DISPERSE-REACTIVE DYES SUITABLE FOR DYEING AND PRINTING POLYESTER-CELLULOSE BLENDED FIBRES

Abstract: Disperse-reactive dyes suitable for dyeing and printing, in one step only, polyester-cellulose blended fibres are described, which are comprised in the general formula D - (SO₂- C₂H₄OCOR) n wherein: D is the residue of the molecule of a dye of the azo, anthra­ quinone methinic or quinophthalonic series, free from solubilizing groups such as the sulphonic and the car­ boxylic groups; n is a number equal to 1 or 2; R is an alkyl, C₁-C₈, optionally substituted by halogen or CN; an alkenyl C₂-C₈, optionally substituted by halogen or CN; an alkoxyl C₁-C₈; a cycloalkoxyl; HN-alkyl C₁-C₄; HN-halogen alkyl C₁-C₄; N(alkyl C₁-C₄)₂. Methods of preparing the dyes and of applicating same on said blends are described as well.

Description: This invention relates to a new series of dyes which are employed for dyeing and printing polyester-cellulose blended material. Processes are known for dyeing polyester-cellulose blended fibres which comprise more than one step, according to whic the blend components are dyed in separate steps with different dyes (disperse dyes plus reactive dyes; disperse dyes plus vat dyes). These processes exhibit serious drawbacks such as complexity of execution, possibility of reciprocal staining, necessity of using considerable amounts of dyes. One of these dyeing processes is described, for example, in U.S. patent 3,313,590. Processes for dyeing polyester-cellulose blended fibres employing only one dye in one step only are known too, the best known of them being the one utilizing the swelling action exerted by water on cellulose. This process exhibits the drawback of requiring the use of an organic solvent subject to evaporate or decompose at the high temperatures at which it is operated, usually around 2000C, so causing problems of environmental pollution. Furthermore the solvent, being water-soluble, pollutes the waste waters. Moreover, the materials dyed according to such process exhibit low values of stability to moisture and sublimation due to the fact that the dyes employed do not bind to the cellulose component of the blend. This process is described, for example, in U.S. patent 3,706,525. Another process, described in Japanese patent application 7,306,932 permits to use only one dye for dyeing the blend and offers the advantage, as compared with the preceding process, of not employing any solvent, since it is based on dyes having a reactive group of the type CH2=CHS02- capable, besides of binding to the cellulose component, also of fixing on the polyester component of the blend. Such dyes, however, exhibit some limitations in the covering consequent power and in the fixing power on the blend, withshade variations on the two components of said blend and unsatisfactory yields; also fastness to light is poor. It is an object of the present invention to provide a new series of disperse reactive dyes carrying at least a variously acylated beta-hydroxyethylsulphonyl group, which are free from solubilizing groups such as the sulphonic and the carboxylic groups, suited to dye and print, in one step, polyester-cellulose blended fibres, as well as to provide the methods of utilizing and preparing same. More in particular the present invention relates to disperse se-reactive dyes of general formula D-(SO2C2H4OCOR)n (I) wherein D is the residue of the molecule of a dye of the azo, anthraquinone, methinic or quinophthalonic series, free from solubilizing groups such as the sulphonic and the carboxylic groups; n is a number equal to 1 or 2; R is an alkyl C1-C8, preferably optionally substituted by halogen or CN; an alkenyl C2-C8, optionally substituted by halogen or CN; an alkoxyl C1-C8; a cycloalkoxyl; HN alkyl C1-C4; HN-halogen alkyl Cl-C4; N(alkyl C1-C4)2. The dyes of general formula (I) are prepared, as illustrated hereinafter, by condensation of the intermediate of general formula D-(SO2C2H4OH)n (II) with a proper acylating agent; among such agents the preferable ones are the following RlCOCl (R2)2NCOCl (R C0)20 (III) (IV) (V) R4OOC-Cl R5 - N=C=0 (VI) (VII) wherein : D and n have the meanings specified hereinbefore, and R1 is an alkyl Cl-C8, optionally substituted by halogen or CN; an alkenyl C2-C8, optionally substituted by halogen or CN; R2 is an alkyl C1-C4; R is an alkyl Cl-C8; 3 R is an alkyl Cl-C8, optionally substituted by halogen; 4 R5 is an alkyl C1-C4, a halogen alkyl Cl-C4. An alternative method of synthetizing the azo dyes may consist in diazotizing, in an aqueous acid medium, an amine of general formula EMI4.1 and in successively coupling, always in an aqueous medium, diazonium salt on a suitable coupling intermediate, such as, for example, the ones exemplified in the formulas from (XI) to (XIV); or in diazotizing an amine of formula Ar - NH (IX) 2 and in coupling the resulting diazo on a coupling intermediate of formula Cop - SO C H OCOR (x) Z24 such as, for example, the one exemplified in formula (XV); wherein : R has the meaning previously defined, and X is H, a halogen, CN, NO2, an alkyl C1-C4, an alkoxyl C1-C4; m is a number equal to t or 2; Ar is the residue of a diazotizable component of the carbocyclic or heterocyclic series, and Cop is the residue of a coupling component. The reaction between the intermediates of general formula (II) and the reagents of general formulas (III) to (VII), as well as the reactions for obtaining the intermediates having formula (VIII) and (X) respectively are generally conduct ed in the presence of aprotic solvents such as, for example, benzene, toluene, xylene, chlorobenzene, orthodichlorobenzene, pyridine, dimethylformamide, dimethylsulphoxide, at temperatures of from 0 to 140 C optionally in the presence of basic catalysts such, for instance, pyridine or acid acceptors such as e.g. triethylamine. Generally the dyes of general formula (I) possess a high purity degree, so that no purification is required. In the series of the disperse-reactive dyes forming the object of the present invention, the preferential classes of dye result to be the ones corresponding to the following formula EMI5.1 EMI6.1 wherein R, X, m, Ar have the meanings specified hereinbefore, and R6 is H; an alkyl C1-C4, an aryl e.g. phenyl optionally substituted by 1 or 2 atoms of Cl or by a group SO2N(alkyl C1-C4)2; R7 is an alkyl C1-C4, COO alkyl C1-C4; R8 is H, an alkyl C1-C4, a hydroxyalkyl C1-C4; R9 and R10 like or unlike each other, are each an alkyl C1-C4, a cyanoalkyl C1-C4, a hydroxyalkyl C -C , an alkoxy -alkyl C1-C4, a halogen alkyl C1-C4, an alcyloxy-al kyl C1-C4, an aralkyl; ; R11 is H, a halogen, an alkyl Cl-C4, an alkoxyl C1-C4; R12 is H, a halogen, an alkyl C1-C4, an alkoxyl C1-C4; R13 is H, an alkyl C1-C4, an alkoxyl C1-C4, a halogen; R@@ is H, CO alkyl C@-C@, optionally substituted, 14 CO alkenyl C2-C8, optionally substituted, CO aikoxyl Cl-C8, CO cycloalkoxyl, COHN. alkyl C1-C4, COHN halogen alkyl C1-C4, CON(alkyl C1-C4)2; p is a number from 1 to 3; q is a number equal to 2 or 3; Z is H, an alkyl C1-C4, a halogen, a group NHCO alkyl C1-C4; Z1 is H, an alkyl Cl-C4, a halogen. The dyes of --------- the present invention are particularly suitable for continuously dyeing according to the pad -steam method or to the pad-thermosol method, and for printing "shade on shade" the polyester-cellulose blended fibres imparting to them shades varying from greenish yellow to greenish blue, characterized by a high fixing and by good stabilities to light, sublimation, washings as well as to friction in dry and wet conditions. As compared with the dyes of the prior art, the dyes of general formula (I) exhibit an easy receptivity and excellent applicative properties as regards the covering of the blend (absence of any shade variations on the two fibres forming the blend), the fixability and the dye yield (capability of providing intense shades). Also the stabilities to sublimation and to rubbing . appear excellent. That can be obtained in particular by using the dyes belonging to the preferential classes. The dyes of general formula (I) preliminarily ground in the presence of proper dispersants (such as, for example; the one obtained by condensation between beta-naphthalene sulphonic acid and forma-ldehyde) up to a particle size of 0.5 are applicated on the polyester-cellulose blended fibre in the form of a liquid or of an aqueous paste, additioned with an alkaline substance, preferably sodium bicarbonate or sodium phosphate, and with an auxiliary component, such as e.g. Anionico OL 495(R), Antarox CO 430 or Tanatrint (R) ASD ( either alone or in admixture with one another in amounts varying from 10 to 40 g/kg of printing paste. Similar results are obtained by using substances which,though they are initially not alkaline, generate alkalis during the process; sodium trichloroacetate is particularly effective. The printing pastes. contain also other additives such as urea, in the amount of 50-100 g/kg of printing paste, and oxidants such as sodium m-nitrobenzene sulphonate. The fixing of the dye on the blend is obtained by subjecting the dyeings and printings to heating treatments by mcans of dry air (Thermosol pracess) or superheated steam (HT process) at temperatures ranging from 1700C to 2200C for stretches of time of from 1 minute to 10 minutes. Successively the dyed or printed blended fibres are subjected to a cleaning process in a bath containing soap or a synthetic detergent and a suitable alkaline agent such as e.g. sodium carbonate and/or sodium hydrate, in order to remove not fixed dye, if any. The blends suited to be dyed and printed with the dyes of general formula (I) include cellulose fibres in the natural form such as, for example, cotton and flax, or in tie regenerated form such as, for example, viscose. The blends may include furthermore polyethylene terephthalate as polyester component. Although the ratio between polyester component and cellulose component of the blend is not critical, it is prefel- able to employ bltnds having a ce)lulosc-polyester ratio ranging from 80:20 to 20:80. The following examples are given to illustrate the characteristics of te present invention, witiiout being izowever a limitation thereof. Unless otherwise specified, the term "parts" is to be under stood as expressed in weight units. EXAMPLE 1 4.02 parts of 4-hydroxyethylsulphonyl aniline were dispersed with 8.0 parts by volume of HCl d = l.18 and with 40 parts by volume of water. The mass was cooled dowii to 0-5 C and iii 5 minutes a sol- ution of 1.4 parts of NaNO2 in 10 parts by volume of water was poured thereinto. It was stirred at 0-5 C for 1 hour whereupon HNO2 in excess was eliniinated by suipliamic acid The diazo solution was clarified and poured at 5-100C into a solution of 3.5 parts of 1-methyl-4-hydroxy-2 quinolone in 40 parts by volume of water and 1.0 part of NaOH; during coupling the pH was maintained alkaline by addition of sodium carbonate. On conclusion of coupling it was filtered, the precipitate was washed to neutrality with water and dried. 6.9 parts of the following azoic intermediate were obtained EMI10.1 .Such intermediate - 6.9 parts - was successively treated temperature at boiling^for 2 hours with 8.0 parts by volume of acetic anhydride. The mass was allowed to cool down, then it was poured into 100 parts by volume of water. After having stirred the mass for 1 hour, tt- was filtered and the precipitate was washed to neutrality. The cake was dried, so obtaining 7.2 parts of the dye EMI10.2 40 parts of such dye were microfined with 40 parts of Saltetra F (a condensate between beta-naphthalene sulphonic acid and formaldehyde), 25 parts of ethylene glycol, 1 (R) part of Parmetol DF12 ) and 94 parts of water. Using 150 parts of such mixture, 1,000 parts of printing paste were prepared by addition of 60 parts of urea, 10 parts of sodium m-nitro-benzene sulphonate, 500 parts of a solution of sodium alginate at 10%, 10 parts of sodium bicarbonate, 20 parts of Tanaprint ASD (R) (a mixture of alkylphenol oxyethylenate and oleic acid oxyethylenate) and 250 parts of water. Such paste was applicated on a fabric of polyester-cotton (65:35) blended fibres, ready for printing, whereupon said paste was allowed to dry at a temperature below 1000C. The fixing of the dye on the two fibres constituting the blen was effected: a) in a thermosol apparatus operating at 2100C for 60 seconds, b) in a steaming apparatus operating at 1800 for 8 seconds. The printing, either heat set or steamed, was subjected to a cleaning process in three steps l) cold and hot washing, 2) soaping at 90 C for 10 minutes with 3 g/l of sodium hy drate, 3 g/l of sodium carbonate, 2 g/l of detergent D pon T (R) and 2 g/l of ethylene diamine tetra-acetate, 3) rinsing. A greenish yellow printing, perfectly hidden and uniform shade was obtained. The strength obtained was l/l (E.C.E.). Good stabilities to light, to moist washings and trichloroethylene cleaning, and to fri#ction corresponded to such strength. EXAMPLE 2 10 parts of the azoic intermediate of example 1 were dissolved with 60 parts by volume of pyridine; the solution was cooled to 0-100C and 14 parts by volume of methyl chloroformate were then gradually added. The reaction continued for 2 hours at 0-10 C, whereupon the solution was poured into 300 parts of water. It was stirred for about 30 minutes, then it was filtered and the cake was repeatedly washed with water. By drying it was possible to obtain 9.4 parts of the dye EMI12.1 Microfining and application were carried out by operating under the same conditions as in the preceding example, so obtaining a greenish yellow pririting with characteri.stics similar to the ones of example- 1. EXAMPLE 3 10 parts of the azoic intermediate of example 1 were reacted at 130-140 C for 10 hours with 2.8 parts of butyl isocyanate and 35 parts by volume-of ortho-dichlorobenzene. At the end of the reaction the mass was allowed to cool,tiwn it was filtered, washed with a few petroleum ether and dried. 10.7 parts of the following dye were obtained EMI12.2 Microfining and application were effected under the same conditions of example 1, so obtaining a greenish yellow print- ing having characteristics similar to the ones of said example. EXAMPLE 4 4.62 parts of 2-methoxy-5-hydroxyethylsulphonyl-aniline were dispersed with 8.0 parts by volume of liCl d = 1.18 and with 40 parts by volume of water. The mass was cooled down to 0-5 C and a solution of 1.4 parts of NaOH2 in 10 parts by volume of water was poured thereinto in about 5 minutes. It was stirred at 0-5 C for 1 hour, then the HNO2 in excess was eliminated with sulphamic acid. The diazo solution was clarified and poured at 0-5 0C into a solution of 3.5 parts of 1-phenyl-3-methyl-2-pyrazol-5-one in 40 parts of water and 1.0 parts of NaOH. At the end of coupling it was filtered, the precipitate was washed to neutrality with water and dried. 6.7 parts of the following azoic intermediate were obtained EMI13.1 3.4 parts of the above intermediate were treated at boiling temperature for 30 minutes with 10 parts by volume of acetic anhydride. The mass was allowed to cool, whereupon it was poured into 100 parts by volume of water. Aftor stirring for further 30 minutes it was filtered and the precipitate was washed to lleu- trality with water. The cake was dried, so obtaining 3.5 parts of the dye EMI14.1 By effecting both micrifining and application under the condit ions of example 1 it was possible to obtain a perfectly hid den and uniform yellow printing endowed with good stabilities to light, moist washings and trichloroethylene cleanings, as well as to friction. EXAMPLE S 4.1 parts of the azoic intermediate of example 4 were reacted with 1.1 parts of chloroethyl-isocyanate in the presence of 15 parts by volume of chlorobenzene at 120 C for 10 hours. At the conclusion the mass was cooled to room temperature,was filtered, washed with a few petroleum ether and dried. 4.9 parts of the following dye were obtained EMI14.2 which, after having been microfined and applicated under tulle conditions of example 1, provided a yellow shade printing having characteristics similar to t ones of example 4. EXAMPLE 6 4.9 parts of 2-methoxy-4-hydroxyethylsulphonyl-5-methyl-anil- ine were diazotized according to the modai-ities described in example 4 and coupled on 4.64 parts of the ethyl ester of 1-phenyl-2-pyrazol-5-one-3-carboxylic acid in solution with 40 parts by volume of acetic acid and 20 parts by volume of water. During coupling the pH of tie mass was maintained at 4-5 by addition of sodium acetate in crystals. was then operated as describcd in example 4, so obtaining 9.2 parts of the intermediate dye EMI15.1 4.9 parts of such intermediate were successively reacted at temperature boilingAfor 1 hour with 10 parts of acetic anhydride. The whole was allowed to cool down to loom temperature, where upon it was poured into 80 parts by volume of water. After having stirred the mass for 1 hour, it was filtered and the precipitate was washed to neutrality with water. The cake was dried, so obtaining 5.0 parts of the dye EMI15.2 which, after having been microfined and applicated under the conditions of example 1, provided a perfectly hidden and uniform reddish yellow printing having good general stabilities. EXAMPLE 7 5.4 parts of 2.5-dichloro-4-hydroxyethylsulphonyl-aniline were diazotized and coupled on 4.65 parts of the ethyl ether of 1-phenyl-2-pyrazol-5-one-3-carboxylic acid according to the modalities described in example 6. 10.85 g of the azoic intermediate EMI16.1 were obtained, which were reacted with 15 parts by volume of propionic anhydride for 2 hours at boiling temperature. It was then operated as described in example 6, so obtain- ing 11.0 parts of the dye EMI16.2 which, after having been microfined aiid applicated under the conditions described in example 1, provided a reddish yeallo printing having characteristics sfliiilar to tlie ones of example 6. EXAMPLE 8 3.9 parts of tile azoic intermediate of example 1 were reacted ed at 1000C for 8 hours witji 1.1 parts of dimethyl carbainyl chloride in the presence of 30 parts by volume of xylene. On completion of the reaction the mass was cooled to room temperature and the separated precipitate was recovered by filtration,was washed with a few petroleum ether and dried. 4.8 parts of the dye EMI17.1 were obtained which, after micrifining and application under teh conditions described in example 1, provided a yellow shade printing having cllaractcristics similar to the ones described in such example. EXAMPLE 9 4.62 parts of 2-methoxy-5 -hydroxy-e thyl-sulphonyl -aniline were diazotized according to the modalities illustrated in example 4 and were coupled on 6.46 parts of 2,5-dimethoxy-anilide of 2-hydroxy-3-naphthoic acid in 50 parts of water and 5.0 parts of NaDH; during coupling the pll of the mass was maintained alkaline by addition of Na CO 23 By operating according to example 4 it was possible to obtain 10.8 parts of the following azoic intermediate : EMI17.2 5.65 parts of which were reacted at boiling temperature for 30 miiiutes with 10 parts by volume of acetic anhydride. By proceeding then as described in example 4, 5.7 parts of the following dye were obtained EMI18.1 The dye was microfined under the conditions of example 1. From 100 parts of such mixture 1000 parts of printing paste were prepared by addition of 80 parts of urea, 10 parts of sodium m-nitro-benzene sulphonate, 500 parts of a solution of sodium alginate at 10%, 10 parts of sodium bicarbonate, 40 parts of Tanaprint ASD ) and 260 parts of water, By operating according to example 1 a perfectly hidden and uniform red shade printing, having a strength of 1/1 (E.C.E.) and good general stabilities was obtained. EXAMPLE 10 5.65 parts of the intermediate azo-dye of example 9 were reacted at 100 C for about 8 hours with 1.3 parts of the chloride of n-pentanoic acid in 20 parts by volume of chlorobenzene and o.8 parts by volume of pyridine. At the conclusion of the reaction the mass was cooled to room temperature, then it was filtered and washed with a few petroleum ether. By dying it was possible to obtain 6.2 parts of the dye EMI18.2 which, after having been microfined and applicated under the conditions described in example 9, provided a red shade plint- ing having characteristics similar to those illustrated in example 9. EXAMPLE 11 2,01 parts of 3-hydroxy-ethyl-sulphonyl-aniline were diazotlzed and coupled,according to the modalities of example 1, on 3.23 parts of the 2.5-dimethoxy-anilide of 2-hydroxy-3-napJi- thoic acid. The intermediate azo-dyes obtained - 5.1 parts - was reacted under the conditions described in example 2, witty 8.0 parts by volume of butyl chloroformate. It was operated analogously with such example, so obtaining 5.2 parts of the dye EMI19.1 which, after having been microfined and applicated under the conditions of example 9, provided a perfectly hidden and urilform yellowish red printing having good general stabilities. EXAMPLE 12 4.9 parts of 2-methoxy-4-hydroxy-ethyl-sulphonyl-5-methyl-aniline were diazotized and coupled, according to the method described in example 6,on 4.12 parts of N.N-diethyl-m-aminoacet- I anilide in 40 parts of water and 5 parts by volume o HCl d = 1.18. During coupling the pll of tiie mass was maintained at 4-5 by addition of sodium acetate in crystals. By operating then according to example 6, it was possible to ' obtain 8.9 parts of the intermediate azo-dye : EMI20.1 4.62 parts of such intermediate were reacted at boiling tcm- perature for about 30 minutes with 6 parts of acetic anhydride. It was successively operated as described in example 1, sn obtaining 4.5 parts of the dye EMI20.2 which, after having been microfined ad applicated under the conditions of example 9, provided a perfectly hidden and uni- form scarlet shade printing having good general stabilities. EXAMPLE 1.R 4.62 pants of the azoic intermediate of example 12 were reacted ed with 1.9 parts of pivalic anhydride in the presence of 1.1 parts-of triethylamine and 25 parts by volume of dimethylformamide at a temperature of about 400C for about 2 hours. At the end of the reaction the solution was poured into 200 parts of water, it was stirred for 30 minutes, whereupon the resulting precipitate was filtered and washed with water. By drying 4.8 parts of the following dye were obtained EMI21.1 which, after having been microfined and applicated under the conditions already described hereinbefore, provided a scarlet shade printing having characteristics similar to tlie ones illustrated inlexample 12. EXAMPLE 14 5.65 parts of the azoic inteiinedi-ite of example 9 were react- ed at 80 C for 12 hours with 1.2 parts of the chloride of vinyl acetic acid in 25 parts by volume of xylene and 0.8 parts by volume of pyridine. At the conclusion of the reaction the mass was cooled to room temperature, then it was filtered and washed with a few petroleum etiier. By drying it was possible to obtain 5.7 parts of the dye EMI21.2 which, after having been microfined and applicated under the described conditions, provided a red shade printing exhibits ing characteristics analogous with the ones of example 9. EXAMPLE 15 4.84 parts of 2-bromo-4-nitro-6-cyanoaniline were added, at 0-50C and in 1 hour, to a solution consisting of 1,38 parts of sodium nitrite in 40 parts by volume of H2SO4 d = 1.84. It was then stirred for 30 minutes whereupon the diazo sol- ution was poured, at 5-1O0C, into a solution of 5.46 parts of N-ethyl-N-(hydroxy-ethyl-sulphonyl)-ethyl-m-amino-toluidine in 40 parts of water and 2.0 parts by volume of HCl d = 1,18. During coupling the pH of the mass was maintained at 4-5 by addition of sodium acetate is crystals. After stirring for 1 hour it was filtered and tI)e precipitate was washed with water. The cake was dried, so obtaining 10.3 parts of tlie followiiig intermediate dye EMI22.1 5.26 parts of such intermediate azo-dyc were reacted with 10 parts by volume of acetic anhydride for 40 minutes at boiling temperature. It was then operated according to example 1, so obtaining 5.3 parts of the dye EMI22.2 which, after having been mierofined and applicated under the conditions of example 1, provided a perfectly hidden bluish violet printing having a uniform shade and good general staabilities. EXAMPLE 16 A solution of 3.26 parts of 2-cyaílo-4-nitro-aniline in 30 parts of acetic acid, 8 parts of propionic acid and 4 parts of water was cooled to 5-10 C and tlicii additioned, in about 1 hour, with 20 parts by volume of nitrosyl sulphuric acid 1N. After stirring for about 1 hour at 5-10 C, the dj.izo solution was gradually poured uto the mass obtained by reacting 5.46 parts of N-ethyl-N-(hydroxyethylsulphonyl)-ethyl- m-amino-toluidine with 10 parts by volume of acetic anhydride then it was boiled for 20 minutes and successively cooled to 5-100C. During coupling the pH was maintained at 4-5 by addition of sodium acetate in crystals. It was filtered after 1 hour, then the precipitate was washed with water and dried. 8.3 parts of the dye EMI23.1 were obtained, which, after having been mierofined and applicated under the conditions of example 1, provided a perfectly hidden ruby printing having a uniform shade and good general stabilities. EXAMPLE 17 5.55 parts of 2-chloro-5-acetoxyethyl-sulphonyl aniline were diazotized and coupled, according to the modalities described in example 1, on 3.5 parts of 1-methyl-4-hydroxy 2-quinolone. 8.8 parts of the dye EMI24.1 were obtained which, after having been microfined and applicated under the conditions already described provided a perfectly hidden yellow printing having a uniform shad and good general stabilities. EXAMPLE 18 5. 14 parts of 3-propioxyethylsulphonyl-aniline were diazotized and coupled on 6.46 parts of 2.5-di.methoxy aniline of 2-hydroxy-3-naphthoic acid accord.ixlg to the modalities described in example 9. 11.2 parts of the dye EMI24.2 were obtained, which provided a l)erlectly hidden yellowish red printing having a uniform shade and good general stabilities. EXAMPLE 19 6.2 parts of 2-mothoxy-5-hydroxy-ethylsulphonyl aniline were reacted at 950C for 2 hours with 5.31 parts of 1-amino- 4-bromo-2-anthraquinone-sulphonic acid in the presence of 8.8 parts of NaHCO3 and 1.0 part of cuprous chloride. At the conclusion of the reaction the mass was cooled to 50 C, acidified with HCl d = 1.18 to a pH value = 1-2 and filtered. The precipitate was washed with a slightly acid solution containing sodium chloride and was successively treated with 8.0 parts of 30% sodium hydrate and 3.0 parts of glucos for 1 hour at 900C. After filtering, washiiig with water and drying, 4.25 parts of the anthraquinone intermediate were obtained. EMI25.1 4.0 parts of such intermediate were dissolved in in t).() parts of H2SO4 d = 1.5 and additioned, at room temperature and in 6 hours, with 6.0 parts of acetic anhydride, The solution was stirred for about 24 hours, whereupon it was diluted with water, filtered and washed to noutrality with water. After drying, 3.4 parts of the dye EMI25.2 were obtained, which, after having becn niicrofjrtcd and applicated under the conditions illustrated in example 9, provided a perfectly hidden neutral blue printing, having a uniform shade and good general stabilities. EXAMPLE 20 4.52 parts of the antliraquinone intermediate of example II) were reacted, at boiling temperature for 60 minutes, with 12 parts by volume of acetic anhydride. By operating them as described in example 1 it was possible to obtain 4.8 parts of the dye EMI26.1 which provided a perfectly hidden violet i)riring having a uniform shade and good general stabilities. EXAMPLE 21 4.52 parts of the anthraquinone intermediate of example 19 were reacted at 80-900C for 4 hours with 3.0 part of butyl isocyanate in 20 parts by volume of orthodichloro-benzene. At the end of the reaction the mass was allowed to cool, then it was filtered and washed with petroleum ether. After drying, 5.6 parts of the dye EMI26.2 were obtained which provided a blue shade printing having characteristics similar to the ones of example 19. Following exactly the modalities described in the preceding examples, the dyes havi.ng respectively the following general formulas were obtained EMI28.1 EMI28.2 Example <SEP> R <SEP> Chain <SEP> (X)m <SEP> R6 <SEP> R7 <tb> No. <SEP> position <SEP> Shade <SEP> on <SEP> blend <tb> 22 <SEP> C2H5 <SEP> meta <SEP> 2-OCH3 <SEP> m-ClC6H4 <SEP> CH3 <SEP> yellow <tb> 23 <SEP> CH3 <SEP> para <SEP> H <SEP> 2.5-Cl2C6H3 <SEP> CH3 <SEP> greenish <SEP> yellow <tb> 24 <SEP> CH3O <SEP> meta <SEP> H <SEP> m-SO2N(CH3)2C6H4 <SEP> CH3 <SEP> yellow <tb> 25 <SEP> CH3 <SEP> para <SEP> H <SEP> C6H5 <SEP> COOC2H5 <SEP> yellow <tb> 26 <SEP> C4H9NH <SEP> para <SEP> 2-OCH3; <SEP> 5-CH3 <SEP> C6H5 <SEP> COOC2H5 <SEP> golden <SEP> yellow <tb> 27 <SEP> CH3 <SEP> para <SEP> 2.5-Cl2 <SEP> C3H7 <SEP> CH3 <SEP> reddish <SEP> yellow <tb> EMI29.1 28 <SEP> C3H7 <SEP> para <SEP> 2.6 <SEP> - <SEP> Br2 <SEP> C6H5 <SEP> CH3 <SEP> brownish <SEP> yellow <tb> 29 <SEP> CH3 <SEP> para <SEP> H <SEP> H <SEP> CH3 <SEP> yellow <tb> 30 <SEP> CH3O <SEP> meta <SEP> 2-OCH3 <SEP> C6H5 <SEP> COOC2H5 <SEP> yellow <tb> 31 <SEP> CH2=CH-CH2 <SEP> para <SEP> H <SEP> C6H5 <SEP> CH3 <SEP> yellow <tb> 32 <SEP> (CH3)3O <SEP> para <SEP> H <SEP> C6H5 <SEP> CH3 <SEP> yellow <tb> EMI30.1 EMI30.2 Example <SEP> R <SEP> Chain <SEP> (X)m <SEP> R8 <tb> No. <SEP> position <SEP> Shade <SEP> on <SEP> blend <tb> 33 <SEP> CH3 <SEP> para <SEP> H <SEP> H <SEP> greenish <SEP> yellow <tb> 34 <SEP> C2H5 <SEP> meta <SEP> 2-OCH3 <SEP> CH3 <SEP> yellow <tb> 35 <SEP> C4H9O <SEP> para <SEP> 2-OCH3; <SEP> 5-CH3 <SEP> CH3 <SEP> golden <SEP> yellow <tb> 36 <SEP> C4H9 <SEP> para <SEP> 2.5-Cl2 <SEP> C2H5 <SEP> golden <SEP> yellow <tb> 37 <SEP> ClC2H4NH <SEP> meta <SEP> H <SEP> CH3 <SEP> greenish <SEP> yellow <tb> 38 <SEP> CH3O <SEP> para <SEP> H <SEP> C2H5 <SEP> greenish <SEP> yellow <tb> 39 <SEP> CH3 <SEP> meta <SEP> 2-Cl <SEP> C2H4OH <SEP> yellow <tb> 40 <SEP> (CH3)3C <SEP> para <SEP> H <SEP> CH3 <SEP> greenish <SEP> yellow <tb> EMI31.1 EMI31.2 Example <SEP> R <SEP> Chain <SEP> (X)m <SEP> R11 <SEP> Z <SEP> R9 <SEP> R10 <SEP> Shade <SEP> on <tb> pos No. <SEP> blend <tb> ition <tb> 41 <SEP> C2H5 <SEP> meta <SEP> 2-OCH3 <SEP> H <SEP> NHCOCH3 <SEP> C2H5 <SEP> C2H5 <SEP> orange <tb> 42 <SEP> C4H9O <SEP> para <SEP> H <SEP> H <SEP> NHCOC2H5 <SEP> C2H5 <SEP> C2H5 <SEP> orange <tb> 43 <SEP> CH3 <SEP> para <SEP> 2.5-Cl2 <SEP> H <SEP> NHCOC(CH3)3 <SEP> C2H5 <SEP> C2H5 <SEP> bluish <SEP> red <tb> 44 <SEP> C4H9NH <SEP> meta <SEP> 2-OCH3 <SEP> H <SEP> CH3 <SEP> C2H5 <SEP> C2H5 <SEP> golden <SEP> yellow <tb> 45 <SEP> CH3 <SEP> para <SEP> 20CH3; <SEP> 5CH3 <SEP> H <SEP> H <SEP> C2H4CN <SEP> C2H4CN <SEP> yellow <SEP> red <tb> 46 <SEP> CH3O <SEP> para <SEP> 20CH3; <SEP> 5CH3 <SEP> H <SEP> NHCOCH3 <SEP> C2H4CN <SEP> C2H5 <SEP> red <tb> 47 <SEP> CH3 <SEP> para <SEP> 2.6-Br2 <SEP> OCH3 <SEP> NHCOCH3 <SEP> CH3 <SEP> CH3 <SEP> bluish <SEP> red <tb> 48 <SEP> C3H7 <SEP> para <SEP> 2.6-Br2 <SEP> H <SEP> CH3 <SEP> C2H5 <SEP> C2H5 <SEP> brownish <SEP> red <tb> EMI32.1 <tb> <SEP> o <SEP> o <SEP> &commat; <SEP> > F <tb> <SEP> r <tb> <SEP> i <SEP> HE <tb> <SEP> &commat; <tb> 49 <SEP> ClC2H4NH <SEP> para <SEP> to <SEP> 0 <tb> 50 <SEP> CR3 <SEP> :eta <SEP> H <SEP> CR3 <SEP> C2H5 <SEP> C2H4OR <SEP> red-yellow <tb> f <SEP> 8 <tb> <SEP> IC\I <SEP> 0 <SEP> 0 <tb> Wcunr <SEP> cu <SEP> 2-NO <SEP> 2 <SEP> P: <tb> <SEP> m <SEP> N <SEP> N <SEP> cm <tb> 53 <SEP> -CR- <SEP> H <SEP> lNHCnCH <SEP> H <SEP> 000CR <SEP> IC <SEP> H <SEP> c > <SEP> I <SEP> reddish <SEP> vellow <tb> <SEP> me <tb> <SEP> cz <tb> <SEP> tZ <SEP> 8 <tb> 54 <SEP> 1 <SEP> e: <SEP> \\.para <SEP> wF <SEP> < <SEP> H <SEP> INHOOCH3 <SEP> CU <SEP> Ln <SEP> Ln <tb> <SEP> cz <SEP> C <SEP> H <SEP> N <SEP> CU <SEP> < y <SEP> cs <SEP> OCR3 <SEP> cJ <tb> 56 <SEP> OH3 <SEP> H <SEP> I <SEP> !c2H5 <SEP> scarlet <tb> <SEP> . <SEP> 46XSdI= <tb> <SEP> L) <SEP> c) <SEP> U <SEP> U <SEP> U <tb> <SEP> tr: <tb> <SEP> R <SEP> E;P;t4RR <tb> <SEP> s; <SEP> t; <SEP> t <SEP> z <SEP> t; <SEP> K <SEP> z <SEP> I <tb> <SEP> n <SEP> e <tb> <SEP> m <SEP> <tb> <SEP> O <SEP> o <SEP> o <tb> <SEP> o <tb> <SEP> F <tb> <SEP> e <SEP> N <SEP> v <tb> <SEP> E <tb> <SEP> 9 <tb> <SEP> h <SEP> e <SEP> f <SEP> f <SEP> h <SEP> h <SEP> h <SEP> h <tb> <SEP> d <tb> <SEP> P <SEP> aj <SEP> v <SEP> P <SEP> A <SEP> v <SEP> p- <SEP> p, <tb> <SEP> N <tb> <SEP> E <tb> <SEP> P: <SEP> tI <tb> <SEP> < M <SEP> e <SEP> e <SEP> n <SEP> CM <SEP> n <SEP> 2 <SEP> e <tb> <SEP> H <SEP> vN <SEP> E <tb> <SEP> o <SEP> R <SEP> - <SEP> N <SEP> e <SEP> + <SEP> > <SEP> m <tb> <SEP> q <SEP> UE <tb> EMI33.1 EMI33.2 Example <SEP> R <SEP> Chain <SEP> (X)m <SEP> (R12)p <SEP> Shade <SEP> on <SEP> blend <tb> No. <SEP> position <tb> 57 <SEP> CH3 <SEP> para <SEP> 2-OCH3; <SEP> 5-CH3 <SEP> 2-OC2H5 <SEP> red <tb> 58 <SEP> C3H7 <SEP> para <SEP> 2-OCH3; <SEP> 5-CH3 <SEP> 2-CH3 <SEP> ruby <tb> 59 <SEP> CH3O <SEP> meta <SEP> 2-OCH3 <SEP> 2-OCH3 <SEP> scarlet <tb> 60 <SEP> C4H9NH <SEP> para <SEP> H <SEP> 2-CH3; <SEP> 4-Cl <SEP> scarlet <tb> 61 <SEP> ClC2H4NH <SEP> para <SEP> 2-OCH3; <SEP> 5-CH3 <SEP> 3.4-Cl2 <SEP> bluish <SEP> red <tb> 62 <SEP> CH3 <SEP> para <SEP> 2.5-Cl2 <SEP> 2.4-(OCH3)2; <SEP> 5-Cl <SEP> ryby <tb> 63 <SEP> C4H9O <SEP> para <SEP> 2-OCH3; <SEP> 5-CH3 <SEP> 2.5-(OCH3)2; <SEP> 4-Cl <SEP> ruby <tb> EMI34.1 64 <SEP> C4H9(C2H5)CH <SEP> para <SEP> H <SEP> 2.5-(OCH3)2 <SEP> scarlet <tb> 65 <SEP> C4H9 <SEP> meta <SEP> H <SEP> 2.5-(OCH3)2 <SEP> scarlet <tb> 66 <SEP> C4H9NH <SEP> para <SEP> 2-OCH3; <SEP> 5-CH3 <SEP> H <SEP> red <tb> 67 <SEP> (CH3)3C <SEP> meta <SEP> 2-OCH3 <SEP> 2.5-(OCH3)2 <SEP> scarlet <tb> 68 <SEP> CH3 <SEP> meta <SEP> 2-OCH3 <SEP> 2-OC2H5 <SEP> reddish <SEP> orange <tb> 69 <SEP> CH3 <SEP> para <SEP> 2-NO2 <SEP> H <SEP> violet <tb> EMI35.1 EMI35.2 Ex- <SEP> Ar-NH2 <SEP> R <SEP> R9 <SEP> q <SEP> Z1 <SEP> Shade <SEP> on <tb> ample <tb> No. <SEP> blend <tb> 70 <SEP> 2-cyano-4-nitro-aniline <SEP> CH3 <SEP> C2H5 <SEP> 2 <SEP> H <SEP> ruby <tb> 71 <SEP> 2-methylsulphonyl-4-nitro- <SEP> C2H5 <SEP> C2H5 <SEP> 3 <SEP> H <SEP> violet <tb> -aniline <tb> 72 <SEP> 2-chloro-4-nitro-aniline <SEP> C4H9NH <SEP> C2H5 <SEP> 3 <SEP> CH3 <SEP> red <tb> 73 <SEP> 2-chloro-4-methylsulphonyl- <SEP> CH3O <SEP> C2H5 <SEP> 2 <SEP> CH3 <SEP> orange <tb> 74 <SEP> 4-nitro-aniline <SEP> ClC2H4NH <SEP> C2H4CN <SEP> 2 <SEP> Cl <SEP> scarlet <tb> 75 <SEP> 6-ethoxy-2-amino-benzothiazole <SEP> CH3 <SEP> C2H4OH <SEP> 2 <SEP> CH3 <SEP> bluish <SEP> red <tb> EMI36.1 76 <SEP> 3-amino-5-nitro-benzoisothi- <SEP> C4H9 <SEP> C2H5 <SEP> 3 <SEP> CH3 <SEP> greenish <SEP> blue <tb> azole <tb> 77 <SEP> 2-nitro-4-dimethylaminosul- <SEP> C4H9O <SEP> C2H4CN <SEP> 2 <SEP> Cl <SEP> reddish <SEP> brown <tb> phonyl-aniline <tb> 78 <SEP> 2.5-dichloro-4-methylsulpho- <SEP> CH3 <SEP> C2H5 <SEP> 2 <SEP> CH3 <SEP> brownish <SEP> red <tb> nyl-aniline <tb> 79 <SEP> 6-methylsulphonyl-2-amino- <SEP> C2H5 <SEP> C2H5 <SEP> 2 <SEP> CH3 <SEP> ruby <tb> -benzothiazole <tb> 80 <SEP> 2-amino-5-nitro-thiazole <SEP> (CH3)3C <SEP> C2H5 <SEP> 2 <SEP> H <SEP> blue <tb> EMI37.1 EMI37.2 Example <SEP> R <SEP> R13 <SEP> R14 <SEP> Shade <SEP> on <SEP> blend <tb> No. <tb> 81 <SEP> CH3O <SEP> OCH3 <SEP> CH3OOC <SEP> reddish <SEP> blue <tb> 82 <SEP> CH3 <SEP> H <SEP> H <SEP> reddish <SEP> blue <tb> 83 <SEP> CLC2H4NH <SEP> OCH3 <SEP> ClC2H4NHCO <SEP> blue <tb> 84 <SEP> CH3 <SEP> H <SEP> CH3CO <SEP> violet <tb> 85 <SEP> C4H9NH <SEP> H <SEP> C4H9NHCO <SEP> blue <tb> 86 <SEP> C4H9O <SEP> H <SEP> C4H9OOC <SEP> reddish <SEP> blue <tb> EMI38.1 87 <SEP> CH3 <SEP> Cl <SEP> H <SEP> neutral <SEP> blue <tb> 88 <SEP> C2H5 <SEP> Cl <SEP> C2H5CO <SEP> violet <tb> 89 <SEP> CH3 <SEP> CH3 <SEP> H <SEP> blue <tb> 90 <SEP> C4H9NH <SEP> CH3 <SEP> C4H9NHCO <SEP> blue <tb> 91 <SEP> C4H9O <SEP> CH3 <SEP> C4H9OOC <SEP> reddish <SEP> blue <tb> 92 <SEP> C2H5 <SEP> CH3 <SEP> C2H5CO <SEP> violet <tb>

Claims: @HAT WE CLAIM IS @) Disperse reactive dyes of general formula D - (SO2C2H4OCOR)n (I) wherein : D is the residue of the molecule of a dye of the azo, anthraquinonic,methinic or quinophthalonic series free from solubilizing groups, such as the sulphonic and the carboxylic groups; n is a number equal to 1 or 2; R is an alkyl C1-C8, optionally substituted by a halogen or CN ; an alkenyl C2-C8, optionally subs- tituted by a halogen or CN ; all alkoxyl C1-C8; a cycloalkoxyl; a HN-alkyl C1-C4 ; a HN-halogen al kyl C1-C4; a N(alkyl C1-C ) 2) A process for preparing the dyes of general formula (1), characterized in that an intermediate dye of general formula D - (SO2C2H4OH)n (II) is reacted with a suitable acylating agent such as, for example EMI39.1 wherein D aid n have the meanings defined hereinbefore, and R1 is an alkyl C1-C8, optionally substituted by a halogen or CN; an alkenyl C2-C8, optionally subs tituted by a halogen or CN; R2 is an alkyl C1-C4; R3 is an alkyl C1-C8; R4 is an alkyl C1-C8, optionally substituted by a halogen; R5 is an alkyl C1-C4; a halogen alkyl C1-C4. 3) A process for preparing azoic dyes of general formula (I). characterized in that an amine of general formula EMI40.1 is diazotized in an aqueous acid medium and the resulting diazo is coupled, always in an aqueous medium, with a suitable coupling intermediate; or an amine of formula Ar - NH2 (IX) is diazotized and its diazonium salt is coupled on a coupling intermediate of formula : Cop - SO2C2H4OCOR (X) wherein R has the meaning defined hereinbefore, and X is H, a halogen, CN, NO2, an alkyl C1-C4, an al koxyl C1-C4; m is a number equal to 1 or 2; Ar is the residue of a diazotizable component of the carbocyclic or heterocyclic series; Cop is the residue of a coupling component. 4) A process for dyeing and printing, in one step only, polyester-cellulose blended fibres, characterized in that the dyes of general formula (1) are employed 5) Cellulose materials blended with synthetic materials, in particular polyester-cotton blended fibres, dyed or printed with the dyes according to claim 1.

Inventors: BUREI, GIOVANNI, DR., CARUGATI, GIOSUE, CIPOLLI, ROBERTO, DR., DA DALT, VINCENZO, DR., NEBULONI, ANTONIO, VERDI, ROBERTO, DR.
Applicants: AZIENDE COLORI NAZIONALI AFFINI ACNA S.P.A.
Application year: 1981
Main classification: C09B62
IPC codes: D06P3, C09B62