EP1141212A1 - Produit de lavage sous forme de pate - Google Patents

Produit de lavage sous forme de pate

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Publication number
EP1141212A1
EP1141212A1 EP99965439A EP99965439A EP1141212A1 EP 1141212 A1 EP1141212 A1 EP 1141212A1 EP 99965439 A EP99965439 A EP 99965439A EP 99965439 A EP99965439 A EP 99965439A EP 1141212 A1 EP1141212 A1 EP 1141212A1
Authority
EP
European Patent Office
Prior art keywords
weight
composition according
fatty acid
agent
alkali
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
EP99965439A
Other languages
German (de)
English (en)
Other versions
EP1141212B1 (fr
Inventor
Khalil Shamayeli
Thomas Merz
Edgar Köppelmann
Heinrich Peter Furitsch
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.)
Ecolab Inc
Original Assignee
Henkel Ecolab GmbH and Co KG
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Filing date
Publication date
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • 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

Definitions

  • the present invention relates to pasty detergents for use in commercial laundries, a method for producing such compositions and a disinfectant washing method in commercial laundries.
  • Detergents used in the household are tailored to the needs there; they are usually powdery or sufficiently liquid to be poured out and dosed easily. Since liquid detergents of this type are also said to be stable in storage within relatively wide temperature ranges, additions of organic solvents and / or hydrotropes are frequently added, but these do not themselves contribute to the washing or cleaning result and are therefore undesirable. A possibility for circumventing possible dosing problems with insufficiently liquid agents is proposed in the European patent application EP 253 151 A2.
  • liquid, partly highly viscous detergents based on nonionic and anionic surfactants which contain polyethylene glycol as hydrotrope and which do not have to be dosed by the user in liquid form, but rather are packed in portions in bags made of water-soluble material, for example polyvinyl alcohol.
  • the paste-like detergent described in the European patent EP 295 525 B1 consists of a phase which is liquid in the temperature range below 10 ° C. and which is formed from nonionic surfactant, and a solid phase of a certain particle size dispersed therein, which is formed from washing alkalis, sequestering agents and optionally anionic surfactants becomes.
  • surfactants or their mixtures are used, the pour point (solidification point) of which must be below 5 ° C in order to avoid solidification of the paste at low transport and storage temperatures.
  • This detergent paste is intended for commercial laundries and is so fluid that it can be conveyed via a suction line using a conventional feed pump.
  • Another paste-like detergent which, as a nonionic surfactant, comprises 40 to 70% by weight of ethoxylated fatty alcohol with 10 to 20 carbon atoms which is liquid at room temperature and an average degree of ethoxylation of 1 to 8 and 20 to 50% by weight of ethoxylated and propoxylated fatty alcohol which is liquid at room temperature
  • ethoxylated fatty alcohol with 10 to 20 carbon atoms which is liquid at room temperature and an average degree of ethoxylation of 1 to 8 and 20 to 50% by weight of ethoxylated and propoxylated fatty alcohol which is liquid at room temperature
  • This pasty washing or cleaning agent is so strictly viscous that it is not flowable at room temperature under the influence of gravity, but has a significantly lower viscosity when sheared and is then flowable under the influence of gravity.
  • the metering of this pasty detergent or cleaning agent is preferably carried out by subjecting the agent to lowering the viscosity to shear and then metering the flowable agent by means of feed pumps.
  • a pasty detergent for use in commercial laundries which contains nonionic surfactant, organic and / or inorganic builders, alkalizing agents and optionally bleaching agent, enzyme, graying-inhibiting polymer and / or other conventional ingredients and characterized in that it contains 5% by weight to 30% by weight of an ethoxylated alcohol of the general formula R 1 - (OC H- 4 ) m -OH (I), in which R 1 is an alkyl or alkenyl radical with 9 is up to 15 carbon atoms and the average degree of ethoxylation m can assume values from 1 to 8, 1% by weight to 20% by weight of an ethoxylated alcohol of the general formula R - (OC 2 H- t ) n -OH (II ), in which R is an alkyl or alkenyl radical having 12 to 22 carbon atoms and the average degree of ethoxylation n can assume values from 3 to 14, with the proviso that
  • alkalizing agent l in particular alkali metal silicate, 1% by weight to 20% by weight medium- to long-chain alcohol or alkyl ether of the general formula R 3 -OR 4 (III), in which R 3 is an alkyl or alkenyl radical with 6 to 22 C- Atoms, in particular 8 to 22 carbon atoms and R 4 hydrogen or an alkyl radical with 1 to 6 carbon atoms, and contains up to 15% by weight of organic builders of the polymeric polycarboxylate type, polymeric polycarboxylates being understood as meaning polymerization products of unsaturated mono- and / or dicarboxylic acids which, apart from Carboxyl groups have no further functionalities.
  • the commercial washing process differs from household laundry, among other things, in that different types of textiles and differently soiled textiles also occur, but largely uniform mass washing occurs within the material to be washed at the same time, which allows a washing technique that is specifically tailored to the respective cleaning task.
  • there is a greater demand for efficient cleaning processes in commercial laundering than in household laundry since extremely soiled laundry and infected hospital laundry can occur.
  • commercial laundries wash almost exclusively with water that has been freed from hardness ions.
  • the agents known from the documents mentioned above have a high cleaning performance and are very well suited for the commercial washing of soiled laundry. If laundry containing possibly even pathogenic microorganisms arises, however, they are unable to meet the requirement for simultaneous disinfection, so that the additional use of disinfectant agents is necessary when they are used.
