US2092429A - Dyeing vegetable fiber - Google Patents

Description

Patented Sept. 7, 1937 UNITED STATES 92,429 DYEING VEGETABLE man PATENT OFFICE 1 Fritz Straub and Walter Anderau, Basel, Switzerland, assignors to Society oi Chemical Industry Basle, Basel, Switzerland No Drawing. Application February 26, 1936, Serial N0. 65,922. In Switzerland March 8, 1935 8 Claims.

invention consistsin the production of fast tints on vegetable fibers by dyeing the vege-.-

table fiber, for instance, cotton or artificial silk made from regenerated cellulose, with a sparingly soluble or insoluble complex metallic compound of a direct cotton dyestufl.

As direct cotton dyestuffs which in this invention are used in, the form of their sparingly soluble or insoluble complex metallic compounds,

are to be understood; for example, such disand polyazo-dyestuffs as have aiiinity for the vegetable fiber; such dyestuffs may be constructed 0 ailinity for vegetable fibers.

ponent for making the direct cotton dyestufl must be one which will ensure at least one lakediazo-components are, for example, those containing in ortho-position to the diazo-group a hydroxyl-, carboxylor alkoxy-group or the salicylic acid grouping. In order to obtain from the direct cotton dyestufi the sparingly solubleor insoluble complex metal compound by treatment with an agent yielding metal there may be used either an insoluble direct cotton dyestufl or a soluble dyestuff of which the complex metal compounds are sparingly soluble or insoluble.

From the preceding it will be' seen that for the construction of the directcotton dyestuffs there are available, besides the usual aromatic amines of the benzene and naphthalene series, which may contain lake-forming groups, as diazocomponents, and besides the usual phenols, naphthols and amines as couplingcomponents, in particular direct dyeing components, for example matic or aromatic series, which may also contain stilbene, derivatives or ureas from ,arylene diamines; also acetoacetic acid arylides, aminonaphthols and their sulfonic acids and the like.

In producing the complex metallic compounds serving as parent material for the invention and which may contain two or'more metals, such as components of chromium, iron, cobalt, nickel, aluminium, manganese, zinc, vanadium, titanium and especially copper, the direct cotton dyestuffs or mixtures of such dyestufl's may be treated with the agent yielding metal in acid, neutral or alkaline medium in a finely divided state, either under pressure or not, and in presence or absence of additions, for instance salts of organic or inorganic acids, or free acids, for example sodium formate, benzenesulfonic acid, naphthalenesulionic acids, sodium acetate, common salt, Glauber's salt, formic acid, acetic acid or tartaric acid.

Vegetable fibers may be dyed with the sparingly soluble or insoluble complex metallic compounds of direct cotton dyestufls in the manner usual for dyeing with direct cotton dyestufis, for example by means of baths containing the dyestufi and Glaubers salt and, advantageously, alkali carbonate, such as sodium carbonate. It is advantageous to use the dyestufi in the most finely subdivided or highly dispersed form; for instance the form obtained by grinding the dyestufi as powder or as a paste containing fluid material, for example an aqueous paste, in the usual apparatus, such as a ball mill or a roller mill, or by wind sifting. In many cases it has been found advisable to dye with the dyestufl in presence of a dispersing agent, a wetting agent or emulsifying agent, that is to say in presence of capillary active anions or cathions or capillary active substances which'are not ionized. Such materials are, in example, organic derivatives of ammonia, for example amines of the aliphatic, hydroarohydroxyl-groups or other substituents (for example pyridine, amines, alkylamines, methanolamines, ethanolamines, cyclohexylethanolamines, butylethanolamines), sulfonic acids of the hen-- zone or naphthalene series, which 'contain alkylganic compounds of high molecular weight, for

example polymerization products from aldehydes and soluble degradation products of cellulose.

In many cases good dyeing results are particularly obtained when the finely dispersed dyestuff is boiled with water for some time in the so-called dissolving vat or when'the finely dispersed dyestufl is added directly to the boiling Ezqmple 1 10 parts of the copper compound of the dyestuif of the formula:

dye-bath, which may contain the usual additions, such as Glauber's salt and sodium carbonate at the beginning of the dyeing; the duration of dyeing can be somewhat longer than that usual, that is to say about 1-2 hours.

