Reactive dyes based on complexed disazo dye derivatives

Abstract

The present invention relates to dyes of the general formula, the use of said dye mixture as a dyeing agent and / or printing agent, a method for dyeing a fabric with said dye mixture, and the dyed fabric obtainable with said method.

Description

[0001] Archroma (Switzerland) GmbH M / ARCH-022-PC April 16, 2026 BL / bl / tm

[0002] Reactive Dyes

[0003] Description

[0004] The present invention relates to reactive dyes that are suitable for the dyeing or printing of fibre materials, in particular nitrogen-containing or hydroxy-group-containing fibre materials, and yield on such materials dyeings or prints having good reproducibility and good all-round fastness properties. The present invention relates also to a method for dyeing or printing wherein the reactive dyes according to the invention are used.

[0005] Over the past years, many countries have committed to improve the quality of the environment by saving natural resources and reducing the emission of substances, which are harmful to the climate. Funds are provided by the governments to support the industry in achieving these goals. The consumer is asking for environmentally friendly textile products, which are produced in accordance with highest ecological standards. Brands and retailers are conveying these demands into real requirements and textile manufacturers are continuously improving their production excellence by investing in modern equipment and selecting environmentally friendly chemical substances.

[0006] As a result, there is a huge demand for novel reactive dyes that are suitable for the reproducible dyeing and printing of fibre materials which fulfil highest ecological and economical requirements while still providing dyeings of the desired colour shades with good fastness properties, such as wash and water fastness and perspiration fastness. Suitable reactive dyes should provide a unique combinability and a low sensitivity to various dyeing parameters. Furthermore, they should have sufficient substantivity and at the same time have good ease of washing off of unfixed dye. They should also exhibit a good tinctorial yield and high reactivity, the objective being to provide especially dyeings having good build-up properties and high degrees of fixing. In many cases, the build-upMeissner Bolte M / ARCH-022-PC 2

[0007] behaviour of reactive dyes is insufficient to meet the demands being made, especially when dyeing very deep shades.

[0008] Further, the taste in fashion has moved towards more restrained colours. The trend is for muted, autumnal colours with, for example, a large amount of brown, grey, olive, beige, khaki, sandy shades, dull yellow shades and aubergine. As a result, about 30 to 40% of the dyed or printed textiles currently produced are in muted colour shades.

[0009] Muted colour shades on e.g. cellulose are usually produced using vat dyes. Vat-dyed textile materials have good fastness properties, for example wet-fastness properties, but dyeing with vat dyes is expensive in terms of equipment. Vat dyeing is carried out in so-called continuous dyeing machines which are not universally available. Furthermore, dyeing on continuous machines is economical only for high meterage.

[0010] Dyed or printed textile materials having good wet-fastness properties can be obtained, for example, using reactive dyes that are covalently bonded to the textile fibre. Dyeing with reactive dyes can be carried out in accordance with, for example, the exhaust method or the pad-dyeing method. Those methods are less expensive in terms of equipment than dyeing on a continuous machine, and suitable apparatus is usually available in the dyeing works. Moreover, relatively low meterage can still be dyed economically in that way.

[0011] A disadvantage in the production of dyed or printed textiles in muted colour shades, however, is their poor reproducibility using the trichromatic principle in which the shade is obtained using mixtures of yellow- or orange-dyeing reactive dyes together with red- and blue-dyeing reactive dyes.

[0012] The present invention is therefore based on the problem of providing new reactive dyes, in particular of brown, grey and olive shade, that are suitable especially for the reproducible dyeing and printing of fibre materials in muted colour shades. The dyes according to the invention should also yield dyeings or prints having good all-round fastness properties. In particular, the dyes according to the invention should provide a unique combinability and a low sensitivity to various dyeing parameters. Furthermore, they should have sufficient substantivityMeissner Bolte M / ARCH-022-PC 3

[0013] and at the same time have good ease of washing off of unfixed dye. They should also exhibit a good tinctorial yield and high reactivity, the objective being to provide especially dyeings having good build-up properties and high degrees of fixing. In many cases, the build-up behaviour of reactive dyes is insufficient to meet the demands being made, especially when dyeing very deep shades.

