EP0637627A2 - Detergent formulations - Google Patents

Detergent formulations Download PDF

Info

Publication number
EP0637627A2
EP0637627A2 EP94109139A EP94109139A EP0637627A2 EP 0637627 A2 EP0637627 A2 EP 0637627A2 EP 94109139 A EP94109139 A EP 94109139A EP 94109139 A EP94109139 A EP 94109139A EP 0637627 A2 EP0637627 A2 EP 0637627A2
Authority
EP
European Patent Office
Prior art keywords
weight
detergent formulations
formulations according
acid
detergent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP94109139A
Other languages
German (de)
French (fr)
Other versions
EP0637627A3 (en
EP0637627B1 (en
Inventor
Rudolf Beck
Frank Dr. Krause
Udo Dr. Schoenkaes
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Stockhausen GmbH and Co KG
Original Assignee
Chemische Werke Huels AG
Chemische Fabrik Stockhausen GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemische Werke Huels AG, Chemische Fabrik Stockhausen GmbH filed Critical Chemische Werke Huels AG
Publication of EP0637627A2 publication Critical patent/EP0637627A2/en
Publication of EP0637627A3 publication Critical patent/EP0637627A3/en
Application granted granted Critical
Publication of EP0637627B1 publication Critical patent/EP0637627B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the invention relates to detergent formulations which are free of phosphates, zeolites and crystalline phyllosilicates and which contain polymers with biodegradability as builder substances.
  • the function of the detergent builder is mainly to eliminate the calcium and magnesium ions from the water or the dirt by complexing, dispersing and sequestering from the washing process and to support the washing action of the surfactants.
  • the builders prevent tissue deposits, reduce the incrustation of the textiles and improve the primary washing effect.
  • the zeolites or crystalline layered silicates contained in the abovementioned agents are not environmentally hazardous, but they do Disadvantage that they contribute to a significant increase in the amount of sewage sludge. For this reason, attempts have been made in the past to also dispense with the use of water-softening silicates in phosphate-free detergent powders.
  • formulations which contain surfactants, biodegradable copolymers, washing alkalis, adjusting agents and other functional auxiliaries.
  • the detergents according to the invention can contain anionic, nonionic or cationic surfactants a.
  • anionic, nonionic or cationic surfactants a In Central Europe, mixtures of anionic and nonionic products are typically used, which show synergistic washing effects and are often combined with soaps. However, only anionic or nonionic surfactants can also be used.
  • the amount of surfactant a is preferably 5 to 40% by weight, with contents of 7 to 25% by weight being very particularly preferred.
  • Sulfonate type surfactants are e.g. B. C11-C13 alkylbenzenesulfonates, C13-C17 alkanesulfonates and ester sulfonates with chain lengths of 12 to 20 carbon atoms.
  • Suitable surfactants of the sulfate type are, for example, the sulfuric acid monoesters from fatty alcohols of synthetic and native origin, such as. B. coconut oil alcohol, tallow fatty alcohol, oleyl alcohol or C10-C20 oxo alcohols.
  • fatty alcohol ether sulfates such as. B. lauryl ether sulfate can be used.
  • anionic surfactants are also soaps, for. B. saturated fatty acid soaps, such as the alkali or alkanolamine soaps of lauric acid, myristic acid, palmitic acid and stearic acid.
  • Natural fatty acids e.g. B. from coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • Suitable nonionic surfactants are, for example, adducts of ethylene oxide and / or propylene oxide with alkylphenols, oxo alcohols or native fatty alcohols, fatty acids, fatty amines and fatty acid amides.
  • alkylphenols oxo alcohols or native fatty alcohols
  • fatty acids fatty acids
  • fatty amines and fatty acid amides fatty acid amide
  • the addition products of 3 to 15 mol of ethylene oxide with coconut oil and tallow fatty alcohols, with oleyl alcohol or with synthetic alcohols with 8 to 18 carbon atoms are particularly important.
  • surfactants of the type of C8-C18 alkyl polyglucosides such as. B. C10-C12 and C12-C16 alkyl polyglucosides, and amine oxides can be used.
  • cationic surfactants and amphoteric products such as ampholytes and betaines can also be used.
  • the detergents according to the invention also contain the copolymers b.
  • the amount of b is preferably 5 to 40% by weight, proportions of 5 to 20% by weight being very preferably set.
  • Monomers of group A are monoethylenically unsaturated C4-C8 dicarboxylic acids, their anhydrides or their alkali and / or ammonium salts and / or amine salts.
  • Suitable dicarboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid and methylene malonic acid.
  • Maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the corresponding sodium, potassium or ammonium salts of maleic or itaconic acid are preferably used.
  • the group A monomers are preferably present in the monomer mixture in an amount of 10 to 70% by weight, more preferably 20 to 60% by weight and very particularly preferably 25 to 55% by weight.
  • Monomers of group B are monoethylenically unsaturated C3-C10 monocarboxylic acids and their alkali and / or ammonium salts and / or amine salts. These monomers include, for example, acrylic acid, methacrylic acid, dimethylacrylic acid, ethyl acrylic acid, vinyl acetic acid and allylacetic acid. From this group of monomers, preference is given to using acrylic acid, methacrylic acid, their mixtures and the sodium, potassium or ammonium salts or mixtures thereof.
  • the group B monomers are preferably 20 to 85% by weight, particularly preferably 25 up to 60% by weight and very particularly preferably 30 to 60% by weight, are present in the monomer mixture.
  • the group C monomers include those which, after copolymerization and subsequent hydrolysis or saponification of the polymer, release one or more hydroxyl groups which are covalently bonded directly to the C-C polymer carbon chain. Examples include: vinyl acetate, vinyl propionate, methyl vinyl acetate, methyl vinyl ether, ethylene glycol monovinyl ether and vinylidene carbonate.
  • the group C monomers are preferably present in the monomer mixture in an amount of 1 to 50% by weight, particularly preferably 4 to 40% by weight and very particularly preferably 8 to 30% by weight.
  • group D monomers that can be used to modify the copolymers are, for. B. sulfone groups and sulfate group-containing monomers, such as meth (allylsulfonic acid), vinylsulfonic acid, styrene sulfonic acid, acrylamidomethylpropanesulfonic acid and monomers containing phosphonic acid groups, such as vinylphosphonic acid, allylphosphonic acid and acrylamidomethylpropanephosphonic acid and their salts, and hydroxyethyl (meth) acrylate sulfates, allyl sulfates.
  • sulfone groups and sulfate group-containing monomers such as meth (allylsulfonic acid), vinylsulfonic acid, styrene sulfonic acid, acrylamidomethylpropanesulfonic acid and monomers containing phosphonic acid groups, such as vinylphosphonic acid, allylphosphonic acid and acrylamidomethylpropan
  • group D monomers it is also possible - because of the required solubility, but only in a limited amount - to use double-ethylenically unsaturated non-conjugated compounds and polyalkylene glycol esters of (meth) acrylic acid and polyalkylene glycol ether with (meth) allyl alcohol, which may or may not be end-capped.
  • the group D monomers are optionally present in the monomer mixture up to 15% by weight, preferably up to 10% by weight.
  • the copolymers can be prepared by radical polymerization in an aqueous medium. Such a polymerization is described in German patent application 43 00 772.
  • the polymers obtained in aqueous solution can, if necessary, be converted into pulverulent products by drying methods, in particular spray drying processes.
  • the copolymers act as dispersants and complexing agents. With them polyvalent metal ions, e.g. B. Ca, Mg and Fe ions, bound in water-soluble complexes. The copolymers disperse unusual water hardness and dirt particles. The products are characterized by their biodegradability. On the use of previously used complexing and dispersing agents, such as. B. of phosphates, phosphonates, poorly degradable polyacrylates, nitrilotriacetic acid and its salts, ethylenediaminetetraacetic acid and its salts, which have ecological disadvantages, can generally be dispensed with or the amounts of the abovementioned agents can be reduced.
  • complexing and dispersing agents such as. B. of phosphates, phosphonates, poorly degradable polyacrylates, nitrilotriacetic acid and its salts, ethylenediaminetetraacetic acid and its salts, which have ecological disadvantages, can generally be dispensed with or the
  • copolymers with water-softening silicates such as. B. zeolites and crystalline layered sodium silicates can be combined. This increases the performance as a cobuilder.
  • water softening silicates are accepted. - The combinations mentioned are not the subject of this invention.
  • the copolymers are biodegradable if they are used in the modified OECD Sturm test (EC Directive 84/449 / EEC C 5 and OECD Guideline 301 B) (see, for example, soap-oil-fat waxes 117 (1991), 740 to 744), have a degree of degradation of ⁇ 60%.
  • Usable washing alkalis c are water-soluble, alkaline salts, such as alkali carbonates, alkali bicarbonates and alkali hydroxides.
  • the group of washing alkalis also includes the water-soluble alkali metal silicates, which also have corrosion-inhibiting properties, such as. B. sodium metasilicates and sodium disilicates.
  • the proportion of washing alkalis in the compositions is preferably 5 to 50% by weight.
  • inorganic neutral salts such as e.g. As sodium sulfate or sodium chloride can be used. If such products are used, they are preferably dosed in amounts of 5 to 60% by weight.
  • the detergent formulations can contain further functional auxiliaries described below.
  • peroxo compounds such as sodium perborate mono- and tetrahydrate and percarbonates are used.
  • the bleaching agents are dosed in amounts of 0 to 30% by weight, with amounts of 5 to 20% by weight being preferred.
  • oxygen bleaching can be carried out by activators such.
  • B. Tetraacetylethylenediamine (TAED) can be improved.
  • the bleach activator TAED is usually used in amounts of 0 to 10% by weight, portions of 2 to 7% by weight being preferred.
  • the formulations can also contain further dispersing and complexing agents.
  • Suitable products are, for example, citrates, phosphonates, biodegradable homopolymers and copolymers of acrylic acid, isoserine diacetic acid, polyaspartic acid, ethylenediaminetetraacetic acid and nitrilotriacetic acid and the alkali metal salts of the aforementioned substances.
  • Such substances are contained in the detergents in concentrations of 0 to 50% by weight, preferably in amounts of 0.5 to 20% by weight.
  • Graying inhibitors such as carboxymethyl cellulose and carboxymethyl starches, can also be used.
  • the products increase the dirt-carrying capacity of the washing liquors and are typically contained in amounts of 0 to 2% by weight.
  • the formulations can optionally also contain enzymes, in particular proteases, amylases and lipases. These enzymes are typically dosed in amounts of 0 to 5% by weight.
  • the detergent formulations according to the invention can furthermore contain defoamers, trickling aids, optical brighteners, color transfer inhibitors and fragrances and dyes.
  • the detergents according to the invention can be powdery types or granules.
  • the powder detergents can be prepared by mixing the solid ingredients and, if appropriate, by spraying on the liquid constituents or by spray-drying an aqueous, liquid to pasty batch of the starting components.
  • Granulated products can e.g. B. by extrusion of pasty premixes.
  • the formulations according to the invention can be used as textile detergents in the household sector and in commercial cleaning processes.
  • the copolymers b contained in the formulations have an excellent binding capacity for alkaline earth metal ions and a high dispersibility, so that the use of water-softening silicates, such as zeolites or crystalline sodium layered silicates, can be dispensed with.
  • the detergents according to the invention bring about good soil detachment and soil dispersion and lead only to a slight incrustation when washing the textiles with hard water.
  • the agents can be highly foaming formulations, such as those used in hand washing, or else foam-regulating surfactant systems used in machine washing.
  • the formulations according to the invention are better or at least equally good in their effectiveness.
  • the formulations now claimed also have improved biodegradability.
  • a copolymer with an average molar mass of approximately 15,000 g / mol is obtained by radical polymerization of the sodium maleinate from 35% by weight of maleic anhydride, 45% by weight of acrylic acid and 20% by weight of vinyl acetate in aqueous solution and saponification.
  • the copolymer obtained in aqueous solution is converted into a powdery product by spray drying.
  • the biodegradability of the copolymers is tested in accordance with the modified OECD Sturm test in accordance with EC Directive 84/449 / EEC C 5 and OECD Guideline 301 B.
  • a degree of degradation of over 60% is determined for the substance mentioned in Example 1.
  • polycarboxylates such as. B. homopolyacrylates and copolymers of acrylic acid and maleic acid, on the other hand, have lower biodegradability.
  • detergents of the following composition are produced (data in% by weight): Detergent powder 1 % 2% n-alkylbenzenesulfonate, Na salt 5.0 4.5 C12-C14 fatty alcohol ethoxylate-7-EO 7.0 5.0 Soap 5.0 7.0 Copolymer, powdery 15.0 10.0 sodium 30.0 25.0 Sodium bicarbonate - 25.0 Sodium perborate tetrahydrate 15.0 15.0 Sodium sulfate, light 23.0 8.5 Detergent powder 3% 4% 5% C12-C18 fatty alcohol sulfate, Na salt - 2.0 15.0 C12-C14 fatty alcohol oxyethylate-7-EO - 5.0 4.0 C13-oxo alcohol ethoxylate mixture (9 EO, 3 EO) 9.0 - - Soap - 5.0 2.0 Copolymer, powdery 15.0 20.0 8.0 sodium 15.0 25.0 8.0 Sodium bicarbonate 26.0 25.0
  • a comparative formulation V1 is prepared using the commercially available polycarboxylate Sokalan CP 5 (BASF, acrylic acid-maleic acid copolymer, Na salt, average molar mass 70,000 g / mol): Comparative formulation V1% n-alkylbenzenesulfonate, Na salt 5.0 C12-C14 fatty alcohol ethoxylate-7-EO 7.0 Soap 5.0 Polycarboxylate, powdery 15.0 sodium 30.0 Sodium perborate tetrahydrate 15.0 Sodium sulfate, light 23.0
  • Table 1 shows the ash content as a measure of the deposits.
  • Table 1 formulation 1 2nd 3rd V1 Ash content (%) 0.47 0.46 0.43 0.51

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

The invention relates to detergent formulations which contain (a) 3 to 70 % by weight of surfactants, (b) 1 to 60 % by weight of copolymers of at least three monomers, (c) 0 to 60 % by weight of detergent alkalis, (d) 0 to 70 % by weight of fillers and (e) difference from 100 % by weight other functional auxiliaries. The formulations according to the invention are distinguished by biodegradability and result in distinctly less sewage sludge compared with conventional formulations.

Description

Die Erfindung betrifft Waschmittelformulierungen, die frei von Phosphaten, Zeolithen und kristallinen Schichtsilikaten sind und als Buildersubstanzen Polymere mit biologischer Abbaubarkeit enthalten.The invention relates to detergent formulations which are free of phosphates, zeolites and crystalline phyllosilicates and which contain polymers with biodegradability as builder substances.

In Waschmitteln benötigt man als Inhaltsstoffe neben den oberflächenaktiven Tensiden die sogenannten Builder (Gerüststoffe). Die Funktion der Waschmittelbuilder besteht überwiegend darin, die aus dem Wasser bzw. dem Schmutz stammenden Calcium- und Magnesiumionen durch Komplexierung, Dispergierung und Sequestrierung aus dem Waschvorgang zu eliminieren und die Waschwirkung der Tenside zu unterstützen. Die Builder verhindern Gewebeablagerungen, verringern die Inkrustierung der Textilien und verbessern die Primärwaschwirkung.In detergents, you need the so-called builders (builders) in addition to the surface-active surfactants. The function of the detergent builder is mainly to eliminate the calcium and magnesium ions from the water or the dirt by complexing, dispersing and sequestering from the washing process and to support the washing action of the surfactants. The builders prevent tissue deposits, reduce the incrustation of the textiles and improve the primary washing effect.

In traditionellen Waschmittelformulierungen wurden Polyphosphate, die auch hervorragende anwendungstechnische Eigenschaften zeigten, als Builder eingesetzt. Die Verwendung von Phosphaten in Waschmitteln ist jedoch unerwünscht, da die Produktgruppe ökologische Nachteile aufweist. So führt die Belastung der Abwässer mit Phosphaten zu einer Überdüngung der Oberflächengewässer und den mit der Eutrophierung verbundenen Problemen.In traditional detergent formulations, polyphosphates, which also had excellent application properties, were used as builders. However, the use of phosphates in detergents is undesirable because the product group has ecological disadvantages. The pollution of the wastewater with phosphates leads to an over-fertilization of the surface waters and the problems associated with eutrophication.

Heute werden in Pulverwaschmitteln Kombinationen von wasserenthärtenden Silikaten, wie z. B. Zeolithen oder kristallinen Natrium-Schichtsilikaten, und carboxylatgruppenhaltigen Polymeren als Builder verwendet. In diesem System fungieren die Zeolithe bzw. die Schichtsilikate als Ionenaustauscher und bewirken durch die Bindung von Calcium- und Magnesiumionen eine Enthärtung des Waschwassers. Die Leistungsfähigkeit der Waschpulver wird durch den Zusatz von Polycarboxylaten als Cobuilder deutlich gesteigert. Derartige Buildersysteme werden z. B. in dem Fachbuch von J. Falbe, Surfactants in Consumer Products, 1987, 262 - 265 und 286 - 290, in der Patentschrift EP 0 025 551 und in Seifen-Öle-Fette-Wachse, Nr. 18, 714 (1990) beschrieben.Today, powder detergent combinations of water-softening silicates, such as. B. zeolites or crystalline layered sodium silicates, and carboxylate-containing polymers used as builders. In this system, the zeolites and the layered silicates act as ion exchangers and soften the washing water by binding calcium and magnesium ions. The performance of the washing powder is significantly increased by the addition of polycarboxylates as cobuilders. Such builder systems are e.g. B. in the specialist book by J. Falbe, Surfactants in Consumer Products, 1987, 262-265 and 286-290, in the patent specification EP 0 025 551 and in Soap-Oil-Fat Waxes, No. 18, 714 (1990) described.

Die in den vorgenannten Mitteln enthaltenen Zeolithe oder kristallinen Schichtsilikate sind zwar nicht umweltgefährdend, sie haben jedoch den Nachteil, daß sie zu einer deutlichen Erhöhung der Klärschlammenge beitragen. Daher hat es schon in der Vergangenheit Versuche gegeben, in phosphatfreien Waschmittelpulvern auch auf den Einsatz der wasserenthärtenden Silikate zu verzichten.The zeolites or crystalline layered silicates contained in the abovementioned agents are not environmentally hazardous, but they do Disadvantage that they contribute to a significant increase in the amount of sewage sludge. For this reason, attempts have been made in the past to also dispense with the use of water-softening silicates in phosphate-free detergent powders.

Die Offenlegungsschrift DE 39 30 791 beschreibt phosphat- und zeolithfreie Waschmittel, die als Inkrustationsinhibitoren Polycarboxylate, insbesondere Copolymere aus Acrylsäure und Maleinsäure enthalten. Ein Nachteil der beanspruchten polymeren Buildersubstanzen ist die nur geringe biologische Abbaubarkeit.The published patent application DE 39 30 791 describes phosphate- and zeolite-free detergents which contain polycarboxylates, in particular copolymers of acrylic acid and maleic acid, as incrustation inhibitors. A disadvantage of the claimed polymeric builder substances is the low biodegradability.

Die Offenlegungsschrift DE 40 22 005 beansprucht die Kombination von Citrat und Polycarboxylaten als Builder in zeolithfreien Feinwaschmitteln. Die verwendeten Polymeren mit Molekulargewichten von 30 000 - 120 000 g/mol weisen ebenfalls nur geringe biologische Abbaubarkeiten auf und können daher nur zum kleinen Teil in der Kläranlage mineralisiert werden.The published patent application DE 40 22 005 claims the combination of citrate and polycarboxylates as builders in zeolite-free mild detergents. The polymers used with molecular weights of 30,000-120,000 g / mol likewise have only low biodegradability and can therefore only be mineralized to a small extent in the sewage treatment plant.

Daher lag der vorliegenden Erfindung die Aufgabe zugrunde, Waschmittelformulierungen zu schaffen, die frei von Zeolithen und kristallinen Schichtsilikaten als wasserenthärtende Silikate sind und die als Phosphatersatzstoff biologisch abbaubare und ökologisch gut verträgliche Polymere enthalten.It is therefore an object of the present invention to provide detergent formulations which are free from zeolites and crystalline phyllosilicates as water-softening silicates and which contain biodegradable and ecologically well-tolerated polymers as phosphate substitutes.

Die Aufgabe wird erfindungsgemäß durch Formulierungen gelöst, die Tenside, biologisch abbaubare Copolymere, Waschalkalien, Stellmittel und weitere funktionelle Hilfsstoffe enthalten.The object is achieved according to the invention by formulations which contain surfactants, biodegradable copolymers, washing alkalis, adjusting agents and other functional auxiliaries.

Gegenstand der Erfindung sind daher Waschmittelformulierungen, die frei von Zeolithen und kristallinen Schichtsilikaten sind und die

  • (a) 3 bis 70 Gew.-% Tenside,
  • (b) 1 bis 60 Gew.-% biologisch abbaubare Copolymere, die aus
    • A. monoethylenisch ungesättigten Dicarbonsäuren und/oder deren Salzen,
    • B. monoethylenisch ungesättigten Monocarbonsäuren und/oder deren Salzen,
    • C. einfach ungesättigten Monomeren, die nach Polymerisation und Hydrolyse oder Verseifung Monomereinheiten ergeben, die eine oder mehrere Hydroxylgruppen an der Kohlenstoffkette aufweisen, und
    • D. 0 bis 15 Gew.-% weiteren, radikalisch copolymerisierbaren Monomeren,
      aufgebaut sind,
  • (c) 0 bis 60 Gew.-% Waschalkalien,
  • (d) 0 bis 70 Gew.-% Stellmittel und
  • (e) Differenz zu 100 Gew.-% weitere funktionelle Hilfsstoffe
enthalten.The invention therefore relates to detergent formulations which are free from zeolites and crystalline phyllosilicates and which
  • (a) 3 to 70% by weight of surfactants,
  • (b) 1 to 60% by weight of biodegradable copolymers made from
    • A. monoethylenically unsaturated dicarboxylic acids and / or their salts,
    • B. monoethylenically unsaturated monocarboxylic acids and / or their salts,
    • C. monounsaturated monomers which, after polymerization and hydrolysis or saponification, give monomer units which have one or more hydroxyl groups on the carbon chain, and
    • D. 0 to 15% by weight of further free-radically copolymerizable monomers,
      are set up
  • (c) 0 to 60% by weight washing alkalis,
  • (d) 0 to 70% by weight of adjusting agent and
  • (e) difference to 100% by weight of other functional auxiliaries
contain.

Die erfindungsgemäßen Waschmittel können anionische, nichtionische oder kationische Tenside a enthalten. In Mitteleuropa werden typischerweise Gemische aus anionischen und nichtionischen Produkten verwendet, die synergetische Wascheffekte zeigen und häufig mit Seifen kombiniert werden. Es können aber auch ausschließlich anionische bzw. nichtionische Tenside eingesetzt werden. Die Tensidmenge a beträgt vorzugsweise 5 bis 40 Gew.-%, wobei Gehalte von 7 bis 25 Gew.-% ganz besonders bevorzugt werden.The detergents according to the invention can contain anionic, nonionic or cationic surfactants a. In Central Europe, mixtures of anionic and nonionic products are typically used, which show synergistic washing effects and are often combined with soaps. However, only anionic or nonionic surfactants can also be used. The amount of surfactant a is preferably 5 to 40% by weight, with contents of 7 to 25% by weight being very particularly preferred.

Als anionische Tenside kommen Produkte aus der Gruppe der Sulfonate und Sulfate in Betracht. Tenside vom Sulfonat-Typ sind z. B. C₁₁-C₁₃-Alkylbenzolsulfonate, C₁₃-C₁₇-Alkansulfonate und Estersulfonate mit Kettenlängen von 12 bis 20 C-Atomen. Geeignete Tenside vom Sulfattyp sind beispielsweise die Schwefelsäuremonoester aus Fettalkoholen synthetischen und nativen Ursprungs, wie z. B. Kokosfettalkohol, Talgfettalkohol, Oleylalkohol oder C₁₀-C₂₀-Oxoalkoholen. Auch Fettalkoholethersulfate, wie z. B. Laurylethersulfat, können Verwendung finden.Products from the group of sulfonates and sulfates come into consideration as anionic surfactants. Sulfonate type surfactants are e.g. B. C₁₁-C₁₃ alkylbenzenesulfonates, C₁₃-C₁₇ alkanesulfonates and ester sulfonates with chain lengths of 12 to 20 carbon atoms. Suitable surfactants of the sulfate type are, for example, the sulfuric acid monoesters from fatty alcohols of synthetic and native origin, such as. B. coconut oil alcohol, tallow fatty alcohol, oleyl alcohol or C₁₀-C₂₀ oxo alcohols. Also fatty alcohol ether sulfates, such as. B. lauryl ether sulfate can be used.

Als anionische Tenside sind weiterhin Seifen, z. B. gesättigte Fettsäureseifen, wie die Alkali- oder Alkanolaminseifen der Laurinsäure, Myristinsäure, Palmitinsäure und Stearinsäure brauchbar. Bevorzugt werden aus natürlichen Fettsäuren, z. B. aus Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengemische.As anionic surfactants are also soaps, for. B. saturated fatty acid soaps, such as the alkali or alkanolamine soaps of lauric acid, myristic acid, palmitic acid and stearic acid. Natural fatty acids, e.g. B. from coconut, palm kernel or tallow fatty acids, derived soap mixtures.

Geeignete nichtionische Tenside sind beispielsweise Anlagerungsprodukte von Ethylenoxid und/oder Propylenoxid an Alkylphenole, Oxoalkohole oder native Fettalkohole, Fettsäuren, Fettamine und Fettsäureamide. Besonders wichtig sind die Anlagerungsprodukte von 3 bis 15 mol Ethylenoxid an Kokos- und Talgfettalkohole, an Oleylalkohol oder an synthetische Alkohole mit 8 bis 18 C-Atomen. Auch Tenside vom Typ der C₈-C₁₈-Alkylpolyglucoside, wie z. B. C₁₀-C₁₂ und C₁₂-C₁₆-Alkylpolyglucoside, und Aminoxide sind verwendbar.Suitable nonionic surfactants are, for example, adducts of ethylene oxide and / or propylene oxide with alkylphenols, oxo alcohols or native fatty alcohols, fatty acids, fatty amines and fatty acid amides. The addition products of 3 to 15 mol of ethylene oxide with coconut oil and tallow fatty alcohols, with oleyl alcohol or with synthetic alcohols with 8 to 18 carbon atoms are particularly important. Also surfactants of the type of C₈-C₁₈ alkyl polyglucosides, such as. B. C₁₀-C₁₂ and C₁₂-C₁₆ alkyl polyglucosides, and amine oxides can be used.

Es können aber auch kationische Tenside und amphotere Produkte, wie Ampholyte und Betaine, eingesetzt werden.However, cationic surfactants and amphoteric products such as ampholytes and betaines can also be used.

Die erfindungsgemäßen Waschmittel enthalten weiterhin die Copolymere b. Die Menge an b beträgt vorzugsweise 5 bis 40 Gew.-%, wobei Anteile von 5 bis 20 Gew.-% ganz bevorzugt eingestellt werden.The detergents according to the invention also contain the copolymers b. The amount of b is preferably 5 to 40% by weight, proportions of 5 to 20% by weight being very preferably set.

Als Monomere der Gruppe A kommen monoethylenisch ungesättigte C₄-C₈-Dicarbonsäuren, deren Anhydride bzw. deren Alkali- und/oder Ammoniumsalze und/oder Aminsalze in Frage. Geeignete Dicarbonsäuren sind beispielsweise Maleinsäure, Fumarsäure, Itaconsäure und Methylenmalonsäure. Bevorzugt verwendet man Maleinsäure, Maleinsäureanhydrid, Itaconsäure, Itaconsäureanhydrid sowie die entsprechenden Natrium-, Kalium- oder Ammoniumsalze von Malein- bzw. Itaconsäure. Die Monomeren der Gruppe A sind vorzugsweise zu 10 bis 70 Gew.-%, besonders bevorzugt zu 20 bis 60 Gew.-% und ganz besonders bevorzugt zu 25 bis 55 Gew.-%, in der Monomermischung vorhanden.Monomers of group A are monoethylenically unsaturated C₄-C₈ dicarboxylic acids, their anhydrides or their alkali and / or ammonium salts and / or amine salts. Suitable dicarboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid and methylene malonic acid. Maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the corresponding sodium, potassium or ammonium salts of maleic or itaconic acid are preferably used. The group A monomers are preferably present in the monomer mixture in an amount of 10 to 70% by weight, more preferably 20 to 60% by weight and very particularly preferably 25 to 55% by weight.

Als Monomere der Gruppe B kommen monoethylenisch ungesättigte C₃-C₁₀-Monocarbonsäuren sowie deren Alkali- und/oder Ammoniumsalze und/oder Aminsalze in Betracht. Zu diesen Monomeren gehören beispielsweise Acrylsäure, Methacrylsäure, Dimethylacrylsäure, Ethylacrylsäure, Vinylessigsäure und Allylessigsäure. Vorzugsweise verwendet man aus dieser Gruppe von Monomeren Acrylsäure, Methacrylsäure, deren Gemische sowie die Natrium-, Kalium- oder Ammoniumsalze oder deren Mischungen. Die Monomeren der Gruppe B sind vorzugsweise zu 20 bis 85 Gew.-%, besonders bevorzugt zu 25 bis 60 Gew.-% und ganz besonders bevorzugt zu 30 bis 60 Gew.-%, in der Monomermischung vorhanden.Monomers of group B are monoethylenically unsaturated C₃-C₁₀ monocarboxylic acids and their alkali and / or ammonium salts and / or amine salts. These monomers include, for example, acrylic acid, methacrylic acid, dimethylacrylic acid, ethyl acrylic acid, vinyl acetic acid and allylacetic acid. From this group of monomers, preference is given to using acrylic acid, methacrylic acid, their mixtures and the sodium, potassium or ammonium salts or mixtures thereof. The group B monomers are preferably 20 to 85% by weight, particularly preferably 25 up to 60% by weight and very particularly preferably 30 to 60% by weight, are present in the monomer mixture.

Zu den Monomeren der Gruppe C sind jene zu rechnen, die nach der Copolymerisation und einer nachfolgenden Hydrolyse oder Verseifung des Polymerisates eine oder mehrere Hydroxylgruppen, die direkt an der C-C-Polymer-Kohlenstoffkette kovalent gebunden sind, freisetzen. Beispielhaft seien genannt: Vinylacetat, Vinylpropionat, Essigsäure-Methylvinylester, Methylvinylether, Ethylenglykolmonovinylether und Vinylidencarbonat. Die Monomeren der Gruppe C sind vorzugsweise zu 1 bis 50 Gew.-%, besonders bevorzugt zu 4 bis 40 Gew.-% und ganz besonders bevorzugt zu 8 bis 30 Gew.-%, in der Monomermischung vorhanden.The group C monomers include those which, after copolymerization and subsequent hydrolysis or saponification of the polymer, release one or more hydroxyl groups which are covalently bonded directly to the C-C polymer carbon chain. Examples include: vinyl acetate, vinyl propionate, methyl vinyl acetate, methyl vinyl ether, ethylene glycol monovinyl ether and vinylidene carbonate. The group C monomers are preferably present in the monomer mixture in an amount of 1 to 50% by weight, particularly preferably 4 to 40% by weight and very particularly preferably 8 to 30% by weight.

Als Monomere der Gruppe D, die zur Modifizierung der Copolymeren eingesetzt werden können, eignen sich z. B. Sulfongruppen und Sulfatgruppen enthaltende Monomere, wie beispielsweise Meth(allylsulfonsäure), Vinylsulfonsäure, Styrolsulfonsäure, Acrylamidomethylpropansulfonsäure sowie Phosphonsäuregruppen enthaltende Monomere, wie beispielsweise Vinylphosphonsäure, Allylphosphonsäure und Acrylamidomethylpropanphosphonsäure und deren Salze sowie Hydroxyethyl(meth)acrylatsulfate, Allylalkoholsulfate und -phosphate. Als Monomere der Gruppe D können außerdem auch - wegen der erforderlichen Löslichkeit jedoch nur in begrenzter Menge - doppelt ethylenisch ungesättigte nicht konjugierte Verbindungen sowie Polyalkylenglykolester von (Meth)Acrylsäure und Polyalkylenglykolether mit (Meth)Allylalkohol, die gegebenenfalls endverschlossen sein können, verwendet werden. Die Monomeren der Gruppe D sind gegebenenfalls bis zu 15 Gew.-%, vorzugsweise bis zu 10 Gew.-%, in der Monomermischung vorhanden.As group D monomers that can be used to modify the copolymers are, for. B. sulfone groups and sulfate group-containing monomers, such as meth (allylsulfonic acid), vinylsulfonic acid, styrene sulfonic acid, acrylamidomethylpropanesulfonic acid and monomers containing phosphonic acid groups, such as vinylphosphonic acid, allylphosphonic acid and acrylamidomethylpropanephosphonic acid and their salts, and hydroxyethyl (meth) acrylate sulfates, allyl sulfates. As group D monomers it is also possible - because of the required solubility, but only in a limited amount - to use double-ethylenically unsaturated non-conjugated compounds and polyalkylene glycol esters of (meth) acrylic acid and polyalkylene glycol ether with (meth) allyl alcohol, which may or may not be end-capped. The group D monomers are optionally present in the monomer mixture up to 15% by weight, preferably up to 10% by weight.

Die Copolymere können durch radikalische Polymerisation in wäßrigem Medium hergestellt werden. Eine derartige Polymerisation wird in der deutschen Patentanmeldung 43 00 772 beschrieben.The copolymers can be prepared by radical polymerization in an aqueous medium. Such a polymerization is described in German patent application 43 00 772.

Die in wäßriger Lösung anfallenden Polymerisate können bei Bedarf durch Trocknungsmethoden, insbesondere Sprühtrocknungsverfahren, in pulverförmige Produkte überführt werden.The polymers obtained in aqueous solution can, if necessary, be converted into pulverulent products by drying methods, in particular spray drying processes.

Die Copolymere wirken als Dispergier- und Komplexiermittel. Mit ihnen werden mehrwertige Metallionen, z. B. Ca-, Mg- und Fe-Ionen, in wasserlöslichen Komplexen gebunden. Die Copolymere dispergieren ausgefallene Wasserhärte und Schmutzteilchen. Die Produkte zeichnen sich durch biologische Abbaubarkeit aus. Auf die Verwendung bisher eingesetzter Komplexier- und Dispergiermittel, wie z. B. von Phosphaten, Phosphonaten, wenig abbaubaren Polyacrylaten, Nitrilotriessigsäure und deren Salzen, Ethylendiamintetraessigsäure und deren Salzen, die ökologische Nachteile aufweisen, kann in der Regel verzichtet werden oder es können die Mengen der vorgenannten Mittel reduziert werden.The copolymers act as dispersants and complexing agents. With them polyvalent metal ions, e.g. B. Ca, Mg and Fe ions, bound in water-soluble complexes. The copolymers disperse unusual water hardness and dirt particles. The products are characterized by their biodegradability. On the use of previously used complexing and dispersing agents, such as. B. of phosphates, phosphonates, poorly degradable polyacrylates, nitrilotriacetic acid and its salts, ethylenediaminetetraacetic acid and its salts, which have ecological disadvantages, can generally be dispensed with or the amounts of the abovementioned agents can be reduced.

Selbstverständlich können die Copolymere auch mit wasserenthärtenden Silikaten, wie z. B. Zeolithen und kristallinen Natrium-Schichtsilikaten, kombiniert werden. Die Leistungsfähigkeit als Cobuilder wird dadurch gesteigert. Allerdings müssen dann die o. g. Nachteile der wasserenthärtenden Silikate in Kauf genommen werden. - Die genannten Kombinationen sind nicht Gegenstand dieser Erfindung.Of course, the copolymers with water-softening silicates, such as. B. zeolites and crystalline layered sodium silicates can be combined. This increases the performance as a cobuilder. However, the above-mentioned Disadvantages of water softening silicates are accepted. - The combinations mentioned are not the subject of this invention.

Im Sinne dieser Erfindung sind die Copolymere biologisch abbaubar, wenn sie im modifizierten OECD-Sturm-Test (EG-Richtlinie 84/449/EWG C 5 und OECD-Guideline 301 B) (siehe z. B. Seifen-Öle-Fette-Wachse 117 (1991), 740 bis 744), einen Abbaugrad von ≧ 60 % aufweisen.For the purposes of this invention, the copolymers are biodegradable if they are used in the modified OECD Sturm test (EC Directive 84/449 / EEC C 5 and OECD Guideline 301 B) (see, for example, soap-oil-fat waxes 117 (1991), 740 to 744), have a degree of degradation of ≧ 60%.

Brauchbare Waschalkalien c sind wasserlösliche, alkalisch reagierende Salze, wie beispielsweise Alkalicarbonate, Alkalibicarbonate und Alkalihydroxide. Zur Gruppe der Waschalkalien zählen ferner die wasserlöslichen Alkalimetallsilikate, die auch korrosionsinhibierende Eigenschaften aufweisen, wie z. B. Natriummetasilikate und Natriumdisilikate. Der Anteil der Waschalkalien in den Mitteln beträgt vorzugsweise 5 bis 50 Gew.-%.Usable washing alkalis c are water-soluble, alkaline salts, such as alkali carbonates, alkali bicarbonates and alkali hydroxides. The group of washing alkalis also includes the water-soluble alkali metal silicates, which also have corrosion-inhibiting properties, such as. B. sodium metasilicates and sodium disilicates. The proportion of washing alkalis in the compositions is preferably 5 to 50% by weight.

Als Stellmittel d können insbesondere anorganische Neutralsalze, wie z. B. Natriumsulfat oder Natriumchlorid, Verwendung finden. Falls derartige Produkte eingesetzt werden, werden sie vorzugsweise in Mengen von 5 bis 60 Gew.-% dosiert.In particular, inorganic neutral salts such as e.g. As sodium sulfate or sodium chloride can be used. If such products are used, they are preferably dosed in amounts of 5 to 60% by weight.

Zusätzlich zu den vorgenannten Produkten können die Waschmittelformulierungen weitere im folgenden beschriebene funktionelle Hilfsstoffe enthalten.In addition to the aforementioned products, the detergent formulations can contain further functional auxiliaries described below.

Insbesondere werden Peroxoverbindungen wie Natriumperboratmono- und tetrahydrat und Percarbonate verwendet. Die Bleichmittel werden in Anteilen von 0 bis 30 Gew.-% dosiert, wobei Mengen von 5 bis 20 Gew.-% bevorzugt werden.In particular, peroxo compounds such as sodium perborate mono- and tetrahydrate and percarbonates are used. The bleaching agents are dosed in amounts of 0 to 30% by weight, with amounts of 5 to 20% by weight being preferred.

Bei niedrigen Waschtemperaturen kann die Sauerstoffbleiche durch Aktivatoren, wie z. B. Tetraacetylethylendiamin (TAED) verbessert werden. Der Bleichaktivator TAED wird üblicherweise in Mengen von 0 bis 10 Gew.-% verwendet, wobei Anteile von 2 bis 7 Gew.-% bevorzugt sind.At low washing temperatures, oxygen bleaching can be carried out by activators such. B. Tetraacetylethylenediamine (TAED) can be improved. The bleach activator TAED is usually used in amounts of 0 to 10% by weight, portions of 2 to 7% by weight being preferred.

Die Formulierungen können auch weitere Dispergier- und Komplexiermittel enthalten. Geeignete Produkte sind beispielsweise Citrate, Phosphonate, biologisch nur wenig abbaubare Homo- und Copolymere der Acrylsäure, Isoserindiessigsäure, Polyasparaginsäure, Ethylendiamintetraessigsäure und Nitrilotriessigsäure sowie die Alkalisalze der vorgenannten Substanzen. Derartige Substanzen sind in den Waschmitteln in Konzentrationen von 0 bis 50 Gew.-%, vorzugsweise in Mengen von 0,5 bis 20 Gew.-%, enthalten.The formulations can also contain further dispersing and complexing agents. Suitable products are, for example, citrates, phosphonates, biodegradable homopolymers and copolymers of acrylic acid, isoserine diacetic acid, polyaspartic acid, ethylenediaminetetraacetic acid and nitrilotriacetic acid and the alkali metal salts of the aforementioned substances. Such substances are contained in the detergents in concentrations of 0 to 50% by weight, preferably in amounts of 0.5 to 20% by weight.

Einsetzbar sind auch Vergrauungsinhibitoren, wie Carboxymethylcellulose und Carboxymethylstärken. Die Produkte erhöhen das Schmutztragevermögen der Waschflotten und sind typischerweise in Mengen von 0 bis 2 Gew.-% enthalten.Graying inhibitors, such as carboxymethyl cellulose and carboxymethyl starches, can also be used. The products increase the dirt-carrying capacity of the washing liquors and are typically contained in amounts of 0 to 2% by weight.

Wahlweise können die Formulierungen auch Enzyme enthalten, insbesondere Proteasen, Amylasen und Lipasen. Diese Enzyme werden typischerweise in Mengen von 0 bis 5 Gew.-% dosiert.The formulations can optionally also contain enzymes, in particular proteases, amylases and lipases. These enzymes are typically dosed in amounts of 0 to 5% by weight.

Des weiteren können in den erfindungsgemäßen Waschmittelformulierungen Entschäumer, Rieselhilfen, optische Aufheller, Farbübertragungsinhibitoren sowie Duft- und Farbstoffe enthalten sein.The detergent formulations according to the invention can furthermore contain defoamers, trickling aids, optical brighteners, color transfer inhibitors and fragrances and dyes.

Bei den erfindungsgemäßen Waschmitteln kann es sich um pulverförmige Typen oder um Granulate handeln.The detergents according to the invention can be powdery types or granules.

Die Herstellung der pulverförmigen Waschmittel kann durch Mischen der festen Inhaltsstoffe und gegebenenfalls durch Aufsprühen der flüssigen Bestandteile bzw. durch Sprühtrocknen eines wäßrigen, flüssigen bis pastösen Ansatzes der Ausgangskomponenten erfolgen. Granulierte Produkte können z. B. durch Extrusion von pastösen Vormischungen hergestellt werden.The powder detergents can be prepared by mixing the solid ingredients and, if appropriate, by spraying on the liquid constituents or by spray-drying an aqueous, liquid to pasty batch of the starting components. Granulated products can e.g. B. by extrusion of pasty premixes.

Die erfindungsgemäßen Formulierungen können als Textilwaschmittel im Haushaltsbereich und in gewerblichen Reinigungsprozessen verwendet werden. Die in den Formulierungen enthaltenen Copolymere b weisen ein hervorragendes Bindevermögen für Erdalkaliionen und ein hohes Dispergiervermögen auf, so daß auf die Verwendung von wasserenthärtenden Silikaten, wie Zeolithen oder kristallinen Natrium-Schichtsilikaten, verzichtet werden kann. Die erfindungsgemäßen Waschmittel bewirken eine gute Schmutzablösung und Schmutzdispergierung und führen nur zu einer geringen Inkrustierung beim Waschen der Textilien mit hartem Wasser.The formulations according to the invention can be used as textile detergents in the household sector and in commercial cleaning processes. The copolymers b contained in the formulations have an excellent binding capacity for alkaline earth metal ions and a high dispersibility, so that the use of water-softening silicates, such as zeolites or crystalline sodium layered silicates, can be dispensed with. The detergents according to the invention bring about good soil detachment and soil dispersion and lead only to a slight incrustation when washing the textiles with hard water.

Bei den Mitteln kann es sich um stark schäumende Formulierungen handeln, wie sie bei der Handwäsche verwendet werden, oder auch um schaumregulierende Tensidsysteme, die in der Maschinenwäsche Verwendung finden.The agents can be highly foaming formulations, such as those used in hand washing, or else foam-regulating surfactant systems used in machine washing.

Im Vergleich zu Formulierungen, in denen die Komponente b durch eine handelsübliche Verbindung ersetzt ist, sind die erfindungsgemäßen Formulierungen in ihrer Wirksamkeit besser oder zumindest gleich gut. Die jetzt beanspruchten Formulierungen weisen jedoch darüber hinaus eine verbesserte biologische Abbaubarkeit auf.In comparison to formulations in which component b is replaced by a commercially available compound, the formulations according to the invention are better or at least equally good in their effectiveness. However, the formulations now claimed also have improved biodegradability.

Die folgenden Beispiele sollen die Erfindung erläutern.The following examples are intended to illustrate the invention.

BeispieleExamples Beispiel 1example 1 CopolymerCopolymer

Durch radikalische Polymerisation des Natriummaleinats aus 35 Gew.-% Maleinsäureanhydrid, 45 Gew.-% Acrylsäure und 20 Gew.-% Vinylacetat in wäßriger Lösung und Verseifung wird ein Copolymer mit einer mittleren molaren Masse von ca. 15 000 g/mol erhalten.A copolymer with an average molar mass of approximately 15,000 g / mol is obtained by radical polymerization of the sodium maleinate from 35% by weight of maleic anhydride, 45% by weight of acrylic acid and 20% by weight of vinyl acetate in aqueous solution and saponification.

Das in wäßriger Lösung anfallende Copolymer wird durch Sprühtrocknung in ein pulverförmiges Produkt überführt.The copolymer obtained in aqueous solution is converted into a powdery product by spray drying.

Beispiel 2Example 2 Biologische AbbaubarkeitBiodegradability

Die biologische Abbaubarkeit der Copolymere wird nach dem modifizierten OECD-Sturm-Test entsprechend der EG-Richtlinie 84/449/EWG C 5 und der OECD-Guideline 301 B geprüft.The biodegradability of the copolymers is tested in accordance with the modified OECD Sturm test in accordance with EC Directive 84/449 / EEC C 5 and OECD Guideline 301 B.

Für die im Beispiel 1 genannte Substanz wird ein Abbaugrad von über 60 % ermittelt.A degree of degradation of over 60% is determined for the substance mentioned in Example 1.

Marktübliche Polycarboxylate, wie z. B. Homopolyacrylate und Copolymere aus Acrylsäure und Maleinsäure, weisen dagegen geringere biologische Abbaubarkeiten auf.Commercial polycarboxylates, such as. B. homopolyacrylates and copolymers of acrylic acid and maleic acid, on the other hand, have lower biodegradability.

Beispiel 3Example 3 FormulierungenWording

Unter Verwendung des Copolymer von Beispiel 1 werden Waschmittel folgender Zusammensetzung hergestellt (Angaben in Gew.-%): Waschmittel, pulverförmig 1 % 2 % n-Alkylbenzolsulfonat, Na-Salz 5,0 4,5 C₁₂-C₁₄-Fettalkoholethoxylat-7-EO 7,0 5,0 Seife 5,0 7,0 Copolymer, pulverförmig 15,0 10,0 Natriumcarbonat 30,0 25,0 Natriumbicarbonat - 25,0 Natriumperborat Tetrahydrat 15,0 15,0 Natriumsulfat, leicht 23,0 8,5 Waschmittel, pulverförmig 3 % 4 % 5 % C₁₂-C₁₈-Fettalkoholsulfat, Na-Salz - 2,0 15,0 C₁₂-C₁₄-Fettalkoholoxethylat-7-EO - 5,0 4,0 C₁₃-Oxoalkoholethoxylat-Mischung (9 EO, 3 EO) 9,0 - - Seife - 5,0 2,0 Copolymer, pulverförmig 15,0 20,0 8,0 Natriumcarbonat 15,0 25,0 8,0 Natriumbicarbonat 26,0 25,0 6,0 Natriummetasilikat, Pentahydrat 10,0 - - Carboxymethylcellulose - 1,5 1,5 Natriumperborat, Tetrahydrat 25,0 - - Natriumsulfat, leicht - 16,5 55,5 Waschmittel, pulverförmig 6 % 7 % C₁₂-C₁₄-Fettalkoholsulfat, Na-Salz 4,0 - C₁₂-C₁₄-Fettalkoholethoxylat-7-EO 6,0 8,0 Seife 12,0 6,0 Copolymer, pulverförmig 6,0 10,0 Natriumcitrat, Dihydrat 30,0 10,0 Natriumcarbonat 20,0 30,0 Natriumdisilikat 20,0 - Enzyme 2,0 1,0 Natriumhydrogencarbonat - 35,0 Using the copolymer from Example 1, detergents of the following composition are produced (data in% by weight): Detergent powder 1 % 2% n-alkylbenzenesulfonate, Na salt 5.0 4.5 C₁₂-C₁₄ fatty alcohol ethoxylate-7-EO 7.0 5.0 Soap 5.0 7.0 Copolymer, powdery 15.0 10.0 sodium 30.0 25.0 Sodium bicarbonate - 25.0 Sodium perborate tetrahydrate 15.0 15.0 Sodium sulfate, light 23.0 8.5 Detergent powder 3% 4% 5% C₁₂-C₁₈ fatty alcohol sulfate, Na salt - 2.0 15.0 C₁₂-C₁₄ fatty alcohol oxyethylate-7-EO - 5.0 4.0 C₁₃-oxo alcohol ethoxylate mixture (9 EO, 3 EO) 9.0 - - Soap - 5.0 2.0 Copolymer, powdery 15.0 20.0 8.0 sodium 15.0 25.0 8.0 Sodium bicarbonate 26.0 25.0 6.0 Sodium metasilicate, pentahydrate 10.0 - - Carboxymethyl cellulose - 1.5 1.5 Sodium perborate, tetrahydrate 25.0 - - Sodium sulfate, light - 16.5 55.5 Detergent powder 6% 7% C₁₂-C₁₄ fatty alcohol sulfate, Na salt 4.0 - C₁₂-C₁₄ fatty alcohol ethoxylate-7-EO 6.0 8.0 Soap 12.0 6.0 Copolymer, powdery 6.0 10.0 Sodium citrate, dihydrate 30.0 10.0 sodium 20.0 30.0 Sodium disilicate 20.0 - Enzymes 2.0 1.0 Sodium bicarbonate - 35.0

VergleichsformulierungComparative formulation

Eine Vergleichsformulierung V1 wird unter Verwendung des handelsüblichen Polycarboxylats Sokalan CP 5 (BASF, Acrylsäure-Maleinsäure-Copolymer, Na-Salz, mittlere Molmasse 70 000 g/mol) hergestellt: Vergleichsformulierung V1 % n-Alkylbenzolsulfonat, Na-Salz 5,0 C₁₂-C₁₄-Fettalkoholethoxylat-7-EO 7,0 Seife 5,0 Polycarboxylat, pulverförmig 15,0 Natriumcarbonat 30,0 Natriumperborat Tetrahydrat 15,0 Natriumsulfat, leicht 23,0 A comparative formulation V1 is prepared using the commercially available polycarboxylate Sokalan CP 5 (BASF, acrylic acid-maleic acid copolymer, Na salt, average molar mass 70,000 g / mol): Comparative formulation V1% n-alkylbenzenesulfonate, Na salt 5.0 C₁₂-C₁₄ fatty alcohol ethoxylate-7-EO 7.0 Soap 5.0 Polycarboxylate, powdery 15.0 sodium 30.0 Sodium perborate tetrahydrate 15.0 Sodium sulfate, light 23.0

Beispiel 4Example 4 Anwendungstechnische PrüfungenApplication tests GewebeinkrustierungTissue incrustation

6,0 g/l der erfindungsgemäßen Waschmittelformulierungen 1 bis 3 bzw. der Vergleichsformulierung V1 werden in einer marktüblichen Haushaltswaschmaschine gewaschen. Testgewebe: Baumwolle Waschcyclen: 12 Wäschen Waschtemperatur: 90 °C Wasserhärte: 13 ° dH 6.0 g / l of the detergent formulations 1 to 3 or the comparison formulation V1 according to the invention are washed in a commercially available household washing machine. Test fabric: cotton Wash cycles: 12 washes Washing temperature: 90 ° C Water hardness: 13 ° dH

Durch den Zusatz der Polymeren werden die Ablagerungen auf dem Gewebe reduziert. In der Tabelle 1 wird als Maß für die Ablagerungen der Aschegehalt angegeben. Tabelle 1 Formulierung 1 2 3 V1 Aschegehalt (%) 0,47 0,46 0,43 0,51 The addition of the polymers reduces the deposits on the fabric. Table 1 shows the ash content as a measure of the deposits. Table 1 formulation 1 2nd 3rd V1 Ash content (%) 0.47 0.46 0.43 0.51

Bei Verwendung der erfindungsgemäßen Waschmittelformulierungen 1 bis 3 erhält man geringere Gewebeinkrustierungen als bei der Vergleichsformulierung V1, die dem Stand der Technik entspricht. Ein weiterer Vorteil der erfindungsgemäßen Formulierungen ist die biologische Abbaubarkeit.When using the detergent formulations 1 to 3 according to the invention, less incrustation of tissue is obtained than with the comparison formulation V1, which corresponds to the prior art. Another advantage of the formulations according to the invention is the biodegradability.

Claims (8)

Waschmittelformulierungen, die frei von Zeolithen und kristallinen Schichtsilikaten sind und die (a) 3 bis 70 Gew.-% Tenside, (b) 1 bis 60 Gew.-% biologisch leicht abbaubare Copolymere, die aus A. monoethylenisch ungesättigten Dicarbonsäuren und/oder deren Salzen, B. monoethylenisch ungesättigten Monocarbonsäuren und/oder deren Salzen, C. einfach ungesättigten Monomeren, die nach Polymerisation und Hydrolyse oder Verseifung Monomereinheiten ergeben, die eine oder mehrere Hydroxylgruppen an der Kohlenstoffkette aufweisen, und D. 0 bis 15 Gew.-% weiteren, radikalisch copolymerisierbaren Monomeren,
aufgebaut sind, (c) 0 bis 60 Gew.-% Waschalkalien, (d) 0 bis 70 Gew.-% Stellmittel und (e) Differenz zu 100 Gew.-% weitere funktionelle Hilfsstoffe enthalten.Detergent formulations which are free from zeolites and crystalline layered silicates and which (a) 3 to 70% by weight of surfactants, (b) 1 to 60% by weight of readily biodegradable copolymers made from A. monoethylenically unsaturated dicarboxylic acids and / or their salts, B. monoethylenically unsaturated monocarboxylic acids and / or their salts, C. monounsaturated monomers which, after polymerization and hydrolysis or saponification, give monomer units which have one or more hydroxyl groups on the carbon chain, and D. 0 to 15% by weight of further free-radically copolymerizable monomers,
are set up (c) 0 to 60% by weight washing alkalis, (d) 0 to 70% by weight of adjusting agent and (e) difference to 100% by weight of other functional auxiliaries contain. Waschmittelformulierungen nach Anspruch 1,
dadurch gekennzeichnet,
daß die Komponenten a zu 5 bis 40 Gew.-% enthalten sind.Detergent formulations according to claim 1,
characterized,
that the components a to 5 to 40 wt .-% are included. Waschmittelformulierungen nach Anspruch 1,
dadurch gekennzeichnet,
daß die Komponenten a zu 7 bis 25 Gew.-% enthalten sind.Detergent formulations according to claim 1,
characterized,
that the components a to 7 to 25 wt .-% are included. Waschmittelformulierungen nach Anspruch 1,
dadurch gekennzeichnet,
daß die Komponenten b zu 5 bis 40 Gew.-% enthalten sind.Detergent formulations according to claim 1,
characterized,
that the components b are contained to 5 to 40 wt .-%. Waschmittelformulierungen nach Anspruch 1,
dadurch gekennzeichnet,
daß die Komponenten b zu 5 bis 20 Gew.-% enthalten sind.Detergent formulations according to claim 1,
characterized,
that the components b are 5 to 20 wt .-% contained. Waschmittelformulierungen nach Anspruch 1,
dadurch gekennzeichnet,
daß 5 bis 50 Gew.% Waschalkalien enthalten sind.Detergent formulations according to claim 1,
characterized,
that 5 to 50 wt.% washing alkalis are contained. Waschmittelformulierungen nach Anspruch 1,
dadurch gekennzeichnet,
daß 5 bis 60 Gew.-% Stellmittel enthalten sind.Detergent formulations according to claim 1,
characterized,
that 5 to 60 wt .-% adjusting agents are included. Verwendung der Formulierungen nach Anspruch 1 als Waschmittel für Textilien.Use of the formulations according to claim 1 as detergents for textiles.
EP94109139A 1993-08-04 1994-06-15 Detergent formulations Expired - Lifetime EP0637627B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4326129A DE4326129A1 (en) 1993-08-04 1993-08-04 detergent formulations
DE4326129 1993-08-04

Publications (3)

Publication Number Publication Date
EP0637627A2 true EP0637627A2 (en) 1995-02-08
EP0637627A3 EP0637627A3 (en) 1995-05-31
EP0637627B1 EP0637627B1 (en) 2000-11-08

Family

ID=6494419

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94109139A Expired - Lifetime EP0637627B1 (en) 1993-08-04 1994-06-15 Detergent formulations

Country Status (4)

Country Link
US (1) US5496495A (en)
EP (1) EP0637627B1 (en)
AT (1) ATE197468T1 (en)
DE (2) DE4326129A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996035728A1 (en) * 1995-05-12 1996-11-14 Stockhausen Gmbh & Co. Kg Water-soluble copolymers, process for producing the same and their use
DE10153551A1 (en) * 2001-10-30 2003-05-22 Henkel Kgaa Detergent or cleaning agent that is essentially dispersible without sediment

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5998360A (en) * 1994-09-22 1999-12-07 Crosfield Limited Granules based on silicate antiredeposition agent mixtures and method for manufacturing same
US6194367B1 (en) 1995-03-01 2001-02-27 Charvid Limited Liability Co. Non-caustic cleaning composition comprising peroxygen compound and specific silicate and method of making the same in free-flowing, particulate form
US6034048A (en) * 1995-03-01 2000-03-07 Charvid Limited Liability Co. Non-caustic cleaning composition using an alkali salt
US5663132A (en) * 1995-03-01 1997-09-02 Charvid Limited Liability Company Non-caustic composition comprising peroxygen compound and metasilicate and cleaning methods for using same
US5898024A (en) * 1995-03-01 1999-04-27 Charvid Limited Liability Non-caustic cleaning composition comprising peroxygen compound and specific silicate, and method of making the same in free-flowing, particulate form
GB9711356D0 (en) * 1997-05-30 1997-07-30 Unilever Plc Particulate detergent composition
AU724226B2 (en) 1997-05-30 2000-09-14 Unilever Plc Free-flowing particulate detergent compositions
US20050176617A1 (en) * 2004-02-10 2005-08-11 Daniel Wood High efficiency laundry detergent
ATE485361T1 (en) * 2005-08-19 2010-11-15 Procter & Gamble SOLID DETERGENT COMPOSITION CONTAINING ALKYLBENZENESULPHONATE, CARBONATE SALT AND CARBOXYLATE POLYMER
US20100056404A1 (en) * 2008-08-29 2010-03-04 Micro Pure Solutions, Llc Method for treating hydrogen sulfide-containing fluids

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2109398A (en) * 1981-10-22 1983-06-02 Unilever Plc Detergent composition for washing fabrics
EP0451508A1 (en) * 1990-03-17 1991-10-16 BASF Aktiengesellschaft Process for preparing homo- and copolymers of monoethyleically unsaturated dicarboxylic acids and their use
EP0497611A1 (en) * 1991-02-01 1992-08-05 Rohm And Haas Company Biodegradable polymers, process for preparation of such polymers, and compositions containing such polymers
WO1994015978A1 (en) * 1993-01-14 1994-07-21 Chemische Fabrik Stockhausen Gmbh Biodegradable copolymers, method of producing them and their use
DE4316741A1 (en) * 1993-05-19 1994-11-24 Huels Chemische Werke Ag Universal cleaner with biodegradable polymers

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4473485A (en) * 1982-11-05 1984-09-25 Lever Brothers Company Free-flowing detergent powders
DE3426368A1 (en) * 1984-07-18 1986-01-23 Basf Ag, 6700 Ludwigshafen COPOLYMERISATE FOR DETERGENT AND CLEANING AGENT
GB8504733D0 (en) * 1985-02-23 1985-03-27 Procter & Gamble Ltd Detergent compositions
DE3528460A1 (en) * 1985-08-08 1987-02-19 Basf Ag USE OF NEUTRALIZED AND AMIDATED CARBOXYL GROUPS OF POLYMERISATES AS ADDITION TO DETERGENTS AND CLEANING AGENTS
DE3716544A1 (en) * 1987-05-16 1988-11-24 Basf Ag USE OF WATER-SOLUBLE COPOLYMERS, WHICH CONTAIN MONOMERS WITH AT LEAST TWO ETHYLENICALLY UNSATURATED DOUBLE BINDINGS IN DETERGENT AND CLEANING AGENTS
IT1229135B (en) * 1989-04-05 1991-07-22 Ausidet Spa TRANSESTERIFIED COPOLYMERS OF MALEIC ANHYDRIDE, PARTICULARLY USEFUL IN THE FIELD OF DETERGENCY.
ATE164623T1 (en) * 1993-02-05 1998-04-15 Henkel Kgaa BUILDING MATERIAL FOR DETERGENT OR CLEANING PRODUCTS

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2109398A (en) * 1981-10-22 1983-06-02 Unilever Plc Detergent composition for washing fabrics
EP0451508A1 (en) * 1990-03-17 1991-10-16 BASF Aktiengesellschaft Process for preparing homo- and copolymers of monoethyleically unsaturated dicarboxylic acids and their use
EP0497611A1 (en) * 1991-02-01 1992-08-05 Rohm And Haas Company Biodegradable polymers, process for preparation of such polymers, and compositions containing such polymers
WO1994015978A1 (en) * 1993-01-14 1994-07-21 Chemische Fabrik Stockhausen Gmbh Biodegradable copolymers, method of producing them and their use
DE4316741A1 (en) * 1993-05-19 1994-11-24 Huels Chemische Werke Ag Universal cleaner with biodegradable polymers

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996035728A1 (en) * 1995-05-12 1996-11-14 Stockhausen Gmbh & Co. Kg Water-soluble copolymers, process for producing the same and their use
US6207780B1 (en) 1995-05-12 2001-03-27 Rohm & Haas Company Interpolymers of unsaturated carboxylic acids and unsaturated sulfur acids
DE10153551A1 (en) * 2001-10-30 2003-05-22 Henkel Kgaa Detergent or cleaning agent that is essentially dispersible without sediment

Also Published As

Publication number Publication date
DE4326129A1 (en) 1995-02-09
DE59409578D1 (en) 2000-12-14
ATE197468T1 (en) 2000-11-11
US5496495A (en) 1996-03-05
EP0637627A3 (en) 1995-05-31
EP0637627B1 (en) 2000-11-08

Similar Documents

Publication Publication Date Title
DE4303320C2 (en) Detergent composition having improved soil carrying power, process for its preparation and use of a suitable polycarboxylate therefor
EP0451508B1 (en) Process for preparing homo- and copolymers of monoethyleically unsaturated dicarboxylic acids and their use
DE19516957C2 (en) Water-soluble copolymers and process for their preparation and their use
EP0609273B1 (en) Washing and cleaning agents with selected builder systems
EP0554287B1 (en) Builder for detergents
DE3717227A1 (en) PHOSPHATE-FREE DETERGENT WITH REDUCED INCRUSTING TENDENCY
JPS6112795A (en) Built detergent composition
DE4313909A1 (en) Water-softening formulations
US5574004A (en) Carbonate built non-bleaching laundry detergent composition containing a polymeric polycarboxylate and a zinc salt
EP0457155B1 (en) Carboxylate-ether derivatives of alkylmono- and alkylpolyglucosides, process for their preparation and their use
EP0637627B1 (en) Detergent formulations
EP1761622B1 (en) Method for producing granulated or powdery detergent compounds
EP0849355B1 (en) Powder washing and cleaning components
EP0622449B1 (en) Water-softening compositions
WO1995000624A1 (en) Dishwasher agents with biodegradable builders
EP0626996A1 (en) Process for producing low-alkaline dishwasher rinsing agents without active chlorine, silicates and phosphates, in the form of heavy granulates
EP0625567B1 (en) Detergent for mechanical dish-washing
DE3930791C2 (en) Phosphate-free zeolite-free, water-soluble laundry detergent
WO1994025558A1 (en) Washing powders containing a silicate builder, a special combination of surfactants and lipase
DE60013646T2 (en) LAUNDRY DETERGENT
DE4316746A1 (en) Phosphate-free machine dishwashing compositions
EP1050575B1 (en) Alkaline detergent compositions comprising alkylbenzene sulfonates and alkanolamines
DE4319807A1 (en) Detergent formulations with biodegradable polymers
CH640261A5 (en) Detergent and its use for washing textiles
DE19719888A1 (en) Powdered washing and cleaning agent useful e.g. for hard surfaces - comprises reaction product of alkali silicate and acid poly:carboxylate

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19950801

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CHEMISCHE FABRIK STOCKHAUSEN GMBH

17Q First examination report despatched

Effective date: 19980528

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: STOCKHAUSEN GMBH & CO. KG

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20001108

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20001108

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 20001108

REF Corresponds to:

Ref document number: 197468

Country of ref document: AT

Date of ref document: 20001111

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59409578

Country of ref document: DE

Date of ref document: 20001214

ITF It: translation for a ep patent filed

Owner name: JACOBACCI & PERANI S.P.A.

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20010208

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: MICHELI & CIE INGENIEURS-CONSEILS

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20010306

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010615

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010615

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010630

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010630

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010630

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
BERE Be: lapsed

Owner name: STOCKHAUSEN G.M.B.H. & CO. K.G.

Effective date: 20010630

EUG Se: european patent has lapsed

Ref document number: 94109139.9

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20010615

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020403

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050615