That form of the invention has proved very satisfactory in which dyeing is conducted in the presence of ammonia or an organic derivative of ammonia; of these the aliphatic amines and particularly those which contain hydroxyl-groups, such as the alkylolamines (for instance mono-, dior triethanolamine or mixtures of these bodies) give good results. Instead of adding these amines and these dyestufis or the mixture of these amines with these dyestuffs, obtainable by grinding the amine with the dyestuff, to the dye-bath, the procedure may be such that the product formed from the agent yielding metal, the amine and the dyestuff may be so added. Such products may be' made, for instance, by treating the dyestuif with the agent yielding metal in presence of the amine or by the action of the amine on the metalliferous dyestufl, water present in the reaction mixture being distilled, if desired. These products are of the consistency of thick liquids; they are soluble in water and in consequence of this property are well suited for the present invention, in which the amine is at least partially decomposed by hydrolysis in the dyeing process.

OH: (L-OEI the Ross 00H m a are heated in the form of an aqueous paste with 20 parts of commercial triethanolamine while stirring on the boiling waterbath until the dyestufi has dissolved. A part of the water is then evaporated and. there is obtained a yellow viscid mass which dissolves clearly in water.

The dye-bath is prepared, consisting of 2000 parts of water at 30-40 C., 2 parts of calcined sodium carbonate and 2.5 parts of the solution of the dyestufi obtained as described above; 100 parts of cotton are entered and the bath is heated in-the course of haliF-an-hour to 90-100 C. 30 parts of crystallized sodium sulfate are added and dyeing is continued at the same temperature for 30-40 minutes. The goods are then rinsed and soaped in another bath containing per litre 5 parts of Marseilles soap for half-an-hour at 50 C. Rinsing and drying follow.

The cotton is dyed yellow tints of very good fastness, particularly to washing. When the dyed goods are washed for half-an-hour in a bath at -90" C. containing, perlitre, 2 parts of calcined sodium carbonate and 5 parts of Marseilles soap, together with white cotton, the latter remains uncoloured.

Instead of triethanolamine there may also be used ethylene-dlamine or polyalkylenediamines. When there is used for the dyeing a dyestuil solution obtained by treating the copper compound of the azo-dyestufl. of the formula CH: (L0H N OM an;

co O OH O OH tan COOH with triethanolamine there is obtained a brown orange tint which also has good fastness to washing.

Blue-violet tints fast to washing are obtained when the dyestuif used is obtained by the action of triethanolamine' on the copper compound of. the dyestui'f of the formula com copper compound of the dyestuii of the formula I aoaaaaa m I 3 In a similar manner to that described in the second paragraph of this example artificial silk rims Q soul I v OCH; Nu 7 00m I 3091a QM N: QM OH 0011 on, n n cm coon a blue dyeing fast to washing is obtained, and

from the product of the action of triethanolamine on the copper compound of the dyestufl of the made from regenerated cellulose can dyed but the temperature of the dyeing operation should be about 75-80 C.

formula I I no,s I I soar I I OCH; NH 0cm no? Gum: N= AON=NQOH I ooH on. I H H I211; oon

there is also obtained a blue dyeing fast to wash- Example 2 7 ing; from the product of the action of triethanolamine on the copper compound of the dyestuif of A boiling dye-bath is prepared consisting of the formula 2000 parts of water, 2 parts of calcined sodium I 0on NH I 0cm H0-QN= Qxhn I (ID-rang :nOon

0011 H; e H OH on, (30011 a blue dyeing fast to washing is obtained; from carbonate. and 0.25 part of the finely ground the product of the action of t'riethanolamine on paste of the copper compound of the dyestuif of the copper compound of the dyestufi of the the formula I Hols soiu ocn. NH I 0on1 HOQ-N: Quitv w-Nat N=N--0n H 00H CH1 H n on. I $0011 formula I V v v I 100 parts of cotton are entered and boiling is H0;S soin OCH:

a greenish-grey dyeing is obtained, and from the product of the action of triethanol amine on the copper compound of the dyestufl of the formula a blue grey fast dyeing is obtained.

continued for about 1% hours. The goods are then rinsed and soaped in another bath containing per litre 5 parts of Marseilles soap for half- Hois OCH;

SOIH- an-hour at 50 C. Rinsing and dyeing follow.

