Патент USA US2110394код для вставки
Patented Mar. 8, 1938 ' 2,110,394 ‘ UNITED STATES PATENT OFFICE 2,110,394 LEATHER DYED 'WITH MONO- 0R DISAZO DYESTUFFS Ernst Fellmer, Leverkusen-I. G. Werk, Gustav Mauthe, Oologne-Holweide, and ‘Hermann Noerr, Leverkusen-I. G. Werk, Germany, *as signors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware N0 Drawing. Application March 18,1936, Serial No. 69,592. In Germany March‘23,,1935 4 Claims. The present invention relates to leather dyed with certain mono- or disazodyestuffs, more par ticularly it relates to leather which has been dyed with mono- or disazodyestu?s of the general formula: on the grain side and on the ?esh side a distinct 5 ’ pound derived from a monamine or monamines respectively, B.’ stands for a 2-aminonaphthol coupling component or a substitution product thereof, especially of such a substitution product 16 ingwhich a hydrogen atom of the amino group is substituted by alkyl or aryl or substituted alkyl or aryl, e. g. the sulfo or carboxylic acids dyeing'of they cut, without change of the char acteristic greenish color of the chrome leather in the interior of the cut. After glacé ?nishing such leathers exhibit an improvement of covering and equalizing properties in comparison with 10 leathers dyed withldyestu?’s which do 5not dye in the'grain in the manner "described. Further, the ?esh side can be easily ground off, an opera tion which is usual inpmany' cases, without pro 15 ducing a bad and, ununiform appearance by the standing out of undyed ?bers. . Example 2.-100 kgs. of dry and ground off thereof, and n stands for a whole number, such as for 1, 2, 3 or 4 etc. chrome calf velours leather are dyed, after a In dyeing chrome leather, it is desired not only to dye the surface of the leather, but also good egging in 500 kgs. of hot water, with 5 kgs. 20 of the dyestu?‘ obtained from diazotized sul to give an even shade to the cut of the leather to a certain depth of penetration, while the zone fanilic acid coupled in an alkaline medium with 1 molecular proportion of a mixture of 60% of the cross-cut remaining undyed is intended 25 to retain the pure greenish chrome color. Of particular technical importance are dyeings of this kind on leathers, the grain side or ?esh side of which is more or less ground off after the 30 dyeing. In accordance with the present invention the desired effect is attained to an excellent degree, when in the dyeing process mono- or disazodye stuffs of the above identi?ed formula are used, 35 the dyeing per se being performed according to the standard methods of dyeing leather, as is more fully described in the annexed examples. If desired the mono- or disazodyestu?s of the above identi?ed formula can be used in mixture 40 with other acid or substantive dyestuffs. The invention is illustrated by the following examples, without being restricted thereto: Example 1.—100 kgs. of neutralized chrome 45 hour, the. dyestuif has been absorbed almost - without residue. Stuffing of the leather is then effected. In. this manner, there is obtained a dyeing of a useful brown' shade, which exhibits In the said formula R stands for the radical of 10 an aromatic diazo compound or a diazoazo com-' 20 (01. 8-5) ’ calf leather are introduced into a drum with about 300 kgs. of water at 60° C. A dyestuif so lution is gradually added prepared from 1 kg. of the dyestuif from diazotized p-sulfanilic acid coupled with phenyl gamma acid (alkaline cou 50 pling) and 25 kgs. of hot water. After half an phenyl-gamma-acid and 40% phenyl-J-acid. In order entirely to exhaust the dye bath, it is acidi 25 fled with formic acid, and ?nally, as usual for velours leather, the latter is subjected to some degree of stu?