EP0010760A1 - Process for dyeing wool with reactive dyestuffs - Google Patents
Process for dyeing wool with reactive dyestuffs Download PDFInfo
- Publication number
- EP0010760A1 EP0010760A1 EP79104239A EP79104239A EP0010760A1 EP 0010760 A1 EP0010760 A1 EP 0010760A1 EP 79104239 A EP79104239 A EP 79104239A EP 79104239 A EP79104239 A EP 79104239A EP 0010760 A1 EP0010760 A1 EP 0010760A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dyeing
- wool
- dye
- dyes
- reactive
- 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.)
- Granted
Links
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
- D06P3/14—Wool
- D06P3/148—Wool using reactive dyes
-
- 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
Definitions
- Felt-free finished wool is wool fibers that e.g. with a polyimine or polyacrylic resin film (as specified in Melliand Textile Reports 9/1971, page 1100, or in the Journal of the Society of Dyers and Colors, Volume 88, Number 3/1972, pages 93-100).
- a textile article made from it must be able to withstand the hard stresses not required and not achieved with normal wool, such as washing multiple times at 60 ° C with the use of household detergents containing perborate, without matting, and consequently be color-fast.
- Such requirements at this high level of fastness, particularly in terms of fastness to washing and sweating, are primarily achieved by dyeing with reactive dyes.
- the dye manufacturers have put together separate ranges of dyes with the reactive dyes best suited for the type of fiber so equipped and put them on the market.
- the reactive groups of such dyes are temporarily, i.e. reversible in the course of the dyeing operation, blocked in order to enable a better equalization of the dyes by a modified reaction mechanism.
- the present invention is based on the object of simplifying the currently known dyeing processes for reactive dyes on wool, reducing the amount of their critical points and maintaining the high level of authenticity of the dyeings, which amounts to bringing about the covalent bond between dyes and fibers.
- This object is achieved according to the invention by using aqueous dye liquors containing at least one reactive dye in commercially available form and composition, the starting pH of which is in the slightly acidic to neutral range, and by adding as soon as possible after adding the dissolved dye the dyeing temperature from 110 ° to 125 ° C and heated at this temperature for 10 to 20 minutes and that during does not add pH-regulating substances to the entire dyeing process.
- the dye baths are completely removed within 10 to 20 minutes when dyeing according to the new process, so that good dye utilization is ensured.
- the wool treated according to the invention does not suffer any damage under the above-mentioned conditions, despite the high dyeing temperature, which is unusual for wool, or is kept within a range such as occurs in the usual dyeing processes and is accepted.
- wool preservatives can be added to the dye baths. It was surprising that the 33% aqueous formaldehyde solution usually used under these conditions in amounts of 5% (by weight of the dry wool) produces only slight color depth losses, i.e. affects the achievable color depth only slightly.
- Other wool protection agents such as Protein condensation products do not provide effective wool protection under the HT conditions used.
- the aqueous dyebath is set at 70 ° to 80 ° C. together with the goods made from the normal wool or from the wool which has already been treated to be felt-free, and which have not been subjected to any pretreatment with the addition of alkalis or alkali donors Run the liquor 5 to 10 minutes ahead to equalize the temperature and to distribute any additives (wool protection agents).
- the reactive dye or the reactive dye mixture is dissolved in water in a conventional manner and added to the dyebath at about 80 ° to 90 ° C.
- a preactivation of the reactive dye by means of alkalis as in the known method according to the magazine "Chemiemaschine" 1965, pages 450- 451 and 525-526 do not take place here.
- the pH of these liquors (measured at 20 ° C) must be in the weakly acidic to neutral range. This means that pH values of approximately 4.0 to 7.0, preferably 6.0 to 7.0, should be maintained. A pH adjustment is not necessary, since aqueous solutions of reactive dyes (in commercial form and quality) are weakly acidic. Process water that has been softened with cation exchangers are often weakly alkaline and therefore require a pH correction in the range mentioned, expediently using acetic acid.
- the dyeing liquor is heated to the dyeing temperature of 110 ° to 125 ° C. as quickly as possible (within 5 to 10 minutes) and the goods are then dyed at this temperature for 10 to 20 minutes.
- the liquor and the material to be dyed are then allowed to cool to about 80 ° C. and the dyeing thus obtained is rinsed with warm and cold water.
- the dyeings produced according to the invention In order to improve the wet fastness properties of the wool dyed in this way, it is advisable in certain cases to subject the dyeings produced according to the invention to aftertreatment with 1 to 2% (by weight of the dry goods) aqueous ammonia solution (25%) after the end of the dyeing operation .
- This aftertreatment can be carried out in the dye bath even after it has been exhausted with reactive dye and after cooling to 70 ° to 80 ° C. for a further 5 to 15 minutes or in a freshly prepared ammoniacal aftertreatment bath under the conditions mentioned above.
- the process according to the invention is also suitable for the single-bath dyeing of mixtures of wool or felt-free finished wool and polyester fibers, the advantages of the novel application technology for the reactive dyes being particularly clear.
- the dyeing liquors used also contain the predispersed disperse dyes; however, the use of acid donors is not necessary.
- the measures according to the invention for dyeing these fiber mixtures can be carried out both in one-stage and in two-stage mode of operation.
- the disperse dye can be added to the dye liquor after it has been exhausted with reactive dye, or the reactive dye can, for example in the case of rapid dyeing processes, also be introduced into the HT apparatus by the disperse dye after a pre-dyeing time for the polyester fiber fraction.
- the new process now also allows the reactive dyes to be used in an HT dyeing process in addition to the disperse dyes for dyeing such mixtures.
- the method according to the invention is distinguished from the known, conventional methods for dyeing of wool due to its simplicity and a considerable reduction in dyeing times.
- the fastness properties which can be achieved correspond in all tests to those of dyeings which have been produced by the two-stage processes which have been customary up to now.
- reactive dyes For the dyeing of normal wool or of wool which has been given a felt-free finish, or of the wool content of fiber blends by the present process, the organic dyes known under this term - regardless of the nature of their reactive group - come into consideration as reactive dyes.
