US3843318A - Process for dyeing cellulose fibres - Google Patents

Abstract

1. IN A PROCESS FOR PAD-DYEING TEXTILE MATERIALS MADE OF OR CONTAINING NATIVE OR REGENERATED CELLULOSE FIBERS WITH DYESTUFFS HAVING AS GROUP CAPABLE OF REACTING WITH THE HYDROXYL GROUPS OF THE FIBER AT LEAST ONE B-(2,2,3,3TETRAFLUORO - CYCLOBUTYL) - ACRYLOYLAMINO OR VINYLSULFONE GROUP OR SULFATOETHYLSULFONE OR THIOSULFATOETHYLSULFONE GROUP, AND FIXING THE DYESTUFFS ACCORDING TO THE DWELLING METHOD, THE IMPROVEMENT WHICH COMPRISES: USING IN SAID PROCESS, PADDING LIQOURS CONTAINING, IN ADDITION TO THE SAID DYESTUFFS AS AN AGENT HAVING ALKALINE REACTION, A LIQUID SODIUM SILICATE HAVING A CONCENTRATION IN THE RANGE OF FROM 37* TO 60*BE., CORRESPONDING TO AN SIO2-CONTENT OF THE AQUEOUS SOLUTION OF 27.2 TO 38.2 PERCENT BY WEIGHT, IN AN AMOUNT RANGING FROM 25 GRAMS TO 350 GRAMS PER LITER OF PADDING LIQOUR.

Description

United States Patent slgnor t0 Farbwerke Hoeehst Aktiengesellschaft vormals Meister L Germany ucrus & Brumng, Frankfurt am Main,

0 Drawing. Continuation of abandoned application Ser No. 706 76 F 1970 Se}. N3. Sig-1525?, 1968. This application Oct. 12,

Claims priority, 21

pplrcatron German F 51,665; Apr. 12, 1967,F 52 l i] 6 1967 Int. o I) 4 U's. L l 2, l

C L 5 C arms ABSTRACT OF THE DISCLOSURE Process for pad-dyeing textile mate V ria ggrtlgsenaerated cellulose fibres with radii/35 562512332 groups of tggotg?) capable of reacting'with the hydroxyl butynlacr 1e 1 re at least one ,8-(2,2,3,3-tetrafluorocycloone groupyfgy amino or a vmylsulfone group or at least group by usiin ng 1n an alkaline medium a vinyl-sulfone in addition to sald process padding liquors containing havin 11k 1 e above -mennoned dyestuffs as a ent g t a me action a llquid alkali metal silicate g s is a continuation of a l' N22. 7 26 7 6 512d Feb. an, 1968, now aba iici iiif Sen fibres can be d slat textlle materials made of cellulose ponent ca ablye with reactive dyestuffs having as comcyclobut 1)p e of reacting the ,B-(2,2,3,3-tetrafluor group f0yrm-izrilcryloylammoor vinylsulfone group or a group by anog n the presence of alkalies a vinylsulfone alkali-136 conafiii 535F332 iiifol l dyestuffs under lose fibres. As agents having alkaliri e 233121222311 example, as soda, sodiuni b iphate, sodium hydroxide, sodi- This application ondar y reaction, more or less large portions of the dye stuff u the strifh ge r i11 eilligiie i e id dyeing In this instance ,us

of the bath and the longer t the higner the temperature g period plays an ahty of the dyeings working, the dyeing nta ner or a preparin adding machine. Thi;

especially important rol e in th prepared. Withln this method of 2115232111 led gradually into the p batcherse,arehc;]wever, has negative effects wh n l is necessar yed for Wl'llCh a large amount of a d abger about mor y,thso that occasionally a time differ ye ath e an one hour between the applicatior i i ti i O C., as rs often the case in countries having a hot climate.

p ice metering pumps or mixing devices are brought into action in such padding processes m which, generally, relatively large amounts of strong alkalies (for example sodium hydroxide or sodium metasihcate) are used and in which-especially when large batches are dyed-the dyebath is abandoned partially for, a prolonged period of time in the preparing vessel. Sa1d arrangements allowthe dissolved dyestuffs to be brought into contact with the alkali only shortly before they are introduced into the padding machine (cf. Textil-Praxls, 1963, page v1189). A disadvantage of this process, how, ever, is that only few dye-houses possess such metering pumps or mixing devices, which is due to the hlgh purchase price for such devices. t

An important padding process for fixing the above mentioned dyestuffs on fabrics made of cellulosefibres is in this respect the so-called pad-batch-process or a variation thereof, the so-called "pad-short-dwell-process (cf. SVF-Fachorgan 1961, page 320, as well as Textil- Praxis 1963, page 1189). According to these processes the textile material is wound up on a roller and allowed to dwell, the wound up textile material being, during the dwelling time, hermetically enveloped in order to prevent the carbon dioxide from the air reacting with the alkalies at the edges of the rolled up material, which would then result in only an insufficient dyestufi fixation in these areas. It is also possible in the above-mentioned processes, to work without a metering pump, but only weak alkalies such, for example, as soda or alkali metal bicarbonate are allowed then to be used. These substances, however, reduce the colour yield due to the insufficient fixation quote of the dyestuffs on the fibre. Furthermore, the applica: tion of weak alkalies in this process may run the risk that, particularly when dyeing greater batches, the edges of the initial portion of the padded, rolled-up material become lighter coloured on account of the long period during which the textile material is rolled up.

A further disadvantage of the pad-batchor the padshortdwell-process lies in the fact that after dwelling, when drying the textile material without preceding acidification of the goods, the colour yield isreduced, owing to cleavage of the dyestuff-fibre-linkage. Therefore it is inappropriate to use the non after-treated textile material in the printing. t a

It has now been found that textile materials made of native or regenerated cellulose fibres can be dyed according to the padding process with reactive dyestuffs having as a group capable of reacting at least one {3-(2,2,3,3- tetrafluoro-cyclobutyl)-acryloylarnino group or a vinylsulfone group or at least one group forming in an alkaline medi um a vinyl sulfonegroup, by using in said process padding Therefore liquors containing besides the above-mentioned dyestuffs as agents having alkaline action a liquid alkali metal silicate. For the fixation of the dyeings, the padded material is allowed to dwell at temperatures of up to 100 C., preferably at room temperature, the fabric being wound up on a roller or piled up. The dwelling period is generally between 1 hour and 30 hours.

By the addition of alkali metal silicate (water glassy when carrying out the process of the present invention a- As reactive dyestuffs representatives of the various organic dyestuff classes can be used according to the present invention, for example azoand anthraquinone dyestuffs, containing either at least one B-(2,2,3,3-tetrafluoro-cyclobutyl)-acryloylaminoor a vinylsulfone group or at least one group which can be converted into a vinylsulfone group when exposed to alkaline agents during the dyeing process. The appropriate azo dyestuffs may, if desired, be used in metallized form.

As examples for such groups in the dyestuffs to be applied which can be converted into the vinylsulfone group in the presence of substances having alkaline reaction during the dyeing process, there are mentioned in particular the sulfuric acid ester or thiosulfuric acid ester of fi-hydroxyethylsulfone groupings.

Of the liquid alkali metal silicates (water-glasses) which are added to the padding baths according to the process of the present invention there are suitably used the commercial sodium silicates (soda water glass). Preferably there are used sodium silicates having a concentration of about 37 to about 60 B., corresponding to an SiO -content of the aqueous solution of about 27.2 to about 38.2 percent by weight.

The amount of the fixing agent used depends on the concentration of the alkali metal silicate applied, on the dyestuif concentration and on the nature of the dyestutf, and ranges generally from about g. to about 350 g., preferably from about 50 g. to 200 g. per liter of padding bath. Furthermore, it is possible to add to the dye baths still a sodium hydroxide solution besides the silicate, but the amount of sodium hydroxide solution (referred to sodium hydroxide solution of 38 B.) is not to exceed 10% of the amount of alkali metal silicate used, since otherwise the stability of the bath is reduced.

The technical advantage which is achieved when using liquid alkali metal silicates as fixing agents lies in the fact that sources of error are avoided which are possible when preparing the conventional aqueous padding liquors, an excellent reproducibility of the desired tints is guaranteed, and the dyeings do not suffer a change of shade during the dwelling period. It is surprising that with the process of the present invention, besides an excellent colour yield and levelness of the dyeing, still an excellent tone-in-tone dyeing on mixed fabrics made of native or regenerated cellulose fibre is obtained which is superior to that according to known conventional processes when other alkalies are used such, for example, as sodium hydroxide solution, trisodium phosphate, soda, an alkali metal bicarbonate or metasilicate.

The following Examples serve to illustrate the invention but they are not intended to limit it thereto.

EXAMPLE 1 A cotton poplin is padded in a padding machine-without using a metering pump or mixing deviceat a squeezing effect of 70 percent by weight with a padding liquor of C. containing per liter of water 10* g. of the dyestuif of the formula ease 4 EXAMPLE 2 A mercerized cotton fabric is padded in a padding machinewithout using a metering pump or a mixing device-at a squeezing effect of percent by weight with a padding liquor of 20 C. containing per liter of water 20 g. of the dyestuif of the formula H0 5 SO3H in commercial form and condition, and 200 g. of sodium silicate of 49 B. After padding the fabric is rolled up continuously and allowed to dwell at 20 C. for 6 hours. Then the dyed goods are rinsed, acidified and soaped.

There is obtained a brillant orange dyeing of an excellent colour yield and having level coloured ends and edges.

EXAMPLE 3 A mercerized cotton fabric is padded in a padding machinewithout using a metering pump or a mixing deviceat a squeezing effect of 80 percent by weight with a padding liquor of 20 C. containing per liter of Water 40 g. of the dyestuff of the formula in commercial form and condition, and 50 g. of sodium silicate of 49 B. After padding the fabric is rolled up continuously and allowed to dwell at 20 C. for 24 hours. Then the dyed goods are rinsed as usual, acidified and soaped.

There is obtained a brilliant violet dyeing of an excellent colour yield and having level coloured ends and edges.

EXAMPLE 4 A mercerized cotton fabric is padded in a padding machinewithout using a metering pump or a mixing device-at a squeezing effect of 80 percent by weight with a padding liquor of 30 C. containing per liter of water 20 g. of the dyestuff of the formula SO H in commercial form and condition, and 300 g. of sodium silicate of 49 B. After padding the fabric is rolled up continuously and allowed to dwell at 30 C. for 6 hours. Then the dyed goods are rinsed as usual, acidified and soaped.

There is obtained a brilliant yellow dyeing of an excellent colour yield and having level coloured ends and edges.

Example 5 A mercerized cotton fabric is padded in a padding machinewithout using a metering pump or a mixing deviceat a squeezing effect of 80 percent by weight with a v .padding liquor of3 C. containing per liter of water 30 g. of the dyestutf of the formula ,colgur yield and having level coloured ends and edges.

. ,,."If, ,in the Example described above, after dwelling, the fabric is .d riedfor-(J. minutes'at 140 C. and then rinsed, acidified and soaped, as usual, a level dark blue dyeing is obtained likewise; re-cleavage of the dyestuif-fibre-linkage, caused while drying, could not be ascertained from the colouristic aspect. Example 6 I I 'A fabric 'made' of staple fibre is padded in a padding machinewithout using'a metering pump or a mixing 'deVice at a squeezing effect of 90 percent by weight with a padding liquor-of 20 C. containing per liter of Water '40 g.-- of the dyestulf of the formula in commercial form and composition, and 200 g. of sodium silicate of 49 B. After padding the fabric is rolled up continuously and allowed to dwell at 20 C. for 8 hours. Then the dyed goods are rinsed as usual, acidified and soaped.

There is obtained a brilliant red dyeing of an excellent colour yield and having level coloured ends and edges.

Example 7 A cotton fabric is padded in a padding machinewithout using a metering pump or a mixing device-at a squeezing effect of 80 percent by weight with a padding liquor of 20 C. containing per liter of water 70 g. of the dyestutf of the following formula in commercial form and composition, and 150 g. of sodium silicate of 49 B. After padding the fabric is rolled up continuously and allowed to dwell at 20 C. for 18 hours. Then the dyed goods are rinsed, acidified and soaped, as usual.

There is obtained a blue dyeing of an excellent colour yield and having level coloured ends and edges.

Example 8 A mixed fabric of staple fibre and cotton in a mixing proportion of 30:70 is padded in a padding machinewithout using a metering pump or a mixing device-at a squeezing effect of 80 percent by weight with a padding in commercial form and composition, and 200 g. of sodium silicate of 49 B. After padding the mixed fabric is rolled up continuously and allowed to dwell at 30 C. for 8 hours. Then the dyed goods are rinsed as usual, acidified and soaped.

There is obtained a yellow tone-in-tone dyeing of an excellent colour yield having level coloured ends and edges.

Example 9 A staple fibre fabric is padded in a paddingmachine at a squeezing effect of 90 percent by weight with a padding liquor of 40 C. containing per liter of water 20 g. of the dyestulf of the formula OsH in commercial form and composition, 50 g. of sodium silicate of 49 B and 5 cc. of a sodium hydroxide solution of 38 B. After padding the fabric is rolled up continuously and allowed to dwell at 40 C. for 24 hours. Then the dyed goods are rinsed, acidified and soaped, as

usual. I

There is obtained a brilliantorange dyeing having level coloured ends and edges.

Example 10 A mercerized cotton fabric is padded in a padding machine at a squeezing effect of 60 percent by Weight with a padding liquor of 30 C. containing per liter of Water 20 g. of the dyestuff of the formula S0311 OH NHC OCH=CHCHOH:

Example 11 A bleached linen fabric is padded in a padding machine at a squeezing effect of percent by weight with a padding liquor of 20 C. containing per liter of water 15 g. of the dyestuff of the formula I I I I GF2CF2 N=N I HOSa SOaH A mercerized cotton fabric is padded in. a padding machine at a squeezing effect of 60 percent by weight with a padding liquor of 20 C. containing per liter of water 20 g. of the dyestulf of the formula in commercial form and composition, and 200 g. of sodium silicate of 49 B. After padding the fabric is rolled up continuously and allowed to dwell at 20 C. for 24 hours.

There is obtained a yellow dyeing having level coloured ends and edges.

Example 13 A mercerized cotton fabric is padded in a padding machine at a squeezing effect of 60 percent by weight with a padding liquor of 20 C. containing per liter of water 30 g. of the dyestufi' of the formula g 0111 in commercial form and composition, and 50 g. of sodium silicate of 49 B. After padding the fabric is rolled up continuously and allowed to dwell for 24 hours.

There is obtained a yellow dyeing having level coloured ends and edges.

1. In a process for pad-dyeing textile materials" made of or containing native or regenerated cellulosefibers with dyestuffs having as group capable of reacting with the hydroxyl groups of the fiber at least one ii-(2,23,3- tetrafluoro cyclo'butyl) acryloylamino or vinylsulfone group or sulfatoethylsulfone or thiosulfatoethylsulfone group, and fixing the dyestuffs according to the dwelling method, the improvement which comprises: using in said process, padding liquors containing, in'addition to the said dyestuffs, as an agent having alkaline reaction, a liquid sodium silicate having a concentration in the range of from 37 to B corresponding to an SiO -content of the aqueous solution of 27.2 to 38.2 percent byweight, in an amount ranging from 25 grams to 350 grams per liter of padding liquor. I v

2. A process as claimed in Claim 1, wherein the liquid sodium silicate is used in an amount of from 50 gra'ms'to 200 grams per liter of padding liquor. I

3. A process as claimed in Claim 1, wherein padding liquors are used which additionally contain a sodium hydroxide solution, the amount thereof, calculated as' so'cli um hydroxide solution of 38 B., not exceeding ten percent by weight of the amount of sodium silicate used.

4. A process as claimed in Claim 1, wherein for the fixation of the dyeings, the textile material padded with reactive dyestuff and sodium silicate is batched up on a roller and is allowed to dwell there at temperatures rang ing from room temperature up to C.

5. A process as claimed in Claim 1, wherein for the fixation of the dyeings, the textile material padded with reactive dyestuif and sodium silicate is cuttled up and'is allowed to dwell there at temperatures ranging from room temperature up to 100 C.

References Cited UNITED STATES PATENTS 3,232,927 2/ 1966 Randall et al. 260163 3,129,052 4/ 1964 Dawson et al 854 3,360,505 12/1967 Scherer et al. 260-447 ROLAND E. MARTIN, JR., Primary Examiner U.'S. Cl. X.R.

81 P, 1 Q, 39, 41 R, 42 R, 82

Claims (1)

1. IN A PROCESS FOR PAD-DYEING TEXTILE MATERIALS MADE OF OR CONTAINING NATIVE OR REGENERATED CELLULOSE FIBERS WITH DYESTUFFS HAVING AS GROUP CAPABLE OF REACTING WITH THE HYDROXYL GROUPS OF THE FIBER AT LEAST ONE B-(2,2,3,3TETRAFLUORO - CYCLOBUTYL) - ACRYLOYLAMINO OR VINYLSULFONE GROUP OR SULFATOETHYLSULFONE OR THIOSULFATOETHYLSULFONE GROUP, AND FIXING THE DYESTUFFS ACCORDING TO THE DWELLING METHOD, THE IMPROVEMENT WHICH COMPRISES: USING IN SAID PROCESS, PADDING LIQOURS CONTAINING, IN ADDITION TO THE SAID DYESTUFFS AS AN AGENT HAVING ALKALINE REACTION, A LIQUID SODIUM SILICATE HAVING A CONCENTRATION IN THE RANGE OF FROM 37* TO 60*BE., CORRESPONDING TO AN SIO2-CONTENT OF THE AQUEOUS SOLUTION OF 27.2 TO 38.2 PERCENT BY WEIGHT, IN AN AMOUNT RANGING FROM 25 GRAMS TO 350 GRAMS PER LITER OF PADDING LIQOUR.

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