  • the present invention is a pasty detergent for use in commercial laundry, containing nonionic surfactant, organic and / or inorganic builders, bleaching agents based on peroxygen, and optionally other conventional ingredients, which is characterized in that it contains 30% by weight to 60% by weight of nonionic surfactant, 0.5% by weight to 5% by weight, in particular 0.5% by weight to 3% by weight of fatty acid and / or fatty acid alkali salt, 5% by weight to 15% by weight of citrate and / or citric acid and 15% by weight to 35 Wt .-% contains inorganic peroxygen compound and is free of alkali metasilicate and bleach activator. It must be surprising that despite the absence of bleach activators, which are to be understood here under perhydrolysis precursor compounds forming percarboxylic acids such as esters and amides, a disinfectant is obtained.
  • Another object of the invention is a method for washing and disinfecting laundry in commercial laundry, using a corresponding paste-like agent. It is preferably used in the 60 ° C wash program, i.e. at a wash temperature of around 60 ° C.
  • the liquid phase of the paste-like composition according to the invention is essentially formed by nonionic surfactants.
  • An agent according to the invention preferably contains 32% by weight to 55% by weight, in particular 35% by weight to 50% by weight nonionic surfactant in the form of one or more ethoxylated and / or propoxylated alcohols, preference being given to using those which correspond to the above-mentioned formulas I or II. The use of mixtures of these is particularly preferred.
  • R 5 is an alkyl or alkenyl radical having 9 to 15 carbon atoms, in particular 12 to 15 carbon atoms, and the average degree of ethoxylation x can assume values from 3 to 7 and the average degree of propoxylation y can assume values from 2 to 8 agents according to the invention may also be present.
  • the viscosity of the agent according to the invention can be adjusted by the combination of ethoxylated alcohols with the formulas I and II.
  • the radicals R 1 , R 2 and R 5 can be linear or branched, for example methyl-branched in the 2-position, linear radicals having primary etherified alcohol functions being preferred.
  • the nonionic surfactant according to formula I preferably has a carbon chain length of 8 to 14, in particular 12 to 14, carbon atoms and an average degree of ethoxylation m of 1 to 8, in particular 1 to 5.
  • the nonionic surfactant according to formula II has a broader carbon chain length distribution towards longer chains with 12 to 22, in particular 12 to 18 and particularly preferably 16 to 18 carbon atoms and a higher average degree of ethoxylation n of 3 to 14, in particular 6 to 12.
  • the ethoxylated alcohols of the formula I and the ethoxylated alcohols of the formula II are preferably in weight ratios of 2: 1 to 1: 1.8.
  • the agent according to the invention can contain further nonionic surfactants commonly used in washing and cleaning agents, such as, for example, alkyl polyglycosides and / or fatty acid polyhydroxyamides.
  • the surfactant component is preferably free from exclusively propoxylated alcohols.
  • R 4 is preferably a methyl, ethyl, propyl or butyl group, hydrogen and the methyl group, in particular hydrogen, being particularly preferred.
  • the agents contain up to 15% by weight, preferably 2% by weight, to
  • Fatty acids or their alkali metal salts the so-called soaps, or mixtures of fatty acids and soaps are preferably in amounts according to the invention in quantities of 0.75% by weight to 2.5% by weight, in particular from 1% by weight to 2% by weight. -%, contain.
  • Suitable soaps are in particular the alkali metal salts of the saturated and / or unsaturated C 2 - 8 fatty acids, for example coconut, palm kernel or tallow fatty acid, the corresponding acids also being able to be used as such.
  • an optionally saponified carboxylic acid mixture is made, in each case based on the total carboxylic acid mixture, 2 wt .-% to 8 wt .-% C 14 -, up to 1% by weight of C 15 - 18 wt .-% to 24 % By weight d 6 -, up to 3% by weight C 17 -, 20% by weight to 42% by weight cis and 30% by weight to 44% by weight C 2 o -22 - Carboxylic acid.
  • the weight ratio of fatty acid to fatty acid alkali salt is preferably in the range from 1:99 to 50:50, in particular from 5:95 to 25:75.
  • the agent can contain up to 10% by weight, preferably up to 5% by weight and in particular 0.5% by weight to 3% by weight of synthetic anionic surfactants, in particular selected from the alkylbenzenesulfonates, alkyl or Alkenyl sulfates and / or ether sulfates.
  • synthetic anionic surfactants which can preferably be incorporated into the agent according to the invention in solid, finely divided, largely anhydrous form, include, in particular, those of the sulfonate or sulfate type, which are normally present as alkali metal salts, preferably as sodium salts.
  • the surfactants of the sulfonate type mentioned can also be used in the form of their free acids.
  • Suitable anionic surfactants of the sulfonate type are linear alkane sulfonates in addition to the C- 13- alkylbenzenesulfonates
  • 1 1 to 15 carbon atoms as can be obtained by sulfochlorination or sulfoxidation of alkanes and subsequent saponification or neutralization, Salts of sulfo fatty acids and their esters derived from saturated C 12 to C 8 fatty acids and lower alcohols, such as methanol, ethanol and propanol, in particular in the ⁇ -position sulfonated, and olefin sulfonates, such as those obtained by sulfonation of terminal C 12 - to form C 1 olefins and subsequent alkaline hydrolysis.
  • Suitable surfactants of the sulfate type are in particular the primary alkyl sulfates with preferably linear alkyl radicals having 10 to 20 carbon atoms, which have an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as countercation.
  • the derivatives of linear alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols are particularly suitable. Accordingly, the sulfation products of primary fatty alcohols with linear dodecyl, tetradecyl or octadecyl radicals and mixtures thereof are particularly useful.
  • alkyl sulfates contain a tallow alkyl radical, that is to say mixtures with essentially hexadecyl and octadecyl radicals.
  • the alkyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
  • ether sulfates can be contained in the compositions.
  • Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.
  • the solid phase of the agent according to the invention is essentially formed by the alkalizing agents, the inorganic peroxygen compounds and the builder substances, it being possible for further particulate auxiliaries to be present.
  • the solid phase should be dispersed as homogeneously as possible in the liquid surfactant phase.
  • the constituents of the paste-like composition contained as a solid phase should be finely divided and have an average grain size in the range from 5 ⁇ m to 200 ⁇ m, with at most 15% of the particles having a grain size of more than 200 ⁇ m.
  • relatively coarse-grained solids for example those which contain 20% to 50% particles with particle sizes above 100 ⁇ m, without disadvantage into the paste-like compositions.
  • the average grain size of the particles forming the solid phase bears 10 ⁇ m to 80 ⁇ m and in particular 10 ⁇ m to 60 ⁇ m, the maximum grain size being below 300 ⁇ m, in particular below 250 ⁇ m. 90% by weight of the solid powdery constituents are preferably less than 200 ⁇ m, in particular less than 150 ⁇ m.
  • the average grain size can be determined using known methods (for example by means of laser diffraction or a Coulter Counter).
  • the alkalizing agents contained as a further component are often also referred to as washing alkalis. They are mainly assigned to the fixed phase. Under the conditions of use of agents according to the invention, they ensure a pH in the alkaline range which is normally in the range from 9.5 to 11.5, in particular from 10 to 11 (measured in a 1% strength by weight solution of the agent in ion-exchanged water).
  • the preferred alkalizing agent is alkali carbonate, which can optionally also be used in a mixture with alkali hydrogen carbonate.
  • Alkali metal silicates as strong alkalizing agents are not contained in the paste-like agents according to the invention.
  • the proportion of alkalizing agents in the agents is generally 20% by weight to 80% by weight, preferably 30% by weight to 70% by weight and in particular 40% by weight to 60% by weight.
  • polymeric alkali metal phosphates such as sodium tripolyphosphate
  • Their proportion is preferably up to 70% by weight, in particular 15% by weight to 40% by weight, based on the total composition, the proportion of the other solids, for example the alkali metal carbonate and / or optionally contained aluminosilicate, accordingly can be reduced.
  • they contain 5% by weight to 15% by weight, in particular 6% by weight to 10% by weight, of alkali metal carbonate and / or alkali metal bicarbonate.
  • An agent according to the invention contains citric acid, alkali citrate or mixtures thereof as an organic builder substance.
  • other monomeric polycarboxylic acids or hydroxycarboxylic acids such as gluconic acid or its salts, and customary co-builders or complexing agents from the class of the aminopolycarboxylic acids and polyphosphonic acids are suitable.
  • To the aminopoly carboxylic acids include nitrilotriacetic acid, ethylenediaminetetraacetic acid,
  • Diethylenetriaminepentaacetic acid and its higher homologues with N, N-bis (carboxymethyl) aspartic acid being preferred.
  • Suitable polyphosphonic acids are l-hydroxyethane-l, l-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and their higher homologs, such as, for example, diethylenetetramine tetra (methylenephosphonic acid).
  • the aforementioned acids are usually used in the form of their alkali metal salts, in particular the sodium or potassium salts.
  • the builders which can also be used include homopolymeric and / or copolymeric carboxylic acids or their alkali metal salts, the sodium or potassium salts also being particularly preferred here.
  • Polymeric carboxylates or polymeric carboxylic acids with a relative molecular weight of at least 350 in the form of their water-soluble salts, in particular in the form of the sodium and / or potassium salts, have proven to be particularly suitable, such as oxidized polysaccharides according to international patent application WO 93/08251, polyacrylates , Polymethacrylates, polymaleinates and in particular copolymers of acrylic acid with maleic acid or maleic anhydride, preferably those of 50 to 70% acrylic acid and 50 to 10% maleic acid, as are characterized, for example, in European patent EP 022 551.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C 4 -C 8 dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Polymers of this type can be produced in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular weight of between 1,000 and 200,000. Further preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
  • polyacetal carboxylic acids as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, which are obtained by polymerizing esters of glycolic acid, introducing stable terminal end groups and saponifying to give the sodium or potassium salts.
  • polymeric acids which are obtained by polymerizing acrolein and disproportionating the polymer according to Canizzaro using strong alkalis. They are essentially made up of acrylic acid units and vinyl alcohol units or acrolein units.
  • An agent according to the invention preferably contains 8% by weight to 12.5% by weight of citrate and / or citric acid. In addition to citrate and / or citric acid, it preferably contains 2% by weight to 12% by weight, in particular 5% by weight to 10% by weight, of further organic builders in the form of polymeric polycarboxylate.
  • crystalline alkali silicates and finely divided alkali alumosilicates are suitable as inorganic builders for use in agents according to the invention.
  • Suitable zeolites normally have a calcium binding capacity in the range from 100 to 200 mg CaO / g, which can be determined according to the information in German patent DE 24 12 837.
  • Their particle size is usually in the range from 1 ⁇ m to 10 ⁇ m. They are used in dry form. The water contained in bound form in the zeolites does not interfere in the present case.
  • Such crystalline layered silicates are described for example in European patent application EP 164 514.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 0 5 "yH 2 O are preferred, whereby ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171.
  • Crystalline silicates which can be used are under the names SKS-6 (manufacturer Hoechst) and Nabion® 15 (manufacturer Rhone-Poulenc)
  • SKS-6 manufactured Hoechst
  • Nabion® 15 manufactured Rhone-Poulenc
  • the content of such inorganic builder material in the paste can be up to 35% by weight, preferably up to 25% by weight and in particular be 10% by weight to 25% by weight.
  • a paste-like agent according to the invention contains oxygen-containing oxidizing agent in the form of inorganic peroxygen compounds, which are preferably selected from the group consisting of alkali perborate, alkali percarbonate and mixtures thereof and the sodium perborate tetrahydrate and the sodium perborate monohydrate in addition to sodium percarbonate are of particular importance.
  • suitable oxidizing agents are, for example, persulfates and peroxypyrophosphates.
  • Inorganic peroxygen compounds can be present in the agents according to the invention preferably in amounts of 20% by weight to 30% by weight, in particular 22.5% by weight to 27.5% by weight.
  • the disinfectant power of the agents according to the invention at temperatures around 60 ° C. is given without the presence of bleach activators, so that the agents according to the invention are free of such bleach activators which usually improve the oxidizing power of such oxidizing agents.
  • an agent according to the invention can contain further washing aids, which can normally be present in amounts of up to about 15% by weight, based on the finished agent.
  • washing aids can normally be present in amounts of up to about 15% by weight, based on the finished agent.
  • Enzymes, graying inhibitors, soil release active substances, color transfer inhibitors such as homo- and / or copolymers of vinylpyrrolidone and / or vinylimidazole, optical brighteners, foam regulators and / or colorants and fragrances can be used, for example, as washing auxiliaries of this type. If fragrances are contained which are generally liquid, these pass into the liquid phase of agents according to the invention. Because of their small amount, however, they have no significant influence on the flow behavior of the pastes.
  • the paste-like detergents according to the invention are preferably essentially free of water. “Substantially free of water” is understood here to mean a state in which the content of free water, that is to say water which is not in the form of hydrate water and constitutional water, is up to 5% by weight, preferably less than 3% by weight. It is noteworthy that, despite the presence of the peroxygen-containing bleach, it is possible to have higher water contents than with conventional pasty, essentially water-free detergents.
  • Organic solvents which include the low-molecular and low-boiling alcohols and ether alcohols usually used in liquid concentrates, and hydrotropic compounds may optionally be present in amounts of up to 6% by weight, but are preferably not present.
  • Enzymes which may be present in the agents according to the invention are in particular those from the class of proteases, lipases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase, Lipase and / or cellulase is particularly preferred.
  • the proportion is preferably 0.2% by weight to 1.5% by weight, in particular 0.5% by weight to 1% by weight.
  • the enzymes can be adsorbed onto carriers in a conventional manner and / or embedded in coating substances or incorporated into the pastes as concentrated liquid formulations which are as anhydrous as possible.
  • Proteases that can be used are, for example, from international patent applications WO 91/02792, WO 92/21760, WO 93/05134, WO 93/07276, WO 93/18140, WO 93/24623, WO 94/02618, WO 94/23053, WO 94 / 25579, WO 94/25583, WO 95/02044, WO 95/05477, WO 95/07350, WO 95/10592, WO 95/10615, WO 95/20039, WO 95/20663, WO 95/23211, WO 95 / 27049, WO 95/30010, WO 95/30011, WO 95/30743 and WO 95/34627.
  • Enzymes stabilized against oxidative damage are preferably used, for example the proteases or amylases known under the trade names Durazym® or Purafect® OxP or Duramyl® or Purafect® OxAm.
  • Suitable graying inhibitors or soil release active substances are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed cellulose ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose.
  • cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed cellulose ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose.
  • sodium Carboxymethyl cellulose and mixtures thereof with methyl cellulose are used.
  • the soil release agents normally used include copolyesters which contain dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Soil-removing copolyesters of the type mentioned and their use in detergents have been known for a long time.
  • German Offenlegungsschrift DT 16 17 141 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers.
  • German laid-open specification DT 22 00 911 relates to detergents which contain nonionic surfactant and a mixed polymer made from polyoxyethylene glycol and polyethylene terephthalate.
  • German laid-open specification DT 22 53 063 mentions acidic textile finishing agents which contain a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally an alkylene or cycloalkylene glycol.
  • European patent EP 066 944 relates to textile treatment agents which contain a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. From the European patent EP 185 427 methyl- or ethyl group-end-capped polyesters with ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents which contain such a soil release polymer are known. European patent EP 241 984 relates to a polyester which, in addition to oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and glycerol units. The proportion of graying inhibitors and or soil-release active substances in agents according to the invention is generally not more than 2% by weight and is preferably 0.5% to 1.5% by weight.
  • Color transfer inhibitors that are suitable for use in agents according to the invention include, in particular, polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole, and mixtures thereof.
  • the proportion of color transfer inhibitors in agents according to the invention is preferably 0.1% by weight to 2% by weight, in particular 0.2% by weight to 1% by weight.
  • diaminostilbenedisulfonic acid for example, can be used as optical brighteners for, in particular, textiles made from cellulose fibers (for example cotton) or their alkali metal salts may be included.
  • salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure are suitable Instead of the morpholine group, wear a diethanolamino group, a methylamino group or a 2-methoxyethylamino group.
  • Brighteners of the optionally substituted dibenzofuranylbiphenyl or optionally substituted 4,4'-distyryl-diphenyl type may also be present, for example 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of brighteners can also be used.
  • Brighteners of the 1,3-diaryl-2-pyrazoline type for example l- (p-sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and compounds of the same structure, are particularly suitable for polyamide fibers.
  • the content of optical brighteners or brightener mixtures in the agent is generally not more than 1% by weight, preferably 0.05% by weight to 0.5% by weight.
  • the usual foam regulators which can be used in the agents according to the invention include, for example, polysiloxane / silica mixtures, the finely divided silica contained therein preferably being silanated.
  • the polysiloxanes can consist of both linear compounds and crosslinked polysiloxane resins and mixtures thereof.
  • Further defoamers are paraffin hydrocarbons, in particular microparaffins and paraffin waxes, whose melting point is above 40 ° C, saturated fatty acids or soaps with in particular 20 to 22 C atoms, for example sodium behenate, and alkali metal salts of phosphoric acid mono- and / or dialkyl esters, in which the alkyl chains each have 12 to 22 carbon atoms.
  • sodium monoalkyl phosphate and or dialkyl phosphate with C 16 -C 8 -alkyl groups is preferably used.
  • the proportion of foam regulators can preferably be 0.2% by weight to 2% by weight. In many cases, the additional use of defoaming agents can be dispensed with entirely.
  • dehydrating agents can also be used, for example in the form of salts which bind water of crystallization, such as anhydrous sodium acetate, calcium sulfate, calcium chloride, sodium hydroxide, magnesium silicate, or metal oxides such as CaO, MgO, P 4 O ⁇ 0 or Al O 3 , are used.
  • dehydration Detergents with which the water content of agents according to the invention can, if desired, be reduced to particularly low values are present in amounts of preferably 1% by weight to 10% by weight and in particular 2% by weight to 8% by weight in the agents of the invention.
  • the procedure is preferably such that the nonionic surfactant or the nonionic surfactants are initially introduced, optionally mixed with the alcohol or ether of the formula III, with the mixture of fatty acid alkali salt and fatty acid and optionally with the foam regulator and the synthetic anionic Surfactant mixed to a homogeneous premix.
  • a premix is largely stable on storage and flowable at temperatures in the range from room temperature to 40 ° C., even if the components of the premix are not always completely liquid or dissolved at these temperatures.
  • This premix preferably after heating to temperatures in the range of approximately 80 ° C., is admixed with the powdery constituents, including the citric acid / citrate of the pasty agent, which are dispersed in the premix, in particular by stirring. Then the premix. The mixture thus obtained is then preferably subjected to a wet grinding process. This gives the product the desired consistency and homogeneity. Additional, in particular temperature- or shear-sensitive, ingredients such as perfume oils and enzymes are then mixed in, the homogeneous incorporation of which should be done as gently as possible so as not to destroy the structure of the paste.
  • the resulting washing or cleaning agents according to the invention are flowable and pumpable immediately after manufacture by the acting shear forces and can thus be filled into conventional sales containers.
  • a paste-like agent according to the invention preferably has a viscosity in the range from 60,000 mPa.s to 100,000 mPa.s, in particular 70,000 mPa.s to 90,000 mPa.s, measured at 25 ° C., using a Brookfield rotary viscometer (spindle no. 7) at 5 revolutions per minute.
  • Brookfield rotary viscometer spindle no. 7
  • these numerical values for viscosity refer to the reading after a measuring time of 3 minutes.
  • the pasty detergent and cleaning agent has one lo
  • Special embodiment of the invention preferably at room temperature such a viscosity that it is not flowable under the influence of gravity. It is then preferably particularly thixotropic and viscous, that is to say it has a significantly lower viscosity when sheared and is flowable under the action of gravity, with an apparent viscosity of approximately 80,000 to 120,000 Pas at 25 ° C. and a shear rate being particularly preferred of 0.0001 s "1 - to be determined using a CS rheometer from Bohlin with a measuring system plate / plate, plate spacing 4 mm.
  • an agent according to the invention preferably has a considerably, usually 100 to 1000 times lower viscosity.
  • the reduction in viscosity during shear is largely reversible, that is to say after the shear has ended, the agent returns to its original physical state without segregation occurring.
  • the viscosities mentioned do not refer to measurements directly after the paste has been made, but to stored pastes that are, so to speak, in equilibrium, since the shear forces acting in the course of the manufacturing process lead to a lower paste viscosity, which only occurs in the Increased over time to the definitive final viscosity. Storage times of 1 month are usually completely sufficient for this.
  • An agent according to the invention normally has a density in the range from 1.3 kg / 1.6 to 1.6 kg / 1.
  • the agent according to the invention can be metered using conventional devices for metering pastes, as described, for example, in international patent application WO 95/29282, German patent application DE 196 05 906, German patent DE 44 30418 or European patent EP 0 295 525 EP 0 356 707 have been described.
  • a device which is particularly well suited for metering structurally viscous pasty detergents is known, for example, from European Patent EP 0 721 521 and is preferably used for metering structurally viscous pastes according to the invention.
  • the detergents and cleaning agents according to the invention can, if appropriate, also be filled in portions, in particular in water-soluble films.
  • a paste-like agent according to the invention is preferably used in commercial laundries for washing and disinfecting dirty laundry. It is used in concentrations of preferably 2 g / 1 to 5 g / 1 in the wash liquor.
  • the substances listed in the table below were mixed together and ground in a milling device (roller mill, continuous throughput). Immediately after production, paste-like detergent Ml to M6 were obtained.
  • the agents had a density of approx. 1.4 g / cm and a viscosity (measured at 25 ° C with a Brookfield rotary viscometer DV-II with spindle no. 7 at 5 revolutions per minute after a measurement period of 3 minutes) of approx 80,000 mPa.s.
  • the viscosity of the pastes did not change significantly when stored for 3 months.
  • Table 1 Composition of pasty detergents (% by weight)
  • Example 2 Determination of the disinfectant effect of MI material and methodology:
  • E. faecium ATCC 6057 9.34 log. ⁇ nl (preculture on brain heart infusion agar, 48 h at 36 ⁇ 1 ° C)
  • Test germ Enterococcus faecium ATCC 6057
  • the lobes of standard cotton fabric (1 x 1 cm, DIN 53919) were immersed in the germ-blood suspension and dried in open petri dishes for 3 hours at 36 ⁇ 1 ° C.
  • Amount of ml 57.0 g 57.0 g 57.0 g
  • Heating time 10 min 54 s 11 min 10 s 11 min 07 s measured temp .:
  • Germ carrier 1 398 + 6.35

Abstract

Produit de lavage sous forme de pâte, destiné à être utilisé dans la blanchisserie commerciale, qui contient un tensioactif non ionique, un adjuvant organique et/ou inorganique, un agent de blanchiment à base de composés peroxygénés ainsi que, le cas échéant, d'autres constituants habituels. Ledit produit est caractérisé en ce qu'il contient 30 à 60 % en poids de tensioactif non ionique, 0,5 à 5 % en poids d'acide gras et/ou de sel alcalin d'acide gras, 5 à 15 % en poids de citrate et/ou d'acide citrique et 15 à 35 % en poids d'un composé peroxygéné inorganique. De plus, ledit produit ne contient pas de métasilicate alcalin, ni d'activateur de blanchiment. Le produit selon la présente invention possède, outre de bonnes performances de nettoyage, un effet désinfectant.
EP99965439A 1998-12-15 1999-12-04 Produit de lavage sous forme de pate Expired - Lifetime EP1141212B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19857687A DE19857687A1 (de) 1998-12-15 1998-12-15 Pastenförmiges Waschmittel
DE19857687 1998-12-15
PCT/EP1999/009503 WO2000036071A1 (fr) 1998-12-15 1999-12-04 Produit de lavage sous forme de pate

Publications (2)

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EP1141212A1 true EP1141212A1 (fr) 2001-10-10
EP1141212B1 EP1141212B1 (fr) 2007-08-08

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US (1) US6627592B1 (fr)
EP (1) EP1141212B1 (fr)
AT (1) ATE369415T1 (fr)
AU (1) AU2095400A (fr)
CA (1) CA2351675A1 (fr)
CZ (1) CZ20012187A3 (fr)
DE (2) DE19857687A1 (fr)
ES (1) ES2293744T3 (fr)
HU (1) HUP0104550A3 (fr)
NO (1) NO20012938D0 (fr)
SK (1) SK8202001A3 (fr)
WO (1) WO2000036071A1 (fr)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE291076T1 (de) * 1999-01-26 2005-04-15 Procter & Gamble Bleichmittelzusammensetzung enthaltend im wesentlichen lineare nichtionische tenside
DE10061416A1 (de) * 2000-12-09 2002-06-20 Henkel Ecolab Gmbh & Co Ohg Alkalische, wasserhaltige Paste
EP1482026A1 (fr) * 2003-05-28 2004-12-01 Ecolab Inc. Détergent biocide
DE102004003286A1 (de) * 2004-01-22 2005-09-29 Henkel Kgaa System zur Wasserenthärtung durch Fällenthärtung
EP1749081B8 (fr) * 2004-05-28 2019-10-16 Ecolab USA Inc. Composition savonneuse en pate compatible avec une membrane
WO2006048047A1 (fr) * 2004-11-08 2006-05-11 Ecolab Inc. Detergent biocide
US7923425B2 (en) * 2006-08-21 2011-04-12 Henkel Ag & Co. Kgaa Low-foaming, acidic low-temperature cleaner and process for cleaning surfaces
US7666828B2 (en) 2008-01-22 2010-02-23 Stepan Company Sulfonated estolides and other derivatives of fatty acids, methods of making them, and compositions and processes employing them
US7998920B2 (en) * 2008-01-22 2011-08-16 Stepan Company Sulfonated estolide compositions containing magnesium sulfate and processes employing them
US7879790B2 (en) * 2008-01-22 2011-02-01 Stepan Company Mixed salts of sulfonated estolides and other derivatives of fatty acids, and methods of making them
US7884064B2 (en) * 2009-01-21 2011-02-08 Stepan Company Light duty liquid detergent compositions of sulfonated estolides and other derivatives of fatty acids
US8124577B2 (en) * 2009-01-21 2012-02-28 Stepan Company Personal care compositions of sulfonated estolides and other derivatives of fatty acids and uses thereof
US8119588B2 (en) * 2009-01-21 2012-02-21 Stepan Company Hard surface cleaner compositions of sulfonated estolides and other derivatives of fatty acids and uses thereof
US8058223B2 (en) * 2009-01-21 2011-11-15 Stepan Company Automatic or machine dishwashing compositions of sulfonated estolides and other derivatives of fatty acids and uses thereof
EP2277860B1 (fr) * 2009-07-22 2015-08-19 Stepan Company Compositions comportant des étholides sulfonés et des sulfates d'ester alkyl, et leurs procédés de fabrication, et compositions et procédés les utilisant
AU2010292056B9 (en) 2009-09-11 2014-07-10 Stepan Company Liquid cleaning compositions containing sulfonated estolides and alkyl ester sulfonates
ES2744315T3 (es) * 2010-10-08 2020-02-24 Ecolab Usa Inc Método para lavado y desinfección a baja temperatura de lavandería
CN104388204B (zh) * 2014-10-31 2017-11-28 魏怀良 含有氧化性漂白剂和酶的浓缩膏状/半固体状洗涤剂组合物及其制备方法
US11603508B2 (en) * 2018-10-26 2023-03-14 Ecolab Usa Inc. Synergistic surfactant package for cleaning of food and oily soils
EP3969551A1 (fr) 2019-06-17 2022-03-23 Ecolab USA, Inc. Blanchiment et désinfection de textiles à l'aide d'une composition mixte d'acides peroxycarboxyliques hydrophiles et hydrophobes

Family Cites Families (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1154730A (en) 1965-10-08 1969-06-11 Ici Ltd Improvements in the Laundering of Synthetic Polymeric Textile Materials
GB1377092A (en) 1971-01-13 1974-12-11 Unilever Ltd Detergent compositions
CA989557A (en) 1971-10-28 1976-05-25 The Procter And Gamble Company Compositions and process for imparting renewable soil release finish to polyester-containing fabrics
AT330930B (de) 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
US4146495A (en) 1977-08-22 1979-03-27 Monsanto Company Detergent compositions comprising polyacetal carboxylates
US4144226A (en) 1977-08-22 1979-03-13 Monsanto Company Polymeric acetal carboxylates
DE2928305A1 (de) 1979-07-13 1981-02-05 Hoechst Ag 2-dihalogenmethylen-3-halogen-3- carboalkoxy-5-oxopyrrolidine, verfahren zu ihrer herstellung und ihre verwendung als fungizide, bakterizide und algizide schaedlingsbekaempfungsmittel
CA1190695A (fr) 1981-05-14 1985-07-16 George J. Stockburger Agent anionique pour le traitement des textiles
DE3413571A1 (de) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
EP0185427B1 (fr) 1984-12-21 1992-03-04 The Procter & Gamble Company Polyesters blocs et composés similaires utiles comme agents de détachage dans les compositions de détergent
US4713194A (en) 1986-04-15 1987-12-15 The Procter & Gamble Company Block polyester and like compounds having branched hydrophilic capping groups useful as soil release agents in detergent compositions
DE3621536A1 (de) 1986-06-27 1988-01-07 Henkel Kgaa Fluessiges waschmittel und verfahren zu seiner herstellung
DE3719906A1 (de) 1987-06-15 1988-12-29 Henkel Kgaa Maschinelles waschverfahren
DE3826110A1 (de) 1988-08-01 1990-02-15 Henkel Kgaa Verfahren zum dosieren pastenfoermiger waschmittel
DE3842007A1 (de) * 1988-12-14 1990-06-21 Henkel Kgaa Fluessiges bis pastoeses, bleichmittelhaltiges waschmittel
EP0493398B1 (fr) 1989-08-25 1999-12-08 Henkel Research Corporation Enzyme proteolytique alcaline et procede de production
YU221490A (sh) 1989-12-02 1993-10-20 Henkel Kg. Postupak za hidrotermalnu izradu kristalnog natrijum disilikata
WO1992009526A1 (fr) 1990-12-01 1992-06-11 Henkel Kommanditgesellschaft Auf Aktien Procede de production hydrothermale de disilicate de sodium cristallin
DE4030850A1 (de) * 1990-09-29 1992-04-02 Henkel Kgaa Bleichmittelzubereitung
US5340735A (en) 1991-05-29 1994-08-23 Cognis, Inc. Bacillus lentus alkaline protease variants with increased stability
DE69229119T2 (de) 1991-09-11 1999-12-30 Novo Nordisk As Reinigungsmittel mit Enzymen aus Verticillium
US5275945A (en) 1991-10-08 1994-01-04 Vista Chemical Company Alkaline proteases stable in heavy-duty detergent liquids
DE4134914A1 (de) 1991-10-23 1993-04-29 Henkel Kgaa Wasch- und reinigungsmittel mit ausgewaehlten builder-systemen
US5244593A (en) * 1992-01-10 1993-09-14 The Procter & Gamble Company Colorless detergent compositions with enhanced stability
DE4221381C1 (de) 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Zuckern, Verfahren zu ihrer Herstellung und ihre Verwendung
DK28792D0 (da) 1992-03-04 1992-03-04 Novo Nordisk As Nyt enzym
DK70292D0 (da) 1992-05-27 1992-05-27 Novo Nordisk As Nyt enzym
PL178045B1 (pl) 1992-07-17 2000-02-29 Genencor Int Mutant proteazy do stosowania w detergentach, sekwencja DNA kodująca mutanta proteazy, sposób otrzymywania mutanta proteazy oraz kompozycja detergentowa
DE4300772C2 (de) 1993-01-14 1997-03-27 Stockhausen Chem Fab Gmbh Wasserlösliche, biologisch abbaubare Copolymere auf Basis von ungesättigten Mono- und Dicarbonsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4303320C2 (de) 1993-02-05 1995-12-21 Degussa Waschmittelzusammensetzung mit verbessertem Schmutztragevermögen, Verfahren zu dessen Herstellung und Verwendung eines geeigneten Polycarboxylats hierfür
DK39093D0 (da) 1993-04-01 1993-04-01 Novo Nordisk As Enzym
EP0623672A1 (fr) 1993-05-04 1994-11-09 Research Institute For Plant Protection Sérine protéase alcaline de Paecilomyces lilacinus
DK52393D0 (fr) 1993-05-05 1993-05-05 Novo Nordisk As
DK81193D0 (da) 1993-07-06 1993-07-06 Novo Nordisk As Enzym
AU7524994A (en) 1993-08-12 1995-03-14 University Of Maryland Thermostable alkaline metalloprotease produced by a hyphomonas, and preparation thereof
DK100893D0 (da) 1993-09-09 1993-09-09 Novo Nordisk As Enzym
US6436690B1 (en) 1993-09-15 2002-08-20 The Procter & Gamble Company BPN′ variants having decreased adsorption and increased hydrolysis wherein one or more loop regions are substituted
DE4332849A1 (de) 1993-09-27 1995-03-30 Henkel Kgaa Pastenförmiges Waschmittel
DE4332850A1 (de) 1993-09-27 1995-03-30 Henkel Ecolab Gmbh & Co Ohg Pastenbehälter mit Entnahmevorrichtung
CZ105296A3 (en) 1993-10-14 1996-09-11 Procter & Gamble Bleaching agent containing protease enzymes, cleansing agents, agent for cleaning fabrics and fabric cleaning method
MA23346A1 (fr) 1993-10-14 1995-04-01 Genencor Int Variantes de la subtilisine
US6187579B1 (en) 1993-10-28 2001-02-13 Carlsberg A/S Customized proteases
EP0740705B1 (fr) 1994-01-27 2006-04-05 Rijksuniversiteit te Groningen Variants thermostables de proteases neutres de bacillus stearothermophilus
IL108775A (en) 1994-02-25 2003-09-17 Univ Ramot Method for efficient incorporation of molecules into cells
DE4411223A1 (de) 1994-03-31 1995-10-05 Solvay Enzymes Gmbh & Co Kg Verwendung alkalischer Proteasen in gewerblichen Textilwaschverfahren
DE4414708A1 (de) 1994-04-27 1995-11-02 Henkel Ecolab Gmbh & Co Ohg Verfahren und Vorrichtung zum Entleeren eines mit einer thixotropen Paste gefüllten Behälters
US6599730B1 (en) 1994-05-02 2003-07-29 Procter & Gamble Company Subtilisin 309 variants having decreased adsorption and increased hydrolysis
AU2445195A (en) 1994-05-04 1995-11-29 Novo Nordisk A/S Protease variants
DE4417734A1 (de) 1994-05-20 1995-11-23 Degussa Polycarboxylate
EP0687733A1 (fr) 1994-06-16 1995-12-20 The Procter & Gamble Company Composition détergente contenant des protéases très alkalines compatible avec de la laine
DE4428958A1 (de) * 1994-08-16 1996-02-22 Henkel Kgaa Flüssigwaschmittel mit Bleiche
DE19535082A1 (de) * 1995-09-21 1997-03-27 Henkel Ecolab Gmbh & Co Ohg Pastenförmiges Wasch- und Reinigungsmittel
DE19605906C2 (de) 1996-02-17 1998-06-04 Henkel Ecolab Gmbh & Co Ohg Gerät zum Entnehmen und Dosieren von Pasten, insbesondere Waschmittelpasten
DE19636035A1 (de) * 1996-09-05 1998-03-12 Henkel Ecolab Gmbh & Co Ohg Pastenförmiges Wasch- und Reinigungsmittel
US5955415A (en) * 1997-08-04 1999-09-21 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing polyethyleneimines for enhanced peroxygen bleach stability
DE10020145A1 (de) * 2000-04-20 2001-10-31 Henkel Ecolab Gmbh & Co Ogh Mikrobizid wirksame Tenside

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0036071A1 *

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HUP0104550A2 (hu) 2002-03-28
NO20012938L (no) 2001-06-14
DE19857687A1 (de) 2000-06-21
CZ20012187A3 (cs) 2002-06-12
ES2293744T3 (es) 2008-03-16
AU2095400A (en) 2000-07-03
CA2351675A1 (fr) 2000-06-22
WO2000036071A1 (fr) 2000-06-22
DE59914446D1 (de) 2007-09-20
SK8202001A3 (en) 2001-12-03
HUP0104550A3 (en) 2002-12-28
NO20012938D0 (no) 2001-06-14
US6627592B1 (en) 2003-09-30
EP1141212B1 (fr) 2007-08-08
ATE369415T1 (de) 2007-08-15

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