- This class of dyes is referred to in the Color Index, 3rd edition 1971 as "reactive dyes". These are predominantly those dyes which contain at least one group which is reactive with polyhydroxyl fibers or wool, a precursor therefor or a substituent which is reactive with polyhydroxyl fibers or wool.
- Particularly suitable as the basic body of the organic dyes are those from the series of the azo, anthraquinone and phthalocyanine dyes, it being possible for the azo and phthalocyanine dyes to be both metal-free and metal-containing.
- Reactive groups and precursors which form such reactive groups include, for example, epoxy groups, the ethyleneimide group, the vinyl grouping in the vinylsulfone or acrylic acid residue, also the ⁇ -sulfatoethylsulfone group, the ⁇ -chloroethylsulfone group or the ⁇ -dialkylaminoethylsulfone group.
- tetrafluorocyclobutyl series for example tetrafluorocyclobutyl acrylic acid
- the reactive substituents in reactive dyes are those that are easily removable and leave an electrophilic residue.
- suitable substituents are 1 to 3 halogen atoms on the following ring system: quinoxaline, triazine, pyrimidine, phthalazine, pyridazine and pyridazone.
- the temporarily blocked reactive dyes mentioned at the outset such as are obtained, for example, by reacting dyes containing ⁇ -sulfatoethylsulfone groups with N-methyl taurine, also give the new process dyeings on normal wool and on felt-free finished wool, but here, depending on the individual dye content, the Color yield can be reduced compared to the usual dyeing process.
- Disperse Dyes are suitable as disperse dyes for dyeing the polyester fiber component. Products of this type originate, for example, from the series of the azo, anthraquinone or quinophthalone dyes, it being possible for the azo dyes to be used both in metal-containing and in metal-free form. Dyes in the category mentioned are well known.
- Dye Reactive Orange 16 with the C.I. 17 757 heats it to 120 ° C within 5 to 10 minutes and dyes the goods at this temperature for 15 minutes.
- the bath is drained and the wool is rinsed with water.
- Dyeing is carried out as in Example 1, but here 54 kg of piece of wool in an HT tree dyeing machine with a liquor ratio of 1:20 1.2% (of the weight of the goods) of the commercial
- aqueous ammonia solution (25%) is added to the dye bath, the dyeing is treated for a further 10 minutes under the given conditions and the yarn thus dyed is rinsed clear with water.
- the wool is given a felt-free finish in accordance with the process described in Melliand Textile Reports 9, 1971, p. 1100, and in the Journal of the Society of Dyers and Colors, Volume 88, p. 93 ff.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
Abstract
Verfahren zum Färben von Textilien, die aus nicht filzfrei ausgerüsteter Wolle bzw. aus mit einer Auflage aus einem Polyiminharz oder einem Polyacrylharz filzfrei ausgerüsteter Wolle bestehen oder solche aufweisen, mit Reaktivfarbstoffen nach der Ausziehmethode, dadurch gekennzeichnet, daß man wäßrige Färbeflotten enthaltend mindestens einen Reaktivfarbstoff in handelsüblicher Form und Beschaffenheit verwendet, dessen Ausgangs-pH-Wert im schwach sauren bis neutralen Bereich liegt, und daß man nach dem Zusatz des gelösten Farbstoffes so rasch wie möglich auf die Färbetemperatur von 110° bis 125° C aufheizt und bei dieser Temperatur 10 bis 20 Minuten färbt und daß man während des gesamten Färbeverfahrens keine pH-regulierenden Substanzen zusetzt.A process for dyeing textiles which consist of wool which has not been finished with a felt or which has or has been treated with a coating of a polyimine resin or a polyacrylic resin with reactive dyes by the exhaust method, characterized in that aqueous dyeing liquors containing at least one reactive dye in commercial form and texture used, the starting pH is in the weakly acidic to neutral range, and that after the addition of the dissolved dye is heated as quickly as possible to the dyeing temperature of 110 ° to 125 ° C and at this temperature 10 to Dyeing for 20 minutes and that no pH-regulating substances are added during the entire dyeing process.
Description
Das Färben von Wolle mit Reaktivfarbstoffen ist allgemein bekannt und in der Praxis seit geraumer Zeit eingeführt. Neben der Erzeugung besonders brillanter Farbtöne hat der Einsatz von Reaktivfarbstoffen auf diesem Sektor vor allem für das Färben von durch spezielle Maßnahmen filzfrei ausgerüsteter Wolle Bedeutung erlangt. Bei filzfrei ausgerüsteter Wolle handelt es sich um Wollfasern, die z.B. mit einem Polyimin- oder Polyacrylharz-Film (entsprechend den Angaben in Melliand Textilberichte 9/1971, Seite 1100, oder im Journal of the Society of Dyers and Colourists, Volume 88, Number 3/1972, Seiten 93-100) überzogen worden sind. Ein daraus gefertigter textiler Artikel muß den bei normaler Wolle nicht verlangten und auch nicht erreichten, harten Beanspruchungen einer mehrfachen Wäsche bei 60°C unter Mitverwendung von perborathaltigen Haushaltswaschmitteln standhalten, ohne zu verfilzen, und demzufolge auch entsprechend farbecht sein. Derartige Anforderungen auf diesem hohen Echtheitsniveau, besonders in der Wasch- und Schweißechtheit, werden in erster Linie von Färbungen mit Reaktivfarbstoffen erreicht. Von den Farbstoffherstellern wurden für diesen Zweck separate Farbstoffsortimente mit den für die so ausgerüstete Faserart bestgeeigneten Reaktivfarbstoffen zusammengestellt und in den Handel gebracht. Teilweise werden, um die Brauchbarkeit im Ausziehfärbeprozeß, vor allem wegen der in diesen Fällen auftretenden Egalisierschwierigkeiten, noch zu verbessern die Reaktivgruppen solcher Farbstoffe, vorübergehend, d.h. im Verlauf der Färbeoperation rücksteuerbar, blockiert, um durch einen abgeänderten Reaktionsmechanismus ein besseres Egalisieren der Farbstoffe zu ermöglichen.The dyeing of wool with reactive dyes is generally known and has been in practice for some time. In addition to the production of particularly brilliant shades, the use of reactive dyes in this sector has become particularly important for dyeing wool that has been made felt-free using special measures. Felt-free finished wool is wool fibers that e.g. with a polyimine or polyacrylic resin film (as specified in Melliand Textile Reports 9/1971, page 1100, or in the Journal of the Society of Dyers and Colors, Volume 88, Number 3/1972, pages 93-100). A textile article made from it must be able to withstand the hard stresses not required and not achieved with normal wool, such as washing multiple times at 60 ° C with the use of household detergents containing perborate, without matting, and consequently be color-fast. Such requirements at this high level of fastness, particularly in terms of fastness to washing and sweating, are primarily achieved by dyeing with reactive dyes. For this purpose, the dye manufacturers have put together separate ranges of dyes with the reactive dyes best suited for the type of fiber so equipped and put them on the market. In part, in order to improve the usability in the exhaust dyeing process, especially because of the leveling difficulties which occur in these cases, the reactive groups of such dyes are temporarily, i.e. reversible in the course of the dyeing operation, blocked in order to enable a better equalization of the dyes by a modified reaction mechanism.
