EP0441745B1 - Process for printing cellulose-containing textile materials with reactive dyes - Google Patents
Process for printing cellulose-containing textile materials with reactive dyes Download PDFInfo
- Publication number
- EP0441745B1 EP0441745B1 EP91810064A EP91810064A EP0441745B1 EP 0441745 B1 EP0441745 B1 EP 0441745B1 EP 91810064 A EP91810064 A EP 91810064A EP 91810064 A EP91810064 A EP 91810064A EP 0441745 B1 EP0441745 B1 EP 0441745B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- printing
- reactive dyes
- water
- cellulose
- urea
- 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.)
- Revoked
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
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
- D06P3/663—Natural or regenerated cellulose using reactive dyes reactive group directly attached to heterocyclic group
-
- 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
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose 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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/001—Special chemical aspects of printing textile materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/916—Natural fiber dyeing
- Y10S8/918—Cellulose textile
Definitions
- the present invention relates to a process for printing cellulose-containing textile material with reactive dyes which contain at least one monohalogenotriazine group, the printing of the fiber material being carried out in a one-step process without the addition of urea.
- urea is an important load factor in the waste water.
- EP-A 0 151 091 discloses a process for printing cellulose-containing textile goods, in which a foamed aqueous preparation containing dye, foaming agent, an acrylamide or methacrylamide polymer and optionally other auxiliaries such as e.g. Applies fixative alkalis, the textile fabric impregnated in this way dries and then fixes the dye to it by heat.
- auxiliaries such as e.g. Applies fixative alkalis
- the dyes used in the process according to the invention are reactive dyes containing a monohalotriazine group, which are suitable for dyeing or printing cellulose textile materials.
- the monohalotriazine group is a monofluoro-, monobromo or preferably a monochlorotriazine group.
- the amount of the dyes generally depends on the desired color strength and is advantageously 0.1 to 300 g / kg of printing ink, advantageously 0.1 to 100 and preferably 5 to 60 g / kg of printing ink.
- the printing inks When using reactive dyes, the printing inks usually contain fixing alkalis.
- alkaline compounds for fixing the reactive dyes are sodium carbonate, sodium bicarbonate, sodium hydroxide, disodium phosphate, trisodium phosphate, borax, aqueous ammonia or alkali donors, such as e.g. Sodium trichloroacetate or sodium formate used.
- a mixture of water glass and a 25% aqueous sodium carbonate solution can also be used as the alkali.
- the pH of the printing inks containing alkali is usually 7.5 to 13.2, preferably 8.5 to 11.5.
- the aqueous printing pastes used for the process according to the invention also contain thickeners, preferably of natural origin, in particular sodium alginate alone or in a mixture with modified cellulose, in particular with at most 20 to 25 percent by weight of carboxymethyl cellulose.
- the printing pastes can also contain preservatives, sequestering agents, emulsifiers, water-insoluble solvents, oxidizing agents and deaerating agents.
- Suitable preservatives are, above all, formaldehyde-releasing agents, such as, for example, paraformaldehyde and trioxane, especially aqueous, approximately 30 to 40% by weight formaldehyde solutions, and sequestering agents, for example sodium nitrilotriacetic acid, sodium ethylenediaminetetraacetic acid, especially sodium polymethaphosphate, in particular sodium hexamethaphosphate, as emulsifiers especially adducts of an alkylene oxide and a fatty alcohol, in particular an adduct of oleyl alcohol and ethylene oxide, as water-insoluble solvents, high-boiling, saturated hydrocarbons, especially paraffins with a boiling range of about 160 to 210 ° C (so-called mineral spirits), as an oxidizing agent, e.g.
- formaldehyde-releasing agents such as, for example, paraformaldehyde and trioxane, especially aqueous, approximately 30 to 40% by
- an aromatic nitro compound especially an aromatic mono- or dinitrocarboxylic acid or sulfonic acid, which is optionally present as an alkylene oxide adduct, especially a nitrobenzenesulfonic acid and as a deaerating agent, for example high-boiling solvents, especially turpentine oils, higher alcohols, preferably C8 to C10 alcohols, terpene alcohols or deaerators based on mineral and / or silicone oils, in particular commercial formulations of about 15 to 25 percent by weight of a mineral and silicone oil mixture and about 75 to 85 percent by weight a C8 alcohol such as 2-ethyl-n-hexanol.
- a deaerating agent for example high-boiling solvents, especially turpentine oils, higher alcohols, preferably C8 to C10 alcohols, terpene alcohols or deaerators based on mineral and / or silicone oils, in particular commercial formulations of about 15 to 25 percent by weight of a mineral and silicone oil mixture and
- the method according to the invention is suitable for printing on textiles which consist of or contain cellulose.
- these are mainly sheet-like textile materials, such as Fleeces, felts, carpets, knitted fabrics and in particular fabrics.
- the process according to the invention is suitable for fiber materials which may have been pretreated with sodium hydroxide solution, preferably for cellulose material and regenerated cellulose, such as Viscose cellulose.
- the printing paste is applied over the entire surface or in places directly to the fiber material
- printing machines of a conventional type e.g. Gravure printing, rotary screen printing and flat film printing machines can be used appropriately.
