US2136757A - After-treatment of dyeings on cellulosic fibers - Google Patents

Description

Patented Nov. 15, 1938 UNITED STATES AFTER-TREATMENT F DYEINGS LULOSIO FIBERS PATENT oI- FlcE ON CEL- Hans Boos, Leverkusen L 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.

wherein R and R stand for aromatic radicals, is improved by aftertreating the same in themanner known per so with diazo compounds of the aromatic series. For the purpose of the present invention there come into consideration quite generally those bases as are used in the manufacture of ice colors, 1. e. bases containing no substltuents inducing solubility in water, especially of the benzene series, such as anisidine, paranitro-ortho-anisidine and, first of all, nitranilines. The process is carried out by introducing the fiber dyed with a dyestufi of the kind above identified into a diazo solution prepared in the ,usual manner and in which the mineral acid has been neutralized, for example, by adding sodium acetate, for about half an hour at room temperature, rinsing the fiber, soaping the samepin a boiling bath, again rinsing and drying. By this aftertreatment the i'astness to washing is considerably improved; further, the dyeings possess a better fastness to light than dyeings with analogously constituteddyestufls produced by other methods, and, moreover, they may have a very good dischargeability with a neutral or alkaline reacting discharge paste.

The following examplesmill illustrate the invention without, however, restricting it thereto?- Example 1 proportion of paraaminoben'zoyl-para-amino- 3-carboxylic acid, saiddyestufl correspondingin its free state to the following formula:

coon SOaH v lhN 0 COOH 10 grams of the dyed cotton are introduced for about half an hour into a bath containing 0.3 gram of diazotized para-nitraniline, said bath being 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 aftertreatment 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 Glaubers salt-soda both with the dyestufl obtainable by coupling diazotized para-nitrobenzoyl-para-phenylenediamlne with i-phenyl-5-pyrazolone-3-carboxyl1c acid, re-

ducing the nitro group to the amino group, diazo-- tizing, coupling with 1-(meta-nitrop'henyD-5- pyrazolone-3-carboxylic acid and reducing the nitro group, said dyestuii corresponding to the following formula:--

coon v a. ,L E- coon I NB- -N was 1 The orange dyeing thus obtained is aftertreated with para-nitraniline and yields a clear yelloworange shade exhibiting properties similar to those of the aftertreated dyeing of Example 1.

Example 3 Cotton is dyed from a Glaubers salt-soda-bath o with a dyestufi obtainable by diazotizing acetylpara-phenylene diamine, coupling with salicylic acid, saponifying the acetylamino group, condensing with para-nitro-benzoylchloride, reducing the nitro group to the amino group, diazotizlng and coupling with 1-(meta-aminophenyD-5- pyramlone-S-carboxylic acid, which dyestufi corresponds to the following formula:-

H0: NH-COO-N=NCE I coon n The yellow dyeing thus obtained is attertreated 40 with diazotized para-nitraniline. It is of a somewhat more greenish shade than that of Example 1, exhibits a better fastness to light and has otherwise similar properties.

When using in the above example instead of the 1- (meta-aminophenyl) -5-pyrazolone-3-carboxylic acid the l-(para-aminophenyl) -5-pyrazolone-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 altertreatment instead of the diazotized para-nitraniline the i-nitro-ortho-anisidine or 5-nitro-orthoanisidine (OCHJ=1) somewhat more reddish shades are obtained.

Example 4 Viscose silk is dyed from a Glaubers salt-soda-v 70 bath'with the dyestuil obtained by coupling one molecular proportion of tetrazotizedpara-aminoben'zyl-para-phenylene-diamine, one molecular proportion of ortho-cresotinic acid and one molecular proportion of 1- (meta-nitrophenyl) -5- pyrazolone-(i-carboxylic acid, and reducing the nitro group, which dyestuif corresponds to the following formula:---

The yellowishorange dyeing is aftertreated with diazotized para-nitraniline. Thus an orange dyeing is obtained exhibiting properties similar to those of the aftertreated dyeing of Example 2.

' Example 5 Cotton is dyed in the usual manner from a Glauber's salt-soda-bath with the dyestuif obtained by diazotizing ortho-amino-benzoic acid and coupling with para-aminobenzoy1-2-amino- 5-naphthol-7-sulfonic acid, diazotizing and coupling with l-(meta-aminodiphenyl) -5-pyrazo1one-3-carboxylic acid, which dyestufl? corresponds to the following formula:-

An orange dyeing is thus obtained which becomes somewhat more yellowish after the aitertreat-' 40 ment with diazotized para-nitraniline. It is distinguished by an excellent clarity and fastness to light combined with a good neutral and alkaline dischargeability.

- Example 6 Cotton is dyed in the usual manner from a Glauber's salt-soda-bath with the dyestufi from diazotized meta-aminobenzoyl-dehydro-thiotoluidine sulfonic acid and 1-(meta-aminophenyl)-5- pyrazolone-3-carboxylic acid of the formula:-

C O OH 1 N Hg The dyeing obtained is similar to that obtained according to Example 3 and possesses similar properties after the aftertreatment with diazotized bases.

I claim:-- 5.

6 1. The process which comprises aitertreating cellulosic fibers which have been dyed with a substantive dyestui! containing at least once the grouping coon 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 the fibers are aftertreated with a diazotized nitraniline.

6. The process as claimed in claim 4, in which the fibers are aftertreated with diazotized paranitraniline.

7. The process which comprises aftertreating cellulosic fibers which have been dyed with the dyestufi of the formula:

with diazotized para-nitraniline.

8. The process which comprises aftertreating cellulosic fibers which have been dyed with the dyestuff of the formula:--

with diazotized para-nitraniline.

9. Cellulosic fibers dyed with a dyestufi containing at least once the grouping:

coon c=N -Nnco-R-N= Ncn c-N-R'-Nn-N=NR" wherein R and R stand for aromatic radicals wherein R and R stand for aromatic radicals.

and R" stands for an aryl radical free from a group inducing solubility in water.

10. Cellulosic fibers dyed with a dyestuff containing at least once the grouping:

11. Cellulosic fibers dyed with a dyestuflz containing at least once the grouping:

wherein R and R stand for aromatic radicals.

12. Cellulosic fibers dyed with a dyestuff of the formula: v I

R stands for an aryl radical free from a group inducing solubility in water, and R' stands for an aromatic radical which may contain an azo group.

13. Cellulosic fibers dyed with a dyestufi of the formula:

wherein R and R stand for aromatic radicals and R' stands for an aryl radical which may contain an azo group.

14. Cellulosic fibers dyed with a dyestufi of the formula:

wherein R and R'stand for aromatic radicals and R stands for an aryl radical which may contain an azo group.

15. Cellulosic fibers dyed with the dyestufl of the formula:

NHQNH-0 o-Qnen-c g CNEN=NONO 16. Cellulosic fibers dyed with the dyestufl' 01 the formula:

COOH

HANS R008.