EP0901515B1 - Use of at least trivalent alcohols and their alkoxylation products for increasing the speed of dissolution of particulate detergent formulations in water - Google Patents

Use of at least trivalent alcohols and their alkoxylation products for increasing the speed of dissolution of particulate detergent formulations in water Download PDF

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Publication number
EP0901515B1
EP0901515B1 EP97923959A EP97923959A EP0901515B1 EP 0901515 B1 EP0901515 B1 EP 0901515B1 EP 97923959 A EP97923959 A EP 97923959A EP 97923959 A EP97923959 A EP 97923959A EP 0901515 B1 EP0901515 B1 EP 0901515B1
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EP
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Prior art keywords
bis
weight
detergent formulations
ethylene oxide
water
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EP97923959A
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German (de)
French (fr)
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EP0901515A1 (en
Inventor
Jürgen HUFF
Hans-Ulrich JÄGER
Martin Aus Dem Kahmen
Matthias Kroner
Jürgen Alfred LUX
Günter OETTER
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BASF SE
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BASF SE
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives thereof

Definitions

  • the invention relates to the use of reaction products of at least trivalent Alcohols with ethylene oxide and / or Propylene oxide as an additive to particulate detergent formulations to increase their rate of dissolution in water Quantities from 0.1 to 5% by weight, based on the detergent formulations.
  • Particulate detergents should be as possible when soaked in water quickly disintegrate into individual components to make the finished one To form wash liquor.
  • the invention has for its object a detergent additive to provide that to increase the rate of dissolution of particulate detergents in water.
  • the object is achieved according to the invention by using reaction products of at least with trihydric alcohols Ethylene oxide and / or propylene oxide as an additive to particulate Detergent formulations to increase their dissolving speed in water in amounts of 0.1 to 5% by weight, based on the detergent formulations.
  • Suitable as at least trihydric alcohols are, for example Glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, Hexaglycerin, heptaglycerin and octaglycerin, pentaerythritol, trimethylolpropane, Erythritol, mannitol, sorbitol, sucrose, glucose and Polyvinyl alcohols with molecular weights up to 20,000.
  • Compounds can also be mixtures of the above Use connections. Is of particular technical interest for example the use of hydrogenated starch hydrolyzates or hydrogenated glucose syrups.
  • Particularly effective products for increasing the dissolving speed of particulate detergent formulations are reaction products of at least trihydric alcohols Ethylene oxide and / or propylene oxide.
  • These implementation products and Processes for their production belong to the state of the art. So is obtained, for example, by reacting glycerol, erythritol, Pentaerythritol, trimethylolpropane, mannitol or sorbitol with ethylene oxide and / or propylene oxide in the presence of the usual alkoxylation catalysts such as KOH, NaOH, Ca hydroxide, Ca oxide or Carrier catalysts detergent additives that increase the dissolution rate of detergent formulations in water versus polyethylene glycol increase considerably.
  • the usual alkoxylation catalysts such as KOH, NaOH, Ca hydroxide, Ca oxide or Carrier catalysts detergent additives that increase the dissolution rate of detergent formulations in water versus polyethylene glycol increase considerably.
  • the alkoxylated products can have a broad or a narrow molecular weight distribution.
  • the reaction products are of particular importance here of glycerin, erythritol, pentaerythritol, trimethylolpropane, Mannitol or sorbitol with ethylene oxide.
  • These products can be modified by if necessary, they react further with up to 20 mol of propylene oxide leaves. In the production of modified add-on products of ethylene oxide, however, one can also proceed in such a way that one at least a mixed gas of ethylene oxide and propylene oxide can act trihydric alcohols.
  • Propylene oxide is preferably used in an amount of 1 to 15 moles per mole of alcohol used. Reaction products are particularly preferred of 1 mole of trimethylolpropane with 1 to 100 moles Ethylene oxide used, mostly reaction products of 1 mole of trimethylolpropane with 3 to 30 moles of ethylene oxide.
  • Ethoxylated hydrogenated sugars such as sorbitol are also suitable or mannitol and ethoxylated polyvinyl alcohol as detergent additive, that the dissolving rate of detergent formulations increased when dissolved in water.
  • Additives to be used are preferably in amounts of 0.1 to 5 Contain 0.5 to 2 wt .-% in the detergent formulation. she preferably with the other detergent ingredients homogeneously mixed. However, you can also surface them apply the fine-particle detergent formulations and let diffuse in.
  • the detergents can be in powder form or as granules, Dandruff, strands, balls, platelets or tablets are present.
  • the average particle diameter of the particulate detergent formulations is, for example, 200 ⁇ m to 5 mm and is preferably in the range of 1 to 3 mm. You can do that However, portion detergent formulations so that for a wash in a washing machine just a ball or a Tablet is required. Have such bullets or tablets then a much larger average particle diameter than mentioned above. The advantage of such relatively large-volume particles lies in the simple dosage.
  • the detergents can be heavy duty or Act special detergents. Both anionic and surfactants come as well as nonionic or mixtures of anionic and nonionic Surfactants into consideration.
  • the surfactant content of the detergent is preferably 8 to 30% by weight.
  • Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, for example C 9 to C 11 alcohol sulfates, C 12 to C 13 alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.
  • Suitable anionic surfactants are sulfated, ethoxylated C 8 to C 22 alcohols or their soluble salts.
  • Compounds of this type are prepared, for example, by first alkoxylating a C 8 to C 22 , preferably a C 10 to C 18 alcohol and then sulfating the alkoxylation product.
  • Ethylene oxide is preferably used for the alkoxylation, 2 to 50, preferably 3 to 20, moles of ethylene oxide being used per mole of fatty alcohol.
  • the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide.
  • Alkoxylated C 8 to C 22 alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide are also suitable.
  • the alkoxylated C 8 to C 22 alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution.
  • alkyl sulfonates such as C 8 to C 24 , preferably C 10 -C 18 alkane sulfonates and soaps such as the salts of C 8 to C 24 carboxylic acids.
  • Suitable anionic surfactants are C 9 to C 20 linear alkylbenzenesulfonates (LAS).
  • the polymers according to the invention are preferably used in low-LAS detergent formulations with less than 4%, particularly preferably in LAS-free formulations.
  • the anionic surfactants are preferably in the detergent Form of salts added. Suitable cations in these salts are alkali metal salts such as sodium, potassium, lithium and Ammonium salts such as Hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.
  • nonionic surfactants are alkoxylated C 8 to C 22 alcohols.
  • the alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as the surfactant.
  • block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. 2 to 5, preferably 3 to 20, mol of at least one alkylene oxide are used per mol of alcohol.
  • the alkylene oxide used is preferably ethylene oxide.
  • the alcohols preferably have 10 to 18 carbon atoms.
  • nonionic surfactants are alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the Alkyl chain. These compounds contain 1 to 20, preferably 1.1 to 5 glucoside units.
  • N-alkylglucamides of the general structure I or II wherein A is a C 6 to C 22 alkyl, B is an H or C 1 to C 4 alkyl and C is a polyhydroxyalkanyl radical having 5 to 12 C atoms and at least 3 hydroxyl groups.
  • A is preferably C 10 to C 18 alkyl, B is CH 3 and C is a C 5 or C 6 radical.
  • such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C 10 -C 18 carboxylic acids.
  • the detergent formulations preferably contain C 10 -C 16 alcohols ethoxylated with 3-12 mol ethylene oxide, particularly preferably ethoxylated fatty alcohols as nonionic surfactants.
  • Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H 2 N- (CH 2 -CH 2 -O) 3 -C 4 H 9 with methyl dodecanoate or the reaction products of ethyl tetraglycolamine of the formula H 2 N- (CH 2 -CH 2 -O) 4 -C 2 H 5 with a commercially available mixture of saturated C 8 "to C 18 fatty acid methyl esters.
  • the powder or granular detergents also contain one or several inorganic builders.
  • inorganic builder substances all common inorganic builders such as aluminosilicates are suitable, Silicates, carbonates and phosphates.
  • Suitable inorganic builders are e.g. Aluminum silicates with ion exchange Properties such as Zeolites.
  • zeolites Various Types of zeolites are suitable, in particular zeolite A, X, B, P, MAP and HS in their Na form or in forms in which Na partly against other cations such as Li, K, Ca, Mg or ammonium are exchanged.
  • Suitable zeolites are, for example described in EP-A-0 038 591, EP-A-0 021 491, EP-A-0 087 035, US-A-4 604 224, GB-A-2 013 259, EP-A-0 522 726, EP-A-0 384 070A and WO-A-94/24251.
  • Suitable inorganic builders are e.g. amorphous or crystalline silicates such as amorphous disilicates, crystalline Disilicates such as the layered silicate SKS-6 (manufacturer Hoechst AG).
  • the silicates can be in the form of their alkali, alkaline earth or Ammonium salts are used. Na, Li, and Mg silicates are used.
  • Suitable inorganic builder substances are carbonates and hydrogen carbonates. These can be in the form of their alkali, alkaline earth or ammonium salts can be used. Preferably be Na, Li and Mg carbonates or hydrogen carbonates, in particular Sodium carbonate and / or sodium bicarbonate used.
  • the inorganic builders can be used in detergents in quantities from 0 to 60% by weight together with those which may be used organic cobuilders.
  • the inorganic builder can either alone or in any combination with each other be incorporated into the detergent.
  • In powder or Granular detergents are used in amounts of 10 to 60% by weight, preferably in amounts of 20 to 50% by weight.
  • powder or granular or other solid detergent formulations are organic cobuilders in quantities from 0.1 to 20 wt .-%, preferably in amounts of 1 to 15 wt .-% together included with inorganic builders.
  • the powder or granular Heavy duty detergents can also be used as other usual Components of a bleaching system consisting of at least one Bleach, optionally in combination with a bleach activator and / or contain a bleaching catalyst.
  • Suitable bleaches are perborates and percarbonate in the form their alkali, especially their Na salts. They are in quantities from 5 to 30% by weight, preferably 10 to 25% by weight in the Formulations included.
  • Other suitable bleaches are inorganic and organic peracids in the form of their alkali or Magnesium salts or partly also in the form of the free acids.
  • suitable organic percarboxylic acids or salts are e.g. Mg monoterephthalate, phthalimidopercaproic acid and Dodecane-1,10-diper acid.
  • Example of an inorganic peracid salt is potassium peroxomonosulfate (oxone).
  • Suitable bleaching catalysts are quaternized imines and Sulfonimines as described in US-A-5 360 568, US-A-5 360 569 and EP-A-0 453 003 and Mn complexes, cf. e.g. WO-A-94/21777. If bleach catalysts in the detergent formulations are used, they are in quantities up to to 1.5 wt .-%, preferably up to 0.5 wt .-%, in the case of very active manganese complexes in amounts up to 0.1% by weight.
  • the detergents preferably contain an enzyme system.
  • Proteases Proteases, lipases, amylases and cellulases.
  • the enzyme system can be limited to a single one of the enzymes or one Combination of different enzymes.
  • Enzymes are usually used in quantities of detergents 0.1 to 1.5 wt .-%, preferably 0.2 to 1.0 wt .-% of the made up Enzyme added.
  • Suitable proteases are e.g. Savinase and Esperase (manufacturer Novo Nordisk).
  • a suitable one Lipase is e.g. Lipolase (manufacturer Novo Nordisk).
  • a suitable one Cellulase is e.g. Celluzym (manufacturer Novo Nordisk).
  • soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides, see. US-A-4 746 456, US-A-4 846 995, DE-A-3 711 299, US-A-4 904 408, US-A-4 846 994 and US-A-4 849 126 or modified Celluloses such as Methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.
  • Graying inhibitors and soil release polymers are in the Detergent formulations at 0 to 2.5% by weight, preferably at 0.2 to 1.5% by weight, particularly preferably 0.3 to 1.2% by weight contain.
  • Soil release polymers that are preferably used are from US-A-4,746,456 known graft polymers of vinyl acetate on polyethylene oxide of molecular weight 2500 - 8000 in weight ratio 1.2: 1 to 3.0: 1, as well as commercially available polyethylene terephthalate / polyoxyethylene terephthalate the molecular weight 3000 to 25000 made of polyethylene oxides with a molecular weight of 750 to 5000 Terephthalic acid and ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate from 8: 1 to 1: 1 and the block polycondensates known from DE-A-4 403 866, which Blocks of (a) ester units from polyalkylene glycols of a molecular weight from 500 to 7500 and
  • the powdered or granular detergents can be used as other usual components up to 60% by weight of inorganic adjusting agents contain. Sodium sulfate is usually used for this used. However, the detergents are preferably low in adjusting agents, i.e. they contain up to 20% by weight, particularly preferably up to 8% by weight of adjusting agents.
  • the detergents can be different Have bulk densities in the range of 300 to 1000 g / l. Modern compact laundry detergents generally have high ones Bulk densities, e.g. 550 to 1000 g / l, and show a granular structure.
  • the detergents can optionally contain other customary additives contain.
  • additives e.g. Complexing agents, Phosphonates, optical brighteners, dyes, perfume oils, Foam dampers and corrosion inhibitors may be included. she can also contain up to 20% by weight of water.
  • Example 1 is repeated with the only exception that the Addition product of 30 moles of ethylene oxide with 1 mole of trimethylolpropane used as a means of increasing the rate of dissolution. After stirring the ball formed from the mixture for 29 minutes 500 ml of water at 30 ° C and 500 rpm, the ball was completely in the individual components disintegrate to form a wash liquor.
  • Example 2 The procedure is as described in Example 1, but is used instead of the addition product of ethylene oxide used there on trimethylolpropane, the ethylene oxide derivatives given in the table.

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Description

Die Erfindung betrifft die Verwendung von Umsetzungsprodukten von mindestens dreiwertigen Alkoholen mit Ethylenoxid und/oder Propylenoxid als Zusatz zu teilchenförmigen Waschmittelformulierungen zur Erhöhung ihrer Lösegeschwindigkeit in Wasser in Mengen von 0,1 bis 5 Gew.-%, bezogen auf die Waschmittelformulierungen.The invention relates to the use of reaction products of at least trivalent Alcohols with ethylene oxide and / or Propylene oxide as an additive to particulate detergent formulations to increase their rate of dissolution in water Quantities from 0.1 to 5% by weight, based on the detergent formulations.

Teilchenförmige Waschmittel sollen beim Eintragen in Wasser möglichst rasch in die Einzelbestandteile zerfallen, um die fertige Waschlauge zu bilden. Die Lösegeschwindigkeit mancher teilchenförmiger Waschmittelformulierungen, insbesondere von Kompaktwaschmitteln, die beispielsweise eine Schüttdichte von mindestens 550 g/l haben, beim Zusammenbringen mit Wasser ist jedoch noch verbesserungsbedürftig.Particulate detergents should be as possible when soaked in water quickly disintegrate into individual components to make the finished one To form wash liquor. The dissolution rate of some particulate Detergent formulations, especially compact detergents, which, for example, has a bulk density of at least Have 550 g / l, but when brought together with water is still in need of improvement.

Der Erfindung liegt die Aufgabe zugrunde, ein Waschmittteladditiv zur Verfügung zu stellen, das zu einer Erhöhung der Auflösegeschwindigkeit von teilchenförmigen Waschmitteln in Wasser führt.The invention has for its object a detergent additive to provide that to increase the rate of dissolution of particulate detergents in water.

Die Aufgabe wird erfindungsgemäß gelöst durch Verwendung von Umsetzungsprodukten von mindestens dreiwertigen Alkoholen mit Ethylenoxid und/oder Propylenoxid als Zusatz zu teilchenförmigen Waschmittelformulierungen zur Erhöhung ihrer Lösegeschwindigkeit in Wasser in Mengen von 0,1 bis 5 Gew.-%, bezogen auf die Waschmittelformulierungen.The object is achieved according to the invention by using reaction products of at least with trihydric alcohols Ethylene oxide and / or propylene oxide as an additive to particulate Detergent formulations to increase their dissolving speed in water in amounts of 0.1 to 5% by weight, based on the detergent formulations.

Als mindestens dreiwertige Alkohole eignen sich beispielsweise Glycerin, Diglycerin, Triglycerin, Tetraglycerin, Pentaglycerin, Hexaglycerin, Heptaglycerin und Octaglycerin, Pentaerythrit, Trimethylolpropan, Erythrit, Mannit, Sorbit, Saccharose, Glukose und Polyvinylalkohole mit Molmassen bis zu 20 000. Anstelle der einzelnen Verbindungen kann man auch Mischungen der genannten Verbindungen einsetzen. Von besonderem technischen Interesse ist beispielsweise die Verwendung von hydrierten Stärkehydrolysaten oder hydrierten Glukosesirupen. Beispielsweise kann man im Handel erhältliche hydrierte Stärkehydrolysate der Firma Cerestar einsetzen, die unter dem Warenzeichen SORBIDEX 200 und SORBIDEX 122 angeboten werden. Suitable as at least trihydric alcohols are, for example Glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, Hexaglycerin, heptaglycerin and octaglycerin, pentaerythritol, trimethylolpropane, Erythritol, mannitol, sorbitol, sucrose, glucose and Polyvinyl alcohols with molecular weights up to 20,000. Instead of the individual ones Compounds can also be mixtures of the above Use connections. Is of particular technical interest for example the use of hydrogenated starch hydrolyzates or hydrogenated glucose syrups. For example, you can in the trade use available hydrogenated starch hydrolysates from Cerestar, under the trademarks SORBIDEX 200 and SORBIDEX 122 Tobe offered.

Besonders wirksame Produkte für die Erhöhung der Lösegeschwindigkeit von teilchenförmigen Waschmittelformulierungen sind Umsetzungsprodukte von mindestens dreiwertigen Alkoholen mit Ethylenoxid und/oder Propylenoxid. Diese Umsetzungsprodukte und Verfahren zu ihrer Herstellung gehören zum Stand der Technik. So erhält man beispielsweise durch Umsetzung von Glycerin,Erythrit, Pentaerythrit, Trimethylolpropan, Mannit oder Sorbit mit Ethylenoxid und/oder Propylenoxid in Gegenwart der üblichen Alkoxylierungskatalysatoren wie KOH, NaOH, Ca-Hydroxid, Ca-Oxid oder Trägerkatalysatoren Waschmitteladditive, die die Lösegeschwindigkeit von Waschmittelformulierungen in Wasser gegenüber Polyethylenglykol beträchtlich erhöhen. Die alkoxylierten Produkte können eine breite oder auch eine enge Molmassenverteilung aufweisen. Von besonderer Bedeutung sind hierbei die Umsetzungsprodukte von Glycerin, Erythrit, Pentaerythrit, Trimethylolpropan, Mannit oder Sorbit mit Ethylenoxid. Beispielsweise setzt man 1 Mol eines mindestens dreiwertigen Alkohols mit 1 bis 100 Mol Ethylenoxid um. Diese Produkte können modifiziert werden, indem man sie gegebenenfalls mit bis zu 20 Mol Propylenoxid weiterreagieren läßt. Bei der Herstellung von modifizierten Anlagerungsprodukten des Ethylenoxids kann man jedoch auch so vorgehen, daß man ein Mischgas aus Ethylenoxid und Propylenoxid auf die mindestens dreiwertigen Alkohole einwirken läßt. Eine weitere Variationsmöglichkeit ist dadurch gegeben, daß man die genannten Alkohole zunächst mit Propylenoxid und anschließend mit Ethylenoxid umsetzt. Propylenoxid wird vorzugsweise in einer Menge von 1 bis 15 Mol pro Mol Alkohol eingesetzt. Besonders bevorzugt werden Umsetzungsprodukte von 1 Mol Trimethylolpropan mit 1 bis 100 Mol Ethylenoxid eingesetzt, wobei man meistens Umsetzungsprodukte von 1 Mol Trimethylolpropan mit 3 bis 30 Mol Ethylenoxid anwendet.Particularly effective products for increasing the dissolving speed of particulate detergent formulations are reaction products of at least trihydric alcohols Ethylene oxide and / or propylene oxide. These implementation products and Processes for their production belong to the state of the art. So is obtained, for example, by reacting glycerol, erythritol, Pentaerythritol, trimethylolpropane, mannitol or sorbitol with ethylene oxide and / or propylene oxide in the presence of the usual alkoxylation catalysts such as KOH, NaOH, Ca hydroxide, Ca oxide or Carrier catalysts detergent additives that increase the dissolution rate of detergent formulations in water versus polyethylene glycol increase considerably. The alkoxylated products can have a broad or a narrow molecular weight distribution. The reaction products are of particular importance here of glycerin, erythritol, pentaerythritol, trimethylolpropane, Mannitol or sorbitol with ethylene oxide. For example, you bet 1 mole of at least trihydric alcohol with 1 to 100 moles Ethylene oxide around. These products can be modified by if necessary, they react further with up to 20 mol of propylene oxide leaves. In the production of modified add-on products of ethylene oxide, however, one can also proceed in such a way that one at least a mixed gas of ethylene oxide and propylene oxide can act trihydric alcohols. Another possible variation is given by the fact that the alcohols mentioned first with propylene oxide and then with ethylene oxide implements. Propylene oxide is preferably used in an amount of 1 to 15 moles per mole of alcohol used. Reaction products are particularly preferred of 1 mole of trimethylolpropane with 1 to 100 moles Ethylene oxide used, mostly reaction products of 1 mole of trimethylolpropane with 3 to 30 moles of ethylene oxide.

Außerdem eignen sich ethoxylierte hydrierte Zucker wie Sorbit oder Mannit sowie ethoxylierter Polyvinylalkohol als Waschmitteladditiv, das die Lösegeschwindigkeit von Waschmittelformulierungen beim Auflösen in Wasser erhöht. Die erfindungsgemäß zu verwendenden Zusätze sind in Mengen von 0,1 bis 5, vorzugsweise 0,5 bis 2 Gew.-% in der Waschmittelformulierung enthalten. Sie werden vorzugsweise mit den übrigen Waschmittelbestandteilen möglichst homogen vermischt. Man kann sie jedoch auch auf die Oberfläche der feinteiligen Waschmittelformulierungen auftragen und eindiffundieren lassen.Ethoxylated hydrogenated sugars such as sorbitol are also suitable or mannitol and ethoxylated polyvinyl alcohol as detergent additive, that the dissolving rate of detergent formulations increased when dissolved in water. According to the invention Additives to be used are preferably in amounts of 0.1 to 5 Contain 0.5 to 2 wt .-% in the detergent formulation. she preferably with the other detergent ingredients homogeneously mixed. However, you can also surface them apply the fine-particle detergent formulations and let diffuse in.

Die Waschmittel können pulverförmig sein oder als Granulat, Schuppen, Stränge, Kugeln, Plättchen oder Tabletten vorliegen. Der mittlere Teilchendurchmesser der teilchenförmigen Waschmittelformulierungen beträgt beispielsweise 200 µm bis 5 mm und liegt vorzugsweise in dem Bereich von 1 bis 3 mm. Man kann die Waschmittelformulierungen jedoch auch so portionieren, daß für einen Waschgang in einer Waschmaschine nur eine Kugel oder eine Tablette erforderlich ist. Solche Kugeln oder Tabletten haben dann einen weitaus größeren mittleren Teilchendurchmesser als oben angegeben. Der Vorteil solcher relativ großvolumiger Teilchen liegt in der einfachen Dosierung.The detergents can be in powder form or as granules, Dandruff, strands, balls, platelets or tablets are present. The average particle diameter of the particulate detergent formulations is, for example, 200 µm to 5 mm and is preferably in the range of 1 to 3 mm. You can do that However, portion detergent formulations so that for a wash in a washing machine just a ball or a Tablet is required. Have such bullets or tablets then a much larger average particle diameter than mentioned above. The advantage of such relatively large-volume particles lies in the simple dosage.

Bei den Waschmitteln kann es sich um Vollwaschmittel oder um Spezialwaschmittel handeln. Als Tenside kommen sowohl anionische als auch nichtionische oder Mischungen aus anionischen und nichtionischen Tensiden in Betracht. Der Tensidgehalt der Waschmittel beträgt vorzugsweise 8 bis 30 Gew.-%.The detergents can be heavy duty or Act special detergents. Both anionic and surfactants come as well as nonionic or mixtures of anionic and nonionic Surfactants into consideration. The surfactant content of the detergent is preferably 8 to 30% by weight.

Geeignete anionische Tenside sind beispielsweise Fettalkoholsulfate von Fettalkoholen mit 8 bis 22, vorzugsweise 10 bis 18 Kohlenstoffatomen, z.B. C9- bis C11-Alkoholsulfate, C12- bis C13-Alkoholsulfate, Cetylsulfat, Myristylsulfat, Palmitylsulfat, Stearylsulfat und Talgfettalkoholsulfat.Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, for example C 9 to C 11 alcohol sulfates, C 12 to C 13 alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Weitere geeignete anionische Tenside sind sulfatierte, ethoxylierte C8- bis C22-Alkohole bzw. deren lösliche Salze. Verbindungen dieser Art werden beispielsweise dadurch hergestellt, daß man zunächst einen C8- bis C22-, vorzugsweise einen C10- bis C18-Alkohol alkoxyliert und das Alkoxylierungsprodukt anschließend sulfatiert. Für die Alkoxylierung verwendet man vorzugsweise Ethylenoxid, wobei man pro Mol Fettalkohol 2 bis 50, vorzugsweise 3 bis 20 Mol, Ethylenoxid einsetzt. Die Alkoxylierung der Alkohole kann jedoch auch mit Propylenoxid allein und gegebenenfalls Butylenoxid durchgeführt werden. Geeignet sind außerdem solche alkoxylierte C8- bis C22-Alkohole, die Ethylenoxid und Propylenoxid oder Ethylenoxid und Butylenoxid enthalten. Die alkoxylierten C8- bis C22-Alkohole können die Ethylenoxid-, Propylenoxid- und Butylenoxideinheiten in Form von Blöcken oder in statistischer Verteilung enthalten.Other suitable anionic surfactants are sulfated, ethoxylated C 8 to C 22 alcohols or their soluble salts. Compounds of this type are prepared, for example, by first alkoxylating a C 8 to C 22 , preferably a C 10 to C 18 alcohol and then sulfating the alkoxylation product. Ethylene oxide is preferably used for the alkoxylation, 2 to 50, preferably 3 to 20, moles of ethylene oxide being used per mole of fatty alcohol. However, the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide. Alkoxylated C 8 to C 22 alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide are also suitable. The alkoxylated C 8 to C 22 alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution.

Weitere geeignete anionische Tenside sind Alkylsulfonate wie C8- bis C24-, vorzugsweise C10-C18-Alkansulfonate sowie Seifen wie beispielsweise die Salze von C8- bis C24-Carbonsäuren.Further suitable anionic surfactants are alkyl sulfonates such as C 8 to C 24 , preferably C 10 -C 18 alkane sulfonates and soaps such as the salts of C 8 to C 24 carboxylic acids.

Weitere geeignete anionische Tenside sind C-9- bis C20-linear-Alkylbenzolsulfonate (LAS). Vorzugsweise werden die erfindungsgemäßen Polymeren in LAS-armen Waschmittelformulierungen mit weniger als 4 %, besonders bevorzugt in LAS-freien Formulierungen eingesetzt. Other suitable anionic surfactants are C 9 to C 20 linear alkylbenzenesulfonates (LAS). The polymers according to the invention are preferably used in low-LAS detergent formulations with less than 4%, particularly preferably in LAS-free formulations.

Die anionischen Tenside werden dem Waschmittel vorzugsweise in Form von Salzen zugegeben. Geeignete Kationen in diesen Salzen sind Alkalimetallsalze wie Natrium-, Kalium-, Lithium- und Ammoniumsalze wie z.B. Hydroxyethylammonium-, Di(hydroxyethyl)ammonium- und Tri(hydroxyethyl)ammoniumsalze.The anionic surfactants are preferably in the detergent Form of salts added. Suitable cations in these salts are alkali metal salts such as sodium, potassium, lithium and Ammonium salts such as Hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

Als nichtionische Tenside eignen sich beispielsweise alkoxylierte C8- bis C22-Alkohole. Die Alkoxylierung kann mit Ethylenoxid, Propylenoxid und/oder Butylenoxid durchgeführt werden. Als Tensid einsetzbar sind hierbei sämtliche alkoxylierten Alkohole, die mindestens zwei Moleküle eines vorstehend genannten Alkylenoxids addiert enthalten. Auch hierbei kommen Blockpolymerisate von Ethylenoxid, Propylenoxid und/oder Butylenoxid in Betracht oder Anlagerungsprodukte, die die genannten Alkylenoxide in statistischer Verteilung enthalten. Pro Mol Alkohol verwendet man 2 bis 5, vorzugsweise 3 bis 20 Mol mindestens eines Alkylenoxids. Vorzugsweise setzt man als Alkylenoxid Ethylenoxid ein. Die Alkohole haben vorzugsweise 10 bis 18 Kohlenstoffatomen.Examples of suitable nonionic surfactants are alkoxylated C 8 to C 22 alcohols. The alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as the surfactant. Here too, block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. 2 to 5, preferably 3 to 20, mol of at least one alkylene oxide are used per mol of alcohol. The alkylene oxide used is preferably ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms.

Eine andere Klasse nichtionischer Tenside sind Alkylpolyglucoside mit 8 bis 22, vorzugsweise 10 bis 18 Kohlenstoffatomen in der Alkylkette. Diese Verbindungen enthalten 1 bis 20, vorzugsweise 1,1 bis 5 Glucosideinheiten.Another class of nonionic surfactants are alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the Alkyl chain. These compounds contain 1 to 20, preferably 1.1 to 5 glucoside units.

Eine andere Klasse nichtionischer Tenside sind N-Alkylglucamide der allgemeinen Struktur I bzw. II

Figure 00040001
wobei A ein C6- bis C22-Alkyl, B ein H oder C1- bis C4-Alkyl und C ein Polyhydroxyalkanyl-Rest mit 5 bis 12 C-Atomen und mindestens 3 Hydroxygruppen ist. Vorzugsweise steht A für C10- bis C18-Alkyl-, B für CH3- und C für einen C5 oder C6-Rest. Beispielsweise erhält man derartige Verbindungen durch die Acylierung von reduzierend aminierten Zuckern mit Säurechloriden von C10-C18-Carbonsäuren. Die Waschmittelformulierungen enthalten vorzugsweise mit 3-12 Mol Ethylenoxid ethoxylierte C10-C16-Alkohole, besonders bevorzugt ethoxylierte Fettalkohole als nichtionische Tenside.Another class of nonionic surfactants are N-alkylglucamides of the general structure I or II
Figure 00040001
wherein A is a C 6 to C 22 alkyl, B is an H or C 1 to C 4 alkyl and C is a polyhydroxyalkanyl radical having 5 to 12 C atoms and at least 3 hydroxyl groups. A is preferably C 10 to C 18 alkyl, B is CH 3 and C is a C 5 or C 6 radical. For example, such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C 10 -C 18 carboxylic acids. The detergent formulations preferably contain C 10 -C 16 alcohols ethoxylated with 3-12 mol ethylene oxide, particularly preferably ethoxylated fatty alcohols as nonionic surfactants.

Weitere, bevorzugt in Betracht kommende Tenside sind die aus der WO-A-95/11225 bekannten endgruppenverschlossenen Fettsäureamidalkoxylate der allgemeinen Formel R1-CO-NH-(CH2)n-O-(AO)x-R2 in der

R1
einen C5- bis C21-Alkyl- oder -Alkenylrest bezeichnet,
R2
eine C1- bis C4-Alkylgruppe bedeutet,
A
für C2- bis C4-Alkylen steht,
n
die Zahl 2 oder 3 bezeichnet und
x
einen Wert von 1 bis 6 hat.
Further preferred surfactants are the end group-capped fatty acid amide alkoxylates of the general formula known from WO-A-95/11225 R 1 -CO-NH- (CH 2 ) n -O- (AO) x -R 2 in the
R 1
denotes a C 5 to C 21 alkyl or alkenyl radical,
R 2
represents a C 1 to C 4 alkyl group,
A
represents C 2 -C 4 -alkylene,
n
denotes the number 2 or 3 and
x
has a value from 1 to 6.

Beispiele für solche Verbindungen sind die Umsetzungsprodukte von n-Butyltriglykolamin der Formel H2N-(CH2-CH2-O)3-C4H9 mit Dodecansäuremethylester oder die Reaktionsprodukte von Ethyltetraglykolamin der Formel H2N-(CH2-CH2-O)4-C2H5 mit einem handelsüblichen Gemisch von gesättigten C8" bis C18-Fettsäuremethylestern.Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H 2 N- (CH 2 -CH 2 -O) 3 -C 4 H 9 with methyl dodecanoate or the reaction products of ethyl tetraglycolamine of the formula H 2 N- (CH 2 -CH 2 -O) 4 -C 2 H 5 with a commercially available mixture of saturated C 8 "to C 18 fatty acid methyl esters.

Die pulver- oder granulatförmigen Waschmittel enthalten außerdem einen oder mehrere anorganische Builder. Als anorganische Buildersubstanzen eignen sich alle üblichen anorganischen Builder wie Alumosilikate, Silikate, Carbonate und Phosphate.The powder or granular detergents also contain one or several inorganic builders. As inorganic builder substances all common inorganic builders such as aluminosilicates are suitable, Silicates, carbonates and phosphates.

Geeignete anorganische Builder sind z.B. Alumosilikate mit ionenaustauschenden Eigenschaften wie z.B. Zeolithe. Verschiedene Typen von Zeolithen sind geeignet, insbesondere Zeolith A, X, B, P, MAP und HS in ihrer Na-Form oder in Formen, in denen Na teilweise gegen andere Kationen wie Li, K, Ca, Mg oder Ammonium ausgetauscht sind. Geeignete Zeolithe sind beispielsweise beschrieben in EP-A-0 038 591, EP-A-0 021 491, EP-A-0 087 035, US-A-4 604 224, GB-A-2 013 259, EP-A-0 522 726, EP-A-0 384 070A und WO-A-94/24251.Suitable inorganic builders are e.g. Aluminum silicates with ion exchange Properties such as Zeolites. Various Types of zeolites are suitable, in particular zeolite A, X, B, P, MAP and HS in their Na form or in forms in which Na partly against other cations such as Li, K, Ca, Mg or ammonium are exchanged. Suitable zeolites are, for example described in EP-A-0 038 591, EP-A-0 021 491, EP-A-0 087 035, US-A-4 604 224, GB-A-2 013 259, EP-A-0 522 726, EP-A-0 384 070A and WO-A-94/24251.

Weitere geeignete anorganische Builder sind z.B. amorphe oder kristalline Silikate wie z.B. amorphe Disilikate, kristalline Disilikate wie das Schichtsilikat SKS-6 (Hersteller Hoechst AG). Die Silikate können in Form ihrer Alkali-, Erdalkali- oder Ammoniumsalze eingesetzt werden. Vorzugsweise werden Na-, Li- und Mg-Silikate eingesetzt.Other suitable inorganic builders are e.g. amorphous or crystalline silicates such as amorphous disilicates, crystalline Disilicates such as the layered silicate SKS-6 (manufacturer Hoechst AG). The silicates can be in the form of their alkali, alkaline earth or Ammonium salts are used. Na, Li, and Mg silicates are used.

Weitere geeignete anorganische Buildersubstanzen sind Carbonate und Hydrogencarbonate. Diese können in Form ihrer Alkali-, Erdalkali- oder Ammoniumsalze eingesetzt werden. Vorzugsweise werden Na-, Li- und Mg-Carbonate bzw. Hydrogencarbonate, insbesondere Natriumcarbonat und/oder Natriumhydrogencarbonat eingesetzt. Other suitable inorganic builder substances are carbonates and hydrogen carbonates. These can be in the form of their alkali, alkaline earth or ammonium salts can be used. Preferably be Na, Li and Mg carbonates or hydrogen carbonates, in particular Sodium carbonate and / or sodium bicarbonate used.

Die anorganischen Builder können in den Waschmitteln in Mengen von 0 bis 60 Gew.-% zusammen mit gegebenenfalls zu verwendenden organischen Cobuildern enthalten sein. Die anorganischen Builder können entweder allein oder in beliebigen Kombinationen miteinander in das Waschmittel eingearbeitet werden. In pulver- oder granulatförmigen Waschmitteln werden sie in Mengen von 10 bis 60 Gew.-%, vorzugsweise in Mengen von 20 bis 50 Gew.-% zugesetzt.The inorganic builders can be used in detergents in quantities from 0 to 60% by weight together with those which may be used organic cobuilders. The inorganic builder can either alone or in any combination with each other be incorporated into the detergent. In powder or Granular detergents are used in amounts of 10 to 60% by weight, preferably in amounts of 20 to 50% by weight.

In pulver- oder granulatförmigen oder anderen festen Waschmittelformulierungen sind organische Cobuilder in Mengen von 0,1 bis 20 Gew.-%, vorzugsweise in Mengen von 1 bis 15 Gew.-% zusammen mit anorganischen Buildern enthalten. Die pulver- oder granulatförmigen Vollwaschmittel können außerdem als sonstige übliche Bestandteile ein Bleichsystem bestehend aus mindestens einem Bleichmittel, gegebenenfalls in Kombination mit einem Bleichaktivator und/oder einem Bleichkatalysator enthalten.In powder or granular or other solid detergent formulations are organic cobuilders in quantities from 0.1 to 20 wt .-%, preferably in amounts of 1 to 15 wt .-% together included with inorganic builders. The powder or granular Heavy duty detergents can also be used as other usual Components of a bleaching system consisting of at least one Bleach, optionally in combination with a bleach activator and / or contain a bleaching catalyst.

Geeignete Bleichmittel sind Perborate und Percarbonat in Form ihrer Alkali- insbesondere ihrer Na-Salze. Sie sind in Mengen von 5 bis 30 Gew.-%, vorzugsweise 10 bis 25 Gew.-% in den Formulierungen enthalten. Weitere geeignete Bleichmittel sind anorganische und organische Persäuren in Form ihrer Alkali- oder Magnesiumsalze oder teilweise auch in Form der freien Säuren. Beispiele für geeignete organische Percarbonsäuren bzw. -Salze sind z.B. Mg-Monoterephthalat, Phthalimidopercapronsäure und Dodecan-1,10-dipersäure. Beispiel für ein anorganisches Persäuresalz ist Kaliumperoxomonosulfat (Oxon).Suitable bleaches are perborates and percarbonate in the form their alkali, especially their Na salts. They are in quantities from 5 to 30% by weight, preferably 10 to 25% by weight in the Formulations included. Other suitable bleaches are inorganic and organic peracids in the form of their alkali or Magnesium salts or partly also in the form of the free acids. Examples of suitable organic percarboxylic acids or salts are e.g. Mg monoterephthalate, phthalimidopercaproic acid and Dodecane-1,10-diper acid. Example of an inorganic peracid salt is potassium peroxomonosulfate (oxone).

Geeignete Bleichaktivatoren sind z.B.

  • Acylamine wie Tetraacetylethylendiamin, Tetraacetylglycoluril, N,N'-Diacetyl-N,N'-dimethylharnstoff und 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin
  • acylierte Lactame wie beispielsweise Acetylcaprolactam, Octanoylcaprolactam und Benzoylcaprolactam
  • substituierte Phenolester von Carbonsäuren wie z.B. Na-acetoxybenzolsulfonat, Na-octanoyloxybenzolsulfonat und Na-nonanoyloxybenzolsulfonat
  • acylierte Zucker wie z.B. Pentaacetylglucose
  • Anthranilderivate wie z.B. 2-Methylanthranil oder 2-Phenylanthranil
  • Enolester wie z.B. Isopropenylacetat
  • Oximester wie z.B. O-Acetylacetonoxim
  • Carbonsäureanhydride, wie z.B. Phthalsäureanhydrid oder Essigsäureanhydrid.
Vorzugsweise werden Tetraacetylethylendiamin und Na-nonanoyloxybenzolsulfonate als Bleichaktivatoren eingesetzt. Die Bleichaktivatoren werden Vollwaschmitteln in Mengen von 0,1 bis 15 Gew.-%, vorzugsweise in Mengen von 1,0 bis 8,0 Gew.-%, besonders bevorzugt in Mengen von 1,5 bis 6,0 Gew.-% zugesetzt.Suitable bleach activators are, for example
  • Acylamines such as tetraacetylethylenediamine, tetraacetylglycoluril, N, N'-diacetyl-N, N'-dimethylurea and 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • acylated lactams such as acetylcaprolactam, octanoylcaprolactam and benzoylcaprolactam
  • substituted phenol esters of carboxylic acids such as Na-acetoxybenzenesulfonate, Na-octanoyloxybenzenesulfonate and Na-nonanoyloxybenzenesulfonate
  • acylated sugars such as pentaacetyl glucose
  • Anthranil derivatives such as 2-methylanthranil or 2-phenylanthranil
  • Enol esters such as isopropenyl acetate
  • Oxime esters such as O-acetylacetone oxime
  • Carboxylic anhydrides, such as phthalic anhydride or acetic anhydride.
Tetraacetylethylenediamine and Na nonanoyloxybenzenesulfonates are preferably used as bleach activators. The bleach activators are added to heavy-duty detergents in amounts of 0.1 to 15% by weight, preferably in amounts of 1.0 to 8.0% by weight, particularly preferably in amounts of 1.5 to 6.0% by weight .

Geeignete Bleichkatalysatoren sind quaternisierte Imine und Sulfonimine wie sie in US-A-5 360 568, US-A-5 360 569 und EP-A-0 453 003 beschrieben sind und Mn-Komplexe, vgl. z.B. WO-A-94/21777. Falls Bleichkatalysatoren in den Waschmittelformulierungen eingesetzt werden, sind sie darin in Mengen bis zu 1,5 Gew.-%, vorzugsweise bis zu 0,5 Gew.-%, im Falle der sehr aktiven Mangankomplexe in Mengen bis zu 0,1 Gew.% enthalten.Suitable bleaching catalysts are quaternized imines and Sulfonimines as described in US-A-5 360 568, US-A-5 360 569 and EP-A-0 453 003 and Mn complexes, cf. e.g. WO-A-94/21777. If bleach catalysts in the detergent formulations are used, they are in quantities up to to 1.5 wt .-%, preferably up to 0.5 wt .-%, in the case of very active manganese complexes in amounts up to 0.1% by weight.

Die Waschmittel enthalten vorzugsweise ein Enzymsystem. Dabei handelt es sich um üblicherweise in Waschmitteln eingesetzte Proteasen, Lipasen, Amylasen sowie Cellulasen. Das Enzymsystem kann auf ein einzelnes der Enzyme beschränkt sein oder eine Kombination verschiedener Enzyme beinhalten. Von den handelsüblichen Enzymen werden den Waschmitteln in der Regel Mengen von 0,1 bis 1,5 Gew.-%, vorzugsweise 0,2 bis 1,0 Gew.-% des konfektionierten Enzyms zugesetzt. Geeignete Proteasen sind z.B. Savinase und Esperase (Hersteller Novo Nordisk). Eine geeignete Lipase ist z.B. Lipolase (Hersteller Novo Nordisk). Eine geeignete Cellulase ist z.B. Celluzym (Hersteller Novo Nordisk).The detergents preferably contain an enzyme system. Here are usually used in detergents Proteases, lipases, amylases and cellulases. The enzyme system can be limited to a single one of the enzymes or one Combination of different enzymes. Of the commercially available Enzymes are usually used in quantities of detergents 0.1 to 1.5 wt .-%, preferably 0.2 to 1.0 wt .-% of the made up Enzyme added. Suitable proteases are e.g. Savinase and Esperase (manufacturer Novo Nordisk). A suitable one Lipase is e.g. Lipolase (manufacturer Novo Nordisk). A suitable one Cellulase is e.g. Celluzym (manufacturer Novo Nordisk).

Die Waschmittel enthalten als sonstige übliche Bestandteile vorzugsweise Soil release Polymere und/oder Vergrauungsinhibitoren. Dabei handelt es sich z.B. um

  • Polyester aus Polyethylenoxiden mit Ethylenglykol und/oder Propylenglykol und aromatischen Dicarbonsäuren oder aromatischen und aliphatischen Dicarbonsäuren. Polyester aus einseitig endgruppenverschlossenen Polyethylenoxiden mit zwei- und/oder mehrwertigen Alkoholen und Dicarbonsäuren. Derartige Polyester sind bekannt, vgl. beispielsweise US-A-3 557 039, GB-A-1 154 730, EP-A-0 185 427, EP-A-0 241 984, EP-A-0 241 985, EP-A-0 272 033 und US-A-5 142 020.
The detergents preferably contain soil release polymers and / or graying inhibitors as other common constituents. This is, for example
  • Polyesters from polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids. Polyester made of polyethylene oxides end capped on one side with di- and / or polyhydric alcohols and dicarboxylic acids. Such polyesters are known, cf. for example US-A-3 557 039, GB-A-1 154 730, EP-A-0 185 427, EP-A-0 241 984, EP-A-0 241 985, EP-A-0 272 033 and US -A-5 142 020.

Weitere geeignete Soil release Polymere sind amphiphile Pfropf- oder Copolymere von Vinyl- und/oder Acrylester auf Polyalkylenoxiden, vgl. US-A-4 746 456, US-A-4 846 995, DE-A-3 711 299, US-A-4 904 408, US-A-4 846 994 und US-A-4 849 126 oder modifizierte Cellulosen wie z.B. Methylcellulose, Hydroxypropylcellulose oder Carboxymethylcellulose.Other suitable soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides, see. US-A-4 746 456, US-A-4 846 995, DE-A-3 711 299, US-A-4 904 408, US-A-4 846 994 and US-A-4 849 126 or modified Celluloses such as Methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.

Vergrauungsinhibitoren und Soil release Polymere sind in den Waschmittelformulierungen zu 0 bis 2,5 Gew.-%, vorzugsweise zu 0,2 bis 1,5 Gew.-%, besonders bevorzugt zu 0,3 bis 1,2 Gew.-% enthalten. Bevorzugt eingesetzte Soil release Polymere sind die aus der US-A-4 746 456 bekannten Pfropfpolymeren von Vinylacetat auf Polyethylenoxid der Molmasse 2500 - 8000 im Gewichtsverhältnis 1,2:1 bis 3,0:1, sowie handelsübliche Polyethylenterephthalat/polyoxyethylenterephthalate der Molmasse 3000 bis 25000 aus Polyethylenoxiden der Molmasse 750 bis 5000 mit Terephthalsäure und Ethylenoxid und einem Molverhältnis von Polyethylenterephthalat zu Polyoxyethylenterephthalat von 8:1 bis 1:1 und die aus der DE-A-4 403 866 bekannten Blockpolykondensate, die Blöcke aus (a) Ester-Einheiten aus Polyalkylenglykolen einer Molmasse von 500 bis 7500 und aliphatischen Dicarbonsäuren und/oder Monohydroxymonocarbonsäuren und (b) Ester-Einheiten aus aromatischen Dicarbonsäuren und mehrwertigen Alkoholen enthalten. Diese amphiphilen Blockcopolymerisate haben Molmassen von 1500 bis 25000.Graying inhibitors and soil release polymers are in the Detergent formulations at 0 to 2.5% by weight, preferably at 0.2 to 1.5% by weight, particularly preferably 0.3 to 1.2% by weight contain. Soil release polymers that are preferably used are from US-A-4,746,456 known graft polymers of vinyl acetate on polyethylene oxide of molecular weight 2500 - 8000 in weight ratio 1.2: 1 to 3.0: 1, as well as commercially available polyethylene terephthalate / polyoxyethylene terephthalate the molecular weight 3000 to 25000 made of polyethylene oxides with a molecular weight of 750 to 5000 Terephthalic acid and ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate from 8: 1 to 1: 1 and the block polycondensates known from DE-A-4 403 866, which Blocks of (a) ester units from polyalkylene glycols of a molecular weight from 500 to 7500 and aliphatic dicarboxylic acids and / or Monohydroxymonocarboxylic acids and (b) ester units from aromatic Contain dicarboxylic acids and polyhydric alcohols. This Amphiphilic block copolymers have molecular weights from 1500 to 25000.

Ein typisches pulver- oder granulatförmiges Vollwaschmittel kann beispielsweise folgende Zusammensetzung aufweisen:

  • 3 bis 50, vorzugsweise 8 bis 30 Gew.-% mindestens eines anionischen und/oder nichtionischen Tensids,
  • 5 bis 50, vorzugsweise 15 bis 42,5 Gew.-% mindestens eines anorganischen Builders,
  • 5 bis 30, vorzugsweise 10 bis 25 Gew.-% eines anorganischen Bleichmittels,
  • 0,1 bis 15, vorzugsweise 1 bis 8 Gew.-% eines Bleichaktivators,
  • 0 bis 1, vorzugsweise bis höchstens 0,5 Gew.-% eines Bleichkatalysators,
  • 0,05 bis 5 Gew.-%, vorzugsweise 0,2 bis 2,5 Gew.-% eines Farbübertragungsinhibitors auf Basis von wasserlöslichen Homopolymerisaten von N-Vinylpyrrolidon oder N-Vinylimidazol, wasserlöslichen Copolymerisaten aus N-Vinylimidazol und N-Vinylpyrrolidon, vernetzten Copolymerisaten aus N-Vinylimidazol und N-Vinylpyrrolidon mit einer Teilchengröße von 0,1 bis 500, vorzugsweise bis zu 250 µm, wobei diese Copolymerisate 0,01 bis 5, vorzugsweise 0,1 bis 2 Gew.-% N,N'-Divinylethylenharnstoff als Vernetzer enthalten. Weitere Farbübertragungsinhibitoren sind wasserlösliche und auch vernetzte Polymerisate von 4-Vinylpyridin-N-oxid, die durch Polymerisieren von 4-Vinylpyridin und anschließende Oxidation der Polymeren erhältlich sind,
  • 0,1 bis 20, vorzugsweise 1 bis 15 Gew.-% mindestens einer modifizierten Polyasparaginsäure als organischer Cobuilder,
  • 0,2 bis 1,0 Gew.-% Protease,
  • 0,2 bis 1,0 Gew.-% Lipase,
  • 0,3 bis 1,5 Gew.-% eines Soil release Polymers.
A typical powder or granular heavy-duty detergent can have the following composition, for example:
  • 3 to 50, preferably 8 to 30% by weight of at least one anionic and / or nonionic surfactant,
  • 5 to 50, preferably 15 to 42.5% by weight of at least one inorganic builder,
  • 5 to 30, preferably 10 to 25% by weight of an inorganic bleaching agent,
  • 0.1 to 15, preferably 1 to 8% by weight of a bleach activator,
  • 0 to 1, preferably up to at most 0.5% by weight of a bleaching catalyst,
  • 0.05 to 5% by weight, preferably 0.2 to 2.5% by weight, of a color transfer inhibitor based on water-soluble homopolymers of N-vinylpyrrolidone or N-vinylimidazole, water-soluble copolymers of N-vinylimidazole and N-vinylpyrrolidone Copolymers of N-vinylimidazole and N-vinylpyrrolidone with a particle size of 0.1 to 500, preferably up to 250 microns, these copolymers 0.01 to 5, preferably 0.1 to 2 wt .-% N, N'-divinylethylene urea included as crosslinker. Further color transfer inhibitors are water-soluble and also crosslinked polymers of 4-vinylpyridine-N-oxide, which can be obtained by polymerizing 4-vinylpyridine and subsequent oxidation of the polymers,
  • 0.1 to 20, preferably 1 to 15% by weight of at least one modified polyaspartic acid as an organic cobuilder,
  • 0.2 to 1.0% by weight of protease,
  • 0.2 to 1.0% by weight lipase,
  • 0.3 to 1.5% by weight of a soil release polymer.

In farbschonenden Spezialwaschmitteln (beispielsweise in sogenannten Colorwaschmitteln) wird oft auf ein Bleichsystem vollständig oder teilweise verzichtet. Ein typisches pulver- oder granulatförmiges Colorwaschmittel kann beispielsweise folgende Zusammensetzung aufweisen:

  • 3 bis 50, vorzugsweise 8 bis 30 Gew.-% mindestens eines anionischen und/oder nichtionischen Tensids,
  • 10 bis 60, vorzugsweise 20 bis 55 Gew.-% mindestens eines anorganischen Builders,
  • 0 bis 15, vorzugsweise 0 bis 5 Gew.-% eines anorganischen Bleichmittels,
  • 0,05 bis 5 Gew.-%, vorzugsweise 0,2 bis 2,5 Gew.-% eines Farbübertragungsinhibitors, vgl. oben,
  • 0,1 bis 20, vorzugsweise 1 bis 15 Gew.-% mindestens einer oben beschriebenen modifizierten Polyasparaginsäure als organischen Cobuilder,
  • 0,2 bis 1,0 Gew.-% Protease,
  • 0,2 bis 1,0 Gew.-% Cellulase,
  • 0,2 bis 1,5 Gew.-% eines Soil release Polymers, z.B. ein Pfropfpolymerisat von Vinylacetat auf Polyethylenglykol.
A bleaching system is often completely or partially dispensed with in color-preserving special detergents (for example in so-called color detergents). A typical powder or granular color detergent can have the following composition, for example:
  • 3 to 50, preferably 8 to 30% by weight of at least one anionic and / or nonionic surfactant,
  • 10 to 60, preferably 20 to 55% by weight of at least one inorganic builder,
  • 0 to 15, preferably 0 to 5% by weight of an inorganic bleaching agent,
  • 0.05 to 5% by weight, preferably 0.2 to 2.5% by weight, of a color transfer inhibitor, cf. above,
  • 0.1 to 20, preferably 1 to 15% by weight of at least one modified polyaspartic acid described above as an organic cobuilder,
  • 0.2 to 1.0% by weight of protease,
  • 0.2 to 1.0% by weight cellulase,
  • 0.2 to 1.5% by weight of a soil release polymer, for example a graft polymer of vinyl acetate on polyethylene glycol.

Die pulver- oder granulatförmigen Waschmittel können als sonstige übliche Bestandteile bis zu 60 Gew.-% an anorganischen Stellmitteln enthalten. Üblicherweise wird hierfür Natriumsulfat verwendet. Vorzugsweise sind die Waschmittel aber arm an Stellmitteln, d.h. sie enthalten bis zu 20 Gew.-%, besonders bevorzugt bis zu 8 Gew.-% an Stellmitteln. Die Waschmittel können unterschiedliche Schüttdichten im Bereich von 300 bis 1000 g/l besitzen. Moderne Kompaktwaschmittel besitzen in der Regel hohe Schüttdichten,z.B. 550 bis 1000 g/l, und zeigen einen Granulataufbau.The powdered or granular detergents can be used as other usual components up to 60% by weight of inorganic adjusting agents contain. Sodium sulfate is usually used for this used. However, the detergents are preferably low in adjusting agents, i.e. they contain up to 20% by weight, particularly preferably up to 8% by weight of adjusting agents. The detergents can be different Have bulk densities in the range of 300 to 1000 g / l. Modern compact laundry detergents generally have high ones Bulk densities, e.g. 550 to 1000 g / l, and show a granular structure.

Die Waschmittel können gegebenenfalls weitere übliche Zusätze enthalten. Als weitere Zusätze können gegebenenfalls z.B. Komplexbildner, Phosphonate, optische Aufheller, Farbstoffe, Parfümöle, Schaumdämpfer und Korrosionsinhibitoren enthalten sein. Sie können außerdem bis zu 20 Gew.-% Wasser enthalten.The detergents can optionally contain other customary additives contain. As further additives, e.g. Complexing agents, Phosphonates, optical brighteners, dyes, perfume oils, Foam dampers and corrosion inhibitors may be included. she can also contain up to 20% by weight of water.

Beispiel 1example 1

25 g handelsübliche Persil® Megaperls werden mit 3,5 g Wasser bei 60°C zu einem Brei verrührt und mit 0,5 g eines Additionsproduktes von 10 Mol Ethylenoxid an 1 Mol Trimethylolpropan innig vermischt. Aus 1,00 g der so erhältlichen Paste wird eine Kugel geformt. Man bestimmt dann die Zeit, die für einen vollständigen Zerfall der Kugel in die Einzelbestandteile unter Bildung einer Waschflotte erforderlich ist, indem man die Kugel in 500 ml Wasser bei 30°C mit einem Magnetrührer bei 500 U/min rührt. Die Kugel war nach einer Zeit von 27 min vollständig in die Einzelbestandteile unter Bildung einer Waschflotte zerfallen.25 g of commercially available Persil® Megaperls are mixed with 3.5 g of water 60 ° C stirred to a slurry and with 0.5 g of an addition product of 10 moles of ethylene oxide intimately mixed with 1 mole of trimethylolpropane. A ball is formed from 1.00 g of the paste obtained in this way. One then determines the time it takes for a complete Disintegration of the ball into the individual components to form one Wash liquor is required by placing the ball in 500 ml of water at 30 ° C with a magnetic stirrer at 500 rpm. The bullet was completely in the individual components after a time of 27 min disintegrate to form a wash liquor.

Beispiel 2Example 2

Beispiel 1 wird mit der einzigen Ausnahme wiederholt, daß man das Additionsprodukt von 30 Mol Ethylenoxid an 1 Mol Trimethylolpropan als Mittel zur Erhöhung der Lösegeschwindigkeit einsetzt. Nach 29 minütigem Rühren der aus der Mischung geformten Kugel in 500 ml Wasser bei 30°C und 500 U/min war die Kugel vollständig in die Einzelbestandteile unter Bildung einer Waschflotte zerfallen.Example 1 is repeated with the only exception that the Addition product of 30 moles of ethylene oxide with 1 mole of trimethylolpropane used as a means of increasing the rate of dissolution. After stirring the ball formed from the mixture for 29 minutes 500 ml of water at 30 ° C and 500 rpm, the ball was completely in the individual components disintegrate to form a wash liquor.

Vergleichsbeispiel 1Comparative Example 1

25 g handelsübliche Persil® Megaperls werden mit 3,5 g Wasser bei 60°C zu einem Brei verrührt. Aus 1,00 g dieser Mischung formt man eine Kugel und bestimmt dann wie in Beispiel 1 angegeben die Zeit, die für einen vollständigen Zerfall der Kugel in die Einzelbestandteile unter Bildung einer Waschflotte erforderlich ist. Hierfür benötigte man 35 min.25 g of commercially available Persil® Megaperls are mixed with 3.5 g of water 60 ° C stirred into a paste. One forms from 1.00 g of this mixture a ball and then determines the as given in Example 1 Time for a complete disintegration of the ball into the Individual components required to form a wash liquor is. This took 35 minutes.

Vergleichsbeispiele 2 bis 6Comparative Examples 2 to 6

Man verfährt wie in Beispiel 1 beschrieben, verwendet jedoch anstelle des dort eingesetzten Additionsproduktes von Ethylenoxid an Trimethylolpropan die in der Tabelle angegebenen Ethylenoxidderivate.The procedure is as described in Example 1, but is used instead of the addition product of ethylene oxide used there on trimethylolpropane, the ethylene oxide derivatives given in the table.

Die Zeit, die für einen vollständigen Zerfall der Kugel in die Einzelbestandteile unter Bildung einer Waschflotte erforderlich war, ist ebenfalls in der Tabelle angegeben. Vergleichsbeispiel Ethylenoxid-derivat Molmasse MN Zeit [min] für den vollständigen Zerfall der Kugel, die aus der Mischung geformt wurde 2 Polyethylenglykol 300 31 3 Polyethylenglykol 600 32 4 Polyethylenglykol 1500 34 5 Polyethylenglykol 4000 32 6 Additionsprodukt von 34 Mol Ethylenoxid an 1 Mol C13/C15-Alkohol 34 The time required for the ball to completely disintegrate into the individual components to form a wash liquor is also given in the table. Comparative example Ethylene oxide derivative Molar mass M N Time [min] for the ball to decay completely, which was formed from the mixture 2nd Polyethylene glycol 300 31 3rd Polyethylene glycol 600 32 4th Polyethylene glycol 1500 34 5 Polyethylene glycol 4000 32 6 Addition product of 34 moles of ethylene oxide with 1 mole of C 13 / C 15 alcohol 34

Claims (8)

  1. The use of reaction products of at least trihydric alcohols with ethylene oxide and/or propylene oxide as additive to particulate detergent formulations to increase their rate of dissolving in water in amounts of from 0.1 to 5 % by weight based on the detergent formulations.
  2. The use as claimed in claim 1, wherein glycerol, erythritol, pentaerythritol, trimethylolpropane, mannitol or sorbitol are reacted as at least trihydric alcohols.
  3. The use as claimed in claim 1 or 2, wherein the reaction products of 1 mol of an at least 3-hydric alcohol with 1 to 100 mol of ethylene oxide and, where appropriate, up to 20 mol of propylene oxide are employed.
  4. The use as claimed in claim 1 or 2, wherein the reaction products of 1 mol of trimethylolpropane with 1 to 100 mol of ethylene oxide are employed.
  5. The use as claimed in claim 1 or 2, wherein the reaction products of 1 mol of trimethylolpropane with 3 to 30 mol of ethylene oxide are employed.
  6. The use as claimed in any of claims 1 to 5, wherein the agents increasing the rate of dissolving are employed in amounts of from 0.5 to 2.5 % by weight based on the detergent formulations.
  7. The use as claimed in any of claims 1 to 6, wherein the detergent formulations have an apparent density of from 550 to 1000 g/l.
  8. The use as claimed in any of claims 1 to 6, wherein the detergent formulations have an apparent density of at least 700 g/l.
EP97923959A 1996-05-22 1997-05-21 Use of at least trivalent alcohols and their alkoxylation products for increasing the speed of dissolution of particulate detergent formulations in water Expired - Lifetime EP0901515B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19620364A DE19620364A1 (en) 1996-05-22 1996-05-22 Use of at least trihydric alcohols and their alkoxylation products to increase the dissolution rate of particulate detergent formulations in water
DE19620364 1996-05-22
PCT/EP1997/002590 WO1997044426A1 (en) 1996-05-22 1997-05-21 Use of at least trivalent alcohols and their alkoxylation products for increasing the speed of dissolution of particulate detergent formulations in water

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EP0901515A1 EP0901515A1 (en) 1999-03-17
EP0901515B1 true EP0901515B1 (en) 2000-03-22

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EP (1) EP0901515B1 (en)
JP (1) JP2000510896A (en)
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DK (1) DK0901515T3 (en)
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WO (1) WO1997044426A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0938539B1 (en) * 1996-11-18 2001-08-16 Basf Aktiengesellschaft Use of alkoxylation products of at least trivalent alcohols for increasing the dissolution rate in water of particulate laundry detergent compositions
EP1201741A1 (en) * 2000-10-31 2002-05-02 The Procter & Gamble Company Detergent compositions
BRPI0619784A2 (en) 2005-12-02 2013-01-15 Basf Se use of a chemical composition
US8197928B2 (en) 2006-12-29 2012-06-12 E. I. Du Pont De Nemours And Company Intrusion resistant safety glazings and solar cell modules
WO2011163657A1 (en) 2010-06-25 2011-12-29 E. I. Du Pont De Nemours And Company Polyoxymethylene compositions with branched polymers

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0080222B2 (en) * 1981-11-16 1991-03-20 The Procter & Gamble Company Process for preparing granular detergent compositions containing an intimately admixed anionic surfactant and an anionic polymer
JPS6088100A (en) * 1983-10-21 1985-05-17 ライオン株式会社 Granular detergent composition
JPS6257500A (en) * 1985-09-05 1987-03-13 ライオン株式会社 Granulation of cationic surfactant
JPH0224399A (en) * 1988-07-14 1990-01-26 Dai Ichi Kogyo Seiyaku Co Ltd Additive for powdered detergent
JPH04146998A (en) * 1990-10-11 1992-05-20 Lion Corp Process for modifying high bulk density detergent
DE4124701A1 (en) * 1991-07-25 1993-01-28 Henkel Kgaa METHOD FOR THE PRODUCTION OF SOLID DETERGENT AND CLEANING AGENT WITH HIGH SHOCK WEIGHT AND IMPROVED SOLUTION SPEED
CA2189752A1 (en) * 1994-05-16 1995-11-23 Charles Louis Stearns Granular detergent composition containing admixed fatty alcohols for improved cold water solubility
JPH10504329A (en) * 1994-06-13 1998-04-28 ザ、プロクター、エンド、ギャンブル、カンパニー Detergent composition containing anionic surfactant and water-soluble saccharide
DE19509752A1 (en) * 1995-03-17 1996-09-19 Henkel Kgaa Compressed washing and cleaning agents with high powder density

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EP0901515A1 (en) 1999-03-17
DE19620364A1 (en) 1997-11-27
DE59701320D1 (en) 2000-04-27
DK0901515T3 (en) 2000-07-17
JP2000510896A (en) 2000-08-22
WO1997044426A1 (en) 1997-11-27
US6147048A (en) 2000-11-14
ES2144865T3 (en) 2000-06-16

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