- the fiber material is dried at temperatures up to 150 ° C., preferably 80 ° to 120 ° C.
- the fiber material is evenly wetted with water on its top, back or on both sides.
- the water can be wetted in various ways, for example by direct or indirect application methods.
- the fiber material can be moistened directly by, for example, spraying on using a commercially available atomizer, by roller systems, stencils or application of water in the form of foam or by so-called rotor dampening, the principle of which is described in detail in Textilpraxis International, 111a (1987).
- the moistening can be carried out indirectly by bringing a cloth moistened with water in the damper into contact with the fiber material to be fixed.
- the cloth serves as a moisture carrier.
- the application amounts of water are between 5 and 50%, preferably between 10 and 40%, based on the printed, dry fiber material.
- the dyes are fixed on the material.
- the fixing is achieved by heat treatment of the material at temperatures of preferably 100 ° to 220 ° C.
- the heat treatment is generally carried out using steam under atmospheric pressure.
- the fiber material is usually washed by a cold and then a hot and, if necessary, a cold rinse.
- level and vivid color prints are obtained which are distinguished by an excellent product appearance.
- color prints with reactive dyes on cellulose-containing textiles, in particular viscose with the exclusion of urea, which is generally used in considerable amounts, can be achieved.
- Example 1 A fabric made from leached viscose is contained with a printing paste
- Example 2 A fabric made from bleached and leached cellulose viscose is containing with a printing paste
- the desired color depth without additional moistening can only be obtained by adding 150 g / kg urea to the printing paste.
- Example 3 A printing ink is prepared according to the following recipe:
- a cellulose fabric is pressed as described in Example 2 and dried.
- the water application is now only 10% (instead of 45%) Goods weight.
- a temperature of 102 ° C is maintained for the subsequent steaming process.
- the steaming time is 8 minutes.
- the turquoise shade resulting after washing has the same color strength as in Example 2. Omitting the moistening leads to a 40% brighter print loss.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zum Bedrucken von cellulosehaltigem Textilgut mit Reaktivfarbstoffen, die mindestens eine Monohalogentriazingruppe enthalten, wobei die Bedruckung des Fasermaterials in einem einstufigen Verfahren ohne den Zusatz von Harnstoff erfolgt.The present invention relates to a process for printing cellulose-containing textile material with reactive dyes which contain at least one monohalogenotriazine group, the printing of the fiber material being carried out in a one-step process without the addition of urea.
Es ist schon seit langem, z.B. aus der US-A-4,604,099, bekannt, cellulosehaltige Fasermaterialien mit Reaktivfarbstoffen zu bedrucken. Dabei ist es im allgemeinen erforderlich, beträchtliche Mengen an Harnstoff zu verwenden, der u.a. für die Erhöhung der Farbstofflöslichkeit und ganz besonders für einen ausreichenden Fixiergrad verantwortlich ist.It has been around for a long time, e.g. from US-A-4,604,099, known to print cellulose-containing fiber materials with reactive dyes. It is generally necessary to use significant amounts of urea, which include is responsible for the increase in dye solubility and especially for a sufficient degree of fixation.
Neben diesen für den Druck-, Färbe- und Fixierprozess mit Reaktivfarbstoffen günstigen Eigenschaften stellt Harnstoff jedoch einen wesentlichen Lastfaktor in den Abwässern dar.In addition to these properties, which are favorable for the printing, dyeing and fixing process with reactive dyes, urea is an important load factor in the waste water.
Es hat daher nicht an Versuchen gefehlt, den Harnstoff zu reduzieren bzw. eliminieren oder Ersatzprodukte zu finden. So ist aus der EP-A 0 151 091 ein Verfahren zum Bedrucken von cellulosehaltigem Textilgut bekannt, worin man auf das Textilgut eine verschäumte wässrige Zubereitung enthaltend Farbstoff, Schaumbildner, ein Acrylamid- oder Methacrylamid-Polymerisat und gegebenenfalls weitere Hilfsstoffe wie z.B. Fixieralkalien aufbringt, das solchermassen imprägnierte Textilgut zwischentrocknet und den Farbstoff daran anschliessend durch Hitzeeinwirkung fixiert. Die Ergebnisse waren jedoch wenig befriedigend.There has been no shortage of attempts to reduce or eliminate the urea or to find replacement products. For example, EP-A 0 151 091 discloses a process for printing cellulose-containing textile goods, in which a foamed aqueous preparation containing dye, foaming agent, an acrylamide or methacrylamide polymer and optionally other auxiliaries such as e.g. Applies fixative alkalis, the textile fabric impregnated in this way dries and then fixes the dye to it by heat. However, the results were not very satisfactory.
Es sind weiterhin aus der DE-B 2 836 417 oder DE-A 3 834 966 Verfahren zum Klotzfärben von cellulosehaltigen Fasermaterialien bekannt, worin die Farbstoff-Fixierung in Abwesenheit von Harnstoff erfolgt.Methods are also known from DE-B 2 836 417 or DE-A 3 834 966 for the block dyeing of cellulose-containing fiber materials, in which the dye fixation takes place in the absence of urea.
