EP1658402A1 - Dyed sponge cloth and method for the production thereof - Google Patents

Dyed sponge cloth and method for the production thereof

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Publication number
EP1658402A1
EP1658402A1 EP04801926A EP04801926A EP1658402A1 EP 1658402 A1 EP1658402 A1 EP 1658402A1 EP 04801926 A EP04801926 A EP 04801926A EP 04801926 A EP04801926 A EP 04801926A EP 1658402 A1 EP1658402 A1 EP 1658402A1
Authority
EP
European Patent Office
Prior art keywords
fibers
sponge cloth
viscose
cellulose
reactive dye
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
Application number
EP04801926A
Other languages
German (de)
French (fr)
Other versions
EP1658402B1 (en
Inventor
Nicole Laber
Erna Kastl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kalle GmbH and Co KG
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Kalle GmbH and Co KG
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Publication date
Application filed by Kalle GmbH and Co KG filed Critical Kalle GmbH and Co KG
Publication of EP1658402A1 publication Critical patent/EP1658402A1/en
Application granted granted Critical
Publication of EP1658402B1 publication Critical patent/EP1658402B1/en
Expired - Fee Related legal-status Critical Current
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—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
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed 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
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • 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
    • 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
    • D06P3/8223—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups
    • D06P3/8228—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using one kind of dye

Definitions

  • the invention relates to a colored sponge cloth based on regenerated cellulose, which is reinforced with fibers. It also relates to a process for producing a colored sponge cloth, in which viscose is mixed with fibers, at least one pore former and at least one colorant, the mixture is applied in layers on a conveyor belt and the viscose is then regenerated to cellulose.
  • Sponge cloths have been known for a long time. They are generally layer-like structures with a thickness of approximately 0.4 to 2.0 cm (in the dry state). They are generally manufactured using the viscose process (cellulose xanthate process). In order to make them mechanically more stable, they usually contain textile fibers or a plastic net. In a common process for producing sponge cloth, for example, about 3 parts by weight
  • about 83 parts by weight of Glauber's salt ( sodium sulfate decahydrate) are added in portions and the resulting mass is kneaded for a further 20 to 30 minutes.
  • the mass is then applied as a thin layer on a perforated steel belt and, on this belt, passed through a bath containing potassium hydroxide at about 95 ° C.
  • the lye is then removed again by treating with dilute sulfuric acid and various washing baths.
  • the sponge cloth thus obtained is then dried and can be wound up.
  • the cotton fibers remain more or less undyed. If the fibers are also distributed inhomogeneously, the appearance of the sponge cloth is impaired, which many consumers perceive as a lack of quality.
  • the object was therefore to provide a sponge cloth which is evenly colored, ie in which the regenerated cellulose and the fibers have the same color.
  • the sponge cloth should also be easy and inexpensive to manufacture.
  • the present invention accordingly relates to a colored sponge cloth based on regenerated cellulose, which is reinforced with fibers, and is characterized in that the fibers and the regenerated cellulose are colored with at least one reactive dye.
  • reactive dyes are those dyes which can form covalent bonds with the cellulose and the fiber material.
  • the dye molecules each have at least one anchor group that is linked to the
  • Suitable reactive anchor groups are in particular 2,4-difluoro- [1,3,5] triazin-2-yl-, 2,4-dichloro- [1,3,5] triazin-2-yl-, 2,5,6 - Trichloropyrimidin-4-yl and vinylsulfonyl groups.
  • the dye molecules optionally also have a plurality of reactive anchor groups which can be the same or different from one another. Instead of vinylsulfonyl groups, too
  • Groups occur from which vinyl sulfonyl groups form under the reaction conditions. These are, for example, groups of the formula -SO 2 - CH 2 -CH 2 -O-SO 3 " from which sulfate is eliminated under the action of aqueous alkali. Suitable reactive dyes are available, for example, under the names ⁇ Procion H-EXL, Procion XL + or ⁇ Levafix EN by
  • These dyes contain, for example, diphenylazo, anthraquinone or triphendioxazin groups as chromophore. So-called are particularly suitable among these dyes
  • Hot dyes which react with cellulose at temperatures of approximately 75 to 103 ° C., preferably 80 to 98 ° C., particularly preferably 90 to 95 ° C.
  • cold and warm dyes can also be used in principle.
  • Cold dyeing is generally carried out in a temperature range from 20 to 70 ° C., preferably in the range from 40 to 65 ° C and especially in the range of 50 to 60 ° C.
  • Cold dyeing dyes are generally more reactive than hot dyes.
  • the proportion of reactive dyes is generally about 0.001 to 5.00% by weight, preferably 0.05 to 3.00% by weight, particularly preferably 0.50 to 1.50% by weight, in each case based on the Total weight of cellulose and fibers.
  • the proportion naturally also depends on the type of dye.
  • the fibers are preferably cotton, viscose or polyamide fibers.
  • Mixed fibers e.g. B. those made of cotton and PA or
  • Cotton fibers which have been dyed with the reactive dyes in a separate step can be used in the production of the sponge cloth according to the invention. This can be done, for example, by a so-called
  • Flakes are stained.
  • the at least one dye is first dissolved in water, if appropriate with heating, and the dye solution is then added to an aqueous salt solution (which contains, for example, 60 g / l NaCl and 20 g / l Na 2 CO 3 ) and the two are mixed together.
  • the cotton fibers are added to the dyeing solution. To avoid color deviations, after the
  • Fix for example with acetic acid
  • the same reactive dye or the same mixture of different reactive dyes can be used for coloring the regenerated cellulose.
  • the sponge cloth according to the invention is preferably produced by a process which comprises the following steps: a) providing viscose solution, fibers wetted with alkali, pore-forming agents and an aqueous solution of at least one reactive dye, b) mixing the fibers with the viscose, c) Admixing the aqueous solution of the at least one reactive dye to the mixture of fibers and viscose, d) admixing the pore former to the mixture according to c), e) forming the mixture into a layer on a conveyor belt (the application is expediently carried out with a metering pump and a Application nozzle; the height of the layer can be regulated with an iron), f) Removing the pore former and regenerating the viscose to cellulose in an aqueous alkaline bath (which contains, for example, KOH or NaOH as an alkaline agent) at a temperature of 90 to 100 ° C, preferably about 95 ° C (after regeneration of the cellulose
  • the pore former is preferably Glauber's salt. It has a melting point of 32.4 ° C. In addition, other low-melting and water-soluble inorganic salts are also suitable in principle. The melting point should generally be below the temperature of the regeneration bath.
  • the pore former also acts as a fixing aid, which ensures that the reactive dye or the dye mixture is particularly firmly bonded to the cellulose.
  • the proportion of the pore former is advantageously 50 to 90% by weight, preferably 70 to 85% by weight, in each case based on the total weight of viscose, fibers and pore former.
  • an acid bath in particular a bath of dilute sulfuric acid
  • the acid is neutralized in the following stage, the sponge cloth is then washed and dried as described.
  • the sponge cloth according to the invention is characterized by a uniform color with good wash fastness, wet fastness and high color strength. It can be printed as usual. A printing paste which contains at least one reactive dye can also be used for printing. The pressure is then fixed at temperatures of around 80 to 230 ° C with steam or with dry heat. In this way, strong-colored prints with very good fastness properties are obtained, in particular with very good light and wash fastness.
  • the following examples serve to illustrate the invention.
  • the reactive dye was first dissolved in warm water. The solution was then added to a viscose / cotton fiber mixture and kneaded for about 20 minutes. The Glauber's salt was then added and the mixture kneaded for a further 30 minutes. The sponge cloth mass obtained was then applied in the form of a thin layer to a perforated steel strip. The cellulose was then regenerated from the viscose in an aqueous KOH bath at a temperature of about 95 ° C. During the 15 min. in the KOH bath, the pore former was simultaneously removed from the sponge cloth. The sponge cloth was then transferred to a bath with dilute sulfuric acid (about 10% by weight). The last remnants of the alkali were then washed out with plenty of water. This way you get a permanently blue colored sponge cloth.
  • Example 2 Example 1 was repeated with the only difference that instead of 0.5 g
  • Example 3 Example 1 was repeated with the only difference that instead of 0.5 g
  • ⁇ Levafix CA a mixture of 0.25 g ⁇ Cibacron HRN01 (a blue reactive dye) and 0.25 g ⁇ Cibacron HG (a yellow reactive dye) was used. With the dye mixture an intensely and permanently green colored sponge cloth was obtained.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)

Abstract

The invention relates to a sponge cloth based on regenerated cellulose. Said cloth is fibre-reinforced and the fibres and regenerated cellulose are dyed using at least one reactive dyestuff. The inventive sponge cloth is produced from a material containing viscose, i.e. an alkaline cellulose xanthogenate solution, cotton or viscose fibres, a pore-forming material, and at least one reactive dyestuff. Said material is applied to a conveyor belt in layers. The cellulose from the viscose is regenerated and the pore forming material dissolved out in a hot alkaline or acid bath.

Description

Eingefärbtes Schwammtuch und Verfahren zu dessen HerstellungColored sponge cloth and process for its production
Die Erfindung betrifft ein eingefärbtes Schwammtuch auf der Basis von regenerierter Cellulose, das mit Fasern verstärkt ist. Sie betrifft daneben ein Verfahren zur Herstellung eines eingefärbten Schwammtuchs, bei dem Viskose mit Fasern, mindestens einem Porenbildner und mindestens einem Farbmittel vermischt, die Mischung schichtförmig auf ein Transportband aufgetragen und die Viskose dann zu Cellulose regeneriert wird.The invention relates to a colored sponge cloth based on regenerated cellulose, which is reinforced with fibers. It also relates to a process for producing a colored sponge cloth, in which viscose is mixed with fibers, at least one pore former and at least one colorant, the mixture is applied in layers on a conveyor belt and the viscose is then regenerated to cellulose.
Schwammtücher sind seit langem bekannt. Es handelt sich allgemein um schicht- förmige Gebilde mit einer Dicke von etwa 0,4 bis 2,0 cm (im trockenen Zustand). Sie werden allgemein nach dem Viskoseverfahren (Cellulosexanthogenat- Verfahren) hergestellt. Um sie mechanisch stabiler zu machen enthalten sie in der Regel Textilfasem oder ein Kunststoffnetz. In einem gebräuchlichen Verfahren zur Herstellung von Schwammtuch werden beispielsweise etwa 3 Gew.-TeileSponge cloths have been known for a long time. They are generally layer-like structures with a thickness of approximately 0.4 to 2.0 cm (in the dry state). They are generally manufactured using the viscose process (cellulose xanthate process). In order to make them mechanically more stable, they usually contain textile fibers or a plastic net. In a common process for producing sponge cloth, for example, about 3 parts by weight
Baumwoll-Kämmlinge mit Lauge benetzt und die benetzten Kämmlinge dann mit etwa 14 Gew.-Teilen Viskose erknetet. Zur Einfärbung werden dann etwa 0,05 Gew.-Teile einer Pigmentdispersion mit einem Pigmentanteil von etwa 20 bis 50 Gew.-%, je nach Farbton, zugemischt. Danach werden portionsweise etwa 83 Gew.-Teile Glaubersalz (= Natriumsulfat-Decahydrat) zugegeben und die resultierende Masse weitere 20 bis 30 Minuten geknetet. Die Masse wird dann als dünne Schicht auf ein gelochtes Stahlband aufgetragen und, auf diesem Band, durch ein etwa 95 °C heiße Kalilauge enthaltendes Bad hindurchgeführt. Durch Behandeln mit verdünnter Schwefelsäure und verschiedenen Waschbädern wird dann die Lauge wieder entfernt. Das so erhaltene Schwammtuch wird dann getrocknet und kann aufgewickelt werden. Bei dem nach diesem Verfahren hergestellten Schwammtuch ist nur die regenerierte Cellulose eingefärbt, die Baumwollfasern bleiben mehr oder weniger ungefärbt. Sind die Fasern auch noch inhomogen verteilt, dann ist die Optik des Schwammtuchs beeinträchtigt, was von vielen Verbrauchern als Qualitätsmangel empfunden wird.Cotton combs wetted with lye and the wetted combs then kneaded with about 14 parts by weight of viscose. About 0.05 part by weight of a pigment dispersion with a pigment content of about 20 to 50% by weight, depending on the color, is then mixed in for the coloring. Then about 83 parts by weight of Glauber's salt (= sodium sulfate decahydrate) are added in portions and the resulting mass is kneaded for a further 20 to 30 minutes. The mass is then applied as a thin layer on a perforated steel belt and, on this belt, passed through a bath containing potassium hydroxide at about 95 ° C. The lye is then removed again by treating with dilute sulfuric acid and various washing baths. The sponge cloth thus obtained is then dried and can be wound up. In the sponge cloth produced by this process, only the regenerated cellulose is dyed, the cotton fibers remain more or less undyed. If the fibers are also distributed inhomogeneously, the appearance of the sponge cloth is impaired, which many consumers perceive as a lack of quality.
Es bestand daher die Aufgabe, ein Schwammtuch zur Verfügung zu stellen, das gleichmäßig eingefärbt ist, d.h. bei dem die regenerierte Cellulose und die Fasern die gleiche Einfärbung aufweisen. Das Schwammtuch soll darüber hinaus einfach und kostengünstig herzustellen sein.The object was therefore to provide a sponge cloth which is evenly colored, ie in which the regenerated cellulose and the fibers have the same color. The sponge cloth should also be easy and inexpensive to manufacture.
Gefunden wurde nunmehr, daß sich die Aufgabe lösen läßt mit Fasern, die mit Reaktivfarbstoffen eingefärbt sind.It has now been found that the problem can be solved with fibers which are colored with reactive dyes.
Gegenstand der vorliegenden Erfindung ist demgemäß ein eingefärbtes Schwammtuch auf der Basis von regenerierter Cellulose, das mit Fasern verstärkt ist, und dadurch gekennzeichnet ist, daß die Fasern und die regenerierte Cellulose mit mindestens einem Reaktivfarbstoff eingefärbt sind.The present invention accordingly relates to a colored sponge cloth based on regenerated cellulose, which is reinforced with fibers, and is characterized in that the fibers and the regenerated cellulose are colored with at least one reactive dye.
Als Reaktivfarbstoffe werden im Zusammenhang mit der vorliegenden Erfindung solche Farbstoffe bezeichnet, die kovalente Bindungen mit der Cellulose und dem Fasermaterial eingehen können. Dazu verfügen die Farbstoffmoleküle neben einem Chromophor über jeweils mindestens eine Ankergruppe, die mit denIn the context of the present invention, reactive dyes are those dyes which can form covalent bonds with the cellulose and the fiber material. In addition to a chromophore, the dye molecules each have at least one anchor group that is linked to the
Hydroxygruppen der Cellulose reagiert. Geeignete reaktive Ankergruppen sind insbesondere 2,4-Difluor-[1 ,3,5]triazin-2-yl-, 2,4-Dichlor-[1 ,3,5]triazin-2-yl-, 2,5,6- Trichlor-pyrimidin-4-yl- und Vinylsulfonyl-Gruppen. Die Farbstoffmoleküle weisen gegebenenfalls auch mehrere reaktive Ankergruppen auf, die untereinander gleich oder verschieden sein können. Anstelle von Vinylsulfonylgruppen können auchHydroxy groups of the cellulose react. Suitable reactive anchor groups are in particular 2,4-difluoro- [1,3,5] triazin-2-yl-, 2,4-dichloro- [1,3,5] triazin-2-yl-, 2,5,6 - Trichloropyrimidin-4-yl and vinylsulfonyl groups. The dye molecules optionally also have a plurality of reactive anchor groups which can be the same or different from one another. Instead of vinylsulfonyl groups, too
Gruppen vorkommen, aus denen sich unter den Reaktionsbedingungen Vinylsulfonylgruppen bilden. Das sind beispielsweise Gruppen der Formel -SO2- CH2-CH2-O-SO3 ", aus denen unter der Einwirkung von wäßrigem Alkali Sulfat abgespalten wird. Geeignete reaktive Farbstoffe sind beispielsweise erhältlich unter den Bezeichnungen ©Procion H-EXL, Procion XL+ oder ©Levafix E-N vonGroups occur from which vinyl sulfonyl groups form under the reaction conditions. These are, for example, groups of the formula -SO 2 - CH 2 -CH 2 -O-SO 3 " from which sulfate is eliminated under the action of aqueous alkali. Suitable reactive dyes are available, for example, under the names © Procion H-EXL, Procion XL + or © Levafix EN by
Zeneca Specialties, Manchester; ©Levafix E-A oder ©Levafix CA von DyStar Textilfarben GmbH & Co., Frankfurt a.M. oder ©Cibacron LS von Ciba Spezialitätenchemie AG, Basel. Als Chromophor enthalten diese Farbstoff beispielsweise Diphenylazo-, Anthrachinon- oder Triphendioxazin-Gruppen. Besonders geeignet unter diesen Farbstoffen sind dabei die sogenanntenZeneca Specialties, Manchester; © Levafix E-A or © Levafix CA from DyStar Textilfarben GmbH & Co., Frankfurt a.M. or © Cibacron LS from Ciba Specialty Chemicals AG, Basel. These dyes contain, for example, diphenylazo, anthraquinone or triphendioxazin groups as chromophore. So-called are particularly suitable among these dyes
Heißfärber, die bei Temperaturen von etwa 75 bis 103 °C, bevorzugt von 80 bis 98 °C, besonders bevorzugt von 90 bis 95 °C mit Cellulose reagieren. Prinzipiell einsetzbar sind jedoch auch Kalt- und Warmfärber. Die Kaltfärberei erfolgt allgemein in einem Temperaturbereich von 20 bis 70 °C, bevorzugt im Bereich von 40 bis 65 °C und speziell im Bereich von 50 bis 60 °C. Kaltfärbende Farbstoffe zeigen gegenüber den Heißfärbern allgemein eine höhere Reaktivität.Hot dyes which react with cellulose at temperatures of approximately 75 to 103 ° C., preferably 80 to 98 ° C., particularly preferably 90 to 95 ° C. However, cold and warm dyes can also be used in principle. Cold dyeing is generally carried out in a temperature range from 20 to 70 ° C., preferably in the range from 40 to 65 ° C and especially in the range of 50 to 60 ° C. Cold dyeing dyes are generally more reactive than hot dyes.
Der Anteil der Reaktiv-Farbstoffe beträgt allgemein etwa 0,001 bis 5,00 Gew.-%, bevorzugt 0,05 bis 3,00 Gew.-%, besonders bevorzugt 0,50 bis 1 ,50 Gew.-%, jeweils bezogen auf das Gesamtgewicht von Cellulose und Fasern. Der Anteil hängt dabei naturgemäß auch von der Art des Farbstoffs ab.The proportion of reactive dyes is generally about 0.001 to 5.00% by weight, preferably 0.05 to 3.00% by weight, particularly preferably 0.50 to 1.50% by weight, in each case based on the Total weight of cellulose and fibers. The proportion naturally also depends on the type of dye.
Die Fasern sind bevorzugt Baumwoll-, Viskose- oder Polyamid-Fasern. Verwendbar sind auch Mischfasern, z. B. solche aus Baumwolle und PA oderThe fibers are preferably cotton, viscose or polyamide fibers. Mixed fibers, e.g. B. those made of cotton and PA or
Viskose und PA.Viscose and PA.
Bei der Herstellung des erfindungsgemäßen Schwammtuchs können Baumwollfasern eingesetzt werden, die in einem separaten Schritt mit den Reaktivfarb- Stoffen eingefärbt wurden. Das kann beispielsweise durch eine sogenannteCotton fibers which have been dyed with the reactive dyes in a separate step can be used in the production of the sponge cloth according to the invention. This can be done, for example, by a so-called
Flockenfärbung erfolgen. Dabei wird zunächst der mindestens eine Farbstoff in Wasser gelöst, gegebenenfalls unter Erwärmen, und die Farbstoff-Lösung dann zu einer wäßrigen Salzlösung (die beispielsweise 60 g/l NaCI und 20 g/l Na2CO3 enthält) gegeben und beide miteinander vermischt. Die Baumwollfasern werden in die Färbelösung gegeben. Um Farbabweichungen zu vermeiden, sollte nach demFlakes are stained. The at least one dye is first dissolved in water, if appropriate with heating, and the dye solution is then added to an aqueous salt solution (which contains, for example, 60 g / l NaCl and 20 g / l Na 2 CO 3 ) and the two are mixed together. The cotton fibers are added to the dyeing solution. To avoid color deviations, after the
Fixieren (beispielsweise mit Essigsäure) zur Einfärbung der regenerierten Cellulose der gleiche Reaktivfarbstoff bzw. das gleiche Gemisch verschiedener Reaktivfarbstoffe verwendet werden.Fix (for example with acetic acid) the same reactive dye or the same mixture of different reactive dyes can be used for coloring the regenerated cellulose.
Bevorzugt erfolgt die Herstellung des erfindungsgemäßen Schwammtuchs jedoch durch ein Verfahren, das die folgenden Schritte umfaßt: a) Bereitstellen von Viskoselösung, mit Alkali benetzten Fasern, Porenbildner und einer wäßrigen Lösung mindestens eines reaktiven Farbstoffs, b) Mischen der Fasern mit der Viskose, c) Zumischen der wäßrigen Lösung des mindestens einen reaktiven Farbstoffs zu der Mischung aus Fasern und Viskose, d) Zumischen des Porenbildners zu der Mischung gemäß c), e) Formen der Mischung zu einer Schicht auf einem Transportband (das Auftragen erfolgt zweckmäßig mit einer Dosierpumpe und einer Auftrags- düse; dabei kann die Höhe der Schicht mit einem Bügler geregelt werden), f) Herauslösen des Porenbildners und Regenerieren der Viskose zu Cellulose in einem wäßrig-alkalischen Bad (das beispielsweise KOH oder NaOH als alkalisches Agens enthält) mit einer Temperatur von 90 bis 100 °C, bevorzugt etwa 95 °C (nach der Regeneration der Cellulose ist das Schwammtuch eigenstabil und kann von dem Transportband getrennt werden), g) Entfernen des wäßrigen Alkalis in einem weiteren Bad mit verdünnter wäßriger Mineralsäure (bevorzugt Schwefelsäure) und Waschen mit Wasser des erhaltenen Schwammtuchs in zusätzlichen Waschbädern und h) Trocknen des Schwammtuchs.However, the sponge cloth according to the invention is preferably produced by a process which comprises the following steps: a) providing viscose solution, fibers wetted with alkali, pore-forming agents and an aqueous solution of at least one reactive dye, b) mixing the fibers with the viscose, c) Admixing the aqueous solution of the at least one reactive dye to the mixture of fibers and viscose, d) admixing the pore former to the mixture according to c), e) forming the mixture into a layer on a conveyor belt (the application is expediently carried out with a metering pump and a Application nozzle; the height of the layer can be regulated with an iron), f) Removing the pore former and regenerating the viscose to cellulose in an aqueous alkaline bath (which contains, for example, KOH or NaOH as an alkaline agent) at a temperature of 90 to 100 ° C, preferably about 95 ° C (after regeneration of the cellulose the sponge cloth is inherently stable and can be separated from the conveyor belt), g) removing the aqueous alkali in a further bath with dilute aqueous mineral acid (preferably sulfuric acid) and washing with water of the sponge cloth obtained in additional washing baths and h) drying the sponge cloth.
Der Porenbildner ist, wie beschrieben, bevorzugt Glaubersalz. Es hat einen Schmelzpunkt von 32,4 °C. Prinzipiell geeignet sind daneben auch andere niedrigschmelzende und wasserlösliche anorganische Salze. Der Schmelzpunkt sollte allgemein unterhalb der Temperatur des Regenerierbades liegen. Der Poren- bildner wirkt gleichzeitig als Fixierhilfsmittel, der dafür sorgt, daß der Reaktivfarbstoff bzw. das Farbstoffgemisch besonders fest mit der Cellulose verbunden ist. Der Anteil des Porenbildners beträgt zweckmäßig 50 bis 90 Gew.-%, bevorzugt 70 bis 85 Gew.-%, jeweils bezogen auf das Gesamtgewicht von Viskose, Fasern und Porenbildner.As described, the pore former is preferably Glauber's salt. It has a melting point of 32.4 ° C. In addition, other low-melting and water-soluble inorganic salts are also suitable in principle. The melting point should generally be below the temperature of the regeneration bath. The pore former also acts as a fixing aid, which ensures that the reactive dye or the dye mixture is particularly firmly bonded to the cellulose. The proportion of the pore former is advantageously 50 to 90% by weight, preferably 70 to 85% by weight, in each case based on the total weight of viscose, fibers and pore former.
Anstelle des alkalischen Bads kann in der Stufe f) auch ein saures Bad (insbesondere ein Bad aus verdünnter Schwefelsäure) eingesetzt werden. Die Säure wird in der folgenden Stufe neutralisiert, das Schwammtuch dann wie beschrieben gewaschen und getrocknet.Instead of the alkaline bath, an acid bath (in particular a bath of dilute sulfuric acid) can also be used in stage f). The acid is neutralized in the following stage, the sponge cloth is then washed and dried as described.
Das erfindungsgemäße Schwammtuch zeichnet sich durch eine einheitliche Färbung bei gleichzeitig guter Waschechtheit, Naßechtheit und hoher Farbstärke aus. Es kann wie üblich bedruckt werden. Zum Bedrucken kann darüber hinaus eine Druckpaste verwendet werden, die mindestens einen Reaktivfarbstoff enthält. Fixiert wird der Druck dann bei Temperaturen von etwa 80 bis 230 °C mit Dampf oder mit trockener Hitze. Erhalten werden auf diese Weise farbstarke Drucke mit sehr guten Echtheitseigenschaften, insbesondere mit einer sehr guten Licht- und Waschechtheit. Die folgenden Beispiele dienen zur Illustration der Erfindung.The sponge cloth according to the invention is characterized by a uniform color with good wash fastness, wet fastness and high color strength. It can be printed as usual. A printing paste which contains at least one reactive dye can also be used for printing. The pressure is then fixed at temperatures of around 80 to 230 ° C with steam or with dry heat. In this way, strong-colored prints with very good fastness properties are obtained, in particular with very good light and wash fastness. The following examples serve to illustrate the invention.
Beispiel 1example 1
Zur Herstellung eines eingefärbten Schwammtuchs wurden verwendet:The following were used to produce a colored sponge cloth:
516 g eines Viskose/Baumwollfaser-Gemischs,516 g of a viscose / cotton fiber mixture,
2.484 g Glaubersalz 0,5 g ©Levafix CA (blau), gelöst in 5,0 ml Wasser.2,484 g Glauber's salt 0.5 g © Levafix CA (blue), dissolved in 5.0 ml water.
Der Reaktivfarbstoff wurde zunächst in warmem Wasser gelöst. Die Lösung wurde dann zu einem Viskose/Baumwollfaser-Gemisch gegeben und das Ganze etwa 20 min lang durch Kneten vermischt. Anschließend wurde das Glaubersalz hinzugefügt und das Gemisch weitere 30 min geknetet. Die erhaltene Schwamm- tuchmasse wurde dann in Form einer dünnen Schicht auf ein gelochtes Stahlband aufgetragen. In einem wäßrigen KOH-Bad mit einer Temperatur von etwa 95 °C erfolgte anschließend die Regeneration der Cellulose aus der Viskose. Während der 15 min. in dem KOH-Bad wurde gleichzeitig der Porenbildner aus dem Schwammtuch herausgelöst. Das Schwammtuch wurde anschließend in ein Bad mit verdünnter Schwefelsäure (etwa 10 gew.-%ig) überführt. Mit viel Wasser wurden dann letzte Rest des Alkalis ausgewaschen. Auf diese Weise ein dauerhaft blau eingefärbtes Schwammtuch erhalten.The reactive dye was first dissolved in warm water. The solution was then added to a viscose / cotton fiber mixture and kneaded for about 20 minutes. The Glauber's salt was then added and the mixture kneaded for a further 30 minutes. The sponge cloth mass obtained was then applied in the form of a thin layer to a perforated steel strip. The cellulose was then regenerated from the viscose in an aqueous KOH bath at a temperature of about 95 ° C. During the 15 min. in the KOH bath, the pore former was simultaneously removed from the sponge cloth. The sponge cloth was then transferred to a bath with dilute sulfuric acid (about 10% by weight). The last remnants of the alkali were then washed out with plenty of water. This way you get a permanently blue colored sponge cloth.
Beispiel 2 Beispiel 1 wurde wiederholt mit der einzigen Abweichung, daß anstelle von 0,5 gExample 2 Example 1 was repeated with the only difference that instead of 0.5 g
©Levafix CA 0,1 g ©Procion HE6G eingesetzt wurde. Es wurde ein intensiv gelbes Schwammtuch erhalten.© Levafix CA 0.1 g © Procion HE6G was used. An intensely yellow sponge cloth was obtained.
Beispiel 3 Beispiel 1 wurde wiederholt mit der einzigen Abweichung, daß anstelle von 0,5 gExample 3 Example 1 was repeated with the only difference that instead of 0.5 g
©Levafix CA eine Mischung aus 0,25 g ©Cibacron HRN01 (ein blauer Reaktivfarbstoff) und 0,25 g ©Cibacron HG (ein gelber Reaktivfarbstoff) verwendet wurde. Mit der Farbstoffmischung wurde ein intensiv und dauerhaft grün eingefärbtes Schwammtuch erhalten. © Levafix CA a mixture of 0.25 g © Cibacron HRN01 (a blue reactive dye) and 0.25 g © Cibacron HG (a yellow reactive dye) was used. With the dye mixture an intensely and permanently green colored sponge cloth was obtained.

Claims

Patentansprüche claims
1. Eingefärbtes Schwammtuch auf der Basis von regenerierter Cellulose, das mit Fasern verstärkt ist, dadurch gekennzeichnet, daß die Fasern und die regenerierte Cellulose mit mindestens einem Reaktivfarbstoff eingefärbt sind.1. Colored sponge cloth based on regenerated cellulose, which is reinforced with fibers, characterized in that the fibers and the regenerated cellulose are colored with at least one reactive dye.
2. Schwammtuch gemäß Anspruch 1 , dadurch gekennzeichnet, daß die Fasern aus Baumwolle, Viskose, PA oder Mischungen davon bestehen.2. Sponge cloth according to claim 1, characterized in that the fibers consist of cotton, viscose, PA or mixtures thereof.
3. Schwammtuch gemäß Anspruch 1 , dadurch gekennzeichnet, daß der Reaktivfarbstoff 2,4-Difluor-[1 ,3,5]triazin-2-yl-, 2,4-Dichlor-[1 ,3,5]triazin-2~ yl-, 2,5,6-Trichlor-pyrimidin-4-yl- und/oder Vinylsulfonyl-Gruppen als reaktive Ankergruppen aufweist.3. Sponge cloth according to claim 1, characterized in that the reactive dye 2,4-difluoro- [1,3,5] triazin-2-yl-, 2,4-dichloro- [1,3,5] triazin-2 ~ yl, 2,5,6-trichloropyrimidin-4-yl and / or vinylsulfonyl groups as reactive anchor groups.
4. Schwammtuch gemäß Anspruch 1 bis 3, dadurch gekennzeichnet, daß der Reaktivfarbstoff ein Warm- oder Heißfärber ist.4. Sponge cloth according to claim 1 to 3, characterized in that the reactive dye is a warm or hot dye.
5. Schwammtuch gemäß einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der Anteil der Reaktiv-Farbstoffe 0,001 bis 5,00 Gew.-%, bevorzugt 0,05 bis 3,00 Gew.-%, besonders bevorzugt 0,5 bis 1 ,50 Gew.-%, beträgt, jeweils bezogen auf das Gesamtgewicht von Cellulose und Fasern.5. sponge cloth according to one or more of claims 1 to 3, characterized in that the proportion of reactive dyes 0.001 to 5.00 wt .-%, preferably 0.05 to 3.00 wt .-%, particularly preferably 0, 5 to 1.50% by weight, based in each case on the total weight of cellulose and fibers.
6. Schwammtuch gemäß einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es bedruckt ist, bevorzugt mit einer Druckpaste, die mindestens einen Reaktivfarbstoff enthält.6. Sponge cloth according to one or more of claims 1 to 4, characterized in that it is printed, preferably with a printing paste which contains at least one reactive dye.
7. Verfahren zur Herstellung eines eingefärbten Schwammtuchs, umfassend die Schritte a) Bereitstellen von Viskoselösung, mit Alkali benetzten Fasern, Porenbildner und einer wäßrigen Lösung mindestens eines reaktiven Farbstoffs, b) Mischen der Fasern mit der Viskose, c) Zumischen der wäßrigen Lösung des mindestens einen reaktiven Farbstoffs zu der Mischung aus Fasern und Viskose, d) Zumischen des Porenbildners zu der Mischung gemäß c), e) Formen der Mischung zu einer Schicht auf einem Transportband, f) Herauslösen des Porenbildners und Regenerieren der Viskose zu Cellulose in einem wäßrig-alkalischen Bad mit einer Temperatur von 90 bis 100 °C, g) Entfernen des wäßrigen Alkalis in einem weiteren Bad mit verdünnter wäßriger Mineralsäure und Waschen mit Wasser des erhaltenen Schwammtuchs in zusätzlichen Waschbädern und h) Trocknen des Schwammtuchs.7. A process for producing a colored sponge cloth, comprising the steps of a) providing viscose solution, fibers wetted with alkali, pore-forming agents and an aqueous solution of at least one reactive dye, b) mixing the fibers with the viscose, c) admixing the aqueous solution of the at least one reactive dye to the mixture of fibers and viscose, d) admixing the pore former to the mixture according to c), e) forming the mixture into a layer on a conveyor belt, f) removing the pore former and regenerating it the viscose to cellulose in an aqueous alkaline bath at a temperature of 90 to 100 ° C., g) removing the aqueous alkali in a further bath with dilute aqueous mineral acid and washing with water of the sponge cloth obtained in additional washing baths and h) drying the sponge cloth ,
8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, daß der Porenbildner Glaubersalz ist.8. The method according to claim 7, characterized in that the pore former is Glauber's salt.
9. Verfahren gemäß Anspruch 7 oder 8, dadurch gekennzeichnet, daß die Fasern Baumwoll- oder Viskosefasern sind.9. The method according to claim 7 or 8, characterized in that the fibers are cotton or viscose fibers.
10. Verfahren gemäß einem oder mehreren der Ansprüche 7 bis 9, dadurch gekennzeichnet, daß der Anteil des Porenbildners 50 bis 90 Gew.-%, bevorzugt 70 bis 85 Gew.-%, beträgt, jeweils bezogen auf das Gesamtgewicht von Viskose, Fasern und Porenbildner. 10. The method according to one or more of claims 7 to 9, characterized in that the proportion of the pore former is 50 to 90 wt .-%, preferably 70 to 85 wt .-%, each based on the total weight of viscose, fibers and pore formers.
EP04801926A 2003-08-22 2004-08-17 Dyed sponge cloth and method for the production thereof Expired - Fee Related EP1658402B1 (en)

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DE2003139113 DE10339113A1 (en) 2003-08-22 2003-08-22 Dyed sponge cloth and process for its preparation
PCT/EP2004/009196 WO2005021861A1 (en) 2003-08-22 2004-08-17 Dyed sponge cloth and method for the production thereof

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DE102007050902A1 (en) 2007-10-23 2009-04-30 Carl Freudenberg Kg cleaning Supplies
CN102343708B (en) * 2010-07-30 2013-06-05 郑乐回 Sponge printing process
CN102212211A (en) * 2011-04-15 2011-10-12 新疆大学 Method for preparing cellulose sponge
AT514473B1 (en) 2013-06-19 2016-06-15 Chemiefaser Lenzing Ag New environmentally friendly process for producing sponges and sponges from polysaccharides
CN105542233A (en) * 2016-01-18 2016-05-04 恒天海龙（潍坊）新材料有限责任公司 Production process of cellulose foamed material
CN107558255B (en) * 2017-08-03 2019-01-15 东华大学 A kind of preparation method of regenerated cellulose mill base
CN116657264A (en) * 2023-06-01 2023-08-29 潍坊欣龙生物材料有限公司 Method for improving color depth and glossiness of black cellulose fiber

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FR2724951A1 (en) * 1994-09-26 1996-03-29 Elysees Balzac Financiere REGENERATED CELLULOSE-BASED MATERIALS WITH IMPROVED JAVEL WATER RESISTANCE AND PROCESS FOR THEIR PREPARATION
FR2748277B1 (en) * 1996-05-06 1998-07-31 Elysees Balzac Financiere METHOD FOR MANUFACTURING CELLULOSIC CELLULOSIC CELLULOSIC CELLULOSIC CELLULOSIC CELLULOSIC CELLULOSE PRODUCTS
DE19623704C1 (en) * 1996-06-14 1997-06-26 Freudenberg Carl Fa Preparation of cellulose sponge cloth free from sulphur compounds
DE10126244B4 (en) * 2001-05-30 2005-05-12 Deutsche Institute für Textil- und Faserforschung Stuttgart Process for the production of a cellulosic fibrous or textile fabric and the use of the fabric, knitted fabric or nonwoven fabric obtained therefrom

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