US1245694A - Process for producing fast tints. - Google Patents

Description

U N ITEI) STATES" PATENT OFFICE.

GADIENT ENGI, OF BASEL, SWITZERLAND, ASSIGNOR TO SOCIETY OF CHEMICAL INDUSTRY IN BASLE, 0F BASEL, SWITZERLAND.

PROCESS FOR PRODUCING FAST TINTS.

no Drawing.

To all whom it may concern.

Be it known that I, GADIENT ENGI, a citizen of the Swiss Republic, and resident of Basel, Switzerland, have invented a new Process for Producing Fast Tints, of which the following is a full, clear, and exact specification.

In the application for United States Letters Patent Ser. No. 43413, filed August 3, 1915, and in the two applications for United States Letters Patent of Berthold Wuth and Carl J agerspacher, Ser. Nos. 54503 and 54504 filed October 7 1915, is described the production of new copper compounds of orthooxyazodyestufi's yielding by their dyeing in an acid bath on animal fibers tints which are fast to light, washing and alkali; however, the fastness of the thus produced dyeings of fulling and potting is not perfect. I have now made the technically valuable observation that those of the copper compounds of orthooxyazodyestufis able to be produced according to the aforesaid applications for Letters Patent, which contain, besides the copper saturated hydroxyl group proceeding from the orthooXydiazo-compound, still one or several groups able to be combined with chromium, as for instance a carboxyl group in the diazocompound, or a hydroxyl group and a. carboxyl group in the component combined with the diazo-compound, can be transformed into chromium lake on the fiber. Hereby the shades of the acid dyeings are not changed or only little changed, but simultaneously the fastness to fulling and potting are increased in such a manner that they satisfy the highest demands. The conversion of the said copper compounds of orthooxyazodyestufi's into the new chromium lakes on the fiber can be obtained by dyeing the same on chromium mordanted wool or by dyeing the same from a bath containing simultaneously soluble salts containing chromium, as for instance chromates or chromium salts or by treating the said dyeings subsequently with soluble salts containing chromium, as for instance chromates or chromium salts.

Specification of Letters Patent.

, Patented Nov. 6, 1917.

Application filed November 4, 1915. Serial No. 59,647.

As the copper compounds of the orthooxyazodyestufi's yield nearly without exception considerably more vivid tints than those hitherto obtained by treating the acid dyelngs of orthooxyazodyestuifs subsequently with chromium' compounds or by dyeing with the said orthoox'yazodyestuffs according to the metachromium process and as the acid dyeings of the copper compounds have, as already pointed out, their shades not changed or not essentially changed by their conversion into chromium lake, the new process permits producing much more vivid tints than those obtainable heretofore with orthooxyazodyestufis dyeing on mordants, the fastness of the dyeings obtained by the new process being without exception at least equal and in part still better than those of the latter dyestuffs. The new process resolves the important problem to furnish the hitherto obtained increasing of fastness by subsequent treatment with chromium compounds, without any change of the shades of the acid dyeings, whereby obtaining of predetermined final shades is facilitated.

The copper compounds ofthe aforesaid oxyazodyestufls are furthermore also suitable for the production of fast tints on vegetable fibers, by dyeing or printing these latter on cotton according to the processes usually employed for dyestuffs dyeing on mordants, whereby the said copper compounds are transformed on the fiber into chromium lakes showing excellent fastness to washing and to light. That could not have been foreseen, as all hitherto prepared orthooxyazodyestufl's dyeing or mordants were not suitable for cotton dyeing.

