US2662806A - Process for the dyeing of cellulosic materials and dyestuff preparations suitable for this purpose - Google Patents

Description

s1. Jigs-6t Patented Dec. 15, 1953 UNITED STATES PROCESS FOR THE DYEING F CELLULOSIC Q MATERIALS AND DYESTUFF PREPARA- TIONS SUITABLE FOR THIS PURPO SE v KarlMenzi, Henri Riat; and Jacques Wegmann Basel, Switzerland, assignors to Ciba Limited Basel, Switzerland, a Swiss firm I N0 Drawing. Application July 20,1950,-

Serial No. 175,014 6 Claims priority, application Switzerland 1 The present invention is based on the observation that cellulosic materials are dyed in a valuable manner when the dyeing is carried out with a metal compound, diflicultly soluble per se, of a direct dyeing azo dyestuff'which contains in complex combination one of the metals with the atomic numbers 27 to 29, or with a mixture for the formation thereof, in the presence of an ali- Phatic base free from acid groups, whichcontains at least one basic nitrogen atom and at least one hydroxyl group separated from the basic nitrogen atom by two carbon atoms,'which base is solid and water-soluble. I The metal compounds which are difllcultly soluble in water per se contain in complex combination one of the metals with'the atomic numbers 27 to 29, that is to say, in the order of'increasing importance, cobalt, nickel "and copper: Espe-'- cially valuable results are obtaianed with such azo dyestuffs containin'g copper as in the metal-free condition are still soluble inwater and suitable for the dyeing of cellulosic materials; but which in the form of copper compounds are difllcultly soluble in water and on account of this property are not of good suitability for dyeing, at allevents when it is not intended to dye from a suspension,

which method as a rule'yields unsatisfactory results. In the present case those complex metal compounds-which give colloidal solutions in water are also to be considered as diflicultly soluble. It is the result of experience that these metal compounds are also unsuitable per se for dyeing on account of their very poor capacity for drawing onto the fiber. r

The diflicultly water-soluble dyestufis to be employed according to the present process, may for example be metal complexes of dyestuffs with o-hydroxy carboxylic acidgrouplngsas are present among others in salicylicacid. In this connection there should also be mentioned metal complexes of dyestuffs with the atom grouping As especially advantageous have proved among others metal compounds of oto -dihydroxyazo dyestuffs, that is to say from dyestufl s w hich contain the atom grouping I I I i I a,

14 Claims.

(Cl. 8-42) 4 Also among the metal ompounds of o: o-'dihy'- droxyazo dyestuffs the copper compounds are chiefly of value. These contain the atom grouping which is usually illustrated by the formula I o-N=Nc p 10 at least once in the molecule. They can contain the atom grouping for example twice and in the following form Z 3 Cu ",0" o \ON=N The copper compounds of such constituti'onwhich are difiicultly soluble to insolublein water can be produced by customary methods known, especially for the production of water-soluble copper compounds, by treatment withage'nts providing copper of the corresponding metal-free azody'e stuffs which contain the atom grouping In the case of azo dyestufis with the last-mentioned grouping the treatment with agents providing copper should ..be carried out in such a manner that the copper complex'formation'takes place with splitting 'ofi of the -O-alkyl group.

In some cases this takes place also with dyestuffs which yield difllcultly s'olublecopper compounds,

by heating with copper tetrammine compounds of ammonia in an alkaline medium for a prolonged period. Particularly effective ishowever in this 40 case the application of the process of U. S. Patent application Serial No.778,734 (now U. S. Patent No. 2,536,957) t In general it is advantageous to employ or produce the complex metal compounds for the dye- 5 stuff preparations in such a condition that their ionogenic salt-forming groups, that is to say especially sulfonic-acid and carboxyl groups (insofar as the latter are not used in the complex formation) exist in the form 01. metal salts, for example alkali metal salts'and not as free acid groups or ammonium salts.

Instead of the complex metalcompounds there can also be used in the presentprocess the mixtures used in the formation thereof. It is thus possible for example "to employ a dyestuff free 3 from complex-forming metal, suitably in the form of an alkali salt, in combination with the necessary quantity of an agent providing metal. As agents providing metal there are also concerned in this case the compounds known per se which' are normally used for the production of complex metal compounds. When" as agents providing metal simply constituted metal salts are employed, as for example sulfates, nitrates or acetates, it is in general advantageous to add to the dyebaths in addition to the-metal salts further suitable additions which during the dyeing are capable of dispersing any metal hydroxide produced. As an example of such an addition'may Y be mentioned the sodium salt of N-rnethyl-;r- 4

analogous manner to that described in German Patent No. 635,904'by condensation of hydroxy- V alkylamines with dihalogenalkyls.

heptadecyl-benzimidazole sulfonic-acldr" There may be used with advantage as agents providing metal such compounds of complex-,1

forming metals as contain the metal in complex combination in the anion. In any case the complex formers should not possess the property of withdrawing metal from the complex metal com pounds of dyes'tuils under the working conditions concerned. As examples of useful complex formers may be mentioned aliphatic hydroxy carboxylic acids such as glycollic acid, lactic acid, fl-hydroxypropionic acid, e-hydroxybutyric acid, tartaric acid and citric acid.

It is to be recommended to employ a certain excess of the agent providing metal over the theoretically necessary quantity.

According to the present invention the dyeing with the complex metal compounds of the above described composition takes place in the presence of an aliphatic base. This base contains at least one basic nitrogen atom and is solid, that is to say its melting point lies above the temperatures at which the preparations are normally stored; it is therefore higher than 40 C. The base is in addition water-soluble and tree from acid groups such as 'sulfonic acid groups and carboxyl groups; on the other hand it contains at least one bydroxyl group,gwhich is separated from the basic nitrogen atom by two "carbon atoms. of art'ic'ularly good suitability are the bases of the composition I'M Q-H1, =(NHCCHr-OH):

in which R1 indicates a hydrogen atom, an 'alkyl group with at the most three carbon atoms or a hydroxymethyl grounRz a hydrogen atom or a methyl group and n awhole number 'whichiis 'at the most 4 but preferably 2. I

Asexamples may be mentioned the bases of the following composition:

HCHr-'CHr-NH- CH1 HO-CHr-CHg-NH- H CH: HO'CHr-YH-NHCH Ho-ourcn-NrF m M. P. 136 to 139' C.

CHI CHI sno-onr-o-inn-onl HO-ClI G NH- n,

G l CH3 I M. P. 177 to 181' C.

- quantity proportion between the complex metal compound or the mixture for the forma- 'tion thereoi'arid the organic base is in the present processwith advantage so selected that a considerable excess of the base is present, that is to say for one atom of complex-bound metal several molecules of base are present, for example more than two 'or a still higher number.

The present invention renders it possible to dye on cellulosic fibers directly in a single bath and a single stage process, as complex metal compounds, without adding further materials to the dyebath apart from the customary auxiliary agents in the direct dyeing process such as sodium sulfate and/or sodium carbonate, direct dyeing azo dyestuffs of which the metal complexes are per se difiicultly soluble in water and which thereforegare unsuitable for dyeing as complex metal compounds, for which reason they are usually employed in the metal-free condition and are only converted into the metal compounds when they are at least for the most part fixed on the fiber. The bath ratio, that is to say the ratio of the quantity of the material to be dyed to the quantity of the dye liquor can in this case be varied within wide limits and can besuited to a far-reaching extent to the requirements of practice. If desired, as is customary in practice, prior to the preparation of the dyebaths, concentrated solutions, so-called stock solutions, can be formed with the base and the complex; metal, compound or with the base. the metal-free dyestufi and the agent providing metal, which solutions are then' diluted to the larger volumes necessary for dyeing.

According to the present process there are obtained in this manner as a rule dyeings which as regards color strength, purity of the dye shade and fastness properties are at least equivalent to and in part are superior to those dyeings which are obtained when a corresponding quantity-of dyestuffs free from metals and bases is dyed by the after-metallisation process.

In certain cases it may further be of advantage .to after-treat dyeings obtainable according to the present process with such agents as increase their wet fastness properties. This after-treatment can also take place in the presence of agents providing copper. As products which improve the wet fastness'properties of dyeing there may be mentioned among others the products of the action of formaldehyde on compounds such as cyanamide, dicyandiamide, dicyandiamidine, melamine and so on. Such after-treating agents are also concerned, in the production of which no formaldehyde is used. The application of after-treating agents containing copper is to be recommended especially when there are indications that during the dyeing a more or less farreaching de-coppering takes place.

Instead of bringing together the base and the complex metal compound or the base, the metalfree dyestufi and the agent providing metal, in the dyebath or in one of the previously mentioned, so-called stock solutions, it is to be recommended in general to work up the materials concerned to dry or if desired paste preparations. These new dyestuff preparations, suitable for carrying out the initially described dyeing process, accordingly contain a metal compound of a direct dyeing azo dyestufi, which compound per se is difficultly soluble and which contains in complex combination one of the metals with the atomic numbers 27 to 29, or a mixture for the formation thereof, and also contain an aliphatic base free from acid groups, which contains at least one basic nitrogen atom and atleast one hydroxyl group separated from the basic nitrogen atom by two carbon atoms and which base is solid, water-soluble and capable of imparting solubility to the complex metal compounds.

The dyestuif preparations are suitably produced by mixing the individual required components, for example in the dry state. They can however also be produced in the moist condition, for example in paste form or by combination of solutions or by association of moist or dissolved components of the mixture with dry components of the mixture followed if desired by drying. In the production of the dyestuff preparations by the wet method it is possible that preparations may be obtained in which at least a portion of the complex metal compound of the dyestuif has undergone chemical combination with the base. The preparations can also be subjected to admixture with further substances, such as urea or water-soluble carbohydrates, for example saccharose. On the other hand it is in general less to be recommended to incorporate in large quantities electrolytes such as sodium sulfate or sodium chloride. 4

The following examples illustrate the invention, the parts and percentages being by weight unless otherwise stated and the relation between parts by weight and parts by volume being the same as that between the kilogram and the liter. Where the production of dyebaths and stock solutions is described, as water preferably sodyelng results of good fastness to light and very ood fastness towashins.

- The same result is obtained when the 1:2-di(phydroxy-ethylamino) -ethan is replaced by the same quantity of any of the products which are obtainedby condensation in each case of 1 mol of 1:2-dichlorethane with 2 mols of isopropanolamine, 1-hydroxy-2-amino-2-methylpropane or 1 :3-dihydroxy-2 amino-2-methylpropane.

called condensed water (distilled water recovered from live steam) is to be employed.

Example 1 2 parts of 1 :Z-di-(p-hydroxyethylamino) -ethane are mixed with 1 part of the copper compound of the dyestuii which is obtained by phosgenation of 1 mol of 4-amino-4'-hydroxy-3'-carboxy-1:1'- azobenzene and 1 mol of the condensation product of 4-amino-2-methyl-5-methoxy-4'-hydroxy- 3'-carboxy-1:1'-azobenzene-5-sulfonic acid with 4-nitrobenzoyl chloride of which product the nitro group has been reduced to the amine.

With this dyestuff preparation cotton can be dyed for example in the following manner:

3 parts of the dyestuflf preparation are covered with 200 parts of hot water and the whole brought to the boil. From the stock solution obtained there is prepared by dilution with water to 3000 parts by volume and addition oi. Z'parts of anhydrous sodium carbonate, a dyebath into which at about 60 C. are entered 100 parts of previously wetted cotton. Within hour the temperature is raised to boiling and it is maintained for one hour at boiling temperature, during which after 5 minutes and after 20 minutes boiling in each case 20 parts of crystalline sodium sulfate ar added.

After rinsing and drying of the cotton a yellow Similar dyeings are obtained when the copper compound is replaced by the nickel or cobalt compound of the dyestufl initially mentioned.

Example 2 Equal parts are mixed of 1:2-di-(p-hydroxyethylamino)- ethane and the copper compound of the dyestufi which is obtained as follows:

1 mol of the monoazo dyestufl from diazotized 1-amino-4-hydroxy-5-carboxybenzene and 1- aminonaphthalene-I-sulfonic acid is diazotized and coupled with 1 mol of l-aminonaphthalene. The amino compound obtained is again diazotized and coupled in an alkaline medium with 1 mol of 2-amino-5-hydroxynaphthalene 7 sulfonic acid.

With this dyestufl preparation cotton can be dyed for example as follows: I

2 parts of the dyestufl preparation are covere with 200 parts of water and the whole brought to the boil. From this stock solution is prepared by dilution to 3000 parts by volume and addition of 2 parts of anhydrous sodium carbonate, a dyebath into which at about 60 C. are entered parts of previously wetted cotton. Within $4; hour the temperature is raised to boiling and the whole is maintained for 1 hour at boiling temperature during which after 5 minutes and after 20 minutes boiling in each case 20 parts of crystalline sodium sulfate are added. The dyeing is rinsed in the cold, in which operation there iS advantageously added to the final rinsing bath 1 part of the condensation product which is obtained when dicyandiamidine is heated with 4 times the quantity of 30 per cent. commercial formaldehyd for about 10 minutes to 100 C. and the dyeing is allowed to remain in this bath for about 5 minutes.

A blue dyeing results of excellent fastness to light and washing.

By employing instead of 1:2-di-(p-hydroxyethylamino) -ethane the bases mentioned in paragraph 5 of Example 1, equal results are obtained.

Example 3 Equal parts are mixed of 1:2-di-(p-hydroxyethylamino) -ethane and the copper compound of the dyestufi' which is obtained as follows:

1 mol of l-(4'-amino-l:1'-diphenyl-4-)-3- methyl-pyrazolone-(S) is converted by means of phosgene into the symmetrical urea derivative and the latter is coupled with 1 mol of diazotized l-amino-2-carboxybenzene-4-sulfonic acid.

With this dyestufl preparation cotton can be dyed for example as follows:

3 parts of the dyestufi preparation are covered with 200 parts of hot water and the whole brought to the boil. From the stock solution obtained there is prepared by dilution with water to 3000 parts by volume and addition of 2 parts of anhydrous sodium carbonate, a dyebath into which at about 60 C. are entered 100 parts of previously wetted cotton. Within 4 hour the temperature is raised to boiling and the whole is maintained for 1 hour at boiling temperature during which after following constitution Y After rinsing and drying of: the cotton a. yellow dyeing results of goodifastnesslto lightand washing.

. Example 4 2 parts -of 1:2 11i-(p-hydroxyethylaminolethane; 3'parts of-saccharose and tpartofthe copper compound of the dyestufi from r'rnol'of tetrazotized 4 :4 -diamino'-3:3"- dihydroxy-1: 1

diphenyl and 2 mol'of 2-amino-5 hydroxynaphthalene-7-sulfonic acid, are mixed together.

With this dyestufl preparation cotton *can be dyed for example as'follows:

-dium carbonate; a dyebath into which at about 60 C. are entered 100 partsof previously wetted cotton. "Within hour the temperature is raised I 2 parts of thedyestufi preparation are covered with 200 parts of water and the whole brought to the -boil.. From .the stock solution obtained there is prepared byidilution with 2800parts 'of water and additionvof 2 parts. oLanhydrous sodium carbonate; a dyebath into whichat about 60 C. are entered 100. parts-of previouslywetted cotton. 'Within 14-hour the temperature is raised to boiling. and theuwholeis maintained for 1 hour at boiling. temperature during which after 5 minutes and after minutes-in each case- 20 parts of crystalline-sodium sulfate .are added.

After rinsing and. drying 'oither-cotton a blue dyeing is produced-=0! excellent fastness to' light and washing.

Prior. to drying' the dyeingzl can :be further treated in a bath ratioof 1:30. ford/ 'hourat ordinary temperaturewith 4 per. cent of a preparation containing per- 100: parts-32 parts of a condensation: product =from dicyandiamidine and formaldehyde; -l1 parts of copper acetate,- 31' parts of sodium carbonateandam parts of ammonium chloride. The dyeing thus treated exhibits a "still further improved *fa'stness' to washing.

..E2ample 5 There'are mixed-together 2 parts of 1:2-di- (fi-hydroxyethylamino) -ethane with 1 part of-the copper compoundofthe dyestuff whichisobtained by careful reduction with glucosein an alkaline medi'um or the disa'zo' 'dye'stuff" of "the -With this fldyestufi preparation cotton can be "dyed for-example as'follows:

2 parts of the dyestufi preparation are covered witliZOO parts or hotwater and the whole brought to-theboil. *From-fthis-stock s'olution'there is preparedby dilution-"with water 'to"30001'parts by 'volume-and addition"of 2-partsof-'anliydrous soto boiling and-the whole is maintained for 1 hour at-boiling-temperature during which after 5 minutes and after 20minutes boiling in each case 20 parts of crystalline sodium sulfate are added.

After rinsing and drying of the cotton a grey dyeing results of very good fastness to light and washing.

Example 6 2*parts'of the dyestuff of the formula areintimately ground with 4 parts of 1:2-di-(flhydroxyethylamino) -ethane and 1 part of sodium copper tartrate.

3 parts of this preparation are dissolved in 200 parts of hot water and added to a dyebath of 2800 parts of water and 2 parts of anhydrous sodium carbonate. At about C. are entered parts The bath is dyeing possesses a good'fastness to washing and an excellent fastness to light.

i using instead of the above dyestuif 2 parts of thedyestuif. of the formula -SO3H oonrcoon l 1103s NHGOC omooon a-preparationis obtained which dyes cotton in navylblue shades fast to washing and light.

What we claim is:

1. Process for dyeing cellulosic materials whichcomprises carrying out the dyeing with 2.

- metal.compound'diflicultly solubleper se of a direct dyeing azo'dyestu'ff which contains in complex union one 'of the metals with the atomic numbers 27 to 29 in the presence of a solid base of the composition R1 CRH2 1i=(-"N'H(J-*CHT OH)2 wherein R1- stands for-a member selected from thegroup consisting of a hydrogen atom, an alkyl groupwith at-the most three carbon atoms and e'ahydroxymethyl. group, R2 stands for a member selected from the group consisting of a hydrogen atom and a 'methyl group and n represents a whole-number up to 4.

2. Process for'dyeing cellulosic materials which comprises" carrying out the 'dye'lng'with a metal compound dimcultlysolubleper se'of a direct dyeing azo dyestuff which contains in complex union -one"-of--tl'1e"rhetdlswith" theatomic numaeeaeoe hers 27 to 29 in the presence of the base correspondingtothe formula p a HOCH2-CH2-HN-CH2 I I CHhNH-CHQ-CHP-O A H 3. Process for dyeing cellulosic materials which v 1 p 7. Process for dyeing cellulosic materials which comprises, carrying out the dyeing with the come '-p1ex copper compound of the dyestufl corresponding to the formula H H? 0 B H0 SOIH H015 NH comprises carrying outthe dyeingiwith a complex copper compound diflicultly soluble per se of a direct dyeing 'azo dyestufi in the presence of the base corresponding to the formula 4. Process for dyeing vcellulosic materials which comprises carrying out the dyeing with the complex copper compound of the dyestufl corre- 30 sponding to the formula HO M WLW CW in the presence of the base corresponding to the formula 5. Process for dyeing cellulosic materials which I comprises carrying out the dyeing with the complex copper compound of the dyestufl correspending to the formula in the presence of the base corresponding to the formula Ho cH1-crre-NH+cma 8. Process for dyeing cellulosic materials which ,comprises carrying out the dyeing with the dyestufi of the formula COOK in the presence of sodium copper tartrate and of the base corresponding to the formula 9. A dyebath containing a metal compound dimcultly soluble per se of a direct dyeing azo dyestufi which contains in complex union one of the metals with the atomic numbers 27 to 29 and also containing a solid base of the composition wherein R1 stands for a member selected from in the presence of the base corresponding to the formula HMHPCHZ-NH-CHQ- 6. Process for dyeing cellulosic materials which comprises carrying out the dyeing with the complex copper compound of the dyestufl corresponding to the formula COOH Z i l C=N lHl in the presence of the base corresponding to the formula HO-CWNH-Cflrthe group consisting of a hydrogen atom, an

alkyl group with at the most three carbon atoms and a hydroxymethyl group, Rx: stands for a member selected from the group consisting of a hydrogen atom and a methyl group and n represents a whole number up to 4.

oo oc -i o-N-N om .Y 10. A dycbath containing a metal compound difncultly soluble per se of a" dyeing azo dyestufi which contains in complexunion one of C I-Ia-NHCH:CHz-OH the metals with the atomic numbers 27 to 29 i i-seO Qs 11 and also containing the'base corresponding to theformulap.

11. A dyebath containing a complex copper compound diflicultly soluble per-se-of' a direct dyeing azo dyestufi and also containingthe base corresponding to the formula 12. A dyestufi preparation containing a metal compound, difllcultly, soluble; per per-f: :a direct:

dyeing azo dyestuif which contains in complex-:- union one of the metals .with ,the atomic hum-r bers,27 to 29 and alsoucontaining a solid base of the composition R1 CH:,. =(-NH !ICHI:OH)L;

wherein R1 stands for a member selected from the group consisting of a hydrogen atom,-an alkyl 7 group with at the most three carbon atoms and a hydroxymethyl group, R1 stands for a member:

selected from the group consisting of'a hydrogen atom and a methyl group and n represents a wholenumbereup to 4.1.

13. A dyestufl preparatiomcontaininga metal.

14.-A;-dyestufi preparation containing a com- 'plex copper compound difficultly soluble per se of -a directadyeing azo dyestufi and also containing thebase corresponding to the formula.

KAI MEN ZI. HENRI RIAT. J ACQUES'" WEGMANN.

References Cited in the file of this patent UNITED STATES PATENTS Name Date Straub Sept. '7, 1937 Number

Claims (1)

1. PROCESS FOR DYEING CELLULOSIC MATERIALS WHICH COMPRISES CARRYING OUT THE DYEING WITH A METAL COMPOUND DIFFICULTY SOLUBLE PER SE OF A DIRECT DYEING AZO DYESTUFF WHICH CONTAINS IN COMPLEX UNION ONE OF THE METALS WITH THE ATOMIC NUMBERS 27 TO 29 IN THE PRESENCE OF A SOLID BASE OF THE COMPOSITION