US3617168A

US3617168A - Dyeing process for blends of cellulosic and polyester fibres

Info

Publication number: US3617168A
Application number: US715517A
Authority: US
Inventors: Rolf Mack
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1967-04-07
Filing date: 1968-03-25
Publication date: 1971-11-02
Anticipated expiration: 1988-11-02
Also published as: FR1561622A; CH499467A4; DE1769090C2; DE1769090B1; CH468516A; GB1189415A; NL6804758A; ES352435A1; BE713162A

Abstract

A process for dyeing blends of natural or regenerated cellulosic fibers and polyester fibers with reactive and disperse dyes, wherein the cellulosic component of the blend is dyed first with reactive dyes at temperatures in the range of 40* to 100* C. and in the pH range of 8.5 to 13, after which the pH is adjusted to 4-7, the disperse dye added and the polyester component of the blend dyed.

Description

United States Patent Rolf Mack Binningen Baselland, Switzerland Mar. 25, 1968 Nov. 2, 1971 Assignee Sandoz Ltd., also known as Sandoz A.G.

Basel, Switzerland [32] Priority Apr. 7, 1967 [3 3] Switzerland Inventor [21 Appl. No.

Filed [45] Patented US. 01 8/21C, 8/14, s/54.2, 8ll79, 8/163 5 l] Tit- Cl D06p 3/82 [50] Field of Search 8/l4, 54.2, I79, 21

Primary Examiner-George F. besmes Assistant Examiner-H. Wolman Anorneylrwin Morton Aisenberg ABSTRACT: A process for dyeing blends of natural or regenerated cellulosic fibers and polyester fibers with reactive and disperse dyes, wherein the cellulosic component of the blend is dyed first with reactive dyes at temperatures in the range of 40 to 100 C. and in the pH range of 8.5 to [3, after which the pH is adjusted to 4-7, the disperse dye added and the polyester component of the blend dyed.

DYEING PROCESS FOR BLENDS OF CELLULOSIC AND POLYESTERFIBRES The dyeing of blends of cellulosic and polyester fibers with reactive and disperse dyes by a one-bath process is already known (cf. French Pat. No. l 377 781). This process, in which not more than grams of a basic fixing agent per litre dyeliquor are used, is timesaving compared with a two-bath procedure and consequently the output is greater for a given period of time. However the process requires that the dyes, more particularly the disperse dyes, are stable to alkalis, and it functions satisfactorily only with selected disperse dyes.

it has now been found that this great disadvantage can be overcome by conducting the one-bath process in two stages, the blend being dyed in the first stage with reactive dyes under alkaline conditions and at temperatures up to 100 C. and in the second stage with disperse dyes under weakly acid conditions, either at about 100 C. in the presence of a carrier or above 100 C. under static pressure.

Thus the distinctive feature of this new process for dyeing blends of natural or regenerated cellulosic fibers and polyester fibers with reactive and disperse dyes is that the cellulosic component is dyed initially with reactive dyes in the presence of atleast one neutral salt and not more than 20 grams of a basic fixing agent per liter dyeliquor at a temperature in the range of 40 to 100 C. and at a pH of 8.5 to 13 or preferably to 13, following which the ph of the bath is adjusted to 4 to 7 the disperse dye added and the polyester component dyed.

Cotton, linen, hemp, jute and ramie may be mentioned as examples of natural cellulosic fibers which may be present in the blend, while viscose filament and spun rayon and cuprammonium rayon are examples of regenerated cellulosic fibers. These materials can be dyed by the new process, which belongs to the group of exhaustion dyeing processes, in the form of monofilament or multifilarnent, yarns, sliver, woven fabrics, knitted goods and other textiles. Cellulosic monofilament and multifilament yarns are blended with polyester yarns, generally those spun from the polyesters formed by polycondensation of terephthalic acid and glycols, preferably ethylene glycol or 1,4-bis-(hydroxymethy1)-cyclohexane, and the blend is dyed either in the yarn form or after weaving or knitting in piece form. For one-bath dyeing the dyebath is set with reactive dyes for the natural or regenerated cellulosic fiber and after the dyeing of the cellulosic fiber with disperse dyes for the polyester component of the blend.

The suitable reactive dyes are those bearing a substituent which forms a chemical linkage with the fiber, for example a halogen atom readily cleavable as an anion, preferably a chlorine or bromine atom, or a group cleavable as an anion, e.g. --OSO,H, or a C-C multiple linkage capable of additive reaction. These dyes may belong to the azo, anthraquinone, phthalocyanine or nitro series and may bear any of the following groups or radicals:

a. at least one dich1oro-, trichloro-, dibromoor tribromopyrimidyl, 2,4-dichloro-6-methyl, 2,4-dibromo-6-methyl, 2,4-dichloroor 2,4-dibromo-phrimidy1-5-methylene group bound through an oxygen or sulfur atom or through an imino group which may itself be substituted;

b. a group of the formula which may be substituted, said group of formula (1) being bound through an oxygen or sulfur atom or an imino group c. a 4,6-dichloro or 4,6-dibromo-1,3,5-triazinyl-2-group which is bound through an oxygen or sulfur atom or an imino group which may be substituted: d. the group SO CH CH,OSO,H or SO,CH

f. a 2,3-dichloroquinoxalylfi-carbonyl, 4-(4',S dichloropyridazon-6'-yl-l ')-phenylcarbonyl or B-(4",5'- dichloropyridazon-6-yl-l')-propionyl group bound through an imino group which may be substituted;

g. a B-chloro-, B-bromoor B-sulphato-propionyl group or acrylyl group bound through an iminov groupwhich may be substituted.