As parent materials for the new process can be employed the copper compound or orthooxyazodyestufl's obtainable according to three above mentioned applications for U. S. Letters Patent, which contain, besides the copper saturated hydroxyl grouporigi nating from the oxydiazocompound, still a rest able to be combined with chromium, as for instance a carboxyl group in the diazocompound or a hydroxyl and a carboxyl group in the component coupled to the diam-compound. The introduction of such a group able to be combined with chromium can for instance be effected by starting from aminooxycarboxylic acids of the benzene and naphthalene series, as for instance,

OH COOH NE orthoaminosalicylic acid U and its derivatcs as HO 0 NE,

nitroaminosalicylic acid HOOC N112 aminosulfosalicyiic acid OH HOOC NE chloraminosaiicylic acid I further from other aminoonycarboxylic acids, as for instance,

coon 4-oxy-3-ami11o-1-benzoic acid I k l-amino-Bzitoxynaphthcic acid /CO 0H g/coon 'etc. The orthooxyazodyestufi's thus obtained are transformed in the known manner into the corresponding copper compounds or intense (a) ANIMAL FIBERS.

Emample 1.

Dyeing of the copper compounds on previously applied mordant.

Wool is mordanted as usually with 3% potassium chromate and 2.5% potassium bitartrate. The so mordanted wool is dyed in a bath containing 3 to 5% acetic acid of 3% and l to 3% dyestuff (copper compound), the goods being introduced into the bath at 50-60 (3., the bath slowly heated to boiling and the boiling maintained for l to 1?; hours.

Example 52.

Dyeing of the copper compounds with acidition of chromotes or chromium amid saZts to the bath.

The dyeing bath for 100 kg. wool is prepared with 15 to 20 kg. crystallized sodium sulfate, 3 to 5 per cent. acetic acid of 10%, the necessary quantity of dyestuif (copper compound) and of potassium chromate (the half of the dyestufi weight) and the material to be dyed is introduced into the bath at a temperature of 50 to 60 C. The bath is slowly heated to boiling and maintained in ebullition for i to 1 hour and exhausted by a further boiling for a} hour after an ad dition of 1 to 2 kg. formic acid of 90%. Instead of potassium chromate can be employed salts of chromium oxid.

E wample 3.

Subsequent treatment of the copper com pounds with chromium compounds.

The dyeing bath is prepared with 1 to 3% dyestuif (copper compound), 10 to 15% crystallized sodium sulfate and 3 to 5% acetic acid of 40%. The well moistened wool is introduced into the bath at a temperature of 50 to 60 C. and the bath is heated in the course of half an hour to boiling. After a boiling for a} hour, '12 to 1% sulfuric acid is added and the bath is boiled for a further quarter of an hour. After an addition of some cold Water to the bath, potassium chromate quantity of the dyestufl' employed) is added to the same and the wool chromated for i to g hour.

Instead of starting from the achieved copvdyestufl' (sodium salt hydroxylgroup proceeding from the orthooxydiazo compound still a group able to combine with chromium, can be dyed by add- .ing simultaneously copper salts and chromates to the bath, whereby the shades of the copper compounds of the said dyestufi's are obtained with the excellent fastness of the 4 chromium lakes.

Example 4.

Production of the copper comp-ownds on previously mordanted goods.

Example 5.

The dyeing bath is prepared With 1 to 3% dyestuif (sodium salt), 2 to 3% copper sulfate, 10% crystallized sodium sulfate, 3 to 5% acetic acid of 40% and a quantity of potassium chromate equal to the half weight of the employed dyestufl', the goods being introduced in the bath at a temperature of 50 to 60 C. and the bath being heated to boiling and boiled for l'to 1 hours.

To obtain a better exhaustion of the bath 1 to 1.5% formic acid of 90% can be added to the same, after a further boiling for g of an hour to 1 hour.

Example 6.

The dyeing bath is repared with 1 to 3% l 2 to 3% copper sulfate, 10% crystallized sodium sulfate and 3 to 5% acetic acid of 40%. The material is introduced in this bath at a temperature of 50 to 60 C. and the bath slowly heated to boiling and boiled for a of an hour to 1 hour. Hereafter, in order to obtain a better exhaustion of the bath, 1 to 1.5% formic acid of 90% are added and the bath is further boiled for 9; of an hour.