Ueberraschenderweise wurde nun ein verbessertes Verfahren zum Bedrucken von cellulosehaltigem Textilgut mit Reaktivfarbstoffen gefunden, welches die Herstellung von Drucken mit einem hohen Fixiergrad ohne Zusatz von Harnstoff ermöglicht.Surprisingly, an improved process for printing cellulose-containing textile material with reactive dyes has now been found, which enables the production of prints with a high degree of fixation without the addition of urea.
Gegenstand der vorliegenden Erfindung ist somit ein Verfahren zum Bedrucken von cellulosehaltigem Textilgut, worin man
- (a) das Fasermaterial in einem einstufigen Verfahren mit Reaktivfarbstoffen, die mindestens eine Monohalogentriazingruppe enthalten, ohne Zusatz von Harnstoff bedruckt,
- (b) das bedruckte Fasermaterial trocknet,
- (c) das getrocknete Fasermaterial mit Wasser befeuchtet und
- (d) die Reaktivfarbstoffe auf dem Fasermaterial mit Wasserdampf unter atmosphärischem Druck fixiert.
- (a) the fiber material is printed in a one-step process with reactive dyes which contain at least one monohalotriazine group, without the addition of urea,
- (b) the printed fiber material dries,
- (c) moistening the dried fiber material with water and
- (d) the reactive dyes are fixed on the fiber material with steam under atmospheric pressure.
Bei den im erfindungsgemässen Verfahren eingesetzten Farbstoffen handelt es sich um eine Monohalogentriazingruppe enthaltende Reaktivfarbstoffe, die zum Färben oder Bedrucken von Cellulose-Textilmaterialien geeignet sind.The dyes used in the process according to the invention are reactive dyes containing a monohalotriazine group, which are suitable for dyeing or printing cellulose textile materials.
Bei der Monohalogentriazingruppe handelt es sich um eine Monofluor-, Monobrom- oder vorzugsweise um eine Monochlortriazingruppe.The monohalotriazine group is a monofluoro-, monobromo or preferably a monochlorotriazine group.
Die Menge der Farbstoffe richtet sich in der Regel nach der gewünschten Farbstarke und beträgt zweckmässig 0,1 bis 300 g/kg Druckfarbe, vorteilhafterweise 0,1 bis 100 und vorzugsweise 5 bis 60 g/kg Druckfarbe.The amount of the dyes generally depends on the desired color strength and is advantageously 0.1 to 300 g / kg of printing ink, advantageously 0.1 to 100 and preferably 5 to 60 g / kg of printing ink.
Bei Verwendung von Reaktivfarbstoffen enthalten die Druckfarben in der Regel Fixieralkalien. Als alkalisch reagierende Verbindungen zur Fixierung der Reaktivfarbstoffe werden beispielsweise Natriumcarbonat, Natriumbicarbonat, Natriumhydroxid, Dinatriumphosphat, Trinatriumphosphat, Borax, wässriges Ammoniak oder Alkalispender, wie z.B. Natriumtrichloracetat oder Natriumformiat eingesetzt. Als Alkali kann auch eine Mischung aus Wasserglas und einer 25 %igen wässrigen Natriumcarbonatlösung verwendetwerden.When using reactive dyes, the printing inks usually contain fixing alkalis. Examples of alkaline compounds for fixing the reactive dyes are sodium carbonate, sodium bicarbonate, sodium hydroxide, disodium phosphate, trisodium phosphate, borax, aqueous ammonia or alkali donors, such as e.g. Sodium trichloroacetate or sodium formate used. A mixture of water glass and a 25% aqueous sodium carbonate solution can also be used as the alkali.
Der pH-Wert der Alkali enthaltenden Druckfarben beträgt in der Regel 7,5 bis 13,2, vorzugsweise 8,5 bis 11,5.The pH of the printing inks containing alkali is usually 7.5 to 13.2, preferably 8.5 to 11.5.
Die für das erfindungsgemässe Verfahren verwendeten wässrigen Druckpasten enthalten neben den Farbstoffen ferner Verdickungsmittel, vorzugsweise natürlicher Herkunft, insbesondere Natriumalginat für sich allein oder in Gemisch mit modifizierter Cellulose, insbesondere mit höchstens 20 bis 25 Gewichtsprozent Carboxymethylcellulose. Gewünschtenfalls können die Druckpasten noch Konservierungsmittel, Sequestriermittel, Emulgatoren, wasserunlösliche Lösungsmittel, Oxidationsmittel und Entlüftungsmittel enthalten.In addition to the dyes, the aqueous printing pastes used for the process according to the invention also contain thickeners, preferably of natural origin, in particular sodium alginate alone or in a mixture with modified cellulose, in particular with at most 20 to 25 percent by weight of carboxymethyl cellulose. If desired, the printing pastes can also contain preservatives, sequestering agents, emulsifiers, water-insoluble solvents, oxidizing agents and deaerating agents.