Verfahren auf dieser Basis sind aus der Literatur hinreichend bekannt, z.B. aus Journal of the Society of Dyers and Colourists 72/03/88 S. 93-100, Melliand Textilberichte 1968/12 S. 1444-1448, Textilveredlung 71/02/6 S. 57-62, Textile World Aug. 1964 S. 82 ff sowie Melliand Textilberichte 1974 S. 468 ff.Methods on this basis are well known from the literature, for example from Journal of the Society of Dyers and Colourists 72/03/88 pp. 93-100, Melliand Textil reports 1968/12 pp. 1444-1448, textile finishing 71/02/6 pp. 57-62, Textile World Aug. 1964 pp. 82 ff and Melliand textile reports 1974 pp. 468 ff.
Allen diesen herkömmlichen Verfahren zum Färben von Wolle bzw. von filzfrei ausgerüsteter Wolle ist gemeinsam, daß die Reaktivfarbstöffe aus saurem Färbebad unter genauer Kontrolle der pH-Werte dem Ausziehprozeß unterworfen und daß gegen Ende der Färbezeit der pH-Wert in den weniger sauren bzw. schwach alkalischen Bereich verschoben werden muß, um die reaktive Bindung zwischen Farbstoffen und Fasern herbeizuführen. Damit haftet solchen Verfahren allerdings der Nachteil an, daß nur allein durch eine peinlich genaue pH-Kontrolle, zuverlässige Temperaturführung und relativ lange Färbezeiten volle Farbausbeuten und vor allem eine ausreichende Egalität der Färbungen erhalten werden kann. Um insbesondere den Forderungen an die Egalität gerecht zu werden, sind sogar spezielle Färbeverfahen entwickelt worden.Common to all of these conventional processes for dyeing wool or wool which has been given a felt-free finish is that the reactive dyestuffs from an acid dyebath are subjected to the exhausting process with precise control of the pH values and that towards the end of the dyeing time the pH value in the less acidic or weakly alkaline range must be shifted to bring about the reactive bond between dyes and fibers. However, such processes have the disadvantage that full color yields and, above all, sufficient levelness of the dyeings can only be obtained by meticulously accurate pH control, reliable temperature control and relatively long dyeing times. In order to meet the requirements for equality in particular, special dyeing processes have even been developed.
Der vorliegenden Erfindung liegt nunmehr die Aufgabe zugrunde, die derzeit bekannten Färbeverfahren für Reaktivfarbstoffe auf Wolle einfacher zu gestalten, die Menge ihrer kritischen Punkte zu verringern und das hohe Echtheitsniveau der Färbungen beizubehalten, was auf die Herbeiführung der kovalenten Bindung zwischen Farbstoffen und Fasern hinausläuft.The present invention is based on the object of simplifying the currently known dyeing processes for reactive dyes on wool, reducing the amount of their critical points and maintaining the high level of authenticity of the dyeings, which amounts to bringing about the covalent bond between dyes and fibers.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß man wäßrige Färbeflotten enthaltend mindestens einen Reaktivfarbstoff in handelsüblicher Form und Beschaffenheit verwendet, dessen Ausgangs-pH-Wert im schwach sauren bis neutralen Bereich liegt, und daß man nach dem Zusatz des gelösten Farbstoffs so rasch wie möglich auf die Färbetemperatur von 110° bis 125°C aufheizt und bei dieser Temperatur 10 bis 20 Minuten färbt und daß man während des gesamten Färbeverfahrens keine pH-regulierenden Substanzen zusetzt.This object is achieved according to the invention by using aqueous dye liquors containing at least one reactive dye in commercially available form and composition, the starting pH of which is in the slightly acidic to neutral range, and by adding as soon as possible after adding the dissolved dye the dyeing temperature from 110 ° to 125 ° C and heated at this temperature for 10 to 20 minutes and that during does not add pH-regulating substances to the entire dyeing process.
Die Färbebäder sind beim Färben nach dem neuen Verfahren innerhalb von 10 bis 20 Minuten vollkommen ausgezogen, so daß eine gute Farbstoffausnutzung sichergestellt ist.The dye baths are completely removed within 10 to 20 minutes when dyeing according to the new process, so that good dye utilization is ensured.