After dyeing the bath is allowed to cool Slightly, a quantity of potassium chromate equal to the half weight of the dyestufi' employed is added thereto and the material is chromated in the boiling bath for 4 an hour to i} of an hour. v

Instead of being utilized for dyeing the various dyestuffs can also be employed the printing of animal fibers according to the usual process by adding acid or chromium salts to the printing color.

Example 7.

10 to 20 gr. dyestufl (copper compound) are dissolved in 270 to 230 com. water and mixed with 700 gr. British gum thickening and 20 to 50 gr. tartaric acid of 50% or 10 to 20 gr. dyestufi' (copper compound) are dissolved in 280-240 ccm. water and mixed with 650 gr. British-gum thickening, 10 gr. tartaric acid of 50% and 50 to 80 gr. chromium acetate or the corresponding quantity of chromium fiuorid.

The paste is printed on chlorinated wool goods, and this latter is steamed in a moistened state, for 1 hour, washed and terminated as usually. J

- (b) VEGETABLE FIBERS.

Example 8.

on chromium mordanted cotton by dyeing the goods in a boiling bath containing 1 to 3% dyestufi', 2 to 3% copper sulfate and 2 to 5% acetic acid of 40%.

Example .9.

For cotton printing.10 to 30 parts dyestufl (copper compound) are dissolved in w 250 com. hot water containing eventually 1 The dyestuffs can also be employed in the usual discharge printing processes. lNith the specified dyestuffs the most various tints of excellent fastness to light and washing can be produced on vegetable fibers.

In the following tabular exhibit are indifor cated various dyestuffs applicable with the their sodium salts and of their copper com new process and the comparative dyeings of pounds:

Dyestufi' derived from Dyeing of the sodium salt.

Dyeing of the copper compound.

Diazo com ound And the following componeut Acid. 3 1 33 322 Acid. OH 1:8-Amidonaphthol-2-4-disulfonic acid... Red violet Dull greonblue. Violetish blue... Blue. mil looou OH 1z8-Amidonaphthol-ZA-disulfonio acid Red violet Black violet..... Pure greenish Greenish blue. blue. NHQK ICOOH N0 :1 1:B-Amidonaphthol-3zo-disulf i aoid Red violet Black Violet..... Grcenish blue... 'Greem'sh blue.

128-Dioxynaplithalene3ifi-disulfonic cid Red violet Dark blue Violet Violet.

u 1:4-Naphtholsulfonic aeid Purebluishred. Bordeaux Bordeaux Bordeaux.

u 1;5Naphth015u1f0nicacid Bluish red Blackish bor- Bluishbordeaux Pure bluish bordeaux. deaux.

u 2:6-Naphtholsulfonic acid Yellowiehred... Bordeaux Bluish red Bluish red.

H 228-Amid0naphtho1-6-su1f0nic a id Violet brown.... Black brown.... Yellowishblack Yellowish black brown. brown.

1;5-Amidonaphthol.7. 1fonj acid Dull red vlolet.. Violetishbrown. Red violet Red violet.

Z-Nafphtholizddisulfonic acid uish red Bluishbordeaux. Strogg bluish Strogg bluish re re OH l-Naphthol-SZB-disulfonic acid Purered Yellowish bor- Pure blue bor- Bordeaux. deaux. deaux. NH i .COOH

1-Naphthol-3:6-disulionic acid Pure bluish red. Violetbordeaux. Bordeaux Bordeaux.

2:5-Amidonaphthol-7-sulionic acid Yellowishred... Ye llowish bor- Pure b0r eaux.. Pure bordeaux.

eaux.

Benggyl-2:5-amidonaphthol-7-sulfonic Yellowishred... Bordeaux Bordeaux rdeaux.

aci

Phen l-2z5-amjdonaphthol-7-su1fonic Yellowish red... Yellowish bor- Bluishbordeaux. Bluishbordeaux.

aci deaux.

m-Amidophenol Yellowishbrown ed brown Black brown.... Black brown.

