US2040927A - Coloration of textile materials - Google Patents

Description

' textile materials by the azoic process.

Patented May 19, 1936 COLORATION. OF TEXTILE MATERIALS George Holland Ellis and Ernest William Kirk, Spondon, near Derby, England, assignors to Celanese Corporation of America, a. corporation of Delaware No Drawing.

Application October 6, 1932, Serial 636,578. In Great Britain October 26,

15 Claims. (Cl. 8-6) This invention relates to the coloration of textile materials and more particularly to the coloration of such materials by the so-called azoic process wherein insoluble or diflicultly soluble azo dyes are formed on the materials by the coupling thereon of diazo compounds and suit-,

able coupling components.

The coloration of cellulosic materials by the azoic process has long been practised on an extensive scale and as an example may be mentioned the production of the well-known paramtraniline red on cotton materials from diazotized para-nitraniline and p-naphthol. During the past decade the scope of the azoic process has been very largely extended by the introduction of new coupling components, more particularly arylamides of 2:3-hydroxy-naphthoic acid and the diacetoacetyl derivatives of aromatic diamines, of which the diaceto-acetyl-orthotolidine is possibly the best known example. By the use of these coupling components in conjunction with diazo compounds, especially those of the benzene and naphthalene series, a wide range of colorations has been produced, many of which exhibit outstanding properties of fastness, particularly to the action of light or the action of hot alkaline or soap solutions. In this series of colors, however, there has in the past been a marked lack of blues and greens, the latter in particular being practically non-existent.

We have found that diazotizable derivatives of 1:4-diamin0' anthraquinone or 1:4-amino-hydroxy anthraquinone constitute veryvaluable diazo components for the production of colorations on By employing these diazo components we have found it possible to produce bright blue and green shades which could hitherto only be obtained with great diificulty or not at all by azoic processes. Further, these colorations so produced exhibit very good fastness properties, particularly in respect of fastness to hot soaping treatments. The latter is a point of particular importance in the case of yarns, particularly artificial yarns, which are to be woven with silk in the gummed state and so are called upon to resist the degumming treatmentto which the resulting fabrics are necessarily subjected. For example, by coupling on the material diazotized I-amino-4' (4-am.ino-.

phenylamino) anthraquinone with the metanitranilide of 2:3-hydroxy-naphthoic acid a full bright blue shade may be produced, and vby coupling with diaceto-acetyl-ortho-tolidine a bright bottle-green of desirable shade and good fastness properties. Again, by coupling the same diazo component with an arylamide of an ortho hydroxy carboxylic acid of carbazole, full neutral grey shades may be produced having outstanding fastness properties.

Broadly, our invention comprises the coloration of'textile materials by coupling thereon suitable coupling components with diazo compounds of diazotizable 1:4-diamino anthraquinone derivatives or 1 :4-amino-hydroxy-anthraquinone derivatives. Preferably in the case of the 1:4-diamino anthraquinone derivatives, neither of the 1:4- amino groups should be acidylated and in the case of 1:4-amino hydroxy derivatives, the amino group should not be acidylated nor should. the hydroxy group be either acidylated or etherified.

A wide range of diazotizable amino anthraquinone derivatives fulfilling the foregoing requirements is available, 'unsulphonated components being preferably employed. As examples of suitable diazo components may be mentioned the mono-aryl, mono-alkyl or mono-aralkyl derivatives of 1:4-diamino anthraquinone, whether the anthraquinone nucleus is further substituted or not. Of particular value are those anthraquinone compounds which may be diazotized so as to yield diazo compounds containing in the 1:4-position two amino groups or one amino group and one hydroxy group, the amino group or groups not being acidylated nor the hydroxy group acidylated or etherified. Of this class of compounds, special mention may be made of arylated 1:4-diamino or 1:4-amino-hydroxyanthraquinone derivatives containing in .the aryl residue or residues, one or more diazotizable amino groups. As examples of such compounds mention may be made of 1- aminoor 1-methylamino-4 (4'-amino-phenylamino) anthraquinone and 1-hydroxy-4 (4- amino-phenylamino) anthraquinone. Other compounds may be employed, however, for example 1:4-diamino or 1:4-amino-hydroxy anthraquinones containing in a position other than the 1:4- position and especially in a hetero-nuclear position, a diazotizable amino group or a substituent, e. g. an arylamino, arylhydroxy, or aracylamino group containing a diazotizable amino group. An example of such a compound is, for instance, 1:5- diamino-i-phenylamino anthraquinone.

Any desired coupling components may be utilized for the formation of dyestuffs by reaction with the foregoing diazo components, for example amines or phenols, whether of the benzene, naphthalene or other series, and compounds containing methylene groups capable of reacting with diazo compounds, for example pyrazolone derivatives or acidyl-acetic esters or acidyl-acetic amides be made, for instance, of the anilides and naphor substituted amides, or other p-keto-acidyl compounds.

Particular mention may, however, be made of those coupling components capable of yielding with diazo compounds azo dyestuffs of very difficultly soluble character and having little or no aflinity for textile materials, whether natural or artificial, when applied thereto in substance. Examples of such coupling components are the acidylamino coupling components referred to in British Patent No. 404,363, and other amides and substituted amides, particularly arylamides, of'

hydroxy carboxylic acids, especially ortho-hydroxy carboxylic acids, of the benzene, naphthalene, carbazole and other series. Mention may thalides and substituted anilides or naphthalides of salicylic acid and its homologues, or of 2:3-' or 1:4-hydroxy naphthoic acid, for example 2:3- oxy naphthoic-ortho-toluidide or meta-nitranilide. Compounds containing more than one hydroxy carboxylic acid residue may also be used, for instance the di(2:3-hydroxy-naphthoyl) dianisidine. Another class of coupling component yielding difficultly soluble dyestuffs, and in consequence shades of excellent fastness, is the class of di-B- keto-acidyl derivatives of aromatic diamines, for example the diaceto-acetyl derivative of orthotolidine or other aromatic diamine.

As regards the shades obtainable in accordance with the invention, it is found that, in general, blue to violet shades are obtained with those coupling components which normally yield orange to red shades with simple diazo compounds of the benzene series, as for example 2:3-hydroxynaphthoic anilide or meta-nitranilide. With those coupling components however which normally yield yellow shades with simple diazo compounds, green shades are in general obtained, as is the case for instance when diaceto-acetyl ortho-tolidine is coupled with one of the special diazo components of the present invention, especially one of those which may be diazotized so as to obtain a diazo compound still containing the 1:4-diaminoor 1:4-amino-hydroxygrouping. Still other shades, some of great value, may

employed in accordance with the present invention include diazotizable 1:4-diamino or 1:4-amino-hydroxyanthraquinone derivatives containing amino groups external to the anthraquinone constitute valuable diazo components for use inthe production of azo dyes, whether in substance or on textile material or other substrata. As examples may be mentioned for instance, in addition to the amino-aryl derivatives of 1:4-diaminoor 1:4-aminohydroxy-anthraquinone above mentioned, aracylated derivatives of 1:4-diaminoor 1:4-amino-hydroxyanthraquinones substituted in the aracyl residue by amino groups. Compounds other than those derived from 1:4- diamino or 1:4-amino-hydroxy-anthraquinones may, however, also be used, for instance amino aracyl derivatives of other amino anthraquinones, for instance l-aminoor 1:5- or.1:8- diamino anthraquinone, or amino aryl derivatives of these amino anthraquinones, for instance 1:5- di(para-amino-phenylamino) anthraquinone or 1-(para-aminoephenylamino) anthraquinone or l-amino- 5-( para-amino-phenylamino )-anthraquinone.

In coloring textile materials in accordance with the new azoic process, any desired mode of working maybe adopted. Thus the materials impregnated with the coupling components may be treated with solutions of the diazo compounds. Again, the diazo component may be applied first, diazotized on the material and the latter thereafter subjected to the action of the coupling component. Another method of operation consists in applying both the diazo component and the coupling component to the materials, either together or separately, and thereafter subjecting the materials to treatment adapted to effect diazotization of the diazo component and coupling with the coupling component.

Where the diazo component contains both a nuclear diazotizable amino group and an external diazotizable amino group, the latter may generally be preferentially diazotized leaving the other intact. Such preferential diazotization often leads to valuable results and may be effected, for instance, by diazotizing with sodium nitrite in the presence of a weak acid, e. g. an organic acid such as acetic acid. For example,

by applying 1-amino-4-p-aminophenylaminoanthraquinone to cellulose acetate, diazotizing with acetic acid and sodium nitrite and coupling with phenol, a green shade is obtained, whereas if the base is tetrazotized by using sodium nitrite and hydrochloric acid a brown shade is obtained.

The new processes may be utilized either for the uniform or for the local coloration of materials. In the former case the components may be applied by dyeing methods, or, if desired, by mechanical impregnation, for instance by padding or by all-over printing. For the production of local colorations, printing, stencilling or any other desired means may be employed, whether the components are applied together or separately or whether diazotization is effected on the material or in a separate operation.

The particular method to be used and the details to be observed in any given case in order to secure the best results depend upon the character of the material to be colored. In the case of cotton or other cellulosic materials, for instance regenerated cellulose artificial silk, it is in general most convenient to apply first the coupling component in the form of an alkali metal salt, for instance by a padding treatment. The impregnated material is thereafter developed in a solution of the desired diazo compound, or such a solution, if necessary suitably thickened, applied by printing or other mode of local application, where localized color effects are required.

In the case of cellulose acetate or other cellulose ester or ether materials, it is in general found most advantageous to apply coupling components in the free state, for instance in the manner described in U. S. Patent No. 1,844,350 in the case of arylamides of hydroxynaphthoic acids,-

or in the manner described in U. S. Patent No. 1,986,883, in the case of aceto-acetic arylidecou- 2,040,927 pling components. In general the most satis-v factory method, both from the point of view of the results obtained and from the point of view of simplicity, is to apply the diazo component and coupling component simultaneously in the form of aqueous dispersions, the diazotization and coupling being subsequently efiected by treatment first in a bath containing sodium nitrite and acetic or other acid followed by treatment with a weakly alkaline solution.

The dispersions of the diazo or coupling components may be obtained by any desired method, for example by fine milling or grinding with or without the aid of dispersators and/or protective colloids, by precipitation in the presence of protective colloids, or by a simple treatment with dispersators, as described for instance in any of U. S. Patents Nos. 1,618,413, 1,618,414, 1,694,413, 1,690,481, 1,803,008, 1,840,572, 1,716,721, 1,928,- 647, 1,959,352 and 390,424 filed 4th September, 1929. In some cases the dispersionof the coupling component may be facilitated by the presence of small quantities of alkali.

In treating cellulose ester and ether materials the absorption of either or both components may be facilitated if desired by incorporating swelling agents in the dyeing or padding liquors or printing pastes employed, or the materials may be pretreated with swelling agents. Alcohol is particularly suitable for this purpose, though other swelling agents may be employed if desired.

The following table shows a few of the numerous shades obtainable on cellulose acetate in accordance with the invention:-

formate, propionate or butyrate or ethyl or benzyl cellulose materials. Other materials may also be colored by the new process, for instance wool, silk and other animal fibres, also mixed materials of all kinds, for instance materials containing both animal and vegetable fibres or materials containing cellulose acetate or other artificial fibres in conjunction with cotton or other natural fibres. In the case of animal fibres the coupling components are preferably applied from very weakly alkaline baths, or evenin the form of dispersions of the free compounds; in fact the methods specified as suitable for the treatment of cellulose ester and ether materials may in general be applied with satisfaction for the coloration of animal fibres.

The dyestuffs obtainable in accordance with the invention may also be produced in substance and in this form, especially when unsulphonated, constitute valuable pigment colors or dyestuffs which may be used for direct coloration of cellulose ester or ether materials. Of particular value are those coloring matters obtainable from the diazo compounds which contain intact the 1:4- diamino or 1:4-amino-hydroxy grouping and es pecially 1-hydroxy-, 1-amino-, or l-aliphatically substituted amino-4-arylamino-anthraquinones' containing a diazo group in the aryl residue. For instance, l-methylamino-, 1-dimethylamino-, 1- hydroxyethylamino or other l-hydroxy-alkylamino-4- (amino-aryla'mino) -anthraquinone may be employed.

As coupling components, amines, phenols or keto-rnethylene compoundsof relatively low mo- Amine Developer Shade on cellulose acetate 1. l-emine-4-para-tolyl-aminoenthrnquinone. Full violet 2. Do; Sage reen 3. l-amino-4-pare-emsylamino-anthraqu1none Bluis violet 4. D Sage green rather brighter than N o'. 2 5. l-am mo 4 (3'- aminophenylamino) anthra- Full bluish violet qumone. 6. Do Do. Full sage green 7. Lam na-4 (4-amino) phenylaminoanthre- Do. Full bright blue qumone. 8. Do Do. AS/OL Full brilliant blue slightly redder than preceding 9. Do Do. Bright blue 10. Do Do. Full, slightly greener blue ll. l-am no-4 (4-amino) phenylaminoanthra- Do. Full neutral grey quinone 12. o Do. Full brig bottle green 13. 1.5 dinmine-4.8-diphenyleminoanthraquinone. Do. Grey-violet 14. o Do. Yellowish sage 15. l-oxy -4- (4-amino phenylamino) anthra- Do. Bright full blue. deeper and quinone redder than No. l0 16. Do Do. Full green sli htly brighter and deeper t an No. 12 17. Do Do. AS/LB Brownish grey 18 l-em1no-4-p. tolylammo anthrequlnone Phenol Puce Olive Deep yellowish olive Violet 21. Do Beta-naphthol 22. D0 Betahydroxynaphthoic acid- Do. 23. l-am no-4 (4'-am1no) phenylaminoanthra- Phenol Fairly bright bottle green qmnone 24. D Phenol-methylpyrazolone. Very deep bottle green 25. Meta-phenylenediamine- Very deep yellowish bottle green 26. Do Beta-naphthol Blackish violet 27. Do Betahydroxynaphthoic ecid Bright reddish blue 28. 'l-lnethylemino 4 (4'-amino) phenylamino- Phenol Bright, clear green anthrequinone 29. 1 amino 4 phenylaniino 5 hydroxyanthra- Resorcin Brownish-grey qumone I 30. Do; Metahydroxy diphenyl- Nigger brown amine V 31. 1-a1nino-4-phenylamino-anthraquinone Do. Do. 32. Do Naphthol AS/LB Chocolate brown 33. l-amino-i-methoxyanthraquinone Do. Deep brick red 34. l-amino-4-acetaminoanthraquinone. Do. Khaki As will be, appreciated from the foregoing description, this invention is of especial value in connection with the coloration of cellulose ester and ether materials. In addition to cellulose acetate the invention may be applied to cellulose lecular weight are advantageous, for example, amines or phenols, particularly monohydric phenols, of the benzene series, acylacetic arylides or pyrazolones. Thus by diazotizing l-methylamino 4 p aminlophenylamino-anthraquinone and coupling with phenol a dyestufi which dyes cellulose acetate directly in fast bright green shades is obtained.

Other coupling components which may be employed are, for instance, orthoor meta-cresol, iii-phenylene-diamine, m-aminophenol, dimethylaniline, m-hydroxy-diphenylamine, l-phenyl- 3-methyl-5-pyrazolone, and acetoacetic anilide or other acetoacetic arylide of the benzene series.

.Where as in the case of 1-amino-4-aminoarylamino-anthraquinones the diazo component contains both a diazotizable amino group in the anthraquinone nucleus and an external diazotizable amino group, one or both may be diazot-ized and coupled. By' effecting diazotiz'ation with nitrite and a weak acid, for example acetic or other organic acid, the external amino group only may be diazotized. This procedure in general gives rise to dyestuffs of greater value, both as regards color and as regards aflinity for cellulose esters or ethers, than when both amino groups are diazotized and coupled.

The new dyestuffs are conveniently applied to cellulose esters or ethers in the form for example of aqueous suspensions or dispersions. The latter may be prepared in any desired manner, for example by grinding or milling with or without dispersators and/or protective colloids, by dissolving in a solvent and pouring into water or by treatment with dispersators as described for instance in any of U. S. Patents Nos. 1,618,413, 1,618,414, 1,694,413, 1,690,481, 1,803,008, 1,840,572, 1,716,721, 1,928,647 and 1,959,352. Liquid, paste, powder or other preparation comprising the new dyestuffs, together with dispersators and/or protective colloids, comprise an important feature of the invention. Such preparations may be of a strength suitable for coloring purposes or, if desired, in more concentrated form adapted to yield dye baths, printing pastes or the like by dilution with water, with or without additional protective colloids and/or dispersing agents.

The following examples illustrate the invention, but are not to be considered as limiting it in any way:-

Example I To dye 10 kilogrammes of cellulose acetate,

yarn a bright grass-green shade resistant to the .conditions necessary for the degumming of silk,

100 grammes of 1-amino-4-(4T-amino)phenylamino anthraquinone and 60 grammes of diacetoacetyl-o-tolidine are dispersed by fine grinding and boiling with 500 grammes of Turkey red oil. This is then stirred into a. dye bath containlng 300 litres of soft water containing half,

- turning in this bath for half an hour, the yarn is again lifted'and rinsed and entered cold into a developing bath containing two grammes per litre Marseilles soap and half a gramme per litre of sodium carbonate. It is worked in this bath for half an hour cold, then heated gradually to C. and kept at this for half an hour. The yarn is then lifted, thoroughly rinsed, and dried or otherwise treated.

Example II To dye 10 kllogrammes of cellulose acetate woven fabric a full bright green shade of good fastness to light and water, grammes of 1- methylamino-4 (4 -amino) phenylamino -anthraquinone are dispersedwith Turkey red oil and-the fabric dyed with this dispersion in the usual manner. The fabric is then rinsed, and the color diazotized by running for half an hour in a diazotizing'bath of the constitution described in Example I, then rinsed and entered into a bath containing 50 grammes of phenol, and worked in this for half an hour. Soda ash and soap are then added to make the bath concentration 1 and 2 grammes per litre respectively, and the temperature raised to 75 C. and the fabric worked at this temperature for half an hour, then rinsed I To dye 10 kilogrammes of cellulose acetate yarn a full nigger-brown of good fastness to water, 100 grammes of 1-amino-4-paratolylamino 5 hydroxy-anthraquinone are dispersed by boiling with 300 grammes of Turkey red oil and diluting with about 10 litres of hot soft water, and added to a dye-bath of 300 litresof soft water. The yarn is entered and worked in this bath for two hours during the first hour the temperature being raised to 70 C. and maintained at this temperature for the remainder of the dyeing period. The yarn is then lifted and entered into a diazotizing bath containing 6 grammes per litre sodium nitrite and 12 cc. per litre-of hydrochloric acid 30 Tw. and turned in this bath for half an hour at 25 C. After rinsing, the yarn is entered cold into 300 litres of soft water to which has beengrammes of soap added and the temperature then raised gradually to 75 C. The yarn is turned at 75 C. for half an hour, and then soaped for a further half hour in a fresh soap bath of similar length and concentration, and is finally lifted, .rinsed and dried or otherwise treated.

Example IV temperature raised over half an hour to 75 C.-

and kept at this until the desired depth of base has been attained. The fabric is then lifted and entered into a diazotizing bath containing 4 grammes per litre sodium nitrite and 8 grammes per litre glacial acetic acid and worked in this bath for half an hour cold, again rinsed and then entered into a bath containing 1 gram per litre sodium carbonate and 5 grammes .per litre soap. 70

After working in this bath for half an hour cold, the temperature is raised slowly to 75 C. and kept'at this for half an hour. The fabric is then lifted, rinsed and dried, or otherwise treated as requisite.

Example V To print cellulose acetate fabric a fast deep grey shade, the printing paste is made up as follows:

The fabric is printed with a suitably engraved roller, dried, steamed for half an hour at a pressure of lbs. to the square inch, washed ofi well and diazotized by treatment in a bath containing 4 grammes per litre of sodium nitrite and 8 cc. per litre of glacial acetic acid. The fabric is then washed off well, and soaped in a bath containing 1 gramme per litre sodium carbonate, and 2 grammes per litre soap, first in the cold and then for half an hour at 75 C. finally being rinsed and dried or otherwise treated as desired.

Example VI To 34.3 grammes of l-methylamino-4-p-aminophenylaminoanthraquinone in the form of a finesolved in water, followed by 30 grammes of glacial acetic acid. The whole is then stirred for 4 hours, after which grammes of phenol in 500 cc. water are added, and a 10% solution of soda ash then run in slowly with stirring till the liquors react alkaline. After furt'her stirring the dyestuff is filtered off and washed wellybeing retained preferably as an aqueous paste.

Applied to cellulose acetate fibres by dispersion methods, it.yields bright green shades of excellent fastness properties.

What we claim and desire to secure by Letters Patent is:

1. Process for the coloration of textile materials which comprises coupling thereon an azo coupling component which couples in an aryl residue with a diazo compound obtainable by diazotizing an anthraquinone compound containing an external diazotizable amino group.

2. Process for the coloration ofv textile materials which comprises coupling thereon an azo coupling component which couples in an aryl residue with a diazo compound obtainable by diazotizing a 4 (amino arylamino) anthraquinone having in the l-position a substituent 'NRiRz, wherein R1 and R2 represent hydrogen positions, said compound having a diazotizable amino group as a substituent in an arylamino group. I

5. Process for the coloration of textile materials which comprises coupling thereon an arylamide of an aromatic hydroxy carboxylic acid with a diazo compound obtainable by diazotizing a 4-(amino-arylamino) -anthraquinone having in the 1-position a substituent N.R1R:, wherein R1 and R2 represent hydrogen or alkyl.

6. Process for the coloration of textile materials which comprises coupling thereon an arylamide of an aromatic hydroxy carboxylic acid with a diazo compound obtainable by diazotizing a 1-amino-4- (4'-amino-phenylamino) -anthraquinone.

7. Process for the coloration of textile materials which comprises coupling thereon an arylamide of 2:3-oxy-naphthoic acid with a diazo compound obtainable by diazotizing an anthraquinone compound containing an external diazotizable amino group.

8. The process comprising coloring organic derivatives of cellulose by means of azo dyestuffs obtainable by coupling azo coupling components with diazo compounds obtainable by diazotizing anthraquinone compounds containing external diazotizable amino groups.

9. Process for the coloration of organic derivatives of cellulose which comprises coupling thereon an azo coupling component with a diazo compound obtainable by diazotizing an anthraquinone compound containing an external diazotizable amino group.

10. Process for the coloration of cellulose acetate which comprises coupling thereon a phenol of the benzene series with a diazotized 4-(aminoarylamino) -anthraquinone having in the l-position a substituent N.R1R2, wherein R1 and R2 represent hydrogen or alkyl.

11. Organic derivatives of cellulose colored by means of azo dyestuffs obtainable by coupling azo coupling components with diazo compounds obtainable by diazotizing anthraquinone compounds containing external diazotizable amino groups.

12. Cellulose acetate materials colored by means of azo dyestuffs. obtainable by coupling azo coupling components with diazocompounds obtainable by diazotizing anthraquinone compounds containing external diazotizable amino groups.

13. An azo dyestufi of the formula in which X is an anthraquinone radical wherein' the group in which R1 and R2 represent hydrogen or alkyl group, is in the 1-position and the -NI-I group in the 4-position, Y is an aryl radical, and Z the residue of a coupling component consisting of an arylamide of an aromatic hydroxy carboxylic acid.

14. Process for the coloration of textile materials, which comprises coupling thereon an azo coupling component with a diazo compound obtainable by diazotizing a 1:i-arriino-hydroxy-anthraquinone containing an external diazotizable amino group. 1

15. An azo dyestufi of the formula the group in which R1 and R: represent hydrogen or alkyl group, is in the l-position and the --NH group in the 4-position, Y is an aryl radical, and Z the residue 0! a coupling component which couples in an aryl residue with a diazo compound.

GEORGE HOLLAND ELLIS. ERNEST WHLIAM KIRK.