EP2992075B1 - Comb polymers as detergency boosters in detergent compositions - Google Patents

Comb polymers as detergency boosters in detergent compositions Download PDF

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Publication number
EP2992075B1
EP2992075B1 EP14718618.3A EP14718618A EP2992075B1 EP 2992075 B1 EP2992075 B1 EP 2992075B1 EP 14718618 A EP14718618 A EP 14718618A EP 2992075 B1 EP2992075 B1 EP 2992075B1
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Prior art keywords
acids
monoethylenically unsaturated
acid
textile
comb polymers
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EP14718618.3A
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German (de)
French (fr)
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EP2992075A1 (en
Inventor
Bernd Horrer
Heike Witzel-Wilhelm
Andrea Fischer-Sturm
Michael Hees
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CHT Germany GmbH
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CHT R Beitlich GmbH
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • 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

Definitions

  • the present invention relates to the use of comb polymers in textile pretreatment, in particular in textile finishing and corresponding agents.
  • the comb polymers used according to the invention are obtainable by A) a free-radical polymerization of monoethylenically unsaturated monomers a group A1) monoethylenically unsaturated acids and their salts and a group A2) monoethylenically unsaturated polyethers.
  • Detergents and cleaners contain surfactants as indispensable ingredients for the washing and cleaning process.
  • the surfactants as a main component influence primarily the result of the To assist the washing performance, a variety of laundry aids, such as builders to mask the water hardness, graying and color transfer inhibitors, foam regulators, bleaching agents and bleach activators in household washing and cleaning agents are already used today.
  • Such excipients also include substances which enhance the detergency of the surfactants. Such substances are often referred to as "soil-release" agents or detergency boosters. As a rule, such substances themselves have no pronounced surfactant properties.
  • Hydrophobic polymers consisting of styrene, methacrylic acid, hydroxyethyl methacrylate and methyl methacrylate are known, which show a very good dirt-removing effect especially on cotton-containing textiles.
  • the EP 2 065 403 A1 discloses the preparation of polymers via esterification of polyacrylic acids with end-capped polyols or amines.
  • a potential application as Builder component for hardness masking in liquid household detergents called.
  • JPH03185184 such as JP 2005 187 742
  • Detergents for textile pretreatment such as desizing, scouring, bleaching and soaps are disclosed which contain methoxy-PEG-methacrylate / (meth) acrylic acid copolymers.
  • US 2005/0113541 discloses polymers as a builder substance in detergents containing acrylic acid, methacrylic acid, acrylic acid PEG esters and polyamine polyethers.
  • sulfonic acid-containing copolymers consist of at least one monoethylenically unsaturated carboxylic acid, at least one monomer containing sulfonic acid groups and at least one nonionic monomer are formed and should be used as an additive to detergents and cleaners.
  • the process conditions in the textile pretreatment of natural or synthetic fibers or mixtures thereof are fundamentally different from the conditions of household laundry.
  • textile finishing processes in the strongly acidic range such as the “acid demineralization” at a pH of about 2
  • strongly alkaline processes such as "alkaline boiling", “cold bleaching” and “pad-steam bleaching” at pH Values from 13 to 14 are performed.
  • the treatment temperatures in the textile pretreatment also differ significantly from those which are usual in household washing.
  • the majority of the finishing processes are carried out at approx. 95 to 100 ° C. In some countries, high-temperature bleaching at 110 ° C is favored.
  • the types of dirt are also fundamentally different from the types of household waste.
  • the natural In textile pretreatment, the natural must Adjacent substances such as fats, waxes and the preparations used for the production of the synthetic fibers or textile fabrics, such as knitting oils and sizes, are removed.
  • the object of the present invention is to overcome the disadvantages described above with regard to insufficient effectiveness for the textile pretreatment of natural or synthetic fibers or mixtures thereof. It is intended to provide polymers which effectively support surfactants and thereby enable a reduced amount of surfactants to be used for optimum washing and cleaning performance.
  • the alkaline bleaching processes are carried out at pH values between 10 and 14 and temperatures between 80 and 130 ° C.
  • the cleaning performance is checked after the bleaching process by a good and uniform hydrophilicity (absorbency) of the cotton.
  • the invention is therefore based, in particular, on the problem of providing polymers having an excellent washing-power-enhancing effect under these conditions.
  • Another object is for the washing of elastane-containing materials (mesh or woven fabric) a polymer which effectively removes the silicone oil used for production and stably emulsifies in the washing solution.
  • the comb polymers used according to the invention thus contain the components A1 + A2 in the first embodiment.
  • the monoethylenically unsaturated acids and their salts include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, Vinylphosphonic.
  • the monomers of group A1 can be used individually or as a mixture of different monomers in an amount of 5 to 95 wt .-%, in particular with an amount of 10 to 90 wt .-% based on the polymer. Preference is given to acrylic acid, methacrylic acid and maleic acid and particular preference is given to acrylic acid or methacrylic acid.
  • the monoethylenically unsaturated polyethers include polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether and polyethylene-polypropylene monoallyl ether; these are commercially available, for example, from Clariant under the Polyglykol® A product line and from BASF under the Pluriol® A ... R product line. Further examples include polyethylene glycol monovinyl ether (product series from Clariant: Polyglycol® R), isoprenyl ethoxylates (product series from BASF: Pluriol® A ... I) and vinyloxybutyl ethoxylates (product series from BASF: Pluriol® A ... V).
  • the monomers of group A2 can be used individually or as a mixture of different monomers in an amount of from 2 to 25% by weight, based on the polymer, in particular in an amount of from 5 to 20% by weight, based on the polymer.
  • Polyalkyl glycol monoallyl ethers are preferred, and polyethylene glycol monoallyl ether and polyethylene-polypropylene monoallyl ether are particularly preferred.
  • the use according to the invention can be carried out as part of a washing, decoction, enzyme, desizing, demineralization or bleaching process in a continuous or discontinuous production process such that the comb polymer is added separately to a detergent-containing liquor, or the comb polymer as a constituent of the detergent in bring in the fleet.
  • Another object of the invention is therefore a detergent for the textile pretreatment of natural or synthetic fibers or mixtures thereof, which contains 0.1 to 20 wt .-%, in particular 0.5 to 15 wt .-%, of a corresponding comb polymer.
  • Detergents containing the comb polymer used in the invention may contain all the usual ingredients of such agents which do not undesirably interact with it.
  • such a detergent contains surfactants, such as fatty alcohol alkoxylates, fatty acid alkoxylates, fatty alkyl polyglycosides, fatty amine alkoxylates and / or fatty acid amides from the field of nonionic surfactants.
  • surfactants such as fatty alcohol alkoxylates, fatty acid alkoxylates, fatty alkyl polyglycosides, fatty amine alkoxylates and / or fatty acid amides from the field of nonionic surfactants.
  • anionic surfactants it is possible to use alkylcarboxylates, alkyl ether carboxylates, alkane sulfates, alkane ether sulfates, alkane sulfonates, alkyl phosphates, alkyl ether phosphates, taurides and / or sarcosides.
  • Table 1 comb polymer Monoethylenically unsaturated polyethers Quantity [g] Monoethylenically unsaturated acid Quantity [g] KP-1 Polyglycol® A 31/1000 61 acrylic acid 365 KP-2 Polyglycol® A 11/1800 61 acrylic acid 365 KP-3 Pluriol® A 10 R 61 acrylic acid 365 KP-4 Polyglycol® A 1100 61 acrylic acid 365
  • the content of residual monomer for the side chains was determined semiquantitatively by thin-layer chromatography.
  • the residual monomer results were always below 0.5% by weight in the polymer solution.
  • a raw cotton jersey knit fabric with a base white of 17 Berger units was bleached in a Labomat from Mathis for 30 minutes at 98 ° C.
  • the liquor ratio was 1:10 and the water used had a set water hardness of 5 ° dH, adjusted with CaCl 2 ⁇ 2 H 2 O.
  • the heating or cooling gradient was 3 ° C / min.
  • the product was rinsed for 10 min at 80 ° C, then neutralized with 0.5 g / L acetic acid 60% for 10 min at 30 ° C and rinsed once more for 10 min at 30 ° C.
  • the product was spun for 30 seconds and dried for 30 seconds at a surface temperature of 120 ° C in the tenter.
  • the bleaching formulations are shown in Table 4.1 and the associated whiteness and absorbency results for the product in Table 4.2.
  • the absorbency also referred to as hydrophilicity
  • the product is dependent on the cleaning performance of the detergent used. It is tested using the TEGEWA Drip Test, which measures the amount of time a stained drop of water needs to sink into the fabric. The exact description is in the Journal Melliand Textilberichte 68 (1987), pages 581-583 released. A better differentiating method is the determination of absorbency according to the riser method according to DIN 53924.
  • the surfactants used were Lutensol® AO 5 and Lutensol® AO 7 from BASF, C 13/15 fatty alcohol ethoxylates with 5 or 7 mol of ethylene oxide.
  • the comb polymers were used as polymer solutions with a solids content of 46% by weight.
  • As comparison polymer V-1 was Sokalan® PA 25 CL PN from BASF, an acrylic acid homopolymer having an average molecular weight of 4,000 g / mol and a solids content of 49% by weight and Comparative Polymer V-2 was Alcosperse® 747 from Akzo Nobel, a hydrophobically modified copolymer having an average molecular weight of 3,000 g / mol and a solids content of 40 wt .-% used.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Polyethers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Description

Die vorliegende Erfindung betrifft die Verwendung von Kammpolymeren in der textilen Vorbehandlung insbesondere bei der Textilveredelung und entsprechende Mittel. Die erfindungsgemäß eingesetzten Kammpolymere sind erhältlich durch A) eine radikalische Polymerisation von monoethylenisch ungesättigten Monomeren
einer Gruppe A1) monoethylenisch ungesättigter Säuren und deren Salzen und
einer Gruppe A2) monoethylenisch ungesättigter Polyether.The present invention relates to the use of comb polymers in textile pretreatment, in particular in textile finishing and corresponding agents. The comb polymers used according to the invention are obtainable by A) a free-radical polymerization of monoethylenically unsaturated monomers
a group A1) monoethylenically unsaturated acids and their salts and
a group A2) monoethylenically unsaturated polyethers.

Wasch- und Reinigungsmittel enthalten als unverzichtbare Inhaltsstoffe Tenside für den Wasch- und Reinigungsprozess. Die Tenside als Hauptkomponente beeinflussen in erster Linie das Resultat des Waschprozesses und stellen auch den größten Kostenblock der Inhaltsstoffe dar. Um die Waschleistung zu unterstützen, werden heute bereits eine Vielzahl an Waschhilfsstoffen, wie Buildersubstanzen zur Maskierung der Wasserhärte, Vergrauungs- und Farbübertragungsinhibitoren, Schaumregulatoren, Bleichmittel und Bleichaktivatoren in Haushaltswasch- und Reinigungsmittel eingesetzt. Zu derartigen Hilfsstoffen gehören auch Substanzen, welche die Waschkraft der Tenside verstärken. Solche Substanzen werden oft als "Soil-Release"-Wirkstoffe oder Waschkraftverstärker bezeichnet. Derartige Substanzen weisen in der Regel selbst keine ausgeprägten tensidischen Eigenschaften auf.Detergents and cleaners contain surfactants as indispensable ingredients for the washing and cleaning process. The surfactants as a main component influence primarily the result of the To assist the washing performance, a variety of laundry aids, such as builders to mask the water hardness, graying and color transfer inhibitors, foam regulators, bleaching agents and bleach activators in household washing and cleaning agents are already used today. Such excipients also include substances which enhance the detergency of the surfactants. Such substances are often referred to as "soil-release" agents or detergency boosters. As a rule, such substances themselves have no pronounced surfactant properties.

Beim 53. SEPAWA-Kongress 2006 wurde im Vortrag von Dr. Marie-Elise Chateau die waschkraftverstärkende Wirkung von hydrophoben Polymeren aus Acrylsäure und Styrol vorgestellt. Auch der Vortrag von Prof. Dr. B. Lindman ging auf die Wechselwirkungen von hydrophob modifizierten Polymeren mit Tensiden zur verbesserten Fettentfernung ein (Conference Proceedings 53rd SEPAWA Congress with European Detergents Conference).At the 53rd SEPAWA Congress 2006 Marie-Elise Chateau presented the detergency enhancing effect of hydrophobic polymers of acrylic acid and styrene. Also the lecture of Prof. Dr. med. B. Lindman discussed the interactions of hydrophobically modified polymers with surfactants for improved grease removal (Conference Proceedings 53 rd SEPAWA Congress with European Detergents Conference).

Aus der WO 2006/131197 A1 sind hydrophobe Polymere bestehend aus Styrol, Methacrylsäure, Hydroxyethylmethacrylat und Methylmethacrylat bekannt, die eine sehr gute schmutzablösende Wirkung gerade an baumwollhaltigen Textilien zeigen.From the WO 2006/131197 A1 Hydrophobic polymers consisting of styrene, methacrylic acid, hydroxyethyl methacrylate and methyl methacrylate are known, which show a very good dirt-removing effect especially on cotton-containing textiles.

Die EP 2 065 403 A1 offenbart die Herstellung von Polymeren über Veresterung von Polyacrylsäuren mit Endgruppenverschlossenen Polyolen oder Aminen. Allgemein wird eine mögliche Anwendung als Builder-Komponente zur Härtemaskierung in flüssigen Haushaltwaschmitteln genannt.The EP 2 065 403 A1 discloses the preparation of polymers via esterification of polyacrylic acids with end-capped polyols or amines. In general, a potential application as Builder component for hardness masking in liquid household detergents called.

Der Einsatz von Polyether-Hydroxycarboxylat-Copolymerisaten aus Maleinsäure und Itaconsäure ist aus der EP 1 020 485 B1 bekannt. Die Steigerung der Reinigungseffizienz wird durch Inaktivierung von Härteionen erreicht.The use of polyether-hydroxycarboxylate copolymers of maleic acid and itaconic acid is known from EP 1 020 485 B1 known. The increase in cleaning efficiency is achieved by inactivating hardness ions.

Die Verbesserung der Primärwaschkraft durch Polymere ausgewählt aus N-Vinylcaprolactam, N-Vinylpyrrolidon und weiteren stickstoffhaltigen Monomeren ist aus der DE 10 2011 112 777 A1 bekannt. Es wurde gefunden, dass bestimmte Polymere, welche die Oberflächenspannung von Aniontensid-Lösungen erhöhen, die Primärwaschwirkung verbessern.The improvement of the primary washing power by polymers selected from N-vinylcaprolactam, N-vinylpyrrolidone and other nitrogen-containing monomers is known from the DE 10 2011 112 777 A1 known. It has been found that certain polymers that increase the surface tension of anionic surfactant solutions improve the primary washing effect.

Eine Verbesserung der Primärwaschkraft wird auch in der DE 10 2011 112 778 A1 offenbart. Die Veröffentlichung beschreibt Polymere, welche sich von N, N-Dimethylacrylamid ableiten zur Steigerung der Primärwaschkraft, insbesondere gegenüber öl- und/oder fetthaltigen Anschmutzungen.An improvement of the primary washing power is also in the DE 10 2011 112 778 A1 disclosed. The publication describes polymers which are derived from N, N-dimethylacrylamide for increasing the primary washing power, especially against oily and / or greasy stains.

Die Verwendung von Kammpolymeren in Wasch- und Reinigungsmittel auf Basis Polycarbonsäure, als Polymerhauptkette mit Polyesterseitenketten ist aus der WO 2010/127809 A1 bekannt. Die hier beschriebenen Kammpolymere zeichnen sich durch eine gute "Soil-Release"-Wirkung aus.The use of comb polymers in detergents and cleaners based on polycarboxylic acid, as a polymer backbone with polyester side chains is known from WO 2010/127809 A1 known. The comb polymers described here are characterized by a good "soil release" effect.

Die schmutzablösende Wirkung von Block-Copolymeren aus ethylenisch ungesättigten Monomeren und Alkylenoxid, Alklyenglycolen und cyclischen Ethern ist aus der WO 2003/054044 A1 bekannt.The soil release action of block copolymers of ethylenically unsaturated monomers and alkylene oxide, alkylene glycols, and cyclic ethers is known from US 5,156,367 WO 2003/054044 A1 known.

Im Übersichtsartikel " Polycarboxylates - Essential and Multifunctional" von Herrn R. Ettl, et al. erschienen in Tenside, Surfactants, Detergents 46 (2009 ) werden hydrophil modifizierte Kammpolymere mit Polyethylen-Seitenketten für die Anwendung in Pigmentsystemen als so genannte "Superplasticizer" bezeichnet.In the review article " Polycarboxylates - Essential and Multifunctional "by Mr. R. Ettl, et al., In Tenside, Surfactants, Detergents 46 (2009 ) are hydrophilically modified comb polymers with polyethylene side chains for use in pigment systems referred to as "superplasticizers".

Aus JPH03185184 sowie JP 2005 187 742 sind Waschmittel für die textile Vorbehandlung wie Entschlichten, Abkochen, Bleichen und Seifen offenbart, die Methoxy-PEG-Methacrylat / (Meth)Acrylsäure Copolymere enthalten.Out JPH03185184 such as JP 2005 187 742 Detergents for textile pretreatment such as desizing, scouring, bleaching and soaps are disclosed which contain methoxy-PEG-methacrylate / (meth) acrylic acid copolymers.

US 5,064,563 beschreibt die Herstellung von Salzen von Maleinsäure-Copolymeren mittels radikalischer Polymerisation unter Einsatz von Wasserstoffperoxid als Katalysator. Das erhaltene Salz ist biologisch abbaubar und lässt sich als Builder-Substanz in Waschmitteln einsetzen. US 5,064,563 describes the preparation of salts of maleic acid copolymers by free radical polymerization using hydrogen peroxide as the catalyst. The resulting salt is biodegradable and can be used as a builder in laundry detergents.

US 2005/0113541 offenbart Polymere als Builder-Substanz in Waschmitteln, die Acrylsäure, Methacrylsäure, Acrylsäure PEG Ester und Polyaminpolyether enthalten. US 2005/0113541 discloses polymers as a builder substance in detergents containing acrylic acid, methacrylic acid, acrylic acid PEG esters and polyamine polyethers.

Aus DE 10 225 794 sind sulfonsäurehaltige Copolymere bekannt, die aus mindestens einer monoethylenisch ungesättigen Carbonsäure, mindestens einem sulfonsäuregruppenhaltigen Monomer und mindestens einem nichtionischen Monomer gebildet sind und als Zusatz zu Wasch- und Reinigungsmitteln verwendet werden sollen.Out DE 10 225 794 sulfonic acid-containing copolymers are known which consist of at least one monoethylenically unsaturated carboxylic acid, at least one monomer containing sulfonic acid groups and at least one nonionic monomer are formed and should be used as an additive to detergents and cleaners.

Die Mehrzahl der aus diesem umfangreichen Stand der Technik bekannten Polymere weist den Nachteil auf, dass sie bei Anwendung in der textilen Vorbehandlung zum Waschen und Bleichen von textilen Rohwaren aus natürlichen oder synthetischen Fasern oder Gemischen hiervon, keine oder nur unzureichende Wirksamkeit besitzen. Für einen nachgeschalteten Färbeprozess der gewaschenen oder gebleichten Ware ist eine optimale Wasch- und Reinigungsleistung essentiell. Nur durch eine optimal vorbehandelte Ware ist es möglich, eine gleichmäßige "egale" Färbung zu erzielen.The majority of the polymers known from this extensive prior art have the disadvantage that they have little or no effectiveness when used in textile pretreatment for washing and bleaching textile raw materials made from natural or synthetic fibers or mixtures thereof. For a subsequent dyeing process of the washed or bleached product optimum washing and cleaning performance is essential. Only by optimally pre-treated goods it is possible to achieve a uniform "level" coloration.

Die Prozessbedingungen in der textilen Vorbehandlung von natürlichen oder synthetischen Fasern oder Gemischen hiervon unterscheiden sich grundlegend von den Bedingungen der Haushaltswäsche. So werden Textilveredlungsprozesse im stark sauren Bereich, wie die "Saure Entmineralisierung" bei einem pH-Wert von ca. 2, bis zu stark alkalischen Prozessen, wie "Alkalisches Abkochen", "Kaltbleiche" und "Pad-Steam-Bleiche" bei pH-Werten von 13 bis 14 durchgeführt. Auch die Behandlungstemperaturen in der textilen Vorbehandlung unterscheiden sich deutlich von denen Temperaturen, welche bei der Haushaltswäsche üblich sind. So wird die Mehrzahl der Veredlungsprozesse bei ca. 95 bis 100 °C durchgeführt. In manchen Ländern werden auch Hochtemperaturbleichen bei 110 °C favorisiert.The process conditions in the textile pretreatment of natural or synthetic fibers or mixtures thereof are fundamentally different from the conditions of household laundry. Thus, textile finishing processes in the strongly acidic range, such as the "acid demineralization" at a pH of about 2, up to strongly alkaline processes, such as "alkaline boiling", "cold bleaching" and "pad-steam bleaching" at pH Values from 13 to 14 are performed. The treatment temperatures in the textile pretreatment also differ significantly from those which are usual in household washing. The majority of the finishing processes are carried out at approx. 95 to 100 ° C. In some countries, high-temperature bleaching at 110 ° C is favored.

Neben den Prozessbedingungen unterscheiden sich auch die Schmutzarten fundamental von den Schmutzarten bei der Haushaltswäsche. In der textilen Vorbehandlung müssen die natürlichen Begleitsubstanzen wie Fette, Wachse und die für die Herstellung der synthetischen Fasern oder textilen Flächengebilden verwendete Präparationen, wie Stricköle und Schlichten, entfernt werden.In addition to the process conditions, the types of dirt are also fundamentally different from the types of household waste. In textile pretreatment, the natural must Adjacent substances such as fats, waxes and the preparations used for the production of the synthetic fibers or textile fabrics, such as knitting oils and sizes, are removed.

Die Aufgabe der vorliegenden Erfindung besteht darin, die oben beschriebenen Nachteile in Bezug auf unzureichende Wirksamkeit für die textile Vorbehandlung von natürlichen oder synthetischen Fasern oder Gemischen daraus zu überwinden. Es sollen Polymere bereitgestellt werden, welche Tenside wirksam unterstützen und dadurch eine reduzierte Einsatzmenge an Tensiden für eine optimale Wasch- und Reinigungsleistung ermöglichen.The object of the present invention is to overcome the disadvantages described above with regard to insufficient effectiveness for the textile pretreatment of natural or synthetic fibers or mixtures thereof. It is intended to provide polymers which effectively support surfactants and thereby enable a reduced amount of surfactants to be used for optimum washing and cleaning performance.

Für die alkalische Bleiche mit Wasserstoffperoxid von Rohbaumwolle als Maschen- oder Webware ist es notwendig, die enthaltenen natürlichen Fette und Wachse der Baumwolle, sowie die zur Herstellung verwendeten Präparationen (z.B. Stricköle, Paraffine) wirksam zu entfernen. Zusätzlich sollen die während der Bleiche aus den natürlichen Triglyceriden, gebildeten Kalkseifen effektiv am Wiederaufziehen gehindert werden. Die alkalischen Bleichprozesse werden je nach Verfahren bei pH-Werten zwischen 10 bis 14 und Temperaturen zwischen 80 bis 130 °C durchgeführt. Die Reinigungsleistung wird nach dem Bleichprozess über eine gute und gleichmäßige Hydrophilie (Saugfähigkeit) der Baumwolle geprüft. Der Erfindung liegt daher insbesondere die Aufgabe zugrunde, Polymere mit unter diesen Bedingungen ausgezeichneter waschkraftverstärkender Wirkung bereitzustellen.For the alkaline bleaching with hydrogen peroxide of raw cotton as a knitted or woven fabric, it is necessary to effectively remove the contained natural fats and waxes of the cotton, as well as the preparations used for the preparation (e.g., knitting oils, paraffins). In addition, the lime soaps formed during bleaching from the natural triglycerides are to be effectively prevented from being rebuilt. Depending on the process, the alkaline bleaching processes are carried out at pH values between 10 and 14 and temperatures between 80 and 130 ° C. The cleaning performance is checked after the bleaching process by a good and uniform hydrophilicity (absorbency) of the cotton. The invention is therefore based, in particular, on the problem of providing polymers having an excellent washing-power-enhancing effect under these conditions.

Eine weitere Aufgabe besteht darin, für die Wäsche von elasthanhaltigen Materialien (Maschen- oder Webware) ein Polymer bereitzustellen, welches das zur Herstellung verwendete Silikonöl wirksam entfernt und stabil in der Waschlösung emulgiert.Another object is for the washing of elastane-containing materials (mesh or woven fabric) a polymer which effectively removes the silicone oil used for production and stably emulsifies in the washing solution.

Überraschenderweise wurde gefunden, dass mit hydrophilen Kammpolymeren, die bisher als Betonverflüssiger, sogenannten "Superplasticizer", eingesetzt wurden, die Wirkung von Tensiden für die textile Vorbehandlung signifikant gesteigert werden kann. Die erfindungsgemäß eingesetzten Polymere verstärken die Reinigungsleistung der eingesetzten Tenside in Bezug auf Erhöhung der Schmutzablösung (Primärwaschwirkung) und Reduzierung des Wiederaufziehens des abgelösten Schmutzes (Sekundärwaschwirkung) durch Stabilisierung des Schmutzes in der Waschflotte.Surprisingly, it has been found that the effect of surfactants for textile pretreatment can be significantly increased with hydrophilic comb polymers which were hitherto used as concrete plasticizers, so-called "superplasticizers". The polymers used according to the invention enhance the cleaning performance of the surfactants used in relation to increasing the soil release (primary washing action) and reducing the re-use of the detached soil (secondary washing effect) by stabilizing the soil in the wash liquor.

Gegenstand der Erfindung in einer ersten Ausführungsform ist daher die Verwendung von Kammpolymeren, erhältlich durch

  • A) eine radikalische Polymerisation von monoethylenisch ungesättigten Monomeren
    einer Gruppe A1) monoethylenisch ungesättigter Säuren oder deren Salzen und
    einer Gruppe A2) monoethylenisch ungesättigter Polyether in der textilen Vorbehandlung.
The invention in a first embodiment is therefore the use of comb polymers obtainable by
  • A) a radical polymerization of monoethylenically unsaturated monomers
    a group A1) monoethylenically unsaturated acids or their salts and
    a group A2) monoethylenically unsaturated polyethers in the textile pretreatment.

Die erfindungsgemäß eingesetzten Kammpolymere enthalten somit in der ersten Ausführungsform die Komponenten A1 + A2.The comb polymers used according to the invention thus contain the components A1 + A2 in the first embodiment.

Die Herstellung der erfindungsgemäß eingesetzten Kammpolymere über radikalische Polymerisation ist dem Fachmann bekannt und kann in Anlehnung an die EP 0 537 870 A1 durchgeführt werden.The preparation of the comb polymers used according to the invention via free-radical polymerization is known to the person skilled in the art and can be based on EP 0 537 870 A1 be performed.

Beispiele für die Monomere der Gruppe A1, der monoethylenisch ungesättigte Säuren und deren Salze umfassen Acrylsäure, Methacrylsäure, Crotonsäure, Maleinsäure, Fumarsäure, Itaconsäure, Vinylsulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, 2-Acrylamido-2-methylpropansulfonsäure, Vinylphosphonsäure. Die Monomere der Gruppe A1 können einzelnen oder als Mischung verschiedener Monomere in einer Menge von 5 bis 95 Gew.-%, insbesondere mit einer Menge 10 bis 90 Gew.-% bezogen auf das Polymer eingesetzt werden. Bevorzugt werden Acrylsäure, Methacrylsäure und Maleinsäure und besonders bevorzugt wird Acrylsäure oder Methacrylsäure.Examples of the monomers of group A1, the monoethylenically unsaturated acids and their salts include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, Vinylphosphonic. The monomers of group A1 can be used individually or as a mixture of different monomers in an amount of 5 to 95 wt .-%, in particular with an amount of 10 to 90 wt .-% based on the polymer. Preference is given to acrylic acid, methacrylic acid and maleic acid and particular preference is given to acrylic acid or methacrylic acid.

Beispiele für die Monomere der Gruppe A2, der monoethylenisch ungesättigte Polyether umfassen Polyethylenglycolmonoallylether, Polypropylenglycolmonoallylether und Polyethylen-Polypropylenmonoallylether; diese sind beispielsweise von der Firma Clariant unter der Produktreihe Polyglykol® A und von der Firma BASF unter der Produktreihe Pluriol® A ... R kommerziell erhältlich. Weitere Beispiele umfassen Polyethylenglycolmonovinylether (Produktreihe der Firma Clariant: Polyglycol® R), Isoprenylethoxilate (Produktreihe der Firma BASF: Pluriol® A ... I) und Vinyloxybutylethoxilate (Produktreihe der Firma BASF: Pluriol® A ... V).Examples of the monomers of the group A2, the monoethylenically unsaturated polyethers include polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether and polyethylene-polypropylene monoallyl ether; these are commercially available, for example, from Clariant under the Polyglykol® A product line and from BASF under the Pluriol® A ... R product line. Further examples include polyethylene glycol monovinyl ether (product series from Clariant: Polyglycol® R), isoprenyl ethoxylates (product series from BASF: Pluriol® A ... I) and vinyloxybutyl ethoxylates (product series from BASF: Pluriol® A ... V).

Die Monomere der Gruppe A2 können einzelnen oder als Mischung verschiedener Monomere in einer Menge von 2 bis 25 Gew.-% bezogen auf das Polymer, insbesondere in einer Menge 5 bis 20 Gew.-% bezogen auf das Polymer eingesetzt werden. Bevorzugt werden Polyalkylglycolmonoallylether, besonders bevorzugt wird Polyethylenglycolmonoallylether und Polyethylen-Polypropylenmonoallylether.The monomers of group A2 can be used individually or as a mixture of different monomers in an amount of from 2 to 25% by weight, based on the polymer, in particular in an amount of from 5 to 20% by weight, based on the polymer. Polyalkyl glycol monoallyl ethers are preferred, and polyethylene glycol monoallyl ether and polyethylene-polypropylene monoallyl ether are particularly preferred.

Die erfindungsgemäße Verwendung kann im Rahmen eines Wasch-, Abkoch-, Enzym-, Entschlichtungs-, Entmineralisierungs- oder Bleichprozess in einem kontinuierlicher oder diskontinuierlichen Produktionsverfahren derart erfolgen, dass man das Kammpolymer einer waschmittelhaltigen Flotte separat zusetzt, oder das Kammpolymer als Bestandteil des Waschmittels in die Flotte einbringt. Ein weiterer Gegenstand der Erfindung ist daher ein Waschmittel für die textile Vorbehandlung von natürlichen oder synthetischen Fasern oder Gemischen daraus, das 0,1 bis 20 Gew.-%, insbesondere 0,5 bis 15 Gew.-%, eines entsprechenden Kammpolymers enthält.The use according to the invention can be carried out as part of a washing, decoction, enzyme, desizing, demineralization or bleaching process in a continuous or discontinuous production process such that the comb polymer is added separately to a detergent-containing liquor, or the comb polymer as a constituent of the detergent in bring in the fleet. Another object of the invention is therefore a detergent for the textile pretreatment of natural or synthetic fibers or mixtures thereof, which contains 0.1 to 20 wt .-%, in particular 0.5 to 15 wt .-%, of a corresponding comb polymer.

Waschmittel, die das erfindungsgemäß eingesetzte Kammpolymer enthalten, können alle üblichen sonstigen Bestandteile derartiger Mittel enthalten, welche nicht in unerwünschter Weise mit diesem wechselwirken.Detergents containing the comb polymer used in the invention may contain all the usual ingredients of such agents which do not undesirably interact with it.

In einer bevorzugten Ausführungsform enthält ein solches Waschmittel Tenside, wie Fettalkoholalkoxilate, Fettsäurealkoxilate, Fettalkylpolyglycoside, Fettaminalkoxilate und/oder Fettsäureamide aus dem Bereich der nichtionogenen Tenside. Aus dem Bereich der anionischen Tenside können Alkylcarboxilate, Alkylethercarboxilate, Alkansulfate, Alkanethersulfate, Alkansulfonate, Alkylphosphate, Alkyletherphosphate, Tauride und/oder Sarkoside verwendet werden.In a preferred embodiment, such a detergent contains surfactants, such as fatty alcohol alkoxylates, fatty acid alkoxylates, fatty alkyl polyglycosides, fatty amine alkoxylates and / or fatty acid amides from the field of nonionic surfactants. From the field of anionic surfactants, it is possible to use alkylcarboxylates, alkyl ether carboxylates, alkane sulfates, alkane ether sulfates, alkane sulfonates, alkyl phosphates, alkyl ether phosphates, taurides and / or sarcosides.

Zusätzlich können die Mittel weitere in Wasch- und Reinigungsmittel übliche Bestandteile, wie

  • ▪ Enzyme, beispielsweise Amylasen, Cellulasen, Lipasen, Pektinasen, Laccasen und Proteasen
  • ▪ Bleichaktivatoren und/oder Bleichkatalysatoren
  • ▪ Komplexbildner für Schwermetalle, beispielsweise Polyphosphonsäuren, Aminophosphonsäuren, Phosphonopolycarbonsäuren, Aminopolycarbonsäuren und/oder Hydroxycarbonsäuren
  • ▪ Farbübertragungsinhibitoren, beispielsweise Polyvinylpyrrolidon, Copolymere aus Vinylpyrrolidon und Vinylimidazol oder Polyvinylpyridin-N-oxid
  • ▪ Entlüftungs- und/oder Schaumdämpfungsmittel, beispielsweise Organopolysiloxane
  • ▪ Anorganische Magnesium-Salze, beispielsweise Magnesiumsulfat, Magnesiumchlorid oder Magnesiumoxid
  • ▪ Anorganische Builder-Substanzen, beispielsweise Wasserglas, Schichtsilikate oder Zeolithe
  • ▪ Lösungsmittel und/oder Lösungsvermittler, beispielsweise Dipropylenglykolmonomethylether, Butyldiglycol, Butyltriglycol und/oder weitere niedere Glycole und abgeleitete Ether daraus.
  • ▪ Optische Aufheller, beispielsweise Stilbenderivate enthalten.
In addition, the agents may contain other ingredients commonly used in detergents and cleaners, such as
  • ▪ Enzymes, for example amylases, cellulases, lipases, pectinases, laccases and proteases
  • ▪ bleach activators and / or bleach catalysts
  • Complexing agents for heavy metals, for example polyphosphonic acids, aminophosphonic acids, phosphonopolycarboxylic acids, aminopolycarboxylic acids and / or hydroxycarboxylic acids
  • ▪ Color transfer inhibitors, for example polyvinylpyrrolidone, copolymers of vinylpyrrolidone and vinylimidazole or polyvinylpyridine N-oxide
  • ▪ deaerating and / or foam-damping agents, for example organopolysiloxanes
  • Inorganic magnesium salts, for example magnesium sulfate, magnesium chloride or magnesium oxide
  • ▪ Inorganic builder substances, such as water glass, phyllosilicates or zeolites
  • Solvents and / or solubilizers, for example dipropylene glycol monomethyl ether, butyl diglycol, butyl triglycol and / or further lower glycols and derived ethers thereof.
  • ▪ Optical brighteners, such as stilbene derivatives.

Die nachfolgenden Beispiele verdeutlichen die Vorteile der beanspruchten KammpolymereThe following examples illustrate the advantages of the claimed comb polymers

Ausführungsbeispiele:EXAMPLES 1. Herstellung Kammpolymere:1. Preparation of comb polymers: Synthesebeispiel 1 (Radikalische Polymerisation):Synthetic Example 1 (Radical Polymerization):

In einem 2-Liter-Vierhalskolben mit Thermometer, Rückflusskühler und Anschlüsse für Zuläufe und Inertgas-Spülung wurden 328 g Wasser, 61 g (0,06 mol) Polyalkylenglycol-1000-monoallylether (Polyglycol® A 31/1000, Clariant) sowie 5 g Butyldiglykol, als Lösungsvermittler, vorgelegt. Getrennt davon wurden folgende Mischungen angesetzt: Monomer-Lösung: 365 g (5,07 mol) Acrylsäure in 65 g Wasser. Lösung 1: 10 g Natriumpersulfat in 80 g Wasser. Lösung 2: 26 g Natriumhypophosphit x 1 H2O in 60 g Wasser. Die Vorlage wurde auf 90 °C erwärmt. Bei dieser Temperatur wurden die oben aufgeführten Lösungen über separate Zuläufe mit einem konstanten Massenstrom über 3 Stunden (Monomer- und Lösung 2) und über 3,5 h (Lösung 1) zudosiert. Nach Zugabeende wurde 1 Stunde bei 90 °C nachreagiert. Man erhielt eine klare, farblose, wässrige Polymerlösung mit einem Feststoffgehalt von 46 Gew.-%.In a 2-liter four-necked flask equipped with thermometer, reflux condenser and feed and inert gas purge ports were added 328 g of water, 61 g (0.06 mol) of polyalkylene glycol 1000 monoallyl ether (Polyglycol® A 31/1000, Clariant) and 5 g Butyl diglycol, as a solubilizer submitted. Separately, the following mixtures were prepared: Monomer solution: 365 g (5.07 mol) of acrylic acid in 65 g of water. Solution 1: 10 g of sodium persulfate in 80 g of water. Solution 2: 26 g of sodium hypophosphite x 1 H 2 O in 60 g of water. The original was heated to 90 ° C. At this temperature, the above solutions were added via separate feeds with a constant mass flow over 3 hours (monomer and solution 2) and over 3.5 hours (solution 1). added. After the end of addition, the reaction was continued at 90 ° C. for 1 hour. A clear, colorless, aqueous polymer solution having a solids content of 46% by weight was obtained.

In analoger weise wurden die in Tabelle 1 aufgeführten Kammpolymere hergestellt. Tabelle 1: Kammpolymer Monoethylenisch ungesättigte Polyether Menge [g] Monoethylenisch ungesättigte Säure Menge [g] KP-1 Polyglycol® A 31/1000 61 Acrylsäure 365 KP-2 Polyglycol® A 11/1800 61 Acrylsäure 365 KP-3 Pluriol® A 10 R 61 Acrylsäure 365 KP-4 Polyglycol® A 1100 61 Acrylsäure 365 In an analogous manner, the comb polymers listed in Table 1 were prepared. Table 1: comb polymer Monoethylenically unsaturated polyethers Quantity [g] Monoethylenically unsaturated acid Quantity [g] KP-1 Polyglycol® A 31/1000 61 acrylic acid 365 KP-2 Polyglycol® A 11/1800 61 acrylic acid 365 KP-3 Pluriol® A 10 R 61 acrylic acid 365 KP-4 Polyglycol® A 1100 61 acrylic acid 365

Bei allen erfindungsgemäßen Beispielen wurde der Gehalt an Restmonomer für die Seitenketten halbquantitative über Dünnschichtchromatographie bestimmt. Die Resultate an Restmonomer lagen immer unter 0,5 Gew.-% in der Polymer-Lösung.In all the examples according to the invention, the content of residual monomer for the side chains was determined semiquantitatively by thin-layer chromatography. The residual monomer results were always below 0.5% by weight in the polymer solution.

2. Anwendung Kammpolymere2. Application comb polymers Anwendungsbeispiel 1: (Diskontinuierliche Bleiche bei 98 °C)Use Example 1: (Discontinuous bleaching at 98 ° C)

Eine Rohbaumwoll-Trikot-Maschenware mit einem Grundweiß von 17 Berger-Einheiten wurde in einem Labomat der Firma Mathis 30 Minuten bei 98 °C gebleicht. Das Flottenverhältnis betrug 1:10 und das eingesetzte Wasser hatte eine eingestellte Wasserhärte von 5 °dH, eingestellt mit CaCl2 x 2 H2O. Der Heiz- bzw. Kühlgradient betrug 3 °C / min. Anschließend wurde die Ware für 10 min bei 80 °C gespült, danach mit 0,5 g/L Essigsäure 60% für 10 min bei 30 °C neutralisiert und ein weiteres Mal für 10 min bei 30 °C gespült. Am Ende wurde die Ware 30 Sekunden geschleudert und 30 Sekunden bei einer Oberflächentemperatur von 120 °C im Spannrahmen getrocknet. Die Bleichrezepturen sind in Tabelle 4.1 und die zugehörigen Ergebnisse bezüglich Weißgrad und Saugfähigkeit der Ware in Tabelle 4.2 aufgeführt.A raw cotton jersey knit fabric with a base white of 17 Berger units was bleached in a Labomat from Mathis for 30 minutes at 98 ° C. The liquor ratio was 1:10 and the water used had a set water hardness of 5 ° dH, adjusted with CaCl 2 × 2 H 2 O. The heating or cooling gradient was 3 ° C / min. Subsequently, the product was rinsed for 10 min at 80 ° C, then neutralized with 0.5 g / L acetic acid 60% for 10 min at 30 ° C and rinsed once more for 10 min at 30 ° C. At the end, the product was spun for 30 seconds and dried for 30 seconds at a surface temperature of 120 ° C in the tenter. The bleaching formulations are shown in Table 4.1 and the associated whiteness and absorbency results for the product in Table 4.2.

Die Saugfähigkeit, auch als Hydrophilie bezeichnet, der Ware ist abhängig von der Reinigungsleistung des eingesetzten Waschmittels. Sie wird geprüft mit Hilfe des TEGEWA-Tropftests, in dem die Zeit gemessen wird, die ein angefärbter Wassertropfen zum Einsinken in das Textil benötigt. Die exakte Beschreibung ist in der Zeitschrift Melliand Textilberichte 68 (1987), Seite 581-583 veröffentlicht. Eine besser differenzierende Methode ist die Bestimmung der Saugfähigkeit nach dem Steighöhenverfahren nach DIN 53924.The absorbency, also referred to as hydrophilicity, the product is dependent on the cleaning performance of the detergent used. It is tested using the TEGEWA Drip Test, which measures the amount of time a stained drop of water needs to sink into the fabric. The exact description is in the Journal Melliand Textilberichte 68 (1987), pages 581-583 released. A better differentiating method is the determination of absorbency according to the riser method according to DIN 53924.

Als Tenside wurde Lutensol® AO 5 und Lutensol® AO 7 der Firma BASF, C13/15-Fettalkoholethoxilate mit 5 bzw. 7 mol Ethylenoxid eingesetzt. Die Kammpolymere wurden als Polymer-Lösungen mit einem Feststoffgehalt von 46 Gew.-% eingesetzt. Als Vergleichspolymer V-1 wurde Sokalan® PA 25 CL PN der Firma BASF, ein Acrylsäure-Homopolymer mit einem durchschnittlichen Molekulargewicht von 4.000 g/mol und einem Feststoffgehalt von 49 Gew.-% und als Vergleichspolymer V-2 wurde Alcosperse® 747 der Firma Akzo Nobel, ein hydrophob modifiziertes Copolymer mit einem durchschnittlichen Molekulargewicht von 3.000 g/mol und einem Feststoffgehalt von 40 Gew.-% eingesetzt. Tabelle 4.1: Bleichrepturen Nr. 1 Nr. 2 Nr. 3 Nr. 4 Nr. 5 Nr. 6 Nr. 7 Nr. 8 Nr. 9 Lutensol® AO 5 g/L 0,6 0,7 0,8 KP-1 g/L 0,06 KP-2 g/L 0,06 KP-3 g/L 0,06 KP-4 g/L 0,06 V-1 g/L 0,06 V-2 g/L 0,06 NaOH 50% g/L 2,0 H2O2 35% g/L 2,3 Blefchrezepturen Nr. 10 Nr. 11 Nr. 12 Nr. 13 Nr. 14 Nr. 15 Nr. 16 Nr. 17 Nr. 18 Lutensol® AO 7 g/L 0,6 0,7 0,8 KP-1 g/L 0,06 KP-2 g/L 0,06 KP-3 g/L 0,06 KP-4 g/L 0,06 V-1 g/L 0,06 V-2 g/L 0,06 NaOH 50% g/L 2,0 H2O2 35% g/L 2,3 Tabelle 4.2: Bleichergebnisse Nr. 1 Nr. 2 Nr. 3 Nr. 4 Nr. 5 Nr. 6 Nr. 7 Nr. 8 Nr. 9 Grundweiß [Berger] 64 66 66 67 65 64 63 65 65 Tropftest [sec] 35 2 3 2 1 25 40 20 2 Steighöhe nach 30 sec [mm] 0 6 3 4 9 1 0 2 11 60 sec [mm] 0 11 5 8 19 3 0 4 20 90 sec [mm] 3 21 10 15 28 5 2 8 29 300 sec [mm] 8 41 25 30 47 14 5 18 48 Bleichergebnisse Nr. 10 Nr. 11 Nr. 12 Nr. 13 Nr. 14 Nr. 15 Nr. 16 Nr. 17 Nr. 18 Grundweiß [Berger] 65 67 67 66 66 65 63 66 67 Tropftest [sec] 55 6 5 6 4 35 72 30 6 Steighöhe nach 30 sec [mm] 0 2 3 4 5 0 0 0 5 60 sec [mm] 0 8 8 9 10 0 0 2 12 90 sec [mm] 1 13 14 16 17 3 0 5 18 300 sec [mm] 5 25 25 26 28 7 3 10 30 The surfactants used were Lutensol® AO 5 and Lutensol® AO 7 from BASF, C 13/15 fatty alcohol ethoxylates with 5 or 7 mol of ethylene oxide. The comb polymers were used as polymer solutions with a solids content of 46% by weight. As comparison polymer V-1 was Sokalan® PA 25 CL PN from BASF, an acrylic acid homopolymer having an average molecular weight of 4,000 g / mol and a solids content of 49% by weight and Comparative Polymer V-2 was Alcosperse® 747 from Akzo Nobel, a hydrophobically modified copolymer having an average molecular weight of 3,000 g / mol and a solids content of 40 wt .-% used. Table 4.1: Bleichrepturen number 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 Lutensol® AO 5 g / L 0.6 0.7 0.8 KP-1 g / L 0.06 KP-2 g / L 0.06 KP-3 g / L 0.06 KP-4 g / L 0.06 V-1 g / L 0.06 V-2 g / L 0.06 NaOH 50% g / L 2.0 H 2 O 2 35% g / L 2.3 Blefchrezepturen No. 10 No. 11 No. 12 No. 13 No. 14 No. 15 No. 16 No. 17 No. 18 Lutensol® AO 7 g / L 0.6 0.7 0.8 KP-1 g / L 0.06 KP-2 g / L 0.06 KP-3 g / L 0.06 KP-4 g / L 0.06 V-1 g / L 0.06 V-2 g / L 0.06 NaOH 50% g / L 2.0 H 2 O 2 35% g / L 2.3 bleaching results number 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 basic White [Berger] 64 66 66 67 65 64 63 65 65 drop test [Sec] 35 2 3 2 1 25 40 20 2 Climbing height after 30 sec [Mm] 0 6 3 4 9 1 0 2 11 60 sec [Mm] 0 11 5 8th 19 3 0 4 20 90 sec [Mm] 3 21 10 15 28 5 2 8th 29 300 sec [Mm] 8th 41 25 30 47 14 5 18 48 bleaching results No. 10 No. 11 No. 12 No. 13 No. 14 No. 15 No. 16 No. 17 No. 18 basic White [Berger] 65 67 67 66 66 65 63 66 67 drop test [Sec] 55 6 5 6 4 35 72 30 6 rising height to 30 sec [Mm] 0 2 3 4 5 0 0 0 5 60 sec [Mm] 0 8th 8th 9 10 0 0 2 12 90 sec [Mm] 1 13 14 16 17 3 0 5 18 300 sec [Mm] 5 25 25 26 28 7 3 10 30

Anwendungsbeispiel 2: (Diskontinuierliche Bleiche bei 110 °C)Application example 2: (discontinuous bleaching at 110 ° C.)

In Anlehnung an Anwendungsbeispiel 1 wurde die Bleichtemperatur auf 110 °C erhöht und die Bleichdauer auf 10 Minuten verkürzt. Spül-, Neutralisations- und Trocknungsprozesse wurden beibehalten. Die Bleichrezepturen sind in Tabelle 5.1 und die zugehörigen Ergebnisse bezüglich Weißgrad und Saugfähigkeit der Ware in Tabelle 5.2 aufgeführt. Tabelle 5.1: Bleichrezepturen Nr. 1 Nr. 2 Nr. 3 Nr. 4 Nr. 5 Nr. 6 Nr. 7 Nr. 8 Nr. 9 Lutensol AO® 5 g/L 0,5 0,6 0,7 KP-1 g/L 0,05 KP-2 g/L 0,05 KP-3 g/L 0,05 KP-4 g/L 0,05 V-1 g/L 0,05 V-2 g/L 0,05 NaOH 50% g/L 3,0 H2O2 35% g/L 2,0 Tabelle 5.2: Bleic hergebnisse Nr. 1 Nr. 2 Nr. 3 Nr. 4 Nr. 5 Nr. 6 Nr. 7 Nr. 8 Nr. 9 Grundweiß [Berg er] 69 70 71 70 72 69 68 71 72 Tropftest [sec] 5 2 1 2 1 4 10 2 1 Steighöhe nach 30 sec [mm] 16 31 32 30 33 25 12 28 34 60 sec [mm] 18 38 38 35 39 30 15 34 40 90 sec [mm] 20 42 40 38 42 34 18 38 43 300 sec [mm] 27 59 59 55 61 45 24 50 61 Following Example of Use 1, the bleaching temperature was increased to 110 ° C and the bleaching time was shortened to 10 minutes. Rinsing, neutralization and drying processes were maintained. The bleach formulas are listed in Table 5.1 and the associated whiteness and absorbency results are shown in Table 5.2. Table 5.1: bleach recipes number 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 Lutensol AO® 5 g / L 0.5 0.6 0.7 KP-1 g / L 0.05 KP-2 g / L 0.05 CP-3 g / L 0.05 KP-4 g / L 0.05 V-1 g / L 0.05 V-2 g / L 0.05 NaOH 50% g / L 3.0 H 2 O 2 35% g / L 2.0 Bleic results number 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 basic White [Mountain he] 69 70 71 70 72 69 68 71 72 drop test [Sec] 5 2 1 2 1 4 10 2 1 Climbing height after 30 sec [Mm] 16 31 32 30 33 25 12 28 34 60 sec [Mm] 18 38 38 35 39 30 15 34 40 90 sec [Mm] 20 42 40 38 42 34 18 38 43 300 sec [Mm] 27 59 59 55 61 45 24 50 61

Anwendungsbeispiel 3: (Kalt-Bleiche bei 30 °C)Use Example 3: (Cold bleaching at 30 ° C.)

Eine Rohbaumwoll-Frotteeware mit einem Grundweiß von 21 Berger-Einheiten wurde mit einer Flottenaufnahme von 100% foulardiert und anschließend 20 Stunden bei 30 °C verweilt. Anschließend wurde die Ware zweimal für 10 min bei 95 °C gespült, danach einmal für 10 min bei 80 °C und am Ende mit 2 mL/kg Essigsäure 60% für 10 min bei 30 °C neutralisiert. Nach den Spülprozessen wurde die Ware 30 Sekunden geschleudert und 30 Sekunden bei einer Oberflächentemperatur von 120 °C im Spannrahmen getrocknet. Die Bleichrezepturen und die zugehörigen Ergebnisse bezüglich Weißgrad und Saugfähigkeit der Ware sind in Tabelle 6 aufgeführt. Tabelle 6: Bleichrezepturen Nr. 1 Nr. 2 Nr. 3 Nr. 4 Nr. 5 Nr. 6 Nr. 7 Nr. 8 Nr. 9 Lutensol® AO 7 g/L 1,2 1,8 2,4 1,2 1,8 2,4 1,2 1,8 2,4 KP-4 g/L 0,048 0,072 0,096 V-1 g/L 0,048 0,072 0,096 NaOH 50% g/L 60 H2O2 35% g/L 100 Bleichergebnisse Nr. 1 Nr. 2 Nr. 3 Nr. 4 Nr. 5 Nr. 6 Nr. 7 Nr. 8 Nr. 9 Grundweiß [Berger] 61 63 66 63 65 67 62 63 66 Tropftest [sec] > 300 12 1 12 3 1 130 10 1 A raw cotton terry cloth with a base white of 21 Berger units was padded with a liquor pick-up of 100% and then dwelt for 20 hours at 30 ° C. Subsequently, the product was rinsed twice for 10 min at 95 ° C, then once for 10 min at 80 ° C and finally neutralized with 2 mL / kg of acetic acid 60% for 10 min at 30 ° C. After the rinsing processes, the product was spun for 30 seconds and dried for 30 seconds at a surface temperature of 120 ° C. in the tenter. The bleaching formulations and the associated whiteness and absorbency results of the product are shown in Table 6. Table 6: bleach recipes number 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 Lutensol® AO 7 g / L 1.2 1.8 2.4 1.2 1.8 2.4 1.2 1.8 2.4 KP-4 g / L 0.048 0.072 0.096 V-1 g / L 0.048 0.072 0.096 NaOH 50% g / L 60 H 2 O 2 35% g / L 100 bleaching results number 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 basic White [Berger] 61 63 66 63 65 67 62 63 66 drop test [Sec] > 300 12 1 12 3 1 130 10 1

Aus den Resultaten der Beispiele 1 bis 3 ist die signifikante waschkraftverstärkende Wirkung der Kammpolymere klar zu erkennen. Durch die Verwendung der Kammpolymere, kann gegenüber einer Verwendung von reinem Tensid eine Einsparung von > 20% realisiert werden. Durch die geringe Einsatzmenge der Kammpolymere können damit die Kosten signifikant reduziert werden.From the results of Examples 1 to 3, the significant washing power enhancing effect of the comb polymers can be clearly seen. By using the comb polymers, a savings of> 20% can be realized compared to a use of pure surfactant. Due to the small amount of comb polymers used, the costs can be significantly reduced.

Claims (7)

  1. Use of comb polymers obtainable by free-radical polymerization of monoethylenically unsaturated monomers of a group A1) of monoethylenically unsaturated acids and salts thereof; and
    a group A2) of monoethylenically unsaturated polyethers
    in textile pretreatment.
  2. The use according to claim 1 for enhancing the cleaning performance of detergents in textile pretreatment.
  3. The use according to claim 1 or 2 for enhancing the cleaning performance in textile finishing, especially in washing, kier boiling, enzyme, desizing, demineralizing or bleaching process in a continuous or discontinuous process.
  4. The use according to claim 2 or 3, characterized in that textiles made from natural or synthetic fibers or mixtures thereof are employed.
  5. A detergent for textile pretreatment of natural or synthetic fibers or mixtures thereof, characterized by containing from 0.1 to 20% by weight, especially from 0.5 to 15% by weight, of the detergency-boosting comb polymer as defined in claim 1.
  6. The detergent according to claim 5, characterized in that it further contains a surfactant ingredient, and said surfactant ingredient is selected from non-ionogenic and anionic surfactants.
  7. The detergent according to either of claims 5 or 6, characterized by containing a complexing agent ingredient selected from phosphonic acids, especially HEDP, ATMP and/or DTPMP, phosphonopolycarboxylic acids, especially PBTC, aminopolycarboxylic acids, especially MGDA, GLDA, IDS and/or EDDS, and/or hydroxycarboxylic acids, especially gluconic acid and/or citric acid.
EP14718618.3A 2013-04-29 2014-04-22 Comb polymers as detergency boosters in detergent compositions Active EP2992075B1 (en)

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DE102013207778.5A DE102013207778A1 (en) 2013-04-29 2013-04-29 Comb polymers as detergency booster for detergents and cleaners
PCT/EP2014/058131 WO2014177423A1 (en) 2013-04-29 2014-04-22 Comb polymers as detergency boosters for washing and cleaning agents

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EP2992075B1 true EP2992075B1 (en) 2018-10-31

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EP14718618.3A Active EP2992075B1 (en) 2013-04-29 2014-04-22 Comb polymers as detergency boosters in detergent compositions

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CN (1) CN105102604B (en)
BR (1) BR112015027088B1 (en)
DE (1) DE102013207778A1 (en)
ES (1) ES2707956T3 (en)
MX (1) MX2015015006A (en)
TR (1) TR201816403T4 (en)
WO (1) WO2014177423A1 (en)

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DE102017200430A1 (en) * 2017-01-12 2018-07-12 CHT Germany GmbH Deposition prevention in pulp production after the sulphate process (power digestion)
CN112708068B (en) * 2020-12-21 2022-08-09 杭州有氧品牌管理有限公司 Water-soluble comb-shaped polymer supramolecular system and application thereof

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CN105102604A (en) 2015-11-25
WO2014177423A1 (en) 2014-11-06
EP2992075A1 (en) 2016-03-09
DE102013207778A1 (en) 2014-10-30
BR112015027088A2 (en) 2017-07-25
BR112015027088B1 (en) 2021-09-21
TR201816403T4 (en) 2018-11-21
ES2707956T3 (en) 2019-04-08
CN105102604B (en) 2018-08-07
MX2015015006A (en) 2016-03-09

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