EP0801165B1 - Pretreatment of textiles - Google Patents

Pretreatment of textiles Download PDF

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Publication number
EP0801165B1
EP0801165B1 EP97103334A EP97103334A EP0801165B1 EP 0801165 B1 EP0801165 B1 EP 0801165B1 EP 97103334 A EP97103334 A EP 97103334A EP 97103334 A EP97103334 A EP 97103334A EP 0801165 B1 EP0801165 B1 EP 0801165B1
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EP
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Prior art keywords
acid
weight
compositions according
glucose
acids
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EP97103334A
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German (de)
French (fr)
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EP0801165A2 (en
EP0801165A3 (en
Inventor
Herbert Dr. Bachus
Andrea Fischer
Silvia Held-Beller
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CHT Germany GmbH
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CHT R Beitlich GmbH
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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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • 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
    • 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
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof

Definitions

  • the invention relates to compositions for the treatment of textile fiber material, a process for the preparation of the composition and the use thereof for finishing textile material.
  • the pretreatment of textile fiber material serves to remove unwanted accompanying substances.
  • Cellulosic substrates in particular contain a number of classes of compounds which may otherwise interfere with subsequent processing steps.
  • Surfactant formulations are used to remove fats in washing processes, complexing agents and dispersants are added to the treatment bath to remove unwanted hardness agents and heavy metals. If complexes of complexing agents are already acid-buffered formulations, their effect can be optimized by an improved acid solubility of alkaline earth or heavy metal salts.
  • complexing agents and dispersants non-biodegradable phosphonates and polyacrylates are used today, especially in commercial formulations.
  • Example 1 is a mixture of citric acid, sodium gluconate and small amounts of mineral acid, in Example a) 5% hydrochloric acid without concentration, described for acidic demineralization.
  • hydrochloric acid can act corrosive on textile machines and, if after pH change without deflation is subsequently bleached, neither Hardness is still hydrogen peroxide stabilized.
  • bleaching additionally produces 10 ml / l of a peroxide stabilizer and hardness dispersing agent, since neither citric acid nor gluconic acid in the pH range of 10 to 13 at high temperatures have sufficient dispersing action on insoluble hardening salts or stabilization to hydrogen peroxide.
  • Alkylpolyglycosides are described as auxiliaries in textile pretreatment.
  • the alkyl polyglycosides have a very high resistance to chemicals and temperatures, which is a mandatory requirement in pretreatment processes such as alkaline decoction, desizing, acid demineralization and bleaching.
  • pretreatment processes such as alkaline decoction, desizing, acid demineralization and bleaching.
  • Examples 2 and 3 it is described to add to the processes Alkaline boiling and bleaching commercial phosphonates to achieve a stabilizing effect of the peroxide and a dispersing action of hardness.
  • the disadvantage of such a procedure is seen in the use of two products and in the use of non-biodegradable phosphonates and polyacrylates.
  • DE-A-4344029 refers to copolymers of unsaturated carboxylic acids with other unsaturated compounds and their blends as sequestering agents, complexing agents and cobuilders in the detergents and cleaning agents industry and as auxiliaries in textile finishing.
  • a stabilizer may be added, which may be a phosphonic acid.
  • DE 43 44 357 A2 describes a liquid washing and cleaning agent which, in addition to nonionic surfactants, especially alkylpolyglycosides, a soil release polymer and organic builders, such as citric acid and water-soluble organic polymers as in DE 42 21 381 C1 , contains. This mixture is used as a washing and cleaning agent.
  • WO 93/13256 describes the use of lipases to remove hydrophobic fatty acid esters from textiles.
  • DE 43 12 010 A1 describes an enzymatic detergent containing as enzymatic components lipases, amylases, proteases and cellulases.
  • anionic, nonionic, cationic and / or amphoteric surfactant and up to 40% of inorganic or organic builders are contained.
  • EP 0 289 895 B1 By contrast, it was already possible in EP 0 289 895 B1 produce well biodegradable Zuckeracrylklarepolymere, wherein capable of enolate-capable saccharides are polymerized in alkaline solution with unsaturated carboxylic acids.
  • This class of substance is described as a complexing agent and co-builder in detergents and cleaners.
  • DE 43 44 029 A1 are special copolymers with saccharides capable of enolate formation, whose EP 0 289 895 B1 Blends described with other complexing agents and their textile applications described.
  • Water glass is a cheap and COD-free hydrogen peroxide stabilizer and alkali buffer. In the application, however, alkaline earth metal ions can lead to deposits on textile goods and machine parts which are no longer removable even with mineral acids.
  • EP 0 585 038 A1 mixtures of water glass are described with complexing agents, wherein the phosphonic acids, aminocarboxylic acids and polyacrylic acids contained therein are not based on renewable resources and are not biodegradable.
  • the polyacrylic acid Alcosperse ® 175 is described only in a narrow SiO 2 / Na 2 O weight ratio (LVN: weight ratio number) storage-stable miscible.
  • Glucose-free in the context of the present invention comprises low-glucose polymers having a glucose content of less than 1% by weight, based on the polymer.
  • a second embodiment of the invention relates to alkaline water glass-buffered compositions having a pH greater than 11.5 for the treatment of textile fiber material, in each case based on the composition 30 to 2 parts by weight (based on dry matter) of a polymer of acrylic acid and enolisierbaren monosaccharides, oligosaccharides and / or polysaccharides prepared in the alkaline pH range, 10 to 95 parts by weight of one or more additives of (i) 10 to 40% by weight (based on dry matter) of water glasses, (j) 0 to 20% by weight. % of a further complexing agent, in particular alkali metal and / or alkaline earth metal salts of gluconic acid or glucoheptonic acid, preferably sodium gluconate.
  • a further complexing agent in particular alkali metal and / or alkaline earth metal salts of gluconic acid or glucoheptonic acid, preferably sodium gluconate.
  • the compositions contain 20 to 80 parts by weight of water, based on 80 to 20 parts by weight of the polymers or of the mixtures of polymer and additive.
  • mixtures according to the invention also have the advantage that they can be diluted with water and thus low-viscosity and thus better pumpable mixtures can be represented.
  • biodegradable dispersing complexing agents can be synergistically supported by the addition of further biodegradable complexing agents such as, for example, sodium gluconate.
  • further biodegradable complexing agents such as, for example, sodium gluconate.
  • the polymers according to the invention which are known per se, despite their polyelectrolyte character, are well suited for formulation with surfactants and do not tend to cause the instability of the mixture even at low pH values. Furthermore, it has surprisingly been found that these blends are outstandingly suitable for the treatment of fiber material in various process stages of textile finishing, in particular pretreatment.
  • polymers of acrylic acid and enolisable monosaccharides, oligosaccharides and / or polysaccharides in the alkaline pH range from 7 to 10. These polymers are expressis verbis in EP 0 289 895 B1 described.
  • Saccharides capable of enolate formation do not necessarily have to be used directly as a raw material as such. These can also be prepared by acidic, alkaline or enzymatic processes before or during polymerization from oligosaccharides or polysaccharides.
  • EP 0 289 895 B1 brings the advantage of the properties the surfactant, wetting and penetration of the textiles with liquor and removing sizings, preparations and accompanying substances of all kinds, with the properties of a polyacrylate, dispersion of hardness and particle dirt, positive to connect while maintaining an environmentally friendly and biodegradable textile auxiliaries.
  • the enzymes are preferably selected from amylases, catalases, cellulases, lipases, pectinases, proteases and / or glucose oxidases.
  • compositions of the invention especially for use, require a greater or lesser amount of water. This depends in particular on the desired application of the compositions.
  • low molecular weight organic and inorganic acids are not particularly limited. Accordingly, it is particularly preferred to select the low molecular weight organic acids from low molecular weight mono- or polycarboxylic acids, in particular citric acid, tartaric acid, lactic acid, gluconic acid and / or glucoheptonic acid.
  • Phosphonic acids for the purposes of the present invention which are preferably used as additives, are preferably selected from HEDP, ATMP, DTPMP and / or HDTMP.
  • the inorganic acids are preferably selected from mineral acids, in particular hydrochloric acid and sulfuric acid, and furthermore amidosulfonic acid.
  • compositions for the treatment of textile fiber material usually contain surfactant-containing constituents.
  • surfactant-containing constituents Particularly preferred in The meaning of the present invention are anionic surfactants, nonionic surfactants and / or alkylpolyglycosides.
  • the anionic surfactants are preferably selected from linear or branched C 8 -C 20 -alkanesulfonates, alkanesulfates, alkanecarboxylates or alkanethercarboxylic acids and also alkylbenzenesulfonates and soaps (maximum 20% by weight).
  • Nonionic surfactants for the purposes of the present invention are in particular selected from linear or branched C 8 -C 20 fatty alcohol alkoxylates.
  • a further embodiment of the present invention consists in a process for the preparation of the above-defined glucose-free compositions, wherein the polymers of acrylic acid and saccharides containing glucose as raw material or reaction product are treated with glucose oxidase. As a result, a glucose-free or low-glucose product is obtained, which can be used particularly advantageously.
  • compositions according to the invention can be used according to processes known per se for refining textile material.
  • a special process of textile finishing are in particular the binding of polyvalent metal ions, the inhibition of water hardness, the dispersion of pigments and the use in washing, bleaching and dyeing liquors, especially for the aftertreatment of dyeings of textile materials mentioned.
  • the polymer was brown in color and clear. It had, as indicated, a viscosity of 40 mPas. There were 4% free glucose and 4% free fructose. The determination of the total elimination, which resulted from biological degradation and elimination by adsorption, generally resulted in values below 40% for several series of measurements according to OECD 302B.
  • acrylic acid was within 2 hours, hydrogen peroxide was metered for 30 minutes longer. The mixture was then stirred at 90 ° C for 30 minutes.
  • the polymer had a viscosity of 400 mPas and contained 1.2% free glucose.
  • compositions for textile finishing were compiled in analogy to the above instructions, the composition of which is shown in the table below.
  • the data in the following Table 1 are in each case for percentages by weight. ⁇ u> Table 1 ⁇ / u> Examples 2 3 4 5 6 7 Polymer according to Reference Example 2 15 15 15 Polymer according to Example 1 30 4 10 gluconic; 50% 10 10 10 10 Citric acid * H 2 O 5 5 5 5 Sulfuric acid conc.
  • compositions for textile finishing were compiled in analogy to the above instructions, the composition of which is shown in the table below.
  • the SiO 2 / Na 2 O weight ratio in Table 2 was adjusted by dissolving solid sodium hydroxide in 38 ° Be (GVZ 3.3) waterglass, but may also be made by mixing with commercially available lower GVZ waterglasses.
  • Example A 1 Acidic Demineralization - Discontinuous Process
  • Raw cotton fabric was treated for 30 minutes at 70 ° C and a liquor ratio of 1:10 with a liquor containing 5 g / l of the mixture according to Example 4. After treatment, the tissue was washed off warm and cold. The result was a textile material that was very well demineralized and could be used for all other treatments.
  • the total hardness on the fabric was reduced by 60%, the iron content by 50%, a treatment with 5 g / l of the polymer according to Reference Example 1 or Reference Example 2 alone reduced the total hardness by only 30% and the iron content by 20% and 30, respectively %.
  • Raw cotton fabric was treated as in Example A1 for 30 minutes at 70 ° C and a liquor ratio of 1:10 with a liquor containing 5 g / l of the mixture according to Example 4. Thereafter, 6 g / l sodium hydroxide solution was 50% without intermediate rinsing the liquor added 8 ml / l 35% hydrogen peroxide and 0.8 g / l of a high affinity fluorescent whitening agent (trade name "VA Tuboblanc ® fl.”). Thereafter, hot and cold rinsed.
  • a high affinity fluorescent whitening agent trade name "VA Tuboblanc ® fl.”
  • the product reached a base white of 81 and a fluorescence of 72 Berger units.
  • a liquor was padded containing 6 g / l of the mixture according to Example 2 and 4 g / l of a wetting agent (trade name "Subitol DM").
  • the liquor pickup was 100%
  • the liquor temperature was 60 ° C
  • the residence time was 30 minutes
  • the residence temperature was also 60 ° C.
  • the textile material was well demineralized and could be subjected to further treatment steps. That's how it became the total hardness on the fabric reduced by 50% and the iron content by 40%, which was not achievable with less acidic complexing agents alone.
  • the degree of desizing according to TEGEWA was 9.
  • a green cotton fabric was impregnated with the following liquor: 0.2 g / l Epsom salt, 7 ml / l of the combination product mentioned in Example 5, 30 g / l sodium hydroxide solution 50%, 10 ml / l water glass 38 ° Bé, 40 ml / l hydrogen peroxide 35 %.
  • the liquor pickup was 100%.
  • the product was left for 24 hours at room temperature according to the KKV method, then washed, rinsed and dried.
  • the basic white rose from 18 to 82 Berger units.
  • the same formulation with 10 ml / l mixture according to Example 9 instead of water glass 38 Be gave 83. Even without 7 ml / l product according to Example 5 here still 81 Berger units were reached.
  • An experiment according to Example D without water glass gave only 75 Berger units.
  • a raw cotton fabric with a base white of 18 Berger units was impregnated with the following liquor: 0.2 g / l of Epsom salt, 2 or 6 ml / l of the product mentioned in Table 3 below, 20 g / l of sodium hydroxide solution 50%, 40 ml / l of hydrogen peroxide 35%. The liquor pickup was 100%. Subsequently, the product was steamed at 102 ° C for 30 minutes, washed, rinsed and dried by pad steam method.
  • a raw cotton fabric was treated with a liquor containing 3 g / l of the combination product of Example 7 and 1 g / l of soda.
  • the liquor ratio was 1:10, the temperature was 95 ° C and the washing time was 30 minutes. Subsequently, hot and cold were washed out.
  • a raw cotton fabric was treated with a liquor containing 3 g / l of the combination product of Example 7 and 3 g / l of soda.
  • the liquor ratio was 1:20, the temperature 90 ° C and the washing time 30 minutes. Subsequently, hot and cold were washed out. The accompanying substances were removed completely and the textile corresponded in its properties the standard of a washing process.
  • Reference Example 1 showed no grease-removing effect and the fabric pattern remained hydrophobic.
  • Example F2 Washing process with standardized EMPA dirt cotton fabric
  • the test fabric was treated with a liquor containing 2 g / l of the combination product of Example 7 and 1 g / l of soda.
  • the liquor ratio was 1:40, the temperature 60 ° C and the washing time was 30 minutes. Subsequently, hot and cold were washed out.
  • the whiteness increased from 19 to 31 Berger units.
  • Raw cotton fabric was boiled at a liquor ratio of 1:10 in the presence of 5 g / l of the combination product according to Example 7 and 20 g / l NaOH 100% for 30 minutes at 98 ° C.
  • the whiteness of the goods rose from 22 to 39 Berger units.
  • Example I Testing for alkaline earth dispersing in the presence of iron ions
  • Example H It was tested as in Example H, but additionally added 25 ° dH calcium ions (calcium chloride) and 10 ° dH magnesium ions (from magnesium sulfate) of the test solution. Residue-free filters received the rating 1, coarse-grained residues such as when using water glass without dispersing agent received the grade 6. ⁇ u> Table 5: ⁇ / u> product grade Water glass GV 3.3 6 Water glass GV 1.6 6 Example 9 3 Example 10 2 Example 11 2 Comparative Example 3 6 Comparative Example 4 5

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Detergent Compositions (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

Formulations (F1), preferably used for treating textile fibre material - contain glucose-free polymers (P1) prepared from acrylic acid and glucose-containing saccharides. Also claimed are the following: (i) formulations (F2) for treating textile fibre material; (ii) the preparation of (F1) and (F2) by treating (P1) or (P2) with glucose-oxidase; (iii) the preparation of (F2) in which the oligo and/or polysaccharides are hydrolysed before, during and/or after polymerisation to form enolisable saccharides in situ; (iv) the preparation of (F2) in which (P2) are formed by reacting acrylic acid with enolisable mono-, oligo- and/or polysaccharides at pH 7-10; and (v) a process for treating textile material, preferably cellulose fibres, with (F1) or (F2). Preferably (F2) comprises 2-30 parts by weight (P2) and 70-98 parts by weight additives. (P2) may be substituted with (P1). (A) are mono- or polycarboxylic acids (preferably citric acid, tartaric acid, lactic acid, gluconic acid and/or glucoheptonic acid), phosphonic acids (preferably HEDP, ATMP, DTPMP and/or HDTMP), mineral acids (preferably hydrochloric acid or sulphuric acid) or amidosulphonic acid. (B), (C) and/or (D) are present as surfactants. (B) are 8-20C fatty alcohol alkoxylates. (C) are 8-20C polyglycosides (n = 1-3). (D) are 8-20C alkane sulph(on)ates, 8-20C alkane carboxylates and/or 8-20C alkane ether carboxylic acids, or alkyl benzene sulphonates. (H) are amylases, catalases, cellulases, lipases, pectinases, proteases and/or glucose-oxidases. (F1) and (F2) have a pH greater than 11.5 and contain an additive system comprising 10-40 wt.% water glass (I), 0-20 wt.% chelating agent (J) and the balance water.

Description

Die Erfindung betrifft Zusammensetzungen zur Behandlung von Textilfasermaterial, ein Verfahren zur Herstellung der Zusammensetzung sowie deren Verwendung zum Veredeln von Textilmaterial.The invention relates to compositions for the treatment of textile fiber material, a process for the preparation of the composition and the use thereof for finishing textile material.

Die Vorbehandlung von textilem Fasermaterial dient dazu, unerwünschte Begleitsubstanzen zu entfernen. Insbesondere Cellulosesubstrate enthalten eine Reihe von Verbindungsklassen, die sonst nachfolgende Veredlungsschritte beeinträchtigen können. Es werden zum Ablösen von Fetten in Waschprozessen Tensidformulierungen eingesetzt, zur Entfernung von unerwünschten Härtebildnern und Schwermetallen Komplexbildner und Dispergiermittel im Behandlungsbad zugegeben. Handelt es sich bei Komplexbildnermischungen um bereits sauer gepufferte Formulierungen, so kann deren Wirkung durch eine im Sauren verbesserte Löslichkeit von Erdalkali- oder Schwermetallsalzen optimiert werden. Als wirksame Komplexbildner und Dispergiermittel werden heute insbesondere in handelsüblichen Formulierungen biologisch nicht abbaubare Phosphonate und Polyacrylate eingesetzt.The pretreatment of textile fiber material serves to remove unwanted accompanying substances. Cellulosic substrates in particular contain a number of classes of compounds which may otherwise interfere with subsequent processing steps. Surfactant formulations are used to remove fats in washing processes, complexing agents and dispersants are added to the treatment bath to remove unwanted hardness agents and heavy metals. If complexes of complexing agents are already acid-buffered formulations, their effect can be optimized by an improved acid solubility of alkaline earth or heavy metal salts. As effective complexing agents and dispersants, non-biodegradable phosphonates and polyacrylates are used today, especially in commercial formulations.

In DE 42 08 106 A1 wird eine Mischung aus Citronensäure, Natriumgluconat und geringen Anteilen an Mineralsäure, im Beispiel a) 5% Salzsäure ohne Konzentrationsangabe, zur sauren Entmineralisierung beschrieben. Diese Mischungen haben den Nachteil, dass, wie aus Beispiel 1 ersichtlich, zur Entmineralisierung mit 20 g/l des erfindungsgemäßen Hilfsmittels unwirtschaftlich hohe Mengen benötigt werden, Salzsäure korrosiv auf Textilmaschinen wirken kann und, falls nach pH-Wechsel ohne abzulassen anschließend gebleicht wird, weder Härte noch Wasserstoffperoxid stabilisiert wird. So werden in Beispiel 5 bei einer Bleiche zusätzlich 10 ml/l eines Peroxidstabilisators und Härtedispergiermittels zugesetzt, da weder Citronensäure noch Gluconsäure im pH-Bereich von 10 bis 13 bei hohen Temperaturen ausreichende Dispergierwirkung auf unlösliche Härtesalze bzw. Stabilisierung auf Wasserstoffperoxid aufweisen.In DE 42 08 106 A1 is a mixture of citric acid, sodium gluconate and small amounts of mineral acid, in Example a) 5% hydrochloric acid without concentration, described for acidic demineralization. These mixtures have the disadvantage that, as can be seen from Example 1, for the demineralization with 20 g / l of the inventive resource uneconomically high amounts are required, hydrochloric acid can act corrosive on textile machines and, if after pH change without deflation is subsequently bleached, neither Hardness is still hydrogen peroxide stabilized. Thus, in example 5, bleaching additionally produces 10 ml / l of a peroxide stabilizer and hardness dispersing agent, since neither citric acid nor gluconic acid in the pH range of 10 to 13 at high temperatures have sufficient dispersing action on insoluble hardening salts or stabilization to hydrogen peroxide.

In EP 0 589 978 B1 werden Alkylpolyglycoside als Hilfsmittel in der textilen Vorbehandlung beschrieben. Die Alkylpolyglycoside weisen eine sehr hohe Chemikalien- und Temperaturbeständigkeit auf, was bei Vorbehandlungsprozessen wie Alkalisches Abkochen, Entschlichtung, Saure Entmineralisierung und Bleiche eine zwingende Voraussetzung darstellt. In den Beispielen 2 und 3 wird beschrieben, zu den Prozessen Alkalisches Abkochen und Bleichen handelsübliche Phosphonate zuzusetzen, um eine Stabilisierwirkung des Peroxids und eine Dispergierwirkung der Härtebildner zu erzielen. Der Nachteil einer solchen Verfahrensweise ist in dem Einsatz von zwei Produkten zu sehen und in der Verwendung von biologisch nicht abbaubaren Phosphonaten und Polyacrylaten.In EP 0 589 978 B1 Alkylpolyglycosides are described as auxiliaries in textile pretreatment. The alkyl polyglycosides have a very high resistance to chemicals and temperatures, which is a mandatory requirement in pretreatment processes such as alkaline decoction, desizing, acid demineralization and bleaching. In Examples 2 and 3 it is described to add to the processes Alkaline boiling and bleaching commercial phosphonates to achieve a stabilizing effect of the peroxide and a dispersing action of hardness. The disadvantage of such a procedure is seen in the use of two products and in the use of non-biodegradable phosphonates and polyacrylates.

DE-A-4344029 betrifft Copolymerisate ungesättigter Carbonsäuren mit anderen ungesättigten Verbindungen sowie deren Abmischungen als Sequestierungsmittel, Komplexbildner und Cobuilder in der Wasch- und Reinigungsmittel-Industrie sowie als Hilfsmittel in der Textilveredelung. Dabei kann ein Stabilisator zugesetzt werden, der eine Phosphonsäure sein kann. DE-A-4344029 refers to copolymers of unsaturated carboxylic acids with other unsaturated compounds and their blends as sequestering agents, complexing agents and cobuilders in the detergents and cleaning agents industry and as auxiliaries in textile finishing. In this case, a stabilizer may be added, which may be a phosphonic acid.

In DE 43 44 357 A2 wird ein flüssiges Wasch- und Reinigungsmittel beschrieben, das neben nichtionogenen Tensiden, vor allem Alkylpolyglycoside, ein schmutzablösendes Polymer und organische Buildersubstanzen, wie zum Beispiel Citronensäure und wasserlösliche organische Polymere wie in DE 42 21 381 C1 , enthält. Diese Mischung wird als Wasch- und Reinigungsmittel eingesetzt.In DE 43 44 357 A2 describes a liquid washing and cleaning agent which, in addition to nonionic surfactants, especially alkylpolyglycosides, a soil release polymer and organic builders, such as citric acid and water-soluble organic polymers as in DE 42 21 381 C1 , contains. This mixture is used as a washing and cleaning agent.

In WO 93/13256 wird der Einsatz von Lipasen zur Entfernung von hydrophoben Fettsäureestern von Textilien beschrieben. DE 43 12 010 A1 beschreibt ein enzymatisches Waschmittel, das als enzymatische Komponenten Lipasen, Amylasen, Proteasen und Cellulasen enthält. Außerdem sind bis zu 10 Gew % anionisches, nichtionisches, kationisches und/oder amphoteres Tensid und bis zu 40 % anorganische bzw. organische Builder enthalten. Zur Peroxidstabilisierung in einer Bleichstufe werden z. B. Natriumsilikat oder andere organische Stabilisatoren eingesetzt. Es ist bekannt, dass Enzymkomponenten Waschprozesse unterstützen und verbessern.In WO 93/13256 describes the use of lipases to remove hydrophobic fatty acid esters from textiles. DE 43 12 010 A1 describes an enzymatic detergent containing as enzymatic components lipases, amylases, proteases and cellulases. In addition, up to 10% by weight of anionic, nonionic, cationic and / or amphoteric surfactant and up to 40% of inorganic or organic builders are contained. For peroxide stabilization in a bleaching stage z. As sodium silicate or other organic stabilizers. It is known that enzyme components support and improve washing processes.

In EP 0 441 197 A2 werden Pfropfpolymerisate von Sacchariden beschrieben, wobei als Monomerkomponenten teilneutralisierte Maleinsäure und das jeweilige Saccharid vorgelegt werden und bei der Acrylsäurezugabe sich ein pH-Wert von 4 einstellt. Bei einem Produkt wurde auf einen zumindest teilweisen biologischen Abbau geschlossen. Die als erfindungsgemäß beschriebenen Produkte sollen sich als Zusatz zu Wasch- und Reinigungsmitteln eignen.In EP 0 441 197 A2 graft polymers of saccharides are described, in which case partially neutralized maleic acid and the respective saccharide are initially charged as monomer components and a pH of 4 is established when the acrylic acid is added. One product was at least partially biodegraded. The products described as being according to the invention should be suitable as an additive to detergents and cleaners.

In DE 42 21 381 C1 werden Polymerisationen von Acrylsäure mit sulfonsäuregruppenhaltigen Monomeren in Gegenwart von Sacchariden beschrieben, welche im Gegensatz zu EP 0 289 895 B1 vorteilhaft bei niedrigen pH-Werten durchgeführt werden und erst am Ende der Polymerisation auf pH 7 - 8 eingestellt werden. Ein Polymer - Beispiel 7 - wurde auf seine biologische Abbaubarkeit untersucht und soll einen Abbaugrad von 78% erreichen. Die Analyse dieses Vergleichsbeispieles ergab, dass die eingesetzte Saccharose und deren Hydrolyseprodukte Glucose und Fructose nahezu vollständig frei vorliegen und die Abbaudaten maximal denen der freien Zucker entsprechen. Die in den beschriebenen Polymerisaten bei der sauren Hydrolyse von Saccharose entstandene Glucose (siehe Beispiel 1: 4 %) hat für textile Anwendungen zudem eine unerwünschte reduzierende Wirkung. Darüber hinaus werden die sulfonsäuregruppenhaltigen Copolymere aufgrund ihrer solubilisierenden Sulfonsäuregruppe in Verbindung mit ihrem niederen Molekulargewichtsmittelwert nur unzureichend in Kläranlagen eliminiert, was aus Untersuchungen nach OECD 302 B hervorgeht.In DE 42 21 381 C1 describes polymerizations of acrylic acid with sulfonic acid monomers in the presence of saccharides, which in contrast to EP 0 289 895 B1 are advantageously carried out at low pH values and are adjusted to pH 7-8 only at the end of the polymerization. A polymer - Example 7 - was tested for its biodegradability and should reach a degree of degradation of 78%. The analysis of this comparative example showed that the sucrose and its hydrolysis products used glucose and fructose are almost completely free and the degradation data correspond to a maximum of those of the free sugars. The resulting in the described polymers in the acid hydrolysis of sucrose glucose (see Example 1: 4%) also has an undesirable reducing effect for textile applications. In addition, the sulfonic acid-containing copolymers due their solubilizing sulfonic acid group in conjunction with their low average molecular weight is insufficiently eliminated in sewage treatment plants, which results from studies according to OECD 302 B.

Dagegen gelang es bereits in EP 0 289 895 B1 gut biologisch abbaubare Zuckeracrylsäurepolymere herzustellen, wobei zur Enolatbildung befähigte Saccharide in alkalischer Lösung mit ungesättigten Carbonsäuren polymerisiert werden. Die Verwendung dieser Substanzklasse wird als Komplexbildner und Co-Builder in Wasch- und Reinigungsmitteln beschrieben. In DE 43 44 029 A1 werden spezielle Copolymerisate mit zur Enolatbildung befähigten Sacchariden, deren in EP 0 289 895 B1 beschriebenen Abmischungen mit anderen Komplexbildnern und deren textile Anwendungen beschrieben.By contrast, it was already possible in EP 0 289 895 B1 produce well biodegradable Zuckeracrylsäurepolymere, wherein capable of enolate-capable saccharides are polymerized in alkaline solution with unsaturated carboxylic acids. The use of this class of substance is described as a complexing agent and co-builder in detergents and cleaners. In DE 43 44 029 A1 are special copolymers with saccharides capable of enolate formation, whose EP 0 289 895 B1 Blends described with other complexing agents and their textile applications described.

Wasserglas ist ein preiswerter und CSB-freier Wasserstoffperoxidstabilisator und Alkalipuffer. In der Anwendung können sich jedoch mit Erdalkaliionen Ablagerungen auf textilen Waren und Maschinenteilen ergeben, die selbst mit Mineralsäuren nicht mehr entfernbar sind. In EP 0 585 038 A1 werden Abmischungen von Wasserglas mit Komplexbildnern beschrieben, wobei die darin enthaltenen Phosphonsäuren, Aminocarbonsäuren und Polyacrylsäuren nicht auf nachwachsenden Rohstoffen basieren und biologisch nicht abbaubar sind. Insbesondere die beschriebene Polyacrylsäure Alcosperse® 175 ist nur in einem engen SiO2/Na2O-Gewichtsverhältnis (GVZ: GewichtsVerhältnis-Zahl) lagerstabil einmischbar. Auf S. 8 und 9 werden deren Abmischungen bei einer GVZ von 1,2 und 1,6 mit 4 % der Polyacrylsäure noch als klar und stabil beschrieben, Mischungsverhältnisse mit 10 % dieses Komplexbildners bereits als extrem wolkig, bei der höheren GVZ von 2,5 ergeben sich bereits mit 4 % Polyacrylat Phasentrennungen.Water glass is a cheap and COD-free hydrogen peroxide stabilizer and alkali buffer. In the application, however, alkaline earth metal ions can lead to deposits on textile goods and machine parts which are no longer removable even with mineral acids. In EP 0 585 038 A1 mixtures of water glass are described with complexing agents, wherein the phosphonic acids, aminocarboxylic acids and polyacrylic acids contained therein are not based on renewable resources and are not biodegradable. In particular, the polyacrylic acid Alcosperse ® 175 is described only in a narrow SiO 2 / Na 2 O weight ratio (LVN: weight ratio number) storage-stable miscible. On pages 8 and 9 their mixtures are still described as clear and stable at a GT of 1.2 and 1.6 with 4% of the polyacrylic acid, mixing ratios with 10% of this complexing agent already as extremely cloudy, at the higher GT of 2, 5 result already with 4% polyacrylate phase separations.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, neue Abmischungen zur Verfügung zu stellen, die die Reinigungswirkung der in EP 0 289 895 B1 oder DE 43 44 029 A1 beschriebenen biologisch abbaubaren Komplexbildner erhöhen. Dabei kann es sich

  1. 1.) um den Zusatz von ökologisch unbedenklichen Tensiden handeln oder, dass die Zuckerpolymerisate
  2. 2.) in einer Formulierung unter einen pH-Wert von 4 eingestellt werden oder
  3. 3.) in einer Abmischung mit Natronwasserglas Bleichprozesse verbessern, indem sie Ablagerungen verhindern, die bei Verwendung von Wasserglas ohne Komplexbildner Störungen bei Produktionsprozessen hervorrufen.
The present invention has for its object to provide new blends that provide the cleaning effect of in EP 0 289 895 B1 or DE 43 44 029 A1 increase the biodegradable complexing agent described. It can be
  1. 1.) to the addition of ecologically harmless surfactants act or that the sugar polymers
  2. 2.) be adjusted in a formulation below a pH of 4 or
  3. 3.) in a blended with soda water glass improve bleaching processes by preventing deposits that cause disturbances in production processes when using water glass without complexing agent.

Die vorgenannte Aufgabe wird in einer ersten Ausführungsform der vorliegenden Erfindung gelöst durch Zusammensetzungen zur Behandlung von Textilfasermaterial, enthaltend jeweils bezogen auf die Zusammensetzung 99 bis 1 Gew.-Teile, bezogen auf Trockensubstanz, eines Polymerisates aus Acrylsäure und enolisierbaren Monosacchariden, Oligosacchariden und/oder Polysacchariden, hergestellt im alkalischen pH-Bereich und 1 bis 99 Gew.-Teile bezogen auf Trockensubstanz, Additive

  1. (a) bis 40 Gew.-% freien, niedermolekularen, organischen und anorganischen Säuren, deren Summe an Säureprotonen zu weniger als 50% neutralisiert sind, und wenigstens eines oder mehrerer der Additive ausgewählt aus
  2. (b) 0-60 Gew.-% Niotensiden,
  3. (c) 0-40 Gew.-% Alkylpolyglycosiden,
  4. (d) 0-40 Gew.-% Aniontensiden,
  5. (e) 0-20 Gew.-% entlüftend wirkenden Hilfsstoffen,
  6. (f) 0-20 Gew.-% schaumdämpfenden Hilfsstoffen,
  7. (g) 0-70 Gew.-% organischen Lösungsmitteln mit Ausnahme von Halogenkohlenwasserstoffen und
  8. (h) 0-10 Gew.-% Enzymen
jeweils bezogen auf die Gesamtmenge der Additive.The above object is achieved in a first embodiment of the present invention by compositions for the treatment of textile fiber material, containing in each case based on the composition 99 to 1 parts by weight, based on dry matter, of a polymer of acrylic acid and enolisierbaren monosaccharides, oligosaccharides and / or polysaccharides , prepared in the alkaline pH range and 1 to 99 parts by weight based on dry matter, additives
  1. (A) to 40 wt .-% of free, low molecular weight, organic and inorganic acids whose sum of acid protons are neutralized to less than 50%, and at least one or more of the additives selected from
  2. (b) 0-60% by weight of nonionic surfactants,
  3. (c) 0-40% by weight of alkylpolyglycosides,
  4. (d) 0-40% by weight of anionic surfactants,
  5. (e) 0-20% by weight of aeration agents,
  6. (f) 0-20% by weight of foam-damping auxiliaries,
  7. (g) 0-70% by weight of organic solvents except halocarbons and
  8. (h) 0-10 wt% enzymes
in each case based on the total amount of additives.

Überraschenderweise wurde gefunden, dass sich vorhandene Restkonzentrationen an Glucose, ob direkt eingesetzt oder durch Isomerisierung oder Hydrolyse aus Sacchariden während einer Reaktion entstanden, durch den Einsatz von Glucoseoxidasen zu Gluconsäure oxidieren lassen. Dabei entsteht aus dem in vielen Anwendungen unerwünschten Reduktionsmittel der ökologisch unbedenkliche und technisch wertvolle Komplexbildner Gluconsäure. Glucosefrei im Sinne der vorliegenden Erfindung umfasst glucosearme Polymerisate mit einem Gehalt an Glucose von weniger als 1 Gew.-%, bezogen auf das Polymerisat.Surprisingly, it was found that existing residual concentrations of glucose, whether used directly or formed by isomerization or hydrolysis from saccharides during a reaction, can be oxidized to gluconic acid by the use of glucose oxidases. This results from the unwanted in many applications reducing agent, the ecologically harmless and technically valuable complexing agent gluconic acid. Glucose-free in the context of the present invention comprises low-glucose polymers having a glucose content of less than 1% by weight, based on the polymer.

Eine zweite Ausführungsform der Erfindung betrifft alkalische wasserglasgepufferte Zusammensetzungen mit einem pH-Wert größer 11,5 zur Behandlung von Textilfasermaterial, enthaltend jeweils bezogen auf die Zusammensetzung 30 bis 2 Gew.-Teile (bezogen auf Trockensubstanz) eines Polymerisats aus Acrylsäure und enolisierbaren Monosacchariden, Oligosacchariden und/oder Polysacchariden, hergestellt im alkalischen pH-Bereich, 10 - 95 Gew.-Teile eines oder mehrerer Additive aus (i) 10 - 40 Gew.-% (bezogen auf Trockensubstanz) Wassergläsern, (j) 0 - 20 Gew.-% eines weiteren Komplexbildners, insbesondere Alkalimetall- und/oder Erdalkalimetallsalze der Gluconsäure oder Glucoheptonsäure, bevorzugt Natriumgluconat.A second embodiment of the invention relates to alkaline water glass-buffered compositions having a pH greater than 11.5 for the treatment of textile fiber material, in each case based on the composition 30 to 2 parts by weight (based on dry matter) of a polymer of acrylic acid and enolisierbaren monosaccharides, oligosaccharides and / or polysaccharides prepared in the alkaline pH range, 10 to 95 parts by weight of one or more additives of (i) 10 to 40% by weight (based on dry matter) of water glasses, (j) 0 to 20% by weight. % of a further complexing agent, in particular alkali metal and / or alkaline earth metal salts of gluconic acid or glucoheptonic acid, preferably sodium gluconate.

In den erfindungsgemäßen Abmischungen ist sichergestellt, dass wenigstens 1 Gew.-Teil eines oder mehrerer der vorgenannten Additive gegebenenfalls in Anwesenheit von Wasser (ad 100 Gew.-%) enthalten ist. Bevorzugt enthalten die Zusammensetzungen 20 bis 80 Gew.-Teile Wasser, bezogen auf 80 bis 20 Gew.-Teile der Polymerisate oder der Gemische aus Polymerisat und Additiv.It is ensured in the blends according to the invention that at least 1 part by weight of one or more of the abovementioned additives is optionally present in the presence of water (ad 100% by weight). Preferably, the compositions contain 20 to 80 parts by weight of water, based on 80 to 20 parts by weight of the polymers or of the mixtures of polymer and additive.

Solche Abmischungen weisen im Vergleich zum Stand der Technik neben ihrer biologischen Abbaubarkeit des Komplexbildneranteils auch Vorteile bei der Dispergierung von Eisen und Härtesalzen auf, wie aus den Beispielen H und I hervorgeht. Daneben lassen sich klare, homogene und lagerstabile Formulierungen mit den Zuckerpolymerisaten herstellen, wobei sowohl der Mischungsanteil wie auch die GVZ des Wasserglases keine engen Grenzen, wie das PolyacrylatBeispiel in EP 0 585 038 A1 aufweisen.Such blends have in comparison to the prior art, in addition to their biodegradability of the complexing agent fraction also advantages in the dispersion of iron and hardening salts, as is apparent from Examples H and I. In addition, clear, homogeneous and storage-stable formulations can be prepared with the sugar polymers, wherein both the mixing proportion and the GVZ of the water glass have no narrow limits, such as the polyacrylate example in EP 0 585 038 A1 exhibit.

Hierbei ist hervorzuheben, dass die erfindungsgemäßen Abmischungen weiterhin den Vorteil aufweisen, dass sie mit Wasser verdünnbar sind und dadurch niederviskosere und somit besser pumpfähige Abmischungen dargestellt werden können.It should be emphasized that the mixtures according to the invention also have the advantage that they can be diluted with water and thus low-viscosity and thus better pumpable mixtures can be represented.

Die peroxidstabilisierende und bleichunterstützende Wirkung der biologisch abbaubaren dispergierend wirkenden Komplexbildner kann durch Zusatz von weiteren biologisch abbaubaren Komplexbildnern, wie zum Beispiel Natriumgluconat, synergistisch unterstützt werden. So ist aus Beispiel D2, Tabelle 3 sowie Beispielen H und I zu entnehmen, dass Natriumgluconat, ob enzymatisch nach Polymerisation im Produkt direkt hergestellt oder beim Abmischen des Produktes einfach zugesetzt, die Wirkung einer Mischung aus Wasserglas und Bezugsbeispiel 2 unterstützt.The peroxide-stabilizing and bleach-supporting action of the biodegradable dispersing complexing agents can be synergistically supported by the addition of further biodegradable complexing agents such as, for example, sodium gluconate. Thus, it can be seen from Example D2, Table 3 and Examples H and I that sodium gluconate, whether enzymatically produced directly in the product after polymerization or simply added during mixing of the product, supports the effect of a mixture of water glass and Reference Example 2.

Überraschenderweise wurde weiterhin gefunden, dass sich die erfindungsgemäßen und an sich bekannte Polymerisate trotz ihres Polyelektrolytcharakters gut zur Formulierung mit Tensiden eignen und auch bei niederen pH-Werten nicht zur Instabilität der Abmischung neigen. Weiterhin wurde überraschenderweise gefunden, dass sich diese Abmischungen hervorragend zur Behandlung von Fasermaterial in den verschiedensten Prozessstufen der Textilveredlung, insbesondere der Vorbehandlung, eignen.Surprisingly, it has furthermore been found that the polymers according to the invention which are known per se, despite their polyelectrolyte character, are well suited for formulation with surfactants and do not tend to cause the instability of the mixture even at low pH values. Furthermore, it has surprisingly been found that these blends are outstandingly suitable for the treatment of fiber material in various process stages of textile finishing, in particular pretreatment.

Besonders bevorzugt im Sinne der vorliegenden Erfindung ist es, die Polymerisate aus Acrylsäure und enolisierbaren Monosacchariden, Oligosacchariden und/oder Polysacchariden im alkalischen pH-Bereich von 7 bis 10 herzustellen. Diese Polymerisate sind expressis verbis in EP 0 289 895 B1 beschrieben.For the purposes of the present invention, it is particularly preferred to prepare the polymers of acrylic acid and enolisable monosaccharides, oligosaccharides and / or polysaccharides in the alkaline pH range from 7 to 10. These polymers are expressis verbis in EP 0 289 895 B1 described.

Zur Enolatbildung befähigte Saccharide müssen als solche nicht unbedingt als Rohstoff direkt eingesetzt werden. Diese lassen sich auch durch saure, alkalische oder enzymatische Prozesse vor oder während einer Polymerisation aus Oligo- oder Polysacchariden herstellen.Saccharides capable of enolate formation do not necessarily have to be used directly as a raw material as such. These can also be prepared by acidic, alkaline or enzymatic processes before or during polymerization from oligosaccharides or polysaccharides.

Die erfindungsgemäße Kombination von Alkylpolyglycosiden mit einem Zuckerpolymerisat entsprechend EP 0 289 895 B1 bringt den Vorteil, die Eigenschaften des Tensides, Benetzen und Durchdringen der Textilien mit Flotte und Entfernen von Schlichte, Präparationen und Begleitsubstanzen aller Art, mit den Eigenschaften eines Polyacrylates, Dispergierung der Härtebildner und des Partikelschmutzes, positiv zu verbinden und dabei ein umweltentlastendes und biologisch abbaubares Textilhilfsmittel zu erhalten.The inventive combination of alkyl polyglycosides with a sugar polymer accordingly EP 0 289 895 B1 brings the advantage of the properties the surfactant, wetting and penetration of the textiles with liquor and removing sizings, preparations and accompanying substances of all kinds, with the properties of a polyacrylate, dispersion of hardness and particle dirt, positive to connect while maintaining an environmentally friendly and biodegradable textile auxiliaries.

Kombinationsprodukte aus Enzymen, biologisch abbaubaren Zuckerpolymerisaten und Tensiden stellen für die textile Vorbehandlung eine neue Generation von ökologisch unbedenklichen All-in-one Hilfsmitteln dar. Bevorzugt sind die Enzyme ausgewählt aus Amylasen, Catalasen, Cellulasen, Lipasen, Pectinasen, Proteasen und/oder Glucose-Oxidasen.Combination products of enzymes, biodegradable sugar polymers and surfactants represent a new generation of ecologically harmless all-in-one auxiliaries for textile pretreatment. The enzymes are preferably selected from amylases, catalases, cellulases, lipases, pectinases, proteases and / or glucose oxidases.

Für den Fachmann ist offensichtlich, dass die erfindungsgemäßen Zusammensetzungen, insbesondere für die Anwendung, eine mehr oder weniger große Menge Wasser erfordern. Diese richtet sich insbesondere nach dem gewünschten Einsatzzweck der Zusammensetzungen.It will be apparent to those skilled in the art that the compositions of the invention, especially for use, require a greater or lesser amount of water. This depends in particular on the desired application of the compositions.

Die Auswahl der niedermolekularen organischen und anorganischen Säuren unterliegt keiner besonderen Beschränkung. Dementsprechend ist es besonders bevorzugt, die niedermolekularen organischen Säuren auszuwählen aus niedermolekularen Mono- oder Polycarbonsäuren, insbesondere Citronensäure, Weinsäure, Milchsäure, Gluconsäure und/oder Glucoheptonsäure. Phosphonsäuren im Sinne der vorliegenden Erfindung, die vorzugsweise als Additive eingesetzt werden, sind vorzugsweise ausgewählt aus HEDP, ATMP, DTPMP und/oder HDTMP. In gleicher Weise sind die anorganischen Säuren vorzugsweise ausgewählt aus Mineralsäuren, insbesondere Salzsäure und Schwefelsäure sowie darüber hinaus Amidosulfonsäure.The selection of low molecular weight organic and inorganic acids is not particularly limited. Accordingly, it is particularly preferred to select the low molecular weight organic acids from low molecular weight mono- or polycarboxylic acids, in particular citric acid, tartaric acid, lactic acid, gluconic acid and / or glucoheptonic acid. Phosphonic acids for the purposes of the present invention, which are preferably used as additives, are preferably selected from HEDP, ATMP, DTPMP and / or HDTMP. In the same way, the inorganic acids are preferably selected from mineral acids, in particular hydrochloric acid and sulfuric acid, and furthermore amidosulfonic acid.

Aus dem in der Beschreibungseinleitung genannten Stand der Technik ist es bekannt, dass Zusammensetzungen zur Behandlung von Textilfasermaterial üblicherweise tensidhaltige Bestandteile enthalten. Besonders bevorzugt im Sinne der vorliegenden Erfindung sind Aniontenside, Niotenside und/oder Alkylpolyglycoside. Die Aniontenside sind vorzugsweise ausgewählt aus linearen oder verzweigten C8-C20-Alkansulfonaten, Alkansulfaten, Alkancarboxylaten oder Alkanethercarbonsäuren sowie Alkylbenzolsulfonaten und Seifen (maximal 20 Gew.-%). Niotenside im Sinne der vorliegenden Erfindung sind insbesondere ausgewählt aus linearen oder verzweigten C8-C20-Fettalkoholalkoxylaten. Alkylpolyglycoside im Sinne der vorliegenden Erfindung sind insbesondere ausgewählt aus linearen oder verzweigten C8-C20-Polyglycosiden mit n = 1 bis 3.It is known from the state of the art mentioned in the introduction that compositions for the treatment of textile fiber material usually contain surfactant-containing constituents. Particularly preferred in The meaning of the present invention are anionic surfactants, nonionic surfactants and / or alkylpolyglycosides. The anionic surfactants are preferably selected from linear or branched C 8 -C 20 -alkanesulfonates, alkanesulfates, alkanecarboxylates or alkanethercarboxylic acids and also alkylbenzenesulfonates and soaps (maximum 20% by weight). Nonionic surfactants for the purposes of the present invention are in particular selected from linear or branched C 8 -C 20 fatty alcohol alkoxylates. Alkylpolyglycosides for the purposes of the present invention are in particular selected from linear or branched C 8 -C 20 -polyglycosides with n = 1 to 3.

Eine weitere Ausführungsform der vorliegenden Erfindung besteht in einem Verfahren zur Herstellung der oben definierten glucosefreien Zusammensetzungen, wobei man die Polymerisate von Acrylsäure und Sacchariden, die Glucose als Rohstoff oder Reaktionsprodukt enthielten, mit Glucose-Oxidase behandelt. Hierdurch wird ein glucosefreies oder glucosearmes Produkt erhalten, das besonders vorteilhaft eingesetzt werden kann.A further embodiment of the present invention consists in a process for the preparation of the above-defined glucose-free compositions, wherein the polymers of acrylic acid and saccharides containing glucose as raw material or reaction product are treated with glucose oxidase. As a result, a glucose-free or low-glucose product is obtained, which can be used particularly advantageously.

Die Abmischung der einzelnen Komponenten erfolgt nach einem an sich im Stand der Technik bekannten Verfahren.The mixing of the individual components takes place according to a method known per se in the prior art.

Die erfindungsgemäßen Zusammensetzungen können nach an sich bekannten Verfahren zum Veredeln von Textilmaterial eingesetzt werden. Als besondere Verfahren der Textilveredlung sind hier insbesondere die Bindung von mehrwertigen Metallionen, die Inhibierung von Wasserhärte, die Dispergierung von Pigmenten sowie der Einsatz in Wasch-, Bleich- und Färbeflotten, insbesondere zum Nachbehandeln von Färbungen von Textilmaterialien zu erwähnen.The compositions according to the invention can be used according to processes known per se for refining textile material. As a special process of textile finishing are in particular the binding of polyvalent metal ions, the inhibition of water hardness, the dispersion of pigments and the use in washing, bleaching and dyeing liquors, especially for the aftertreatment of dyeings of textile materials mentioned.

BeispieleExamples Bezugsbeispiel 1 (gemäß DE 42 21 381, Beispiel 7):Reference Example 1 (according to DE 42 21 381, Example 7):

Eine Mischung aus 154 g Acrylsäure, 108,9 g Saccharose, 54,5 g Natriummethallylsulfonat und Wasser wurde mit 39,6 g 50 %iger Natronlauge im Reaktor teilneutralisiert, auf 25 °C abgekühlt und mit 8,8 g Mercaptoethanol, 0,02 g Eisensulfat in 10,0 g Wasser und 3 g 35 %igem Wasserstoffperoxid versetzt. Wenn die durch die einsetzende Polymerisationsreaktion ansteigende Temperatur im Reaktor über 75 °C gestiegen war, wurde nach Erreichen der maximalen Temperatur auf 75 °C zurückgekühlt. Blieb die Temperatur unter 75 °C, wurde nach Erreichen des Temperaturmaximums auf 75 °C aufgeheizt. Dann wurden 2 g Hydroxylammoniumchlorid in 15,7 g Wasser und 14,3 g 35 %iges Wasserstoffperoxid in den Reaktor gegeben und ein erneutes Ansteigen der Temperatur abgewartet. Nach dem Abklingen der exothermen Reaktion wurde auf 95°C erhitzt und 2 Stunden bei dieser Temperatur gehalten, dann abgekühlt und bei 40 bis 45 °C mit 126,2 g 50 %iger Natronlauge neutralisiert.A mixture of 154 g of acrylic acid, 108.9 g of sucrose, 54.5 g of sodium methallylsulfonate and water was partially neutralized with 39.6 g of 50% sodium hydroxide solution in the reactor, cooled to 25 ° C and with 8.8 g of mercaptoethanol, 0.02 g of iron sulfate in 10.0 g of water and 3 g of 35% hydrogen peroxide. When the temperature in the reactor rising due to the onset of the polymerization reaction had risen above 75 ° C., it was cooled back to 75 ° C. after reaching the maximum temperature. The temperature remained below 75 ° C, was heated to 75 ° C after reaching the maximum temperature. Then 2 g of hydroxylammonium chloride in 15.7 g of water and 14.3 g of 35% hydrogen peroxide were added to the reactor and a renewed rise in temperature was awaited. After the decay of the exothermic reaction was heated to 95 ° C and held for 2 hours at this temperature, then cooled and neutralized at 40 to 45 ° C with 126.2 g of 50% sodium hydroxide solution.

Das Polymerisat war braun gefärbt und klar. Es hatte, wie angegeben, eine Viskosität von 40 mPas. Es entstanden 4 % freie Glucose und 4 % freie Fructose. Die Bestimmung der Gesamtelimination, die sich aus biologischem Abbau und Elimination durch Adsorption addierte, ergab bei mehreren Messreihen nach OECD 302 B generell Werte unter 40 %.The polymer was brown in color and clear. It had, as indicated, a viscosity of 40 mPas. There were 4% free glucose and 4% free fructose. The determination of the total elimination, which resulted from biological degradation and elimination by adsorption, generally resulted in values below 40% for several series of measurements according to OECD 302B.

Bezugsbeispiel 2 (gemäß EP 0 289 895 B1):Reference Example 2 (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 Zutropfphase ein pH-Wert 9 und eine Temperatur von 90 °C konstant gehalten wurde.134 g of glucose were dissolved in 238 g of water and adjusted to pH 9 with sodium hydroxide solution 50%. At the same time, 161 g of acrylic acid, 228 g of hydrogen peroxide 14% and 50% sodium hydroxide solution were metered into this solution at the same time during the dropping phase, a pH 9 and a temperature of 90 ° C was kept constant.

Die Zugabe von Acrylsäure erfolgte innerhalb 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 und enthielt 1,2 % freie Glucose.The addition of acrylic acid was within 2 hours, hydrogen peroxide was metered for 30 minutes longer. The mixture was then stirred at 90 ° C for 30 minutes. The polymer had a viscosity of 400 mPas and contained 1.2% free glucose.

Beispiel 1:Example 1:

100 g des Polymerisats gemäß Bezugsbeispiel 2 wurden mit Salzsäure auf pH 5 eingestellt und auf 200 g verdünnt. Danach wurden 2000 units einer Glucose-Oxidase der Fa. Sigma, Typ II-S, zugegeben und 24 Stunden bei 35 °C gerührt. Dabei verringerte sich der Glucosegehalt von 6 g/l auf weniger als 0,1 g/l und gleichzeitig erhöhte sich der Gluconsäureanteil von 0,5 g/l auf 7 g/l.100 g of the polymer according to Reference Example 2 were adjusted to pH 5 with hydrochloric acid and diluted to 200 g. Thereafter, 2000 units of a glucose oxidase from. Sigma, type II-S, were added and stirred at 35 ° C for 24 hours. At the same time the glucose content decreased from 6 g / l to less than 0.1 g / l and at the same time the gluconic acid fraction increased from 0.5 g / l to 7 g / l.

Beispiele 2 bis 7:Examples 2 to 7:

Analog den obigen Vorschriften wurden Zusammensetzungen zur Textilveredlung zusammengestellt, deren Stoffzusammensetzung der nachfolgenden Tabelle zu entnehmen ist. Die Angaben der folgenden Tabelle 1 stehen jeweils für Gewichtsprozente. Tabelle 1 Beispiele 2 3 4 5 6 7 Polymerisat gemäß Bezugsbeispiel 2 15 15 15 Polymerisat gemäß Beispiel 1 30 4 10 Gluconsäure; 50 % 10 10 10 10 Citronensäure * H2O 5 5 5 5 Schwefelsäure konz. 10 10 10 10 2-Ethylhexylsulfat-Na; 50 % 10 C12-C14-Alkansulfonat; 60 % 10 10 Fettalkoholethoxylat C8-C11, 8 Mol EO 30 Alkylpolyglycosid, C8-C14, n ca. 1-3; 50 % 20 20 Natrium-Kalium-Cumolsulfonat; 40 % 7 5 Hexylenglykol 5 Wasser 45 50 43 35 61 60 Compositions for textile finishing were compiled in analogy to the above instructions, the composition of which is shown in the table below. The data in the following Table 1 are in each case for percentages by weight. <u> Table 1 </ u> Examples 2 3 4 5 6 7 Polymer according to Reference Example 2 15 15 15 Polymer according to Example 1 30 4 10 gluconic; 50% 10 10 10 10 Citric acid * H 2 O 5 5 5 5 Sulfuric acid conc. 10 10 10 10 2-ethylhexyl-Na; 50% 10 C 12 -C 14 alkanesulfonate; 60% 10 10 Fatty alcohol ethoxylate C 8 -C 11 , 8 moles EO 30 Alkylpolyglycoside, C 8 -C 14 , n ca. 1-3; 50% 20 20 Sodium potassium cumene sulfonate; 40% 7 5 hexylene 5 water 45 50 43 35 61 60

Beispiele 8 bis 12/ Vergleichsbeispiele 3 und 4:Examples 8 to 12 / Comparative Examples 3 and 4:

Analog den obigen Vorschriften wurden Zusammensetzungen zur Textilveredlung zusammengestellt, deren Stoffzusammensetzung der nachfolgenden Tabelle zu entnehmen ist.Compositions for textile finishing were compiled in analogy to the above instructions, the composition of which is shown in the table below.

Das SiO2/Na2O-Gewichtsverhältnis in Tabelle 2 wurde durch Lösen von festem Natriumhydroxid in Wasserglas 38° Be (GVZ 3,3) eingestellt, kann aber auch durch Abmischen mit handelsüblichen Wassergläsern mit niedrigerer GVZ erfolgen. Tabelle 2 Beipiele 8 Gew.- Teile 9 Gew.- Teile 10 Gew.- Teile 11 Gew.- Teile 12 Gew.- Teile Vgl. 3 Gew.-Teile Vgl. 4 Gew.-Teile Polymerisat gemäß Bezugsbeispiel 2 14 14 25 45 Polymerisat gemäß Beispiel 1 20 Natriumgluconat 5 5 Alcosperse®175 10 25 Wasserglas SiO2/Na2O =1,6 80 81 75 55 90 75 Wasserglas SiO2/Na2O= 2,4 78 Wasserzusatz 3 Aussehen der Lösung klar klar klar klar klar klar trüb The SiO 2 / Na 2 O weight ratio in Table 2 was adjusted by dissolving solid sodium hydroxide in 38 ° Be (GVZ 3.3) waterglass, but may also be made by mixing with commercially available lower GVZ waterglasses. <u> Table 2 </ u> Beipiele 8 parts by weight 9 parts by weight 10 parts by weight 11 parts by weight 12 parts by weight See 3 parts by weight See 4 parts by weight Polymer according to Reference Example 2 14 14 25 45 Polymer according to Example 1 20 sodium gluconate 5 5 Alcosperse ® 175 10 25 Water glass SiO 2 / Na 2 O = 1.6 80 81 75 55 90 75 Water glass SiO 2 / Na 2 O = 2.4 78 water additive 3 Appearance of the solution clear clear clear clear clear clear cloudy

Anwendungstechnische Beispiele:Application examples: Beispiel A 1: Saure Entmineralisierung - Diskontinuierlicher ProzeßExample A 1: Acidic Demineralization - Discontinuous Process

Rohbaumwollgewebe wurde 30 Minuten bei 70 °C und einem Flottenverhältnis von 1:10 mit einer Flotte behandelt, die 5 g/l der Mischung gemäß Beispiel 4 enthielt. Nach der Behandlung wurde das Gewebe warm und kalt ausgewaschen. Es resultierte ein Textilmaterial, das sehr gut entmineralisiert war und für alle weiteren Behandlungenverwendet werden konnte. Die Gesamthärte auf der Ware wurde um 60 %, der Eisengehalt um 50 % reduziert, eine Behandlung mit je 5 g/l des Polymerisats gemäß Bezugsbeispiel 1 oder Bezugsbeispiel 2 allein reduzierte die Gesamthärte nur um jeweils 30 % und den Eisengehalt um 20 % beziehungsweise 30 %.Raw cotton fabric was treated for 30 minutes at 70 ° C and a liquor ratio of 1:10 with a liquor containing 5 g / l of the mixture according to Example 4. After treatment, the tissue was washed off warm and cold. The result was a textile material that was very well demineralized and could be used for all other treatments. The total hardness on the fabric was reduced by 60%, the iron content by 50%, a treatment with 5 g / l of the polymer according to Reference Example 1 or Reference Example 2 alone reduced the total hardness by only 30% and the iron content by 20% and 30, respectively %.

Beispiel A 2: Saure Entmineralisierung - Diskontinuierlicher ProzeßExample A 2: Acid Demineralization - Discontinuous Process

Rohbaumwollgewebe wurde wie in Beispiel A1 30 Minuten bei 70 °C und einem Flottenverhältnis von 1:10 mit einer Flotte behandelt, die 5 g/l der Mischung gemäß Beispiel 4 enthielt. Danach wurde ohne Zwischenspülen der Flotte 6 g/l Natronlauge 50 %, 8 ml/l Wasserstoffperoxid 35 % und 0,8 g/l eines hochaffinen optischen Aufhellers (Handelsname "Tuboblanc® VA fl.") zugegeben. Danach wurde heiß und kalt gespült.Raw cotton fabric was treated as in Example A1 for 30 minutes at 70 ° C and a liquor ratio of 1:10 with a liquor containing 5 g / l of the mixture according to Example 4. Thereafter, 6 g / l sodium hydroxide solution was 50% without intermediate rinsing the liquor added 8 ml / l 35% hydrogen peroxide and 0.8 g / l of a high affinity fluorescent whitening agent (trade name "VA Tuboblanc ® fl."). Thereafter, hot and cold rinsed.

Die Ware erreichte ein Grundweiß von 81 und eine Fluoreszenz von 72 Berger Einheiten.The product reached a base white of 81 and a fluorescence of 72 Berger units.

Beispiel B: Saure Entmineralisierung- Kontinuierlicher ProzeßExample B: Acid Demineralization - Continuous Process

Auf Rohbaumwollmaschenware wurde eine Flotte foulardiert, die 6 g/l der Mischung gemäß Beispiel 2 und 4 g/l eines Netzmittels (Handelsname "Subitol DM") enthielt. Die Flottenaufnahme betrug 100 %, die Flottentemperatur lag bei 60 °C, die Verweilzeit betrug 30 Minuten und die Verweiltemperatur lag ebenfalls bei 60 °C. Das Textilmaterial war gut entmineralisiert und konnte weiteren Behandlungsschritten unterzogen werden. So wurde die Gesamthärte auf der Ware um 50 % und der Eisengehalt um 40 % reduziert, was mit weniger sauer eingestellten Komplexbildnern allein nicht erreichbar war.On cotton wool knitwear, a liquor was padded containing 6 g / l of the mixture according to Example 2 and 4 g / l of a wetting agent (trade name "Subitol DM"). The liquor pickup was 100%, the liquor temperature was 60 ° C, the residence time was 30 minutes and the residence temperature was also 60 ° C. The textile material was well demineralized and could be subjected to further treatment steps. That's how it became the total hardness on the fabric reduced by 50% and the iron content by 40%, which was not achievable with less acidic complexing agents alone.

Beispiel C: EntschlichtungExample C: Desizing

Ein Rohbaumwollgewebe, mit Stärke geschlichtet, wurde mit folgender Flotte bei 40 °C imprägniert: 5 g/l einer Amylase (Beisol LZV) und 6 ml/l des in Beispiel 7 genannten Waschmittels. Nach vier Stunden wurde ausgewaschen. Der Entschlichtungsgrad nach TEGEWA betrug 9.A raw cotton fabric, sized with starch, was impregnated with the following liquor at 40 ° C: 5 g / l of an amylase (Beisol LZV) and 6 ml / l of the detergent mentioned in Example 7. After four hours was washed out. The degree of desizing according to TEGEWA was 9.

Beispiel D1; KaltbleicheExample D1; cold bleaching

Ein Rohbaumwollgewebe wurde mit folgender Flotte imprägniert: 0,2 g/l Bittersalz, 7 ml/l des in Beispiel 5 genannten Kombinationsprodukts, 30 g/l Natronlauge 50 %, 10 ml/l Wasserglas 38°Bé, 40 ml/l Wasserstoffperoxid 35 %. Die Flottenaufnahme betrug 100 %. Anschließend wurde die Ware nach dem KKV-Verfahren 24 Stunden bei Raumtemperatur belassen, dann gewaschen, gespült und getrocknet. Das Grundweiß stieg von 18 auf 82 Berger-Einheiten. Die gleiche Rezeptur mit 10 ml/l Abmischung gemäß Beispiel 9 anstelle Wasserglas 38 Be ergab 83. Selbst ohne 7 ml/l Produkt gemäß Beispiel 5 wurden hier immer noch 81 Berger-Einheiten erreicht. Ein Versuch nach Beispiel D ohne Wasserglas ergab nur 75 Berger-Einheiten.A green cotton fabric was impregnated with the following liquor: 0.2 g / l Epsom salt, 7 ml / l of the combination product mentioned in Example 5, 30 g / l sodium hydroxide solution 50%, 10 ml / l water glass 38 ° Bé, 40 ml / l hydrogen peroxide 35 %. The liquor pickup was 100%. Subsequently, the product was left for 24 hours at room temperature according to the KKV method, then washed, rinsed and dried. The basic white rose from 18 to 82 Berger units. The same formulation with 10 ml / l mixture according to Example 9 instead of water glass 38 Be gave 83. Even without 7 ml / l product according to Example 5 here still 81 Berger units were reached. An experiment according to Example D without water glass gave only 75 Berger units.

Beispiel D2: HeißbleicheExample D2: hot bleaching

Ein Rohbaumwollgewebe mit einem Grundweiß von 18 Berger-Einheiten wurde mit folgender Flotte imprägniert:
0,2 g/l Bittersalz, 2 oder 6 ml/l des in nachfolgender Tabelle 3 genannten Produktes, 20 g/l Natronlauge 50 %, 40 ml/l Wasserstoffperoxid 35 %. Die Flottenaufnahme betrug 100 %. Anschließend wurde die Ware nach dem pad steam-Verfahren 30 Minuten bei 102°C gedämpft, gewaschen, gespült und getrocknet. Die Weißgrade in Berger-Einheiten sind Tabelle 3 zu entnehmen: Tabelle3: Weißgrad [Berger] Abmischung nach 2 ml/l 6 ml/l Beispiel 8 80 84 Beispiel 9 82 86 Beispiel 10 82 86 Beispiel 11 81 84 Bezugsbeispiel 1 78 78 Bezugsbeispiel 2 79 80 ohne Hilfsmittel 77 77 A raw cotton fabric with a base white of 18 Berger units was impregnated with the following liquor:
0.2 g / l of Epsom salt, 2 or 6 ml / l of the product mentioned in Table 3 below, 20 g / l of sodium hydroxide solution 50%, 40 ml / l of hydrogen peroxide 35%. The liquor pickup was 100%. Subsequently, the product was steamed at 102 ° C for 30 minutes, washed, rinsed and dried by pad steam method. The degrees of whiteness in Berger units are shown in Table 3: <U> Table 3: </ u> Whiteness [Berger] Mix after 2 ml / l 6 ml / l Example 8 80 84 Example 9 82 86 Example 10 82 86 Example 11 81 84 Reference Example 1 78 78 Reference Example 2 79 80 without aids 77 77

Beispiel E: Diskontinuierliches Vorreinigen und WaschenExample E: Batch pre-cleaning and washing

Ein Rohbaumwollgewebe wurde mit einer Flotte behandelt, die 3 g/l des Kombinationsproduktes gemäß Beispiel 7 und 1 g/l Soda enthielt. Das Flottenverhältnis betrug 1:10, die Temperatur lag bei 95 °C und die Waschdauer betrug 30 Minuten. Anschließend wurde heiß und kalt ausgewaschen.A raw cotton fabric was treated with a liquor containing 3 g / l of the combination product of Example 7 and 1 g / l of soda. The liquor ratio was 1:10, the temperature was 95 ° C and the washing time was 30 minutes. Subsequently, hot and cold were washed out.

Beispiel F1: WaschprozeßExample F1: Washing process

Ein Rohbaumwollgewebe wurde mit einer Flotte behandelt, die 3 g/l des Kombinationsproduktes gemäß Beispiel 7 und 3 g/l Soda enthielt. Das Flottenverhältnis betrug 1:20, die Temperatur 90 °C und die Waschdauer 30 Minuten. Anschließend wurde heiß und kalt ausgewaschen. Die Begleitsubstanzen wurden restlos entfernt und das Textil entsprach in seinen Eigenschaften dem Standard eines Waschprozesses. Das Bezugsbeispiel 1 zeigte keine fettentfernende Wirkung und das Gewebemuster blieb hydrophob.A raw cotton fabric was treated with a liquor containing 3 g / l of the combination product of Example 7 and 3 g / l of soda. The liquor ratio was 1:20, the temperature 90 ° C and the washing time 30 minutes. Subsequently, hot and cold were washed out. The accompanying substances were removed completely and the textile corresponded in its properties the standard of a washing process. Reference Example 1 showed no grease-removing effect and the fabric pattern remained hydrophobic.

Beispiel F2: Waschprozeß mit standardisiertem EMPA-Schmutzgewebe aus Baumwolle Example F2: Washing process with standardized EMPA dirt cotton fabric

Das Testgewebe wurde mit einer Flotte behandelt, die 2 g/l des Kombiproduktes gemäß Beispiel 7 und 1 g/l Soda enthält. Das Flottenverhältnis betrug 1:40, die Temperatur 60 °C und die Waschdauer betrug 30 Minuten. Anschließend wurde heiß und kalt ausgewaschen. Der Weißgrad stieg von 19 auf 31 Berger-Einheiten. Wurde anstelle des Produktes gemäß Beispiel 7 das Produkt gemäß Bezugsbeispiel 2, beziehungsweise ein reines Niotensid, Isotridecylalkohol 6-fach ethoxyliert, verwendet, so ergaben sich nur 22 beziehungsweise 26 Berger-Einheiten.The test fabric was treated with a liquor containing 2 g / l of the combination product of Example 7 and 1 g / l of soda. The liquor ratio was 1:40, the temperature 60 ° C and the washing time was 30 minutes. Subsequently, hot and cold were washed out. The whiteness increased from 19 to 31 Berger units. Was used instead of the product according to Example 7, the product according to Reference Example 2, or a pure nonionic surfactant, isotridecyl alcohol 6-fold ethoxylated, so there were only 22 or 26 Berger units.

Beispiel G: Alkalisches AbkochenExample G: Alkaline decoction

Rohbaumwollgewebe wurde bei einem Flottenverhältnis 1:10 in Gegenwart von 5 g/l des Kombinationsproduktes gemäß Beispiel 7 und 20 g/l NaOH 100 % 30 Minuten bei 98 °C abgekocht. Der Weißgrad der Ware stieg dabei von 22 auf 39 Berger-Einheiten.Raw cotton fabric was boiled at a liquor ratio of 1:10 in the presence of 5 g / l of the combination product according to Example 7 and 20 g / l NaOH 100% for 30 minutes at 98 ° C. The whiteness of the goods rose from 22 to 39 Berger units.

Beispiel H: Prüfung auf EisenhydroxiddispergierungExample H: Test for iron hydroxide dispersion

Je 2 g/l Produkt gemäß Tabelle 4 wurden 20 Minuten in 200 ml destilliertem Wasser unter Rückfluß gekocht, die 30 ppm Eisenionen (aus Eisen-IIIchlorid), 5 g/l Natriumhydroxid und 2 g/l Soda enthielten.2 g / l of product according to Table 4 were refluxed for 20 minutes in 200 ml of distilled water containing 30 ppm iron (ferric chloride) ions, 5 g / l sodium hydroxide and 2 g / l soda.

Danach wurde die heiße Lösung durch einen weißen Rundfilter, Typ 2329 G, Fa. Schleicher & Schuell, gesaugt und die Filterrückstände nach Trocknung bewertet. Rückstandslose Filter erhielten die Note 1, dunkelbraune Rückstände, wie beim Einsatz von Wasserglas ohne Dispergiermittel, erhielten die Note 6. Tabelle 4: Produkt Filterfarbe Note Wasserglas GV 3,3 braun 6 Wasserglas GV 1,6 braun 6 Beispiel 8 hellbraun 4 Beispiel 9 weiß 1 Beispiel 10 weiß 1 Vergleichsbeispiel 3 braun 5 Vergleichsbeispiel 4 braun 5 Thereafter, the hot solution through a white round filter, type 2329 G, Fa. Schleicher & Schuell, sucked and evaluated the filter residues after drying. Residue-free filters were rated 1, dark brown residues, as when using water glass without dispersant, received the grade 6. <u> Table 4: </ u> product filter Color grade Water glass GV 3.3 brown 6 Water glass GV 1.6 brown 6 Example 8 tan 4 Example 9 White 1 Example 10 White 1 Comparative Example 3 brown 5 Comparative Example 4 brown 5

Beispiel I: Prüfung auf Erdalkalidispergierung in Gegenwart von EisenionenExample I: Testing for alkaline earth dispersing in the presence of iron ions

Es wurde wie in Beispiel H geprüft, jedoch zusätzlich 25 °dH Calciumionen (aus Calciumchlorid) und 10 °dH Magnesiumionen (aus Magnesiumsulfat) der Testlösung zugegeben. Rückstandlose Filter erhielten die Note 1, grobkörnige Rückstände wie beim Einsatz von Wasserglas ohne Dispergiermitttel erhielten die Note 6. Tabelle 5: Produkt Note Wasserglas GV 3,3 6 Wasserglas GV 1,6 6 Beispiel 9 3 Beispiel 10 2 Beispiel 11 2 Vergleichsbeispiel 3 6 Vergleichsbeispiel 4 5 It was tested as in Example H, but additionally added 25 ° dH calcium ions (calcium chloride) and 10 ° dH magnesium ions (from magnesium sulfate) of the test solution. Residue-free filters received the rating 1, coarse-grained residues such as when using water glass without dispersing agent received the grade 6. <u> Table 5: </ u> product grade Water glass GV 3.3 6 Water glass GV 1.6 6 Example 9 3 Example 10 2 Example 11 2 Comparative Example 3 6 Comparative Example 4 5

Selbst 6 g/l der Abmischungen gemäß den Vergleichsbeispielen 3 und 4 ergaben Filternoten von 5 beziehungsweise 3.Even 6 g / l of the blends according to Comparative Examples 3 and 4 gave filter scores of 5 and 3, respectively.

Claims (20)

  1. Compositions for the treatment of textile fiber material, containing, respectively based on the composition, from 99 to 1 part by weight, based on the dry matter, of a polymer of acrylic acid and enolizable monosaccharides, oligosaccharides and/or polysaccharides, prepared in the alkaline pH range, and from 1 to 99 parts by weight, based on the dry matter, of additive
    (a) up to 40% by weight of free low-molecular weight organic and inorganic acids of which less than 50% of the sum of acid protons are neutralized; and at least one or more of the additives selected from
    (b) from 0 to 60% by weight of non-ionic surfactants;
    (c) from 0 to 40% by weight of alkyl polyglycosides;
    (d) from 0 to 40% by weight of anionic surfactants;
    (e) from 0 to 20% by weight of auxiliary agents having a deaerating effect;
    (f) from 0 to 20% by weight of anti-foaming auxiliary agents;
    (g) from 0 to 70% by weight of organic solvents except for halohydrocarbons; and
    (h) from 0 to 10% by weight of enzymes;
    respectively based on the total amount of additives.
  2. The compositions according to claim 1, characterized by containing glucose- free polymers of acrylic acid and saccharides that contained glucose as a raw material or reaction product.
  3. The compositions according to claim 1 or 2, comprising from 2 to 30 parts by weight, based on the dry matter, of the polymer and from 70 to 98 parts by weight, based on the dry matter, of the additives.
  4. The compositions according to any of claims 1 to 3, characterized in that from 0 to 100% by weight of the polymers of acrylic acid and enolizable monosaccharides, oligosaccharides and/or polysaccharides, prepared in the alkaline pH range, are substituted by glucose-free polymers of acrylic acid and saccharides that contain glucose as a raw material or reaction product.
  5. The compositions according to any of claims 1 to 3, characterized in that said low-molecular weight organic acid is selected from mono- or polycarboxylic acids, especially citric acid, tartaric acid, lactic acid, gluconic acid and/or glucoheptonic acid.
  6. The compositions according to any of claims 1 to 3, characterized in that said organic acid is selected from phosphonic acids, especially HEDP, ATMP, DTPMP and/or HDTMP.
  7. The compositions according to any of claims 1 to 3, characterized in that said inorganic acid is selected from mineral acids, especially hydrochloric acid and sulfuric acid as well as amidosulfonic acid.
  8. The compositions according to any of claims 1 to 3, characterized in that said surfactant-containing component is selected from anionic surfactant, non-ionic surfactant and/or alkyl polyglycoside.
  9. The compositions according to any of claims 1 to 3, characterized in that said anionic surfactant is selected from linear or branched C8-C20 alkanesulfonates, -sulfates, carboxylates and/or -ethercarboxylic acids as well as alkylbenzenesulfonates.
  10. The compositions according to any of claims 1 to 3, characterized in that said non-ionic surfactant is selected from linear or branched C8-C20 fatty alcohol alkoxylates.
  11. The compositions according to any of claims 1 to 3, characterized in that said alkyl polyglycoside is selected from linear or branched C8-C20 polyglycosides (n = 1 to 3).
  12. The compositions according to any of claims 1 to 3, characterized in that said enzymes are selected from amylases, catalases, cellulases, lipases, pectinases, proteases and/or glucose oxidases.
  13. The compositions according to any of claims 1 to 3, having a pH value of greater than 11.5, characterized in that said additives are selected from
    (i) from 10 to 40% by weight (based on the dry matter) of water glass;
    (j) from 0 to 20% by weight of a complexing agent, the balance being water ad 100% by weight.
  14. The compositions according to claim 13, characterized in that said complexing agent is selected from the alkali and alkaline earth metal salts of gluconic acid or glucoheptonic acid.
  15. The compositions according to one or more of claims 1 to 14, containing from 20 to 80 parts by weight of water, based on 80 to 20 parts by weight of the polymers or mixtures of polymer and additive.
  16. A process for the preparation of compositions according to one or more of claims 1 to 15, characterized in that said polymers of acrylic acid and saccharides that contained glucose as a raw material or reaction product are treated with glucose oxidase.
  17. A process for the preparation of compositions according to one or more of claims 1 to 15, wherein said enolizable saccharides are prepared in situ before and/or during the polymerization reaction from oligo- and/or polysaccharides by hydrolysis.
  18. A process for the preparation of compositions according to one or more of claims 1 to 15, wherein said polymers of acrylic acid and enolizable monosaccharides, oligosaccharides and/or polysaccharides are prepared in a pH range of from 7 to 10.
  19. A process for finishing textile material, especially cellulose fiber material, characterized in that said material is treated with a mixture according to one or more of claims 1 to 15.
  20. The process according to claim 19, characterized in that from 0.2 to 50 ml, preferably from 1 to 20 ml, of the composition is employed per liter of treatment liquor.
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CN100436702C (en) * 2007-01-30 2008-11-26 厦门光达融通科技有限公司 Nano-biological enzyme additive and device and method for making same

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DE58906163D1 (en) * 1988-10-07 1993-12-16 Grillo Werke Ag Copolymers of unsaturated carboxylic acids and their use.
DE4003172A1 (en) * 1990-02-03 1991-08-08 Basf Ag PFROPOPOPOLYMERISATES OF MONOSACCHARIDES, OLIGOSACCHARIDES, POLYSACCHARIDES AND MODIFIED POLYSACCHARIDES, PROCESS FOR THEIR PREPARATION AND THEIR USE
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DE4344029A1 (en) * 1993-12-23 1995-06-29 Grillo Werke Ag Copolymers of unsaturated carboxylic acids, process for their preparation and their use

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CN109371667A (en) * 2018-12-27 2019-02-22 福建省健为医疗用品有限公司 A kind of pure cotton non-woven cloth kiering reagent and kiering method and pure cotton non-woven cloth
CN109371667B (en) * 2018-12-27 2021-05-14 福建省健为医疗用品有限公司 Scouring reagent and bleaching method for pure cotton non-woven fabric and pure cotton non-woven fabric

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