrate was evaporated in vacuo. Yield: 43.35 g (99.8%) of a dark gray solid. 1 H-NMR (DMSO-d6, 400 MHz): δ = 6.82, 6.49 (AA'BB', 4H, aromatic H), 4.88 (s broad, 2H, NH2), 2.40 (t, 2H, CH2), 2.17 (t, 2H, CH2), 1.71 (m, 2H, CH2).

[0045] The third step describes the esterification of 4-(4-nitrophenyl)butanoic acid to ethyl 4-(4-aminophenyl)butanoate. [ka] 2.5 g of 4-(4-aminophenyl)butanoic acid is added to 25.0 g of ethanol, followed by 4.5 g of sulfuric acid (95%), and the temperature rises to 40 °C. After the reaction is complete, the reaction mixture is added to 200 g of water, forming a brown, clear solution. The solution is neutralized with 10 g of sodium bicarbonate. The resulting emulsion is finally extracted three times with 60 g of toluene. The combined organic phases are dried over sodium sulfate and filtered from the residue. After evaporating the solvent, 2.8 g of a dark oil is obtained. 1 H-NMR (CDCl3, 400 MHz): δ = 6.92, 6.62 (AA'BB', 4H, aromatic H), 4.05 (2H, ethyl-CH2), 2.48 (t, 2H, CH2), 2.22 (t, 2H, CH2), 1.81 (m, 2H, CH2), 1.18 (t, 3H, ethyl-CH3).

[0046] I.1.2 Synthesis of dye (100) [ka]

[0047] 1. Diazotization To 11.0 g of acetic acid (80%), 1.3 g of ethyl 4-(4-aminophenyl)butanoate is added. Then, 7.5 g of ethanol and 3.0 g of water are added. The solution is cooled to 0°C using an ice bath. After reaching this temperature, 0.9 g of hydrochloric acid (32%) and 0.7 g of sodium nitrite are added, and the temperature rises to 5°C. After stirring for an additional 2 hours at 0°C, the diazotization is complete.

[0048] 2. Coupling reaction 1.2 g of bonatic acid was added to 100.0 g of deionized water. 4.0 g of NaOH (25%) was then added, and the mixture was cooled to 4 °C using an ice bath. After reaching this temperature, the diazotization solution was added dropwise at 4 °C to 12 °C, while maintaining the pH at 6 to 10 by adding 19.6 g of NaOH (25%). The ice bath was then removed, and 50.0 g of water was added. The reaction mixture was allowed to stir overnight at room temperature. The next day, the mixture was suction filtered, and the filter cake was washed with 300 g of water. The neutralized filter cake was mixed with 350 g of water and stirred in a beaker for 15 minutes, then acidified (pH = 1) with 4.0 g of 32% HCl. Finally, the thick red suspension was again suction filtered. The filter cake was washed with 400 g of water until the filtrate was neutral. The product was dried under vacuum. Yield: 2.4 g of a red solid. 1H-NMR (DMSO-d3, 400 MHz): δ = 16.23 (s, 1H, COOH), 13.49 (s, 1H, OH), 8.67 (s, 1H, naphthalene H), 8.52, 7.99, 7.74, 7.53 (ABCD, 4H, naphthalene H), 7.87, 7.40 (AA'BB', 4H, aromatic H), 4.07 (2H, ethyl-CH2), 2.68 (t, 2H, CH2), 2.33 (t, 2H, CH2), 1.87 (m, 2H, CH2), 1.19 (t, 3H, ethyl-CH3).

[0049] The dyes of formulae (101) to (129) shown in Tables 1 and 2 below can be produced in accordance with the above method.

[0050] II. Application Examples Application example 1: One part by weight of the dye of formula (100) according to Preparation 100 is milled with 4 parts of a commercial dispersing agent and 15 parts of water.

[0051] This formulation is used to produce a 1% dyeing (based on dye and substrate) on polyester fabric by the high temperature exhaust method at 135°C.

[0052] Test results: The lightfastness of the dyeings is excellent, as are the results of the AATCC 61 and ISO 105 tests. The build-up of the dye is very good.

[0053] Application Examples 101 to 135: Application example 1 is repeated using other dyes of Preparation Examples 101 to 135 instead of the dye of formula (100) of Preparation Example 100.

[0054] The build-up of these dyes is very good and the dyeings show good lightfastness and very good results in the AATCC 61 and ISO 105 tests.

[0055] [Table 1] TIFF2026504705000012.tif216170TIFF2026504705000013.tif216170TIFF2026504705000014.tif226170TIFF2026504705000015.tif227170TIFF2026504705000016.tif206170TIFF2026504705000017.tif153170

Claims

1. Formula (1): 【Chemistry 1】 (In the formula, R １ is hydrogen, halogen, nitro, cyano or C １ ~C ４ represents alkoxy, preferably hydrogen, bromine or methoxy, D is a compound of the formula: 【Chemistry 2】 (wherein n represents a number from 1 to 6, R ２ is unsubstituted or contains one or more C １ ~C １２ Alkoxy group, C １ ~C １２ Alkylcarbonyl group, C ７ ~C ２５ Aryl group, C ７ ~C ２５ C substituted by an arylcarbonyl group, a hydroxyl group, an amino group, a cyano group or a halogen atom １ ~C １２ represents an alkyl chain, or is unsubstituted or contains one or more C １ ~C １２ Alkoxy group, C １ ~C １２ Alkylcarbonyl group, C ７ ~C ２５ C substituted by an arylcarbonyl group, a hydroxyl group, an amino group, a cyano group or a halogen atom １ ~C １２ may be substituted with an alkyl group, and may be substituted with —O—, —S—, or —NR ２ represents an aryl group, which may be interrupted one or more times by -, -COO- or -OOC- radicals, X is hydrogen, halogen, preferably bromine or chlorine, nitro, C １ ~C ６ azo dyes, wherein R represents a radical of alkyl, preferably methyl, or trifluoromethyl.

2. 2. An azo dye of formula (1) according to claim 1, wherein n represents a number from 1 to 4.

3. R ２ 3. An azo dye of formula (1) according to claim 1 or 2, wherein represents methyl, ethyl, n-propyl, iso-propyl, n-butyl, n-pentyl, n-hexyl, 2-methoxy-ethyl, 2-ethoxy-ethyl, 2-(n-propoxy)-ethyl, 2-(n-butoxy)-ethyl, 2-ethoxy-iso-propyl, 2-(2-methoxyethoxy)ethyl, 2-(2-ethoxyethoxy)ethyl, benzyl, 2-phenylethyl, methoxy-carbonyl-methyl, ethoxy-carbonyl-methyl.

4. A method for producing an azo dye of formula (1) is provided, comprising the steps of: ２ is diazotized, and then the diazotized amine compound is reacted with a compound of formula (3): 【Transformation 3】 (In the formula, R １ is defined above and is preferred) with a BON acid (2-hydroxynaphthalene-3-carboxylic acid) coupling component.

5. 5. The dye of formula (1) according to any one of claims 1 to 4, wherein the dye is selected from the group consisting of C.I. Disperse Red 050, C.I. Disperse Red 060, C.I. Disperse Red 072, C.I. Disperse Red 082, C.I. Disperse Red 86:1, C.I. Disperse Red 167, C.I. Disperse Red 277, C.I. Disperse Red 279, C.I. Disperse Red 302, C.I. Disperse Red 302:1, C.I. Disperse Red 342, C. I. Disperse Red 349, C. I. Disperse Red 356, C. I. Disperse Red 362, C. I. Disperse Red 376, C. I. Disperse Red 377, C. I. Disperse Red 378, C. I. Disperse Red 380, C. I. Disperse Red 383, C. I. Disperse Red 385, and / or formula: 【Chemistry 4】 The dye mixture is used in admixture with at least one further dye selected from the group consisting of dyes of formula (I).

6. Use of an azo dye according to any one of claims 1 to 4 or a dye mixture according to claim 5 in the dyeing or printing of semi-synthetic or synthetic hydrophobic fibre materials, in particular synthetic hydrophobic fibre materials, more particularly textile polyester materials.

7. 6. Semi-synthetic or synthetic hydrophobic fibre materials, in particular textile polyester materials, dyed or printed with an azo dye according to any one of claims 1 to 4 or with a dye mixture according to claim 5.

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