‘ing. There are obtained dyeings of a reddish brown 30 shade, which exhibit a very strong dyeing in the grain. The leathers dyed in this manner show a good fastness to grinding 01f and to water, and there is not the lightening of shade, which in other cases is a troublesome result of re 35 grinding. , Example'3.-—l00 kgs. of chrome tanned and neutralized horse leather are dyed in a bath with 0.75 kgs. of the dyestuff from diazotized 4l-ni traniline-2-sulfonic acid coupled with phenyl 40 gamma acid (acid coupling) with the addition to the bath of 0.75 kgs. of direct deep black E extra (Schultz Farbstofftabellen 1931, p. 271), and then stuffed. The leather dyed in this man- 45 ner gives a black shade with a deep dyeing in the grain, so that it is possible to grind off the grain, as is usual in the manufacture of horse leather, without rendering visible undyed inte rior zones. 50 2 2,110,394 1 The-following table ‘contains some further examples and the shades obtained on leather: Diazo components 7 Coupling oombonents " 5 ' v ' 7 line coupling) consisting of radicals of 2-aminonaphthol-c0u Brown ' Dung components and 0f N-substitution Products ‘ thereof, and n stands for a whole niimber. Plm?iféwd (alkalm 3“ D° ------------- z-na hthylamine-4.8-di1o the group consisting of radicals of diam and 7‘ diazoazo compounds ‘derived from monamines, R’ stands _ for a member selected from the group‘ Shadev _ ‘ O-Sulphanilio acid_'_ _____ __ Phenyl gamma acid (alka- 1 in which R. stands for a member selected from' 7 Phpnyl gamma acid (alka- sul onic acid 7 lme coupling)‘ 2. Leather ‘dyed with a dyestu? of the general Brown _ Q _ ' formula: , ‘ Amino-ambeniene;___-.'__ 7 t , ' r, . - ‘2 S-aminonaphth acld(alkaime coupling) -3 6-di- a Phenglgamma acid (acid ac Phenyl oouplm gamma in”:-acid~(acidw ~ E'nitro-Z-anisidine 4-sul ionic acid oouping) . rown i ‘ Do __________________ __ i , V ra ‘ whtl ' n " ‘ h c t . ' d f _1 Sulianilic acid ___________ ._ ' l ' “7011i. . 1» r‘ -- ~ YhenyigammaacidKalkaF" line coupling)- ‘ » * .7 ' * d tize 15 ' v _ 7 if,‘ 7 » > . N=N ‘H0’ ' e-if‘ . rm} 4; Léathér-dyedavitn '7 NEG ' they ‘can also ‘be usedetogetlren'withbthenisnitable W ‘ > s wezclaim: h -. 1. Leather dyed-*avithiatdyeistumof the-generala ‘" ' ydyestu?having'irrthew - ‘vxfree'stateithe'following formula: ~ ' able‘ forfchrdm'etleathef; armparticularlyisuitabie for dyeing lot-hen kindsoi’ leather?‘ especially veg table and se'michrome :tannedrleathe‘m ‘401' acid» orrvsubstantive J dyestu?sni. s --Y ‘ to al'kalies'iiand aeidszand'in gener , d1 azo7 8 - naphthol -6 - sulionfdo' "'5; ~3 Iastness to alkalies andsacidsmzi ' a’ Tnewdyestu?smn ‘question; i f 'nén't inwhich one‘ hydrogen atom of the amino ' ' Besides:the?exdéilentsdyeini; iobtainedseiin at r;' 40 d1 *i'vildw‘giliili'radicaluot a} 2-aminonaphthol-ooupling compo-V neutral rbath; 1 the‘ dye'stu?sz-rhavei a good; stability formula-:1 h R s an s or t e Ia ' cal o a whol'eimmber. :> " 7' a ‘ _ ' ' 2.3-aminonapbtholg9e5pl-z ?’égf?fgiuhin ionic acid (aoidmuplmg) .Jjrotnx .! i 3. LeatheredyédI'mithJhe‘dyestuffr having in Z-(o-hydroxyethylami'no); ' ‘7 rthe?treeistateé‘iths following formula: plimz) ' 10 . \(smrr) ‘ I mum“? “I monaminenof thevbenzena'series and R.’ for the Aminoazobenzene disul 25 ’ V Ygnpvféish \grQiip-iv'isl supstituted by-aryLand 1:. stands for a‘v Metanilic acid_ - . _'._..V_.._; Do--.‘ ............. -;__ m ionic acid (acidw'vupling) acid ionicacid “ r (R_;1>I=N_‘.RI) ' Phenyi-I'acid (acid couj @3328“; >2 - 'nitraniline-d - sulfonic 20 ' ,‘ , V brownm i o l a t sulioiid: )acid (alkaline 00“ a ' 4-‘niiaraniline - 2 -sulionic , ' Aniline _________ __, ______ __ m-Garboqnhenylgammw =Beddish :- -. a0: a "