Salicylic acid Brown olive..... Bronce brown... Brown o1ive..... Brown olive;

o-Cresotinica'cid....; Brown olive..... Red olive Brownolive..... Brownolive.

Reeorcinolm. Yellowislibrown Red brown Brown Brown.

B-Oxynaphthoic acid Reddish brown. Violet brown.... Brow-n Brown.

3-Oxy-1-thionaphthene Red Red brown...... Bordeaux Bordeaux.

Dloetohydroindene.. Rad orange Red orange Yellowbrown... Yellow brown.

Dyestufl derived from Dyeing of the sodium salt. Dyeing of the copper compound.

mam ggE And the following component- Acid. g gi ggggg Acid. i' gg gigg y CO o-Carboxylated benzoylaoetlc acid....... Brown Destroyed Blue violet Blue violet. NH, c0011' I I I 0003 co-cm-ooon 0H B-Naphthol Yellowred Yellowlsh bor- Red.....'.. R ddeaux. NH COOH K61 1:5-Naphtholsul1onlcacid Bluered Violet brown... Bluered B1119 xf 2:6-Naphtholsu1fonic acid Yellowred Red Red R i a-Naphthylamin Yellow brown... Brown Red brown Brown 1:5-Amidonaphthol' Violet brown... Black brown. Black brown.... Black o fi-Oxynaphthoic acid Bluish bor- Dullviolet Bordeam Bordeauxdeaux.

a-Oxynephthoic acid Red brown....., Violet brown.... Brown Brown.

1:4-Naphtholsulfonic acid Bluered Violet Bluishred hr d.

1:8:5-Amidonapl1th0lsulfonicacid.... Red blue Blue black Red blue Red bluel:8-Amidonaphthol-2z4-disulfonlc acid... Red violet Dull blue Pure blue Pure b OH l-Phenyl-B-methyl-S-pyrazolone Yellow orange... Red orange Reddish' yellow. Reddisll yellow. NH (30011 Diamldodiphenylemindisulfonie Orange brown... Red brown Brow-n B wn- Aoetaoetio-anilid Lemonyellow". Green ye1low.... Green yellow... G een ye ow.

s-Qx -l-thignaphehene ....Red..- Brow-nred Red violet R d violet.

Dieetohydminden .J. Orange Yellowred Red brown Brown- Perinyphthindandlun Orange Yellowred Brownm. Yellowbrown.

o-Carboxylated benzof'laeetlc acid Brown Destroyed....... Pure blue Iure blue.

COOH

oo-cn -coon Dyestufi derived from- Dyeing of the sodium salt.

Dyeing of the copper compound.

Diazo 32 And the following comp onent- Acid. Acid. l ggi g y OH l:8AmidoI1ephthol-2:4-disu1fonic acid. Blue violet Greenish blue Greenisli blue Greenish blue. NH WCOOH v 1:8-Amidonapl1tl1ol-3:6disulionic acid. Red violet Greenish blue Greenish blue Greenlsh blu OH 1:5-Naphtl1olsulfonic ecid.. Yellow bordeaux Blue violet Blue bordeeux.. B1 1 horde/$111K- NH COOH 2:3:6-Naphtholdisulfonic acid Yellow bordeaux Blue violet Bordeaux BOYdQeUX- l:4-Naphtholsulonic acid Yellow bordeaux Blue violet Bordeaux grdefiux- 2:6-Naphtholsulfonic acid Red Red violet Bordeaux Bordeaux 2:5-Amidonephtl1ol-7-sulfonic acid Yellow red Violet l l Violet brown. Violet brown- 2:S-Amidonaphthol-fi-Sulfonic acid Violet brown. Black violet.v Black brown. r Black brown- 1:8-Dioxynaphthalene-3zfi disullonio acid Violet Green blue Blue violet 1 9 o Phenylmethylpyrezolonsulfonic acid... Yellow orange... Yellow red Brown orange. Brown Orange- Resorcinol Yellow red Red brown Yellow brown... BYOWTI- 1:8-Amidonaphthol-4-sulionic acid Blue violet Red brown Green blue Green blue.