Die nach der Erfindung behandelte Wolle erleidet unter den oben genannten Bedingungen trotz der hohen und für Wolle ungewöhnlichen Färbetemperatur keine Schädigung bzw. hält sich diese in einem Rahmen, wie sie bei den üblichen Färbeverfahren auch eintritt und in Kauf genommen wird. Zum Schutz der Wolle können den Färbebädern Wollschutzmittel zugesetzt werden. Es war dabei überraschend, daß die üblicherweise unter diesen Bedingungen in Mengen von 5 % (vom Gewicht der trockenen Wolle) verwendete 33 %ige, wäßrige Formaldehyd-Lösung nur geringfügige Farbtiefenverluste erzeugt, d.h. die erreichbare Farbtiefe nur wenig beeinflußt. Andere Wollschutzmittel, wie z.B. Eiweißkondensationsprodukte ergeben unter den angewandten HT-Bedingungen keinen wirksamen Wollschutz.The wool treated according to the invention does not suffer any damage under the above-mentioned conditions, despite the high dyeing temperature, which is unusual for wool, or is kept within a range such as occurs in the usual dyeing processes and is accepted. To protect the wool, wool preservatives can be added to the dye baths. It was surprising that the 33% aqueous formaldehyde solution usually used under these conditions in amounts of 5% (by weight of the dry wool) produces only slight color depth losses, i.e. affects the achievable color depth only slightly. Other wool protection agents such as Protein condensation products do not provide effective wool protection under the HT conditions used.
Zur Durchführung des erfindungsgemäßen Verfahrens setzt man das wäßrige Färbebad zusammen mit der Ware aus der normalen bzw. aus der bereits filzfrei ausgerüsteten Wolle, welche keinerlei Vorbehandlung unter Zusatz von Alkalien oder Alkalispendern unterzogen worden sind, bei 70° bis 80°C an und läßt die Flotte zur Vergleichmäßigung der Temperatur und zur Verteilung eventuell zugesetzter Hilfsmittel (Wollschutzmittel) 5 bis 10 Minuten vorlaufen. Getrennt davon wird der Reaktivfarbstoff bzw. die Reaktivfarbstoffmischung in herkömmlicher Weise in Wasser gelöst und dem Färbebad bei ca. 80° bis 90°C zugesetzt. Eine Voraktivierung des Reaktivfarbstoffes mittels Alkalien wie beim bekannten Verfahren gemäß der Zeitschrift "Chemiefasern" 1965, Seiten 450-451 und 525-526 findet hier nicht statt. Der pH-Wert dieser Flotten (bei 20°C gemessen) muß dabei im schwach sauren bis neutralen Bereich liegen. Das bedeutet, daß pH-Werte von ungefähr 4,0 bis 7,0, vorzugsweise 6,0 bis 7,0 eingehalten werden sollen. Eine pH-Einstellung ist nicht erforderlich, da wäßrige Lösungen von Reaktivfarbstoffen (in handelsüblicher Form und Beschaffenheit) schwach sauer sind. Betriebswässer, die mit Kationenaustauschern enthärtet worden sind, sind häufig schwach alkalisch und bedürfen deshalb der pH-Korrektur in den genannten Bereich, zweckmäßig mittels Essigsäure.To carry out the process according to the invention, the aqueous dyebath is set at 70 ° to 80 ° C. together with the goods made from the normal wool or from the wool which has already been treated to be felt-free, and which have not been subjected to any pretreatment with the addition of alkalis or alkali donors Run the liquor 5 to 10 minutes ahead to equalize the temperature and to distribute any additives (wool protection agents). Separately, the reactive dye or the reactive dye mixture is dissolved in water in a conventional manner and added to the dyebath at about 80 ° to 90 ° C. A preactivation of the reactive dye by means of alkalis as in the known method according to the magazine "Chemiefaser" 1965, pages 450- 451 and 525-526 do not take place here. The pH of these liquors (measured at 20 ° C) must be in the weakly acidic to neutral range. This means that pH values of approximately 4.0 to 7.0, preferably 6.0 to 7.0, should be maintained. A pH adjustment is not necessary, since aqueous solutions of reactive dyes (in commercial form and quality) are weakly acidic. Process water that has been softened with cation exchangers are often weakly alkaline and therefore require a pH correction in the range mentioned, expediently using acetic acid.
Sofort nach dem erfolgten Zusatz des gelösten Farbstoffes wird die Färbeflotte so rasch wie möglich (innerhalb von 5 bis 10 Minuten) auf die Färbetemperatur von 110° bis 125°C aufgeheizt und dann die Ware bei dieser Temperatur 10 bis 20 Minuten gefärbt. Sodann läßt man Flotte samt Färbegut auf etwa 80°C abkühlen und spült die so erhaltene Färbung mit warmem und kaltem Wasser.Immediately after the dissolved dye has been added, the dyeing liquor is heated to the dyeing temperature of 110 ° to 125 ° C. as quickly as possible (within 5 to 10 minutes) and the goods are then dyed at this temperature for 10 to 20 minutes. The liquor and the material to be dyed are then allowed to cool to about 80 ° C. and the dyeing thus obtained is rinsed with warm and cold water.
Zur Verbesserung der Naßechtheitseigenschaften der in dieser Weise gefärbten Wolle ist es zweckmäßig, die erfindungsgemäß erzeugten Färbungen nach Beendigung der Ausziehfärbeoperation in gewissen Fällen einer Nachbehandlung mit 1 bis 2 % (vom Gewicht der trockenen Ware) wäßriger Ammoniak-Lösung (25 %ig) zu unterziehen. Diese Nachbehandlung kann im Färbebad selbst nach dessen Erschöpfung an Reaktivfarbstoff sowie nach Abkühlen auf 70° bis 80°C während weiterer 5 bis 15 Minuten oder in einem frisch bereiteten ammoniakalischen Nachbehandlungsbad unter den vorstehend erwähnten Bedingungen erfolgen.In order to improve the wet fastness properties of the wool dyed in this way, it is advisable in certain cases to subject the dyeings produced according to the invention to aftertreatment with 1 to 2% (by weight of the dry goods) aqueous ammonia solution (25%) after the end of the dyeing operation . This aftertreatment can be carried out in the dye bath even after it has been exhausted with reactive dye and after cooling to 70 ° to 80 ° C. for a further 5 to 15 minutes or in a freshly prepared ammoniacal aftertreatment bath under the conditions mentioned above.
