CA1186457A - Process for the pad-dyeing or printing of textile material of natural or synthetic polyamide fibers or mixtures thereof with other fibers with reactive dyestuffs - Google Patents
Process for the pad-dyeing or printing of textile material of natural or synthetic polyamide fibers or mixtures thereof with other fibers with reactive dyestuffsInfo
- Publication number
- CA1186457A CA1186457A CA000404551A CA404551A CA1186457A CA 1186457 A CA1186457 A CA 1186457A CA 000404551 A CA000404551 A CA 000404551A CA 404551 A CA404551 A CA 404551A CA 1186457 A CA1186457 A CA 1186457A
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- Prior art keywords
- dyestuff
- reactive
- fiber
- dyeing
- printing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/10—Material containing basic nitrogen containing amide groups using reactive dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0072—Preparations with anionic dyes or reactive dyes
- C09B67/0073—Preparations of acid or reactive dyes in liquid form
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
- D06P3/8214—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing ester and amide groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
- D06P3/8219—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and amide groups
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
Abstract of the disclosure:
Certain reactive dyestuffs of commercial constitution are available in a form which does not react with natural or synthetic polyamide fibers and have therefore to be converted to their reactive form before being able to undergo a covalent bond with the fiber material. The methods hitherto applied in the practice for this purpose are unsatisfactory because they either do not produce a sufficient amount of reactive dyestuff under the prevailing conditions, or due to susceptibility of the converted form to hydrolysis portions of the dyestuff are inactivated, thus resulting in dyestuff losses in both cases.
In accordance with the invention these drawbacks are overcome by converting first the dyestuffs into their fiber-reactive form, before dyeing or printing, by treating them under correspondingly typical conditions, for example in an alkaline medium, and chemically stabilizing then this converted form by alteration of the pH, for example to the acidic range. The dyestuff formulations so obtained are then used for the dyeing or printing of natural or synthetic polyamide fibers in a neutral to acidic pH range This is the decisive condition for acceptable yields as compared to the hitherto known operation modes.
Certain reactive dyestuffs of commercial constitution are available in a form which does not react with natural or synthetic polyamide fibers and have therefore to be converted to their reactive form before being able to undergo a covalent bond with the fiber material. The methods hitherto applied in the practice for this purpose are unsatisfactory because they either do not produce a sufficient amount of reactive dyestuff under the prevailing conditions, or due to susceptibility of the converted form to hydrolysis portions of the dyestuff are inactivated, thus resulting in dyestuff losses in both cases.
In accordance with the invention these drawbacks are overcome by converting first the dyestuffs into their fiber-reactive form, before dyeing or printing, by treating them under correspondingly typical conditions, for example in an alkaline medium, and chemically stabilizing then this converted form by alteration of the pH, for example to the acidic range. The dyestuff formulations so obtained are then used for the dyeing or printing of natural or synthetic polyamide fibers in a neutral to acidic pH range This is the decisive condition for acceptable yields as compared to the hitherto known operation modes.
Description
7~ t~7
- 2 - ~IOE ~1/F' 190 The present invention relates to the pad--dyeing or pri.nting of textile material macle from natural or synthetic polyamide fibers.or mixtures thereof wi.th other fibers with reactive dyestuffs which in comme~^cial constitution are present in a form incapable of reacti.ng by itself with the .
fiber substance, and which from an aqueous medium are otherwise induced to fixation on the fiber in the case of exhaust dyeing accordincJ to known processes (i) either directly in their non-reactive form under acidic conditions o~ (ii) be converted ~o their reactive form by the influence of alkaline agents durin~ the dyeing operation prior to being fixed uncler subsequently adjusted acidic conditions. The invention comprises furthermore special formulations of such reactive dyes suitable for application in the novel procoss.
Dyeing with so-called reaetive dyes is, as principally eellulose fibers are concerned, already known for a certain ime and has fully proved its wor-th in the practice because of the clear and dull shades and the fas-tnesses so obtainable.
Such coloring agen-ts are of organic origin and listed i.n Colour Index, 3rd edition 1971, under the generic term "Reactive Dyes". Dyestuffs of said species belony to the series of azo-, anthraquinone- or phthalocyanine compounds which may be present in the form of metal cornplexes and which cont:ain at least one group capable of reacting with the fiber. In sorne.cases, however, such a group reacting with the fiber is not present a priori but formed by suitable operati.orls only in the dyeing process from a precursor thereo A current example of this latter type are reactive dyes on the basis of esters of mono- or poly-valent, inorganic or organic acids which can easily be s~lit Or~, especially of sulfuri.c acid esters, ~ith B-hydroxyethylsulfone compounds (Ester dyestuffs), from which in the course of the dyeing process by the influence of alkaline agents the fiber-reactive vinylsulfone form ~VS form) of the dyestuff i.s formed.
For coloring cellulose textiles of all ~inds, reclc~i.ve dyes arc? applied accordillc3 to texti1.e pri.nting processes as '`~
~8~i~57
fiber substance, and which from an aqueous medium are otherwise induced to fixation on the fiber in the case of exhaust dyeing accordincJ to known processes (i) either directly in their non-reactive form under acidic conditions o~ (ii) be converted ~o their reactive form by the influence of alkaline agents durin~ the dyeing operation prior to being fixed uncler subsequently adjusted acidic conditions. The invention comprises furthermore special formulations of such reactive dyes suitable for application in the novel procoss.
Dyeing with so-called reaetive dyes is, as principally eellulose fibers are concerned, already known for a certain ime and has fully proved its wor-th in the practice because of the clear and dull shades and the fas-tnesses so obtainable.