1:4:8-Napl1tholdisulfonic acid Bordeaux Blue violet Violet Violet.

1:3:8-Naphtl1oldlsulfonicacid. Bordeaux Blue violet Red violet. Bordeaux.

OE 1:8-Amidonaphthol-3z6-disulionic acid Red violet Bluish green Blue Blue- OOH 1:8'Amidonephthol-2A-disulfonic acid... Red violet. Blulsh green.... Blue Blue.

OH Salicylic acld.. Yel1ow.. Red orange. Yellow Reddish yellow. NH,

fi-Oxynaphtholc *Yeilgvlvish bor- Violet Blulsh bordeaux Bluish bordoaux.

OH p-Oxynaphthoic acid.................... Violet black..... Violet.. Bluishbordeaux Bluish bordoaux.

rim wmz, K41

Dyestufl derived lrom- Dyeing of the sodium salt. Dyeing of the copper compound.

Dino 32 And the following component- Acid. ggfgf gzgg .Aeld. gg gggggg OH Cilia-fill, Red brown Red Bed" Red.

0 NQONH, \N/

/CO0H OH Yellow red Orange Yellow orange... Yellow orange. QNE,

OH Red yellow. Red orange. Orange Orange. \0...

NH: CH;;(I3CH Red orange. Blue red Blue red Blue red.

N O H /GOOH OH N11 OH Dull violet Blue green Pure blue violet Pure blue violet. @(W \l xo au OOH OH Blue red Dull violet...... Bordeaux... Bordeaux.

1 NH, \o...

lVhat I claim is:

1. The described process for producing fast tints on animal and vegetable goods, which consists in forming the dye in the presence of the goods by combining a soluble salt containing chromium with a copper compound of orthooxyazodyestufi, which contains besides the copper saturated hydroxyl group proceeding from the orthooxydiazocompound, at least one group capable of being chromated.

2. The described process for producing fast tints on animal and vegetable goods, consisting in first dyeing the goods in a bath formed by a solution of a copper compound of orthooxyazodyestufi containing besides the copper saturated hydroxyl group proceeding from the orthooxydiazocompound, at least one group capable of being chromated, and treating afterward the thus obtained dyeings with a solution of a salt containing chromium.

3. The described process for producing fast tints on animal and vegetable goods,

8 i aeepee Disazo dyestufi derived from- Dyeing of the sodium salt. Dyeing of the copper compound.

| Th followingto A dth n 1 s b tl s ediazo compound be urther diazon e na compou sequen y ubsequently oftized component Acld' chromated. Acld' chromated.

nent- OH Acid of Cleve.... 2:5-Amidonaphthol-7- Red blue Green blue Blue Green blue.

sulionic acid.

NH CODE Acid 0fCleve.... 2:6-l (Iiaphtholsu1fonic Red blue Blue black ...Blue Blue.

aci

Acid of Cleve.. 1:8-Amidonaphthol- Green blue Blue green Green blue Green blue.

3:6-disulfonic acid.

Acid of Cleve.... 2-Naphtl1ol-3:6-disul- Blue Green blue Green blue Green blue.

ionic acid.

consisting in dyeing the goods in a bath formed by a solution of a copper compound of orthooxyazodyestufi containing besides the copper saturated hydroxyl group proceeding from the orthooxydiazocompound, at least one group capable of being chromated, and of a salt containing chromium.

4:. The described process for producing fast tints on animal and vegetable goods consisting in dyeing the goods with a solution of a copper salt and of an orthooxyazodyestufi' containing besides the hydroxyl group proceeding from the orthooxydiazocompound at least one group capable of being chromated and treating the thus obtained dyeings afterward with a solution of a salt containing chromium.

In witness whereof I have hereunto signed my name this 6th day of October 1915, in the presence of two subscribing witnesses.

DR. GADIENT ENGI.

Witnesses:

ARNOLD ZUBER, AMAiIn BITTER.