Das erfindungsgemäße Verfahren kommt auch in Betracht für das einbadige Färben von Mischungen aus Wolle bzw. filzfrei ausgerüsteter Wolle und Polyesterfasern, wobei die Vorteile der neuartigen Applikationstechnik für die Reaktivfarbstoffe besonders deutlich hervortreten.The process according to the invention is also suitable for the single-bath dyeing of mixtures of wool or felt-free finished wool and polyester fibers, the advantages of the novel application technology for the reactive dyes being particularly clear.
In solchen Fällen enthalten die zur Anwendung gelangenden Färbeflotten zusätzlich noch die vordispergierten Dispersionsfarbstoffe; der Einsatz von Säurespendern ist hierbei jedoch nicht erforderlich. Die erfindungsgemäßen Maßnahmen zum Färben dieser Fasermischungen lassen sich sowohl in einstufiger als auch in zweistufiger Arbeitsweise durchführen. Entsprechend dem letztgenannten Prinzip kann man den Dispersionsfarbstoff der Färbeflotte nach deren Erschöpfen an Reaktivfarbstoff zusetzen oder der Reaktivfarbstoff kann, zum Beispiel bei Schnellfärbeverfahren, auch nach einer Vorfärbezeit für den Polyesterfaseranteil durch den Dispersionsfarbstoff anschließend in den HT-Apparat eingeschleust werden.In such cases, the dyeing liquors used also contain the predispersed disperse dyes; however, the use of acid donors is not necessary. The measures according to the invention for dyeing these fiber mixtures can be carried out both in one-stage and in two-stage mode of operation. According to the last-mentioned principle, the disperse dye can be added to the dye liquor after it has been exhausted with reactive dye, or the reactive dye can, for example in the case of rapid dyeing processes, also be introduced into the HT apparatus by the disperse dye after a pre-dyeing time for the polyester fiber fraction.
Beim Färben von solchen Polyesterfasern/Wolle-Mischungen ist man nach den bisherigen Färbeverfahren gezwungen gewesen, diese Färbungen zur Schonung der Wolle bei maximal 106°C sowie mit einem Zusatz von Carriern und mit Färbezeiten von 45 Minuten bzw. länger durchzuführen. Der Carrierzusatz war in diesen Fällen notwendig, um unter den geschilderten Färbebedingungen den Dispersionsfarbstoff in der Polyesterfaser zu fixieren.When dyeing such polyester fibers / wool blends, previous dyeing processes have been forced to carry out these dyeings to protect the wool at a maximum of 106 ° C. and with the addition of carriers and with dyeing times of 45 minutes or longer. The carrier addition was necessary in these cases in order to fix the disperse dye in the polyester fiber under the dyeing conditions described.
Das neue Verfahren erlaubt es nun, auch die Reaktivfarbstoffe in einem HT-Färbeverfahren neben den Dispersionsfarbstoffen zum Färben solcher Mischungen einzusetzen.The new process now also allows the reactive dyes to be used in an HT dyeing process in addition to the disperse dyes for dyeing such mixtures.
Für die Durchführung des neuen Verfahrens sind alle Färbeapparate bzw. Färbemaschinen geeignet, die eine HT-Behandlung des Färbegutes erlauben. Damit können Wollfasern in praktisch allen Verarbeitungsstadien gefärbt werden. Schwierigkeiten mit streifigfärbendem Material sind nicht aufgetreten.All dyeing machines or dyeing machines are suitable for carrying out the new process, which allow HT treatment of the dyeing material. This means that wool fibers can be dyed in practically all stages of processing. There were no difficulties with streak-coloring material.
Das erfindungsgemäße Verfahren zeichnet sich gegenüber den bekannten, herkömmlichen Methoden zum Ausziehfärben von Wolle durch seine Einfachheit und durch eine beträchtliche Verkürzung der Färbezeiten aus. Die erzielbaren Echtheitseigenschaften entsprechen in allen Prüfungen denen von Färbungen, die man nach den bisher üblichen zweistufigen Verfahren hergestellt hat.The method according to the invention is distinguished from the known, conventional methods for dyeing of wool due to its simplicity and a considerable reduction in dyeing times. The fastness properties which can be achieved correspond in all tests to those of dyeings which have been produced by the two-stage processes which have been customary up to now.
Für das Färben von normaler Wolle bzw. von filzfrei ausgerüsteter Wolle oder des Wollanteils von Fasermischungen nach dem vorliegenden Verfahren kommen als Reaktivfarbstoffe die unter diesem Begriff bekannten organischen Farbstoffe - unabhängig von der Art ihrer reaktiven Gruppe - in Betracht. Diese Farbstoffklasse wird im Colour Index, 3. Auflage 1971 als "Reactive Dyes" bezeichnet. Es handelt sich hierbei vorwiegend um solche Farbstoffe, die mindestens eine mit Polyhydroxylfasern oder Wolle reaktionsfähige Gruppe, eine Vorstufe hierfür oder einen mit Polyhydroxylfasern oder Wolle reaktionsfähigen Substituenten enthalten. Als Grundkörper der organischen Farbstoffe eignen sich besonders solche aus der Reihe der Azo-, Anthrachinon-und Phthalocyaninfarbstoffe, wobei die Azo- und Phthalocyaninfarbstoffe sowohl metallfrei als auch metallhaltig sein können. Als reaktionsfähige Gruppen und Vorstufen, die solche reaktionsfähige Gruppen bilden, seien beispielsweise Epoxygruppen, die Äthylenimidgruppe, die Vinylgruppierung im Vinylsulfon- oder im Acrylsäurerest, ferner die ß-Sulfatoäthylsulfongruppe, die β-Chloräthyl- sulfongruppe oder die ß-Dialkylaminoäthylsulfongruppe genannt. Außerdem kommen für dieses Verfahren Derivate der Tetrafluorcyclobutyl-Reihe, z.B. der Tetrafluorcyclobutylacrylsäure in Frage. Als reaktionsfähige Substituenten in Reaktivfarbstoffen dienen solche, die leicht abspaltbar sind und einen elektrophilen Rest hinterlassen. Als Substituenten kommen beispielsweise 1 bis 3 Halogenatome an folgenden Ringsystem in Betracht: Chinoxalin, Triazin, Pyrimidin, Phthalazin, Pyridazin und Pyridazon.For the dyeing of normal wool or of wool which has been given a felt-free finish, or of the wool content of fiber blends by the present process, the organic dyes known under this term - regardless of the nature of their reactive group - come into consideration as reactive dyes. This class of dyes is referred to in the Color Index, 3rd edition 1971 as "reactive dyes". These are predominantly those dyes which contain at least one group which is reactive with polyhydroxyl fibers or wool, a precursor therefor or a substituent which is reactive with polyhydroxyl fibers or wool. Particularly suitable as the basic body of the organic dyes are those from the series of the azo, anthraquinone and phthalocyanine dyes, it being possible for the azo and phthalocyanine dyes to be both metal-free and metal-containing. Reactive groups and precursors which form such reactive groups include, for example, epoxy groups, the ethyleneimide group, the vinyl grouping in the vinylsulfone or acrylic acid residue, also the β-sulfatoethylsulfone group, the β-chloroethylsulfone group or the β-dialkylaminoethylsulfone group. Derivatives of the tetrafluorocyclobutyl series, for example tetrafluorocyclobutyl acrylic acid, are also suitable for this process. The reactive substituents in reactive dyes are those that are easily removable and leave an electrophilic residue. Examples of suitable substituents are 1 to 3 halogen atoms on the following ring system: quinoxaline, triazine, pyrimidine, phthalazine, pyridazine and pyridazone.
Es können auch Farbstoffe mit mehreren gleich- oder verschiedenartigen Reaktivgruppen verwendet werden.Dyes with several identical or different reactive groups can also be used.
Auch die eingangs genannten vorübergehend blockierten Reaktivfarbstoffe, wie sie beispielsweise durch Umsetzung von ß-Sulfatoäthylsulfongruppen enthaltenden Farbstoffen mit N-Methyltaurin erhalten werden, ergeben nach dem neuen Verfahren Färbungen auf normaler Wolle sowie auf filzfrei ausgerüsteter Wolle, jedoch kann hier, vom Farbstoffindividium abhängig, die Farbausbeute gegenüber den üblichen Färbeverfahren vermindert sein.The temporarily blocked reactive dyes mentioned at the outset, such as are obtained, for example, by reacting dyes containing β-sulfatoethylsulfone groups with N-methyl taurine, also give the new process dyeings on normal wool and on felt-free finished wool, but here, depending on the individual dye content, the Color yield can be reduced compared to the usual dyeing process.
Als Dispersionsfarbstoffe für das Färben der Polyesterfaserkomponente sind alle wasserunlöslichen Farbstoffe geeignet, die im Colour Index, 3. Auflage 1971 unter dem Begriff "Disperse Dyes" aufgeführt werden. Derartige Produkte stammen beispielsweise aus der Reihe der Azo-, Anthrachinon- oder Chinophthalon-Farbstoffe, wobei die Azofarbstoffe sowohl in metallhaltiger als auch in metallfreier Form eingesetzt werden können. Farbstoffe der genannten Kategorie sind hinlänglich bekannt.All water-insoluble dyes which are listed in the Color Index, 3rd edition 1971 under the term "Disperse Dyes" are suitable as disperse dyes for dyeing the polyester fiber component. Products of this type originate, for example, from the series of the azo, anthraquinone or quinophthalone dyes, it being possible for the azo dyes to be used both in metal-containing and in metal-free form. Dyes in the category mentioned are well known.
In einem HT-Färbeapparat werden bei einem Flottenverhältnis von 1:15 Kreuzspulen aus Wollgarn im Gesamtgewicht von 80 kg gefärbt. Das hierzu benötigte Färbebad wird mit Wasser von 80°C sowie
- 5 % vom Wollgewicht = (4 kg) wäßriger Formaldehyd- lösung (33 %ig)
angesetzt und 10 Minuten durch das aufgespulte Fasermaterial zirkulieren gelassen. Dann fügt man dieser Flotte noch - 2 % vom Wollgewicht (= 1,6 kg) des handelsüblichen
- 5% of wool weight = (4 kg) aqueous formaldehyde solution (33%)
prepared and allowed to circulate through the wound fiber material for 10 minutes. Then you add this fleet - 2% of the wool weight (= 1.6 kg) of the commercially available
Farbstoffes Reactive Orange 16 mit der C.I.-Nr. 17 757 zu, erhitzt dieselbe innerhalb von 5 bis 10 Minuten auf 120°C und färbt die Ware 15 Minuten bei dieser Temperatur.Dye Reactive Orange 16 with the C.I. 17 757, heats it to 120 ° C within 5 to 10 minutes and dyes the goods at this temperature for 15 minutes.
Nach dem Abkühlen von Flotte samt Färbegut auf 80°C wird das Bad abgelassen und die Wolle mit Wasser gespült.After the liquor and the dyed material have cooled to 80 ° C., the bath is drained and the wool is rinsed with water.
Man erhält eine kräftige, echte Scharlachfärbung der Wolle.You get a strong, real scarlet color of the wool.
Man färbt wie in Beispiel 1, hier jedoch 54 kg Wollstückware in einem HT-Baumfärbeapparat beim Flottenverhältnis von 1:20 mit
1,2 % (vom Warengewicht) des handelsüblichenDyeing is carried out as in Example 1, but here 54 kg of piece of wool in an HT tree dyeing machine with a liquor ratio of 1:20
1.2% (of the weight of the goods) of the commercial
Farbstoffes der Formel
Man färbt wie in Beispiel 1, hier jedoch ohne den Formaldehydzusatz 35 kg filzfrei ausgerüstetes Wollgarn mit
- 6 % (vom Wollgewicht) des handelsüblichen Farbstoffes Reactive Black 5 mit der C.I.-Nr. 20 505
und - 0,1 % (vom Wollgewicht) Chrom(III)-acetat-sulfat.
- 6% (of the wool weight) of the commercial dye Reactive Black 5 with the CI no. 20 505
and - 0.1% (by wool weight) of chromium (III) acetate sulfate.
Nach Erschöpfung der Flotte an Reaktivfarbstoff sowie dem Abkühlen auf 80°C setzt man dem Färbebad 1,5 % (vom Wollgewicht) wäßriger Ammoniaklösung (25 %ig) zu, behandelt die Färbung weitere 10 Minuten unter den gegebenen Bedingungen und spült das so gefärbte Garn klar mit Wasser.After exhaustion of the liquor of reactive dye and cooling to 80 ° C., 1.5% (by weight of wool) aqueous ammonia solution (25%) is added to the dye bath, the dyeing is treated for a further 10 minutes under the given conditions and the yarn thus dyed is rinsed clear with water.
Man erhält eine sehr echte, blumige Schwarzfärbung.You get a very real, flowery black color.
Die Filzfrei-Ausrüstung der Wolle erfolgt nach dem in Melliand-Textilberichte 9, 1971, S. 1100, sowie im Journal of the Society of Dyers and Colourists, Volume 88, S. 93 ff. beschriebenen Verfahren.The wool is given a felt-free finish in accordance with the process described in Melliand Textile Reports 9, 1971, p. 1100, and in the Journal of the Society of Dyers and Colors, Volume 88, p. 93 ff.
Man färbt 67 kg Wollgarn gemäß Beispiel 1 mit folgenden Badzusätzen:
- 5 % vom Wollgewicht (= 3,35 l) wäßriger Formaldehydlösung (33 %ig)
- 1,3 % vom Wollgewicht (0,871 kg) des handelsüblichen Farbstoffes der Formel
- 5% of the wool weight (= 3.35 l) aqueous formaldehyde solution (33%)
- 1.3% of the wool weight (0.871 kg) of the commercial dye of the formula
Bei der Durchführung der Färbungen verfährt man wie in Beispiel 4:
Claims (9)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2847913 | 1978-11-04 | ||
| DE2847913A DE2847913B1 (en) | 1978-11-04 | 1978-11-04 | Process for dyeing wool with reactive dyes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0010760A1 true EP0010760A1 (en) | 1980-05-14 |
| EP0010760B1 EP0010760B1 (en) | 1983-07-27 |
Family
ID=6053880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP79104239A Expired EP0010760B1 (en) | 1978-11-04 | 1979-10-31 | Process for dyeing wool with reactive dyestuffs |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4304566A (en) |
| EP (1) | EP0010760B1 (en) |
| JP (1) | JPS5567080A (en) |
| DE (2) | DE2847913B1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58186682A (en) * | 1982-04-27 | 1983-10-31 | 日本化薬株式会社 | Dyeing of cellulose or cellulose containing fiber material |
| DE3502960A1 (en) * | 1985-01-30 | 1986-07-31 | Hoechst Ag, 6230 Frankfurt | BLOCK COLORING PROCEDURE FOR WOOL |
| JPS6285086A (en) * | 1985-10-08 | 1987-04-18 | 三星染整株式会社 | Method for forming different color uneven pattern by partialshrink-proof processing of wool product |
| DE3539475A1 (en) * | 1985-11-07 | 1987-05-14 | Hoechst Ag | METHOD FOR DYING WOOLSTUFFED GOODS |
| DE3544795A1 (en) * | 1985-12-18 | 1987-06-19 | Hoechst Ag | METHOD FOR DYING WOOL WITH REACTIVE DYES |
| DE3544793A1 (en) * | 1985-12-18 | 1987-06-19 | Hoechst Ag | ISOTHERMAL FASTENING METHOD FOR WOOL |
| ES2067902T5 (en) * | 1990-02-14 | 1998-04-16 | Ciba Geigy Ag | PROCEDURE FOR THE DYEING OF WOOL WITH REACTIVE DYES. |
| KR102176303B1 (en) | 2010-01-21 | 2020-11-09 | 더 아벨 파운데이션, 인크. | Ocean thermal energy conversion power plant |
| CN103243589A (en) * | 2013-05-30 | 2013-08-14 | 常熟市众望经纬编织造有限公司 | Low-temperature dyeing process of modified polyester and wool interwoven fabric through one-bath process |
| CN104790228A (en) * | 2015-05-04 | 2015-07-22 | 苏州佳一纺织科技有限公司 | Low-temperature dyeing method of wool |
| CN113235316A (en) * | 2021-05-20 | 2021-08-10 | 张家港扬子染整有限公司 | One-bath dyeing process for wool-vinegar-blue blended yarn |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB875106A (en) * | 1959-05-08 | 1961-08-16 | Ici Ltd | New dyeing process |
| FR2199032A1 (en) * | 1972-09-08 | 1974-04-05 | Hoechst Ag | |
| FR2199031A1 (en) * | 1972-09-08 | 1974-04-05 | Hoechst Ag |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2869969A (en) * | 1955-08-22 | 1959-01-20 | Du Pont | Formaldehyde as an assistant in the dyeing of polyester fibers and blends thereof athigh temperatures |
| US3086832A (en) * | 1958-03-21 | 1963-04-23 | Process for finishing dyeings | |
| GB1533847A (en) * | 1974-12-02 | 1978-11-29 | Holliday & Co Ltd L | Dyeing methods |
| US4120647A (en) * | 1976-06-04 | 1978-10-17 | Ciba-Geigy Corporation | Process for the dyeing of wool-containing fibre materials |
| US4115457A (en) * | 1976-07-07 | 1978-09-19 | Sandoz Ltd. | Polyglycol ether derivatives |
| DE2841800A1 (en) * | 1977-09-29 | 1979-04-12 | Ciba Geigy Ag | METHOD OF COLORING WOOL-BASED FIBER MATERIALS |
-
1978
- 1978-11-04 DE DE2847913A patent/DE2847913B1/en not_active Withdrawn
-
1979
- 1979-10-31 EP EP79104239A patent/EP0010760B1/en not_active Expired
- 1979-10-31 DE DE7979104239T patent/DE2966000D1/en not_active Expired
- 1979-11-01 US US06/090,262 patent/US4304566A/en not_active Expired - Lifetime
- 1979-11-02 JP JP14143579A patent/JPS5567080A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB875106A (en) * | 1959-05-08 | 1961-08-16 | Ici Ltd | New dyeing process |
| FR2199032A1 (en) * | 1972-09-08 | 1974-04-05 | Hoechst Ag | |
