Novel dispersed azo dyes, method for production thereof and use thereof

Abstract

The present invention relates to an azo dye of formula (1), a dye mixture comprising said azo dye, a process for the preparation of said azo dye, the specific use of said azo dye, and a semi-synthetic or synthetic hydrophobic fibrous material dyed or printed by said azo dye or said dye mixture. # imgabs0 #

Description

[0001] manual

[0002] The present invention relates to azo disperse dyes based on BON acid (2-hydroxynaphthalene-3-carboxylic acid) or BON derivatives as coupling components, and dye mixtures containing such azo dyes. The invention also relates to a process for producing such azo dyes, their use in dyeing or printing semisynthetic and synthetic hydrophobic fiber materials, in particular textile materials, and semisynthetic or synthetic hydrophobic fiber materials dyed or printed with the azo dyes in the dye mixtures.

[0003] Azo dyes based on BON acid as a coupling component have been known for many years. These dyes can be used in a variety of dyeing applications. Salts of some BON acid monoazo dyes, such as copper or barium salts, can be used as lakes, for example Pigment Red 64.

[0004] So far, there are few reports on the use of BON acid azo dyes for the coloring of synthetic textile materials. The relevant technical literature can be traced back to the 1960s and 1970s. The textile applications of BON acid azo dyes using the free acid form or the alkali metal salt or alkaline earth metal salt form are limited to the coloring of polypropylene fibers, such as described in US 3 758 270. However, these attempts have not achieved much success.

[0005] Some azo dyes based on BON-acids are described for dyeing polyester fibers. However, in this case, the BON-acid coupling component is used as an amide, as described, for example, in DE 2 612 964 and DE 2 643 801. These documents hardly mention the use of BON-acid azo dyes in the form of the free acid for dyeing polyester fibers.

[0006] In one example, F. Urseanu et al. (Revista de Chimie, 36(6), 450-495 (1985)) described a single azo dye synthesized by coupling 4-aminobenzanilide with BON-acid, which had poor adhesion to polyester substrates and was therefore unsuitable for practical applications.

[0007] Surprisingly, it has now been found that the novel azo dyes according to claim 1, in particular azo dyes of formula (1) based on BON acid (or BON acid derivatives) as coupling compound and diazo compounds of formula (2), show excellent results with regard to light fastness and wash fastness.

[0008] In particular, the present invention relates to azo dyes of formula (1),

[0009]

[0010] where R 1represents hydrogen, halogen, nitro, cyano or C1-C4 alkoxy, preferably hydrogen, bromine or methoxy,

[0011] wherein D represents a group of formula (2),

[0012]

[0013] Where n is a number between 1 and 6.

[0014] where R 2 Indicates C1-C 12 Alkyl chains, which are unsubstituted or replaced by one or more C1-C 12 Alkoxy, C1-C 12 Alkylcarbonyl, C7-C 25 Aryl, C7-C 25 substituted with arylcarbonyl, hydroxyl, amino, cyano or halogen atom; or R 2 Indicates that it can be C1-C 12 Alkyl-substituted aryl, the C1-C 12 The alkyl group is unsubstituted or substituted with one or more C1-C 12 Alkoxy, C1-C 12 Alkylcarbonyl, C7-C 25 substituted by an arylcarbonyl, hydroxyl, amino, cyano or halogen atom and which may be interrupted one or more times by -O-, -S-, -NR2-, -COO- or -OOC- groups, and

[0015] wherein X represents hydrogen, halogen, preferably bromine or chlorine, nitro, C1-C6 alkyl, preferably methyl, or trifluoromethyl.

[0016] Preferably, R 1 represents hydrogen, bromine or methoxy.

[0017] Preferably, X represents hydrogen, methyl, chloro or trifluoromethyl.

[0018] Preferably, n is a number between 1 and 4.

[0019] Preferably, n is 1, 2, 3 or 4, more preferably 1, 2 or 3, especially 1 or 2.

[0020] Preferably, R 2 It represents methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, 2-methoxy-ethyl, 2-ethoxy-ethyl, 2-(n-propoxy)-ethyl, 2-(n-butoxy)-ethyl, 2-ethoxy-isopropyl, 2-(2-methoxyethoxy)ethyl, 2-(2-ethoxyethoxy)ethyl, benzyl, 2-phenylethyl, methoxy-carbonyl-methyl, and ethoxy-carbonyl-methyl.

[0021] The present invention also relates to a method for preparing an azo dye represented by formula (1), in particular an azo dye represented by formula (1) as defined above, the method comprising: diazotizing an amine compound D-NH2 according to a conventional method, and then subjecting the diazotized amine compound to a coupling reaction with a BON-acid (2-hydroxynaphthalene-3-carboxylic acid) coupling component of the following formula:

[0022]

[0023] where R 1 The definitions and preferred embodiments are as described above.

[0024] All definitions and preferred embodiments mentioned above with respect to the azo dyes of formula (1) also apply to the process according to the invention.

[0025] The diazotization of the amine compound D-NH2 is carried out in a manner known per se, for example, in an acidic (for example hydrochloric acid or sulfuric acid) aqueous medium, diazotization is carried out with sodium nitrite. However, diazotization can also be carried out using other diazotizing agents, for example nitrosylsulfuric acid. In the diazotization process, additional acid, for example phosphoric acid, sulfuric acid, acetic acid, propionic acid or hydrochloric acid, or a mixture of these acids, for example a mixture of propionic acid and acetic acid, can be present in the reaction medium. The diazotization reaction is advantageously carried out at a temperature of -10 to 30°C, for example -10°C to room temperature, particularly -5 to 10°C.

[0026] The coupling reaction of the diazotized amine compound D-NH2 with the BON-acid coupling component of formula (3) is likewise carried out in a known manner, for example in an acidic, neutral or alkaline aqueous or aqueous-organic medium, advantageously at a temperature of 0 to 30°C, in particular below 20°C.

[0027] The BON-acid coupling components of the formula (3) are known or can be prepared by methods known per se, as described, for example, in US Pat. No. 1,503,984, US Pat. No. 1,947,819 and DE 561,425.

[0028] The present invention also relates to an azo dye obtained by the aforementioned method.

[0029] The dyes of formula (1), in particular as defined above, can advantageously be used in admixture with other dyes to prepare mixed shades, for example red shades.

[0030] Therefore, the present invention also relates to a dye mixture, wherein the dye represented by formula (1) is used in admixture with at least one other dye, wherein the other dye is selected from 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 a dye of the following formula:

[0031]

[0032] The content of the individual dyes in the dye mixture can vary within wide ranges.

[0033] The dyes and dye mixtures according to the invention can be used for dyeing or printing semisynthetic hydrophobic fiber materials and, in particular, synthetic hydrophobic fiber materials, more particularly textile materials. Textile materials consisting of blends containing such semisynthetic and / or synthetic hydrophobic fiber materials can likewise be dyed or printed using the dyes or dye mixtures according to the invention.

[0034] The content of the individual dyes in the dye mixture can vary within wide ranges. The dyeings obtained according to the process of the invention are characterized by a uniform color tone with very good fastness properties in use, for example, especially good fastness to light, heat setting, wrinkling, chlorine, and wet fastnesses (e.g., fastness to water, perspiration, and washing); the finished dyeings also have very good fastness to rubbing. Particular emphasis is placed on the good overall fastness and excellent brightness of these dyeings.

[0035] Semisynthetic fiber materials that come into consideration are, in particular, cellulose 2 1 / 2-acetate and cellulose triacetate.

[0036] Synthetic hydrophobic fiber materials consist, in particular, of linear aromatic polyesters, for example polyesters of terephthalic acid and diols (especially ethylene glycol), or condensation products of terephthalic acid and 1,4-bis(hydroxymethyl)cyclohexane, of polycarbonates (for example polycarbonate of α,α-dimethyl-4,4-dihydroxydiphenylmethane and phosgene), or of fibers based on polyvinyl chloride or polyamide.

[0037] The dyes and dye mixtures according to the invention are applied to fiber materials according to known dyeing methods. For example, polyester fiber materials are dyed from aqueous dispersion using the exhaust process in the presence of conventional anionic or nonionic dispersants and, optionally, conventional swelling agents (carriers) at temperatures of 80 to 140° C. Cellulose 2½-acetate is preferably dyed at temperatures of 65 to 85° C., and cellulose triacetate at 65 to 115° C.

[0038] The dyes and dye mixtures according to the invention do not color wool and cotton also present in the dyebath, or color these materials only slightly (with very good retention), so that they can also be used satisfactorily for dyeing polyester / wool and polyester / cellulose fiber blends.

[0039] Dyestuff and dye mixture according to the present invention are applicable to thermosol dyeing, exhaust dyeing and printing dyeing.In these processes, described fiber material can be multiple processing forms, for example the form of fiber, yarn or nonwoven, weaving or knitted cloth.

[0040] Advantageously, dyestuff of the present invention and dye mixture are converted into dye preparation before use.For this purpose, dyestuff is ground so that its particle diameter is on average 0.1 to 10 micron.Grinding can be carried out in the presence of a dispersant.For example, dry dyestuff is ground together with a dispersant, or it is kneaded into a pasty form together with a dispersant, then under vacuum or by atomization drying.After adding water, the obtained preparation can be used for preparing printing and dyeing paste and dye bath.

[0041] For printing, customary thickeners can be used, for example modified or unmodified natural products, such as alginates, English gum, gum arabic, crystal gum, locust bean flour, gum tragacanth, carboxymethylcellulose, hydroxyethylcellulose, starch, or synthetic products, such as polyacrylamide, polyacrylic acid or copolymers thereof or polyvinyl alcohol.

[0042] Dye according to the present invention and dye mixture are also suitable for use as the colorant in the recording system.This type of recording system is for example a commercially available inkjet printer for paper or textile printing, or a writing instrument, for example a fountain pen or ballpoint pen, especially an inkjet printer. For this purpose, at first dye of the present invention is made into the form that is applicable to the recording system. Suitable form is for example an aqueous ink, which comprises dye of the present invention as colorant. Said printing ink can be prepared in a conventional manner, that is, each component is mixed in the water of the aequum, if desired, adding a suitable dispersant.

[0043] The dyes and dye mixtures according to the invention impart to the materials, in particular polyester materials, uniform shades with very good fastness properties in use, for example, especially good fastnesses to light, heat setting, wrinkling, chlorine, and wet fastnesses (e.g., water, perspiration, and washing); the finished dyeings also have very good fastnesses to rubbing. Particular emphasis should be placed on the good overall fastnesses and excellent brightness of these dyeings.

[0044] Furthermore, the dyes and dye mixtures according to the invention are also very suitable for dyeing hydrophobic fiber materials from supercritical carbon dioxide (CO2).

[0045] The present invention relates to the use of the dyes and dye mixtures according to the invention as described above, and to a method 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 the materials or incorporated therein. The hydrophobic fiber materials are preferably textile polyester materials.

[0046] In inkjet printing, individual ink droplets are ejected from a nozzle onto a substrate in a controlled manner. For this purpose, the continuous inkjet and drop-on-demand methods are primarily used. In the continuous inkjet method, droplets are produced continuously; those not required for the printing operation are discharged into a container and recycled. In the drop-on-demand method, on the other hand, droplets are produced and used for printing as needed; in other words, droplets are only generated when required for the printing operation. Droplet generation can be achieved, for example, using piezoelectric inkjet heads or thermal energy (bubble jet). Printing with piezoelectric inkjet heads and printing according to the continuous inkjet method are preferred.

[0047] The present invention also relates to a hydrophobic fiber material, preferably a polyester textile material, dyed or printed by the above method.

[0048] Furthermore, the dyes of the present invention are also suitable for use in modern reproduction processes, such as thermal transfer printing.

[0049] Therefore, another aspect of the present invention relates to the use of a dye of formula (1) as defined above or a dye mixture as defined above for dyeing or printing a semisynthetic or synthetic hydrophobic fiber material, in particular a synthetic hydrophobic fiber material, more in particular a textile polyester material. Another aspect of the present invention relates to a semisynthetic or synthetic hydrophobic fiber material, in particular a textile polyester material, dyed or printed with a dye of formula (1) as defined above or a dye mixture as defined above.

[0050] The following examples illustrate the present invention. Unless otherwise indicated, parts are by weight and percentages are by weight. Temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as the relationship between grams and cubic centimeters. Example

[0051] I. Preparation Examples

[0052] I.1 Synthesis of Precursors:

[0053] I.1.1 Synthesis of the diazotized component of dye (100)

[0054]

[0055] The synthesis of the diazotized component of dye (100) starts with 4-phenylbutyric acid, which can be obtained by a Friedel-Crafts acylation reaction (as described by J. Cai et al. (Bioorg. Med. Chem. 23 (2015) S. 657-667) or in WO2019202607) and then by a Clemensen reduction reaction (as described by LM Elmore (J. Am. Chem. Soc. 1936, 58, 8, S. 1438-1442)).

[0056] The first step is nitration of 4-phenylbutyric acid.

[0057]

[0058] 50.0 g of 4-phenylbutyric acid was added to 75.0 g of deionized water. After cooling to 0° C., 485.0 g of sulfuric acid (95%) was added dropwise, followed by 33.0 g of nitric acid (65%) at 0-12° C. 170.0 g of water was then added and the temperature was raised to 32° C. After adding another 200 g of water, the reaction was stirred overnight under cooling. The precipitated crystals were filtered off and washed with water until neutral. Purification was carried out by column filtration (toluene / ethanol 2:1) to remove the ortho isomer. Yield: 40.2 g (pale yellow solid) of 4-(4-nitrophenyl)butyric acid.

[0059] 1 H-NMR (CDCl3, 400MHz): δ=8.18, 7.38 (AA'BB', 4H, aromat.H), 2.82 (t, 2H, CH2), 2.44 (t, 2H, CH2), 2.03 (m, 2H, CH2).

[0060] The second step involves the reduction of 4-(4-nitrophenyl)butyric acid to 4-(4-nitrophenyl)butyric acid.

[0061]

[0062] 50.70 g of 4-(4-nitrophenyl)butyric acid were added to 500 ml of methanol, followed by 4.10 g of sodium bicarbonate and 2.55 g of palladium (5% palladium on carbon). 15.7 liters of hydrogen (1 bar pressure) were added over 2 hours. After the reaction was complete, the reaction mixture was filtered from the catalyst and the filtrate evaporated in vacuo. Yield: 43.35 g (99.8%) of a dark gray solid.

[0063] 1 H-NMR (DMSO-d6, 400MHz): δ = 6.82, 6.49 (AA'BB', 4H, aromat.H), 4.88 (s width, 2H, NH2), 2.40 (t, 2H, CH2), 2.17 (t, 2H, CH2), 1.71 (m, 2H, CH2).

[0064] The third step describes the esterification of 4-(4-nitrophenyl)butyrate to ethyl 4-(4-aminophenyl)butyrate.

[0065]

[0066] 2.5 g of 4-(4-aminophenyl)butyric acid was added to 25.0 g of ethanol, followed by 4.5 g of 95% sulfuric acid, and the mixture was heated to 40° C. After the reaction was complete, the reaction mixture was added to 200 g of water to form a clear brown solution. The solution was neutralized with 10 g of sodium bicarbonate. Finally, the resulting emulsion was extracted three times with 60 g of toluene. The combined organic phases were dried over sodium sulfate and filtered from the residue. After evaporation of the solvent, 2.8 g of a dark oil was obtained.

[0067] 1 H-NMR (CDCl3, 400 MHz): δ = 6.92, 6.62 (AA'BB', 4H, aromat.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).

[0068] I.1.2 Synthesis of dye (100)

[0069]

[0070] 1. Diazotization reaction

[0071] 1.3 g of ethyl 4-(4-aminophenyl)butyrate was added to 11.0 g of acetic acid (80%). 7.5 g of ethanol and 3.0 g of water were then added. The solution was cooled to 0° C. in an ice bath. After reaching this temperature, 0.9 g of hydrochloric acid (32%) and 0.7 g of sodium nitrite were added, and the temperature was raised to 5° C. After stirring for an additional 2 hours at 0° C., the diazotization reaction was complete.

[0072] 2. Coupling reaction

[0073] 1.2 g of Bon 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. in an ice bath. After reaching this temperature, the diazotization solution was added dropwise at 4-12° C. while maintaining the pH between 6 and 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 stirred at room temperature overnight. The next day, the mixture was filtered and the filter cake was washed with 300 g of water. The mixture of the neutralized filter cake in 350 g of water was stirred in a beaker for 15 minutes and then acidified with 4.0 g of 32% HCl (pH = 1). Finally, the red thick suspension was filtered again. The filter cake was washed with 400 g of water until the filtrate was neutral. The product was vacuum dried, yield: 2.4 g of red solid.

[0074] 1 H-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, aromat. 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).

[0075] The dyes of formulae (101) to (129) listed in Tables 1 and 2 below can be prepared similarly to the above-described method.

[0076] II. Application Examples

[0077] Application Example 1:

[0078] 1 part by weight of the dye of formula (100) according to Preparation Example 100 is ground together with 4 parts of a commercial dispersant and 15 parts of water.

[0079] This formulation produces a 1% dyeing (based on dye and substrate) on woven polyester at 135°C using a high temperature exhaust dyeing process.

[0080] Test results: The lightfastness of the dyeing was excellent as well as the results in the AATCC 61 and ISO 105 tests. The build-up properties of the dye were very good.

[0081] Application Examples 101 to 135:

[0082] Example 1 was repeated, but the dye of formula (100) in Preparation Example 100 was replaced by the other dyes of Preparation Examples 101 to 135.

[0083] The dye builds up very well and the dyeings show good lightfastness and give very good results in the AATCC 61 and ISO 105 tests.

[0084] Table 1: Preparation Examples 101 to 129

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

Claims

1. an azo dye represented by formula (1), where R 1 represents hydrogen, halogen, nitro, cyano or C1-C4 alkoxy, preferably hydrogen, bromine or methoxy, wherein D represents a group of the formula Where n is a number between 1 and 6. where R 2 Indicates C1-C 12 Alkyl chains, which are unsubstituted or replaced by one or more C1-C 12 Alkoxy, C1-C 12 Alkylcarbonyl, C7-C 25 Aryl, C7-C 25 substituted with arylcarbonyl, hydroxyl, amino, cyano or halogen atom; or R 2 Indicates that it can be C1-C 12 Alkyl-substituted aryl, the C1-C 12 The alkyl group is unsubstituted or substituted with one or more C1-C 12 Alkoxy, C1-C 12 Alkylcarbonyl, C7-C 25 arylcarbonyl, hydroxyl, amino, cyano or halogen atoms and which may be interrupted one or more times by -O-, -S-, -NR2-, -COO- or -OOC- groups, and wherein X represents hydrogen, halogen, preferably bromine or chlorine, nitro, C1-C6 alkyl, preferably methyl, or trifluoromethyl. 2 . The azo dye of formula (1) according to claim 1 , wherein n represents a number between 1 and 4.

3. Azo dyes of formula (1) according to any one of the preceding claims, wherein R 2 It represents methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, 2-methoxyethyl, 2-ethoxyethyl, 2-(n-propoxy)ethyl, 2-(n-butoxy)ethyl, 2-ethoxyisopropyl, 2-(2-methoxyethoxy)ethyl, 2-(2-ethoxyethoxy)ethyl, benzyl, 2-phenylethyl, methoxycarbonylmethyl, and ethoxycarbonylmethyl.

4. A method for preparing the azo dye represented by formula (1), the method comprising: The amine compound D-NH2 is diazotized according to a conventional method, and then the diazotized amine compound is coupled with the BON-Acid (2-hydroxynaphthalene-3-carboxylic acid) coupling component of formula (3). where R 1 The definitions and preferred embodiments are as described above.

5. Dye mixtures, wherein the dye of formula (1) according to any one of claims 1 to 4 is used in admixture with at least one other dye selected from 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 a dye of the following formula:

6. Use of the azo dye according to any one of claims 1 to 4 or the dye mixture according to claim 5 for dyeing or printing semisynthetic or synthetic hydrophobic fiber materials, especially synthetic hydrophobic fiber materials, more especially textile polyester materials.

7. Semisynthetic or synthetic hydrophobic fiber materials, especially textile polyester materials, dyed or printed with the azo dyes according to any one of claims 1 to 4 or the dye mixture according to claim 5.

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