[0014] These above-mentioned problems could be solved by the dyes according to claim 1.

[0015] The present invention provides new reactive dyes that are suitable especially for the reproducible dyeing and printing of fibre materials in the desired colour shades, especially shades of brown, grey and olive, and fulfil the above indicated requirements to the highest possible extent. The dyes should also yield dyeings having good build-up properties, high fixation rates and good washing off properties of the unfixed dyes, and good all-round fastness properties, for example fastness to light and to wetting.

[0016] Throughout the description and claims of this specification, the words "comprise" and "contain" and variations of the words, for example "comprising" and "comprises", mean "including but not limited to", and do not exclude other moieties, additives, components, integers or steps. Moreover, the singular encompasses the plural unless the context otherwise requires: in particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise.

[0017] Where upper and lower limits are quoted for a property, for example for the concentration of a component, then a range of values defined by a combination of any of the upper limits with any of the lower limits may also be implied.

[0018] The expression "comprised between X and Y" includes boundaries, unless explicitly stated otherwise. This expression means that the target range includes the X and Y values, and all values from X to Y.

[0019] The present invention accordingly relates to a dye of formula (I)Meissner Bolte M / ARCH-022-PC

[0020]

[0021] Ri, R2, R3 and R are independent from each other and wherein

[0022] Ri is selected from -NH2, -C1-4 alkyl,

[0023] R2 is selected from -H, -O-C1-4 alkyl, -C1-4 alkyl, -SO3H,

[0024] R3is selected from -H, -O-C1-4 alkyl, -C1-4 alkyl, -SO3H,

[0025] R4is selected from -H, -O-C1-4 alkyl, -C1-4 alkyl, -SO3H, -NO2,

[0026] Y2is -CH2-CH2-OSO3H or -CH=CH2,

[0027] m is selected from 0 to 3, and

[0028] n is selected from 0 to 2.

[0029] C1-4 alkyl may be linear or branched C1-4 alkyl. Preferably, C1-4 alkyl is CH3.

[0030] The residues R4, (Y2-SO2)nand (SO3H)mmay be bound independently of each other to any C atom of the indicated naphthalene moiety.

[0031] The residues (Y2-SO2)n and (SO3H)mmay be bound independently of each other to any C atom of the naphthalene moiety wherein he bond is between any C atom of the indicated naphthalene and the S atom of the respective residue.Meissner Bolte M / ARCH-022-PC 5

[0032] The linking groups -N = N- and -O-M-O- may be bound to any C atom of the indicated naphthalene moiety. Preferably, the linking groups -N = N- and -O-M-O-are bound to the indicated naphthalene moiety in ortho position to each other.

[0033] The dye according to the invention comprises a metal M, which is selected from Cu, Fe, Mn, Co, Cr, Ni or Zn. The metals are preferably in the oxidation state +11. Suitable sources for the metals are mainly the Cu, Fe, Mn, Co, Cr, Ni and Zn salts of inorganic or organic acids.

[0034] The metal ion M may also coordinate with a free electron pair of the proximate -N = N- group.

[0035] Preferably, M is Cu, so that in a preferred embodiment, the present invention relates to a dye of formula (la)

[0036]

[0037] R1, R2, R3and R4are independent from each other and wherein

[0038] Ri is selected from -NH2, -C1-4 alkyl,

[0039] R2 is selected from -H, -O-C1-4 alkyl, -C1-4 alkyl, -SO3H,

[0040] R3is selected from -H, -O-C1-4 alkyl, -C1-4 alkyl, -SO3H,

[0041] R4is selected from -H, -O-C1-4 alkyl, -C1-4 alkyl, -SO3H, -NO2,

[0042] Y2is -CH2-CH2-OSO

[0043] m is selected from

[0044]

[0045] Meissner Bolte M / ARCH-022-PC 6

[0046] n is selected from 0 to 2.

[0047] The dye according to formula (la) comprises Cu as metal (M). The Cu is preferably in the oxidation state +11, thus Cu2+. Suitable sources for the Cu comprise copper salts such as copper carbonate, copper chloride, copper sulphate and copper acetate.

[0048] Yi is -CH2-CH2-OSO3H or -CH=CH2. Under dyeing conditions, the OSO3H group may be eliminated to form an intermediate vinyl group or the vinyl form of the dye may be provided by synthesis before dyeing step

[0049] Preferably, Yi is -CH2-CH2-OSO3H

[0050] Preferably, X is -Cl.

[0051] Preferably, Ri is NH2.

[0052] Preferably, R2 is -H.

[0053] Preferably, R3 is -H.

[0054] Preferably, R4is -H or NO2.

[0055] Y2 is -CH2-CH2-OSO3H or -CH=CH2. Under dyeing conditions, the OSO3H group may be eliminated to form an intermediate vinyl group or the vinyl form of the dye may be provided by synthesis before dyeing step

[0056] Preferably, Y2is -CH2-CH2-OSO3H.

[0057] Preferably, m is 1, 2 or 3. Preferably, m is 1. Preferably, m is 2. Preferably, m is 3.

[0058] Preferably, n is 0 or 1. Preferably, n is 0. Preferably, n is 1.

[0059] In one embodiment, the dye according to the invention is characterized in that M is CuMeissner Bolte M / ARCH-022-PC 7

[0060] Yi is -CH2-CH2-OSO3H or -CH=CH2,

[0061] X is -Cl,

[0062] Ri is NH2,

[0063] R2is -H,

[0064] R3is -H,

[0065] R4is -H

[0066] m is 3, and

[0067] n is 0.

[0068] Such dyes correspond to the following formulae (Ila or lib)

[0069]

[0070] In one embodiment, the dye according to the invention is characterized in that M is Cu

[0071] Yi is -CH2-CH2-OSO3H or -CH=CH2,

[0072] X is -Cl,

[0073] Ri is NH2,

[0074] R2is -H,Meissner Bolte M / ARCH-022-PC 8

[0075] R3is -H,

[0076] R4is -NO2,

[0077] m is 1, and

[0078] n is 0.

[0079] Such dyes correspond to the following formulae (Illa or Illb)

[0080]

[0081] In one embodiment, the dye according to the invention is characterized in that M is Cu

[0082]

[0083] Meissner Bolte M / ARCH-022-PC 9

[0084] Such dyes correspond to the following formulae (IVa or IVb)

[0085]

[0086] In one embodiment, the dye according to the invention is characterized in that M is Cu

[0087]

[0088] Meissner Bolte M / ARCH-022-PC 10

[0089] Such dyes correspond to the following formulae (Va or Vb)

[0090]

[0091] Dyes similar to those of formulae (I), (la), (Ila, lib), (Illa, Illb), (IVa, IVb) and (Va, Vb) are known in the art, or they can be prepared in accordance with processes known per se, such as by customary diazotization, coupling and condensation reactions as described, for example, in EP 0141367 Al, US-A-4341699, GB-A-1576237, US-A-4754023, EP-A-94055, US-A-5298607 and WO 2002085986 Al.

[0092] Methods of coupling of metal ions, such as Cu, to the dyes are also known in the art, e.g. from EP0022485A1.Meissner Bolte M / ARCH-022-PC 11

[0093] A variant of the processes known per se comprises first condensing one of (i) the amino substituted azo compound and (ii) the amine carrying the reactive group with (iii) cyanuric halide, for example, cyanuric chloride or cyanuric fluoride, and reacting the resulting reaction product with the other of the (i) amino substituted azo dye and (ii) the amine carrying the reactive group, which has been condensed beforehand with cyanuric halide. Alternatively, the precursor of (i) the amino azo dye is condensed with the primary condensation product of (ii) the amine carrying the reactive group and (iii) cyanuric halide, and the resulting secondary condensation product is subsequently diazotated and coupled (analogously to the process described in Example 3 of US-A-5298607).

[0094] The condensation reactions between (i) the amino substituted azo compound, the precursor of (i), (ii) the amine carrying the reactive group and cyanuric halide are generally carried out analogously to known processes, usually in aqueous solution at temperatures of, for example, from 0 to 70°C and a pH of, for example, from 3 to 10.

[0095] The dyes according to the invention are suitable for the dyeing and / or printing of an extremely wide variety of materials, especially hydroxy-group-containing or nitrogen-containing fibre materials. Examples thereof are paper, silk, leather, wool, polyamide fibres and polyurethanes as well as, especially, cellulosic fibre materials of all kinds. Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen and hemp, as well as cellulose and regenerated cellulose. The dye mixture according to the invention invention are also suitable for the dyeing or printing of hydroxy-group-containing fibres that are contained in blend fabrics, for example mixtures of cotton with polyester fibres or polyamide fibres.

[0096] The said textile fibre material may be in an extremely wide variety of processing forms, such as, for example, in the form of fibres, yarn, woven fabric or knitted fabric.

[0097] Accordingly, the present invention also relates to a method for the dyeing or printing of fibre materials, in particular hydroxy-group-containing or nitrogencontaining fiber material, wherein the method comprises using at least one dyeMeissner Bolte M / ARCH-022-PC 12

[0098] as defined above, in particular one dye of the above-mentioned formula (IIa or IIb), formula (IIIa or IIIb), formula (IVa or IVb) and / or formula (Va or Vb).

[0099] The dyes according to the invention are suitable for customary dyeing and printing methods and can be applied to the fibre material and fixed thereto in a wide variety of ways, especially in the form of aqueous dye solutions or print pastes.

[0100] Preferably, the dyes are used for dyeing or printing a fabric. Preferably, the fabric contains cellulose acetate, cotton, polyamide, polyester, polyacrylonitrile and / or wool. In another embodiment, the fabric consists of cellulose acetate, cotton, polyamide, polyester, polyacrylonitrile and / or wool.

[0101] The invention further relates to a method for dyeing a fabric with a dye, comprising the following steps:

[0102] i) dyeing or printing a fabric, preferably a fabric containing or consisting of cellulose acetate, cotton, polyamide, polyester, polyacrylonitrile and / or wool, with a dye according to the invention, and

[0103] ii) drying the dyed or printed fabric of i), preferably with dry heat or steam.

[0104] All definitions and preferred embodiments, as set forth above, apply analogously, to the method for dyeing a fabric with the dye.

[0105] The method for dyeing a fabric with a dye or dye mixture according to the invention can be carried out in accordance with customary dyeing methods, for example, according to the so-called cold pad-batch process, in which the dye mixture is applied, together with the alkali, on the padder and is then fixed by storage for several hours at about room temperature, for example, from 25 to 35°C. Preferably, the method for dyeing according to the invention is carried out according to the exhaust-dyeing method, in which the goods, preferably materials or fabrics, more preferably hydroxy-containing or nitrogen-containing fibre, are impregnated with aqueous, optionally salt-containing dye solutions, and the dyesMeissner Bolte M / ARCH-022-PC 13

[0106] are fixed after an alkali treatment or in the presence of alkali, optionally under the action of heat.

[0107] The dye solution, also called dye liquor, in addition to containing water and the dyes, may also comprise further additives, for example shading dyes known per se, salts, buffer substances, wetting agents, anti-foams, levelling agents or agents that influence the properties of the textile material, for example softeners, additives for flame-resistant finishes or dirt-, water- or oil-repellents, as well as water-softeners and natural or synthetic thickeners, e.g. alginates or cellulose ethers.

[0108] The amounts in which the individual dyes are used in the dye solution vary within wide limits in dependence upon the desired depth of shade; in general, amounts of from 0.01 to 15% by weight, especially from 0.1 to 10% by weight, based on the goods being dyed or on the print paste, have proved advantageous.

[0109] The inventive dyes used in accordance with the method of the present invention are distinguished by high and uniform colour build-up, good exhaustion and fixing behaviour, good constancy of shade even in different concentrations, a low sensitivity to various dyeing parameters and, in particular, very good combinability. Dyeing times can be reduced. Furthermore, they can advantageously be applied at a range of liquor ratios, for example, at a liquor ratio of from 1:8 to 1:30. The dyeings produced in accordance with the method of the invention exhibit brilliant shades of very good fastness properties, such as fastness to washing, to water, to sea water, to cross-dyeing and to perspiration, as well as good fastness to chlorine, to pleating, to hot-pressing and to rubbing, and good reproducibility.

[0110] The invention further relates to a dyed fabric obtainable by the method of dyeing a fabric with a dye according to the invention.

[0111] All definitions and preferred embodiments, as set forth above, apply analogously, to the dyed fabric.

[0112] The dyes according to the invention are also suitable as colorants for use in recording systems. Such recording systems are, for example, commerciallyMeissner Bolte M / ARCH-022-PC 14

[0113] available inkjet printers for paper or textile printing, or writing implements, such as fountain pens or ballpoint pens, and especially ink-jet printers. For that purpose, the dyes according to the invention are first converted into a form suitable for use in recording systems. A suitable form is, for example, an aqueous ink comprising at least one dye of the dye mixture according to the invention as colorant. The inks can be prepared in customary manner by mixing together the individual constituents customary in ink-jet printing in the desired amount of water. Conveniently, individual inks, comprising at least one dye of formula (1) are used in a multi color ink-jet printer and mixing is affected on the substrate by digital printing.

[0114] Examples of substrates that come into consideration for ink-jet printing, in addition to paper or plastics films, include the above-mentioned hydroxy-group-containing or nitrogen containing fibre materials, especially cellulosic fibre materials. The substrates are preferably textile fibre materials.

[0115] The instant invention further relates to the use of a dye according to the invention for dyeing or printing a fabric.

[0116] Preferably for dyeing or printing a fabric containing or consisting of cellulose acetate, cotton, polyamide, polyester, polyacrylonitrile and / or wool.

[0117] The following Examples serve to illustrate the invention. Unless otherwise indicated therein, parts are parts by weight and percentages are percentages by weight. Temperatures are given in degrees Celsius.Meissner Bolte M / ARCH-022-PC

[0118] Examples

[0119] Synthesis

[0120] Exemplary dyes 1 to 4 according to the invention have been synthesised as described below. The structures of the examples are shown in the following Table 1.

[0121] Table 1:

[0122]

[0123] Meissner Bolte M / ARCH-022-PC

[0124]

[0125] Meissner Bolte M / ARCH-022-PC

[0126]

[0127] Example 1 (formula Ila and lib):

[0128] 1-A) 21.68 parts of 2-Amino-5-(2-sulfatoethylsulfonyl)benzenesulfonic acid was suspended in 100 parts of water, to this suspension, 15.42 parts of 35% hydrochloric acid was added. 17.87 parts of 4N sodium nitrite solution added over 1 hr at 20-30°C. reaction mass stirred for 2 hr and then 0.2 parts of sulfamic acid added.

[0129] 1-B) 9.06 parts of (3-Aminophenyl) urea was suspended in 40 parts of water. 9 parts of 30% sodium hydroxide solution was added to the solution, cooled to 0- 5°C and part 1-A was added slowly over 1.5-2 hr. 19 parts of 20% sodium carbonate solution was added to maintain pH between 4.0-6.0 simultaneously and stirred for 1 hr.

[0130] 1-C) 23 parts of 2-Naphthylamine-3,6,8-trisulfonic acid was suspended in 100 parts of water, 15.42 parts of 35% hydrochloric acid was added, reaction mass cooled to 0-5°C and 17.87 parts of 4N sodium nitrite solution was added in 1 hr. stirred for 1 hr and then 0.2 parts of sulfamic acid was added.

[0131] 1-D) 19.15 parts of 4-Amino-5-hydroxy-2,7-naphthalenedisulfonic acid was suspended in 55 parts of water and 12.5 parts of 30% sodium hydroxide solutionMeissner Bolte M / ARCH-022-PC

[0132] was added. 11.07 parts of 2,4,6-trichloro-1,3,5-triazine were finely dispersed in 90 parts of water / ice mixture at 0-5°C and above solution slowly added over 2 hr and stirred for 2 hr. Further the solution was cooled to 10°C. To this solution, diazo solution 1-C was added slowly in 30 min. pH was maintained 6.5 with 48 parts of 20% sodium carbonate solution and stirred for 1 hr.

[0133] 1-E) Part 1-B and part 1-D were mixed and heated to 65-85°C for 6-8 hr. pH was maintained 5.0-6.0 with 2 parts of 20% sodium carbonate solution. Then 14.98 parts of copper sulfate pentahydrate was added at 25°C and then 28 parts of 30% hydrogen peroxide was added slowly over 30 min. pH was maintained 6.0 simultaneously with 20% sodium carbonate solution and stirred for 1 hr. The final dye solution was dried under vacuum to obtain the crude dye having formula (IIa):

[0134]

[0135] 1-F) Part 1-E from example 1 was taken and further heated to 25-45°C and pH was adjusted to 8.0-10.0 and stirred for 20-60 min. The final dye solution was dried under vacuum to obtain the crude dye having formula (IIb):

[0136]

[0137] Example 2 (formula IIIa and IIIb):Meissner Bolte M / ARCH-022-PC

[0138] 2-A) 19.15 parts of 4-Amino-5-hydroxy-2,7-naphthalenedisulfonic acid was suspended in 100 parts of water. 13.3 parts of 30% sodium hydroxide was added.

[0139] 11.07 parts of 2,4,6-trichloro-1,3,5-triazine were finely dispersed in 90 parts of water / ice mixture and above solution was added to suspension over 2 hr and stirred for 2-3 hr at 0-5°C.

[0140] 2-B) 17.71 parts of 6-Nitro-l-diazo-2-hydroxy-napthalene-4-sulfonic acid was suspended in 100 parts of water and cooled to 0-5°C. 15 parts of 35% hydrochloric acid was added. 17.87 parts of 4N sodium nitrite solution added over 1 hr at 0-5°C and stirred for 1 hr. further 0.2 parts of sulfamic acid was added.

[0141] 2-C) Part 2-A cooled to 0-15°C, to this solution, above diazo solution 2-B was added in 30 min and pH was increased to 5.0 by 30 parts of 20% sodium carbonate solution.

[0142] 2-D] Part 2-C and 1-B from example 1 were mixed equivalent and heated to 65-85°C for 6-8 hr. pH was maintained 5.0-6.0 with 2 parts of 20% sodium carbonate solution. To this mass 14.98 parts of copper sulfate pentahydrate was added and heated the mass to 40°C and pH was maintained 5.0 by 20% sodium carbonate solution for 1 hr. The final dye solution was dried under vacuum to obtain the crude dye having formula (IIIa):

[0143]

[0144] 2-E) Part 2-D from example 2 was taken and further heated to 25-45°C and pH was adjusted to 8.0-10.0 and stirred for 20-60 min. The final dye solution was dried under vacuum to obtain the crude dye having formula (IIIb):Meissner Bolte M / ARCH-022-PC

[0145]

[0146] Example 3 (formula IVa and IVb):

[0147] 3-A) 18.18 parts of 2-Naphthylamine-4,8-disulfonic acid was suspended in 100 parts of water, 15.42 parts of 35% hydrochloric acid was added, reaction mass cooled to 0-5°C and 17.87 parts of 4N sodium nitrite solution was added in 1 hr. stirred for 1 hr and then 0.2 parts of sulfamic acid was added.

[0148] 3-D) 19.15 parts of 4-Amino-5-hydroxy-2,7-naphthalenedisulfonic acid was suspended in 55 parts of water and 12.5 parts of 30% sodium hydroxide solution was added. 11.07 parts of 2,4,6-trichloro-1,3,5-triazine were finely dispersed in 90 parts of water / ice mixture at 0-5°C and above solution slowly added over 2 hr and stirred for 2 hr. Further the solution was cooled to 10°C. To this solution, diazo solution 3-A was added slowly in 30 min. pH was maintained 6.5 with 48 parts of 20% sodium carbonate solution and stirred for 1 hr.

[0149] 3-C) Part 3-D and part 1-B from example 1 were mixed and heated to 65-85°C for 6-8 hr. pH was maintained 5.0-6.0 with 2 parts of 20% sodium carbonate solution. Then 14.98 parts of copper sulfate pentahydrate was added at 25°C and then 28 parts of 30% hydrogen peroxide was added slowly over 30 min. pH was maintained 6.0 simultaneously with 20% sodium carbonate solution and stirred for 1 hr. The final dye solution was dried under vacuum to obtain the crude dye having formula (IVa):Meissner Bolte M / ARCH-022-PC

[0150]

[0151] 3-D) Part 3-C from example 3 was taken and further heated to 25-45°C and pH was adjusted to 8.0-10.0 and stirred for 20-60 min. The final dye solution was dried under vacuum to obtain the crude dye having formula (IVb):

[0152]

[0153] Example 4 (formula Va and Vb):

[0154] 4-A) 19.15 parts of 4-Amino-5-hydroxy-2,7-naphthalenedisulfonic acid was suspended in 100 parts of water. 13.3 parts of 30% sodium hydroxide was added.

[0155] 11.07 parts of 2,4,6-trichloro-1,3,5-triazine were finely dispersed in 90 parts ofMeissner Bolte M / ARCH-022-PC

[0156] water / ice mixture and above solution was added to suspension over 2 hr and stirred for 2-3 hr at 0-5°C.

[0157] 4-B) 24.68 parts of 2-Amino-6-(2-(sulfooxy)ethylsulfonyl)naphthalene-l-sulfonic acid was suspended in 100 parts of water and cooled to 0-5°C. 15 parts of 35% hydrochloric acid was added. 17.87 parts of 4N sodium nitrite solution added over 1 hr at 0-5°C and stirred for 1 hr. further 0.2 parts of sulfamic acid was added.

[0158] 4-C) Part 4-A cooled to 0-15°C, To this solution, above diazo solution 4-B was added in 30 min and pH was increased to 5.0 by 30 parts of 20% sodium carbonate solution.

[0159] 4-D] Part 4-C and 1-B from example 1 were mixed equivalent and heated to 65- 85°C for 6-8 hr. pH was maintained 5.0-6.0 with 2 parts of 20% sodium carbonate solution. To this mass 14.98 parts of copper sulfate pentahydrate was added at 20-30°C and then 28 parts of 30% hydrogen peroxide was added slowly over 30 min. pH was maintained 6.0 simultaneously with 20% sodium carbonate solution and stirred for 1 hr. The final dye solution was dried under vacuum to obtain the crude dye having formula (Va):

[0160]

[0161] 4-E) Part 4-D from example 4 was taken and further heated to 25-45°C and pH was adjusted to 8.0-10.0 and stirred for 20-60 min. The final dye solution was dried under vacuum to obtain the crude dye having formula (Vb):

[0162]

[0163] Meissner Bolte M / ARCH-022-PC 23

[0164] Properties

[0165] The washing fastness, fixation properties, and exhaustion and build-up properties of dyes according to formula (IIIa) and (IVa) have been determined as outlined in Table 2.

[0166] The Higher the fastness rating, the better the behaviour regarding the considered property.

[0167] RD:

[0168] Reference Depth (RD) is a unit to determine / classify a depth of a color / shade.

[0169] It is determined how much dyestuff is needed to reach a specific depth, which is in the present case 1 RD. Similar strength comparisons could also be done with the Hilfstypen-Richttyptiefen / Standard Depth (SD). Measurements are done with a Datacolor spectrophotometer.

[0170] L* / a* / b*CIELAB values:

[0171] Color values in the CIELAB color space (also referred to as L*a*b*) are determined with a standard spectrophotometer.Meissner Bolte M / ARCH-022-PC

[0172] 24

[0173] Table 2:

[0174]

[0175] 1: COLOR FASTNESS TO DOMESTIC AND COMMERCIAL LAUNDERING ISO 105 C06 CIS ( 60°C X 30 min ) 2010 2: COLOR FASTNESS TO WATER ISO 105 E01 ( 37°C X 4 HRS ) 2013E

[0176] 3: COLOR FASTNESS TO LIGHT XENON ARC AATCC 16.3 20 AFU & 40 AFU 2014

[0177] 4: COLOR FASTNESS TO CHLORINATED POOL WATER: SWIMMING POOL ISO 105 E03 2010

[0178] 5. COLOR FASTNESS TO OXIDATIVE BLEACH M& S C10A

[0179] SC: Shade change

[0180] CS: Color stain

Claims

Meissner Bolte M / ARCH-022-PC 25Claims1. Dye of the formula (I)R1, R2, R3and R4are independent from each other and whereinR1is selected from -NH2, -C1-4alkyl,R2 is selected from -H, -O-C1-4 alkyl, -C1-4 alkyl, -SO3H,R3is selected from -H, -O-C1-4 alkyl, -C1-4 alkyl, -SO3H,R4is selected from -H, -O-C1-4 alkyl, -C1-4 alkyl, -SO3H, -NO2,Y2is -CH2-CH2-OSO3H or -CH=CH2,m is selected from 0 to 3, andn is selected from 0 to 2.

2. Dye according to claim 1, wherein M is Cu.

3. Dye according to any of the preceding claims, wherein Yi is -CH2-CH2-OSO3H.

4. Dye according to any of the preceding claims, wherein X is -Cl.Meissner Bolte M / ARCH-022-PC5. Dye according to any of the preceding claims, wherein Ri is NH2.

6. Dye according to any of the preceding claims, wherein R2 is -H.

7. Dye according to any of the preceding claims, wherein R3 is -H.

8. Dye according to any of the preceding claims, wherein R4is -H or NO2.

9. Dye according to any of the preceding claims, wherein m is 1, 2 or 3.

10. Dye according to any of the preceding claims, wherein n is 0 or 1.

11. Dye according to claim 1, which is a compound of formulae (Ila) or (lib)Meissner Bolte M / ARCH-022-PC12. Dye according to claim 1, which is a compound of formulae (Illa) or (Illb)13. Dye according to claim 1, which is a compound of formula (IVa) or (IVb)Meissner Bolte M / ARCH-022-PC14. Dye according to claim 1, which is a compound of formula (Va) or (Vb)Meissner Bolte M / ARCH-022-PC15. Method for dyeing or printing a fabric with a dye, comprising the following steps:i) dyeing or printing a fabric, preferably a fabric containing or consisting of cellulose acetate, cotton, polyamide, polyester, polyacrylonitrile and / or wool, with a dye according to at least one of claims 1 to 14, andii) drying the dyed or printed fabric of i), preferably with dry heat or steam.

16. A dyed fabric obtainable by the method according to claim 15.

17. Use of a dye according to at least one of claims 1 to 14 for dyeing or printing a fabric, preferably for dyeing or printing a fabric containing or consisting of cellulose acetate, cotton, polyamide, polyester, polyacrylonitrile and / or wool.

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