I I NH-C o-1-m I OCH: I

on; I H on ocm '0 on can. I NH-C O'-N I HO-QN= N=N N= -N=NQOH 7 00K H v v H 00H OHQMPQ-n O OH CH! The cotton is dyed blue tints fast to washing.

In like manner the copper compounds of the dyestuffs named in Example 1 may be used.

A similar result is obtained if 30 parts of crystallized Glaubers salt are added to the dye-bath after it has been boiling for 1 hour.

The result in respect of the uniformity of the tints obtained is favourably influenced when the dye-bath receives an addition of 2-5 parts of sulfite cellulose waste liquor.

Example 3 A dye-bath is prepared from 2000 parts of boiling water, 2 parts of calcined sodium carbonate, 1 parts of Marseilles soap and 2 parts of the OCR 0011 very finely subdivided copper compound of the dyestufi of the formula COOH CH: H

100 parts of cotton are entered and are handled for 1-1 hours, whereupon 30 parts of crystallized Glaubers salt are added and dyeing is continued for half-an-hour at boiling temperature. The goods are then rinsed and soaped in a bath containing per litre grams of soap at 50 C. Rinsing and drying follow. The dyeings obtained are excellently fast to washing.

Similar results are produced when the dyestufl is boiled in the dissolving vat together with the sodium carbonate and the soap and then added to the boiling dye-bath. Good results are also obtained by treating the finely subdivided dyestufi in the'form of paste or powder in a dispersing mill before it is used for dyeing.

If, in the dye-bath prescribed above, there is substituted for the Marseilles soap 1 part of Turkey red oil or 2 parts of sulfite cellulose waste liquor or 1 part of sodium l-lso-propyl-naphtha- SOaH . BOZH oorn m: I I

con m n n on,

Example 4 A dye-bath is prepared consisting of 2500-3000 parts of water, a. solution of the copper compound of the dyestufl of the formula :8 E I) H my I .per liter 5 grams of Marseilles soap for ,5 hour at 50 C., rinsed again and dried. The cotton is dyed greenish-blue tints of very good fastness to washing.

Example 5 2.5 parts of the azo-dyestuif of the formula are converted into the copper compound by treatment with copper sulfate. The insoluble precipi- SOxH -CH: OOH

tate is filtered, pressed and treated in the form of a moist paste with 7 .5 parts of triethanolamine on the water-bath until a syrupy mass clearly soluble in water has been formed, whereupon the water is distilled off. There are obtained 10 parts of the complex copper compound of the azo-dyestuff which has been rendered soluble and which is dissolved in 3000 parts of water. 100 parts of boiled jute yarn are entered into this solution, mixed with 40 parts of Glaubers salt and dyed for 1 hour while boiling. v

The jute yarn is dyed yellow fast to light and water.

Instead of jute yarn, wood bast and straw-plaiting may be dyed in analogous manner.

tints which are Example 6 10 parts of the copper compound of OH: COOH are dissolved with 40 parts of triethanolamine in 500 parts of hot water. The clear solution is added to a paper mass containing 1000 parts of cellulose. The whole is mixed for sometime whereby the cellulose is strongly dyed by the dyestufl. 60 parts of aluminium sulfate and 40 parts of resin glue are then added to the mixture and worked up in the manner usual for 0 CIHI H can} 0 0 OH paper. There is obtained a grey-blue colored paper of excellent tastness to water and light.

I Example 7 m 10 parts of the azo-dyestufl of the formula SOiH OCH:

are dissolved in 500 parts 01' water and mixed at 70-80 C. with a solution of 6 parts of thecopper salt of glycollic acid in warm water. The whole is stirred for sometime at TO-80 C. For dyeing there may be used either the solution of the amdye'stufi containing copper and glyeocollic acid complexly bound which has formed, or the new nos N=N N=N COOH CH: H

complex compound can be separated by means of common salt and dried. The complex copper compound which has separated remains watersoluble also after drying, whereas by treating with the usual Vcoppering agents;-such as copper I sulfate, copper acetate, ammoniacal copper oxide,

sparingly soluble to insoluble complex copper compounds are obtained.

A paper mass containing 1000 parts of solid cellulose mass is dyed with the solution of the copper complex of the dyestufi obtained in the preceding paragraph, by treating the paper mass with the dyestuff solution for some time in theshaking machine or the rolling mill. The complex copper compound of the dyestufi is SOaH OCH:

I NH I 0011. HOQN= -Q-N=N N=N N=NQ-OH A 00H I on} 'H a on. con

with 2 parts of the sodium salt of the sulfonated Example 8 3 parts of the dyestufl obtainable by condensing 1 mole of dinitrostilbene-disulfonic acid with 2 moles of the .azo-dyestuflf from diazotized 1- amino-4-hydroxybenzene-3-carboxylic acid and 1:3-phenylenediamine in the presence of caustic soda solution according to the process of U. S. Patent 1,861,323, are boiled with 1.5-part oi the copper salt of glycocollic acid in 100 parts of water, and the solution thus obtained is diluted with water to 3000 parts by volume. 100 parts of jute yarn are introduced into the dyeing liquor and after addition of 40 parts of Glaubers salt the material is dyed for 1 hour at 95 C. Therevis obtained a brown dyeing of very good ta'stness to water.

SOaH I 0cm Coconut fiber can be dyed in analogous manner. 1

Example 9 2 parts of the copper compound of the 'azo-dyestuff of the formula NH I OH:

I H on, con

are ground in a ball mill with parts of the sodium salt of the sulfonated condensation prodnot from benzylchloride and naphthalene until a,

which 100 parts of cotton are introduced at 30-,

40 C. The temperature of the bath is raised to boiling in the course of hour, whereupon 30 parts of Glaubers salt are added and dyeing is continued for 1 hour at 95-100 C. The cotton is then washed and dried. There are obtained blue tints of very good fastness to light and washing.

Similar results are obtained when dyeing with a mixture which has been obtained by grinding together 2 parts of the copper compound of the dyestufl? of the formula SOIH condensation product from benzylchloride and naphthalene.

Greenish-blue dyeings of good tastness to light and washing are obtained.

A yellowdyeing of very good rastness to washing and light is obtained by a similar method of working when using the copper compound of the dyestufl! Example 1o- OOH Hz in the form of an aqueous paste containing 20 per cent. of dyestuif are suspended in 200 parts of water, mixed with 10 parts of an emulsifying agent consisting of glue andsoap, heated for a long time to 40 to 60 0., and vigorously stirred. This treatment may also be carried out for a shorter or longertime at higher temperatures, for example at -100 C. The mixture thus obtained is used either directly for dyeing, or it may be partly or completely evaporated in a vacuum and then ground.

For dyeing there is prepared a bath having a temperature of 30-40 C. and containing per 100 parts of cotton 2 parts of calcined sodium carbonate and 2 parts of the above mentioned aqueous paste. The cotton is introduced and the bath is heated to boiling temperature within /2 hour, whereupon 30 parts of Glaubers salt are added and dyeing is continued for a further hour at -100 C. 'After washing and drying there'are obtained blue tints of very good fastness to light and washing.

If instead of the emulsifying agent mentioned 0 in this example there is used a pyridine solution of castor oil sulfonate similar results are obtained.

Example 11 10 parts of the dyestuif of the formula are converted into the complex copper compound with copper sulfate in usual manner. The water-insoluble copper compound is filtered, washed and pressed. The pressed material is made up into a paste of 50 parts by weight by means of water, mixed with 10 parts of the sulfonated condensation product from stearic acid and orthophenylenediamine, and vigorously stirred for a long time, until a homogeneous mass has been formed. A dye-bath is now prepared consisting of 2000 parts of water, 2 parts of sodium carbonate and 6 parts of the above named mixture, into which parts. of cotton are introduced at 30-40 C. The temperature is raised. to boiling in the course of 5 hour, whereupon 30 parts of Glaubers salt are added and dyeing is continued for 1 hour at 95-100 C. The cotton is then washed and dried. There are obtained yellow tints of very good fastness to light and washing.

Similar results are obtained when using under otherwise unchanged conditions instead of the sulfonated condensation product from stearic acid and ortho-phenylenediamine an emulsifying agent consisting of glue and soap or sodium isopropylnaphthalenesulfonate.

I OH:

H OH| OOH Example 12 The dyestufl of Example 9 of U. 8. Patent 1,861,323, pa e 3, lines 102-106, obtained by condensation of dinitrostilbene-disulfonic acid with the azo-dyestufl from diazotized l-acetylaminolater use.

A dye-bath is prepared, consisting of 2000 parts of water, 2 parts of calcined sodium carbonate,

and 2 parts of the dispersed dyestufl; 100 parts of cotton are entered at 3040 0., and the bath is heated to boiling in the course of hour, whereupon 30 parts of Glaubers salt are added and dyeing is continued for a further hour at 95-100 C. The cotton is then washed and dried.

There are obtained orange tints of very good fastness to light and washing.

Example 13 The dyestuff of the formula Hols 803K I! on NH on =N N=N n on NO:

is converted in an aqueous solution into the very dimcultly soluble copper compound by treating it in the usual manner with agents yielding copper. After filtering and washing the copper compound is dried and ground in a ball mill or roller mill with equal parts of the sodium salt of the diamylsulfophthalic acid ester.

2 parts of the dyestuff mixture thus obtained are boiled in about 10 litres of water and added to a dye-bath at 30-40 .C. and containing 1500- 2000 parts of water as well as 2 parts of calcined sodium carbonate. 100 parts of cotton are entered and the temperature of the bath is raised to boiling in the course of hour, whereupon temperature is maintained between 95-l00 C. for

ness to light and washing.

Example 14 The dyestufi of the formula parts of crystallized nickel sulfate in aqueous solution. The separated water-insoluble precipitate is filtered. Into a dye-bath consisting oi! 1500 parts of water, 2 parts of calcined sodium carbonate, 30 parts of Glaubers salt, 2 parts of the sodium salt of the diamylsulfophthalic acid ester and the complex nickel compound produced above, are introduced 100 parts of cotton at- 30-40 C.; the temperature of the bath is raised to boiling in the course of A hour and maintained for about %-1 hour, whereupon the material is emulsifying agent consisting of glue and soap.

, Example 15 The dyestuff of the formula is converted into the complex-cobalt compound by mixing for example 2 parts of this azo-dyestuff, dissolved in 100 parts of water, at 80100 C. with an aqueous solution of 1.5 parts or cobalt chloride, stirring for some time and filtering the waterinso'luble cobalt compound of the dyestuif which has separated; For dyeing 100 parts of cotton 2 parts of the complex cobalt compound are added to a dye-bath consisting of 1500 parts of water, 2 parts of the sodium salt of the diamylsulfophthalic acid ester, 2 parts of calcined sodium carbonate and '30 parts of Glaubers salt. The material is introduced at 30-40 C., the temperature of the bath is raised to boiling within /2 hour and maintained for about 1 hour, whereupon the cotton is washed and dried.

There are obtained brown-violet tints of veryole 4 r OCH: NH

' OOH CH: H e 1 H 7 good fastness to, washing and light which may still be improved by soaping in another bath containing per liter 0.5 gram, of Marseilles soap at 40 C.

Instead of the sodium salt of the diamylsulfophthalic acid-ester there may also be usedthe on I NH I oiN H n i 0011 same quantity of an emulsifying agent consisting of a mixture of. glue and soap, or the corresponding quantity of the sodium salt of the sultonated condensation product .from. benzylchloride and naphthalene.

Example 16 The dyestuff obtained by condensation of 1 mole of dinitrostilbene sulfonic acid with 2 moles of the azo dyestuif from diazotized 1-amino-4- hydroxybenzene-3-carboxylic' acid and 1.3-phenylenedlamine, in the presence of caustic soda solution according to the process of U. S. Patent 1,861,323, is converted in an aqueous solution into' the water-insoluble complex copper com pound'by treatment in the usual manner with agents yielding copper. The copper compound is separated, washed, dried and extremely finely ground. v

2 parts of this cupriferous dyestufi are ground with 1 part of the sodium salt of glycocollic acid,

whereby there is obtained a water-soluble form of thecomplex copper. compound which is suitable for dyeing cotton from a neutral or sodaalkaline Glaubers-salt bath.

2 parts of the ground material are boiled with about 100 parts of water and added to a dyebath containing 1500-2000 parts of water and 2 parts of calcined sodium carbonate at 30-40 C. 100 parts of cotton are introduced into this bath and the temperature is raised to boiling in the course of ii -V hour, whereupon 30 parts of Glaubers salt are added and the temperature is maintained for 1 hour between 95-.-100 C. The cotton is then rinsed and dried. There are obtained brown tints of good fastness to'light and washing. v

. Example 17 I 1 part of the dyestufl of the formula 4 80:11 I OCH:

(sodium salt) is ground in a. mill with 0.5 part oi. the copper salt of glycocollic acid and 0.5 part of the nickel salt of glycocollic acid. The ground material is used for dyeing 100 parts of cotton by dissolving it in 1500 parts of water, 2 parts of calcined sodium carbonate, and dyeing the cotton for 1 hour at 90-l00 C. Washing and drying follow. There are obtained blue tints of good iastness to washing and light. Before drying the dyeing may be soaped for about hour in another bath containing per cent or soap, whereby the fastness to washing is improved.

Example 18 The dyestufi' of the iorumla OOH H OH is converted into the complex nickel-cobalt compound by mixing 1 part of the dyestui'i! in aqueous solution with the solutions of 0.28 part of crystallized nickel sulfate and 0.28 part of cobait sulfate, stirring the whole in the heat and filtering the precipitate. To the paste of the complex metal compound thus obtained there is added 1 part of a mixture consisting of equal parts of Marseilles soap and glue, the whole is homogeneously mixed and evaporated to dryness in a vacuum. The dried material is then finely ground.

A dye-bath is prepared consisting of 1000-1500 parts of water, 2 parts of calcined sodium carbonate and 30 parts of Glaubers salt. 100 parts of cotton are dyed by introducing the material at 30-40 C.. heating the bath to boiling in the course of 20-30 minutes, maintaining this temperature for about 1 hour, washing and drying. The dyeing thus obtained has good fastness to washing and light.

Example 19 v 1 part of the dyestufi of the formula OHIO ' ing and drying follow. There are obtained bluegrey tints of good iastness to washing andlight.

What we claim is: 1

1. Process for the production oi fast tints on vegetable fiber, comprising dyeing the vegetable fiber with finely subdivided complex metal compounds of direct azo-dyestuils for cotton, said compounds being sparingly soluble to insoluble in water and in dilute alkalies.

2. Process for the Production of fast tints on vegetable fiber, comprising dyeing the vegetable fiber with finely subdivided complex copper compounds of direct azo-dyestuilfs for cotton, said compounds being sparingly soluble to insoluble in water and in dilute alkalies.

3. Process for the production oi fast tints on vegetable fiber, comprising dyeing the vegetable fiber with complex copper compounds of direct azo-dyestufis for cotton, said compounds being sparingly soluble to insoluble in water and in sosn dilute alkalies, in presence of compounds selected from the group consisting of dispersing, wetting and emulsifying agents.

4. Process for the production of fast tints on vegetable fiber, comprising dyeing the vegetable fiber with complex copper compounds of direct azo-dyestufls for cotton, said compounds being sparingly soluble to insoluble in water and in dilute alkalies, in presence of organic ammonium bases.

5. Process for the production 01' fast tints on vegetable fiber, comprising dyeing the vegetable fiber with complex copper compounds of direct azo-dyestufis for cotton, said compounds being sparingly soluble to insoluble in water and in dilute alkalies, in presence of aliphatic amines.

6. Process for the production 01' fast tints on vegetable fiber. comprising dyeing the vegetable fiber with complex copper compounds of direct azo-dyestufis for cotton, said compounds being sparingly soluble to insoluble in water and in dilute alkalies, in presence of aliphatic amines containing hydroxyl groups.

7. Process for the production of fast tints on I CH:

N=N N=NQOH a on. 0 on vegetable fiber, comprising dyeing the vegetable fiber with finely subdivided complex copper compounds of direct azo-dyestufls for cotton, said compounds being sparingly soluble to insoluble in water and in dilute alkalies, and soaping the dyeing thus obtained.

8. Process for the production of fast tints on vegetable fiber, comprising dyeing the vegetable fiber with complex copper compounds of direct azo-dyestuils for cotton, said compounds being sparingly soluble to insoluble in water and in dilute alkalies, in'presence of aliphatic amines containing hydroxyl groups, and soaping the dveings thus obtained.

' FRI'I'Z B'I'RAUB.

WALTER. ANDERAU.