| FR2199031A1 (en) * | 1972-09-08 | 1974-04-05 | Hoechst Ag |
Non-Patent Citations (2)
| Title |
|---|
| JOURNAL OF THE SOCIETY OF DYERS AND COLOURISTS, Band 92, Nr. 4, April 1976, Bradford, GB, COCKETT et al.: "Reactive dyes and resin-treated wool-keys to the attainment of superwash standards", Seiten 141-148 * Seiten 144, 145 ganz und insbesondere Seite 145, linke Spalte, vorletzter Absatz; Seite 146 ganz; Seite 147, rechte Spalte; Anspruche * * |
| MELLIAND TEXTILBERICHTE, Band 58, Nr. 6, Juni 1977, Heidelberg, DE, BAUMANN et al.: "Chemische Veranderungen und Schutz der Wolle beim HT-Farben von Polyester/Wolle Stuckware", Seiten 495-500 * Seite 499, rechte Spalte, "Schlussfolgerung" * * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2847913B1 (en) | 1980-02-07 |
| JPS5567080A (en) | 1980-05-20 |
| JPS6225793B2 (en) | 1987-06-04 |
| DE2966000D1 (en) | 1983-09-01 |
| US4304566A (en) | 1981-12-08 |
| EP0010760B1 (en) | 1983-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE3314663C2 (en) | Process for dyeing cellulosic fibers or mixed cellulosic fibers according to the exhaust dyeing method | |
| DE1111142B (en) | Process for dyeing fiber mixtures which contain fibers made from polyacrylonitrile and / or from its copolymers and fibers which can be colored with anionic dyes | |
| EP0010760B1 (en) | Process for dyeing wool with reactive dyestuffs | |
| DE2834997C2 (en) | Process for dyeing synthetic polyamide fibers with reactive dyes using the exhaust method | |
| DE2834998A1 (en) | METHOD FOR BLOCKING OR PRINTING CELLULOSE FIBERS WITH REACTIVE DYES | |
| DE2835035A1 (en) | METHOD FOR COLORING CELLULOSE FIBERS WITH REACTIVE DYES BY THE EXTRACTION METHOD | |
| EP0017805A1 (en) | Process for the exhaust dyeing of cellulose materials with reactive dyes | |
| EP0596323A2 (en) | Mixture of reactive phthalocyanine dyes | |
| DE2244060B2 (en) | Process for evenly dyeing wool that has been made felt-free with polyimine or polyamine resin | |
| EP0060433A1 (en) | Process for dyeing hydrophobic fibrous material | |
| EP0222269B1 (en) | Process for dyeing woollens | |
| DE3544795A1 (en) | METHOD FOR DYING WOOL WITH REACTIVE DYES | |
| EP0058432B1 (en) | Process for the continuous dyeing of wool fibres | |
| EP0474594B1 (en) | Process for dyeing of wool and mixtures thereof with other fibres with reactive dyestuffs | |
| DE2658061B1 (en) | PROCESS FOR DYING MIXED FABRICS MADE OF MODIFIED POLYESTER FIBERS AND WOOL AFTER A DWELLING PROCESS | |
| DE2836417C2 (en) | Continuous color process for polyester fiber / cellulose fiber blended fabric | |
| DE2166485C3 (en) | Process for one-bath dyeing and printing of base-modified polyolefin materials with metal complex dyes | |
| DE3643752A1 (en) | METHOD FOR ONE-BAND / ONE-STAGE COLORING MIXTURES FROM CARRIER-FREE COLORABLE POLYESTER FIBERS AND CELLULOSE FIBERS | |
| DE1909517C3 (en) | Process for the single bath dyeing of mixtures of polyester and polyacrylonitrile fibers | |
| DE2635990C2 (en) | Method of dyeing wool | |
| DE4306717A1 (en) | Reactive dye brilliant blue mixture | |
| EP0014852B1 (en) | Process for the continuous or semi-continuous dyeing of mixtures of cellulose fibres and synthetic polyamide fibres with azo developing dyestuffs | |
| DE2542007C3 (en) | Process for dyeing natural and synthetic polyamide fibers | |
| EP0014384B1 (en) | Process for dyeing in one single bath of mixtures of cellulose fibres and synthetic polyamide fibres with azo developing dyestuffs | |
| DE4406785A1 (en) | Discontinuous dyeing of cellulosic textiles with indigo |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Designated state(s): CH DE FR GB IT |
|
| 17P | Request for examination filed |
Effective date: 19800930 |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: HOECHST AKTIENGESELLSCHAFT |
|
| ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Designated state(s): CH DE FR GB IT |
|
| REF | Corresponds to: |
Ref document number: 2966000 Country of ref document: DE Date of ref document: 19830901 |
|
| ET | Fr: translation filed | ||
| ET | Fr: translation filed | ||
| PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
| 26 | Opposition filed |
Opponent name: CIBA-GEIGY AG Effective date: 19840427 |
|
| PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
| R26 | Opposition filed (corrected) |
Opponent name: CIBA-GEIGY AG Effective date: 19840427 |
|
| PLBN | Opposition rejected |
Free format text: ORIGINAL CODE: 0009273 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: OPPOSITION REJECTED |
|
| 27O | Opposition rejected |
Effective date: 19850808 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19900912 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19900919 Year of fee payment: 12 |
|
| ITTA | It: last paid annual fee | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19901217 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19901218 Year of fee payment: 12 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19911031 Ref country code: CH Effective date: 19911031 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19920630 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19920701 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |