EP1583861A1 - Method for finishing textile fibrous materials - Google Patents

Method for finishing textile fibrous materials

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Publication number
EP1583861A1
EP1583861A1 EP03799488A EP03799488A EP1583861A1 EP 1583861 A1 EP1583861 A1 EP 1583861A1 EP 03799488 A EP03799488 A EP 03799488A EP 03799488 A EP03799488 A EP 03799488A EP 1583861 A1 EP1583861 A1 EP 1583861A1
Authority
EP
European Patent Office
Prior art keywords
acid
ids
textile
auxiliary
complexing
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
EP03799488A
Other languages
German (de)
French (fr)
Other versions
EP1583861B1 (en
Inventor
Herbert Bachus
Bernd Horrer
Heike Witzel-Wilhelm
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.)
CHT Germany GmbH
Original Assignee
CHT R Beitlich GmbH
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Publication date
Application filed by CHT R Beitlich GmbH filed Critical CHT R Beitlich GmbH
Publication of EP1583861A1 publication Critical patent/EP1583861A1/en
Application granted granted Critical
Publication of EP1583861B1 publication Critical patent/EP1583861B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
    • D06L1/14—De-sizing
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/40—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using enzymes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
    • 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
    • D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/647—Nitrogen-containing carboxylic acids or their salts

Definitions

  • the invention relates to a process for refining keratin-free textile fiber material in textile treatment stages at pH values from 4 to 7, which contain no oxidizing chemicals.
  • WO 00/68492 AI describes the use of a sodium salt of iminodisuccinic acid for washing raw wool in a pH-neutral medium.
  • DE 197 35 796 AI relates to the finishing of generally keratin-containing substrates for protection against keratin pests using iminodibisuccinic acid as a setting agent.
  • Another task for complexing agents is to remove heavy metal ions from native fibers and to mask them effectively in the treatment solution.
  • iron, copper and manganese ions cause the spontaneous decomposition of hydrogen peroxide; in dyeing processes, such cations can interact with the dye Light absorption of this dye and thus also change the coloring result.
  • copper ions in dyes for polyamide dyeing can shift the absorption maximum of the dyes and reduce the absorption itself.
  • metal ions can change the reflectance values.
  • NTA should be less problematic in well-working clarification stages due to its easy biodegradability, the detection in many drinking water reservoirs such as Lake Constance is an unsolved challenge. Studies on metabolites and maximum quantity restrictions as well as bans in individual countries show that NTA is also possible is a controversial chemical.
  • NTA as a comparatively weak complexing agent, cannot be compared with today's standard products in many textile applications.
  • phosphonates have become established here, which can be easily eliminated in sewage treatment plants, but are not biodegradable.
  • DE 42 08 106 AI describes mixtures of citric acid and sodium gluconate, which act for all conceivable textile applications between pH values of 2 and 13 as a complexing agent, peroxide stabilizer or just as a buffer. Such mixtures work without the use of nitrogen-containing complexing agents, but the complexing effect of these hydroxycarboxylic acids becomes negligibly small, especially at elevated temperatures.
  • EP 0 892 040 A2 examines aminocarboxylic acids, including iminodisuccinic acid (IDS), for cleaning hard surfaces and glasses, especially in mixtures with sorbitol or sodium gluconate.
  • IDS iminodisuccinic acid
  • WO 98/45251 describes the use of IDS in peroxide bleaching and prewashing of wood pulp in paper production, a higher degree of whiteness being achieved after subsequent bleaching.
  • DE 100 04 893 AI describes a two-component system for achieving a “stone wash ⁇ effect. It mentions IDS for the production of a bright, little-colored dispersion "- in order to complex the heavy metal ions which may be used in the polymerization process and thereby increase the storage stability of the dispersion. In the examples, only EDTA is used. Complexing agents are only used for production and storage stabilization the dispersion used.
  • GB-A-1 306 331 relates to a process for the preparation of IDS and mentions the potential utility of IDS and its derivatives for achieving uniform, light colors in the dyeing industry.
  • EP 0 831 165 A2 describes a large number of possible uses for IDS, including generally an “enzymatic bleaching”. However, the methods disclosed each require an oxidizing agent or take place in highly alkaline or strongly acidic media.
  • EP 0 831 165 A2 describes the use of, inter alia, IDS as a stabilizer in alkaline oxidative cotton bleaching with hydrogen peroxide, IDS always being used in combination with hydrogen peroxide.
  • the object of the present invention was therefore to provide complexing agents for oxidant-free treatment stages in textile finishing, which have the disadvantages of Avoid prior art complexing agents known for this purpose. Improving the biodegradation behavior is a special requirement.
  • the object is achieved according to the invention by a process for finishing textile fiber material in treatment stages free of oxidizing agents at pH values from 4 to 7, which is characterized in that iminodisuccinic acid or salts thereof are used as auxiliaries.
  • Iminodisuccinic acid and its salts are also referred to as IDS for the purposes of the invention.
  • the auxiliary preferably contains further complexing agents or dispersing agents such as, for example, hydroxycarboxylic acids, polyaspartic acids, acrylic acid homopolymers or acrylic acid copolymers.
  • hydroxycarboxylic acids are citric acid or gluconic acid, since they have proven to be particularly suitable for the complexation ability of To increase IDS, especially with regard to calcium.
  • Acrylic acid copolymers are preferably derivatives containing maleic acid or sugar.
  • the weight ratio of IDS to the sum of further complexing agents or dispersing agents is particularly advantageously set at 1:10 to 10: 1.
  • the auxiliary is used in an amount of 0.02 to 5% by weight, preferably 0.1 to 2.0% by weight, based on the weight of the goods. This ensures that a minimum complexing effect is achieved. At the same time, disadvantages associated with an excessively high proportion of IDS are avoided: If the complexation is too high, all hardness can be bound, which in some enzyme classes has a negative effect on their activity. In addition to the pure product costs, textile refiners also have to pay wastewater fees depending on the COD and BOD load. In addition, despite the fact that they are easily biodegradable, complexing agents such as NTA are found in drinking water reservoirs to a considerable extent. It is therefore preferable to use a small amount of each complexing agent and the smallest possible proportion as a blending component in product formulations.
  • the textile treatment stage is preferably carried out at 20 to 130 ° C., which ensures optimum complex stability.
  • Textiles are prewashed at pH values between 4 and 7, with enzymes often being added simultaneously for desizing, particularly in the case of woven goods.
  • Complexing agents are also used here. After the subsequent peroxide bleaching, which is usually stabilized with phosphonate blends, the effect can be derived from the pre-cleaning stage via the desizing and whiteness level.
  • Acrylic acid homo- and copolymers as well as biodegradable additives such as citric acid, polyaspartic acid and sugar acrylic acid copolymers improve both desizing and whiteness results.
  • Amylases are preferably used as enzymes at pH 4 to 7 in desizing processes of woven goods; combinations with pectinases, proteases, lipases, hemicellulases and cellulases are also suitable for woven goods, whereas the same enzyme classes are used alone or in combination for knitted goods, but usually without the addition of amylases.
  • the method according to the invention can also be carried out in such a way that the auxiliary is used together with enzymes. This is particularly important for enzymatic desizing. Desizing is simultaneously demineralized.
  • the IDS-containing auxiliary of the process according to the invention has surprisingly proven to be particularly suitable, since it does not impair the effectiveness of the enzymes used, in particular of alpha-amylases, and also does not cause a higher sensitivity to temperature increases. These problems often prevent the use of complexing agents in the desizing step.
  • Polyamide and polyester are dyed in an acidic environment. Heavy metals can interfere here because they form a complex with the dye, which can change its type non-specifically. Whether a complexing agent prevents this cannot be deduced from its complexing constants alone, but must be checked in a realistic system. Aids containing IDS surprisingly avoid the disadvantages mentioned in the process according to the invention.
  • IDS can very effectively suppress heavy metal effects.
  • mixtures are also well suited for this, so that the absolute amount of complexing agent with a high heavy metal binding constant is reduced.
  • R3 acrylic acid polymer, 20% of the acid groups neutralized with sodium hydroxide solution, K value 25, 48% DM.
  • R4 Commercial polyaspartic acid, adjusted to pH 10, 45%
  • examples according to the invention are identified as B1 to B7, IDS-free comparative examples are identified as VB1 to VB4.
  • Calcium binding value Determined by turbidity titration with light guide photometer at pH 11 in the presence of 2 g / l soda, at a start of 900 mV and a final value of 600 mV. Unit: mg calcium carbonate / g product.
  • VB4 DTPMP, commercially available sodium salt as a 25% aqueous solution based on free acid.
  • Application examples Application example 1: desizing and subsequent peroxide bleaching
  • Starch-sized cotton weaves are impregnated at 60 ° C with 4 g / l of a commercial wetting agent, Kollasol ® MCE and a commercial amylase-containing enzyme preparation, Beisol ® T 2090, as well as 5 g / l of the complexing agents according to the invention, liquor absorption 100%. After 4 hours at 30 ° C is washed out at 90 ° C and dried.
  • Example B4 shows that a mixture of IDS and polyaspartic acid also improved the degree of whiteness in comparison to pure IDS, especially if the. lower active substance content of example B4 taken into account.
  • Example B2 shows that this effect is also achieved at a product pH of 7.
  • Application example 2 polyamide dye solution with a copper-sensitive dye.

Abstract

Treatment of textile fibers in an oxidant-free process at pH 4-7 involves use of iminodisuccinic acid or its salts as an auxiliary.

Description

Verfahren zur Veredlung von textilem Fasermaterial Process for finishing textile fiber material
Die Erfindung betrifft ein Verfahren zur Veredlung von keratinfreiem textilem Fasermaterial in textilen Behandlungsstufen bei pH-Werten von 4 bis 7, welche keine oxidierenden Chemikalien enthalten.The invention relates to a process for refining keratin-free textile fiber material in textile treatment stages at pH values from 4 to 7, which contain no oxidizing chemicals.
In modernen textilen Behandlungsstufen werden Komplexbildner bei einer Vielzahl von Veredlungsschritten eingesetzt. Eine Hauptaufgabe dieser Hilfsmittel ist neben der Enthärtung von Betriebswässern die Extraktion von Härtebildnern aus textilem Fasermaterial.In modern textile treatment stages, complexing agents are used in a large number of finishing steps. In addition to the softening of process water, a main task of these aids is the extraction of hardness formers from textile fiber material.
WO 00/68492 AI beschreibt die Verwendung eines Natriumsalzes der Iminodibemsteinsäure zur Rohwollwäsche in pH-neutralem Medium. DE 197 35 796 AI betrifft die Ausrüstung allgemein keratinhaltiger Substrate zum Schutz gegen Keratinschädlinge unter Einsatz von Iminodibemsteinsäure als Stellmittel.WO 00/68492 AI describes the use of a sodium salt of iminodisuccinic acid for washing raw wool in a pH-neutral medium. DE 197 35 796 AI relates to the finishing of generally keratin-containing substrates for protection against keratin pests using iminodibisuccinic acid as a setting agent.
Eine weitere Aufgabe für Komplexbildner besteht darin, Schwermetallionen aus nativen Fasern zu entfernen sowie in Behaπdlungslösung diese wirksam zu maskieren. In Bleichprozessen mit Wasserstoffperoxid bewirken Eisen-, Kupfer- und Manganionen den spontanen Zerfall von Wasserstoffperoxid; in Färbeprozessen können solche Kationen durch Wechselwirkung mit dem Farbstoff die Lichtabsorption dieses Farbstoffes und somit auch das Färbeergebnis verändern. Beispielsweise können Kupferionen bei Farbstoffen zum Polyamidfärben das Absorptionsmaximum der Farbstoffe verschieben sowie die Absorption selbst reduzieren. Beim Polyesterfärben mit metallsensitiver Trichromie können Metallionen die Remissionswerte verändern.Another task for complexing agents is to remove heavy metal ions from native fibers and to mask them effectively in the treatment solution. In bleaching processes with hydrogen peroxide, iron, copper and manganese ions cause the spontaneous decomposition of hydrogen peroxide; in dyeing processes, such cations can interact with the dye Light absorption of this dye and thus also change the coloring result. For example, copper ions in dyes for polyamide dyeing can shift the absorption maximum of the dyes and reduce the absorption itself. When dyeing polyester with metal-sensitive trichrome, metal ions can change the reflectance values.
Ein bekannter und verbreiteter Komplexbildner ist EDTA, das allerdings infolge mangelnder Abbaubarkeit und der Gefahr von Remobilisierung von Schwermetallen für die Textilveredlung in Deutschland nicht mehr erlaubt ist. Da Ersatzstoffe aus der Aminocarbonsäurereihe wie DTPA oder HEDTA keine günstigeren ökologischen Eigenschaften aufweisen, wird heute vermehrt NTA eingesetzt.A well-known and widespread complexing agent is EDTA, which is no longer permitted in Germany due to its lack of degradability and the risk of heavy metals being remobilized for textile finishing. Since substitutes from the amino carboxylic acid series such as DTPA or HEDTA do not have any more favorable ecological properties, NTA is increasingly used today.
Obwohl NTA in gut arbeitenden Klärstufen infolge leichter biologischer Abbaubarkeit weniger problematisch sein sollte, stellt der Nachweis in vielen Trinkwasserreservoiren wie dem Bodensee eine ungelöste Herausforderung dar. Studien über Metaboliten sowie Höchstmengen- beschränkungen und auch Verbote in einzelnen Ländern zeigen, dass es sich auch bei NTA um eine umstrittene Chemikalie handelt.Although NTA should be less problematic in well-working clarification stages due to its easy biodegradability, the detection in many drinking water reservoirs such as Lake Constance is an unsolved challenge. Studies on metabolites and maximum quantity restrictions as well as bans in individual countries show that NTA is also possible is a controversial chemical.
Daneben ist NTA als vergleichsweise schwacher Komplexbildner in vielen textilen Anwendungen nicht mit heutigen Standardprodukten vergleichbar. Insbesondere Phosphonate haben sich hier etabliert, die sich in Kläranlagen zwar einfach eliminieren lassen, jedoch keine biologische Abbaubarkeit aufweisen.In addition, NTA, as a comparatively weak complexing agent, cannot be compared with today's standard products in many textile applications. In particular, phosphonates have become established here, which can be easily eliminated in sewage treatment plants, but are not biodegradable.
So wurden in den vergangenen zwei Jahrzehnten eine Vielzahl an neuen Hilfsmitteln entwickelt: DE 42 08 106 AI beschreibt Mischungen aus Citronensäure und Natiumgluconat, die für alle denkbaren textilen Applikationen zwischen pH-Werten von 2 und 13 als Komplexbildner, Peroxidstabilisator oder auch nur als Puffer wirken. Solchen Mischungen arbeiten zwar unter Verzicht auf stickstoffhaltige Komplexbildner, jedoch wird die komplexierende Wirkung dieser Hydroxycarbonsäuren insbesondere bei erhöhter Temperatur vernachlässigbar klein.A large number of new aids have been developed in the past two decades: DE 42 08 106 AI describes mixtures of citric acid and sodium gluconate, which act for all conceivable textile applications between pH values of 2 and 13 as a complexing agent, peroxide stabilizer or just as a buffer. Such mixtures work without the use of nitrogen-containing complexing agents, but the complexing effect of these hydroxycarboxylic acids becomes negligibly small, especially at elevated temperatures.
DE 43 17 060 AI beschreibt Mischungen von stickstoffhaltigen Komplexbildnern wie Aminopolycarbonsäuren oder Phosphonaten zusammen mit Polyacrylsauren, die in einer Vorreinigungsstufe zur Peroxidbleiche bei pH-Werten im Bereich von 5 bis 11 eingesetzt werden. Dabei werden insbesondere NTA und nicht abbaubare Polyacrylsauren verwendet.DE 43 17 060 AI describes mixtures of nitrogen-containing complexing agents such as aminopolycarboxylic acids or phosphonates together with polyacrylic acids, which are used in a pre-cleaning stage for peroxide bleaching at pH values in the range from 5 to 11. NTA and non-degradable polyacrylic acids are used in particular.
Vergleichbare Mischungen wie in DE 43 17 060 AI sind in EP 0 824 155 AI enthalten, wobei wiederum NTA-haltige Formulierungen mit Polyacrylaten für die Textilveredlung beschrieben sind.Mixtures comparable to those in DE 43 17 060 AI are contained in EP 0 824 155 AI, which in turn contains NTA-containing formulations with polyacrylates for textile finishing.
In EP 0 892 040 A2 werden Aminocarbonsäuren, unter anderem auch Iminodibemsteinsäure (IDS), für die Reinigung von harten Oberflächen und Gläsern untersucht, insbesondere in Abmischungen mit Sorbitol oder Natriumgluconat. Als Vorteil werden die besseren Abbaudaten im Vergleich zur EDTA und NTA dargestellt.EP 0 892 040 A2 examines aminocarboxylic acids, including iminodisuccinic acid (IDS), for cleaning hard surfaces and glasses, especially in mixtures with sorbitol or sodium gluconate. The better degradation data compared to EDTA and NTA are presented as an advantage.
WO 98/45251 beschreibt die Verwendung von IDS bei der Peroxidbleiche und Vorwäsche von Holzstoff bei der Papierherstellung, wobei nach anschließender Bleiche ein höherer Weißgrad erzielt wird. DE 100 04 893 AI beschreibt ein Zweikomponentensystem zur Erzielung eines „Stone-Washλλ-Effektes. Darin wird IDS zur Herstellung einer hellen, wenig gefärbten Dispersion" erwähnt, -um die im Polymerisationsprozess gegebenenfalls verwendeten Schwermetallionen zu komplexieren und dadurch die Lagerstabilität der Dispersion zu erhöhen. In den Beispielen wird dabei ausschließlich EDTA eingesetzt. Komplexbildner werden lediglich zur Herstell- und Lagerstabilisierung der Dispersion eingesetzt.WO 98/45251 describes the use of IDS in peroxide bleaching and prewashing of wood pulp in paper production, a higher degree of whiteness being achieved after subsequent bleaching. DE 100 04 893 AI describes a two-component system for achieving a “stone wash λλ effect. It mentions IDS for the production of a bright, little-colored dispersion "- in order to complex the heavy metal ions which may be used in the polymerization process and thereby increase the storage stability of the dispersion. In the examples, only EDTA is used. Complexing agents are only used for production and storage stabilization the dispersion used.
GB-A-1 306 331 betrifft ein Verfahren zur Herstellung von IDS und erwähnt die potentielle Nützlichkeit von IDS und seiner Derivate zur Erzielung einheitlicher, heller Farben in der Färbeindustrie.GB-A-1 306 331 relates to a process for the preparation of IDS and mentions the potential utility of IDS and its derivatives for achieving uniform, light colors in the dyeing industry.
EP 0 831 165 A2 beschreibt eine Vielzahl von Einsatzmöglichkeiten für IDS, darunter allgemein eine „enzymatische Bleiche". Jedoch benötigen die offenbarten Verfahren jeweils ein Oxidationsmittel oder finden in hochalkalischen oder stark sauren Medien statt.EP 0 831 165 A2 describes a large number of possible uses for IDS, including generally an “enzymatic bleaching”. However, the methods disclosed each require an oxidizing agent or take place in highly alkaline or strongly acidic media.
EP 0 831 165 A2 beschreibt die Verwendung von unter anderem IDS als Stabilisator in der alkalischen oxidativen Baumwollbleiche mit Wasserstoffperoxid, wobei IDS stets in Kombination mit Wasser- toffperoxid eingesetzt wird.EP 0 831 165 A2 describes the use of, inter alia, IDS as a stabilizer in alkaline oxidative cotton bleaching with hydrogen peroxide, IDS always being used in combination with hydrogen peroxide.
Dabei sollen Weißgradremissionssteigerungen von 14 bis 26 Einheiten erzielt werden, sowie mit Zusätzen an Magnesiumchlorid, Gluconsäure oder Citronensäure reduzierte Ergebnisse, jedoch immer noch 12 bis 23 Einheiten erzielt werden.Whiteness remission increases of 14 to 26 units should be achieved, as well as reduced results with the addition of magnesium chloride, gluconic acid or citric acid, but still 12 to 23 units.
Obwohl diese Anmeldung bereits 1997 erfolgte und diese Weißgradsteigerung um ein Mehrfaches besser als Ergebnisse mit heute eingesetzten phosphonsäurehaltigen Produkte wäre, findet man in Literatur und Praxis wenig über tatsächliche Wirkung solcher Stabilisatoren unter den angegebenen Bedingungen von textilen Bleichen. Hingegen wäre eher anzunehmen, dass IDS in Gegenwart von 10-60 ml/1 Peroxid 35% sowie 6 - 30 ml/1 Natronlauge und Temperaturen bis 100°C rasch an komplexierender Wirkung verliert, da solch drastische Bedingungen für Monoaminocarbonsäuren wie NTA oder IDS deren rasche Oxidation und somit Unwirksamkeit bewirken würden.Although this application was made in 1997 and this whiteness increase would be several times better than the results with products containing phosphonic acid used today, can be found in Literature and practice little about the actual effect of such stabilizers under the specified conditions of textile bleaching. On the other hand, it would be more likely that IDS in the presence of 10-60 ml / 1 peroxide 35% and 6 - 30 ml / 1 sodium hydroxide solution and temperatures up to 100 ° C quickly loses its complexing effect, since such drastic conditions for monoaminocarboxylic acids such as NTA or IDS would cause rapid oxidation and thus ineffectiveness.
Vergleichsversuche zu den Anwendungsbeispielen ergaben wesentlich bessere Resultate für die Bleichflotten ohne Peroxidregulator, der Zusatz von IDS jedoch keine Steigerung dieses Weißgrades.Comparative tests on the application examples gave significantly better results for the bleaching liquors without a peroxide regulator, but the addition of IDS did not increase this whiteness.
In gleicher Anmeldung sind eine Vielzahl von weiteren Vorbehandlungsverfahren beiläufig erwähnt, in denen IDS ebenfalls eingesetzt werden könnte: Natriumchlorit- und -hypochloritbleiche, Bedingungen wo IDS chemisch kaum stabil sein kann sowie eine nicht näher beschriebene "enzymatische" Bleiche.In the same application, a large number of other pretreatment processes are mentioned in which IDS could also be used: sodium chlorite and hypochlorite bleaching, conditions where IDS can hardly be chemically stable and an "enzymatic" bleaching which is not described in detail.
Im Internet sind unter der Adresse http://www.baypure.de Anwendungsempfehlungen für IDS unter anderem für die Textilindustrie enthalten. Dabei wird speziell auf die Stabilisierung von Peroxid sowie die Baumwollbleiche hingewiesen. Ferner wird allgemein erwähnt, dass es auch für das Bleichen und Färben von Baumwolle praktizierte Anwendungen gibt. Daneben wird auf die verbesserte Wirkung gegenüber EDTA und Aminomethylenphosphonaten in stark calciumbelasteten Wässern verwiesen wird.On the Internet at http://www.baypure.de application recommendations for IDS for the textile industry are included. Special attention is drawn to the stabilization of peroxide and the bleaching of cotton. Furthermore, it is generally mentioned that there are also practical applications for bleaching and dyeing cotton. In addition, reference is made to the improved effect compared to EDTA and aminomethylene phosphonates in water heavily contaminated with calcium.
Die Aufgabe der vorliegenden Erfindung bestand daher darin, Komplexbildner für oxidationsmittelfreie Behandlungsstufen in der Textilveredlung zur Verfügung zu stellen, die die Nachteile der aus dem Stand der Technik für diesen Einsatzzweck bekannten Komplexbildner vermeiden. Eine besondere Anforderung stellt hierbei auch eine Verbesserung des biologischen Abbauverhaltens dar.The object of the present invention was therefore to provide complexing agents for oxidant-free treatment stages in textile finishing, which have the disadvantages of Avoid prior art complexing agents known for this purpose. Improving the biodegradation behavior is a special requirement.
Die Aufgabe wird erfindungsgemäß gelöst durch ein Verfahren zur Veredlung von textilem Fasermaterial in oxidationsmittelfreien Behandlungsstufen bei pH-Werten von 4 bis 7, das dadurch gekennzeichnet ist, dass als Hilfsmittel Iminodibemsteinsäure oder Salze hiervon eingesetzt werden.The object is achieved according to the invention by a process for finishing textile fiber material in treatment stages free of oxidizing agents at pH values from 4 to 7, which is characterized in that iminodisuccinic acid or salts thereof are used as auxiliaries.
Iminodibemsteinsäure und ihre Salze werden im Sinne der Erfindung gleichermaßen als IDS bezeichnet.Iminodisuccinic acid and its salts are also referred to as IDS for the purposes of the invention.
Bevorzugte Anwendungsgebiete sind dabei:Preferred areas of application are:
1. Entmineralisierung durch Komplexierung von Schwermetallionen bei pH-Werten im Bereich von 4 bis 7, gegebenenfalls unter gleichzeitiger Verwendung von Enzymen, insbesondere der Entschlichtung oder der Behandlung mit einer sauren Pektinase.1. Demineralization by complexing heavy metal ions at pH values in the range from 4 to 7, optionally with simultaneous use of enzymes, in particular desizing or treatment with an acidic pectinase.
2. Einsatz beim Färben von polyamid- oder polyesterhaltigem Fasermaterial, wobei der negative Einfluss von Schwermetallionen verringert wird.2. Use in dyeing polyamide or polyester-containing fiber material, whereby the negative influence of heavy metal ions is reduced.
3. Kombinationen der genannten und weiterer Anwendungsgebiete.3. Combinations of the above and other areas of application.
Dabei enthält das Hilfsmittel neben IDS bevorzugt noch weitere Komplexbildner oder Dispergiermittel wie beispielsweise Hydroxy- carbonsäuren, Polyasparaginsäuren, Acrylsäurehomopolymere oder Acrylsäurecopolymere. Als Hydroxycarbonsäuren kommen insbesondere Citronensäure oder Gluconsäure in Betracht, da sie sich durch besonders geeignet erwiesen haben, die Komplexierungsfähigkeit von IDS, insbesondere in Bezug auf Calcium, zu steigern. Acrylsäure- copolymere sind bevorzugt maleinsäure- oder zuckerhaltige Derivate.In addition to IDS, the auxiliary preferably contains further complexing agents or dispersing agents such as, for example, hydroxycarboxylic acids, polyaspartic acids, acrylic acid homopolymers or acrylic acid copolymers. Particularly suitable hydroxycarboxylic acids are citric acid or gluconic acid, since they have proven to be particularly suitable for the complexation ability of To increase IDS, especially with regard to calcium. Acrylic acid copolymers are preferably derivatives containing maleic acid or sugar.
Besonders vorteilhaft wird das Gew. -Verhältnis von IDS zur Summe an weiteren Komplexbildnern oder Dispergiermitteln zu 1 : 10 bis 10: 1 eingestellt.The weight ratio of IDS to the sum of further complexing agents or dispersing agents is particularly advantageously set at 1:10 to 10: 1.
Nach dem erfindungsgemäßen Verfahren setzt man das Hilfsmittel mit 0,02 bis 5 Gew.-%, bevorzugt 0,1 bis 2,0 Gew.-%, bezogen auf das Warengewicht ein. Dadurch ist sichergestellt, dass eine Mindestkomplexierungswirkung erreicht wird. Zugleich werden aber auch Nachteile vermieden, die mit einem zu hohen Anteil an IDS verbunden sind: Bei zu hoher Komplexierung kann sämtliche Härte gebunden werden, was in manche Enzymklassen deren Aktivität negativ beeinflusst. Neben den reinen Produktkosten müssen daneben Textilveredler je nach CSB- und BSB-Fracht Abwassergebühren entrichten, außerdem werden trotz leichter biologischer Abbaubarkeit in Kläranlagen Komplexbildner wie NTA in erheblichen Umfang unerwünscht in Trinkwasserreservoiren gefunden. Deshalb ist bei jedem Komplexbildner eine geringe Einsatzmenge sowie ein möglichst geringer Anteil als Abmischungskomponente in Produktformulierungen vorzuziehen.In the process according to the invention, the auxiliary is used in an amount of 0.02 to 5% by weight, preferably 0.1 to 2.0% by weight, based on the weight of the goods. This ensures that a minimum complexing effect is achieved. At the same time, disadvantages associated with an excessively high proportion of IDS are avoided: If the complexation is too high, all hardness can be bound, which in some enzyme classes has a negative effect on their activity. In addition to the pure product costs, textile refiners also have to pay wastewater fees depending on the COD and BOD load. In addition, despite the fact that they are easily biodegradable, complexing agents such as NTA are found in drinking water reservoirs to a considerable extent. It is therefore preferable to use a small amount of each complexing agent and the smallest possible proportion as a blending component in product formulations.
Nach dem erfindungsgemäßen Verfahren führt man die textile Behandlungsstufe vorzugsweise bei 20 bis 130°C durchführt, wodurch optimale Komplexstabilität gegeben ist.In the process according to the invention, the textile treatment stage is preferably carried out at 20 to 130 ° C., which ensures optimum complex stability.
Bei pH-Werten zwischen 4 und 7 werden Textilien vorgewaschen, wobei insbesondere bei Webwaren gleichzeitig oft Enzyme zur Entschlichtung zugesetzt werden. Hierbei werden ebenfalls Komplexbildner eingesetzt. Nach der anschließenden Peroxidbleiche, die üblicherweise mit Phosphonat-Abmischungen stabilisiert wird, lassen sich die Wirkung aus der Vorreinigungsstufe über den Entschlichtungs- und Weißgrad ableiten.Textiles are prewashed at pH values between 4 and 7, with enzymes often being added simultaneously for desizing, particularly in the case of woven goods. Complexing agents are also used here. After the subsequent peroxide bleaching, which is usually stabilized with phosphonate blends, the effect can be derived from the pre-cleaning stage via the desizing and whiteness level.
Es wurde nun gefunden, dass IDS ohne weitere Additive bereits positive Wirkung zeigt.It has now been found that IDS already has a positive effect without further additives.
Erfindungsgemäße Abmischungen mit weiteren organischen Komplexbildnern bzw. Dispergiermitteln ergeben darüber hinaus überraschenderweise deutliche Wirkungssteigerungen:Mixtures according to the invention with further organic complexing agents or dispersants also surprisingly result in significant increases in activity:
Acrylsäurehomo- und copolymere ebenso wie biologisch abbaubare Zusatzstoffe wie Citronensäure, Polyasparaginsäure und Zuckeracryl- säurecopolymere verbessern sowohl Entschlichtungs- wie auch Weißgradergebnisse. Als Enzyme bei pH 4 bis 7 werden in Entschlichtungsprozessen von Webware bevorzugt Amylasen eingesetzt, für Webwaren sind ebenfalls Kombinationen mit Pektinasen, Proteasen, Lipasen, Hemicellulasen und Cellulasen geeignet, für Maschenwaren hingegen die gleichen Enzymklassen allein oder in Kombination, jedoch üblicherweise ohne den Zusatz von Amylasen.Acrylic acid homo- and copolymers as well as biodegradable additives such as citric acid, polyaspartic acid and sugar acrylic acid copolymers improve both desizing and whiteness results. Amylases are preferably used as enzymes at pH 4 to 7 in desizing processes of woven goods; combinations with pectinases, proteases, lipases, hemicellulases and cellulases are also suitable for woven goods, whereas the same enzyme classes are used alone or in combination for knitted goods, but usually without the addition of amylases.
Bei nicht erfindungsgemäßen Verfahren mit Säureextraktion und entsprechenden pH-Werten von 1-3 müssen Enzyme in einer zusätzlichen Behandlungsstufe eingesetzt werden, da die meisten Enzyme unter solch aciden Bedingungen unwirksam werden.In the case of methods according to the invention with acid extraction and corresponding pH values of 1-3, enzymes have to be used in an additional treatment step, since most enzymes become ineffective under such acidic conditions.
Das erfindungsgemäße Verfahren kann auch dergestalt ausgeführt werden, dass man das Hilfsmittel zusammen mit Enzymen einsetzt. Dies ist insbesondere bei der enzymatischen Entschlichtung von Bedeutung. Bei der Entschlichtung wird gleichzeitig entmineralisiert. Dabei hat sich das IDS-enthaltende Hilfsmittel des erfindungsgemäßen Verfahrens überraschend als besonders geeignet erwiesen, da es die Wirksamkeit der eingesetzten Enzyme, insbesondere von alpha-Amylasen, nicht beeinträchtigt und auch keine höhere Empfindlichkeit gegenüber Temperaturerhöhungen bewirkt. Diese Probleme verhindern vielfach den Einsatz von Komplexierungsmitteln im Entschlichtungs-schritt.The method according to the invention can also be carried out in such a way that the auxiliary is used together with enzymes. This is particularly important for enzymatic desizing. Desizing is simultaneously demineralized. The IDS-containing auxiliary of the process according to the invention has surprisingly proven to be particularly suitable, since it does not impair the effectiveness of the enzymes used, in particular of alpha-amylases, and also does not cause a higher sensitivity to temperature increases. These problems often prevent the use of complexing agents in the desizing step.
Im Fall des erfindungsgemäßen Verfahrens zur Textilfärbung werden synthetisches, insbesondere polyamid- und/oder polyesterhaltiges Fasermaterial eingesetzt. Beim Färben werden Komplexbildner zugesetzt, um geringe Mengen an Störmetallen des Behandlungsbades zu maskieren. Diese können die Wellenlänge des Absorptionsmaximums von Farbstoffen verschieben und die Absorption des Farbstoffes verändern, was schon aus Gründen der Reproduzierbar-keit des Färbeergebnisses unerwünscht ist.In the case of the textile dyeing process according to the invention, synthetic, in particular polyamide and / or polyester-containing fiber material is used. Complexing agents are added during dyeing in order to mask small amounts of interfering metals in the treatment bath. These can shift the wavelength of the absorption maximum of dyes and change the absorption of the dye, which is undesirable for reasons of the reproducibility of the dyeing result.
Polyamid und Polyester werden im sauren Milieu gefärbt. Hier können Schwermetalle stören, weil diese mit dem Farbstoff einen Komplex bilden, der ihn in seiner Art unspezifisch verändern kann. Ob ein Komplexbildner dies verhindert, kann nicht allein aus seinen Komplexbildungskonstanten abgeleitet werden, sondern muss in einem realitätsnahen System geprüft werden. IDS-haltige Hilfsmittel vermeiden im erfindungsgemäßen Verfahren überraschend die genannten Nachteile.Polyamide and polyester are dyed in an acidic environment. Heavy metals can interfere here because they form a complex with the dye, which can change its type non-specifically. Whether a complexing agent prevents this cannot be deduced from its complexing constants alone, but must be checked in a realistic system. Aids containing IDS surprisingly avoid the disadvantages mentioned in the process according to the invention.
Beim Färben von Polyamid verschiebt sich die Wellenlänge des in Gegenwart von Schwermetallionen, was durch den Zusatz von NTA oder DTPMP verringert werden kann. Es wurde nun gefunden, dass IDS besser als DTPMP und nahezu wie NTA ebenfalls dem Schwermetalleffekt entgegenwirkt. Durch Abmischungen mit weiteren Komplexbildnern lässt sich dieser Effekt noch deutlich über die Wirkung von NTA steigern.When dyeing polyamide, the wavelength shifts in the presence of heavy metal ions, which can be reduced by adding NTA or DTPMP. It has now been found that IDS counteracts the heavy metal effect better than DTPMP and almost like NTA. By mixing with other complexing agents, this effect can be significantly increased over the effect of NTA.
Beim Färben von Polyester verändern Schwermetallionen die Remissionswerte. Dispergiermittel mit geringen komplexbildenden Eigenschaften wie Polyacrylsauren oder Polyasparaginsäure zeigen kaum Effekte.When dyeing polyester, heavy metal ions change the reflectance values. Dispersants with low complex-forming properties such as polyacrylic acids or polyaspartic acid hardly show any effects.
Es wurde gefunden, dass IDS sehr effektiv Schwermetalleffekte unterdrücken kann. Darüber hinaus wurde gefunden, dass Abmischungen hierfür ebenfalls gut geeignet sind, so dass die absolute Einsatzmenge an Komplexbildner mit hoher Schwermetallbindungskonstante erniedrigt wird.It has been found that IDS can very effectively suppress heavy metal effects. In addition, it was found that mixtures are also well suited for this, so that the absolute amount of complexing agent with a high heavy metal binding constant is reduced.
Es wurde weiterhin gefunden, dass sich die Calciumbindekapazität durch Abmischungen der IDS mit weiteren Hilfsstoffen selbst unter Reduzierung der Summe des Wirkstoffgehaltes einer Abmischung beibehalten oder sogar steigern lässt.It was also found that the calcium binding capacity can be maintained or even increased by mixing the IDS with other auxiliaries even by reducing the total active substance content of a mixture.
Ausführungsbeispiele:EXAMPLES
Bezugsbeispiel 1 (gemäß EP 0 289 895 Bl):Reference example 1 (according to EP 0 289 895 B1):
134 g Glucose wurden in 238 g Wasser gelöst und mit Natronlauge 50% auf pH 9 eingestellt. Zu dieser Lösung wurden gleichzeitig 161 g Acrylsäure, 228 g Wasserstoffperoxid 14% und Natronlauge 50 % so zudosiert, dass während der Zulaufphase ein pH-Wert von 9 und eine Temperatur von 90 °C konstant gehalten wurde. Die Zugabe von Acrylsäure erfolgte innerhalb von 2 Stunden, Wasserstoffperoxid wurde 30 Minuten länger dosiert. Anschließend wurde noch 30 Minuten bei 90 °C gerührt. Das Polymer wies eine Viskosität von 400 mPas auf.134 g of glucose were dissolved in 238 g of water and adjusted to pH 9 with 50% sodium hydroxide solution. 161 g of acrylic acid, 228 g of 14% hydrogen peroxide and 50% sodium hydroxide solution were simultaneously metered into this solution in such a way that a pH of 9 and a temperature of 90 ° C. were kept constant during the feed phase. Acrylic acid was added within 2 hours, and hydrogen peroxide was metered in for 30 minutes longer. The mixture was then stirred at 90 ° C for 30 minutes. The polymer had a viscosity of 400 mPas.
Als Bestandteile für weitere Abmischungen wurden eingesetzt (R= Rohstoff):The following were used as components for further blends (R = raw material):
Rl : IDS - als flüssiges Tetranatriumsalz, 34% TS (Trockensubstanz).Rl: IDS - as a liquid tetrasodium salt, 34% TS (dry substance).
Handelsprodukt: Baypure® CX 100. R2: Copolymerisat Maleinsäure / Acrylsäure, K-Wert 20, 50% TS.Commercial product: Baypure® CX 100. R2: copolymer maleic acid / acrylic acid, K value 20, 50% TS.
R3: Acrylsäurepolymer, 20% der Säuregruppen mit Natronlauge neutralisiert, K-Wert 25, 48% TS. R4: Handelsübliche Polyasparaginsäure, auf pH 10 eingestellt, 45%R3: acrylic acid polymer, 20% of the acid groups neutralized with sodium hydroxide solution, K value 25, 48% DM. R4: Commercial polyaspartic acid, adjusted to pH 10, 45%
TS. R5 Zuckerpolyacrylsäure entsprechend Bezugsbeispiel 1 der EP 0289TS. R5 sugar polyacrylic acid according to Reference Example 1 of EP 0289
895 Bl.895 sheets
R6 Citronensäure als Monohydrat. R7 Natronlauge 50%. R8 Salzsäure 32%.R6 citric acid as a monohydrate. R7 caustic soda 50%. R8 hydrochloric acid 32%.
Herstellung der erfindungsgemäßen Abmischungen:Production of the Mixtures According to the Invention:
Wasser wurde vorgelegt und die einzelnen Komponenten nacheinander zugegeben, erfindungsgemäße Beispiele sind als Bl bis B7, IDS-freie Vergleichsbeispiele sind als VB1 bis VB4 gekennzeichnet. Water was introduced and the individual components were added in succession, examples according to the invention are identified as B1 to B7, IDS-free comparative examples are identified as VB1 to VB4.
Calcium-Bindewert: Ermittelt über Trübuπgstitration mit Lichtleiterphotometer bei pH 11 in Gegenwart von 2 g/l Soda, bei einem Start von 900 mV und einer Endwert von 600 mV. Einheit: mg Calciumcarbonat / g Produkt.Calcium binding value: Determined by turbidity titration with light guide photometer at pH 11 in the presence of 2 g / l soda, at a start of 900 mV and a final value of 600 mV. Unit: mg calcium carbonate / g product.
Weitere nicht erfindungsgemäße Vergleichsbeispiele (TS=Trocken- substanz): VB3: NTA, handelsübliches Natriumsalz als- 40%ige (TS) wässrigeFurther non-inventive comparative examples (TS = dry substance): VB3: NTA, commercially available sodium salt as a 40% (TS) aqueous
Lösung. VB4: DTPMP, handelsübliches Natriumsalz als 25%ige wässrige Lösung bezogen auf freie Säure.Solution. VB4: DTPMP, commercially available sodium salt as a 25% aqueous solution based on free acid.
Anwendungstechnische Beispiele: Anwendungsbeispiel 1 : Entschlichtung und anschließende PeroxidbleicheApplication examples: Application example 1: desizing and subsequent peroxide bleaching
Stärkegeschlichtete Baumwoll-Webware wir bei 60°C mit je 4 g/l eines handelsüblichen Netzmittels, Kollasol® MCE und eines handelsüblichen amylasenhaltigen Enzympräparates, Beisol ®T 2090, sowie zusätzlich je 5 g/l der erfindungsgemäßen Komplexbildner imprägniert, Flottenaufnahme 100%. Nach 4 Stunden Verweilen bei 30°C wird bei 90°C ausgewaschen und zwischengetrocknet.Starch-sized cotton weaves are impregnated at 60 ° C with 4 g / l of a commercial wetting agent, Kollasol ® MCE and a commercial amylase-containing enzyme preparation, Beisol ® T 2090, as well as 5 g / l of the complexing agents according to the invention, liquor absorption 100%. After 4 hours at 30 ° C is washed out at 90 ° C and dried.
Danach wurde eine kontinuierliche Peroxidbleiche durchgeführt: 3 g/l Waschmittel Felosan® JET, 6 ml/1 Peroxidstabilisator Contavan® GAL, 20 mg/1 Natronlauge 50% und 40 ml/1 Wasserstoffperoxid 35%. Imprägniert wurde bei 25°C, die Flottenaufnahme betrug 100%. Nach 20 Minuten Dämpfen wurde heiß und kalt ausgewaschen. Bewertet wurde das Ergebnis nach der Bleichstufe bezüglich Entschlichtung und Weißgrad.Thereafter, a continuous peroxide bleaching was performed: 3 g / l detergent JET ® Felosan, 6 ml / 1 GAL peroxide stabilizer Contavan ®, 20 mg / 1 of sodium hydroxide solution 50% and 40 ml / 1 of hydrogen peroxide 35%. Was impregnated at 25 ° C, the liquor absorption was 100%. After 20 minutes of steaming, hot and cold washing was carried out. The result after the bleaching stage was evaluated with regard to desizing and whiteness.
Beim Einsatz von IDS in der Entschlichtungsstufe wie in Beispiel 1 resultierte eine Verbesserung des Weißgrades. Die Abmischung von IDS mit Citronensäure (B6) verbesserte sowohl die Entschlichtung als auch den Weißgrad, die besten Entschlichtungsergebnisse wurden mit Zusatz von Polyacrylaten wie in Beispielen B2, B3, B5 und B7 erzielt. Beispiel B4 zeigt, dass auch eine Abmischung von IDS und Polyasparaginsäure den Weißgrad im Vergleich zur reinen IDS verbesserte, insbesondere wenn man den. niedrigeren Wirkstoffgehalt von Beispiel B4 berücksichtigt. Beispiel B2 belegt, dass dieser Effekt auch bei einem Produkt-pH von 7 erzielt wird. Wird IDS dagegen wie beispielsweise in EP 0831 165 A2 beschrieben, Anstelle in der Entschlichtungsstufe in der Bleichstufe eingesetzt, wurde keine Verbesserung im Vergleich zum Versuch ohne Komplexbildnerzusatz erzielt.When using IDS in the desizing stage as in Example 1, the whiteness was improved. Mixing IDS with citric acid (B6) improved both the desizing and the whiteness, the best desizing results were achieved with the addition of polyacrylates as in Examples B2, B3, B5 and B7. Example B4 shows that a mixture of IDS and polyaspartic acid also improved the degree of whiteness in comparison to pure IDS, especially if the. lower active substance content of example B4 taken into account. Example B2 shows that this effect is also achieved at a product pH of 7. On the other hand, if IDS is described, for example, in EP 0831 165 A2, instead of in the desizing stage in the Bleaching level used, no improvement was achieved compared to the test without the addition of complexing agents.
Anwendungsbeispiel 2: Polyamid-Farbstofflösung mit einem kupfersensitiven Farbstoff.Application example 2: polyamide dye solution with a copper-sensitive dye.
Es wurden Lösungen mit 0,15 g/l Supraminrot® GG, 2 mg/1 Cu2+-Ionen aus Kupfersulfat und 0,5 g/l an Komplexbildnerlösungen hergestellt. Danach wurde mit Essigsäure ein pH-Wert von 5 eingestellt und die UV/VIS-Absorptionsspektren aufgenommen.Solutions with 0.15 g / l Supraminrot ® GG, 2 mg / 1 Cu 2+ ions from copper sulfate and 0.5 g / l of complexing agent solutions were prepared. Then a pH of 5 was set with acetic acid and the UV / VIS absorption spectra were recorded.
Im Vergleich zu Versuch 1 ohne Komplexbildner und ohne Metallzugabe erfolgte bereits bei einer Kupferkonzentration von 2 ppm eine drastische Reduzierung der Extinktion. Daneben wurde auch das Maximum verschoben, was eine Farbtonänderung zur Folge hatte. Übliche Komplexbildner wie NTA mit VB3 oder DTPMP aus VB4 ergeben keine Wellenlängenverschiebung und verminderten den Absorptionsverlust. IDS aus Bl ergab vergleichbare Effekte, die Abmischungen B6 und insbesondere B7 steigerten die Wirksamkeit der IDS deutlich auch gegenüber den Resultaten der Vergleichsbeispiele VB3 und VB4. Anwendungsbeispiel Polyester-Färbung mit metallsensitiver TrichromieCompared to experiment 1 without complexing agent and without metal addition, the extinction was drastically reduced at a copper concentration of 2 ppm. In addition, the maximum was shifted, which resulted in a change in color. Common complexing agents such as NTA with VB3 or DTPMP from VB4 do not result in a wavelength shift and reduce the loss of absorption. IDS from B1 gave comparable effects, the blends B6 and in particular B7 significantly increased the effectiveness of the IDS compared to the results of the comparative examples VB3 and VB4. Application example polyester dyeing with metal-sensitive trichrome
Es wurden Lösungen mit 0,440 g/l Palanilgelb® 3G 200%, 0,600 g/l Resolinrot® FB, 0,195 g/l Resolinblau® FBL, 1 g/l eine handelsüblichen Egalisiermittels Egasol® AME, verschiedenen Cu2+-Ionen-Konzen- trationen aus Kupfersulfat und 0,5 g/l an Komplexbildnerlösungen hergestellt. Danach wurde mit Essigsäure ein pH-Wert von 5,5 eingestellt. PES-Gewebe wurde im Labomat® bei einem Flottenverhältnis 1: 10 60 min bei 130°C behandelt. Der Heizgradient betrug 3°C/min.Solutions with 0.440 g / l Palanilgelb ® 3G 200%, 0.600 g / l Resolinrot ® FB, 0.195 g / l Resolinblau ® FBL, 1 g / l a commercially available leveling agent Egasol ® AME, various Cu 2+ ion concentrations trations of copper sulfate and 0.5 g / l of complexing agent solutions. Then a pH of 5.5 was set with acetic acid. PES fabric was treated in the Labomat ® at a liquor ratio of 1:10 for 60 min at 130 ° C. The heating gradient was 3 ° C / min.
Farbmetrische Auswertung:Colorimetric evaluation:
Der Zusatz von Kupferionen verschob die Remissionswerte bei allen drei Wellenlängen. Bl, B6 und B7 zeigten selbst bei 20 ppm Kupfer nur geringe Verschiebungen, die Polyasparaginsäure ohne weiteren Komplexbildnerzusatz in VBl reduzierte die Abweichung dagegen nur ungenügend. The addition of copper ions shifted the reflectance values at all three wavelengths. Bl, B6 and B7 showed only slight shifts even with 20 ppm copper, the polyaspartic acid without additional complexing agent in VBl, however, reduced the deviation insufficiently.

Claims

Patentansprüche: claims:
1. Verfahren zur Veredlung von keratinfreiem textilem Fasermaterial in oxidationsmittelfreien Behandlungsstufen bei pH-Werten von 4 bis 7, dadurch gekennzeichnet, dass man als Hilfsmittel Iminodibemsteinsäure oder Salze hiervon einsetzt.1. Process for the refinement of keratin-free textile fiber material in treatment stages free of oxidizing agents at pH values from 4 to 7, characterized in that iminodisuccinic acid or salts thereof are used as auxiliaries.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass man als Hilfsmittel neben Iminodibemsteinsäure weitere Komplexbildner •oder Dispergiermittel einsetzt.2. The method according to claim 1, characterized in that in addition to iminodisuccinic acid, other complexing agents or dispersants are used as auxiliaries.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass man als Komplexbildner oder Dispergiermittel Hydroxycarbonsäuren, Polyasparaginsäuren, Acrylsäurehomopolymere oder Acrylsäurecopolymere einsetzt.3. The method according to claim 2, characterized in that one uses as a complexing agent or dispersant hydroxycarboxylic acids, polyaspartic acids, acrylic acid homopolymers or acrylic acid copolymers.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass man als Hydroxycarbonsäuren Citronensäure und/ oder Gluconsäure verwendet.4. The method according to claim 3, characterized in that the hydroxycarboxylic acids used are citric acid and / or gluconic acid.
5. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass man als Acrylsäurecopolymere maleinsäure- oder zuckerhaltige Derivate verwendet.5. The method according to claim 3, characterized in that one uses maleic acid or sugar-containing derivatives as acrylic acid copolymers.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass man ein Gew. -Verhältnis von Iminodibemsteinsäure zur Summe an weiteren Komplexbildnern oder Dispergiermitteln von 1 : 10 bis 10: 1 einsetzt. 6. The method according to any one of claims 1 to 5, characterized in that a weight ratio of iminodisuccinic acid to the sum of other complexing agents or dispersants is used from 1:10 to 10: 1.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass man das Hilfsmittel mit 0,02 bis 5 Gew. % bezogen auf das Warengewicht einsetzt.7. The method according to any one of claims 1 to 6, characterized in that the auxiliary is used with 0.02 to 5% by weight, based on the weight of the goods.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass man die textile Behandlungsstufe bei 20 bis 130°C durchführt.8. The method according to any one of claims 1 to 7, characterized in that one carries out the textile treatment stage at 20 to 130 ° C.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass man das Hilfsmittel zusammen mit cellulasefreien Enzymen.9. The method according to any one of claims 1 to 8, characterized in that the auxiliary together with cellulase-free enzymes.
10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass man das Hilfsmittel in Kombination mit Amylasen und/oder Pektinasen einsetzt.10. The method according to any one of claims 1 to 9, characterized in that the auxiliary is used in combination with amylases and / or pectinases.
11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass man eine enzymatische Entschlichtung durchführt.11. The method according to any one of claims 1 to 10, characterized in that one carries out an enzymatic desizing.
12. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass man eine Textilfärbebehandlung von Synthesefasern durchführt.12. The method according to any one of claims 1 to 10, characterized in that one carries out a textile dyeing treatment of synthetic fibers.
13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass man das Hilfsmittel in Färbebädern einsetzt.13. The method according to claim 12, characterized in that the auxiliary is used in dye baths.
14. Verfahren nach Anspruch 12 oder 13, dadurch gekennzeichnet, dass man zur Textilfärbung polyamid- und/oder polyesterhaltiges Fasermaterial einsetzt. 14. The method according to claim 12 or 13, characterized in that polyamide and / or polyester-containing fiber material is used for textile dyeing.
EP03799488A 2003-01-17 2003-12-18 Method for finishing textile fibrous materials Expired - Lifetime EP1583861B1 (en)

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PCT/EP2003/014484 WO2004065683A1 (en) 2003-01-17 2003-12-18 Method for finishing textile fibrous materials

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EP03799488A Expired - Lifetime EP1583861B1 (en) 2003-01-17 2003-12-18 Method for finishing textile fibrous materials

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EP (1) EP1583861B1 (en)
AT (1) ATE461314T1 (en)
AU (1) AU2003299317A1 (en)
DE (2) DE10301535A1 (en)
WO (1) WO2004065683A1 (en)

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WO2006065579A2 (en) * 2004-12-02 2006-06-22 Novozymes North America, Inc. Desizing process
EP1876285A1 (en) * 2006-07-05 2008-01-09 DyStar Textilfarben GmbH & Co. Deutschland KG Combined demineralization and desizing of textile materials
DE102007006908A1 (en) * 2007-02-13 2008-08-14 Cht R. Beitlich Gmbh Catalyzed peroxide bleaching ("catalyst bleaching")
CN103410005B (en) * 2013-07-31 2015-04-08 绍兴中纺院江南分院有限公司 Cotton fabric pretreatment working solution, and preparation method and application thereof
EP4053328A1 (en) * 2021-03-02 2022-09-07 CHT Germany GmbH Combined bleaching treatment for textiles

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DE4317060A1 (en) * 1993-05-21 1994-11-24 Basf Ag Process for the continuous pretreatment of cellulose-containing textile goods
DE19638569A1 (en) * 1996-09-20 1998-04-02 Bayer Ag Bleach regulators and bleaching processes with it
DE19735796A1 (en) * 1996-12-02 1998-06-04 Bayer Ag Finishing substrates containing keratin
DE19703447A1 (en) * 1997-01-30 1998-08-06 Basf Ag Complexing agents for textile dyeing and pre- or post- treatment
DE19713911A1 (en) * 1997-04-04 1998-10-08 Bayer Ag Preparation and process of iminodisuccinic acid salts
EP0892040B1 (en) * 1997-07-16 2003-03-05 Nippon Shokubai Co., Ltd. Use of Chelating compositions for cleaning
DE19859293A1 (en) * 1998-12-22 2000-06-29 Bayer Ag New acid-addition salts of iminodisuccinic acid and related compounds, useful as crosslinking agents for easy-care finishing of cellulosic textiles
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Also Published As

Publication number Publication date
DE10301535A1 (en) 2004-07-29
EP1583861B1 (en) 2010-03-17
DE50312539D1 (en) 2010-04-29
WO2004065683A1 (en) 2004-08-05
AU2003299317A1 (en) 2004-08-13
ATE461314T1 (en) 2010-04-15

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