Dyes of the aforementioned type are described for example in the following patent specifications:

a. French Pat. No. 1,221,621 (dichloroor dibromopyrimidylamino radical) Belgian P atent 578,742 and Austrian Patent 214,546

g. Belgian Pat. No. 565,279 B-chloropropionyl or acrylyl radical.

The preferred reactive dyes are those which exhaust on cellulosic fibers to an acceptable degree for a bath containing a neutral salt. This practical rule is well known to the textile colorist and its application in the present process can be illustrated by saying that dyes are used which exhaust on the cellulosic fibers in the presence of about grams or more of sodium sulfate or sodium chloride per liter of the dyebath.

Reactive dyes of special interest for the process are those which bear one of the reactive groups defined in (a) or (b) above and which are absorbed by cellulosic fibers in the presence of about 40 to 80 grams of sodium sulfate or sodium chloride per liter of dyebath at pH 10 to 13 to a degree which leaves the bath practically exhausted. The disperse dyes used may belong, for example, to the monoazo, disazo, anthraquinone, nitro, styryl'or quinophthalone series. These form stable dispersions in the weakly to very weakly acid dyebaths at the stated dyeing temperatures and have good affinity for polyester fibers and good light fastness. Their melting points are almost invariably higher than 100 C. and in general are superior to 140 C. [see the table in the Journal of the Society of Dyers and Colorists 70, pages 69-71, 1954) and the Discussion in 74, page 389, (1958)]. The water solubility of these dyes at 80 C. is in general not greater than 100 milligrams per liter, i.e. 1:10.000 [Journal of the Society of Dyers and Colorists 70, 69-7] (1954)] and is preferably between about 0.2 and 50 milligrams per liter. The dyes contain no ionizing groups, such as COOH and SO,H, and no groups radical;

-whieliare readily convened into -COH or -$O H groups under the dying conditions.

Examples of disperse dyes of the aforedescribed nature are described in the following journals and books:

Journal of the Society of Dyers 6c Colourists 70, 68-75,

Canadian Textile Journal, May 1, 1959, 49-59;

American Dyestufr' Reporter 48, 14,35-47 (1959) 49,

Ullmann, Enzyklopadie der technischen Chemie, V01. 3 726-8, 1953, (anthraquinone dyes); Vol. 4 128-9, 1953 (azo dyes);

French Patents 1 167 704; 1,177,337; 1,207,000; 1,220,194; 1,222,237; 1,226,501; 1,237,149; 1,264,972; 1,280,998; 1,281,023; 1,291,988; 1,261,580;

Frgnch) Additional Patents 75,125; 76,452; 78,167; (Azo French Patents 1,163,682; 1,218,936; 1,225,449 (anthraquinone dyes;

French Patent 1,129,460; British Patent 1,040,607

(nitro dyes);

Ggrmssn Patent 677,641; British Patent 843,644 (styryl yes Fixing agents are used which have a pH value of at least 8.5 in aqueous solution at C., for example sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium or potassium bicarbonate, trisodium phosphate, or a sodium or potassium silicate with a molecular ratio of SiO :Na O or siO zK o of 1:1 to 3.5:], e.g. a sodium or potassium metasilicate or sodium water-glass.

Suitable neutral salts include sodium chloride or sulfate and potassium chloride or sulfate.

The cellulosic component of the blend is dyed at 40 to 100 C. or, preferably, at 80-95 C. at a goods to liquor ratio of 1 about 1:4 to 1:30 or, preferably, 1:5 to 1:15. The amount of basic fixing agent used musfiaeso bzdculated that Ii'riJEre' amount of hydrogen halide liberated in fixation is bound and the pH of the bath does not fall below 10. At short liquor ratios, e.g. 1:4 to about 1:8, and high reactive dye concentrations, e.g. 5-10 percent on the weight of the goods, the amount of basic fixing agent per liter must be greater than the amount used for dyeing at medium or long liquor ratios. Generally, an addition of 2 to 20 grams of potassium or sodium carbonate or trisodium phosphate or 0.2 to 1.2 grams of potassium or sodium hydroxide per liter dyebath suffices. The dyeing time is about 15 minutes at least and generally 30 to 60 minutes; it depends on the reactive dye used, the nature of the cellulosic component of the blend, the dyeing temperature, the alkali concentration and the alkalinity of the dyebath.

For pale dyeings which require less than 1.0 to 1.5 percent the weight of the goods) of a solid disperse dye preparation consisting of about 30-35 percent dye, about 50 percent dispersing agent and 15-20 percent standardizing material, it is advisable to add about 0.5 to 2.0 grams per liter of a dispersing agent to the dyebath prior to the addition of the dye; this recommendation also applies when disperse dyes in liquid form are used,

After the cellulosic component has been dyed to shade, the pH of the bath is adjusted to 4 to 7 or, preferably, 5-6.5. For this purpose any of the acids commonly used in dyeing can be employed, such as acetic, sulfuric or phosphoric acid, or an acid salt, such as sodium or, potassium hydrogen sulfate, or preferably, a primary phosphate of formula Mel-130,, where Me represents an alkali metal (sodium, potassium), ammonia or a low molecular alkylammonium radical (CB -N11 (CH NHB? etc.). When the alkali has been neutralized am the pH adjusted to 4 to 7, the disperse dye is added, for example, in aqueous dispersion or in solution in a suitable organic solvent or mixture of such solvents. The polyester component is then dyed in the presence of a carrier, for example a chlorinated benzene, 1-hydroxy-2-phenylbenzene or a mixture of terephthalic acid dimethyl ester, benzoylaminobenzene and sodium sulfate, at 95-100 C. or at at temperatures about C., e.g. 1 10-140 C. or, preferably, l20-l 30 C., under static pressure.

The dyed yarn or fabric is rinsed, washed off with soap and sodium carbonate or with an anionic or nonanionic detergent and sodium carbonate as required, then rinsed again and dried. When the carrier used is 1-hydroxy-2-phenylbenzene, it is advisable to expose the dried yarn or fabric to dry heat for a short time, for example for 1 minute at 190200 C., in order to eliminate all traces of this compound. The dyeings are of full shade and have good fastness to light, sublimation, dry heat treatments and dry cleaning, together with excellent fastness to water, perspiration, rubbing and washing at temperatures up to 100 C.

in comparison with the process described in French Pat. specification No. 1,377,781 the present process has the advantage that any desired disperse dyes can be used, including those which are not stable to alkaline solutions on heating. For example, the dyes whose formulas are shown below give excellent results when applied by the present process, whereas in the known process the dye mai'ked is entirely decomposed and dye builds up only to weak depth on the polyester fiber, probably owing to saponification of the ester group to the COOH- group:

and

British Patent 841,927, Example 33 in the examples that follow the parts and percentages are by weight and the temperatures in degrees centigrade.

EXAMPLE 1 The bath is set at 60 with 500 parts of water, 1 part of sodium 3-nitrobenzenesulphonate, 20 parts of calcined sodium sulfate, 2.5 parts of calcined sodium carbonate and 1 part of the dye of the formula NBOQS OzNB 100 parts of a blend yarn consisting of 33 parts of regenerated cellulosic fiber and 67 pans of polyester fiber of the polyethylene-terephthalate type are entered into the bath. The bath is circulated for 15 minutes at 60, its temperature then raised to 85 in 30 minutes and this temperature held a further 30 minutes with constant circulation. At this point 15 parts of primary sodium phosphate (NaH,PO;2H O) and 2 parts of a dye preparation of 35 percent of the dye 2,6-dich1oro-4-nitro- 4'-(N-B-cyanethyl- N-B-acetoxyethylamino)-l ,1 azobenzene 25 percent sodiumdinaphthylmethanedisulphonate, 20 percent sodium cetyl sulfate and 20 percent calcined sodium sulfate are added. The bath is raised to over the next 30 minutes or so and dyeing is continued at this temperature for l the boil. Alternatively, it can be dyed in the absence of carrier 75 hour. it is then cooled to 60 in 20 minutes and the dyed yarn is rinsed with hot water, soaped for minutes at the boil, rinsed again in hot and cold water and dried. The resulting yellow-orange dyeing is fast to light and has very good wash fastness.

EXAMPLE 2 100 parts of a blend yarn consisting of 33 parts of cotton and 67 parts of polyester fiber are entered into a bath at 60 composed of 1500 parts of water, l.5 parts of sodium 3- nitrobenzenesulphonate, 60 parts of calcined sodium sulfate, 7.5 parts of trisodium phosphate (Na PO -l0l-l O) and 0.9 part of the dye of the formula The circulating liquor is held at 60 for 15 minutes and then raised to 85 in 30 minutes. Dyeing is continued for 30 minutes at this temperature, after which time are added 9.5 parts of primary sodium phosphate and 2 parts of a dye preparation made up of 35 percent of the dye 2-chloro-4- nitro-4'-( N-B-cyanethyl-N-fl acetoxyethylamino l ,l azobenzene (g), percent sodium dinaphthylmethanedisulphonate, 20 percent sodium cetyl suphate and 20 percent calcined sodium sulfate. The dyeing cycle is brought to a close as described in example l. The scarlet dyeing obtained has very good light and wash fastness.

EXAMPLE 3 100 parts of a blend yarn spun with 67 parts of a polyester fiber of the type named in example 1 and 33 parts of regenerated cellulosic fiber are entered into a bath consisting of 3,000 parts of water, 6 parts of sodium 3- nitrobenzenesulphonate, 120 parts of calcined sodium suphate, 1.2 parts of sodium hydroxide and 0.9 part of the dye of the formula The dyeliquor is circulated for 15 minutes at 60 and then raised to 85 in minutes. The blend yarn is dyed at this temperature for a further 30 minutes. After this time 10 parts of primary sodium phosphate are added to the circulating liquor, followed by 1.8 parts of a dye preparation consisting of percent brominated l,5-dihydroxy-4,S-diaminoanthraquinone (5) 25 percent sodium dinaphthylmethanedisulphonate, methanedisulphonate, 20 percent sodium cetyl sulfate and 20 percent calcined sodium sulfate. The bath is raised to 130 in 30 minutes and held at this temperature for minutes. Over the next 20 minutes it is cooled to 60 and subsequently the dyed yarn is rinsed with hot water, soaped for 20 minutes at the boil, rinsed again with hot and cold water and dried. A

level blue dyeing is obtained which is fast to light and wet treatme HIS b The bromin ated l,S-dihydrmty i,S-diaminoanthraquinone of the aforestated dye preparation can be replaced by the dye Z-hydroxy- 5-methyl-4'-benzoylamino-l ,l -azobenzene 7 or the dye of the formula Alternatively, dye 5 can be replaced by dye l to give two-color effects on the blend with a green overall appearance.

EXAMPLE 4 A dyebath is set at 60 with 1,500 parts of water, l.5 parts of sodium 3-nitrobenzenesulphonate, 90 parts of calcined sodium sulfate, 0.9 part of sodium hydroxide and 1.8 parts of the dye of the formula 100 parts of a blend yarn consisting of 33 parts of cotton and 35 67 parts of a polyester fiber of the type mentioned in example I are entered into the bath, which is then circulated for 30 minutes while the temperature is raised to 90". This temperature is maintained for a further 30 minutes. At this point the bath is set for polyester dyeing with 7 parts of primary sodium phosphate and 3.8 parts of a dye preparation composed of 30 percent 2-bromo-4,6-dinitro-2'-acetylamino-4'-[N,N-bis (B- acetoxyethyl)-amino] -5'-ethoxy-l,l-azobenzene 10, 30 percent sodium dinaphthylmethanedisulphonate, 20 percent sodium cetyl sulfate and 20 percent calcined sodium sulfate. This second stage of dyeing is carried out as detailed in example l. A level navy dyeing is obtained which is fast to light and wet treatments.

E EXAMPL 5 100 parts of a blend yarn composed of 33 parts of cotton and 67 parts of a polyester fiber of the type named in example I are entered into a bath consisting of 1,500 parts of water at 60, 1.5 parts of sodium 3nitrobenzenesulphonate, 60 parts of calcined sodium sulfate, 0.75 part of sodium hydroxide and 0.9 part of the dye of the formula The circulating liquor is held at for 15 minutes, raised to 95 in 30 minutes and held at this temperature for l hour for cellulosic fiber dyeing. Subsequently the bath is set with 6 parts of primary sodium phosphate and 1.8 parts of a dye preparation of 35 percent 2-cyano-4-nitro-4'-(N-ethylN-B- cyanethylamino)-l,l '-azobenzene l2, 30 percent sodium dinaphthylmethanedisulphonate, 20 percent sodium cetyl sulfate and 15 percent calcined sodium sulfate. Dyeing is finalized as detailed in example I and gives a ruby dyeing which is fast to light and wet treatments.

EXAMPLE 6 A dyebath is prepared at 60 with 2,000 parts of soft water, 4 parts of 3-nitrobenzenesulphonate, 80 parts of calcined sodium sulfate, parts of trisodium phosphate (Na PO,-l0H O) and I part of the dye of the formula S O;Na O CH;

NONE-triehloropyrimidyl 100 parts of a blend yarn consisting of 33 parts of regenerated cellulosic fiber and 67 parts of polyester fiber and entered into the bath, which is circulated for IS minutes at 60, after which the temperature is increased to 85 in 30 minutes. Dyeing is continued for 30 minutes at this temperature. At this point further additions ar e made as follows: 8 parts of 60 percent acetic acid, 2 parts of sodium methanedisulphonate, 4.5 parts of the sodium salt of lhydroxy-2-phenylbenzene in aqueous solution, 0.5 part of a highly sulfonated castor oil and 1.5 parts of a dye preparation composed of 35 percent dye 4 (example 2), 25 percent sodium dinaphthylmethanedisulphonate, percent sodium cetyl sulfate and 20 percent calcined sodium sulfate. The bath is raised to the boil in 30 minutes and dyeing is conducted for l-2 hours at this temperature. Subsequently the dyed yarn is removed, rinsed with hot water, soaped at the boil for at least 20 minutes in a weakly alkaline bath, rinsed again with hot and cold water and dried. The orange-red dyeing is fast to light and washing.

EXAMPLE 7 A dyebath is prepared in a high temperature dyeing machine with 1,500 parts of water, 3 parts of sodium 3- nitrobenzenesulphonate, 60 parts of calcined sodium sulfate, 7.5 parts of trisodium phosphate (Na,PO -l0H,O), 0.8 part of the dye of the formula N H-trlchloropyrlmldyl and 0.08 part of dye 1 (example 1). At 60 100 parts of a blend yarn consisting of 67 parts of polyester fiber and 33 parts of regenerated cellulosic fiber are introduced into the bath. It is then circulated for IS minutes at 60 and over the next 30 minutes is raised to 85, the blend being dyed for a further 30 minutes at this temperature. Circulation is continued while the bath is set with the additions for the second stage of dyeing: 3.8 parts of 60 percent acetic acid, 1.5 parts of sodium dinaphthylmethanedisulphonate and 1 part of a mixture of percent sodium dinaphthylmethanedisulphonate, 20 percent sodium cetyl sulfate, 20 percent anhydrous sodium sulfate, 17 percent dye 4 (example 2) and [8 percent dye of the formula S O NH 11 I dinaphthyl-.

The bath is raised to l in 30-40 minutes and held at this temperature for 45 minutes. It is then cooled to 80 and the dyed blend is removed, rinsed with hot water, soaped for 20 minutes at the boil, rinsed again with hot and cold water and At 30 I00 parts of a blend yarn consisting of 33 parts of regenerated cellulosic fiber and 67 parts of polyester fiber are entered into the bath and turned regularly for IS minutes at the same temperature, after which time the bath is raised to 60 in 30 minutes and the yarn dyed for a further 45 minutes at this temperature. At this point the following additions are made: 7.5 parts of 60 percent acetic acid, 0.75 part of sodium dinaphthylmethanedisulphonate and 2 parts of the dye preparation used in example 3 (dye 6). Over the next 30-40 minutes the bath is raised to l30 under static pressure and the dyeing process is brought to a close in l hour at this temperature. The dyed yarn is removed from the bath. rinsed with water, soaped at the boil for 20 minutes in a neutral or weakly alkaline bath, rinsed again with hot and cold water and finally 40 dried. The blue dyeing is fast to light and very fast to washing.

EXAMPLE 9 100 parts of a blend yarn composed of 67 parts of polyester fiber and 33 parts of viscose staple fiber are entered at into Over the next 30 minutes 75 parts of calcined sodium sulfate are added and over the subsequent 30 minutes l8 parts of trisodium phosphate (Na,PO,'l0H,O), in both cases in three portions. After the addition of the final portion of trisodium phosphate dyeing is conducted for 90 minutes at 40. The circulating bath is then set for polyester dyeing with 9 parts of percent acetic acid and 5 parts of a dye preparation formulated with 30 percent lamino-2-phenoxy-4-hydroxyanthraquinone I8, 60 percent sodium dinaphthylmethanedisulphonate and 10 percent sodium ligninsulphonate. The bath temperature is increased to I30 in 30-40 minutes and this temperature is maintained for 60 minutes. Subsequently the bath is cooled to 90 and dropped. After a short rinse with hot water the dyed yarn is soaped at the boil for l5-30 minutes, rinsed again with hot and cold water and dried. It is dyed in a brilliant red which is fast to light and wet treatments.

EXAMPLE 10 75 a p a parts of a blend yarn spun with 67 parts of polyester fiber and 33 parts of viscose staple fiber are entered at 50 into a dyebath set with 1,500 parts of water and 0.7 part of the dye of the formula After minutes 60 parts of calcined dium sulfate are added to the circulating bath and after a further 10 minutes 9.75 parts of sodium bicarbonate. Dyeing is continued for 90 minutes at 50, following which the bath is set with l 1.6 parts of 60 percent acetic acid and after brief intermediate circulation with 2 parts of a dye preparation composed of percent l-amino-4-hydroxy-2-methoxy-ethoxy-etho )xyanthraquinone 20, 50 percent sodium dinaphthylmethanedisulphonate and 25 parts sodium ligninsulphonate. Over the next -40 minutes the bath temperature is increased to 130 and the dyeing cycle completed in 60 minutes at this temperature. The bath is then cooled and dropped, the dyed material rinsed with hot water, soaped at 100 for 20 minutes, rinsed again with hot and cold water and dried. The resulting red dyeing is fast to light and wet treatments. The following table contains further examples of dyeing in accordance with the present process, for which the procedures and conditions detailed in examples 1 to 10 were employed. In the following the composition of the blend fabric dyed in these examples and the additions to 30 figf f h gggg the dyebaths are set forth.

Blend Fabric:

33 percent Cotton/67 percent polyethylene terephthalate fiber in examples 17, 26, 28 and 37 33 percent Viscose filament/67 percent polyethylene terephthalate fiber in examples 1 l and 29 33 percent Viscose staple fiber/67 percent polyethylene terephthalate fiber in examples [2 to l6, 19, 22, 27, 31, 32, 33 and 36.

50 percent Cotton/50 percent polyethylene terephthalate fiber in examples 18, 25, and 30.

50 percent Viscose staple fiber/50 percent polyethylene terephthalate fiber in examples 20, 21 and 24.

33 percent Cotton/67 percent polyester fiber from terephthalic acid and l,4-di-(hydroxymethyl)-cyclohex- @912 ex mp es 3 and Neutral Salt (terme salt" in the table) 7 Basic compounds (termed alkali in the table) K,CO, in examples l4. l6 and 30 Li,CO in examples l2 NaHCO, in examples l8 and 20 KHCO in example l9 Na,SiO,9l-l,0 in example 23 K,Si0, in example 26 Na,B,O,-l0H O in example 22 Na,PO,lly.l0H,O in examples I7, 21, 24, 27,

28, 31 to 33 and 35 K 1 0 in examples l5 and 29 Neutralizing agent (termed acid in the table) Some of the dyebaths contained additionally sodium 3- nitrobenzene-l-sulfonate as a mild oxidizing agent, i.e.

2 parts in examples 13,28, 26, 33 and 37 3 parts in examples l4, 15, 22, 23, 24, 31, 34, 35, 36

4 parts in examples 1 l, 12, 27 and 32 5 parts in example 29 Further, a carrier was used for the disperse dyes in the following instances:

in Examples 11, 12, 16, 29 and 32 emulsion 1.2 parts of a highly sulphononated castor oil 10 parts of methyl salicylate 1 part of a. highly sulphonated Castor oil 10 parts of a mixture of equal parts of dimethyl terephthalate and benzoic acid anilide 4 parts of para-chlorophenoxyethyl acetate 1 part of the compound lJH19)2= O a( 2 l) 50-O--CH2 COONa The disperse dyes were applied in the form of dye preparations of the following composition:

35 percent Dye 35 percent Sodium dinaphthylmethanedisulphonate 15 percent Sodium cetyl sulfate 15 percent Sodium sulfate The dyeing process was phased as follows: 30 minutes for heating up to the dyeing temperature for the cellulosic component of the blend: 60 minutes at the dyeing temperature for the cellulosic component; cooling and addition of the acid and in Examples 14 and 15 }in Example 36 in Examples 27, 30, 31 and 33 1" the disperse dye; 30 minutes for heating up to the dyeing tem- 1" erature for the ol ester com onent; 1 hour at the d ein K0 in examples 34 p p y p y g 'Na'coi in "mph, 25 and 37 temperature for the polyester componeptgf the blend.

J; TAB LE Reactive Prepara- Water (1 e Alkali Salt Dyed at Acid Disperse tion Dyed at No. of Example (parts) (parts) (parts) (parts) (deg) (parts) dye (parts) (deg.) Shade 2,000 1. 5 (D 0. 80 85 2. 3 g 3 95-100 Orange yellow. 2, 000 1. 5 g 7 80 85 10. 2 3 95-100 D0. 1, 01: 1 0.? $3 560520 g 2 130 1 5 5 1.8 115-100 e ow. 1: 500 1 s. 4 00 -65 7. 5 1. 5 05100 Violet.

1% 32 2s s 02.122 ts:- 11500 1. 5 9. 5 60 50 1113 1. 5 125-130 Greenish yellow. 1, 200 1 11. 3 50 50 11. 3 1. 5 125-130 Yellow. 1, 500 1. 5 9. 5 50 14. 0 1. 5 125-100 Qmnge. 2, 000 1. 5 18 30 40-45 9. 0 8 1. 5 125-130 1 allow. 1, 500 1 19 60 4&50 10 1. 5 125-130 Blue.

s 1% 22 -12 a as; 5 1,5 1 w 1. o. 1, 500 1. 5 Q) 7 70 85 13. 2 2 125-130 Turquoise blue. as as 53 s as 32-; a .1 0 0W. 1,000 1 10.0 40 85-90 4.8 2 125-130 Orange-yellow. 2, 500 1 11. 0 100 85-90 12. 5 8 1. 8 05-100 Blue/yellow. 1' "3 g 128 23 8533 112 3 12188 51 ue. 21000 1 15. 0 -90 51. a 2 05-100 Orange-yellow. 1, 000 1 15. 0 40 85-90 27. 5 2 05-100 Red. 1' 2% 1 s 1? 38 35533 if; 8 3 1 2128 it'lf 1 L e 1,500 1 0.9 70 85-90 7.0 g 2 -100 Green/red. 1, 000 4 5. 0 40 85-90 29. 5 58 4 -130 Green.

The reactive or disperse dyes employed in the foregoing examples have the following constitution. 2l 1-(4'-Hydroxyphenylazo)-4-phenylazoberizgene NH-trlchloropyrimldyl 23. Potassium l-(2' chloro-6'-methylphenyl)3-methyl-4-(2 '-metlioxy-5 -sulfato-ethylsulfonyl-phenylazo )-5-pyrazolone- 4'-sulfonate 24. The copper complex compound of potassium l-hydroxy-2-(2'-hydroxy-4'-vinylsulfonylphenylazo)-8- acetylaminonaphthalene-3,6-disulphonate 25. l-Hydroxy-4-( 2'ethoxycarbonyl-ethylamino anthraquinone 26. Potassium 1-hydroxy-8-amino-2,7-bis(sulphate-ethylsulfonylphenylazo )-naphthalene-3 ,-disulphonate 27. Mixture of 45 percent of 2,4-dinitro-6-bromo-2' acetylamino-S '-ethoxy-4 '-N ,N'-bis-(acetoxyethyl )-aminol,l'-azobenzene, 20 percent of 2,4-dinitro-6-chloro-2'- acetylamino-S '-methoxy-4'-N,N-bis-( acetoxyethyl )-amino- 1,1 -azobenzene, 25 percent of 4-nitro-2-bromo-4'-N-acetoxyethyl-n-cyanethylamino-l,l'-azobenzene and 10 percent of 4-nitro-2,6-dibromo-4'-N-methyl-N-cyanethylaminol ,1 azobenzene 28. The 2:1 mixed chromium-cobalt complex of sodium-lhydroxy-2-(2'-hydroxy-6'-nitronaphthyl-l '-azo )-6-(4"- chloro-6-amino-l 3", 5"-triazinyl-2"-amino)- naphthalene-3,4'-disulphonate.

29. Mixture of 41 percent of 2,6-dichloro-4-nitro-4-N- cyanetliyl-N-acetoxyethylamino-1,1 '-azobenzene, 49 percent of 1,5-diamino-2-bromo-4,8-dihydroxyanthraquinone and 10 percent of 2-cyano-4-nitro-4-N-ethyl-N-cyanethylaminol l'-azobenzene.

30. Sodium l-(2', 5-dichloropheyl)-3-methyl-4-{3"-(4"', 6"-dichloro-1"', 3", 5'"-triazinyl-2"-amino)-phenylazo]-5 pyrazolone-4 6' -disulphonate 31. S-Benzoylarnino-l ,9-thiazolanthrone 32. 4-Nitro9-acridone 33. Sodium l-hydroxy-2-phenylazo-6-(4", 6"-dichloro-1 3 5 '-triazinyl2' '-amino )-naphthalene-3 ,2 -disulphonate 34. Sodium 2-[4'-(2", 3"-dichloroquinoxalyl-6"-carbonylamino)-2'-methyl-phenylazo]-naphthalene-4,8-disulphonate N \CO 36. Sodium 1amino-4-[3'-(4", 6-dichloro-1", 3", triazinyl-Z"-amino)-phenylamino]-anthraquinone-2,4'- disulphonate.

37. Sodium l-amino-4-(3'-trichloropyrimidylamino-phenylamino)-anthraquinone-2,4'-disulphonate.

38. 1:1 Mixture of l,5-diamino-4,8-dihydroxy-2-(4'- hydroxyphenyl )-anthraquinone and l,5-diamiito-4,8- dihydroxy-2-(4'-methoxyphenyl)-anthraquinone 39. Sodium 1-amino-4- 4'[-N(2", 3"-dichloroquinoxalyl-6 "-carbonyl)-N-methyl-amino-methyll-phenylamino-l anthraquinone 2,3'-disulphonate 40. Disodium salt of copperphthalocyanine-(3)-disulfonic acid-sulfonic acid/amide-sulfonic acid -[3-(4"-amino-6"- chloro-l", 3", 5"-triazinyl-2"-amino)-6'-sulphophenylamide] 4l. 1,4-Diamino-anthraquinone-2,3-dicarboxylic acid -(3'- methoxypropylimide.)

42. Disodium salt of copperphthalocyanine-(3)-disulfonic acid-sulfonic acid/amide-sulfonic acid 3 trichloropyrimidylaminophenylamide) 43. Sodium 4-trichloropyrimidy1amino-4'-[3-methyl-4"- (2"'-methylphenylazo)-5"-pyrazolonyl-l ]-stilbene-2,2', 5 "-trisulphonate 45. Bis-copper complex compound of sodium 1,6-dihydroxy-2-(2'-hydroxy-5'-trichloropyrirnidylaminophenylazo)-5-(1" -hydroxynaphthyl-2"-azo)-naphthalene-3, 3', 4", 6"- tetrasulphonate 46. 2-Cyano-4-nitro-4'-N-B-cyanethyl-N'B-acetoxyethylamino-1,1 '-azobenzene 1. A process for dyeing a blend of natural or regenerated cellulosic fiber component and linear polyester fiber component with reactive dye and disperse dye comprising exhaustion dyeing the cellulosic component first with the reactive dye in a dyebath in the presence of at least one neutral salt and of not more than 20 grams of basic fixing agent per liter of dyeliquor at a temperature in the range of 40 to 100 C. and at a pH in the range of 8.5 to 13, then adjusting the pH to from 4 to 7, adding the disperse dye to the dyeliquor and dyeing the poli'ester component of the blend.

. A process according to claim I wherein the basic fixing agent is from 0.2 to 1.2 grams of sodium or potassium hydroxide per liter ofdyeliquor.

3. A process according to claim 1 wherein the basic fixing agent is from 2 to 20 grams of sodium or potassium carbonate or trisodium phosphate per liter of dyeliquor.

4. A process according to claim I wherein dyeing is carried out at a goods-to-liquor ratio of 1:4 to 1:30.

5. A process according to claim 1 wherein the temperature for dyeing the cellulosic component is from to C.

6. A process according to claim 1 wherein the reactive dye bears a dihalogenopyrimidyl or trihalogenopyrimidyl group.

7. A process according to claim 1 wherein the reactive dye bears a monohalogenotriazinyl or a dihalogenotriazinyl group.

8. A process according to claim 1 wherein the reactive dye bears a 2,3-dihaloquinoxalyl-6-carbonyl, -6-sulphonylor -6- aminocarbonyl group.

9. A process according to claim I wherein the reactive dye bears a sulphatoethylsulphonyl or a vinylsulphonyl group.

10. A process according to claim 1 wherein the pH value is reduced to from 4 to 7 by adding an organic lower aliphatic acid to the dyebath.

11. A process according to claim 1 wherein the pH value is reduced to from 4 to 7 by adding to the dyebath a phosphate of the formula MeH Po. wherein Me is an alkali metal. ammonium or a low-molecular alkylammonium radical.

12. A process according to claim 1 wherein the dyebath is adjusted to a pH of from 5 to 6.5 before adding the disperse dye thereto.

13. A process according to claim 1 wherein the polyester I component of the blend is dyed at from 95 to C. or at the boil in the presence of a carrier for dyeing linear polyester fiber.

14. A process according to claim 1 wherein the polyester component is dyed in the temperature range of from 1 10 to C. under pressure in the absence of carrier for dyeing linear polyester fiber.

' PO-WEO UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 31617'l68 Dated November 2, 1971 Inventor(s) ROLF MACK It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 7 "timesaving" should read timesaving; line 27, "ph" should read pH-; line 57, "phrimidyl" should read -pyrimidyl--; line 64, in the formula, "G-X-Z" should read CXZ-. Column 2, line 4, "or SO CH" should read or SO CH=-; line 6, "CH OSO H" should read CH -OSO H;; line 7 "dichloroquinoxalyl6" should read dichloroquinoxalyl-6-;

line 27, "CH OSO H" should read -CH OSO H line 28,

"-SO CH CH should read SO -CH=CH line 49, "for" should read from; line 60, "The disperse" should start a new paragraph. Column 3, line 66, "(CH NHB? should read (CH NH "neutralized an" should read neutralized and-. Column 4, line 68, "NaH PO 2H O" should read NaH PO .2H O-.

Column 5, line 12, "Na PO lOH O" should read Na PO .lOH O-; n ll fl II II should read O NA should read O Na,- line 37, "suphate" should read -sulphate--;

line 49, "suphate" should read sulphate; line 69, delete "methanedisulphonate" Column 6, line 3 "7" should read (D line 8, after the formula insert line 11, 5" should read (5) l should read line 25 in the formula,

" SO Na" should read SO Na--; line 42, "10" should read line 54, "3nitrobenzenesulphonate" should re d --3nitrobenzenesulphonate-; line 72, "12" should read line 25, in the formula,

page 2 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION patent 3,617,168 Dated November 2, 1971 Inventor(s) ROLF MACK It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

C olumn 7, line 16 in the formula, "N-ONH-" should read .1

-- NONH- line 20, "and entered" should read are entered; line 29, "4" should read Q1) line 54 in the formula, "NH-trichloropyrimidyl" should read NH-trichloropyrimidyl--- line 55, "1" should read (D line 67 "4" should read line 70, in the formula, S

should read H line 77, in the formula should read NH C Column 8, line 21, in the formula,

SO C H O-SO K should read SO -C H O-SO K--;

line 33 "6" should read line 50, in the formula,

01 NQ-Cl N should read Q11 line 63, "18" N c1 N Cl should read Column 9, line 17, "etho)xyanthraquinone" should read ethoxyanthraquinone-; line 19, "20" should read 2O line 25, "The following" should start a new paragraph. Column 10, line 7, "Na PO ay.l0H 0" should read Na PO .lOH O;

shdul 2 3 4 2 line 33, "nonated" read UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent 3,617 ,168 Dated November 2, 1971 Inventor(s) ROLF MACK It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

--nated-; example 32, in the table, under "Acid (parts) 1 "51.3" should read l5.3--. Column ll, line 13, in the formula,

d NH-trichloropyrimidyl;

"NH-trichloropyrimidyl should rea line 14, ")3methyl4(2" should read )-3methyl4-(2"-; line 29, "yethyln should read yethyl-N- line 39, "**percent" should read -percent-; line 40, "l 1" should read l,l-; line 50, before the formula, insert "35."; line 64, "4- 4 [N" should read -4{4'[N line 66, "2,3'" should read 2,3'- Column 12, line 19, in the formula,

should read i Signed and sealed this 19th day of March 197L (SEAL) Attest:

EDWARD M.FLETCHER,JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents

Claims

2. A process according to claim 1 wherein the basic fixing agent is from 0.2 to 1.2 grams of sodium or potassium hydroxide per liter of dyeliquor.
3. A process according to claim 1 wherein the basic fixing agent is from 2 to 20 grams of sodium or potassium carbonate or trisodium phosphate per liter of dyeliquor.
4. A process according to claim 1 wherein dyeing is carried out at a goods-to-liquor ratio of 1:4 to 1:30.
5. A process according to claim 1 wherein the temperature for dyeing the cellulosic component is from 80* to 95* C.
6. A process according to claim 1 wherein the reactive dye bears a dihalogenopyrimidyl or trihalogenopyrimidyl group.
7. A process according to claim 1 wherein the reactive dye bears a monohalogenotriazinyl or a dihalogenotriazinyl group.
8. A process according to claim 1 wherein the reactive dye bears a 2,3-dihaloquinoxalyl-6-carbonyl, -6-sulphonyl- or -6-aminocarbonyl group.
9. A process according to claim 1 wherein the reactive dye bears a sulphatoethylsulphonyl or a vinylsulphonyl group.
10. A process according to claim 1 wherein the pH value is reduced to from 4 to 7 by adding an organic lower aliphatic acid to the dyebath.
11. A process according to claim 1 wherein the pH value is reduced to from 4 to 7 by adding to the dyebath a phosphate of the formula MeH2PO4 wherein Me is an alkali metal, ammonium or a low-molecular alkylammonium radical.
12. A process according to claim 1 wherein the dyebath is adjusted to a pH of from 5 to 6.5 before adding the disperse dye thereto.
13. A process according to claim 1 wherein the polyester component of the blend is dyed at from 95* to 100* C. or at the boil in the presence of a carrier for dyeing linear polyester fiber.
14. A process according to claim 1 wherein the polyester component is dyed in the temperature range of from 110* to 140* C. under pressure in the absence of carrier for dyeing linear polyester fiber.