In Betracht kommen als Konservierungsmittel vor allem formaldehydabgebende Mittel, wie z.B. Paraformaldehyd und Trioxan, vor allem wässrige, etwa 30 bis 40-gewichtsprozentige Formaldehydlösungen, als Sequestriermittel z.B. nitrilotriessigsaures Natrium, ethylendiamintetraessigsaures Natrium, vor allem Natrium-Polymethaphosphat, insbesondere Natrium-Hexamethaphosphat, als Emulgatoren vor allem Addukte aus einem Alkylenoxid und einem Fettalkohol, insbesondere einem Addukt aus Oleylalkohol und Ethylenoxid, als wasserunlösliche Lösungsmittel hochsiedende, gesättigte Kohlenwasserstoffe, vor allem Paraffine mit einem Siedebereich von etwa 160 bis 210°C (sogenannte Lackbenzine), als Oxidationsmittel z.B. eine aromatische Nitroverbindung, vor allem eine aromatische Mono- oder Dinitrocarbonsäure oder -sulfonsäure, die gegebenenfalls als Alkylenoxidadukkt vorliegt, insbesondere eine Nitrobenzolsulfonsäure und als Entlüftungsmittel z.B. hochsiedende Lösungsmittel, vor allem Terpentinöle, höhere Alkohle, vorzugsweise C₈- bis C₁₀-Alkohole, Terpenalkohole oder Entlüftungsmittel auf Basis von Mineral- und/oder Silikonölen, insbesondere Handelsformulierungen aus etwa 15 bis 25 Gewichtsprozent eines Mineral- und Silikonölgemisches und etwa 75 bis 85 Gewichtsprozent eines C₈-Alkohols wie z.B. 2-Ethyl-n-hexanol.Suitable preservatives are, above all, formaldehyde-releasing agents, such as, for example, paraformaldehyde and trioxane, especially aqueous, approximately 30 to 40% by weight formaldehyde solutions, and sequestering agents, for example sodium nitrilotriacetic acid, sodium ethylenediaminetetraacetic acid, especially sodium polymethaphosphate, in particular sodium hexamethaphosphate, as emulsifiers especially adducts of an alkylene oxide and a fatty alcohol, in particular an adduct of oleyl alcohol and ethylene oxide, as water-insoluble solvents, high-boiling, saturated hydrocarbons, especially paraffins with a boiling range of about 160 to 210 ° C (so-called mineral spirits), as an oxidizing agent, e.g. an aromatic nitro compound, especially an aromatic mono- or dinitrocarboxylic acid or sulfonic acid, which is optionally present as an alkylene oxide adduct, especially a nitrobenzenesulfonic acid and as a deaerating agent, for example high-boiling solvents, especially turpentine oils, higher alcohols, preferably C₈ to C₁₀ alcohols, terpene alcohols or deaerators based on mineral and / or silicone oils, in particular commercial formulations of about 15 to 25 percent by weight of a mineral and silicone oil mixture and about 75 to 85 percent by weight a C₈ alcohol such as 2-ethyl-n-hexanol.
Das erfindungsgemässe Verfahren eignet sich für das Bedrucken von Textilien, die aus Cellulose bestehen oder diese enthalten.The method according to the invention is suitable for printing on textiles which consist of or contain cellulose.
Es handelt sich dabei in der Regel vor allem um flächenförmige Textilmaterialien, wie z.B. Vliese, Filze, Teppiche, Gewirke und insbesondere Gewebe. Das erfindungsgemässe Verfahren ist geeignet für Fasermaterialien, die gegebenenfalls mit Natronlauge vorbehandelt sind, vorzugsweise für Cellulose-Material und Regenerat-Cellulose, wie z.B. Viskose-Cellulose.As a rule, these are mainly sheet-like textile materials, such as Fleeces, felts, carpets, knitted fabrics and in particular fabrics. The process according to the invention is suitable for fiber materials which may have been pretreated with sodium hydroxide solution, preferably for cellulose material and regenerated cellulose, such as Viscose cellulose.
Beim Bedrücken der Fasermaterialien wird die Druckpaste ganzflächig oder stellenweise direkt auf das Fasermaterial aufgebracht, wobei Druckmaschinen üblicher Bauart, z.B. Tiefdruck-, Rotationssiebdruck- und Flachfilmdruckmaschinen zweckmässig eingesetzt werden.When printing on the fiber materials, the printing paste is applied over the entire surface or in places directly to the fiber material, printing machines of a conventional type, e.g. Gravure printing, rotary screen printing and flat film printing machines can be used appropriately.
Das Fasermaterial wird nach dem Bedrücken bei Temperaturen bis 150°C, vorzugsweise 80° bis 120°C getrocknet. Vor der Fixierung der Farbstoffe wird das Fasermaterial auf seiner Oberseite, Rückseite oder beidseitig gleichmässig mit Wasser benetzt. Die Wasserbenetzung kann dabei auf verschiedene Weisen erfolgen, beispielsweise durch direkte oder indirekte Auftragsmethoden. Direkt kann die Befeuchtung des Fasermaterials durch beispielsweise Aufsprühen mittels eines handelsüblichen Zerstäubers, durch Walzensysteme, Schablonen oder Auftrag von Wasser in Form von Schaum oder durch die sogenannte Rotorenfeuchtung erfolgen, deren Funktionsprinzip in Textilpraxis International, 111a (1987) ausführlich beschrieben ist. Indirekt kann die Befeuchtung dadurch erfolgen, dass ein mit Wasser befeuchtetes Tuch im Dämpfer mit dem zu Fixierenden Fasermaterial in Kontakt gebracht wird. Das Tuch dient hier als Feuchtigkeitsüberträger. Die Auftragsmengen an Wasser liegen dabei zwischen 5 und 50 %, vorzugsweise zwischen 10 und 40 %, bezogen auf das bedruckte, trockene Fasermaterial.After printing, the fiber material is dried at temperatures up to 150 ° C., preferably 80 ° to 120 ° C. Before the dyes are fixed, the fiber material is evenly wetted with water on its top, back or on both sides. The water can be wetted in various ways, for example by direct or indirect application methods. The fiber material can be moistened directly by, for example, spraying on using a commercially available atomizer, by roller systems, stencils or application of water in the form of foam or by so-called rotor dampening, the principle of which is described in detail in Textilpraxis International, 111a (1987). The moistening can be carried out indirectly by bringing a cloth moistened with water in the damper into contact with the fiber material to be fixed. The cloth serves as a moisture carrier. The application amounts of water are between 5 and 50%, preferably between 10 and 40%, based on the printed, dry fiber material.
Nach dem Benetzen werden die Farbstoffe auf dem Material fixiert. Das Fixieren wird durch eine Wärmebehandlung des Materials bei Temperaturen von vorzugsweise 100° bis 220°C erzielt. Die Wärmebehandlung erfolgt im allgemeinen mit Wasserdampf unter atmosphärischem Druck.After wetting, the dyes are fixed on the material. The fixing is achieved by heat treatment of the material at temperatures of preferably 100 ° to 220 ° C. The heat treatment is generally carried out using steam under atmospheric pressure.
Anschliessend wird das Fasermaterial in der Regel durch ein kaltes und hierauf ein heisses und gegebenenfalls wiederum ein kaltes Spülen nachgewaschen.Subsequently, the fiber material is usually washed by a cold and then a hot and, if necessary, a cold rinse.
Man erhält mit dem erfindungsgemässen Verfahren egale und farbkräftige Farbdrucke, die sich durch ein hervorragendes Warenbild auszeichnen. Insbesondere können mittels des erfindungsgemässen Fixierverfahrens Farbdrucke mit Reaktivfarbstoffen auf cellulosehaltigen Textilien, insbesondere Viskose unter Ausschluss von Harnstoff, der in der Regel in beträchtlichen Mengen verwendet wird, erzielt werden.With the method according to the invention, level and vivid color prints are obtained which are distinguished by an excellent product appearance. In particular, using the fixing method according to the invention, color prints with reactive dyes on cellulose-containing textiles, in particular viscose with the exclusion of urea, which is generally used in considerable amounts, can be achieved.
Im folgenden Beispiel beziehen sich Teile und Prozentsätze, wenn nicht anders angegeben, jeweils auf das Gewicht.In the following example, parts and percentages are by weight unless otherwise noted.
7 g/kg einer handelsüblichen, pulverförmigen Farbstofformulierung der Formel (101)
50 g/kg einer handelsüblichen, flüssigen Farbstofformulierung der Formel (102)
32 g/kg eines handelsüblichen, flüssigen Farbstoffgemisches der Formeln (103)
und (104)
8,9 g/kg m-Nitrobenzolsulfonsäure-Na-Salz
89 g/kg 25 %ige Na₂CO₃-Lösung
490 g/kg 6 %ige Natrium-Alginat-Lösung
1,8 g/kg eines Entlüftungsmittels und
321,3 g/kg Wasser
musterförmig bedruckt, bei 120°C während einer Minute getrocknet, mittels eines Minimalauftraggerätes mit Wasser befeuchtet (Auftragsmenge: 30 %, bezogen auf das Gewicht des Fasermaterials), danach in einem Dämpfer während 8 Minuten bei 105°C bei atmosphärischem Druck gedämpft und anschliessend mit kaltem und dann kochendem Wasser gespült, bis die nicht fixierten Anteile der eingesetzten Farbstoffe und die Hilfsmittel entfernt sind.7 g / kg of a commercially available, powdery dye formulation of the formula (101)
50 g / kg of a commercial liquid dye formulation of the formula (102)
32 g / kg of a commercially available liquid dye mixture of the formulas (103)
and (104)
8.9 g / kg m-nitrobenzenesulfonic acid Na salt
89 g / kg 25% Na₂CO₃ solution
490 g / kg 6% sodium alginate solution
1.8 g / kg of a deaerating agent and
321.3 g / kg water
Printed in a pattern, dried at 120 ° C for one minute, moistened with water using a minimal applicator (application quantity: 30%, based on the weight of the fiber material), then steamed for 8 minutes at 105 ° C at atmospheric pressure and then with cold and then boiling water until the non-fixed portions of the dyes used and the auxiliaries are removed.
Nach Trocknung des Gewebes bei 90 bis 100°C erhält man einen tiefen, braunen Druck.After drying the fabric at 90 to 100 ° C you get a deep, brown print.
Verfährt man wie oben angegeben, aber ohne Wasserbefeuchtung des Fasermaterials vor dem Dämpfen, erhält man einen unbrauchbaren, sehr hellen Druck, da unter diesen Bedingungen nur eine geringe Farbstoff-Fixierung erfolgt.If one proceeds as stated above, but without dampening the water of the fiber material before steaming, an unusable, very bright print is obtained, since under these conditions there is only a slight dye fixation.
25 g/kg einer handelsüblichen granulatförmigen Formulierung des Farbstoffes der Formel (105)
9 g/kg m-Nitrobenzolsulfonsäure-Natriumsalz
60 g/kg 25%ige Na₂CO₃-Lösung
406 g/kg Wasser und
500 g/kg 6%ige Natriumalginatlösung
bedruckt. Anschliessend wird normal getrocknet, wobei der Gesamtfeuchtigkeitsgrad nach der Trocknung 5,5%, bezogen auf das Warengewicht, beträgt. Mittels eines Sprühdüsengerätes werden nun weitere 45 % Wasser aufgebracht und anschliessend in einem Dämpfer während 8 Minuten unter atmosphärischem Druck bei einer Temperatur von 115°C behandelt, anschliessend mit kaltem und kochendem Wasser gespült, bis die nichtfixierten Farbstoffanteile und die Hilfsmittel entfernt sind. Nach der Trocknung erhält man eine volle, tiefe Türkis-Nuance.25 g / kg of a commercial granular formulation of the dye of the formula (105)
9 g / kg m-nitrobenzenesulfonic acid sodium salt
60 g / kg 25% Na₂CO₃ solution
406 g / kg water and
500 g / kg 6% sodium alginate solution
printed. It is then dried normally, the total degree of moisture after drying being 5.5%, based on the weight of the goods. A further 45% of water is then applied by means of a spray nozzle device and then treated in a steamer for 8 minutes under atmospheric pressure at a temperature of 115 ° C., then rinsed with cold and boiling water until the unfixed dye components and the auxiliaries have been removed. After drying you get a full, deep turquoise shade.
Wird unmittelbar nach dem Trocknen ohne Sprühbefeuchtung gedämpft, resultiert eine Nuance, die 60 % heller und damit unbrauchbar ist.Steaming immediately after drying without spray moistening results in a shade that is 60% lighter and therefore unusable.
Die gewünschte Farbtiefe ohne zusätzliche Befeuchtung erhält man erst, wenn man der Druckpaste 150 g/kg Harnstoff zusetzt.The desired color depth without additional moistening can only be obtained by adding 150 g / kg urea to the printing paste.
40 g des Farbstoffes der Formel (106)
in einer handelsüblichen Granulatformulierung werden unter Rühren in 960 g einer Stammverdickung enthaltend
9,5 g m-Nitrobenzolsulfonsäure-Natriumsalz
60 g 25%ige Na₂CO₃-Lösung
410,5 g Wasser
480 g 6%ige Natriumalginat-Lösung
zugegeben, auf eine gebleichte und mercerisierte Baumwollmaschenware gedruckt und auf einen Restfeuchtigkeitsgehalt von 3,5%, bezogen auf das Warengewicht, getrocknet.40 g of the dye of the formula (106)
in a commercial granule formulation containing 960 g of a stock thickening with stirring
9.5 g m-nitrobenzenesulfonic acid sodium salt
60 g 25% Na₂CO₃ solution
410.5 g water
480 g of 6% sodium alginate solution
added, printed on a bleached and mercerized cotton knitwear and dried to a residual moisture content of 3.5%, based on the weight of the goods.
Unmittelbar vor der 8-minütigen Fixierung in einem Dämpfer unter atmosphärischem Druck bei 115°C wird mit einer Spritzdüse Wasser bis zu einem Feuchtigkeitsgehalt von 50%, bezogen auf das trockene Warengewicht, aufgetragen.Immediately before the 8-minute fixation in a damper under atmospheric pressure at 115 ° C, water is applied with a spray nozzle up to a moisture content of 50%, based on the dry fabric weight.
Nach dem praxisüblichen Auswaschen resultiert ein königsblauer, tiefer Druckausfall.After the usual washing out, a royal blue, deep pressure drop results.
Wird ohne zusätzlichen Wasserauftrag vor dem Dämpfen gearbeitet, Fällt der Druck deutlich heller und unruhig aus.If you work without steaming before steaming, the pressure is much brighter and restless.
Ein Cellulosegewebe wird wie in Beispiel 2 beschrieben, bedrückt und getrocknet. Der Wasserauftrag beträgt jetzt lediglich 10% (anstelle von 45%) des Warengewichtes. Für den anschliessenden Dämpfprozess wird eine Temperatur von 102°C eingehalten. Die Dämpfzeit beträgt 8 Minuten. Die nach dem Waschen resultierende Türkis-Nuance hat die gleiche Farbstärke wie in Beispiel 2. Ein Weglassen der Befeuchtung führt zu einem um 40% helleren Druckausfall.A cellulose fabric is pressed as described in Example 2 and dried. The water application is now only 10% (instead of 45%) Goods weight. A temperature of 102 ° C is maintained for the subsequent steaming process. The steaming time is 8 minutes. The turquoise shade resulting after washing has the same color strength as in Example 2. Omitting the moistening leads to a 40% brighter print loss.
Erst ein Zusatz von 100 g/kg Harnstoff bewirkt ohne Befeuchtung vor dem Dämpfen eine ähnlich tiefe Nuance.Only an addition of 100 g / kg of urea produces a similarly deep shade without humidification before steaming.
Claims (3)
- A process for printing cellulosic textile material, in which(a) the fibre material is printed in a one-step process with reactive dyes which contain at least one monohalotriazine group without the addition of urea,(b) the printed fibre material is dried,(c) the dried fibre material is wetted with water, and(d) the reactive dyes are fixed on the fibre material with steam under atmospheric pressure.
- A process according to claim 1, wherein the cellulosic textile material used is regenerated cellulose.
- A process according to claim 2, wherein the cellulosic textile material used is viscose rayon.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH376/90 | 1990-02-06 | ||
| CH37690 | 1990-02-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0441745A1 EP0441745A1 (en) | 1991-08-14 |
| EP0441745B1 true EP0441745B1 (en) | 1995-07-12 |
Family
ID=4185608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91810064A Revoked EP0441745B1 (en) | 1990-02-06 | 1991-01-29 | Process for printing cellulose-containing textile materials with reactive dyes |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5106388A (en) |
| EP (1) | EP0441745B1 (en) |
| JP (1) | JPH04214480A (en) |
| AT (1) | ATE125009T1 (en) |
| DE (1) | DE59105947D1 (en) |
| ES (1) | ES2074685T3 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1256253B (en) * | 1992-12-28 | 1995-11-29 | Mario Beretta | DEVICE TO REDUCE THE USE OF UREA AND / OR HYGROSCOPIC CHEMICALS, IN PRINTING PASTES OF COTTON FABRICS, VISCOUS AND SIMILAR, AND RELATED PROCEDURE |
| DE59402856D1 (en) * | 1993-02-05 | 1997-07-03 | Ciba Geigy Ag | Process for dyeing or printing cellulosic fiber materials |
| KR101768668B1 (en) | 2011-02-01 | 2017-08-17 | 삼성디스플레이 주식회사 | Method for driving liquid crystal display device |
| EP3473767A1 (en) * | 2017-10-23 | 2019-04-24 | EFESON - Chemical Research & Engineering Development | Composition for printing fibrous materials |
| CN109594364B (en) * | 2018-11-29 | 2021-03-23 | 太仓宝霓实业有限公司 | Reactive printing urea substitute and preparation method thereof |
| IT201900002219A1 (en) | 2019-02-15 | 2020-08-15 | Lamberti Spa | TEXTILE PRINT OR DYE |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2836417C2 (en) * | 1978-08-19 | 1980-04-24 | Hoechst Ag, 6000 Frankfurt | Continuous color process for polyester fiber / cellulose fiber blended fabric |
| US4604099A (en) * | 1984-01-30 | 1986-08-05 | Ciba-Geigy Corporation | Process for printing cellulose-containing textile material with foam-containing reactive dyes and addition of (meth) acrylamide polymers |
| DE3834966A1 (en) * | 1987-10-16 | 1989-04-27 | Ciba Geigy Ag | Process for pad-dyeing cellulose textile materials |
-
1991
- 1991-01-29 DE DE59105947T patent/DE59105947D1/en not_active Revoked
- 1991-01-29 ES ES91810064T patent/ES2074685T3/en not_active Expired - Lifetime
- 1991-01-29 EP EP91810064A patent/EP0441745B1/en not_active Revoked
- 1991-01-29 AT AT91810064T patent/ATE125009T1/en not_active IP Right Cessation
- 1991-02-01 US US07/648,953 patent/US5106388A/en not_active Expired - Fee Related
- 1991-02-06 JP JP3014620A patent/JPH04214480A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| ATE125009T1 (en) | 1995-07-15 |
| ES2074685T3 (en) | 1995-09-16 |
| DE59105947D1 (en) | 1995-08-17 |
| US5106388A (en) | 1992-04-21 |
| EP0441745A1 (en) | 1991-08-14 |
| JPH04214480A (en) | 1992-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0885999B1 (en) | Process for ink jet printing textile materials | |
| DE3709766A1 (en) | METHOD FOR ALKALI-FREE DYEING WITH REACTIVE DYES | |
| DE2417774B2 (en) | PROCESS FOR DRY COLORING OF TEXTILE FABRICS | |
| DE2926098C2 (en) | ||
| DE3831464A1 (en) | METHOD FOR ALKALI-FREE DYEING AND PRINTING OF CELLULOSE FIBERS | |
| EP0441745B1 (en) | Process for printing cellulose-containing textile materials with reactive dyes | |
| EP0885997A2 (en) | Process for printing fibrous materials | |
| EP0457728A1 (en) | Process for dyeing cellulosic fibres without tailing | |
| EP0029804B1 (en) | Process for the printing or pad-dyeing of textile materials of cellulosic fibres or mixtures thereof with synthetic fibres, as well as printing pastes or padding liquors for carrying out this process | |
| EP0665326A2 (en) | Process for printing fibrous material by direct printing | |
| DE3121043A1 (en) | Process for printing cellulose fibres with reactive dyes | |
| EP1399607B1 (en) | Cellulose-based material suitable for low-salt dyeing and printing providing high dyestuff yields and color fastness and for printing using an inkjet method and wet transfer printing | |
| DE1235257B (en) | Process for dyeing or printing cellulose-containing materials with a fibrous structure | |
| EP0526400A1 (en) | Process for fixation of reactive dye stuffs on cellulose containing textile material | |
| DE2343317C3 (en) | ||
| EP0021055A1 (en) | Process for the local "white discharging" or "coloured discharging" of dyes on textile materials | |
| DE1041912B (en) | Process for dyeing or printing cellulosic textile fabrics | |
| DE2736563C2 (en) | Process for the production of real pad dyeings and prints on cellulose fiber materials and their mixtures with synthetic fibers | |
| DE4223859A1 (en) | Dyeing or printing cellulose textile with reactive dyestuffs - using di:alkyl-, alkylene-, or alkenylene sulphone additive instead of urea | |
| SU1143786A1 (en) | Method of printing on cellulose-polyester textile materials | |
| CH689291GA3 (en) | A process for preparing resist printing stains. | |
| DE4133995A1 (en) | Two=stage two bath dyeing of cellulose hydrophobic fibre mixt. - using reactive dyestuff then disperse dyestuff in bath contg. neutral salt to prevent sepn. | |
| AT225143B (en) | Process for printing cellulose fibers | |
| DE1052945B (en) | Process for dyeing or printing cellulosic textile fabrics | |
| DE745220C (en) | Process for printing fibrous materials of vegetable or animal origin by printing printing pastes containing water-soluble dyes, catalysts and urea, and fixing with formaldehyde-containing water vapor |
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 |
Kind code of ref document: A1 Designated state(s): AT CH DE ES FR GB IT LI NL |
|
| 17P | Request for examination filed |
Effective date: 19910131 |
|
| 17Q | First examination report despatched |
Effective date: 19930618 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT CH DE ES FR GB IT LI NL |
|
| REF | Corresponds to: |
Ref document number: 125009 Country of ref document: AT Date of ref document: 19950715 Kind code of ref document: T |
|
| ET | Fr: translation filed | ||
| REF | Corresponds to: |
Ref document number: 59105947 Country of ref document: DE Date of ref document: 19950817 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2074685 Country of ref document: ES Kind code of ref document: T3 |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19950829 |
|
| ITF | It: translation for a ep patent filed |
Owner name: SOCIETA' ITALIANA BREVETTI S.P.A. |
|
| PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
| PLBQ | Unpublished change to opponent data |
Free format text: ORIGINAL CODE: EPIDOS OPPO |
|
| 26 | Opposition filed |
Opponent name: ZENECA LIMITED Effective date: 19960316 |
|
| PLBF | Reply of patent proprietor to notice(s) of opposition |
Free format text: ORIGINAL CODE: EPIDOS OBSO |
|
| NLR1 | Nl: opposition has been filed with the epo |
Opponent name: ZENECA LIMITED |
|
| PLBF | Reply of patent proprietor to notice(s) of opposition |
Free format text: ORIGINAL CODE: EPIDOS OBSO |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PUE Owner name: CIBA-GEIGY AG TRANSFER- CIBA SC HOLDING AG |
|
| PLBF | Reply of patent proprietor to notice(s) of opposition |
Free format text: ORIGINAL CODE: EPIDOS OBSO |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19961125 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19961127 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19961205 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19961211 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19961212 Year of fee payment: 7 |
|
| PLBF | Reply of patent proprietor to notice(s) of opposition |
Free format text: ORIGINAL CODE: EPIDOS OBSO |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19961223 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 19970124 Year of fee payment: 7 |
|
| NLS | Nl: assignments of ep-patents |
Owner name: CIBA SC HOLDING AG |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP Ref country code: CH Ref legal event code: PFA Free format text: CIBA SC HOLDING AG TRANSFER- CIBA SPECIALTY CHEMICALS HOLDING INC. |
|
| RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: CIBA SPECIALTY CHEMICALS HOLDING INC. |
|
| PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
| PLBQ | Unpublished change to opponent data |
Free format text: ORIGINAL CODE: EPIDOS OPPO |
|
| PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
| NLT1 | Nl: modifications of names registered in virtue of documents presented to the patent office pursuant to art. 16 a, paragraph 1 |
Owner name: CIBA SPECIALTY CHEMICALS HOLDING INC. |
|
| NLT2 | Nl: modifications (of names), taken from the european patent patent bulletin |
Owner name: CIBA SPECIALTY CHEMICALS HOLDING INC. |
|
| R26 | Opposition filed (corrected) |
Opponent name: BASF AKTIENGESELLSCHAFT Effective date: 19960316 |
|
| R26 | Opposition filed (corrected) |
Opponent name: BASF AKTIENGESELLSCHAFT Effective date: 19960316 |
|
| NLR1 | Nl: opposition has been filed with the epo |
Opponent name: BASF AKTIENGESELLSCHAFT |
|
| NLR1 | Nl: opposition has been filed with the epo |
Opponent name: BASF AKTIENGESELLSCHAFT |
|
| RDAH | Patent revoked |
Free format text: ORIGINAL CODE: EPIDOS REVO |
|
| RDAG | Patent revoked |
Free format text: ORIGINAL CODE: 0009271 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT REVOKED |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| 27W | Patent revoked |
Effective date: 19970731 |
|
| GBPR | Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state |
Free format text: 970731 |
|
| NLR2 | Nl: decision of opposition | ||
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: CD |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: PC2A |
|
| PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |