Патент USA US2136757код для вставки
Patented Nov. 15, 1938 2,136,757 I UNITED STATES’ PATENT oI-jFlcE AFTER-TREATMENT 0F DYEINGS ON CEL - LULOSIO FIBERS Hans Boos, LeverkuseniL G.-Werk, Germany, as signor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No, Drawing. Application June 5, 1935, Serial No. 25,182. In Germany June 29, 1934 16 Claims. (Cl. 8-46) This invention relates to a process for the im provement of the fastness to washing of dyeings on cellulosic ?bers with substantive dyestuffs and to the improved dyeings obtained by this process. In accordance with the present invention the 3-carboxylic acid, saiddyestu? correspondingin its free state to the following formula:— ‘ ‘ coon SOaH v lhN , fastness to washing of dyeings on cellulosic ?bers with substantive dyestuffs containing at least once the grouping ' 0 COOH 10 10 wherein R‘ and R’ stand for aromatic radicals, is improved by aftertreating the same in the‘man ner known per so with diazo compounds of the NH: 10 grams of the dyed cotton are introduced for ' about half an hour into a bath containing 0.3 ' aromatic series. For the purpose of the present , gram of diazotized para-nitraniline, said bath be 2” invention there come into consideration quite generally those bases as‘ are used in the manu facture of ice colors, 1. e. bases containing no sub stltuents inducing solubility in water, especially of the benzene series, such as anisidine, para 25 nitro-ortho-anisidine and, ?rst of all, nitrani lines. The process is carried out by introducing the ?ber dyed with a dyestu? of the kind above identi?ed into a diazo solution prepared in the ,usual manner and in which the mineral acid has been neutralized, for example, by adding sodium ing prepared by diazotizing in the usual manner para-‘nitraniline with hydrochloric acid ; and sodium nitrite and neutralizing the mineral acid by theaddition of sodium acetate. By this after treatment a reddish-yellow shade is obtained of very good fastness to light and dischargeability in a the neutral and alkaline processes. I Example 2 ' 1 Cotton is dyed from a Glauber’s salt-soda both with the dyestu? obtainable by coupling diazo- ' tized para-nitrobenzoyl-para-phenylenediamlne acetate, for about half an hour at room tempera , ture, rinsing the ?ber, soaping the samepin a with i-phenyl-5-pyrazolone-3-carboxyl1c acid, re boiling bath, again rinsing and drying. By this aftertreatment the i'astness to washing is consid 35 erably improved; further, the dyeings possess a better fastness to light than dyeings with analo gously constituteddyestu?s produced by other tizing, coupling with 1-(meta-nitrop'henyD-5 pyrazolone-3-carboxylic acid and reducing the 40 ducing the nitro group to the amino group, diazo-~ ' nitro group, said dyestuii corresponding to the following formula:-- , _ methods, and, moreover,‘ they may have a very goodrdischargeability with a neutral or alkaline reacting discharge paste. . , coon v The following examplesmill illustrate the in vention without, however, restricting it thereto? 45 Example 1 Cotton is dyed from a Glauber’s salt-soda-bath with the reduced dyestu? from one molecular proportion of para-laminoben'zoyl-para-amino- = phenylurea-disuli'onic acid and 2 molecular pro w'portions oi’ 1-‘-(meta-nitrophenyl) -5-pyrazolcne E , coon (gr-N was 1 I ' ,LQ .éa. ‘NB _ 2 2,186,757 The orange dyeing thus obtained is aftertreated with para-nitraniline and yields a clear yellow orange shade exhibiting properties‘ similar to those of the aftertreated dyeing of Example 1. nitro group,_which dyestuif corresponds to the following formula:-- Example 3 Cotton is dyed from a Glauber’s salt-soda-bath o with a dyestu? obtainable by diazotizing acetyl 10 para-phenylene diamine, coupling with salicylic acid, saponifying the acetylamino group, condens ing with para-nitro-benzoylchloride, reducing the nitro group to the amino group, diazotizlng and coupling with 1-(meta-aminophenyD-5 15 pyramlone-S-carboxylic acid, which dyestu? cor responds to the following formula: The yellowishorange dyeing is aftertreated with diazotized para-nitraniline. coon 20 N: Thus an orange dyeing is obtained exhibiting properties similar to those of the aftertreated dyeing of Example 2. 011' 20 ' Example 5 Cotton is dyed in the usual manner from a _ 25 NH-C Glauber's salt-soda-bath with the dyestuif ob coon / C: N=N-—-Ol\1 tained by diazotizing ortho-amino-benzoic acid and coupling with para-aminobenzoy1-2-amino- 25 5-naphthol-7-sulfonic acid, diazotizing and coupling with l-(meta-aminodiphenyl) -5-pyraz . o1one-3-carboxylic acid, which dyestu?? corre sponds to the following formula: NH, 30 H0: ~ ‘ coon The yellow dyeing thus obtained is attertreated 40 with diazotized para-nitraniline. It is of a somewhat more greenish shade than that of Ex ample 1, exhibits a better fastness to light and has otherwise similar properties. / NH-COO-N=N—CE I ‘ When using in the above example instead ‘of '45 the 1- (meta-aminophenyl) -5-pyrazolone-3-car n NH’ An orange dyeing is thus obtained which becomes somewhat more yellowish after the aitertreat-' 40 ment with diazotized para-nitraniline. It is dis tinguished by an excellent clarity and fastness to light combined with a good neutral and alka line dischargeability. ~ boxylic acid the l-(para-aminophenyl) -5-pyraz olone-3-carboxylic acid and aftertreating in the usual manner with diazotized para-nitraniline, , brownish-yellow shades are obtained of an espe 50 cially good neutral .or alkaline dischargeability. When using in the above example for the alter 11018 I110 ' 46 Example 6 Cotton is dyed in the usual manner from a Glauber's salt-soda-bath with the dyestu? from diazotized meta-aminobenzoyl-dehydro-thiotolui dine sulfonic acid and 1-(meta-aminophenyl)-5-_ 50 pyrazolone-3-carboxylic acid of the formula: N\ \ 900mg; C O OH (',=N 1 55 NHg treatment instead of the diazotized para-nitrani The dyeing obtained is similar to that obtained line the i-nitro-ortho-anisidine or 5-nitro-ortho according to Example 3 and possesses similar properties after the aftertreatment with diazo tized bases. ‘ anisidine (OCHJ=1) , somewhat more ‘reddish shades are obtained. I claim:-- Example 4_ Viscose silk is dyed from a Glauber’s salt-soda-v 70 bath'with the dyestuil obtained by coupling one molecular proportion of tetrazotizedpara-amino . ben'zyl-para-phenylene-diamine, one molecular proportion of ortho-cresotinic acid and one molecular proportion of 1- (meta-nitrophenyl) -5 75- pyrazolone-(i-carboxylic acid, and reducing the ' ’ 1. The process which comprises aitertreating cellulosic ?bers which have been dyed with a substantive dyestui! containing at least once the grouping - ‘ - coon O=N 60 6 5. 3 2,136,757 wherein R and R’ stand for aromatic radicals, with a diazo compound of an aromatic amine free from a group-inducing solubility in water. 2. The process as claimed in claim 1, in which the ?bers are aftertreated with a diazotized nitraniline. and‘ R" stands for an aryl radical free from a group inducing solubility in water. " 10. Cellulosic ?bers dyed with a dyestuff con taining at least once the grouping: . ‘ 3. The process as claimed in claim 1, in which the ?bers are aftertreated with diazotized para nitraniline. 4. The process which comprises aftertreating 10 cellulosic ?bers which have been dyed with a substantive dyestuff of the formula:-— 10 | NO: wherein R and R’ stand for aromatic radicals. 11. Cellulosic ?bers dyed with a dyestu?z‘ con taining at least once the grouping: 15 15 20 wherein R and R’ stand for aromatic radicals and R2 stands for an aromatic radical which may contain an azo group, with a diazo compound of an aromatic amine free from a-group inducing solubility in water. 5. The process as claimed in claim 4, in which 20 wherein R and R’ stand for aromatic radicals. 12. Cellulosic ?bers dyed with a dyestuff of the formula: v I 25 the ?bers are aftertreated with a diazotized nitraniline. 6. The process as claimed in claim 4, in which the ?bers are aftertreated with diazotized para- _ 30 30 nitraniline. 7. The process which comprises aftertreating ' cellulosic ?bers which have been dyed with the dyestu? of the formula:— " R” stands for an aryl radical free from a group‘ inducing solubility in water, and R'” stands for 35 35 ‘NE, 40 40 45 NH: with diazotized para-nitraniline. 8. The process which comprises aftertreating 5 O cellulosic ?bers which have been dyed with the dyestuff of the formula:-- ' an aromatic radical which may contain an azo group. , 13. Cellulosic ?bers dyed with a dyestu? of the 50 formula: 55 55 1110: wherein R and R’ stand for aromatic radicals 60' and R'” stands for an aryl radical which may 60 contain an azo group. ' 14. Cellulosic ?bers dyed with a dyestu? of the formula: 65 , with diazotized para-nitraniline. 65 9. Cellulosic ?bers dyed with a dyestu? con taining at least once the grouping: 70 ' ' coon 70 c=N / -Nn—co-R-N=_N—cn ’ c-N-R'~Nn-N=N—R" 0 wherein R and R’ stand for aromatic radicals wherein R and R'stand for aromatic radicals and R’” stands for an aryl radical which may contain an azo group. ' v 4 2,130,757 15. Cellulosic ?bers dyed with the dyestu? of the formula: . 80:11 00011 5 No, E—N 00 $003.’ 10 C=N 10 NHQNH~0 o-Qnen-cé ’ S 0111 g _CNE—N=NONO : 15 15 16. Cellulosic ?bers dyed with the dyestu?' 01 the formula: c0011 20 COOH 25 30 HANS R008.