Such coloring agen-ts are of organic origin and listed i.n Colour Index, 3rd edition 1971, under the generic term "Reactive Dyes". Dyestuffs of said species belony to the series of azo-, anthraquinone- or phthalocyanine compounds which may be present in the form of metal cornplexes and which cont:ain at least one group capable of reacting with the fiber. In sorne.cases, however, such a group reacting with the fiber is not present a priori but formed by suitable operati.orls only in the dyeing process from a precursor thereo A current example of this latter type are reactive dyes on the basis of esters of mono- or poly-valent, inorganic or organic acids which can easily be s~lit Or~, especially of sulfuri.c acid esters, ~ith B-hydroxyethylsulfone compounds (Ester dyestuffs), from which in the course of the dyeing process by the influence of alkaline agents the fiber-reactive vinylsulfone form ~VS form) of the dyestuff i.s formed.
For coloring cellulose textiles of all ~inds, reclc~i.ve dyes arc? applied accordillc3 to texti1.e pri.nting processes as '`~
~8~i~57
- 3 - HOE 81/F 1~0 well as exhaust or continuous dyeing processes. In the industrial practice these dyestuffs are usually fixed on the fiber prevailing Erom an aqueous medium and prlmarily in the presence of al}aline agents. Suitable fixation alkali5are those which cause the conversion from the commercial form of the Ester dyestuffs to the VS form reac-ting with the polyhydroxy fiher, either at room temperature or with the ai.d of heating, depending on the reactivity degree of the dyestuffs. In the exhaust processes, as a ruleJsodium hydroxide solution, sodium carbonate ox tri-sodium phosphate are used for said purpose, while in pad-dyeing water glass and sodium bicarbonate are suitable as well as sodium hydroxide solution and sodium carbonate.
Fixation of the reactive dyes in the exhaust process occurs immediately after their absorption by the fiber at temperatures of up to the boiling point of the dyeing bath, while in pad-dyeing after the application of the dyestuff a separate operation including dwelling, steaming or dry heat treatment is required for the saicl proceeding.
Disadvantageous for the pad-dyeing processes is the reduced stability of the reactive dyes in the alkaline range. Under these conditions, for example, from ~S dyestuffs due to hydrolysis B-hydroxyethylsulfone dyestuffs are forrned which canno-t react with the fiber. AlthoucJh this undesirable behavlor can be overcome by a two-bath trea-tment rnethod accorc1j.ncJ to which first the non-reactive Ester dyestuff is applied without alkalis, and then the required amount of alkali is supplied in a second paddlng operation, as the COnSeqUenCQ for such a tactical round3 bout way, 3Q ho~ever, the disaclvantage of an intermediate drying must be paid.
When printing with reactive dye~, the reduced s-tability of these dyes in an alkaljne medium can be avoided by mixillcJ to the printing pastes so-called alkali donors which se-t free the alkali in the fixation process at elevated temperature.C; only. Such alkali donor., are for examl?le sodium bicarbonate, sodium tricllloroacetic acLd or dicyano-diam i.de .
For the dyeing of wool and polyamide fibers, commercialreactive dyestuffs of the above type are used either in their form non-reacting with -the fiber, :in an acidic medium and under high temperature (HT) conditions (German Patent No. 2,834,997, German Auslegeschrift No. 2,847,913 and German Offenlegungsschrift No. 2,933,343), or they are converted first to -their fiber-reactive form in the course of the dyeing process and then applied in this latter form in an acidic medium (TED process, see Technischer Rat aus Hoechst, Textil No. 73). However, applic-ability oE these two operation modes remained as yet be limitedto the exhaust dyeing only. On the other hand, a continuous process for the pad-dyeing or printing of wool and polyamide fibers with reactive dyes which ls feasible in the industrial practice does not exist until now.
It has now been found that reactive dyestuffs which in cornmercial constitution are present in a form non-reactive by itself with the fiber substance give a good color yield on dyeing or printing of natural or synthetic polyamide fibers when the said dyestuffs are pretreated (before dyeing or prin-ting) in an aqueous medium in such a manner that they are converted to their fiber-reactive form, and then chemically stabilized in this latter form. Pad-dyeing or printing with these dyestuff formulations is then carried ou-t exclusively from an aqueous, neutral to acidic medium according to the opera-tional procedures us-ual for these application types.
Accordingly, in a process for the pad-dyeing or printing of textile material made from natural or synthetic polyamide fibers or mix-tures thereof with other fibers, using a reactive dyestuff whi.ch in commercial cons-titu-tion is present in a form incapable of reacting on its own with the fiber substance and containing reactive groups being derived from esters of mono- or polyvalent, inorganic or organic acids easily split off, with a ~-hydroxyethylsulfone compound, the present invention provides the improvement which comprises converting the reactive dyestuff before application, in an aqueous medium by treatment with an alkaline agent from the non-fiber-reactive to the fiber-reactive vinylsu:Lfone form and chemically stabilizing i-t in this converted form by adjusting to a neutral to acidic pH range by adding acid to the alkaline dyestuff solution, and subsequently applying -the dyestuff formulation -thus obtained to the fiber material from an aqueous, neutral to acidic medium by pad-dyeing or printing, and fixing the dyestufE on the fiber.
By the example of the sulfuric acid esters o:E ~-hydroxyethylsulfone dyestuffs (sul:Eatoethylsulfone dyestuffs), that is, the most impor-tant and most widely used -4a--5t7 - 5 -- HO~. 81/F 1~0 co~nercia] form of thi.s type of reactive dyes, the formu-lations prepared in accordance with the inventiorl anc3 tne coxrespondinq dyeing processes for texti.les containing or consisting of polyamide fihers are explained in detail as follows:
For carrying out the process oE the inven-tion the Ester dyestuffs are first dissolved in wa~er. Suhsequently, an al~aline agent is added t-o t}le concentrated dyestuff solv.tion so ob;:ained or a dyestuff solution diluted pre-viously to the intended concentrat~Aon, in order to splitthe ester grouping withi.n the su].fatoethylsulfone radical and to convert +the latter one to the directly fiber-reactive vinylsulfone radical. This is carri.ed out at a temperature of from room temperature to boilinq temperature, preferably .15 25 to 60C, and in the alkaline range, preferably at a pH
of above 10. As alkaline agents, aqueous solutions of alkali. metal hydroxides and/or sa].ts having an alk.aline reaction in water, such as sodium carbonate, sodium hydroxide solution, water glass, trisodium phosphate etc.
may be used. Depending on th~ temperature, the chemical nature of the alkaline agent and the amount thereof, the treatment period for dyes-tuff conversion to the VS form is ~rorn 10 seconds.to 10 minutes. SubsecJuently, the alkaline liquor so handled is aci.di.fied and adjust.e~ to a pH of frorn 7 to abov.t 3, preferably 6.5 to 5, for chelrlical stabili.7a--tion of the VS form formed. AcidifLcation is ensure~ by addition of a mineral acid, for example hydrochloric, sul-furic or phosphoric acid, or an organic acid, for e~ample formic or acetic acid, to the alkaline dyestuff soluti.on.
If adjustecl to the intended dyestuff concenkration already prior to the treatment wi-th alkalis the dyestuff formulatlon so prepared can be di.rectly used for the padding of the textile material. Padding is preferably carri.ed OUt at room temperature.
For reasors of a ra~ional opera-tion mode, prepor1deran-t-ly such soluti.ons of the Es+er dyestuff obtained in a concentr;lted form are treated ~i.ch the alkc.llirle aqr.-`nt, and after acldificatiorl only diluted ~7ith wate.r ko the int.ended - 6 - IIOE ~ 0 concen-t?ation for t:he dyelncJ or pac~ding bath or the pr:inti~
paste. It; is xecommended to check the pH after dilution onee more and to correct it if necessary. It is, however, no-t required to prepare the concentrated dyestuf formulations immediately before dyeiny, padding or printiny; they can be made for stock and are stable to storage for a prolonged time in the form of 'lliquid dyestuffs" or printing pastes.
By evaporation, optionally to dryness, the concentration of sueh a dyestuff formulation can be increased accordinc~ to the requirements of the practice.
For use in continuous processes where lic~uor concen-tration and liquor volume have to be maintained constant by steady feeding-up addition, production of the spontaneously reaetive VS form from the Ester dyestufE ~y treatment with alkalis in accordanee with the invention can also be per-formed automatieally by simply dosing and mixincJ the commer~
eial dyestuff solution and the alkaline agent, while, how-ever, taking into consideration a certain residence time.
Subsecluently, by means of a seeond dosaye device aeidifi--cation of the dyeing medium diree-tly introdueed into the applieation opera-tion can be reali~ed, in dependenee on a predeterrrined, weakly acidic pH.
In view of a simplifi.ed applieability, it has proved to he advantageous that in the liquid formulations of the invention the solubility in water of the vinylsulfo11e dyes1:uffs, which hefore had been presel1t already in the form of dissolved sulfatoethylsulfone dyestuffs, is greater than in the case where pulverulent ~inylsu]fone dyest1lffs are directly used for preparing such a so]ution. This is of practieal importance in the case of formulations where due to a high concentration and poor solubility crysta]lized dyestuff has settled on storage, and this precipitate mus-t b~ redi.sso]ved on dilution.
In the special dyeincJ and printi~lc~ tec~miq~es described as follows in order to il]ustrate the utllization, the dye-stuff formulat:ions obtained in accorclance wi-th the inverl'_io are used ln the acldic range at a pII of prefera~bly from 5 to 6.5. In an acid:Lc mediur~l, the hydrolys1s ra-te is relatively lo~., sc that less hydroly7.ed dyestuff is formed;
thus avoiding the formation of a large arnoun-t of inactive hydroxyethylsulfone dyestuff from the vinylsulforIe form, whi.ch cannot react any more with the f:iber and is -therefore lost.
When pad-dyeing or printing natural or synthetic poly amide fibers of their mixtures with other fibers, the reac-tive dye formulations obtained are applied to the flber in the acidic pH range. The dyestuff is fixed subsequently hy dwelling, steaming or dry heat treatment. Preferably, such a heat fixation directly after padding or printin~ is effected upon the rnoist goods. ~lternatively, the padded or printed flber material. can be subjected to an inter-mediate drying at a teMperature a.round 100~C after the application step of the dyestuff.
The dry heat treatment is carried out within 30 seconds to 10 minutes, preferably 2 to 5 minu-tes, at a temperature of from 120 to 240C, preferably 150 to 200C. Steaming or high tempera-ture steaming is c~rried ou-t within 30 seconds to 30 minut:es at 100 to 240C. Preferred is high temperature steaming, for example for 5 minutes at 180C.
A saturated stearn atmosphere is not absolu-tely required.
Good results are for example obtainecI wherI the moisture in the steami.ng apparal:us is about 90 % of the satura-tion amount present at the corresponding temperature.
As compar~d to known operation modes for the dyeing of wool and polyamlde fibers with reactive dyes, the novel process has the follow:incJ advantages:
~ Wool and polyamide fibers can ~e dyed conti.nuously according to a pad-dyeing process.
- Due to the fact that in accordance with the inventio nearly no inactive BA-hydroxyethylsulforle dyestuff is formed~
there are srna].l dyestuff losses only.
- Moreover, due to the improved clyestlIff utili~.atlon, ]ess waste water pollution occurs.
-- Mi.xed fabr:i.cs can be dyed in one single bathO For e~ample, these speciGl reacti.ve dyestuff formulatioIls can be used together w~ h di.sperse dyes ln an acld:ic I~at;h for. the ~6~
- 8 - llO~I 8~ o dyeing of mixt-lre~s of polyester fibers and wool. Furtherl~loj-e, mixed fabrics of natural or synthetic polyamide fihers and cellulose fibers can jointly be treated with these reactive dyc formulations; both fiber types being dyed sim~lltaneous~y in this case.
As in -the krlo~ll processes, the clyestuEf yield of the process of the invelltion can be improved by increasirlg the dyestuff substantivity, for example by addition o electro--lytes.
The following Examples illustrate the inventionO Tlle p~rcenta~es are by weight unless otherwise stated, and relative to the weight of the dry goods in the case of textile n~aterial.
E X A M P L E
50 g of the reactive dyes-tuff of the formula 02S~N = N - C -- C - CH3 OS03Na ~3 ~5 S03Na are dissolved in 50 cm3 of hot water, and dilu-tecl wi-th cold water to 1 liter. 20 cmJ of sodium hydroxide so~ution (32.5 ~ strength) are added to this dyestuff solution, and after 1 minute of dwelling the formulation ls neutralized hy means of acetic acid, and adjus-t~d to pH ~.5. Jsillg the liquor so obtained, fabrics of a) wool, b~ polyamide 6 fibers, and c) polyarnide 6,6 fibers are padded. Subscquently, -the padded fabrics are trea-'.ed in all cases for dyestuff fixation as follows (I~ for one part ~7;-th hot air for 3 min-l-tes at 180~C, and fo~ the o~her part - 9 - _F 81/F 140 (II) hy steaming for 5 minutes at 130C, the steam amourt being 95 ~ of t:he saturation amount possible at this temL~erature.
Subsequel1tly, the dyei.ngs are rinsed with hot and cold water, and soaped at 70C for 10 ml.nutes in an aqueous bath containing 1 g/l of a nonionic detergent. Yellow dyeincJs are obtained in all cases. Similar results i.n the corres-pondiny shades are obtained when accordi.ng to the operation mode of the above Example the dyestuffs indicated in the following Examples S to 9 are used:
_ _ .
Reactive dyestuff of the formula / Cu\
SO3~1 /
-N = N - ~ N = N- ~
E X ~ M P L E 3 _ Dyestuff Reactive Orange 16, C.I~-No. 17757.
E X ~ M P L E 4 Dyestuff Reactive Blue 19, C.I.-No. 61200.
DyestuEf Reactive B1.ack 5, C~ No. 20205.
F. X A M_ L E 6 30 g of the dyestuff of Exarnple 3 are formulated as described in Examp].e 1. Two mixed fabr~~cs of polyamide/
cotton and polyamide/spun rayon, respcctively, are padded with this liquor, and subsequen-tly for dyestuff fixation steamed for 6 minuces at 130C (90 % moisture in the steamina apparatus~. ~he dyeinys are then rinsed with hot and colcl water, and soaped at 60C in an aqueous bath containing 1 g/l of a norlionic detergent. Orange dyeings are obtained; in each case both fi.ber compone~lts of the mi~ecl fa~rics are dyed in i.dentical shades.
~ 10 - HO~ n E X A ~I P L ~ 7 _. __ _ _ _ _ - ~l0 g of the reactive dyesturf of the formula CH3CO~HN OI-I
~ ~-N = N- ~ -CO-NH~
HO3S- -~SO H ~-~
SO2-CH2-CH2~OSO3H
are dissol~ed in 200 cm3 of hot water. Af-ter cooling, 10 cm3 of a 32.5 % sodium hydroxide solution are added to the d~estuff solution, the batch is allowed to dwell for 1 minute, and is then neutralized with the aid of acetic acid, and adjusted to plI 6.5.
The dyestuff formulation so prepared is then nlade up to 1 kg of print.ing paste by adding water and a usual thic~ener, and 50 g/kg of urea are added to the printing paste. A T~ool fabric is subseqllently printed with this paste, and the dyestuff is fixed by steaming for 5 minutes at 130C (98 ~ rnoisture in the steaming apparatus). Subse-quently, the textile material is rinsed with hot and cold water, and soaped at boiling ternperature for 15 rninutcs at 60C in an aqueous liquor Contai.rlincJ 1 g/l of a nonionic detergent. A rcd print on the fabric is ob-tained.
E X ~ M P L E
50 g of the dyestuEf Reactive Blue 19,.C.~.-No. 61200 ~re formula~ted as described in Example 1. 40 g of the dyestuff Disperse Yellow 64, C~ o. 47023 and 2 g of a cor~.ercial wetting agent- are added to this dyestuff liquor.
A mixed fabric of polyester/~700l ~mixincJ ratio 55/45) i5 padded with -this padding liquor. Thereafter, -the fabric is steamed for 4 minutes at 150C ~95 % of moisture in the steamin(~ apparatus) for f.ixation of the two dye~tuffs.
Subsequently, the goods so dyed are rinsed with hot and colcl water/ and soaped for 10 rninutes a-t 70C in an aqueous bath containing ~ c3/l of a nc-,nionic deter(3ent. A bicolor dyeing is ohtained on the r.~ ed fabric; the polyester fi.ber port:i.on ~ein(~ dyed yelloT.A7 and the woo:l portion b~-:i.ncJ uycd h1ue~
~6'~
~ HOE 81/F_1~0 E X A ~ P L F, 9 50 g of the dyest~ff as used in Example 3 are formul-atecl as descrihed in Example 1. After havirl~ adde~ to the batch 10 g of sodium acetate and 2 g of a commercial wetting agent, a fab.ric of wool is padded wi.th the paclding liquor so prepared, and wound up. After a dwelling time of 12 hours at room temperature for dyes-tuff fixation, the dyed fabric is rinsed with cold and ho-t water arld subse-quently soapecl for 10 minutès at 60C i.n an aqueous ba-th containing 2 g/l of a nonionic detergent. An orange dyeing 10 i.s obtained.
Fixation of the reactive dyes in the exhaust process occurs immediately after their absorption by the fiber at temperatures of up to the boiling point of the dyeing bath, while in pad-dyeing after the application of the dyestuff a separate operation including dwelling, steaming or dry heat treatment is required for the saicl proceeding.
Disadvantageous for the pad-dyeing processes is the reduced stability of the reactive dyes in the alkaline range. Under these conditions, for example, from ~S dyestuffs due to hydrolysis B-hydroxyethylsulfone dyestuffs are forrned which canno-t react with the fiber. AlthoucJh this undesirable behavlor can be overcome by a two-bath trea-tment rnethod accorc1j.ncJ to which first the non-reactive Ester dyestuff is applied without alkalis, and then the required amount of alkali is supplied in a second paddlng operation, as the COnSeqUenCQ for such a tactical round3 bout way, 3Q ho~ever, the disaclvantage of an intermediate drying must be paid.
When printing with reactive dye~, the reduced s-tability of these dyes in an alkaljne medium can be avoided by mixillcJ to the printing pastes so-called alkali donors which se-t free the alkali in the fixation process at elevated temperature.C; only. Such alkali donor., are for examl?le sodium bicarbonate, sodium tricllloroacetic acLd or dicyano-diam i.de .
For the dyeing of wool and polyamide fibers, commercialreactive dyestuffs of the above type are used either in their form non-reacting with -the fiber, :in an acidic medium and under high temperature (HT) conditions (German Patent No. 2,834,997, German Auslegeschrift No. 2,847,913 and German Offenlegungsschrift No. 2,933,343), or they are converted first to -their fiber-reactive form in the course of the dyeing process and then applied in this latter form in an acidic medium (TED process, see Technischer Rat aus Hoechst, Textil No. 73). However, applic-ability oE these two operation modes remained as yet be limitedto the exhaust dyeing only. On the other hand, a continuous process for the pad-dyeing or printing of wool and polyamide fibers with reactive dyes which ls feasible in the industrial practice does not exist until now.
It has now been found that reactive dyestuffs which in cornmercial constitution are present in a form non-reactive by itself with the fiber substance give a good color yield on dyeing or printing of natural or synthetic polyamide fibers when the said dyestuffs are pretreated (before dyeing or prin-ting) in an aqueous medium in such a manner that they are converted to their fiber-reactive form, and then chemically stabilized in this latter form. Pad-dyeing or printing with these dyestuff formulations is then carried ou-t exclusively from an aqueous, neutral to acidic medium according to the opera-tional procedures us-ual for these application types.
Accordingly, in a process for the pad-dyeing or printing of textile material made from natural or synthetic polyamide fibers or mix-tures thereof with other fibers, using a reactive dyestuff whi.ch in commercial cons-titu-tion is present in a form incapable of reacting on its own with the fiber substance and containing reactive groups being derived from esters of mono- or polyvalent, inorganic or organic acids easily split off, with a ~-hydroxyethylsulfone compound, the present invention provides the improvement which comprises converting the reactive dyestuff before application, in an aqueous medium by treatment with an alkaline agent from the non-fiber-reactive to the fiber-reactive vinylsu:Lfone form and chemically stabilizing i-t in this converted form by adjusting to a neutral to acidic pH range by adding acid to the alkaline dyestuff solution, and subsequently applying -the dyestuff formulation -thus obtained to the fiber material from an aqueous, neutral to acidic medium by pad-dyeing or printing, and fixing the dyestufE on the fiber.
By the example of the sulfuric acid esters o:E ~-hydroxyethylsulfone dyestuffs (sul:Eatoethylsulfone dyestuffs), that is, the most impor-tant and most widely used -4a--5t7 - 5 -- HO~. 81/F 1~0 co~nercia] form of thi.s type of reactive dyes, the formu-lations prepared in accordance with the inventiorl anc3 tne coxrespondinq dyeing processes for texti.les containing or consisting of polyamide fihers are explained in detail as follows:
For carrying out the process oE the inven-tion the Ester dyestuffs are first dissolved in wa~er. Suhsequently, an al~aline agent is added t-o t}le concentrated dyestuff solv.tion so ob;:ained or a dyestuff solution diluted pre-viously to the intended concentrat~Aon, in order to splitthe ester grouping withi.n the su].fatoethylsulfone radical and to convert +the latter one to the directly fiber-reactive vinylsulfone radical. This is carri.ed out at a temperature of from room temperature to boilinq temperature, preferably .15 25 to 60C, and in the alkaline range, preferably at a pH
of above 10. As alkaline agents, aqueous solutions of alkali. metal hydroxides and/or sa].ts having an alk.aline reaction in water, such as sodium carbonate, sodium hydroxide solution, water glass, trisodium phosphate etc.
may be used. Depending on th~ temperature, the chemical nature of the alkaline agent and the amount thereof, the treatment period for dyes-tuff conversion to the VS form is ~rorn 10 seconds.to 10 minutes. SubsecJuently, the alkaline liquor so handled is aci.di.fied and adjust.e~ to a pH of frorn 7 to abov.t 3, preferably 6.5 to 5, for chelrlical stabili.7a--tion of the VS form formed. AcidifLcation is ensure~ by addition of a mineral acid, for example hydrochloric, sul-furic or phosphoric acid, or an organic acid, for e~ample formic or acetic acid, to the alkaline dyestuff soluti.on.
If adjustecl to the intended dyestuff concenkration already prior to the treatment wi-th alkalis the dyestuff formulatlon so prepared can be di.rectly used for the padding of the textile material. Padding is preferably carri.ed OUt at room temperature.
For reasors of a ra~ional opera-tion mode, prepor1deran-t-ly such soluti.ons of the Es+er dyestuff obtained in a concentr;lted form are treated ~i.ch the alkc.llirle aqr.-`nt, and after acldificatiorl only diluted ~7ith wate.r ko the int.ended - 6 - IIOE ~ 0 concen-t?ation for t:he dyelncJ or pac~ding bath or the pr:inti~
paste. It; is xecommended to check the pH after dilution onee more and to correct it if necessary. It is, however, no-t required to prepare the concentrated dyestuf formulations immediately before dyeiny, padding or printiny; they can be made for stock and are stable to storage for a prolonged time in the form of 'lliquid dyestuffs" or printing pastes.
By evaporation, optionally to dryness, the concentration of sueh a dyestuff formulation can be increased accordinc~ to the requirements of the practice.
For use in continuous processes where lic~uor concen-tration and liquor volume have to be maintained constant by steady feeding-up addition, production of the spontaneously reaetive VS form from the Ester dyestufE ~y treatment with alkalis in accordanee with the invention can also be per-formed automatieally by simply dosing and mixincJ the commer~
eial dyestuff solution and the alkaline agent, while, how-ever, taking into consideration a certain residence time.
Subsecluently, by means of a seeond dosaye device aeidifi--cation of the dyeing medium diree-tly introdueed into the applieation opera-tion can be reali~ed, in dependenee on a predeterrrined, weakly acidic pH.
In view of a simplifi.ed applieability, it has proved to he advantageous that in the liquid formulations of the invention the solubility in water of the vinylsulfo11e dyes1:uffs, which hefore had been presel1t already in the form of dissolved sulfatoethylsulfone dyestuffs, is greater than in the case where pulverulent ~inylsu]fone dyest1lffs are directly used for preparing such a so]ution. This is of practieal importance in the case of formulations where due to a high concentration and poor solubility crysta]lized dyestuff has settled on storage, and this precipitate mus-t b~ redi.sso]ved on dilution.
In the special dyeincJ and printi~lc~ tec~miq~es described as follows in order to il]ustrate the utllization, the dye-stuff formulat:ions obtained in accorclance wi-th the inverl'_io are used ln the acldic range at a pII of prefera~bly from 5 to 6.5. In an acid:Lc mediur~l, the hydrolys1s ra-te is relatively lo~., sc that less hydroly7.ed dyestuff is formed;
thus avoiding the formation of a large arnoun-t of inactive hydroxyethylsulfone dyestuff from the vinylsulforIe form, whi.ch cannot react any more with the f:iber and is -therefore lost.
When pad-dyeing or printing natural or synthetic poly amide fibers of their mixtures with other fibers, the reac-tive dye formulations obtained are applied to the flber in the acidic pH range. The dyestuff is fixed subsequently hy dwelling, steaming or dry heat treatment. Preferably, such a heat fixation directly after padding or printin~ is effected upon the rnoist goods. ~lternatively, the padded or printed flber material. can be subjected to an inter-mediate drying at a teMperature a.round 100~C after the application step of the dyestuff.
The dry heat treatment is carried out within 30 seconds to 10 minutes, preferably 2 to 5 minu-tes, at a temperature of from 120 to 240C, preferably 150 to 200C. Steaming or high tempera-ture steaming is c~rried ou-t within 30 seconds to 30 minut:es at 100 to 240C. Preferred is high temperature steaming, for example for 5 minutes at 180C.
A saturated stearn atmosphere is not absolu-tely required.
Good results are for example obtainecI wherI the moisture in the steami.ng apparal:us is about 90 % of the satura-tion amount present at the corresponding temperature.
As compar~d to known operation modes for the dyeing of wool and polyamlde fibers with reactive dyes, the novel process has the follow:incJ advantages:
~ Wool and polyamide fibers can ~e dyed conti.nuously according to a pad-dyeing process.
- Due to the fact that in accordance with the inventio nearly no inactive BA-hydroxyethylsulforle dyestuff is formed~
there are srna].l dyestuff losses only.
- Moreover, due to the improved clyestlIff utili~.atlon, ]ess waste water pollution occurs.
-- Mi.xed fabr:i.cs can be dyed in one single bathO For e~ample, these speciGl reacti.ve dyestuff formulatioIls can be used together w~ h di.sperse dyes ln an acld:ic I~at;h for. the ~6~
- 8 - llO~I 8~ o dyeing of mixt-lre~s of polyester fibers and wool. Furtherl~loj-e, mixed fabrics of natural or synthetic polyamide fihers and cellulose fibers can jointly be treated with these reactive dyc formulations; both fiber types being dyed sim~lltaneous~y in this case.
As in -the krlo~ll processes, the clyestuEf yield of the process of the invelltion can be improved by increasirlg the dyestuff substantivity, for example by addition o electro--lytes.
The following Examples illustrate the inventionO Tlle p~rcenta~es are by weight unless otherwise stated, and relative to the weight of the dry goods in the case of textile n~aterial.
E X A M P L E
50 g of the reactive dyes-tuff of the formula 02S~N = N - C -- C - CH3 OS03Na ~3 ~5 S03Na are dissolved in 50 cm3 of hot water, and dilu-tecl wi-th cold water to 1 liter. 20 cmJ of sodium hydroxide so~ution (32.5 ~ strength) are added to this dyestuff solution, and after 1 minute of dwelling the formulation ls neutralized hy means of acetic acid, and adjus-t~d to pH ~.5. Jsillg the liquor so obtained, fabrics of a) wool, b~ polyamide 6 fibers, and c) polyarnide 6,6 fibers are padded. Subscquently, -the padded fabrics are trea-'.ed in all cases for dyestuff fixation as follows (I~ for one part ~7;-th hot air for 3 min-l-tes at 180~C, and fo~ the o~her part - 9 - _F 81/F 140 (II) hy steaming for 5 minutes at 130C, the steam amourt being 95 ~ of t:he saturation amount possible at this temL~erature.
Subsequel1tly, the dyei.ngs are rinsed with hot and cold water, and soaped at 70C for 10 ml.nutes in an aqueous bath containing 1 g/l of a nonionic detergent. Yellow dyeincJs are obtained in all cases. Similar results i.n the corres-pondiny shades are obtained when accordi.ng to the operation mode of the above Example the dyestuffs indicated in the following Examples S to 9 are used:
_ _ .
Reactive dyestuff of the formula / Cu\
SO3~1 /
-N = N - ~ N = N- ~
E X ~ M P L E 3 _ Dyestuff Reactive Orange 16, C.I~-No. 17757.
E X ~ M P L E 4 Dyestuff Reactive Blue 19, C.I.-No. 61200.
DyestuEf Reactive B1.ack 5, C~ No. 20205.
F. X A M_ L E 6 30 g of the dyestuff of Exarnple 3 are formulated as described in Examp].e 1. Two mixed fabr~~cs of polyamide/
cotton and polyamide/spun rayon, respcctively, are padded with this liquor, and subsequen-tly for dyestuff fixation steamed for 6 minuces at 130C (90 % moisture in the steamina apparatus~. ~he dyeinys are then rinsed with hot and colcl water, and soaped at 60C in an aqueous bath containing 1 g/l of a norlionic detergent. Orange dyeings are obtained; in each case both fi.ber compone~lts of the mi~ecl fa~rics are dyed in i.dentical shades.
~ 10 - HO~ n E X A ~I P L ~ 7 _. __ _ _ _ _ - ~l0 g of the reactive dyesturf of the formula CH3CO~HN OI-I
~ ~-N = N- ~ -CO-NH~
HO3S- -~SO H ~-~
SO2-CH2-CH2~OSO3H
are dissol~ed in 200 cm3 of hot water. Af-ter cooling, 10 cm3 of a 32.5 % sodium hydroxide solution are added to the d~estuff solution, the batch is allowed to dwell for 1 minute, and is then neutralized with the aid of acetic acid, and adjusted to plI 6.5.
The dyestuff formulation so prepared is then nlade up to 1 kg of print.ing paste by adding water and a usual thic~ener, and 50 g/kg of urea are added to the printing paste. A T~ool fabric is subseqllently printed with this paste, and the dyestuff is fixed by steaming for 5 minutes at 130C (98 ~ rnoisture in the steaming apparatus). Subse-quently, the textile material is rinsed with hot and cold water, and soaped at boiling ternperature for 15 rninutcs at 60C in an aqueous liquor Contai.rlincJ 1 g/l of a nonionic detergent. A rcd print on the fabric is ob-tained.
E X ~ M P L E
50 g of the dyestuEf Reactive Blue 19,.C.~.-No. 61200 ~re formula~ted as described in Example 1. 40 g of the dyestuff Disperse Yellow 64, C~ o. 47023 and 2 g of a cor~.ercial wetting agent- are added to this dyestuff liquor.
A mixed fabric of polyester/~700l ~mixincJ ratio 55/45) i5 padded with -this padding liquor. Thereafter, -the fabric is steamed for 4 minutes at 150C ~95 % of moisture in the steamin(~ apparatus) for f.ixation of the two dye~tuffs.
Subsequently, the goods so dyed are rinsed with hot and colcl water/ and soaped for 10 rninutes a-t 70C in an aqueous bath containing ~ c3/l of a nc-,nionic deter(3ent. A bicolor dyeing is ohtained on the r.~ ed fabric; the polyester fi.ber port:i.on ~ein(~ dyed yelloT.A7 and the woo:l portion b~-:i.ncJ uycd h1ue~
~6'~
~ HOE 81/F_1~0 E X A ~ P L F, 9 50 g of the dyest~ff as used in Example 3 are formul-atecl as descrihed in Example 1. After havirl~ adde~ to the batch 10 g of sodium acetate and 2 g of a commercial wetting agent, a fab.ric of wool is padded wi.th the paclding liquor so prepared, and wound up. After a dwelling time of 12 hours at room temperature for dyes-tuff fixation, the dyed fabric is rinsed with cold and ho-t water arld subse-quently soapecl for 10 minutès at 60C i.n an aqueous ba-th containing 2 g/l of a nonionic detergent. An orange dyeing 10 i.s obtained.
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a process for the pad-dyeing or printing of textile material made from natural or synthetic polyamide fibers or mixtures thereof with other fibers, using a reactive dyestuff which in commercial constitution is present in a form incapable of reacting on its own with the fiber substance and containing reactive groups being derived from esters of mono- or polyvalent, inorganic or organic acids easily split off, with a .beta.-hydroxy-ethylsulfone compound, the improvement which comprises converting the reactive dyestuff, before application, in an aqueous medium by treatment with an alkaline agent from the non-fiber-reactive to the fiber-reactive vinylsulfone form and chemically stabilizing it in this converted form by adjusting to a neutral to acidic pH
range by adding acid to the alkaline dyestuff solution, and subsequently applying the dyestuff formulation thus obtained to the fiber material from an aqueous, neutral to acidic medium by pad-dyeing or printing, and fixing the dyestuff on the fiber.
range by adding acid to the alkaline dyestuff solution, and subsequently applying the dyestuff formulation thus obtained to the fiber material from an aqueous, neutral to acidic medium by pad-dyeing or printing, and fixing the dyestuff on the fiber.
2. A process as claimed in claim 1, wherein as reactive dyestuff there is used a dyestuff containing as reactive group at least one sulfatoethylsulfone radical.
3. A process as claimed in claim 1, wherein as alkaline agent there is used an aqueous solution of alkali metal hydroxide or salt having an alkaline reaction in water or a mixture of such hydroxide and salt.
4. A process as claimed in claim 1, wherein fixation of the dyestuff after padding or printing is carried out by maintaining the material at about room temperature, by dry heat treatment for 30 seconds to 10 minutes at a temperature of from 120° to 240°C, by steaming for 30 seconds to 30 minutes at a temperature of from 100° to 240° or by a combination of dry heat treatment and steaming.
5. A process according to claim 4 wherein the fixation is effected following an intermediate drying of the material after the dyestuff application operation.
6. A process as claimed in claim 1, wherein for the dyeing or printing of fiber mixtures the formulation of the reactive dyestuff is used together with one or more dyestuffs of other categories.
7. A process as claimed in claim 1, wherein fiber mixtures of natural or synthetic polyamide fibers with cellulose fibers or of natural polyamide fibers with polyester fibers are dyed or printed.
8. A liquid reactive dyestuff formulation capable of being infinitely diluted with water and suitable for carrying out the process as claimed in claim 1, in which a dyestuff of commercial constitution is present in a form incapable of reacting on its own with the fiber substance and containing reactive groups being derived from esters of mono- or polyvalent, inorganic or organic acids easily split off, with a .beta.-hydroxy-ethylsulfone compound, the reactive dyestuff having been converted in an aqueous medium by treatment with an alkaline agent from the non-fiber-reactive to the fiber-reactive vinylsulfone form and having been chemically stabilized in this converted form by adjusting to a neutral to acidic pH range by adding acid to the alkaline dyestuff solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3122559.4 | 1981-06-06 | ||
| DE19813122559 DE3122559A1 (en) | 1981-06-06 | 1981-06-06 | METHOD FOR BLOCKING OR PRINTING SYNTHETIC POLYAMIDE FIBERS OR MIXTURES THEREOF WITH OTHER FIBERS WITH REACTIVE DYES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1186457A true CA1186457A (en) | 1985-05-07 |
Family
ID=6134098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000404551A Expired CA1186457A (en) | 1981-06-06 | 1982-06-04 | Process for the pad-dyeing or printing of textile material of natural or synthetic polyamide fibers or mixtures thereof with other fibers with reactive dyestuffs |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0066820A1 (en) |
| JP (1) | JPS57210078A (en) |
| CA (1) | CA1186457A (en) |
| DE (1) | DE3122559A1 (en) |
| ZA (1) | ZA823935B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3539475A1 (en) * | 1985-11-07 | 1987-05-14 | Hoechst Ag | METHOD FOR DYING WOOLSTUFFED GOODS |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE507417A (en) * | 1950-01-09 | |||
| IN143734B (en) * | 1974-04-09 | 1978-01-21 | Hoechst Ag | |
| DE2834997C2 (en) * | 1978-08-10 | 1980-08-28 | Hoechst Ag, 6000 Frankfurt | Process for dyeing synthetic polyamide fibers with reactive dyes using the exhaust method |
-
1981
- 1981-06-06 DE DE19813122559 patent/DE3122559A1/en not_active Withdrawn
-
1982
- 1982-05-29 EP EP82104753A patent/EP0066820A1/en not_active Ceased
- 1982-06-04 JP JP57095037A patent/JPS57210078A/en active Pending
- 1982-06-04 ZA ZA823935A patent/ZA823935B/en unknown
- 1982-06-04 CA CA000404551A patent/CA1186457A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3122559A1 (en) | 1982-12-23 |
| JPS57210078A (en) | 1982-12-23 |
| ZA823935B (en) | 1983-03-30 |
| EP0066820A1 (en) | 1982-12-15 |
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